Patent Application
20250101228
The present disclosure relates to a composition and an article.
As organic silane compounds used for coatings and formed articles, organic silane compounds having an epoxy group are known.
Patent Literature 1 describes a curable composition comprising: a fluorine-containing amide compound; a fluorine-containing organohydrogen siloxane; a catalytic amount of a platinum group element; and an organosiloxane having each of one or more hydrogen atoms directly bonded to a silicon atom and one or more epoxy groups and/or trialkoxysilyl groups bonded to a silicon atom via a carbon atom or carbon and oxygen atoms in one molecule.
Patent Literature 2 describes an epoxy group-containing cyclic organosiloxane.
The present disclosure includes the following embodiments.
A composition comprising an organic silane compound (A),
The composition of the present disclosure provides a film that achieves both anti-icing performance and transparency, and preferably, a composition further capable of forming a film that also has excellent weather resistance. The present disclosure further provides an article having such a film.
The term “hydrolyzable silyl group”, as used herein, represents a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.
The term “hydrolyzable group”, as used herein, refers to a group that can undergo a hydrolysis reaction, namely, refers to a group that can be removed from a main backbone of the compound by a hydrolysis reaction. Examples of the hydrolyzable group include —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, and halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and it is preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among such groups, an alkyl group, in particular an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. The hydroxyl group in the hydrolyzable silyl group is not limited, and may be generated by hydrolysis of a hydrolyzable group.
The term “organic group”, as used herein, refers to a monovalent group containing carbon. The organic group may be a hydrocarbon group or a derivative thereof, unless otherwise specified. The derivative of a hydrocarbon group refers to a group that has one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, and the like at the terminal or in the molecular chain of the hydrocarbon group. The simple term “organic group” refers to a monovalent organic group. The term “divalent organic group” refers to a divalent group containing carbon. The divalent organic group may be, but is not limited to, a divalent group obtained by further removing one hydrogen atom from an organic group.
The term “hydrocarbon group”, as used herein, refers to a group that contains carbon and hydrogen and that is obtained by removing one hydrogen atom from a hydrocarbon. The hydrocarbon group is not limited, and examples thereof include a C1-20 hydrocarbon group optionally substituted with one or more substituents, such as an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above “aliphatic hydrocarbon group” may be either linear, branched, or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may contain one or more ring structures.
Each substituent of the “hydrocarbon group”, as used herein, is not limited, and examples thereof include a halogen atom; and one or more groups selected from a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C3-10 cycloalkyl group, a C3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, a C6-10 aryl group, and a 5- to 10-membered heteroaryl group, each of which is optionally substituted with one or more halogen atoms.
As used herein, unless otherwise specified, examples of the “alkyl group” include C1-12 (preferably C1-6, more preferably C1-3, and still more preferably C1) alkyl groups (such as a methyl group, an ethyl group, a propyl group, and an isopropyl group). Such an “alkyl group” may be linear or branched, but is preferably linear. Furthermore, the “alkyl group” may contain a functional group.
Hereinafter, a composition of the present disclosure will be described.
The composition of the present disclosure comprises
This composition provides a film that achieves both anti-icing performance and transparency.
The composition of the present disclosure may further comprise a cross-linking agent (B) and may further comprise a catalyst (C).
The organic silane compound (A) is a compound having at least a Si atom to which an organic group is bonded, and comprises a reaction product (A3) between a silane compound (A1) having a fluoropolyether group and a hydrolyzable silyl group (hereinafter, also referred to as “fluoropolyether group-containing silane compound (A1)”) and a silicone compound (A2) having an epoxy group and a hydrolyzable silyl group (hereinafter, also referred to as “epoxy group-containing silicone compound (A2)”).
In one embodiment, the reaction product (A3) may be a reaction product in which the hydrolyzable silyl group of the fluoropolyether group-containing silane compound (A1) has reacted with the hydrolyzable silyl group of the epoxy group-containing silicone compound (A2).
In one embodiment, the organic silane compound (A) preferably has a hydrolyzable silyl group.
The fluoropolyether group-containing silane compound (A1) differs from the epoxy group-containing silicone compound (A2). In one embodiment, the fluoropolyether group-containing silane compound (A1) is preferably free from an epoxy group. In another embodiment, the epoxy group-containing silicone compound (A2) is preferably free from a fluoropolyether group (for example, the group represented by PFPE, described later), and more preferably free from a fluorine atom.
In the reaction product (A3), units derived from the fluoropolyether group-containing silane compound (A1) can be preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, and still more preferably 20 parts by mass or more and 60 parts by mass or less, with respect to 100 parts by mass of units derived from the epoxy group-containing silicone compound (A2).
The organic silane compound (A) may further comprise, in addition to the reaction product (A3) of the fluoropolyether group-containing silane compound (A1) and the epoxy group-containing silicone compound (A2), the epoxy group-containing silicone compound (A2). This can result in good adhesion between the composition of the present disclosure and the substrate and miscibility with solvents and other materials.
In the organic silane compound (A), the content of units derived from the fluoropolyether group-containing silane compound (A1) can be preferably 0.1% by mass or more, more preferably 0.1% by mass or more and 2% by mass or less, and still more preferably 0.5% by mass or more and 1.7% by mass or less.
In a preferred embodiment, the fluoropolyether group-containing silane compound (A1) preferably comprises at least one compound represented by the following formula (1) or (2):
RF1α—XA—RSiβ (1)
RSiγ—XA—RF2—XA—RSiγ (2)
In the formula (1), RF1 is each independently at each occurrence Rf1—RF—Oq.
In the formula (2), RF2 is —Rf2p—RF—Oq—.
In the formula, Rf1 is each independently at each occurrence a C1-16 alkyl group optionally substituted with one or more fluorine atoms.
In the C1-16 alkyl group optionally substituted with one or more fluorine atoms, the “C1-16 alkyl group” may be linear or branched, and is preferably a linear or branched C1-6 alkyl group, in particular linear or branched C1-3 alkyl group, and more preferably a linear C1-6 alkyl group, in particular linear C1-3 alkyl group.
Rf1 is preferably a C1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF2H—C1-15 perfluoroalkylene group, and still more preferably a C1-16 perfluoroalkyl group.
The C1-16 perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C1-6 perfluoroalkyl group, in particular C1-3 perfluoroalkyl group, more preferably a linear C1-6 perfluoroalkyl group, in particular C1-3 perfluoroalkyl group, and specifically —CF3, —CF2CF3, or —CF2CF2CF3.
In the formula, Rf2 is a C1-6 alkylene group optionally substituted with one or more fluorine atoms.
In the C1-6 alkylene group optionally substituted with one or more fluorine atoms, the “C1-6 alkylene group” may be linear or branched, and is preferably a linear or branched C1-3 alkylene group, and more preferably a linear C1-3 alkylene group.
Rf2 is preferably a C1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C1-6 perfluoroalkylene group, and still more preferably a C1-3 perfluoroalkylene group.
The C1-6 perfluoroalkylene group may be linear or branched, and is preferably a linear or branched C1-3 perfluoroalkylene group, more preferably a linear C1-3 perfluoroalkylene group, and specifically —CF2—, —CF2CF2—, or —CF2CF2CF2—.
In the formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.
In the formulae, q is each independently at each occurrence 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.
In the formulae (1) and (2), RF is each independently at each occurrence a divalent fluoropolyether group.
RF is preferably a group represented by the formula:
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3RFa6)d—(OC2F4)e—(OCF2)f—
RFa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom. However, when all RFa groups are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or more.
Preferably, a, b, c, d, e, and f may be each independently an integer of 0 to 100.
The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and it may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and it may be, for example, 50 or less or 30 or less.
These repeating units may be linear or branched, or they may contain a ring structure. For example, —(OC6F12)— may be —(OCF2CF2CF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2CF2CF2)—, —(OCF2CF(CF3)CF2CF2CF2)—, —(OCF2CF2CF(CF3)CF2CF2)—, —(OCF2CF2CF2CF(CF3)CF2)—, —(OCF2CF2CF2CF2CF(CF3))—, or the like. —(OC5F10)— may be —(OCF2CF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2CF2)—, —(OCF2CF(CF3)CF2CF2)—, —(OCF2CF2CF(CF3)CF2)—, —(OCF2CF2CF2CF(CF3))—, or the like. —(OC4F8)— may be any of —(OCF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2)—, —(OCF2CF(CF3)CF2)—, —(OCF2CF2CF(CF3))—, —(OC(CF3)2CF2)—, —(OCF2C(CF3)2)—, —(OCF(CF3)CF(CF3))—, —(OCF(C2F5)CF2)—, and —(OCF2CF(C2F5))—. —(OC3F6)— (that is, in the above formula, RFa is a fluorine atom) may be any of —(OCF2CF2CF2)—, —(OCF(CF3)CF2)—, and —(OCF2CF(CF3))—. —(OC2F4)— may be any of —(OCF2CF2)— and —(OCF(CF3))—.
The ring structure may be any of the following 3-membered ring, 4-membered rings, 5-membered rings, and 6-membered rings:
The ring structure may be preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 4-membered ring or a 6-membered ring.
The repeating units having a ring structure may be preferably any of the following units:
In one embodiment, the repeating units are linear. When the repeating units are linear, the surface lubricity, abrasion durability, and the like of the film (surface-treating layer) can be improved.
In one embodiment, the repeating units are branched. When the repeating units are branched, the dynamic friction coefficient of the film (surface-treating layer) can be increased.
In one embodiment, RF is each independently at each occurrence a group represented by any of the following formulae (f1) to (f6):
—(OC3F6)d—(OC2F4)e (f1)
—(OC4F8)c—(OC3RFa6)d—(OC2F4)e—(OCF2)f— (f2)
—(R6—R7)g— (f3)
—(R6—R7)g—Rr—(R7′—R6′)g— (f4)
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f5)
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f6)
In the formula (f1), d is preferably 5 to 200, more preferably 10 to 100, and still more preferably 15 to 50, and is, for example, an integer of 25 to 35. OC3F6 in the formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). OC2F4 in the formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.
In the formula (f2), e and f are each independently an integer of preferably 5 to 200, and more preferably 10 to 200. The sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and it may be, for example, 15 or more or 20 or more. In one embodiment, the formula (f2) is preferably a group represented by —(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f—, and more preferably a group represented by —(OCF2CF2CF2CF2)c—(OCF2CF2CF2)d—(OCF2CF2)e—(OCF2)f—. In another embodiment, the formula (f2) may be a group represented by —(OC2F4)e—(OCF2)f—. In still another embodiment, the formula (f2) may be —(OC4F8)c—(OCF2CF2(CRFa)2)d10—(OCF2CF(CF3))d11—(OCF2CF2)e—(OCF2)f—. d10 and d11 are each independently an integer of 0 to 200, and is an integer of preferably 5 to 200, and more preferably 10 to 200. However, the sum of d10 and d11 is 0 to 200, preferably 5 to 200, and more preferably 10 to 200.
In the formula (f3), R6 is preferably OC2F4, and in another embodiment, it is OCF2. In (f3), R7 is preferably a group selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 is not limited, and examples thereof include —OC2F4OC3F6—, —OC2F4OC4F8—, —OC3F6OC2F4—, —OC3F6OC3F6—, —OC3F6OC4F8—, —OC4F8OC4F8—, —OC4F8OC3F6—, —OC4F8OC2F4—, —OC2F4OC2F4OC3F6—, —OC2F4OC2F4OC4F8—, —OC2F4OC3F6OC2F4—, —OC2F4OC3F6OC3F6—, —OC2F4OC4F8OC2F4—, —OC3F6OC2F4OC2F4—, —OC3F6OC2F4OC3F6—, —OC3F6OC3F6OC2F4—, and —OC4F8OC2F4OC2F4—. In the formula (f3), g is an integer of preferably 3 or more, and more preferably 5 or more. g is preferably an integer of 50 or less. In the formula (f3), OC2F4, OC3F6, OC4F8, OC5F10, and OC6F12 may be either linear or branched, and are preferably linear. In this embodiment, the formula (f3) is preferably —(OC2F4—OC3F6)g— or —(OC2F4—OC4F8)g—.
In the formula (f4), R6, R7, and g have the same definition as described for the formula (f3) and have the same embodiments. R6′, R7′, and g′ have the same definition as R6, R7, and g described in the formula (f3), respectively, and have the same embodiments. Rr is preferably any of the following:
In the formula (f5), e is an integer of preferably 1 or more and 100 or less, and more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and it is, for example, 10 or more and 100 or less.
In the formula (f6), f is an integer of preferably 1 or more and 100 or less, and more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and it is, for example, 10 or more and 100 or less.
In one embodiment, RF is a group represented by the formula (f1).
In one embodiment, RF is a group represented by the formula (f2).
In one embodiment, RF is a group represented by the formula (f3).
In one embodiment, RF is a group represented by the formula (f4).
In one embodiment, RF is a group represented by the formula (f5).
In RF, the ratio of e to f (hereinafter, referred to as “e/f ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. With an e/f ratio of 10 or less, the lubricity, abrasion durability, and chemical resistance of a film (surface-treating layer) obtained from the compound are further improved. The lower the e/f ratio is, the more improved the lubricity and the abrasion durability of the film are. On the other hand, with an e/f ratio of 0.1 or more, the stability of the compound can be further enhanced. The larger the e/f ratio is, the more improved the stability of the compound is.
In the fluoropolyether group-containing silane compound, the number average molecular weight of the RF1 and RF2 moieties is, but is not limited to, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. Herein, the number average molecular weight of RF1 and RF2 is a value obtained by 19F-NMR measurement.
In another embodiment, the number average molecular weight of the RF1 and RF2 moieties is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000, and may be, for example, 3,000 to 6,000.
In another embodiment, the number average molecular weight of the RF1 and RF2 moieties may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.
In the formulae (1) and (2), RSi is each independently at each occurrence a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group is bonded, and at least one RSi is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. RSi contributes to adhesion to the substrate and may chemically react with the material of the substrate.
In a preferred embodiment, RSi is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.
In a preferred embodiment, RSi is a group represented by the following formula (S1), (S2), (S3), or (S4):
SiR11n1R123-n1 (S2)
SiRa1k1Rb1l1Rc1m1 (S3)
CRd1k2Re1l2Rf1m2 (S4)
NRg1Rh1 (S5)
In the formulae, R11 is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
R11 is preferably, each independently at each occurrence, a hydrolyzable group.
Preferably, R11 is each independently at each occurrence —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
In the formulae, R12 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In R12, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
In the formulae, n1 is each independently an integer of 0 to 3 for each (SiR11n1R123-n1) unit. However, when RSi is a group represented by the formula (S1) or (S2), the RSi moiety at the terminal of the formulae (1) and (2) (hereinafter, also referred to simply as “terminal moiety” of the formulae (1) and (2)) has at least one (SiR11n1R123-n1) unit wherein n1 is 1 to 3. That is, in such terminal moieties, not all n1 are 0 at the same time. In other words, in the terminal moieties of the formula (1) and the formula (2), at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present.
n1 is each independently an integer of preferably 1 to 3, more preferably 2 to 3, and still more preferably 3 for each (SiR11n1R123-n1) unit.
In the formula, X11 is each independently at each occurrence a single bond or a divalent organic group. Such a divalent organic group is preferably —R28—Ox-R29— (wherein R28 and R29 are each independently at each occurrence a single bond or a C1-20 alkylene group, and x is 0 or 1). Such a C1-20 alkylene group may be linear or branched, and is preferably linear. Such a C1-20 alkylene group is preferably a C1-10 alkylene group, more preferably a C1-6 alkylene group, and still more preferably a C1-3 alkylene group.
