Patent Application
20230406974
The present disclosure relates to a surface-treating agent comprising a fluoropolyether group-containing polymer and a siloxane polymer.
Certain types of fluorine-containing compounds are known to be capable of providing excellent water-repellency, oil-repellency, antifouling property, and the like when used in surface treatment of a substrate. Patent Literature 1 discloses a composition comprising a fluorine-containing polymer and a silicon-containing polymer that can provide a surface-treating layer with excellent friction durability.
The present disclosure includes the following embodiments.
[1] A composition comprising a (A) fluoropolyether group-containing polymer and a (B) siloxane polymer, wherein
wherein
The surface-treating agent of the present disclosure provides a substrate with high surface lubricity in addition to water- and oil-repellency, and also has excellent solubility in a solvent.
The “monovalent organic group”, as used herein, refers to a monovalent group containing carbon. The monovalent organic group may be a hydrocarbon group or a derivative thereof, unless otherwise specified. The derivative of 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 end 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. Examples of such a divalent organic group include, but are 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. Such a 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.
The substituent of the “hydrocarbon group”, as used herein, is not limited, and examples thereof include one or more groups selected from 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 optionally substituted with one or more halogen atoms.
Hereinafter, a composition of the present disclosure will be described.
The composition of the present disclosure comprises a (A) fluoropolyether group-containing polymer and a (B) siloxane polymer.
The above fluoropolyether group-containing polymer is a copolymer represented by the following formula (1) or (2):
wherein
In the above formula (1), RF1 is Rf1—RF—Oq—.
In the above formula (2), RF2 is —Rf2p—RF—Oq—.
In the above formula, Rf1 is each independently a C1-16 alkyl group optionally substituted with one or more fluorine atoms.
In the above 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 C1-3 alkyl group, and more preferably a linear C1-6 alkyl group, in particular linear C1-3 alkyl group.
The above 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 above 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 linear C1-3 perfluoroalkyl group, and specifically —CF3, —CF2CF3, or —CF2CF2CF3.
In the above formula, Rf2 is a C1-6 alkylene group optionally substituted with one or more fluorine atoms.
In the above 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.
The above 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 above 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 perfluoroalkyl group, and specifically —CF2—, —CF2CF2—, or —CF2CF2CF2—.
In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.
In the above formulae, q is each independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.
In the above formulae (1) and (2), RF is each independently 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—
wherein
RFa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.
a, b, c, d, e, and f may be preferably, each independently, an integer of 0 to 100.
The sum of a, b, c, d, e, and f is preferably 5 or more and 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, and 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. For example, in the above repeating units, —(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))—.
In one embodiment, the above repeating units are linear. When the above repeating units are linear, the surface lubricity, friction durability, and the like of the surface-treating layer can be improved.
In one embodiment, the above repeating units are branched. When the above repeating units are branched, the dynamic friction coefficient of the surface-treating layer can be increased.
In one embodiment, RF is each independently a group represented by any one of the following formulae (f1) to (f5):
(OC3F6)d—(OC2F4)e— (f1)
wherein d is an integer of 1 to 200, and e is 0 or 1;
—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f2)
wherein c and d are each independently an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less;
—(R6—R7)g— (f3)
wherein R6 is OCF2 or OC2F4;
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f4)
wherein e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e, and f is at least 1, and the occurrence order of the respective repeating units enclosed in parentheses provided with a, b, c, d, e, or f is not limited in the formula; and
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f5)
wherein f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e, and f is at least 1, and the occurrence order of the respective repeating units enclosed in parentheses provided with a, b, c, d, e, or f is not limited in the formula.
In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, and still more preferably 15 to 50, and it is, for example, an integer of 25 to 35. In one embodiment, e is 0. In another embodiment, e is 1. The above formula (f1) is preferably a group represented by —(OCF2CF2CF2)d—(OCF2CF2)e— or —(OCF(CF3)CF2)d—(OCF(CF3))e—, and more preferably a group represented by —(OCF2CF2CF2)d—(OCF2CF2)e—.
In the above formula (f2), e and f are each independently an integer of preferably 5 or more and 200 or less, and more preferably 10 to 200. Also, the sum of c, d, e, and f is preferably 5 or more and more preferably 10 or more, and it may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is 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 the above formula (f3), R6 is preferably OC2F4. In the above (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 is 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 above formula (f3), g is preferably an integer of 3 or more, and more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F10, and OC6F12 may be either linear or branched, and are preferably linear. In this embodiment, the above formula (f3) is preferably —(OC2F4—OC3F6)g— or —(OC2F4—OC4F8)g—.
In the above formula (f4), 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, and more preferably 10 or more, and it is, for example, 10 or more and 100 or less.
In the above formula (f5), 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, and more preferably 10 or more, and it is, for example, 10 or more and 100 or less.