In one embodiment, X11 is each independently at each occurrence a —C1-6 alkylene-O—C1-6 alkylene- or a —O—C1-6 alkylene-.
In a preferred embodiment, X11 is each independently at each occurrence a single bond or a linear C1-6 alkylene group, preferably a single bond or a linear C1-3 alkylene group, more preferably a single bond or a linear C1-2 alkylene group, and still more preferably a linear C1-2 alkylene group.
In the formula, R13 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably a C1-20 alkyl group. Such a C1-20 alkyl group may be linear or branched, but is preferably linear.
In a preferred embodiment, R13 is each independently at each occurrence a hydrogen atom or a linear C1-6 alkyl group, preferably a hydrogen atom or a linear C1-3 alkyl group, and preferably a hydrogen atom or a methyl group.
In the formula, t is each independently at each occurrence an integer of 2 or more.
In a preferred embodiment, t is each independently at each occurrence an integer of 2 to 10, and preferably an integer of 2 to 6.
In the formula, R14 is each independently at each occurrence a hydrogen atom, a halogen atom, or —X11—SiR11n1R123-n1. Such a halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom, and more preferably a fluorine atom. In a preferred embodiment, R14 is a hydrogen atom.
In the formula, R15 is each independently at each occurrence a single bond, an oxygen atom, a C1-6 alkylene group, or a C1-6 alkyleneoxy group.
In one embodiment, R15 is each independently at each occurrence an oxygen atom, a C1-6 alkylene group, or a C1-6 alkyleneoxy group.
In a preferred embodiment, R15 is a single bond.
In one embodiment, the formula (S1) is the following formula (S1-a):
In a preferred embodiment, the formula (S1) is the following formula (S1-b):
In the formula, Ra1 is each independently at each occurrence —Z1—SiR21p1R22q1R23r1.
Z1 is each independently at each occurrence an oxygen atom or a divalent organic group. The structure denoted as Z1 hereinafter is bonded to (SiR21p1R22q1R23r1) on the right side.
In a preferred embodiment, Z1 is a divalent organic group.
In a preferred embodiment, Z1 does not include a group that forms a siloxane bond with the Si atom to which Z1 is bonded. Preferably, in the formula (S3), (Si—Z1—Si) does not contain a siloxane bond.
Z1 is preferably a C1-6 alkylene group, —(CH2)z1—O—(CH2)z2— (wherein z1 is an integer of 0 to 6, such as an integer of 1 to 6, and z2 is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH2)z3-phenylene-(CH2)z4— (wherein z3 is an integer of 0 to 6, such as an integer of 1 to 6, and z4 is an integer of 0 to 6, such as an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, but is preferably linear. These groups are optionally substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, and are preferably unsubstituted.
In a preferred embodiment, Z1 is a C1-6 alkylene group or —(CH2)z3-phenylene-(CH2)z4—, and preferably -phenylene-(CH2)z4—. When Z1 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z1 is a C1-3 alkylene group. In one embodiment, Z1 may be —CH2CH2CH2—. In another embodiment, Z1 may be —CH2CH2—.
R21 is each independently at each occurrence —Z1′—SiR21′p1′R22′g1′R23′r1′.
Z1′ is each independently at each occurrence an oxygen atom or a divalent organic group. The structure denoted as Z1′ hereinafter is bonded to (SiR21′p1′R22′g1′R23′r1′) on the right side.
In a preferred embodiment, Z1′ is a divalent organic group.
In a preferred embodiment, Z1′ does not include a group that forms a siloxane bond with the Si atom to which Z1′ is bonded. Preferably, in the formula (S3), (Si—Z1′—Si) does not contain a siloxane bond.
Z1′ is preferably a C1-6 alkylene group, —(CH2)z1′—O—(CH2)z2′— (wherein z1′ is an integer of 0 to 6, such as an integer of 1 to 6, and z2′ is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH2)z3′-phenylene-(CH2)z4′— (wherein z3′ is an integer of 0 to 6, such as an integer of 1 to 6, and z4′ is an integer of 0 to 6, such as an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, but is preferably linear. These groups are optionally substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, and are preferably unsubstituted.
In a preferred embodiment, Z1′ is a C1-6 alkylene group or —(CH2)z3′-phenylene-(CH2)z4′—, and preferably -phenylene-(CH2)z4′—. When Z1′ is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z1′ is a C1-6 alkylene group. In one embodiment, Z1′ may be —CH2CH2CH2—. In another embodiment, Z1′ may be —CH2CH2—.
R21′ is each independently at each occurrence —Z1″—SiR22″q1″R23″r1″.
Z1″ is each independently at each occurrence an oxygen atom or a divalent organic group. The structure denoted as Z1″ hereinafter is bonded to (SiR22″q1″R23″r1″) on the right side.
In a preferred embodiment, Z1″ is a divalent organic group.
In a preferred embodiment, Z1″ does not include a group that forms a siloxane bond with the Si atom to which Z1″ is bonded. Preferably, in the formula (S3), (Si—Z1″—Si) does not contain a siloxane bond.
Z1″ is preferably a C1-6 alkylene group, —(CH2)z1″—O—(CH2)z2″— (wherein z1″ is an integer of 0 to 6, such as an integer of 1 to 6, and z2″ is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH2)z3″-phenylene-(CH2)z4″— (wherein z3″ is an integer of 0 to 6, such as an integer of 1 to 6, and z4″ is an integer of 0 to 6, such as an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, but is preferably linear. These groups are optionally substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, and are preferably unsubstituted.
In a preferred embodiment, Z1″ is a C1-6 alkylene group or —(CH2)z3″-phenylene-(CH2)z4″—, and preferably -phenylene-(CH2)z4″—. When Z1″ is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z1″ is a C1-3 alkylene group. In one embodiment, Z1″ may be —CH2CH2CH2—. In another embodiment, Z1″ may be —CH2CH2—.
R22″ is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
R22″ is preferably, each independently at each occurrence, a hydrolyzable group.
Preferably, R22″ is each independently at each occurrence —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R23″ is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In R23″, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
q1″ is each independently at each occurrence an integer of 0 to 3, and r1″ is each independently at each occurrence an integer of 0 to 3. The total of q1″ and r1″ is 3 in the (SiR22″q1″R23″r1″) unit.
q1″ is each independently an integer of preferably 1 to 3, more preferably 2 to 3, and still more preferably 3 for each (SiR22″q1″R23″r1″) unit.
R22′ is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
R22′ is preferably, each independently at each occurrence, a hydrolyzable group.
Preferably, R22′ is each independently at each occurrence —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R23′ is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In R23′, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
p1′ is each independently at each occurrence an integer 0 to 3, q1′ is each independently at each occurrence an integer of 0 to 3, and r1′ is each independently at each occurrence an integer of 0 to 3. The total of p′, q1′, and r1′ is 3 in the (SiR21p1′R22′q1′R23′r1′) unit.
In one embodiment, p1′ is 0.
In one embodiment, p1′ may be each independently an integer of 1 to 3, an integer of 2 to 3, or 3 for each (SiR21′p1′R22′q1′R23r1′) unit. In a preferred embodiment, p1′ is 3.
In one embodiment, q1′ is each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR21′p1′—R22′q1′R23′r1′) unit.
In one embodiment, p1′ is 0, and q1′ is each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR21′p1′R22′q1′R23′r1′) unit.
R22 is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
R22 is preferably, each independently at each occurrence, a hydrolyzable group.
Preferably, R22 is each independently at each occurrence —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R23 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In R23, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
p1 is each independently at each occurrence an integer of 0 to 3, q1 is each independently at each occurrence an integer of 0 to 3, and r1 is each independently at each occurrence an integer of 0 to 3. The total of p1, q1, and r1 is 3 in the (SiR21p1R22q1R23r1) unit.
In one embodiment, p1 is 0.
In one embodiment, p1 may be each independently an integer of 1 to 3, an integer of 2 to 3, or 3 for each (SiR21p1R22q1R23r1) unit. In a preferred embodiment, p1 is 3.
In one embodiment, q1 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR21p1R22q1R23r1) unit.
In one embodiment, p1 is 0, and q1 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, and still more preferably 3 for each (SiR21p1R22q1R23r1) unit.
In the formula, Rb1 is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
Rb1 is preferably, each independently at each occurrence, a hydrolyzable group.
Preferably, Rb1 is each independently at each occurrence —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
In the formula, Rc1 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In Rc1, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
k1 is each independently at each occurrence an integer of 0 to 3, l1 is each independently at each occurrence an integer of 0 to 3, and m1 is each independently at each occurrence an integer of 0 to 3. The total of k1, l1, and m1 is 3 in the (SiRa1k1Rb1l1Rd1m1) unit.
In one embodiment, k1 is each independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3 for each (SiRa1k1Rb1l1Rc1m1) unit. In a preferred embodiment, k1 is 3.
In the formulae (1) and (2), when RSi is a group represented by the formula (S3), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal moieties of the formulae (1) and (2).
In a preferred embodiment, the group represented by the formula (S3) has any one of —Z1—SiR22q1R23r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, and r1 is an integer of 0 to 2), —Z1′—SiR22′q1′R23′r1′ (wherein q1′ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, and r1′ is an integer of 0 to 2), and —Z1″—SiR22″q1″R23″r1″ (wherein q1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, and r1″ is an integer of 0 to 2). Z1, Z1′, Z1″, R22, R23, R22′, R23′, R22″, and R23″ have the same definition as described above.
In a preferred embodiment, when R21′ is present in the formula (S3), q1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, preferably all of R21′ groups.
In a preferred embodiment, when R21 is present in the formula (S3), p1′ is 0, and q1′ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, preferably all of R21 groups.
In a preferred embodiment, when Ra1 is present in the formula (S3), p1 is 0, and q1 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, preferably all of Ra1 groups.
In a preferred embodiment, in the formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.
Rd1 is each independently at each occurrence —Z2—CR31p2R32q2R33r2.
Z2 is each independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. The structure denoted as Z2 hereinafter is bonded to (CR31p2R32q2R33r2) on the right side.
In a preferred embodiment, Z2 is a divalent organic group.
Z2 is preferably a C1-6 alkylene group, —(CH2)z5—O—(CH2)z6— (wherein z5 is an integer of 0 to 6, such as an integer of 1 to 6, and z6 is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH2)z7-phenylene-(CH2)z8— (wherein z7 is an integer of 0 to 6, such as an integer of 1 to 6, and z8 is an integer of 0 to 6, such as an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, but is preferably linear. These groups are optionally substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, and are preferably unsubstituted.
In a preferred embodiment, Z2 is a C1-6 alkylene group or —(CH2)z7-phenylene-(CH2)z8—, and preferably -phenylene-(CH2)z8—. When Z2 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z2 is a C1-3 alkylene group. In one embodiment, Z2 may be —CH2CH2CH2—. In another embodiment, Z2 may be —CH2CH2—.
R31 is each independently at each occurrence —Z2′—CR32′q2—R33′r2′—.
Z2′ is each independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. The structure denoted as Z2′ hereinafter is bonded to (CR32′q2—R33′r2′) on the right side.
Z2′ is preferably a C1-6 alkylene group, —(CH2)z5′—O—(CH2)z6′— (wherein z5′ is an integer of 0 to 6, such as an integer of 1 to 6, and z6′ is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH2)z7′-phenylene-(CH2)z8′— (wherein z7′ is an integer of 0 to 6, such as an integer of 1 to 6, and z8′ is an integer of 0 to 6, such as an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, but is preferably linear. These groups are optionally substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, and are preferably unsubstituted.
In a preferred embodiment, Z2′ is a C1-6 alkylene group or —(CH2)z7′-phenylene-(CH2)z8′—, preferably -phenylene-(CH2)z8′—. When Z2′ is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z2′ is a C1-3 alkylene group. In one embodiment, Z2′ may be —CH2CH2CH2—. In another embodiment, Z2′ may be —CH2CH2—.
R32′ is each independently at each occurrence —Z3—SiR34n2R35n2.
Z3 is each independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. The structure denoted as Z3 hereinafter is bonded to (SiR34n2R353-n2) on the right side.
In one embodiment, Z3 is an oxygen atom.
In one embodiment, Z3 is a divalent organic group.
Z3 is preferably a C1-6 alkylene group, —(CH2)z5″—O—(CH2)z6″— (wherein z5″ is an integer of 0 to 6, such as an integer of 1 to 6, and z6″ is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH2)z7′-phenylene-(CH2)z8″— (wherein z7″ is an integer of 0 to 6, such as an integer of 1 to 6, and z8″ is an integer of 0 to 6, such as an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, but is preferably linear. These groups are optionally substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, and are preferably unsubstituted.
In a preferred embodiment, Z3 is a C1-6 alkylene group or —(CH2)z7″-phenylene-(CH2)z8″—, and preferably -phenylene-(CH2)z8″—. When Z3 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z3 is a C1-3 alkylene group. In one embodiment, Z3 may be —CH2CH2CH2—. In another embodiment, Z3 may be —CH2CH2—.
R34 is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
R34 is preferably, each independently at each occurrence, a hydrolyzable group.
Preferably, R34 is each independently at each occurrence —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R35 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In R35, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
In the formula, n2 is each independently an integer of 0 to 3 for each (SiR34n2R353-n2) unit. However, when RSi is a group represented by the formula (S4), the terminal moieties of the formulae (1) and (2) have at least one (SiR34n2R353-n2) unit wherein n2 is 1 to 3. That is, in such terminal moieties, not all n2 are 0 at the same time. In other words, in the terminal moieties of the formula (1) and the formula (2), at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present.
n2 is each independently an integer of preferably 1 to 3, more preferably 2 to 3, and still more preferably 3 for each (SiR34n2R353-n2) unit.
R33′ is each independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In R33′, the monovalent organic group is preferably a C1-20 alkyl group or —(CsH2s)t1—(O—CsH2s)t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 2 to 6), more preferably a C1-20 alkyl group, still more preferably a C1-6 alkyl group, and particularly preferably a methyl group.
In one embodiment, R33′ is a hydroxyl group.
In another embodiment, R33′ is a monovalent organic group, preferably a C1-20 alkyl group, and more preferably a C1-6 alkyl group.
q2′ is each independently at each occurrence an integer of 0 to 3, and r2′ is each independently at each occurrence an integer of 0 to 3. The total of q2′ and r2′ is 3 in the (CR32′q2′R33r2′) unit.
q2′ is each independently an integer of preferably 1 to 3, more preferably 2 to 3, and still more preferably 3 for each (CR32′q2′R33′r2′) unit.
R32 is each independently at each occurrence —Z3—SiR34n2R353-n2. Such —Z3—SiR34n2R353-n2 has the same definition as described for R32′.
R33 is each independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In R33, the monovalent organic group is preferably a C1-20 alkyl group or —(CsH2s)t1—(O—CsH2s)t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 2 to 6), more preferably a C1-20 alkyl group, still more preferably a C1-6 alkyl group, and particularly preferably a methyl group.
In one embodiment, R33 is a hydroxyl group.
In another embodiment, R33 is a monovalent organic group, preferably a C1-20 alkyl group, and more preferably a C1-6 alkyl group.
p2 is each independently at each occurrence an integer of 0 to 3, q2 is each independently at each occurrence an integer of 0 to 3, and r2 is each independently at each occurrence an integer of 0 to 3. The total of p2, q2, and r2 is 3 in the (CR31p2R32q2R33r2) unit.