In one embodiment, the above RF is a group represented by the above formula (f1).
In one embodiment, the above RF is a group represented by the above formula (f2).
In one embodiment, the above RF is a group represented by the above formula (f3).
In one embodiment, the above RF is a group represented by the above formula (f4).
In one embodiment, the above RF is a group represented by the above formula (f5).
In the above RF, the ratio of e to f (hereinafter, referred to as an “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, friction durability, and chemical resistance (such as durability against artificial sweat) of a surface-treating layer obtained from this compound are further increased. The smaller the e/f ratio is, the higher the lubricity and the friction durability of the surface-treating layer are. On the other hand, with an e/f ratio of 0.1 or more, the stability of the compound can be further increased. The larger the e/f ratio is, the more improved the stability of the compound is.
In one embodiment, the above e/f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.
In one embodiment, from the viewpoint of heat resistance, the above e/f ratio is preferably 1.0 or more, and more preferably 1.0 to 2.0.
In the above fluoropolyether group-containing compound, the number average molecular weight of the RF1 and RF2 moieties is not limited, and it is, 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 defined as 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 it may be, for example, 3,000 to 6,000.
In another embodiment, the number average molecular weights of 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 above formulae, R4 is each independently at each occurrence R4a or R4b.
The above R4a is each independently at each occurrence a divalent organic group having a crosslinkable group.
The above crosslinkable group means a group that is capable of reacting under certain conditions and forming a crosslinked structure.
The above crosslinkable group is: preferably a group containing a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphoric acid-containing group, or a silane coupling group; or a precursor group thereof.
Examples of the above crosslinkable group include an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, an optionally substituted acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether (vinyloxy) group, a hydroxyl group, an oxetanyl group, an isocyanate group, a catechol group, a thiol group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphoric acid-containing group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a halogen atom, or a silane coupling group, or a precursor group thereof.
The above alicyclic epoxy group is preferably a group represented by the following formula:
wherein n is an integer of 1 to 5.
The above alicyclic epoxy group is more preferably
The above optionally substituted acryloyl group is a group represented by CH2═CX1—C(O)—.
The above X1 represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms optionally substituted with fluorine, and it is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group.
The above optionally substituted acryloyl group is preferably an acryloyl group or a methacryloyl group. Hereinafter, an acryloyl group and a methacryloyl group are also collectively referred to as a “(meth)acryloyl group”.
The above phosphoric acid-containing group is not limited as long as it contains a phosphoric acid group, and it may be a C1-6 alkylene-OP(O)(OH)(OR) (wherein R is a hydrogen atom or a C1-3 alkyl.).
In one embodiment, the above crosslinkable group may be an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, a (meth)acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, or a vinyl ether (vinyloxy) group.
In a preferred embodiment, the above crosslinkable group is an epoxy group, a glycidyl group, or CH2═CX1′—C(O)— (wherein X1′ represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms optionally substituted with fluorine), and it may be preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group.
In another preferred embodiment, the above crosslinkable group may be an epoxy group, a glycidyl group, an alicyclic epoxy group, or a (meth)acryloyl group, preferably an epoxy group, a glycidyl group, or an alicyclic epoxy group, and more preferably an epoxy group or a glycidyl group.
In a preferred embodiment, R4a is a group represented by the following formula:
wherein
In the above formula, R31 each independently at each occurrence represents a hydrogen atom or an alkyl group. The above alkyl group is preferably a C1-6 alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. R31 is preferably a hydrogen atom.
In the above formula, R32 each independently at each occurrence represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group optionally substituted with fluorine. The above alkyl group is preferably a C1-6 alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. R32 is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom.
The above R33 is each independently at each occurrence a crosslinkable group. Such a crosslinkable group has the same definition as described above.
In a preferred embodiment, R33 may be an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, an optionally substituted acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether (vinyloxy) group, a hydroxyl group, an oxetanyl group, an isocyanate group, a catechol group, a thiol group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphoric acid-containing group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a halogen atom, or a silane coupling group, or a precursor group thereof.
In a more preferred embodiment, R33 may be an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, a (meth)acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, or a vinyl ether (vinyloxy) group.
In a still more preferred embodiment, the above crosslinkable group may be an epoxy group, a glycidyl group, an alicyclic epoxy group, or a (meth)acryloyl group, and preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group.
In the above formula, Y1 is a single bond, —C(═O)O—, —C(═O)NH—, —OC(═O)—, —NHC(═O)—, —O—, —N(Rc)—, phenylene, or carbazolylene. Here, Rc represents an organic group, and is preferably an alkyl group. The above alkyl group is preferably a C1-6 alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. As for these groups with respect to Y1, the left side thereof is bonded to C in the formula, and the right side thereof is bonded to Y2.
In one embodiment, Y1 is —C(═O)O—, —C(═O)NH—, —OC(═O)—, —NHC(═O)—, —O—, —N(Rc)—, phenylene, or carbazolylene. Here, RC represents an organic group, and is preferably an alkyl group.
Y1 is preferably —C(═O)O—, —O—, or carbazolylene, more preferably —C(═O)O— or —O—, and still more preferably —C(═O)O—.
In the above formula, Y2 represents a single bond or a linker having 1 to 16, preferably 2 to 12, and more preferably 2 to 10 atoms in a main chain thereof. Here, the above main chain means the portion in Y2 that links Y1 and R33 by the minimum number of atoms.
Examples of such Y2 include, but are not limited to:
Examples of the preferred Y2 include —(CH2—CH2—O)p1— (p1 represents an integer of 1 to 10), —(CHRd)p2—O— (p2 is an integer of 1 to 40, and Rd represents hydrogen or a methyl group), —(CH2)p3—O—(CH2)p4— (p3 is an integer of 1 to 10, and p4 represents an integer of 1 to 10), and —(CH2)p7—O—CONH—(CH2)p8— (p7 represents an integer of 1 to 8, preferably 2 or 4, and p8 represents an integer of 1 to 6, preferably 3). Note that, as for these groups, the left end thereof is bonded to the side of the molecular backbone (the side of Y1), and the right end thereof is bonded to the side of the functional group selected from substituent group A (the side of R33).
R4a is still more preferably a group represented by the following formula:
(wherein R33 has the same definition as described above, q2 is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and still more preferably an integer of 2 to 4, and q3 is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and still more preferably an integer of 1 to 2.).
The above R4b is each independently at each occurrence a divalent organic group not having a crosslinkable group.
R4b is preferably —CHR4c—CR4dR4e—. Here, R4c and R4d each independently represent a hydrogen atom or an alkyl group, and the R4e group is —Y3—R4f. Here, Y3 has the same definition as the above Y1, and R4f is an organic group not having a crosslinkable group, and is a group that a R4g group described later is bonded via a linker or directly to Y3. That is, R4f is -linker-R4g or —R4g.
Such a linker is preferably any of the following:
R4g is preferably any of the following groups:
In the above formula, R11, R12, R13, R14, R15, R16, and R17 each independently represent an alkyl group or an aryl group.
Examples of the above alkyl group include, but are not limited to, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms. It is preferably an alkyl group having 1 to 6 carbon atoms, and specifically a n-butyl group for R11 and a methyl group for R12 to R17.
Examples of the above aryl group include, but are not limited to, an aryl group having 6 to 20 carbon atoms. Such an aryl group may contain 2 or more rings. The preferred aryl group is a phenyl group.
The above alkyl group and aryl group may contain a heteroatom such as a nitrogen atom, an oxygen atom, and a sulfur atom in their molecular chain or ring, if desired.
Furthermore, the above alkyl group and aryl group may be substituted with one or more substituents selected from a halogen; 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 halogens, if desired.
In the above formula, R18 represents a divalent organic group.
The above R18 is preferably —(CH2)r″— (wherein r″ is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 10 or less), and is more preferably —(CH2)r″— (wherein r″ is an integer of 1 or more and 10 or less).
In the above formula, n4 is each independently an integer of 1 or more and 500 or less. Such n4 is preferably an integer of 1 or more and 200 or less, and is more preferably 10 or more and 200 or less.
R4g is more preferably a hydrogen atom (excluding hydrogen bonded to O to form a hydroxyl group) or an alkyl group that may be fluorinated and bonded via an ethylene chain or an oxyethylene chain; more preferably a hydrogen atom, a methoxyethyl group, an isobutyl group, or R4i—CF2—(CF2)s6—(CH2)s7—O—(CH2)2— (R4i is a fluorine atom or a hydrogen atom, s6 is an integer of 0 to 6, and s7 is an integer of 1 to 6); and still more preferably a 3-(perfluoroethyl)propoxyethyl group [rational formula: CF3—(CF2)—(CH2)3—O—(CH2)2—].
In the above R4, the constituent unit R4a and the constituent unit R4b may each form a block or may be bonded randomly.
In one embodiment, in R4, the constituent unit R4a and the constituent unit R4b each form a block.
In one embodiment, in R4, the constituent unit R4a and the constituent unit R4b are bonded randomly.
In one embodiment, R4 is R4a. That is, R4 consists of the constituent unit R4a having a crosslinkable group.
In a preferred embodiment, the number of R4a (polymerization degree) is 1 to 100, preferably 2 to 70, more preferably 2 to 50, still more preferably 3 to 30, even more preferably 3 to 20, and particularly preferably 5 to 10.
In one embodiment, R4 is R4b. That is, R4 consists of the constituent unit R4b not having a crosslinkable group.