In one embodiment, p2 is 0.
In one embodiment, p2 may be each independently an integer of 1 to 3, an integer of 2 to 3, or 3 for each (CR31p2R32q2R33r2) unit. In a preferred embodiment, p2 is 3.
In one embodiment, q2 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (CR31p2R32q2R33r2) unit.
In one embodiment, p2 is 0, and q2 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, and still more preferably 3 for each (CR31p2R32q2R33r2) unit.
Re1 is each independently at each occurrence —Z3—SiR34n2R353-n2. Such —Z3—SiR34n2R353-n2 has the same definition as described for R32′.
Rf1 is each independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
In Rf1, the monovalent organic group is preferably a C1-20 alkyl group or —(CsH2s)t1—(O—CsH2s)t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 2 to 6), more preferably a C1-20 alkyl group, still more preferably a C1-6 alkyl group, and particularly preferably a methyl group.
In one embodiment, Rf1 is a hydroxyl group.
In another embodiment, Rf1 is a monovalent organic group, preferably a C1-20 alkyl group, and more preferably a C1-6 alkyl group.
k2 is each independently at each occurrence an integer of 0 to 3, l2 is each independently at each occurrence an integer of 0 to 3, and m2 is each independently at each occurrence an integer of 0 to 3. The total of k2, l2, and m2 is 3 in the (CRd1k2Re1l2Rf1m2) unit.
In the formulae (1) and (2), when RSi is a group represented by the formula (S4), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal moieties of the formulae (1) and (2).
In one embodiment, when RSi is a group represented by the formula (S4), 2 or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3 (SiR34n2R353-n2) units in which n2 is 1 to 3, preferably 2 or 3, and more preferably 3 are present in each terminal moiety of the formula (1) and the formula (2).
In a preferred embodiment, when R32′ is present in the formula (S4), n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, preferably all of R32′ groups.
In a preferred embodiment, when R32 is present in the formula (S4), n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, preferably all of R32 groups.
In a preferred embodiment, when Re1 is present in the formula (S4), n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, preferably all of Ra groups.
In a preferred embodiment, in the formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
Rg1 and Rh1 are each independently at each occurrence —Z4—SiR11n1R123-n1, —Z4—SiRa1k1Rb1l1Rc1m1, or —Z4—CRd1k2Re1l2Rf1m2. Here, R11, R12, Ra1, Rb2, Rc1, Rd1, Re1, Rf1, n1, k1, l1, m1, k2, l2, and m2 have the same definition as described above.
In a preferred embodiment, Rg1 and Rh1 are each independently —Z4—SiR11n1R123-n1.
Z4 is each independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. The structure denoted as Z4 hereinafter is bonded to (SiR11n1R123-n1) on the right side.
In one embodiment, Z4 is an oxygen atom.
In one embodiment, Z4 is a divalent organic group.
Z4 is preferably a C1-6 alkylene group, —(CH2)z5—O—(CH2)z6″— (wherein z5″ is an integer of 0 to 6, such as an integer of 1 to 6, and z6″ is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH2)z7″-phenylene-(CH2)z8″— (wherein z7″ is an integer of 0 to 6, such as an integer of 1 to 6, and z8″ is an integer of 0 to 6, such as an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, but is preferably linear. These groups are optionally substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, and are preferably unsubstituted.
In a preferred embodiment, Z4 is a C1-6 alkylene group or —(CH2)z7″-phenylene-(CH2)z8″—, and preferably -phenylene-(CH2)z8″—. When Z3 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z4 is a C1-3 alkylene group. In one embodiment, Z4 may be —CH2CH2CH2—. In another embodiment, Z4 may be —CH2CH2—.
In one embodiment, RSi is a group represented by the formula (S2), (S3), (S4), or (S5). These compounds are capable of forming a film (surface-treating layer) having high surface lubricity.
In one embodiment, RSi is a group represented by the formula (S3), (S4), or (S5). These compounds have a plurality of hydrolyzable groups at one terminal, and are therefore capable of forming a film (surface-treating layer) that firmly adheres to a substrate and that has high abrasion durability.
In one embodiment, RSi is a group represented by the formula (S3) or (S4). These compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one terminal, and are therefore capable of forming a film having higher abrasion durability.
In one embodiment, RSi is a group represented by the formula (S1).
In one embodiment, RSi is a group represented by the formula (S2).
In one embodiment, RSi is a group represented by the formula (S3).
In one embodiment, RSi is a group represented by the formula (S4).
In one embodiment, RSi is a group represented by the formula (S5).
In one embodiment, the hydrolyzable group contained in the formulae (1) and (2) may be condensed with other hydrolyzable groups. In this case, the hydrolyzable group contained in the formula (1) or (2) may be a divalent group excluding the moiety involved in the condensation, and those in which hydrolyzability is replaced by such a divalent group in the formula (1) or (2) are also included in the compound (1) or (2). The same is true for the hydrolyzable group contained in the formulae (1a) and (2a), which will be described later.
In the formulae (1) and (2), XA is interpreted as a linker connecting fluoropolyether moieties (RF1 and RF2), which mainly provide water-repellency, surface lubricity and the like, to a moiety (RSi) providing a binding ability to a substrate. Accordingly, such XA may be a single bond or any group as long as the compounds represented by the formulae (1) and (2) can stably exist.
In the formula (1), α is an integer of 1 to 9, and β is an integer of 1 to 9. These a and β may vary depending on the valence of XA. The sum of α and β is the same as the valence of XA. For example, when XA is a decavalent organic group, the sum of α and β is 10; for example, a case where α is 9 and β is 1, α is 5 and β is 5, or α is 1 and β is 9, can be considered. When XA is a divalent organic group, α and β are 1.
In the formula (2), γ is an integer of 1 to 9. γ may vary depending on the valence of XA. That is, γ is a value obtained by subtracting 1 from the valence of XA.
XA may be each independently a single bond or a di- to decavalent organic group.
The di- to decavalent organic group in XA is preferably a di- to octavalent organic group. In one embodiment, such a di- to decavalent organic group is preferably a di- to tetravalent organic group, and more preferably a divalent organic group. In another embodiment, such a di- to decavalent organic group is preferably a tri- to octavalent organic group, and more preferably a tri- to hexavalent organic group.
In one embodiment, XA is a single bond or a divalent organic group, α is 1, and β is 1.
In one embodiment, XA is a single bond or a divalent organic group, and γ is 1.
In one embodiment, XA is a tri- to hexavalent organic group, α is 1, and β is 2 to 5.
In one embodiment, XA is a tri- to hexavalent organic group, and γ is 2 to 5.
In one embodiment, XA is a trivalent organic group, α is 1, and β is 2.
In one embodiment, XA is a trivalent organic group, and γ is 2.
When XA is a single bond or a divalent organic group, the formulae (1) and (2) are represented by the following formulae (1a) and (2a).
RF1—XA—RSi (1a)
RSi—XA—RF2—XA—RSi (2a)
In each of the formula (1a) or the formula (2a), at least one RSi is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.
In one embodiment, XA is a single bond.
In another embodiment, XA is a divalent organic group.
In one embodiment, examples of XA include a single bond or a divalent organic group represented by the following formula:
—(R51)p5—(X51)q5—
In a preferred embodiment, XA is each independently —(R51)p5—(X51)q5—R52—. R52 represents a single bond, —(CH2)t5—, or an o-, m- or p-phenylene group, and is preferably —(CH2)t5—. t5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R52 (typically a hydrogen atom of R52) is optionally substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group, and a C1-3 fluoroalkyl group. In a preferred embodiment, R56 is not substituted with any of these groups.
Preferably, XA may be each independently
More preferably, XA is each independently
More preferably, XA may be each independently
In a preferred embodiment, XA may be each independently
In a preferred embodiment, XA may be each independently
In one embodiment, XA is each independently
In the formula, —(CvH2v)— may be linear or branched, and it may be, for example, —CH2CH2—, —CH2CH2CH2—, —CH(CH3)—, or —CH(CH3)CH2—.
XA is each independently optionally substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group, and a C1-3 fluoroalkyl group (preferably a C1-3 perfluoroalkyl group). In one embodiment, XA is unsubstituted.
XA is bonded to RF1 or RF2 on the left side, and bonded to RSi on the right side.
In one embodiment, XA may be each independently a group other than an —O—C1-6 alkylene group.
In another embodiment, examples of XA include the following groups:
Specific examples of XA include
and the like.
In still another embodiment, XA is each independently a group represented by the formula: —(R16)x1—(CFR17)y1—(CH2)z1—. In the formula, x1, y1, and z1 are each independently an integer of 0 to 10, the sum of x1, y1, and z1 is 1 or more, and the occurrence order of the respective repeating units enclosed in parentheses is not limited in the formula.
In the formula, R16 is each independently at each occurrence an oxygen atom, phenylene, carbazolylene, —NR18— (in the formula, R18 represents a hydrogen atom or an organic group), or a divalent organic group. Preferably, R11 is an oxygen atom or a divalent polar group.
Examples of the “divalent polar group” include, but are not limited to, —C(O)—, —C(═NR19)—, and —C(O)NR19— (in these formulae, R19 represents a hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, a C1-6 alkyl group, such as methyl, ethyl, or n-propyl, that is optionally substituted with one or more fluorine atoms.
In the formula, R17 is each independently at each occurrence a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, and is preferably a fluorine atom. The “lower fluoroalkyl group” is, for example, a C1-6, preferably C1-3, fluoroalkyl group, preferably a C1-3 perfluoroalkyl group, more preferably a trifluoromethyl group or a pentafluoroethyl group, and still more preferably a trifluoromethyl group.
In still another embodiment, examples of XA include the following groups:
The radical scavenging group is not limited as long as it can scavenge a radical generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonates, organoacrylates, hindered amines, hindered phenols, and triazines.
The UV absorbing group is not limited as long as it can absorb ultraviolet rays, and examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxy cinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.
In a preferred embodiment, examples of the preferred radical scavenging group or UV absorbing group include groups represented by the following formulae.
In this embodiment, XA may be each independently a tri- to decavalent organic group.
In still another embodiment, examples of XA include the following group:
In one embodiment, R25 is a single bond, a C1-20 alkylene group, a C3-20 cycloalkylene group, a C5-20 arylene group, —R57—X58—R59—, —X58—R59—, or —R57—X58—. R57 and R59 are each independently a single bond, a C1-20 alkylene group, a C3-20 cycloalkylene group, or a C5-20 arylene group. X58 is —O—, —S—, —CO—, —O—CO—, or —COO—.
In one embodiment, R26 and R27 are each independently a hydrocarbon, or a group having at least one atom selected from N, O, and S at a terminal or in the main chain of a hydrocarbon, and preferred examples thereof include a C1-6 alkyl group, —R36—R37—R36, and —R36—CHR382—. Here, R36 is each independently a single bond or a C1-6 alkyl group, and preferably a C1-6 alkyl group. R37 is N, O, or S, and preferably N or O. R38 is —R45—R46—R45—, —R46—R45—, or —R45—R46—. Here, R45 is each independently a C1-6 alkyl group. R46 is N, O, or S, and preferably O.
In this embodiment, XA may be each independently a tri- to decavalent organic group.
In still another embodiment, examples of XA include a group represented by the following:
Xa is a single bond or divalent linking group directly bonded to the isocyanuric ring. Xa is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, and more preferably a single bond, a C1-10 alkylene group, or a divalent C1-10 hydrocarbon group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.
Xa is still more preferably a group represented by the following formula:
—(CX121X122)x1—(Xa1)y1—(CX123X124)z1—
Xa1 is preferably —O— or —C(═O)O—.
Xa is particularly preferably
—(CF2)m11—(CH2)m12—O—(CH2)m13—
—(CF2)m14—(CH2)m15—O—CH2CH(OH)—(CH2)m16—
—(CF2)m17—(CH2)m18—
—(CF2)m19—(CH2)m20—O—CH2CH(OSi(OCH3)3)—(CH2)m21—
—(CH2)m22—
Xa is not limited, and specific examples thereof include —CH2—, —C2H4—, —C3H6—, —C4H8—, —C4H8—O—CH2—, —CO—O—CH2—CH(OH)—CH2—, —(CF2)n5— (n5 is an integer of 0 to 4), —(CF2)n5—(CH2)m5— (n5 and m5 are each independently an integer of 0 to 4), —CF2CF2CH2OCH2CH(OH)CH2—, and —CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2—.
In this embodiment, XA may be each independently a di- or trivalent organic group.
In a preferred embodiment, the fluoropolyether group-containing compound may be a compound represented by formula (1b) or formula (2b):
R1 is preferably a monovalent organic group containing a fluoropolyether group (provided that those containing a urethane bond are excluded).
R1′ is preferably a divalent organic group containing a fluoropolyether group (provided that those containing a urethane bond are excluded).
X1″ is preferably F.
m31 to m36 are each preferably an integer of 0 to 200, and more preferably an integer of 0 to 100. The total of m31 to m36 is preferably 1 or more, more preferably 5 or more, and still more preferably 10 or more. The total of m31 to m36 is preferably 200 or less, and more preferably 100 or less. The total of m31 to m36 is preferably 10 to 200, and more preferably 10 to 100.
In the fluoropolyether group, each repeating unit may be linear or branched, or may contain a ring structure, and is preferably linear. For example, —(OC6F12)— may be —(OCF2CF2CF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2CF2CF2)—, —(OCF2CF(CF3)CF2CF2CF2)—, —(OCF2CF2CF(CF3)CF2CF2)—, —(OCF2CF2CF2CF(CF3)CF2)—, —(OCF2CF2CF2CF2CF(CF3))—, or the like, and is preferably —(OCF2CF2CF2CF2CF2CF2)—, —(OC5F10)— may be —(OCF2CF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2CF2)—, —(OCF2CF(CF3)CF2CF2)—, —(OCF2CF2CF(CF3)CF2)—, —(OCF2CF2CF2CF(CF3))—, or the like, and is preferably —(OCF2CF2CF2CF2CF2)—, —(OC4F8)— may be any of —(OCF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2)—, —(OCF2CF(CF3)CF2)—, —(OCF2CF2CF(CF3))—, —(OC(CF3)2CF2)—, —(OCF2C(CF3)2)—, —(OCF(CF3)CF(CF3))—, —(OCF(C2F5)CF2)—, and —(OCF2CF(C2F5))—, and is preferably —(OCF2CF2CF2CF2)—. —(OC3F6)— may be any of —(OCF2CF2CF2)—, —(OCF(CF3)CF2)—, and —(OCF2CF(CF3))—, and is preferably —(OCF2CF2CF2)—. In addition, —(OC2F4)— may be any of —(OCF2CF2)— and —(OCF(CF3))—, and is preferably —(OCF2CF2)—.
The ring structure may be any of the following 3-membered ring, 4-membered rings, 5-membered rings, and 6-membered rings:
The ring structure may be preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 4-membered ring or a 6-membered ring.
The repeating units having a ring structure may be preferably any of the following units:
In one embodiment, the fluoropolyether group is a chain represented by —(OC3F6)m34—(OC2F4)m35— (wherein m34 is an integer of 1 to 200 and m35 is 0 or 1). (OC3F6) in the fluoropolyether group is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). (OC2F4) in the fluoropolyether group is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2). m34 is preferably an integer of 5 to 200, and more preferably an integer of 10 to 200. In one embodiment, m35 is 0. In another embodiment, m35 is 1.
In another embodiment, the fluoropolyether group is a chain represented by —(OC4F8)m33—(OC3F6)m34—(OC2F4)m35—(OCF2)m36— (wherein m33 and m34 are each an integer of 0 to 30, and m35 and m36 are each an integer of 1 to 200; the total of m33 to m36 is 5 or more; and the occurrence order of the respective repeating units is not limited). m35 and m36 are each preferably an integer of 5 to 200, and more preferably an integer of 10 to 200. The total of m33 to m36 is preferably 10 or more. The fluoropolyether group is preferably —(OCF2CF2CF2CF2)m33—(OCF2CF2CF2)m34—(OCF2CF2)m35—(OCF2)m36—. In one embodiment, the fluoropolyether group may be a chain represented by —(OC2F4)m35—(OCF2)m36— (wherein m35 and m36 are each an integer of 1 to 200; and the occurrence order of the respective repeating units is not limited). m35 and m36 are each preferably an integer of 5 to 200, and more preferably an integer of 10 to 200.
In still another embodiment, the fluoropolyether group is a group represented by —(Rm1—Rm2)m37—. In the formula, Rm10 is OCF2 or OC2F4, and preferably OC2F4. In the formula, R12 is a group selected from OC2F4, OC3F6, OC4F8, OC5F10, and OC6F12, or is a combination of two or three groups independently selected from these groups. Preferably, Rm1 is a group selected from OC2F4, OC3F6, and OC4F8, a group selected from OC3F6, OC4F8, OC5F10, and OC6F12, or a combination of two or three groups independently selected from these groups. The combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 is not limited, and examples thereof include —OC2F4OC3F6—, —OC2F4OC4F8—, —OC3F6OC2F4—, —OC3F6OC3F6—, —OC3F6OC4F8—, —OC4F8OC4F8—, —OC4F8OC3F6—, —OC4F8OC2F4—, —OC2F4OC2F4OC3F6—, —OC2F4OC2F4OC4F8—, —OC2F4OC3F6OC2F4—, —OC2F4OC3F6OC3F6—, —OC2F4OC4F8OC2F4—, —OC3F6OC2F4OC2F4—, —OC3F6OC2F4OC3F6—, —OC3F6OC3F6OC2F4—, and —OC4F8OC2F4OC2F4—. m37 is an integer of 2 or more, preferably an integer of 3 or more, and more preferably an integer of 5 or more, and is an integer of 100 or less, and preferably an integer of 50 or less. In the formulae, OC2F4, OC3F6, OC4F8, OC5F10, and OC6F12 may be linear or branched, and are preferably linear. In this embodiment, the fluoropolyether group is preferably —(OC2F4—OC3F6)m37— or —(OC2F4—OC4F8)m37—.
In still another embodiment, the fluoropolyether group is a group represented by —(Rm1—Rm2)m37—Rr—(Rm1′—Rm2′)m37′—. In the formula, Rm1 is OCF2 or OC2F4; Rm2 is a group selected from OC2F4, OC3F6, OC4F8, OC5F10, and OC6F12, or is a combination of two or three groups independently selected from these groups; Rm1′ is OCF2 or OC2F4; Rm2′ is a group selected from OC2F4, OC3F6, OC4F8, OC5F10, and OC6F12, or is a combination of two or three groups independently selected from these groups; m37 is an integer of 2 to 100; m37′ is an integer of 2 to 100; and Rr is any of the following:
Rm1, Rm2, and m37 have the same definition as described above and have the same embodiments. Rm1′, Rm2′, and m37′ have the same definition as Rm1, Rm2, and m37, respectively, and have the same embodiments.
Rr is preferably any of the following:
In still another embodiment, the fluoropolyether group is a group represented by —(OC6F12)m31—(OC5F10)m32—(OC4F8)m33—(OC3F6)m34—(OC2F4)m35—(OCF2)m36— (wherein m35 is an integer of 1 or more and 200 or less; m31, m32, m33, m34, and m36 are each independently an integer of 0 or more and 200 or less; the sum of m31, m32, m33, m34, m35 and m36 is at least 1; and the occurrence order of the respective repeating units enclosed in parentheses provided with m31, m32, m33, m34, m35 or m36 is not limited in the formula). m35 is preferably an integer of 1 or more and 100 or less, and more preferably 5 or more and 100 or less. The sum of m31, m32, m33, m34, m35 and m36 is preferably 5 or more, and more preferably 10 or more, for example, 10 or more and 100 or less.
In still another embodiment, the fluoropolyether group is a group represented by —(OC6F12)m31—(OC5F10)m32—(OC4F8)m33—(OC3F6)m34—(OC2F4)m35—(OCF2)m36— (wherein m36 is an integer of 1 or more and 200 or less; m31, m32, m33, m34, and m35 are each independently an integer of 0 or more and 200 or less; the sum of m31, m32, m33, m34, m35 and m36 is at least 1; and the occurrence order of the respective repeating units enclosed in parentheses provided with m31, m32, m33, m34, m35 or m36 is not limited in the formula). m36 is preferably an integer of 1 or more and 100 or less, and more preferably 5 or more and 100 or less. The sum of m31, m32, m33, m34, m35 and m36 is preferably 5 or more, and more preferably 10 or more, for example, 10 or more and 100 or less.
The ratio of m35 to m36 in the fluoropolyether group (hereinafter, referred to as “m35/m36 ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. With an m35/m36 ratio of 10 or less, the lubricity, friction durability, and chemical resistance of a film (surface-treating layer) are further improved. The lower the m35/m36 ratio is, the more improved the lubricity and the friction durability of the film (surface-treating layer) are. On the other hand, with an m35/m36 ratio of 0.1 or more, the stability of the compound can be further enhanced. The larger the m35/m36 ratio is, the more improved the stability of the compound is.
The fluoropolyether group may be at least one chain selected from the group consisting of a chain represented by formula: —(OCF2CF2CX112)n11(OCF2CF(CF3))n12(OCF2CF2)n13(OCF2)n14(OC4F8)n15—
X11 is preferably F.
n11 to n15 are each preferably an integer of 0 to 200. The total of n11 to n15 is preferably 2 or more, more preferably 5 to 300, still more preferably 10 to 200, and particularly preferably 10 to 100.
R11 is a group selected from OC2F4, OC3F6 and OC4F8, or is a combination of two or three groups independently selected from these groups. The combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 is not limited, and examples thereof include —OC2F4OC3F6—, —OC2F4OC4F8—, —OC3F6OC2F4—, —OC3F6OC3F6—, —OC3F6OC4F8—, —OC4F8OC4F8—, —OC4F8OC3F6—, —OC4F8OC2F4—, —OC2F4OC2F4OC3F6—, —OC2F4OC2F4OC4F8—, —OC2F4OC3F6OC2F4—, —OC2F4OC3F6OC3F6—, —OC2F4OC4F8OC2F4—, —OC3F6OC2F4OC2F4—, —OC3F6OC2F4OC3F6—, —OC3F6OC3F6OC2F4—, and —OC4F8OC2F4OC2F4—. f is an integer of 2 to 100, and preferably an integer of 2 to 50. In the formulae, OC2F4, OC3F6, and OC4F8 may be linear or branched, and are preferably linear. In this embodiment, the formula: —(OC2F4—R11)f10— is preferably formula: —(OC2F4—OC3F6)f10— or formula: —(OC2F4—OC4F8)f10—.
In the isocyanuric compound, the number average molecular weight of the fluoropolyether group portion is not limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. The number average molecular weight is a value obtained by 19F-NMR measurement.
In another embodiment, the number average molecular weight of the fluoropolyether group portion may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000, for example, 3,000 to 6,000.
In another embodiment, the number average molecular weight of the fluoropolyether group portion may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.
R1 is preferably a monovalent organic group represented by formula: R3—(OR2)a10-L-
R1′ is preferably a monovalent organic group represented by formula: -L′-(OR2)a10-L-
The number of carbon atoms in R3 is preferably 1 to 16, and preferably 1 to 8.
R3 may be a linear or branched chain, and is preferably a linear or branched alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms, more preferably a linear or branched alkyl group or fluorinated alkyl group having 1 to 8 carbon atoms, still more preferably a linear or branched alkyl group or fluorinated alkyl group having 1 to 6 carbon atoms, even more preferably a linear or branched alkyl group or fluorinated alkyl group having 1 to 3 carbon atoms, and particularly preferably a linear alkyl group or fluorinated alkyl group having 1 to 3 carbon atoms.
R3 is preferably a fluorinated alkyl group having 1 to 16 carbon atoms, more preferably a CF2H—C1-15 fluoroalkylene group or a perfluoroalkyl group having 1 to 16 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 16 carbon atoms.
The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and is preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms and particularly 1 to 3 carbon atoms, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, and specifically —CF3, —CF2CF3, or —CF2CF2CF3.
L is a single bond or a divalent linking group directly bonded to the isocyanuric ring of the formula (1b). L is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond and an ester bond.
L is still more preferably a group represented by formula: —(CX221X222)o10-(L′)p10-(CX223X22)q10—
L′ is still more preferably a group represented by
—(CX226X227)r10—(CX221X222)o10-(L1)p10-(CX223X224)q10—
L1 is preferably —O— or —C(═O)O—.
L is particularly preferably
—(Rm1—Rm2)m37—Rr′—(Rm1′—Rm2′)m37′—, or
L is not limited, and specific examples thereof include —C2H4—, —C3H6—, —C4H8—O—CH2—, —CO—O—CH2—CH(OH)—CH2—, —(CF2)n10— (n10 is an integer of 0 to 4), —CH2—, —C4H8—, —(CF2)n10—(CH2)m10— (n10 and m10 are independently an integer of 0 to 4), —CF2CF2CH2OCH2CH(OH)CH2—, and —CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2—.
X1 is a monovalent silane-containing reactive crosslinking group.
The silane-containing reactive crosslinking group contributes to adhesion to the substrate. The crosslinkable group may chemically react with the material of the substrate.
In one embodiment, the silane-containing reactive crosslinking group is preferably a group represented by formula: -L2-{Si(Ra)s10(Rb)t10(Rc)u10(Rd)v10}n10
Preferably, Ra, Rb, and Rc are the same or different, and at least one of them is a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or an amino group having 1 to 10 carbon atoms and the others are each an acetoxy group having 1 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, or a glycidyl group having 3 to 10 carbon atoms; more preferably, Ra, Rb, and Rc are the same or different, and at least one of them is a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or an amino group having 1 to 10 carbon atoms and the others are each an acetoxy group having 1 to 10 carbon atoms or an allyl group having 3 to 10 carbon atoms; still more preferably, Ra, Rb, and Rc are the same or different, and they are each a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms; and even more preferably, Ra, Rb, and Rc are the same or different, and they are alkoxy groups having 1 to 4 carbon atoms. Preferably, when n10 is 2 to 20, s10+t10+u10 is the same or different and is 0 to 2, and v10 is 0 to 2.
In Ra, Rb, and Rc, halogen is preferably Cl, Br, or I, and more preferably Cl.
In Ra, Rb, and Rc, the number of carbon atoms in the alkoxy group is preferably 1 to 5. The alkoxy group may be linear, cyclic, or branched. A hydrogen atom is optionally substituted with a fluorine atom or the like. The alkoxy group is preferably a methoxy group, an ethoxy group, a propyloxy group, or a butoxy group, and more preferably a methoxy group or an ethoxy group.
Rd is the same or different, and is —O—, —NH—, —C≡C—, or a silane bond. Rd is preferably —O—, —NH—, or —C≡C—. Rd is a divalent group bonded to two Si atoms, and due to Rd, two or more silicon atoms can be bonded in a linear, ladder, cyclic, or polycyclic form via Rd. When n is an integer of 2 or more, silicon atoms may be bonded to each other.
In one embodiment, X1 is a silane-containing reactive crosslinking group represented by formula:
-L2-{Si(Ra)s10(Rb)t10(Rc)u10(Rd′)v10}n10
In the formula, Z is the same or different, and represents a single bond or a divalent linking group.
Specific examples of Z include —C2H4—, —C3H6—, —CO—O—CH2—CH(OH)—CH2—, —CH2—, and —C4H8—.
In the formula, Rd2 is the same or different, and represents Rd′. Rd′ has the same definition as Rd′.
In Rd′, the number of Si atoms linearly linked via Z group is at most 5. That is to say, in Rd, when at least one Rd2 is present, the number of Si atoms linearly linked via Z group in Rd′ is two or more, and the number of Si atoms linearly linked via Z group is at most 5. Note that “the number of Si atoms linearly linked via Z group in Rd′” is equal to the number of repeats of —Z—Si— linearly linked in Rd′.
One example where Si atoms are linked via Z group in Rd′ is shown below:
In the formula, “*” means a site to be bonded to the Si atom of the main chain, and “ . . . ” means that a predetermined group except ZSi is bonded, or that is to say, when three bonds of a Si atom are all expressed by “ . . . ”, the repeat of ZSi ends there. The superscripted number on Si means the number of Si atoms that appear and that are linearly linked via Z group when counted from “*”. That is to say, a chain where the repetition of ZSi terminates at Si2 is a chain where the “number of Si atoms linearly linked via Z group in Rd′” is 2, and similarly, chains where the repetition of ZSi terminates at Si3, Si4, and Si5 mean chains where the “number of Si atoms linearly linked via Z group in Rd′” is 3, 4, and 5, respectively. As is clear from the formula, a plurality of ZSi chains are present in Rd′, and all these chains do not necessarily have the same length, and may each have any length.
In a preferred embodiment, as shown below, “the number of Si atoms linearly linked via Z group in Rd′” is one (left formula) or two (right formula) in all chains.
In one embodiment, the number of Si atoms linearly linked via Z group in Rd′ is one or two, and preferably one.
In the formula, Rd3 is the same or different, and represents a hydroxyl group or a hydrolyzable group. The hydroxyl group is not limited, and may be generated by hydrolysis of a hydrolyzable group.
Preferably, Rd3 is —OR (wherein R represents a substituted or unsubstituted C1-3 alkyl group, and more preferably a methyl group).
In the formula, Rd4 is the same or different, and represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
In the formula, p11 is the same or different, and is an integer of 0 to 3; q11 is the same or different, and is an integer of 0 to 3; and r11 is the same or different, and is an integer of 0 to 3, provided that the sum of p11, q11, and r11 is 3.
In a preferred embodiment, q11 in Rd′ (Rd in the case where no Rd′ is present) at an end of Rd is preferably 2 or more, such as 2 or 3, and is more preferably 3.
In a preferred embodiment, Rd may have at least one —Si(—Z—SiRd3q11Rd4r11)2 or —Si(—Z—SiRd3q11Rd4r11)3 at an end, and preferably —Si(—Z—SiRd3q11Rd4r11)3. In the formula, the (—Z—SiRd3q11Rd4r11) unit is preferably (—Z—SiRd33). In a still more preferred embodiment, all ends of Rd are preferably —Si(—Z—SiRd3q11Rd4r11)3, and more preferably —Si(—Z—SiRd43)3. The larger the number of Rd3 bonded to each Si at an end is, the greater the adhesion to the substrate is, and thus excellent durability can be obtained.
In a preferred embodiment, in the formula, the number of Si atoms having a hydroxyl group or a hydrolyzable group in the formula (1b) may be preferably 1 to 6, more preferably 2 to 4, and still more preferably 3, and in the formula (2b), it may be preferably 2 to 12, more preferably 4 to 8, and still more preferably 6.
In a preferred embodiment, v10 is 3, and Rd is each independently —Z—SiRd3q11Rd4r11.