In a preferred embodiment, the number of R4b (polymerization degree) is 1 to 100, preferably 2 to 70, more preferably 2 to 50, still more preferably 3 to 30, even more preferably 3 to 20, and particularly preferably 5 to 10.
In the above formula, n is an integer of 1 to 100, preferably an integer of 2 to 70, more preferably 2 to 50, still more preferably 3 to 30, even more preferably an integer of 3 to 20, and particularly preferably an integer of 5 to 10.
In the above formulae (1) and (2), Xa is each independently a divalent organic group.
In the above formulae (1) and (2), Xb is each independently a divalent organic group.
In the above formulae, —Xa—Xb— is understood to be part of a linker connecting RF1 or RF2 and R4 in the fluoropolyether group-containing polymers represented by the formulae (1) and (2). Accordingly, Xa and Xb may be any divalent organic group as long as the compounds represented by the formulae (1) and (2) can be stably present.
In one embodiment, Xa is each independently a group represented by the following formula:
-(Q)e-(CFZ)f—(CH2)g—.
In the formula, e, f, and g are each independently an integer of 0 to 10, the sum of e, f, and g is 1 or more, and the occurrence order of the respective repeating units enclosed in parentheses is not limited in the formula. Note that, as for the above group, the left side thereof is bonded to RF1 or RF2, and the right side thereof is bonded to Xb.
In the above formula, Q is each independently at each occurrence an oxygen atom, phenylene, carbazolylene, —NRq-(wherein Rq1 represents a hydrogen atom or an organic group), or a divalent polar group. Preferably, Q is an oxygen atom or a divalent polar group.
Examples of the “divalent polar group” in the above Q include, but are not limited to, —C(O)—, —C(═NRb)—, and —C(O)NRq2— (wherein Rq2 represents a hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, and n-propyl, which are optionally substituted with one or more fluorine atoms.
In the above formula, Z 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 fluoroalkyl group having 1 to 6 carbon atoms and preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or pentafluoroethyl group, and still more preferably a trifluoromethyl group.
Xa is preferably a group represented by the following formula:
—(O)e—(CF2)f—(CH2)g—
wherein e, f, and g have the same definition as described above, and the occurrence order of the respective repeating units enclosed in parentheses is not limited in the formula. Note that, as for this group, the left side thereof is bonded to RF1 or RF2, and the right side thereof is bonded to Xb.
In one embodiment, Xa may be a group represented by
—(O)e1—(CH2)g2—O—[(CH2)g3—O—]g4, or
—(O)e1—(CF2)f2—(CH2)g2—O—[(CH2)g3—O—]g4
wherein
In a preferred embodiment, Xa may be a group represented by
—(CH2)g2—O—
wherein g2 is an integer of 1 to 10.
As for this group, the left side thereof is bonded to RF1 or RF2, and the right side thereof is bonded to Xb.
In the above formulae, Xb is each independently a divalent organic group.
In one embodiment, Xb may be a group represented by the following formula:
—CO—Rb3—CRb1Rb2—
wherein
The above Rb1 and Rb2 are, each independently, preferably a C1-3 alkyl group, a phenyl group, or —CN, and more preferably a C1-3 alkyl group or —CN. The C1-3 alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.
In one embodiment, Rb1 is a C1-3 alkyl group, preferably a methyl group, and Rb2 is a hydrogen atom or —CN.
The substituent in the “optionally substituted C1-6 alkylene group” in the above Rb3 is preferably a C1-3 alkyl group or a phenyl group, and preferably a C1-3 alkyl group. The C1-3 alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group. The number of the substituents may be one or two or more.
The C1-6 alkylene group in the above Rb3 may be preferably a C1-3 alkylene group, and more preferably a C2-3 alkylene group, such as a dimethylene group.
In one embodiment, Rb3 is a single bond.
In another embodiment, Rb3 is an optionally substituted C1-6 alkylene group, and is preferably a C1-6 alkylene group.
In the above formulae, Ra is an alkyl, phenyl, —SRa1, —ORa2, —NRa32,
Ra may be part of a so-called RAFT agent.
In the above formulae, Ra1, Ra2, Ra3, Ra4, Ra5, and Ra6 are each independently an alkyl group or a phenyl group.
The above Ra1 is preferably a C1-20 alkyl group, more preferably a C3-18 alkyl group, and still more preferably a C4-12 alkyl group.
The above Ra2 is preferably a phenyl group or a C1-20 alkyl group. The C1-20 alkyl group is preferably a C1-10 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a C1-3 alkyl group.
The above Ra3 is preferably a C1-20 alkyl group, more preferably a C1-10 alkyl group, still more preferably a C1-6 alkyl group, and even more preferably a C1-3 alkyl group.
The above Ra4 is preferably a C1-6 alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group.
The above Ra5 is preferably a C1-6 alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group.
The above Ra6 is preferably a C1-6 alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group.
The above Ra7 is a hydrogen or halogen atom (such as fluorine, chlorine, bromine, or iodine, and preferably chlorine).
In one embodiment, Ra is —SRa1 or —ORa2.
In one embodiment, the (A) fluoropolyether group-containing polymer may be a fluoropolyether group-containing polymer represented by the formula (1).
In one embodiment, the (A) fluoropolyether group-containing polymer may be a fluoropolyether group-containing polymer represented by the formula (2).
The number average molecular weight of the above fluoropolyether group-containing polymer may be, but is not limited to, 2×102 to 1×105, preferably 1×103 to 5×104, and more preferably 3×103 to 2×104. When the number average molecular weight is within such a range, the solubility in a solvent and the contact angle of the surface-treating layer can be further increased. The number average molecular weight can be determined by gel permeation chromatography (GPC).
The polydispersity (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the above fluoropolyether group-containing polymer may be preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less, and even more preferably 1.5 or less. By reducing the polydispersity, a more homogeneous surface-treating layer can be formed, and the durability of the surface-treating layer can be improved.
The above fluoropolyether group-containing polymer can be synthesized by utilizing, for example, so-called reversible addition-fragmentation chain transfer (RAFT) type radical polymerization.
At first, a RAFT agent having a perfluoropolyether group is prepared. For example, a compound (A) having a perfluoropolyether and a compound (B1) or (B2) having a RAFT skeleton (—SC(═S)—):
[wherein Ra, RF1, RF2, Xa, and Xb have the same definition as described above; and
wherein Ra, RF1, RF2, Xa, and Xb have the same definition as described above.
The chain transfer agent (1a) or (2a) obtained as described above is allowed to react with a monomer having an unsaturated bond to obtain the compound represented by the above formula (1) or (2). Such a reaction is so-called RAFT polymerization, and as the reaction conditions, conditions generally used in RAFT polymerization can be used.
The above siloxane polymer is a siloxane polymer represented by the following formula:
wherein
In the above formula, R21 and R22 are each independently at each occurrence a hydrogen atom, a C1-6 alkyl group, or an aryl group.
In the above formula, R23 and R24 are each independently a hydrogen atom, a C1-6 alkyl group, or an aryl group.
R21, R22, R23, and R24 may be the same group or may be different groups. In a preferred embodiment, R21, R22, R23, and R24 are the same group.
The above C1-6 alkyl group may be linear or branched. The above C1-6 alkyl group may also contain a cyclic structure. In one embodiment, the C1-6 alkyl group is linear. In another embodiment, the C1-6 alkyl group is branched. In another embodiment, the C1-6 alkyl group is a C3-6 cyclic alkyl group.
The above C1-6 alkyl group is preferably a C1-4 alkyl group, more preferably a C1-3 alkyl group, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
The above aryl group may be monocyclic or polycyclic.
The above aryl group is preferably a C5-20 aryl group, more preferably a C6-16 aryl group, still more preferably a C6-12 aryl group, and even more preferably a C6-10 aryl group.
In one embodiment, R21, R22, R23, and R24 are each a hydrogen atom.
In another embodiment, R21, R22, R23, and R24 are each a C1-6 alkyl group or an aryl group, and preferably a C1-6 alkyl group.
The above R25 and R26 are each independently a hydrogen atom or a monovalent organic group.
The above monovalent organic group is preferably —R27—R28.
The above R27 is understood to be part of a linker connecting the siloxane skeleton of the above siloxane polymer and R28, which is the end functional group. Accordingly, R27 may be any divalent organic group as long as the above siloxane polymer can be stably present.
The above R27 is a divalent organic group, an oxygen atom, or a single bond.
In one embodiment, examples of the above divalent organic group include a divalent organic group represented by
—(R51)q5—(R52)q6—(R53)q7—
wherein
The above R27 is preferably a single bond, an oxygen bond, or a group represented by the formula:
—(R51)q5—(R61)q6—(R53)q7—
wherein
The above R28 is a hydrogen atom, —OH, —CO—CH═CH2, —CO—C(CH3)═CH2, an epoxy group, an alicyclic epoxy group, an amino group, a carboxyl group, a vinyl group, an alkoxy group, or a thiol group.
In a preferred embodiment, the above R28 is a hydrogen atom, —OH, —CO—CH═CH2, or —CO—C(CH3)═CH2.
In one embodiment, R25 and R26 are each a C1-6 alkyl group, and preferably a C1-3 alkyl group.
In a preferred embodiment,
In another preferred embodiment,
The above siloxane polymer has a number average molecular weight of more than 350 and less than 10,000, preferably 800 to 8,000, and more preferably 900 to 7,000. When the above siloxane polymer has a number average molecular weight in the above range, the surface lubricity and appearance of a surface-treating layer obtained by the composition of the present disclosure are improved.