L2 is a single bond or a divalent linking group directly bonded to the ring of the formula (α1). L2 is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond and an ester bond.
Specific examples of L2 include —C2H4—, —C3H6—, —C4H8—O—CH2—, —CO—O—CH2—CH(OH)—CH2—, —CH2—, and —C4H8—.
Examples of the silane-containing reactive crosslinking group include -L2-SiR3, -L2-Si(OR60)3, -L2-Si(NR602)3, and -L2-Si(OCOR60)3 (in each formula, L2 is as described above, R5 is a halogen atom, and R60 is independently an alkyl group having 1 to 4 carbon atoms).
In one embodiment, the silane-containing reactive crosslinking group is preferably a group represented by formula: -L6-{C(Ra6)s6(Rb6)t6(Rc6)u6(Rd6)v6}n6
L6 is a single bond or a divalent linking group directly bonded to the ring of the formula (α1) or the formula (α2). L6 is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond and an ester bond.
Specific examples of L6 include —C2H4—, —C3H6—, —C4H8—O—CH2—, —CO—O—CH2—CH(OH)—CH2—, —CH2—, and —C4H8—.
In Ra, Rb, Rc, Ra6, Rb6, and Rc6, halogen is preferably Cl, Br, or I, and more preferably Cl.
In Ra, Rb, Rc, Ra6, Rb6, and Rc6, the number of carbon atoms in the alkoxy group is preferably 1 to 5. The alkoxy group may be linear, cyclic, or branched. A hydrogen atom is optionally substituted with a fluorine atom or the like. The alkoxy group is preferably a methoxy group, an ethoxy group, a propyloxy group, or a butoxy group, and more preferably a methoxy group or an ethoxy group.
Z6 is preferably a C1-6 alkylene group, —(CH2)g10—O—(CH2)h10—, wherein g10 is an integer of 0 to 6, such as an integer of 1 to 6, and h10 is an integer of 0 to 6, such as an integer of 1 to 6, or -phenylene-(CH2)i10—, wherein i10 is an integer of 0 to 6, and is more preferably a C1-3 alkylene group. These groups are optionally substituted with one or more substituents selected from, for example, a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group.
In the formula, R61 each independently at each occurrence represents Rd6′. Rd6 has the same definition as Rd6.
In Rd6, the number of C atoms linearly linked via Z6 group is at most 5. That is to say, in Rd6, when at least one R61 is present, the number of Si atoms linearly linked via Z6 in Rd6 is two or more, and the number of C atoms linearly linked via Z6 group is at most 5. The “number of C atoms linearly linked via Z6 group in Rd6” is equal to the number of repeats of —Z6—C— linearly linked in Rd6.
In a preferred embodiment, as shown below, “the number of C atoms linearly linked via Z6 group in Rd6” is one (left formula) or two (right formula) in all chains.
In one embodiment, the number of C atoms linearly linked via Z6 group in Rd6 is 1 or 2, and preferably 1.
In the formula, R62 represents —Y6—SiR65j6R663-j6.
Y6 each independently at each occurrence represents a divalent organic group.
In a preferred embodiment, Y6 is a C1-6 alkylene group, —(CH2)g11—O—(CH2)h11—, wherein g11 is an integer of 0 to 6, such as an integer of 1 to 6, and h11 is an integer of 0 to 6, such as an integer of 1 to 6, or -phenylene-(CH2)i11—, wherein i11 is an integer of 0 to 6. These groups are optionally substituted with one or more substituents selected from, for example, a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group.
In one embodiment, Y6 may be a C1-6 alkylene group or -phenylene-(CH2)i11—. In the case where Y is any of the above groups, light resistance, in particular, ultraviolet resistance can be more enhanced.
R65 each independently at each occurrence represents a hydroxyl group or a hydrolyzable group. Examples of the “hydrolyzable group” are the same as those described above.
Preferably, R65 is —OR (wherein R represents a substituted or unsubstituted C1-3 alkyl group, more preferably an ethyl group or a methyl group, and particularly a methyl group).
R66 each independently at each occurrence represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
j6 independently represents an integer of 1 to 3 in each (—Y—SiR65j6R663-j6) unit, preferably an integer of 2 or 3, and more preferably 3.
R63 each independently at each occurrence represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
In the formula, p6 is each independently at each occurrence an integer of 0 to 3, q6 is each independently at each occurrence an integer of 0 to 3, and r6 is each independently at each occurrence an integer of 0 to 3, provided that the sum of p6, q6, and r6 is 3.
In a preferred embodiment, q6 in Rd6′ (Rd6 itself in the case where no Rd6′ is present) at an end of Rd6 is preferably 2 or more, such as 2 or 3, and is more preferably 3.
In one embodiment, X1 group is a group represented by
-L2-{Si(Ra)s10(Rb)t10(Rc)u10(Rd)v10}n11, or
-L6-{C(Ra6)s6(Rb6)t6(Rc6)u6(Rd6)v6}n6,
In one embodiment, X2 may be independently a monovalent organic group containing the above polyether chain. Preferred groups of the organic group are the same as those of R1.
In another embodiment, X2 may be independently the above silane-containing reactive crosslinking group.
In another embodiment, X2 may be independently at least one group selected from the group consisting of a silicone residue, a silsesquioxane residue, and a silazane group.
Examples of the silicone residue include the following groups.
In each formula, L2 is a single bond or a divalent linking group, n6 is an integer of 1 to 20, m6 is an integer of 0 to 10, R81 is each independently a monovalent group, and among R81 of each group, at least one is a reactive group.
A plurality of R81 contained in each group are independently a monovalent group, and may be the above reactive group or may be a group different from the above reactive group, provided that at least one of the plurality of R81 contained in each group is the above reactive group.
The reactive group is preferably H, a halogen atom, or at least one selected from the group consisting of —OR82 (R82 is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms), -L3-SiR53 (L3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R5 is a halogen atom), -L3-Si(OR60)3 (L3 is as described above, and R61 is independently an alkyl group having 1 to 4 carbon atoms), -L3-Si(NR602)3 (L3 and R60 are as described above), -L3-Si(OCOR60)3 (L3 and R60 are as described above), and a group containing any of these groups.
The group different from the reactive group is preferably at least one selected from the group consisting of an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkyl amide group, a halogenated alkyl amide group, a uril group, a halogenated uril group, a urea group, a halogenated urea group, —CONRkCORl (Rk and Rl are independently H, an alkyl group, or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
L2 is a single bond or a divalent linking group directly bonded to the ring of the formula (1b) or formula (2b). Suitable examples of L2 are as described above.
Examples of the silicone residue also include the following groups.
In each formula, L2 is a single bond or a divalent linking group, R83 is each independently a monovalent group, and among R83 of each group, at least one is a reactive group.
A plurality of R83 contained in each group are independently a monovalent group, and may be the above reactive group or may be a group different from the above reactive group, provided that at least one of the plurality of R83 contained in each group is the above reactive group.
The reactive group is preferably at least one selected from the group consisting of —H, —OR84 (R84 is an alkyl group having 1 to 4 carbon atoms), a halogen atom, —OH, —O—CR84═CH2 (R84 is as described above), —OCOR84 (R84 is as described above), —OCOORj2 (Rj2 is an alkyl group or a halogenated alkyl group), —NR842 (R84 is as described above), and a group containing any of these groups.
The group different from the reactive group is preferably at least one selected from the group consisting of an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkyl amide group, a halogenated alkyl amide group, a uril group, a halogenated uril group, a urea group, a halogenated urea group, —CONRkCORl (Rk and Rl are independently H, an alkyl group, or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
L2 is a single bond or a divalent linking group directly bonded to the ring of the formula (α1) or the formula (α2). Suitable examples of L2 are as described above.
Examples of the silsesquioxane residue include the following groups.
In each formula, L2 is a single bond or a divalent linking group; R85 is each independently a monovalent group; among R85 of each group, at least one is a reactive group; and p10 is independently an integer of 0 to 5000.
A plurality of R85 contained in each group are independently a monovalent group, and may be the above reactive group or may be a group different from the above reactive group, provided that at least one of the plurality of R85 contained in each group is the above reactive group.
The reactive group is preferably at least one selected from the group consisting of —H, —OR84 (R84 is an alkyl group having 1 to 4 carbon atoms), a halogen atom, —OH, —O—CR84═CH2 (R84 is as described above), —OCOR84 (R84 is as described above), —OCOORj2 (Rj2 is an alkyl group or a halogenated alkyl group), —NR842 (R84 is as described above), and a group containing any of these groups.
The group different from the reactive group is preferably at least one selected from the group consisting of an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkyl amide group, a halogenated alkyl amide group, a uril group, a halogenated uril group, a urea group, a halogenated urea group, —CONRkCORl (Rk and Rl are independently H, an alkyl group, or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
L2 is a single bond or a divalent linking group directly bonded to the ring of the formula (1b) or the formula (2b). Suitable examples of L2 are as described above.
X2 may be a group different from the monovalent organic group containing a polyether chain, the silane-containing reactive crosslinking group, the silicone residue, the silsesquioxane residue, and the silazane group described above.
That is to say, X2 may be at least one selected from the group consisting of H, an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkyl amide group, a halogenated alkyl amide group, a uril group, a halogenated uril group, a urea group, a halogenated urea group, —OCOORj2 (Rj2 is an alkyl group or a halogenated alkyl group), —CONRkCORl (Rk and Rl are independently H, an alkyl group, or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, a halogenated aryl group, a silicone residue (excluding those having a reactive group), and a silsesquioxane residue (excluding those having a reactive group).
Examples of the silicone residue (excluding those having a reactive group) include the following groups. The reactive group is what is exemplified as a reactive group that can constitute R85.
In each formula, L4 is a single bond or a divalent linking group, and R86 is each independently a group different from a monovalent reactive group.
The group different from the reactive group is preferably at least one selected from the group consisting of an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkyl amide group, a halogenated alkyl amide group, a uril group, a halogenated uril group, a urea group, a halogenated urea group, —CONRkCORl (Rk and Rl are independently H, an alkyl group, or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
L4 is a single bond or a divalent linking group directly bonded to the ring of the formula (1b) or the formula (2b). L4 is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond and an ester bond.
Specific examples of L4 include —C2H4—, —C3H6—, —C4H8—O—CH2—, and —CO—O—CH2—CH(OH)—CH2—.
Examples of the silsesquioxane residue (excluding those having a reactive group) include the following groups. The reactive group is what is exemplified as a reactive group that can constitute R85.
In each formula, L4 is a single bond or a divalent linking group, R86 is each independently a group different from the monovalent reactive group, and p10 is independently an integer of 0 to 5000.
The group different from the reactive group is preferably at least one selected from the group consisting of an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkyl amide group, a halogenated alkyl amide group, a uril group, a halogenated uril group, a urea group, a halogenated urea group, —CONRkCORl (Rk and Rl are independently H, an alkyl group, or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
L4 is a single bond or a divalent linking group directly bonded to the ring of the formula (α1) or the formula (α2). Suitable examples of L4 are as described above.
Examples of the silazane group include the following groups.
In each formula, L5 is a single bond or a divalent linking group; m is an integer of 2 to 100; n is an integer of 100 or less; R87 is each independently H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylsilyl group, an alkylcyano group, or an alkoxy group having 1 to 4 carbon atoms.
L5 is a single bond or a divalent linking group directly bonded to the ring of the formula (α1) or the formula (α2). L5 is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond and an ester bond.
Specific examples of L5 include —C2H4—, —C3H6—, —C4H8—O—CH2—, and —CO—O—CH2—CH(OH)—CH2—.
Specific examples of the silazane group include the following groups.
In the above compound, the average molecular weight of R1 is not limited, and is 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000.
The compound may have an average molecular weight of, although the average molecular weight is not limited, 5×102 to 1×105. In particular, the compound preferably has an average molecular weight of 2,000 to 30,000, and more preferably 2,500 to 12,000, from the viewpoint of UV resistance and friction durability. In the present disclosure, the “average molecular weight” refers to a number average molecular weight, and the “average molecular weight” is a value obtained by 19F-NMR measurement.
In one embodiment, the compound (A1) may be preferably a compound represented by the formula (1), more preferably a compound represented by the formula (1a), and still more preferably a compound represented by the formula (1b), and in another embodiment, the compound (A1) may be preferably a compound represented by the formula (2), more preferably a compound represented by the formula (2a), and still more preferably a compound represented by the formula (2b).
The average molecular weight of the fluoropolyether group-containing silane compound represented by the formula (1) or the formula (2) may be, but is not limited to, 5×102 to 1×105. In this range, the average molecular weight is preferably 2,000 to 32,000 and more preferably 2,500 to 12,000 from the viewpoint of abrasion durability. The “average molecular weight” refers to a number average molecular weight, and the “average molecular weight” is a value obtained by 19F-NMR measurement.
In the compound (A1), the total content of compounds represented by the formula (1) or the formula (2) may be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and still more preferably 95% by mass or more and 100% by mass or less.
The epoxy group-containing silicone compound (A2) preferably comprises a compound represented by formula (3):
Ma1Db1Tc1Qd1 (3)
Examples of the group having an epoxy ring include an epoxy group (monocyclic epoxy group); and a polycyclic epoxy group such as an epoxycyclohexyl group and an epoxynorbornyl group.
Examples of the hydrolyzable group include —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and it is more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
SiO1/2 indicates that an O atom is bonded to a Si atom, and the Si atom shares the 0 atom with the other atom bonded via the O atom. SiO1/2, SiO2/2, and SiO3/2 mean that the Si atom has one, two, or three of such O atoms, respectively.
In the formula (3), Rs1 is each independently at each occurrence a hydrogen atom, a hydroxyl group, —Xs1—COOH, a group having an epoxy ring, a hydrolyzable group, a monovalent organic group, —Xs1—NRs22, or —Xs1—SiRs3n11Rs43-n11, provided that Rs2 is each independently at each occurrence a hydrogen atom or a C1-20 alkyl group; Rs3 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; Rs4 is each independently at each occurrence a C1-20 alkyl group; and Xs1 is each independently at each occurrence a divalent organic group.
Examples of the hydrolyzable group include —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and it is more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
In Rs1, the monovalent organic group is preferably a C1-400 hydrocarbon group, and more preferably a C1-400 aliphatic hydrocarbon group. —CH2— contained in the hydrocarbon group (preferably aliphatic hydrocarbon group) may be replaced by —O—, —CO—, —NRj3—(R3 represents a hydrogen atom; or a substituted or unsubstituted C1-4 alkyl group), and hydrogen atoms in such a hydrocarbon group (preferably aliphatic hydrocarbon group) may be replaced by a hydroxyl group, a carboxy group, a group having an epoxy ring. The hydrocarbon group (preferably aliphatic hydrocarbon group) may be either linear, branched, or cyclic, and may be either saturated or unsaturated. The hydrocarbon group (preferably aliphatic hydrocarbon group) may also contain one or more ring structures. The group having an epoxy ring has the same definition as described above.
In one embodiment, the C1-400 hydrocarbon group may be a C1-30 aliphatic hydrocarbon group or may be a C1-25 aliphatic hydrocarbon group. In another embodiment, the C1-400 hydrocarbon group may be a C1-300 aliphatic hydrocarbon group, may be a C100-150 aliphatic hydrocarbon group, or may be a C15-120 aliphatic hydrocarbon group. In still another embodiment, the C1-400 hydrocarbon group may be a C10-50 aliphatic hydrocarbon group or may be a C15-40 aliphatic hydrocarbon group.