The content of the above siloxane polymer is 0.1 to 300 parts by mass, preferably 1 to 300 parts by mass, more preferably 1 to 250 parts by mass, even more preferably 1 to 200 parts by mass, and particularly preferably 1 to 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer.
The composition of the present disclosure may further comprise a (non-reactive) fluoropolyether compound, preferably a perfluoro(poly)ether compound, that can be interpreted as a fluorine-containing oil (hereinafter, collectively referred to as the “fluorine-containing oil”). The composition of the present disclosure may also comprise other components, such as a solvent, an active energy ray radical curing initiator, a thermal acid generator, and an active energy ray cationic curing initiator.
The above fluorine-containing oil is not limited, and examples thereof include a compound (perfluoro(poly)ether compound) represented by the following general formula (3):
Rf5—(OC4F8)a′—(OC3F6)b′—(OC2F4)c′—(OCF2)d′—Rf6 (3)
Examples of the perfluoro (poly) ether compound represented by the above general formula (3) include a compound represented by any of the following general formulae (3a) and (3b) (which may be used singly or as a mixture of two or more):
Rf5—(OCF2CF2CF2)b″—Rf6 (3a)
Rf5—(OCF2CF2CF2CF2)a″—(OCF2CF2CF2)b″—(OCF2CF2)c″—(OCF2)d″—Rf6 (3b)
Also, from another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf3—F (wherein Rf3 is a C5-16 perfluoroalkyl group.). Alternatively, the fluorine-containing oil may be a chlorotrifluoroethylene oligomer.
The above fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of the fluorine-containing oil can be measured using GPC.
The fluorine-containing oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, based on the composition of the present disclosure. In one embodiment, the composition of the present disclosure is substantially free from the fluorine-containing oil. Being substantially free from the fluorine-containing oil means that the fluorine-containing oil is not contained at all, or an extremely small amount of the fluorine-containing oil may be contained.
In one embodiment, the average molecular weight of the fluorine-containing oil may be greater than the average molecular weight of the fluoropolyether group-containing silane compound. With such average molecular weights, better abrasion durability and surface lubricity can be obtained, in the case of forming the surface-treating layer by the vacuum deposition method.
In one embodiment, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluoropolyether group-containing silane compound. With such average molecular weights, it is possible to form a cured product having high abrasion durability and high surface lubricity while suppressing reduction in the transparency of the surface-treating layer obtained from such a compound.
The fluorine-containing oil contributes to improving the surface lubricity of a layer formed of the composition of the present disclosure.
As the above solvent, a fluorine-containing organic solvent and a fluorine-free organic solvent can be used.
Examples of the above fluorine-containing organic solvent include perfluorohexane, perfluorooctane, perfluorodimethyl cyclohexane, perfluorodecalin, perfluoroalkyl ethanol, perfluorobenzene, perfluorotoluene, perfluoroalkyl amine (for example, Fluorinert (trade name)), perfluoroalkyl ether, perfluorobutyl tetrahydrofuran, polyfluoroaliphatic hydrocarbons (ASAHIKLIN AC6000 (trade name)), hydrochlorofluorocarbons (for example, ASAHIKLIN AK-225 (trade name)), hydrofluoroether (for example, Novec (trade name), HFE-7100 (trade name)), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorine-containing alcohols, perfluoroalkyl bromide, perfluoroalkyl iodide, perfluoropolyether (for example, Krytox (trade name), Demnum (trade name), Fomblin (trade name)), 1,3-bistrifluoromethylbenzene, 2-(perfluoroalkyl)ethyl methacrylate, 2-(perfluoroalkyl)ethyl acrylate, perfluoroalkyl ethylene, chlorofluorocarbon 134a, and hexafluoropropene oligomers.
Examples of the above fluorine-free organic solvent include acetone, methyl isobutyl ketone, cyclohexanone, 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 pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglyme, triglyme, ethyl acetate, butyl acetate, dimethylformamide, dimethyl sulfoxide, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.
One of the above solvents may be used singly, or two or more thereof may be used in combination.
The above solvent is contained in an amount of 5 to 100,000 parts by mass, and preferably 5 to 50,000 parts by mass, based on 100 parts by mass of the total of the above fluoropolyether group-containing polymer and siloxane polymer, as well as a fluorine-containing oil (C), which will be described below, if present.
As the above active energy ray radical curing initiator, for example, one is used that generates radicals for the first time upon irradiation with electromagnetic waves in a wavelength region of 350 nm or less, such as ultraviolet rays, electron beams, X-rays, γ-rays, or the like, functions as a catalyst that initiates curing (crosslinking reaction) of a curable site (for example, carbon-carbon double bond) of the above fluoropolyether group-containing polymer, and usually generates radicals with ultraviolet rays.