In the formula, Xs1 is preferably, each independently at each occurrence, —Rs8—Ox10—Rs9— (wherein RSS and Rs9 are each independently at each occurrence a single bond or a C1-20 alkylene group, and x10 is 0 or 1). Such a C1-20 alkylene group may be linear or branched, and is preferably linear. Such a C1-20 alkylene group is preferably a C1-10 alkylene group, more preferably a C1-6 alkylene group, and still more preferably a C1-3 alkylene group.
In the formula, Rs2 is each independently at each occurrence a hydrogen atom or a C1-20 alkyl group. Such a C1-20 alkyl group may be linear or branched, and is preferably a linear or branched C1-16 alkyl group, furthermore linear or branched C1-6 alkyl group, and in particular linear or branched C1-3 alkyl group, and is preferably a linear C1-6 alkyl group, and in particular linear C1-3 alkyl group.
In the formula, Rs3 is each independently at each occurrence a hydroxyl group or a hydrolyzable group. Examples of such a hydrolyzable group include —ORj, —OCORj, —O—N═ CRj2, —NRj2, —NHRj, —NCO or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and it is more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
In the formula, Rs4 is each independently at each occurrence a C1-20 alkyl group. Such a C1-20 alkyl group may be linear or branched, and is preferably a linear or branched C1-16 alkyl group, furthermore linear or branched C1-6 alkyl group, and in particular linear or branched C1-3 alkyl group, and is preferably a linear C1-6 alkyl group, and in particular linear C1-3 alkyl group.
The above —Xs1—NRs22, monovalent organic group, or —Xs1—SiRs3n11Rs43-n11 is optionally substituted with one or more substituents. Examples of such substituents include a halogen atom; and a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C3-10 cycloalkyl group, a C3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, a C6-10 aryl group, and a 5- to 10-membered heteroaryl group, each of which is optionally substituted with one or more halogen atoms; a hydroxyl group, hydrolyzability, and an epoxy group. Examples of such a hydrolyzable group include —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group), and it is more preferably —ORj (that is, an alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
Examples of Rs1 include groups represented by the following formulae.
In the formulae, Rj5 represents a substituted or unsubstituted C1-4 alkyl group. Examples of Rj5 include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, Rj5 is a methyl group, and in another embodiment, Rj5 is an ethyl group.
m50 represents an integer of 6 to 20, and preferably represents an integer of 8 to 18. n50 represents an integer of 2 to 18, and preferably represents an integer of 4 to 8. o50 represents an integer of 0 to 30, and preferably represents an integer of 2 to 20, in particular an integer of 5 to 15. p50 represents an integer of 0 to 30, and preferably represents an integer of 0 to 10. q50 represents an integer of 0 to 30, and preferably represents an integer of 2 to 20, in particular an integer of 5 to 15. r50 represents an integer of 0 to 30, and preferably represents an integer of 0 to 10. s50 represents an integer of 0 to 10, and preferably represents an integer of 1 to 5. t50 represents an integer of 1 to 20, and preferably represents an integer of 1 to 10. u50 represents an integer of 1 to 10, and preferably represents an integer of 2 to 4. v50 represents an integer of 1 to 10, and preferably represents an integer of 2 to 5. w50 represents an integer of 1 to 6, and preferably represents an integer of 1 to 3.
In the formula (3), at least one Rs1 contains an epoxy ring and at least one other Rs1 is a hydroxyl group or a hydrolyzable group. The epoxy ring may be a monocyclic epoxy ring, or may be a polycyclic epoxy ring, such as an epoxycyclodecane ring or an epoxynorbornane ring. The epoxy ring-containing group in Rs1 includes any of the following cases: when Rs1 is an epoxy group; when a substituent of —Xs1—NRs22, a monovalent organic group, or —Xs1—SiRs3n11Rs43-n11 represented by Rs1 is an epoxy group; and when —CH2-contained in Rs1 is replaced by —O—, thereby forming an epoxy group.
The epoxy equivalent in the epoxy group-containing silicone compound (A2) (molecular weight of the epoxy group-containing silicone compound (A2)/number of epoxy rings contained in one molecule of the epoxy group-containing silicone compound (A2)) is, for example, 50 g/eq or more and 1,000 g/eq or less, more preferably 100 g/eq or more and 800 g/eq or less, and still more preferably 200 g/eq or more and 600 g/eq or less.
In the formula (3), still other at least one Rs1 preferably has a group selected from the group consisting of an organic group having a hydroxyl group as a substituent, a carboxylate group, a hydroxyethylpropyl group, an alkoxysilylalkyl, a dodecyl group, or an aminoalkyl group.
a1 represents an integer of 3 to 60, preferably an integer of 3 to 40, and more preferably an integer of 3 to 24. b1 represents an integer of 10 to 1,100, preferably an integer of 30 to 920, and more preferably 50 to 820. c1 represents an integer of 0 to 30, and preferably represents an integer of 0 to 20. d1 represents an integer of 0 to 15, and preferably represents an integer of 0 to 12. Note that the total of c1 and d1 is 1 or more. Since the total of c1+d1 is 1 or more, the epoxy group-containing silicone compound (A2) contains a branched structure.
It can be understood that a1, b1, c1, and d1 are average values in the epoxy group-containing silicone compound (A2) contained in the composition described above.
In the formula (3), the bonding order of M, D, T, and Q is not limited. In one embodiment, M, D, T, and Q may be randomly distributed. For example, individual M, D, T, and Q may be randomly bonded, individual M, D, T, and Q may be alternately arranged, or blocks containing an arbitrary number of M, D, T, or Q may be arbitrarily contiguous. Alternatively, M, D, T, and Q may form a distribution gradient in the formula (3), and in particular, may form any mixed form.
The epoxy group-containing silicone compound (A2) may include both a side chain-modified siloxane and an α,ω-modified siloxane. It can also be said that since the epoxy group-containing silicone compound (A2) contains a branched structure, it has more substitution possibilities and may have a higher degree of modification compared to a pure linear structure. This results in a structure having a long, continuous siloxane main chain. When the number of functional groups in the siloxane is larger, the crosslink density in the resulting film (surface-treating layer) may be higher, the resistance (strength) of the film (surface-treating layer) may be further improved, and a significant anti-adhesion effect can be expected.
The epoxy group-containing silicone compound (A2) is preferably an organo-modified siloxane that is mono-branched (so-called mono-T structure or mono-Q structure) or multi-branched (so-called multi-T structure or multi-Q structure) in the siloxane moiety.
The epoxy group-containing silicone compound (A2) is described in, for example, WO 2011/088937 A, EP 2176319 B, and EP 2159248 B, and can be used.
The average degree of branching of the epoxy group-containing silicone compound (A2) is preferably more than 1, and more preferably more than 1.25.
The average degree of branching K is understood in the scope of the present disclosure to be the ratio of the number of M units (a1) to the total of the number of T units (c1) and the number of Q units (d1) (a1/(c1+d1)). The names of the units correspond to internationally recognized nomenclature, and their names can also be found in, for example, the Thieme Roempp Online, Georg Thieme Verlag, 2008. The degree of branching is determined by specifying the ratio of the area integrals of the peaks in the 29Si NMR spectrum assigned to the respective units.
The average number of directly contiguous D units, F1, in the epoxy group-containing silicone compound (A2) is preferably 5 or more, and more preferably 10 or more.
The above coefficient F1 is understood in the scope of the present disclosure to mean the average number of directly contiguous D units and to be calculated as b1/(1+2×c1+3×d1) based on the number of D units (b1), the number of T units (c1), and the number of Q units (d1). The coefficient F1 represents the silicone characteristics of the epoxy group-containing silicone compound (A2). The F1 is determined by forming the ratio of the area integrals of the peaks in the 29Si NMR spectrum assigned to the respective units.
The weight average molecular weight of the epoxy group-containing silicone compound (A2) is preferably 1,000 to 70,000, more preferably 1,500 to 50,000, and still more preferably 2,000 to 35,000.
The viscosity of the epoxy group-containing silicone compound (A2) is preferably 50 mPa·s or more and 5,000 mPa·s or less, more preferably 100 mPa·s or more and 3,500 mPa·s or less, and still more preferably 150 mPa·s or more and 2,000 mPa·s or less. The viscosity of the silicone compound represented by the formula (3) can be measured at 25° C. in accordance with DIN 53015.
The above reaction product (A3) can be produced by allowing the compounds (A1) and (A2) to react with each other. Such a reaction may be carried out in the presence of a reaction solvent or in the absence of a solvent. In one embodiment, the reaction temperature may be preferably 20° C. or higher and 150° C. or lower, and more preferably 50° C. or higher and 130° C. or lower, and the reaction time may be preferably 10 minutes or longer and 50 hours or shorter. As the reaction solvent, the following may be used: fluorinated solvents such as 1,3-bistrifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, perfluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane; carboxylic acid esters such as ethyl acetate, n-butyl acetate, tert-butyl acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, and diethyl acetate; carbonic acid esters such as dimethyl carbonate and ethylene carbonate; ester solvents such as γ-butyrolactone and other cyclic esters; aliphatic hydrocarbon solvents such as alkanes, alkenes, alkynes, and cycloalkanes; aromatic hydrocarbon solvents such as benzene, toluene, and naphtha cut.
In the organic silane compound (A), the content of the reaction product (A3) between the fluoropolyether group-containing silane compound (A1) and the epoxy ring-containing silicone compound (A2) can be preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 35% by mass or less, and still more preferably 3% by mass or more and 20% by mass or less.
The content of the organic silane compound (A) in the non-volatile components in the composition of the present disclosure can be preferably 60% by mass or more and 99% by mass or less, and more preferably 70% by mass or more and 95% by mass or less.
In the composition of the present disclosure, the non-volatile components may be the portion obtained by excluding the solvent (D) from the entire composition.
The composition of the present disclosure may further comprise a cross-linking agent (B). This allows the organic silane compound (A) to be cured. In one embodiment, such a cross-linking agent preferably comprises a compound (B1) having two or more groups capable of reacting with at least one of an epoxy group and a hydrolyzable silyl group.
As the groups capable of reacting with at least one of an epoxy group and a hydrolyzable silyl group, at least one selected from the group consisting of —ORb5, a carboxy group, an epoxy group, —NRb52, and —SiRb6n6Rb73-n6, is preferred. Note that Rb5 is each independently at each occurrence a hydrogen atom or a C1-20 alkyl group; Rb6 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; Rb7 is each independently at each occurrence a C1-20 alkyl group; and n6 may be an integer of 1 to 3.
In the cross-linking agent (B), the number of groups capable of reacting with at least one of an epoxy group and a hydrolyzable silyl group is 2 or more in one molecule, and for example, it may be 6 or less, and further 4 or less.
Examples of the cross-linking agent (B) may include:
In the organic silicon compound, the two silanol groups are preferably present at both terminals of the molecular backbone. The molecular backbone here represents a relatively longest binding chain in a molecule of the organic silicon compound.
Examples of the compound having silanol groups at both terminals of the molecular backbone may include a compound represented by the following formula (B1) or (B2).
In the formula (B1) or (B2), Rb11 is each independently at each occurrence a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Specific examples of Rb11 include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; alkenyl groups such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a hexenyl group, and a cyclohexenyl group; aryl groups such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; aralkyl groups such as a benzyl group, a phenylethyl group, and a phenylpropyl group; groups in which some or all of the hydrogen atoms of these groups are replaced by halogen atoms (for example, a chloromethyl group, a bromoethyl group, a chloropropyl group, a trifluoropropyl group, and a nonafluorohexyl group).
Examples of the substituent for the hydrocarbon group include at least one selected from the group consisting of —ORb5, a carboxy group, an epoxy group, —NRb52, and —SiRb6n6Rb73-n6. Rb5, Rb6, and Rb7 have the same definition as described above.
In the formula (B1) or (B2), Rb12 is each independently at each occurrence a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms. As Rb12, specifically, the following are exemplified: alkylene groups such as a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, and a hexamethylene group; cycloalkylene groups such as a cyclohexylene group; arylene groups such as a phenylene group, a tolylene group, a xylylene group, a naphthylene group, and a biphenylene group; groups in which some or all of the hydrogen atoms of these groups are replaced by halogen atoms or the like; and combinations of these substituted or unsubstituted alkylene groups and arylene groups. Among these, as Rb12, a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, a cyclohexylene group, and a phenylene group are preferred, and in particular, an ethylene group, a propylene group, a butylene group, and a phenylene group are preferred. Examples of the compound having silanol groups in the molecule include a resinous compound constituted by bonds between one of or a combination of two or more of Rb113SiO1/2, Rb112SiO2/2, Rb11SiO3/2, and SiO2 units and silanol groups. The constituent units in the resinous compound may be directly bonded to each other or may be bonded via a divalent or higher hydrocarbon group.
Examples of the substituent for the hydrocarbon group include at least one selected from the group consisting of —ORb5, a carboxy group, an epoxy group, —NRb52 and —SiRb6n6Rb73-n6. Rb5, Rb6 and Rb7 have the same definition as described above.
In the formula (B1) or (B2), 31 is each independently at each occurrence an integer of 1 or more. R1 is preferably 2 or more, more preferably 5 or more, and is preferably 50 or less, more preferably 20 or less.
The organic silicon compound having at least two silanol groups in one molecule (specifically, the compound represented by the formula (B1) or (B2)) is preferably free from a PFPE structure in the molecular structure.
Organic silicon compound represented by formula (B3), (B4), or (B5):
In the formulae (B3) and (B4), Rb13 is a hydrogen atom or a monovalent organic group. Rb13 is the moiety capable of reacting with a hydrolyzable silyl group.
Rb13 is preferably a monovalent organic group.
Rb13— is more preferably, each independently at each occurrence, CH3—, C2H5—, C3H7—, CF3CH2—, CH3CO—, CH2═C(CH3)—, CH3CH2C(CH3)═N—, (CH3)2N—, (C2H5)2N—, CH2═C(OC2H5)—, (CH3)2C═C(OC8H17)—, or
In the formulae (B3) and (B4), Rb14 is each independently at each occurrence a monovalent organic group. Rb14 is preferably a substituted or unsubstituted monovalent hydrocarbon group, and more preferably a substituted or unsubstituted monovalent C1-12 hydrocarbon group. Specific examples of Rb14 may include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; aryl groups such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; aralkyl groups such as a benzyl group, a phenylethyl group, and a phenylpropyl group; alkenyl groups such as a vinyl group, an allyl group, a propenyl group, and a butenyl group; and groups in which some or all of the hydrogen atoms of these groups are replaced by halogen atoms such as fluorine, chlorine, and bromine, or the like (for example, a chloromethyl group, a bromoethyl group, a chloropropyl group, a trifluoropropyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group).
Examples of the substituent for the above hydrocarbon group include at least one selected from the group consisting of —ORb5, a carboxy group, an epoxy group, —NRb52, and —SiRb6n6Rb73-n6. Rb5, Rb6, and Rb7 have the same definition as described above.
In one embodiment, Rb14 may be a group represented by the following general formula.
Rf1—Rb15—
In the formula, Rf1 is a monovalent fluorinated polyether group. As Rf1, those with a structure in which CF3O—, CF3CF2O—, CF3CF2CF2O—, (CF3)2CFO—, CF3CF2CF2CF2O—, or the like is bonded to the CF2 terminal of the PFPE are exemplified.
Rb15 is a divalent organic group. The divalent organic group has the same definition as described above.