The above active energy ray radical curing initiator is appropriately selected depending on the type of curable site in the above fluoropolyether group-containing polymer, the type of active energy ray to be used (wavelength range or the like), irradiation intensity, or the like, and generally, the following can be exemplified as the initiator for curing the above fluoropolyether group-containing polymer having a radical-reactive curable site (carbon-carbon double bond) using the active energy ray in the ultraviolet region.
Acetophenones
acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and the like.
Benzoins
benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.
Benzophenones
benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, and the like.
Thioxanthones
thioxanthone, chlorothioxanthone, methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, and the like.
Others
benzyl, α-acyloxime ester, acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, and the like.
One of these active energy ray curing initiators may be used singly, or two or more thereof may be used in combination.
The above active energy ray curing initiator is contained in an amount of 0.01 to 1,000 parts by mass, and preferably 0.1 to 500 parts by mass, based on 100 parts by mass of the total of the above fluoropolyether group-containing polymer and siloxane polymer, as well as the fluorine-containing oil, if present, although there is no limitation on the amount thereof.
By using the above thermal acid generator, decomposition reaction of the compound containing a cationic species is caused by heat, and curing (crosslinking reaction) of a curable site (for example, cyclic ether) of the fluoropolyether group-containing polymer having the curable site is initiated.
The above thermal acid generator is suitably, for example, a compound represented by the following general formula (a):
(R1aR2bR3cR4dZ)+m(AXn)−m (a)
(wherein Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, 0, N, and halogen elements; R1, R2, R3, and R4 are the same or different and represent an organic group; a, b, c and d are each 0 or a positive number, and the total of a, b, c, and d is equal to the valence of Z; the cation (R1aR2bR3cR4dZ)+m represents an onium salt; A represents a metal element or a metalloid element, which is the central atom of the halide complex, and is at least one selected from the group consisting of B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co; X represents a halogen element; m is the net charge of the halide complex ion; and n is the number of halogen elements in the halide complex ion.
Specific examples of the anion (AXn)−m of the above general formula (a) include tetrafluoroborate (BF4−), hexafluorophosphate (PF6−), hexafluoroantimonate (SbF6−), hexafluoroarsenate (AsF6−), and hexachloroantimonate (SbCl6−). Furthermore, anions represented by the general formula AXn(OH)− can also be used. Examples of other anions include perchlorate ion (ClO4−), trifluoromethylsulfite ion (CF3SO3−), fluorosulfonate ion (FSO3−), toluenesulfonate ion, and trinitrobenzenesulfonate ion.
Specific examples of commercial products of the above thermal acid generator include: diazonium salt products such as AMERICURE series (manufactured by American Can Company), ULTRASET series (manufactured by Adeka Corporation), and WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.); iodonium salt products such as UVE series (manufactured by General Electric Company), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicones Ltd.), Photoinitiator 2074 (manufactured by Rhone-Poulenc), and WPI series (manufactured by Wako Pure Chemical Industries, Ltd.); and sulfonium salt products such as CYRACURE series (manufactured by Union Carbide Corporation), UVI series (manufactured by General Electric Company), FC series (manufactured by 3M), CD series (manufactured by Sartomer Company Inc.), Optomer SP series and Optmer CP series (manufactured by Adeka Corporation), San Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), and CPI series (manufactured by San-Apro Ltd.).
One of these thermal acid generators may be used singly, or two or more thereof may be used in combination.
The above thermal acid generator is contained in an amount of 0.01 to 1,000 parts by mass, and preferably 0.1 to 500 parts by mass, based on 100 parts by mass of the total of the fluoropolyether group-containing polymer and the siloxane polymer, as well as the fluorine-containing oil, if present, although there is no limitation on the amount thereof.
By using the above active energy ray cationic curing initiator, a compound containing a cationic species is excited by light to cause a photodecomposition reaction, thereby initiating curing (crosslinking reaction) of a curable site (for example, cyclic ether) of the fluoropolyether group-containing polymer.
Suitable examples of the above active energy ray cationic curing initiator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, p-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl)benzene]-Fe-hexafluorophosphate, and diaryliodonium hexafluoroantimonate.