Rb15 may be, for example, a substituted or unsubstituted divalent hydrocarbon group that may contain one of or two or more of an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom, and may contain an amide bond or a sulfonamide bond. The divalent hydrocarbon group preferably has 2 to 20 carbon atoms. Here, specific examples of the substituted or unsubstituted divalent hydrocarbon group in which no oxygen atom, nitrogen atom, silicon atom, or sulfur atom intervenes and that does not contain an amide bond or a sulfonamide bond include the following: alkylene groups such as an ethylene group, a propylene group, a methylethylene group, a butylene group, and a hexamethylene group; cycloalkylene groups such as a cyclohexylene group; arylene groups such as a phenylene group, a tolylene group, a xylylene group, a naphthylene group, and a biphenylene group; combinations of these alkylene groups and arylene groups; and groups in which some or all of the hydrogen atoms of these alkylene groups and arylene groups are replaced by halogen atoms.
In the divalent hydrocarbon group, an oxygen atom may be contained as —O—, a nitrogen atom may be contained as —NRb51— (Rb51 is a hydrogen atom, a C1-10 alkyl group, or a C1-10 aryl group) or as —N═, a silicon atom may be contained as —SiRb52Rb53— (Rb52 and Rb53 are each independently at each occurrence an alkyl group or aryl group having 1 to 10 carbon atoms), and a sulfur atom may be contained as —S—. Also, in the divalent hydrocarbon group, an amide bond may be contained as —C(═O)NRb51— (Rb51 is the same as described above), and a sulfonamide bond may be contained as —SO2NRb51— (Rb51 is the same as described above). Specific examples of such a divalent hydrocarbon group include the following. Note that in the following formulae, Me represents a methyl group and Ph represents a phenyl group, and in each of the following formulae, the Rf1 group is bonded to the left side (J in each formula).
Examples of the substituent for the above hydrocarbon group include at least one selected from the group consisting of —ORb5, a carboxy group, an epoxy group, —NRb52 and —SiRb6n6Rb73-n6. Rb5, Rb6 and Rb7 have the same definition as described above.
and β3 is each independently at each occurrence 2 or 3.
In the formula (B5), Rb13 and Rb14 have the same definition as described above. In the formula (B5), Rb16— each independently at each occurrence represents Rb18—Rb17—.
Rb17 each independently at each occurrence represents a single bond, an oxygen atom, or a divalent organic group. The divalent organic group is as described above.
Rb17 is preferably a C1-10 alkylene group, or a group having 1 to 10 carbon atoms and containing a nitrogen atom or an oxygen atom in the main chain.
Rb17 is more preferably
Rb18 is a reactive functional group. Rb18 is preferably, each independently at each occurrence, an amino group, an epoxy group, a methacrylic group, a vinyl group, or a mercapto group, and is more preferably an amino group.
In the formula (B5), β4 is an integer of 2 or more, preferably 2 or 3, and more preferably 3. In the formula (B5), β5 is an integer of 0 or more, and preferably 0 or 1. In the formula (B5), β6 is 1 or 2, and preferably 1. Note that the sum of β4, β5, and β6 is 4.
In the formula (B5), preferably, β4 is 2 or 3, β5 is 0 or 1, and β6 is 1 or 2, and more preferably, β4 is 3, β5 is 0, and β6 is 1.
Preferably, the cross-linking agent (B) is a compound represented by the formula (B3) or the formula (B5), in one embodiment, more preferably a compound represented by the formula (B5), and in another embodiment, more preferably a compound represented by the formula (B3).
In one embodiment, the cross-linking agent (B) is free from a group represented by PFPE in the molecular chain.
In one embodiment, the molecular weight of the cross-linking agent (B) is 1,000 or less, preferably 600 or less, and more preferably 400 or less. The lower limit value of the molecular weight of the cross-linking agent may be 50 or more, or may be 100 or more.
In a preferred embodiment, the cross-linking agent (B) is at least one selected from the group consisting of tetraethoxysilane, tetratrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, tridecafluoro-n-octyltriethoxysilane, and tridecafluoro-n-octyltrimethoxysilane.
It is preferable to use the cross-linking agent (B) together with the organic silane compound (A). In this case, —O—Rb13 bonded to a Si atom of the cross-linking agent (B) and a hydrolyzable silyl group contained in the organic silane compound (A) can undergo a crosslinking reaction (condensation reaction).
In the cross-linking agent (B), the total content of compounds represented by the formula (B1), (B2), (B3), (B4) or (B5) may be, for example, 50% by mass or more and 100% by mass or less, and preferably 70% by mass or more and 100% by mass or less.
The cross-linking agent (B) may comprise an amine cross-linking agent (B6) or an epoxy cross-linking agent (B7). In one embodiment, the cross-linking agent (B) may comprise an amine cross-linking agent (B6) or an epoxy cross-linking agent (B7), in addition to the compounds represented by the formula (B1), (B2), (B3), (B4), or (B5).
The amine cross-linking agent (B6) is typically a polyfunctional amine compound having two or more amino groups in one molecule, and may be any of an aliphatic polyfunctional amine compound, an aromatic polyfunctional amine compound, an alicyclic polyfunctional amine compound, and a cyclic polyfunctional amine compound. The polyfunctional amine compound includes a condensation product between at least one selected from the group consisting of an aliphatic polyfunctional amine compound, an aromatic polyfunctional amine compound, and an alicyclic polyfunctional amine compound, and a dimeric acid; an adduct of at least one selected from the group consisting of an aliphatic polyfunctional amine compound, an aromatic polyfunctional amine compound, and an alicyclic polyfunctional amine compound; and a reaction product (ketimine) between at least one selected from the group consisting of an aliphatic polyfunctional amine compound, an aromatic polyfunctional amine compound, and an alicyclic polyfunctional amine compound, and a ketone, as well.
Examples of the aliphatic polyfunctional amine compound include diethylenetriamine, triethylenetetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, and hexamethylenediamine.
Examples of the aromatic polyfunctional amine compound include meta-xylylenediamine, xylylenediamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, benzylmethylamine, xylylenediamine trimer, xylylenediamine derivatives, meta-phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
Examples of the alicyclic polyfunctional amine compound include N-aminoethylpiperazine, bis(4-amino-3-methylcyclohexyl)methane, menthenediamine, isophoronediamine, bis(4-aminocyclohexyl)methane, and 1,3-bis(aminomethyl)cyclohexane.
Examples of the cyclic polyfunctional amine compound include piperidine, N,N-dimethylpiperazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-undecylimidazolium trimellitate.
Examples of the adduct include an adduct with a polyfunctional epoxy compound such as bisphenol A diglycidyl ether. Examples of the dimer acid include a dimerized product of an unsaturated fatty acid such as oleic acid, linolic acid, linolenic acid, and erucic acid, as well as a hydrogenated product thereof. Examples of the ketone include methyl ethyl ketone and methyl isobutyl ketone.
The number of amino groups contained in the amine cross-linking agent (B6) may be 2 to 3.
The epoxy cross-linking agent (B7) can typically be a polyfunctional epoxy compound having two or more epoxy groups in one molecule, and may be any of an aliphatic polyfunctional epoxy compound, an aromatic polyfunctional epoxy compound, and an alicyclic polyfunctional epoxy compound.
Examples of the aliphatic polyfunctional epoxy compound include 1,4-butanediol diglycidyl, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, and trimethylolpropane triglycidyl ether.
Examples of the aromatic polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and biphenyl diglycidyl ether.
Examples of the alicyclic polyfunctional epoxy compound include 2,2′-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexenedioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, an F-caprolactone-modified product of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, and triglycidyl isocyanurate.
The following can be used: a hydrogenated epoxy resin, an alicyclic epoxy resin, an isocyanurate ring-containing epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl aralkyl type epoxy resin, a hydrogenated epoxy resin obtained by hydrogenating aromatic rings of the various epoxy resins, and a dicyclopentadiene type epoxy resin.
The number of epoxy groups contained in the epoxy cross-linking agent (B7) may be 2 to 3.
Commercially available products may be used as the epoxy cross-linking agent (B7), and specific examples thereof include Celloxide® 2021P, 2081, and EHPE® 3150 (these are manufactured by Daicel Corporation), and Epodil® 733, 749, 750, and 762 (these are manufactured by Evonik Industries AG).
The cross-linking agent (B) can be contained in the composition of the present embodiment in an amount of preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, and still more preferably 15 parts by mass or more and 35 parts by mass or less, with respect to 100 parts by mass of the organic silane compound (A).
The cross-linking agent (B) can be contained in an amount in the range of 5 to 60 parts by mass, for example, and specifically in the range of 10 to 45 parts by mass, in 100 parts by mass of the composition of the present embodiment.
The composition of the present disclosure may further comprise a catalyst (hereinafter, sometimes referred to as “catalyst (C)”). The catalyst promotes the condensation reaction between the organic silane compound (A) and the cross-linking agent.
As the catalyst, a metal-based catalyst, an organic acid-based catalyst, an inorganic acid-based catalyst, a base-based catalyst (such as ammonia, triethylamine, and diethylamine), and others can be used.
Examples of the organic acid-based catalyst may include a compound having carboxylic acid, sulfonic acid, or phosphoric acid, and specific examples thereof may include acetic acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, and alkylphosphoric acid.
Examples of the inorganic acid-based catalyst may include hydrochloric acid and sulfuric acid.
The catalyst above is preferably a metal-based catalyst.
In one embodiment, examples of the metal atoms contained in the metal-based catalyst may include titanium, zirconium, zinc, and tin. Among these metal atoms, it is preferable to use tin, titanium, or zirconium.
In the present embodiment, it is preferable to use as the metal-based catalyst at least one selected from the group consisting of tetra-n-butyl titanate, tetraisopropyl titanate, n-butyl zirconate, n-propyl zirconate, dibutyltin dimethoxide, dioctyltin dicarboxylate, and dibutyltin dilaurate, and more preferably, the metal-based catalyst is at least one selected from the group consisting of tetraisopropyl titanate, dioctyltin dicarboxylate, and n-propyl zirconate. The use of the metal-based catalysts as described above promotes the condensation reaction between the organic silane compound (for example, the reaction product (A3), fluoropolyether group-containing silane compound (A1), and epoxy group-containing silicone compound (A2)) and the cross-linking agent. The metal-based catalysts as described above are easily dissolved or dispersed in the curable composition and can contribute to the promotion of uniform reaction. The curable composition of the present embodiment comprising the metal-based catalysts as described above can contribute to the formation of a cured product of the curable composition with low foreign matter and high transparency.
It is preferable to use the catalyst (C) of the present embodiment together with the fluoropolyether group-containing silane compound (A1).
It is preferable to use the catalyst (C) of the present embodiment together with the organic silane compound (A) and the cross-linking agent (B).
In the present embodiment, the content of the catalyst (C) in the composition is preferably 0.01 to 5.0 parts by mass, and more preferably 0.07 to 3 parts by mass, with respect to 100 parts by mass of the organic silane compound (A).
Only one of the catalysts described above may be used, or two or more may be used at the same time.
The composition of the present disclosure may further comprise a solvent (D). By comprising the solvent (D), the handleability of the composition becomes good. When such a composition is used to form a layer, the layer formed can be a continuous thin film. Such a composition can also contribute to the formation of a thin film with an arbitrary thickness.
Examples of the solvent (D) include a hydrocarbon solvent; a halogenated hydrocarbon solvent; an ester solvent; an ether solvent; a ketone solvent; an amide solvent; a nitrile solvent such as acetonitrile; a urea solvent such as tetramethylurea or dimethylpropyleneurea (DMPU); a sulfoxide solvent such as dimethyl sulfoxide (DMSO); a sulfone solvent such as sulfolane; an alcohol solvent such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, tert-butanol, and diacetone alcohol; a fluorinated solvent such as 1,3-bisfluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, perfluorohexane, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane; an amine solvent; a carboxylic anhydride; and a nitro compound. Also, under high pressure, the solvent (D) may be carbon dioxide or the like.
Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent such as alkane, alkene, alkyne, and cycloalkane; and an aromatic hydrocarbon solvent such as benzene, toluene, and naphtha cut.
Examples of the ester solvent include a carboxylic acid ester such as ethyl acetate, n-butyl acetate, tert-butyl acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, and diethyl acetate; a carbonic acid ester such as dimethyl carbonate and ethylene carbonate, and a cyclic ester such as γ-butyrolactone.
Examples of the ether solvent include a chain ether such as t-butyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; and a cyclic ether such as tetrahydrofuran.
Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, acetone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone.
Examples of the amide solvent include a carboxylic acid amide such as formamide or dimethylformamide; and a cyclic amide such as N-methyl-2-pyrrolidone.
The content of the solvent (D) is preferably 1 to 300 parts by mass, more preferably 20 to 200 parts by mass, and still more preferably 50 to 100 parts by mass, with respect to 100 parts by mass of the total amount of the organic silicon compound (A), and the cross-linking agent (B) and catalyst (C) used as necessary.
The composition may comprise other optional components in addition to the organic silane compound (A), the cross-linking agent (B), the catalyst (C), and the solvent (D). Examples of such optional components include one or more substances selected from the group including: a stabilizer (dehydrating agent, molecular sieve, magnesium sulfate, or methyl orthoformate), a viscosity regulator, a filler, a fluorescent agent, a storage stabilizer, a filling agent, a coloring agent, a heat resistance improver, a cold resistance improver, a rust inhibitor, an adhesion improver, a liquid reinforcing agent, a plasticizer, a viscosity regulator, a flexibility imparting agent, an adhesion promoter, a co-cross-linking agent, a flame retarder, a defoaming additive, a curing accelerator for amine epoxide reactions, an antibacterial agent and a preservative, a dye, a coloring agent and a pigment, an antifreezing agent, a bactericide, and/or a reaction diluent and a complexing agent, a spray aid, a wetting agent, a fragrance, a photoprotectant, a radical scavenger, a UV absorber and a stabilizer, in particular a stabilizer against thermal and/or chemical loads and/or loads due to ultraviolet rays and visible light, such as a (non-reactive) fluoropolyether compound, preferably a perfluoro(poly)ether compound, which can be understood as a fluorine-containing oil (hereinafter, referred to as “fluorine-containing oil”).
Examples of the UV absorber and stabilizer include benzophenones, benzotriazoles, hydroxyphenyltriazines, cyclic iminoesters, cyanoacrylates, hindered phenols, hindered amines, and oxalic anilides.
Examples of the benzophenones include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone.
Examples of the benzotriazoles include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2′-methylenebis(4-cumyl-6-benzotriazolphenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, a polymer containing units derived from 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, and a polymer containing units derived from 2-(2′-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole.
Examples of the hydroxyphenyltriazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-propyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-butyloxyphenol, 2-[4-([2-hydroxy-3-dodecyloxypropyloxy]-2-hydroxyphenyl]-4,6-diphenyl-1,3,5-triazine, 2-[4-([2-hydroxy-3-dodecyloxypropyloxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-([2-hydroxy-3-tridecyloxypropyloxy]-2-hydroxyphenyl]-4,6-diphenyl)-1,3,5-triazine, 2-[4-([2-hydroxy-3-tridecyloxypropyloxy]-2-hydroxyphenyl]-4,6-bis(2,4 dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2′-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-diphenyl-1,3,5-triazine, and 2-[4-[(2-hydroxy-3-(2′-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, as well as a polymer containing units derived from 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole and 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole.
Examples of the cyclic iminoesters include 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-m-phenylenebis(3,1-benzoxazin-4-one), and 2,2′-p,p′-diphenylenebis(3,1-benzoxazin-4-one).
Examples of the cyanoacrylates include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.
Examples of the hindered amines include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, mono(2,2,6,6-tetramethyl-4-piperidyl) sebacate, mono(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2,2,6,6-tetramethyl-4-methacryloyloxypiperidine, 1,2,2,6,6-pentamethyl-4-methacryloyloxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2-hydroxyethylamino-4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-1-cyclohexyloxypiperidyl)amino)-1,3,5-triazine, and an oligomer of 2,2,4,4-tetramethyl-7-oxa-3,20-diazabispiro[5.1.11.2]-henicosan-21-one and epichlorohydrin.
Examples of the oxalic anilides include N-(4-dodecylphenyl)-N′-(2-ethoxyphenyl)oxalic acid and N-(2-ethylphenyl)-N′-(2-ethoxyphenyl)oxalic acid.
Commercially available products may be used as the UV absorber and stabilizer, and specific examples thereof include Tinuvin® 400, 405, 479, 152, and 292 (these are manufactured by BASF SE), Hostavin® 3400, 3206, and 3070 (these are manufactured by Clariant AG), Adekastab® LA-82 and 87 (these are manufactured by ADEKA Corporation), and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).
The amounts of these optional components to be blended are arbitrary to the extent that they do not impair the objects of the present disclosure, and as long as the characteristics of the composition and the physical properties of the cured product are not impaired.
In one embodiment, the composition may be a so-called one-component curable composition containing all of the organic silane compound (A) and the cross-linking agent (B), catalyst (C), solvent (D), and other optional components used as necessary, as a single composition. In another embodiment, the composition may be a two-component curable composition containing a main agent (I) and a curing agent (II), wherein the main agent (I) may contain the organic silane compound (A) and the curing agent (II) may contain the cross-linking agent (B).
The present disclosure provides an article comprising: a substrate; and a film (hereinafter, also referred to as “surface-treating layer” or “layer”) provided on the substrate (on the surface of the substrate) and formed from the composition of the present disclosure (hereinafter, also referred to as “surface-treating composition”). This article can be produced as follows, for example.
At first, a substrate is provided. The substrate usable in the present disclosure may be composed of any suitable material such as a glass, a resin (this may be a natural or synthetic resin such as a common plastic material, preferably a polycarbonate resin, a poly(meth)acrylate resin, a polyethylene terephthalate resin, a triacetyl cellulose resin, a polyimide resin, a modified (transparent) polyimide resin, a polycycloolefin resin, and a polyethylene naphthalate resin, and may be in the form of a plate, a film, or others), a metal (this may be a simple substance of a metal such as aluminum, copper, silver, or iron, or a complex such as an alloy or the like), a ceramic, a semiconductor (silicon, germanium, or the like), a fiber (a fabric, a non-woven fabric, or the like), a fur, a leather, a wood, a pottery, a stone, an architectural member, or the like.
For example, when the article to be produced is an optical member, the material constituting the surface of the substrate may be a material for an optical member, such as a glass or a transparent plastic. The substrate, according to its specific specifications or the like, may also have an insulating layer, an adhesive layer, a protecting layer, a decorated frame layer (I-CON), an atomizing film layer, a hard coating layer, a polarizing film, a phase difference film, an organic EL display module, a liquid crystal display module, or the like.
The shape of the substrate is not limited. The surface region of the substrate on which a film (surface-treating layer) is to be formed may be at least part of the substrate surface, and may be suitably determined according to the application, specific specifications, and the like of an article to be produced.
Then, a film of the surface-treating composition of the present disclosure is formed on the surface of such a substrate, and this film is post-treated as necessary, thereby forming a film (surface-treating layer) from the surface-treating composition of the present disclosure.
The film of the surface-treating composition of the present disclosure can be formed by applying the surface-treating composition to the surface of the substrate such that the composition coats the surface. The coating method is not limited. For example, a wet coating method can be used.
Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, micro-gravure coating, bar coating, die coating, screen printing, and similar methods.
When using the wet coating method, the surface-treating composition of the present disclosure can be applied to the substrate surface after being diluted with a solvent. As such a solvent, the fluorine-containing organic solvents and fluorine-free organic solvents described above can be used. From the viewpoint of the stability of the surface-treating composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: C5-12 perfluoroaliphatic hydrocarbons (for example, perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons; cellosolve solvents such as hydrofluoroether (HFE) (for example, alkyl perfluoroalkyl ethers such as perfluoropropyl methyl ether (C3F7OCH3), perfluorobutyl methyl ether (C4F9OCH3), perfluorobutyl ethyl ether (C4F9OC2H5), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (perfluoroalkyl group and alkyl group may be linear or branched)), hydrochlorofluorocarbon (for example, ASAHIKLIN AK-225 (trade name)), methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; ester solvents such as diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, and diacetone alcohol; and aromatic hydrocarbons such as toluene and xylene. One of these solvents may be used singly, or two or more may be used as a mixture. Among them, hydrofluoroethers, glycol solvents, ester solvents, ketone solvents, and alcohol solvents are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and/or perfluorobutyl ethyl ether (C4F9OC2H5), propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, isopropanol, butanol, and diacetone alcohol are particularly preferred.
The film is then post-treated. This post-treatment is not limited, but is performed, for example, by irradiating with active energy rays, for example, electromagnetic waves in a wavelength region of 350 nm or less, such as ultraviolet rays, electron beams, X-rays, γ-rays, and the like. Alternatively, the post-treatment is performed by heating for a predetermined period of time. By performing such a post-treatment, curing of the curable site of the silicone copolymer having the curable site and, if present, the curable site of the matrix-forming composition is initiated, and bonds are formed between these compounds and between these compounds and the substrate.
In the above-described manner, a film (that is, a surface-treating layer) is formed from the surface-treating composition of the present disclosure on the substrate surface, and thus the article of the present disclosure is produced. The film (surface-treating layer) obtained from this can form a film that can achieve both anti-icing performance and transparency. Furthermore, such a film (surface-treating layer) can further have both high surface lubricity (or lubricity, such as wiping property for fouling including fingerprints and the like and excellent tactile sensations to the fingers) and high friction durability. Moreover, this film (surface-treating layer) may have not only high friction durability and surface lubricity but also have, depending on the formulation of the surface-treating composition used, water-repellency, oil-repellency, antifouling properties (for example, preventing fouling such as fingerprints from adhering), and the like, and may be suitably used as a functional thin film.
The water contact angle of the film (surface-treating layer) may be, for example, 900 or more, even 950 or more, preferably 100° or more, more preferably 105° or more, and still more preferably 1100 or more, and it may be, for example, 1400 or less, even 1200 or less. The water contact angle of the film (surface-treating layer) can be measured in accordance with JIS R3257:1999.
The haze of the film (surface-treating layer) may be, for example, 1.5 or less, even 1.2 or less, preferably 1 or less, more preferably 0.9 or less, still more preferably 0.8 or less, and it may be, for example, 0.1 or more.
The haze of the film (surface-treating layer) can be measured in accordance with JIS K7136:2000.
The icing property index of the film (surface-treating layer), as evaluated by the following method, may be, for example, 750 kPa or less, even 700 kPa or less, preferably 650 kPa or less, more preferably 600 kPa or less, and still more preferably 550 kPa or less, and it may be, for example, 10 kPa or more, even 50 kPa or more.
The film is formed on a stainless steel substrate (NIRO 1.4301), and a bottomless cell with an inner base area of 110 mm2 is arranged on the film such that the film and the bottom of the cell are in contact with each other. Next, 0.5 mL of water is placed in the cell, the water is brought into contact with the film, and the stainless steel substrate is cooled to −32° C. to freeze the water in the cell. A load is applied to the cell in a direction parallel to the film surface, the cell is moved at a speed of 10 mm/min, and a load at which ice begins to move is used as the icing property index.
The present disclosure further relates to an optical material having the film (surface-treating layer) in the outermost layer.
The optical material preferably includes a wide variety of optical materials in addition to optical materials relating to displays and the like as exemplified below: for example, displays such as cathode ray tubes (CRTs; for example, TV, PC monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs); protective plates for such displays; and those obtained by performing an antireflection film treatment on films or their surfaces.
In one embodiment, the article having a film (surface-treating layer) obtained according to the present disclosure may be, but is not limited to, an optical member. Examples of the optical member include lenses of glasses or the like; front surface protective plates, anti-scattering films, antireflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; and optical fibers.
In one embodiment, examples of the article having a film (surface-treating layer) obtained according to the present disclosure include LiDAR (a light detection and ranging) cover member, a sensor member, a head lamp member, a sunroof member, an emblem member, a bumper member, a windshield, a side glass, a rear glass, an instrument panel cover member, an automobile interior member, and the like, and in particular, these members for automobiles.
The thickness of the film (surface-treating layer) is not limited. The thickness of the film (surface-treating layer) in the case of an optical member is in the range of 0.1 to 50 μm, preferably 0.5 to 30 μm, from the viewpoint of optical performance, surface lubricity, friction durability, and antifouling property.
The article obtained by using the surface-treating composition of the present disclosure has been described in detail above. The application of the surface-treating agent of the present disclosure, the method of use thereof, the method of producing the article, and the like are not limited to those exemplified above.
The present invention will be further specifically described by the following Examples, but the present invention is not limited to them. Note that, in the present Examples, all the chemical formulae shown below represent average compositional features.
0.44 g of Optool UD120 (manufactured by Daikin Industries, Ltd.) as the silane compound (A1) was dissolved in 5.41 g of 1,3-bis-trifluoromethylbenzene and 0.31 g of Silikopon EF (manufactured by Evonik Industries AG) as the silicone compound (A2) was added. After stirring for 5 minutes, 0.14 g of dioctyltin dicarboxylate was added, and the mixture was stirred at room temperature for 12 hours and then stirred at 100° C. for 30 minutes to obtain the reaction product (A3). After cooling to room temperature, 13.40 g of Silikopon EF as the silicone compound (A2) was added. 0.15 g of Tinuvin 292 (manufactured by BASF SE), 0.3 g of Tinuvin 400 (manufactured by BASF SE), and 3.05 g of (3-aminopropyl)triethoxysilane dissolved in 3.61 g of butyl acetate were added, and the mixture was stirred for 2 hours to obtain the composition.
The composition was obtained in the same manner as in Synthetic Example 1, except that the amounts of Optool UD120, Silikopon EF added for the first time, and Silikopon EF added for the second time were changed to 0.88 g, 0.62 g, and 13.09 g, respectively.
The composition was obtained in the same manner as in Synthetic Example 1, except that the amounts of Optool UD120, Silikopon EF added for the first time, and Silikopon EF added for the second time were changed to 1.15 g, 0.81 g, and 12.90 g, respectively.
The composition was obtained in the same manner as in Synthetic Example 1, except that the amounts of Optool UD120, Silikopon EF added for the first time, and Silikopon EF added for the second time were changed to 1.59 g, 1.12 g, and 12.59 g, respectively.
The composition was obtained in the same manner as in Synthetic Example 1, except that the amounts of Optool UD120, Silikopon EF added for the first time, and Silikopon EF added for the second time were changed to 2.22 g, 1.57 g, and 12.14 g, respectively.
13.71 g of Silikopon EF was dissolved in 9.94 g of butyl acetate, 0.14 g of dioctyltin dicarboxylate, 0.15 g of Tinuvin 292, 0.3 g of Tinuvin 400, and 3.05 g of (3-aminopropyl)triethoxysilane were added, and the mixture was stirred for 2 hours to obtain the composition.
The compositions obtained in Synthetic Examples 1 to 4 and Comparative Synthetic Example 1 were applied onto a stainless steel substrate (NIRO 1.4301) using a 100 micrometer bar coater, left at room temperature for 30 minutes, and then heated at 120° C. for 30 minutes to form films (surface-treating layers).
The film was formed on a stainless steel substrate (NIRO 1.4301), and a bottomless cell with an inner base area of 110 mm2 was arranged on the film such that the film and the bottom of the cell were in contact with each other. Next, 0.5 mL of water was placed in the cell, the water was brought into contact with the film, and the stainless steel substrate was cooled to −32° C. to freeze the water in the cell. A load was applied to the cell in a direction parallel to the film surface, the cell was moved at a speed of 10 mm/min, and a load at which ice began to move was used as the icing property index.
For the films (surface-treating layers), the water contact angle was measured in accordance with JIS R3257:1999.
The compositions obtained in Synthetic Examples 2 and 3 were applied onto polycarbonate or soda-lime glass (SGG Planiclear, manufactured by Saint-Gobain Glass UK Ltd.) using a 100 micrometer bar coater, left at room temperature for 10 minutes, and then heated at 120° C. for 30 minutes to obtain films (surface-treating layers).
The composition obtained in Comparative Synthetic Example 1 was applied onto polycarbonate (Makrolon GP farblos 099, manufactured by Covestro AG) or soda-lime glass (SGG Planiclear, manufactured by Saint-Gobain Glass UK Ltd.) using a 100 micrometer bar coater, left at room temperature for 10 minutes, and then heated at 120° C. for 30 minutes to obtain a film (surface-treating layer).
The composition obtained in Synthetic Example 5 was applied onto polycarbonate or soda-lime glass (SGG Planiclear, manufactured by Saint-Gobain Glass UK Ltd.) using a 100 micrometer bar coater, left at room temperature for 10 minutes, and then heated at 120° C. for 30 minutes to obtain a film (surface-treating layer). In Table 2, “PC” indicates that the composition was applied onto polycarbonate, and “Glass” indicates that the composition was applied onto the soda-lime glass.
0.44 g of Optool UD120 was dissolved in 5.41 g of 1,3-bis-trifluoromethylbenzene, and 13.71 g of Silikopon EF was added. After stirring for 5 minutes, 0.14 g of dioctyltin dicarboxylate, 0.15 g of Tinuvin 292, 0.3 g of Tinuvin 400, and 3.05 g of (3-aminopropyl)triethoxysilane dissolved in 3.61 g of butyl acetate were added, and the mixture was stirred for 2 hours to obtain the composition.
The composition was applied onto polycarbonate or soda-lime glass (SGG Planiclear, manufactured by Saint-Gobain Glass UK Ltd.) using a 100 micrometer bar coater, left at room temperature for 10 minutes, and then heated at 120° C. for 30 minutes to obtain a film (surface-treating layer).
For the films (surface-treating layers), the water contact angle (°) was measured in accordance with JIS R3257:1999.
For the films (surface-treating layers), the haze (%) was measured in accordance with JIS K7135:2000.
The measurement was performed with the model 413 manufactured by Erichsen GmbH & Co. KG using a Bosch tip (p 0.75 mm).
In Comparative Example 3, the haze value of the film (surface-treating layer) is high, suggesting that Optool UD120 and Silikopon EF are not miscible and no reaction product between Optool UD120 and Silikopon EF are produced.
The treated substrate obtained in Example 6 was used to perform a xenon test.
The treated substrate obtained in Example 7 was used to perform a xenon test.
An accelerated weathering test was performed in accordance with DIN EN ISO 16474-2, and the water contact angle (°) was measured after a certain period of time.
In Example 9, peeling of the coating film was observed after 600 hours, and the test was discontinued.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-091037 | Jun 2022 | JP | national |
This application is a continuation application of International Application No. PCT/JP2023/020312 filed on May 31, 2023 which claims the benefit of priority from Japanese Patent Application No. 2022-091037 filed on Jun. 3, 2022 and designating the U.S., the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2023/020312 | May 2023 | WO |
| Child | 18964925 | US |