Specific examples of commercial products of the above active energy ray cationic curing initiator preferably include diazonium salt, iodonium salt, and sulfonium salt products such as UVI-6950, UVI-6970, UVI-6974, and UVI-6990 (manufactured by Union Carbide Corporation); Adeca Optomer SP-150, SP-151, SP-170, and SP-172 (manufactured by ADEKA CORPORATION); Irgacure 250 (manufactured by Chiba Japan); CI-2481, CI-2624, CI-2639, and CI-2064 (manufactured by Nippon Soda Co., Ltd.); CD-1010, CD-1011, and CD-1012 (manufactured by Sartomer Company Inc.); DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, and BBI-103 (manufactured by Midori Kagaku Co., Ltd.); PCI-061T, PCI-062T, PCI-020T, and PCI-022T (manufactured by Nippon Kayaku Co., Ltd.); CPI-100P, CPT-101A, and CPI-200K (manufactured by San-Apro Ltd.); San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid ST-110L, San-Aid SI-145, San-Aid SI-150, San-Aid SI-160, and San-Aid SI-180L (manufactured by Sanshin Chemical Industry Co., Ltd.); and WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.).
One of these active energy ray cationic curing initiators may be used singly, or two or more thereof may be used in combination.
The above active energy ray radical curing initiator is contained in an amount of 0.01 to 1,000 parts by mass, and preferably 0.1 to 500 parts by mass, based on 100 parts by mass of the total of the fluoropolyether group-containing polymer and the siloxane polymer, as well as the fluorine-containing oil, if present, although there is no limitation on the amount thereof.
The composition of the present disclosure is useful as a surface-treating agent. Accordingly, the present disclosure provides a surface-treating agent comprising the composition of the present disclosure.
In a preferred embodiment, the composition of the present disclosure is a surface-treating agent.
The present disclosure provides a curable composition comprising the composition and the surface-treating agent of the present disclosure described above, and/or a matrix-forming composition.
The above matrix-forming composition means a composition containing a compound having at least one carbon-carbon double bond, for example, a compound that is a monofunctional and/or polyfunctional acrylate and methacrylate (hereinafter, acrylate and methacrylate are also collectively referred to as “(meth)acrylate”), a monofunctional and/or polyfunctional urethane (meth)acrylate, or a monofunctional and/or polyfunctional epoxy (meth)acrylate, although not limited thereto. Examples of such a matrix-forming composition include, but are not limited to, a composition generally used as a hard coating agent or an anti-reflective agent, for example, a hard coating agent containing a polyfunctional (meth)acrylate or an anti-reflective agent containing a fluorine-containing (meth)acrylate. Such a hard coating agent is commercially available, for example, as Beam set 502H, 504H, 505A-6, 550B, 575CB, 577, 1402 (trade name) from Arakawa Chemical Industries, Ltd.; as EBECRYL40 (trade name) from Daicel Cytec company LTD.; and as HR300 series (trade name) from Yokohama Rubber Co., Ltd. The above anti-reflective agent is commercially available, for example, as Optool AR-110 (trade name) from Daikin Industries, Ltd.
As the above matrix-forming composition, a composition containing a compound that is a monofunctional and/or polyfunctional epoxy is also preferred. For example, epoxy compounds such as bisphenol A diglycidyl ether, 2,2′-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, and triglycidyl isocyanurate can be used. Also usable are hydrogenated epoxy resins, alicyclic epoxy resins, epoxy resins containing isocyanurate rings, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, hydrogenated epoxy resins obtained by hydrogenating aromatic rings of the various epoxy resins, and dicyclopentadiene type epoxy resins, although some overlap with the aforementioned.
In one embodiment, the above curable composition comprises 0.01 to 20% by mass, preferably 0.01 to 10% by mass, and more preferably 0.1 to 10% by mass of the fluoropolyether group-containing polymer and the siloxane polymer, based on the solid of the matrix-forming composition.
The curable composition of the present disclosure may further comprise antioxidants, thickening agents, leveling agents, antifoaming agents, antistatic agents, antifogging agents, ultraviolet absorbers, pigments, dyes, inorganic fine particles such as silica, fillers such as aluminum paste, talc, glass frit, and metal powder, and polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ), and the like.
Next, an article of the present disclosure will be described.
The present disclosure provides an article comprising a substrate and a layer (surface-treating layer) on a surface of the substrate, wherein the layer is formed of the composition, surface-treating agent, or curable composition of the present disclosure. 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 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 above composition, surface-treating agent, or curable 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 surface-treating layer from the composition, surface-treating agent, or curable composition of the present disclosure.
The film of the composition, surface-treating agent, or curable composition of the present disclosure can be formed by applying the above composition, surface-treating agent, or curable composition to the surface of the substrate so as to coat 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 composition, surface-treating agent, or curable 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 solvent and fluorine-free organic solvent described above can be used. From the viewpoint of the stability of the composition, surface-treating agent, or curable composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons; cellosolve solvents such as hydrofluoroethers (HFEs) (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) (the perfluoroalkyl group and the alkyl group may be linear or branched)), hydrochlorofluorocarbons (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 thereof 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, it is performed by heating for a predetermined time. By performing such post-treatment, curing of the curable site of the fluoropolyether group-containing polymer 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 surface-treating layer derived from the composition, surface-treating agent, or curable composition of the present disclosure is formed on the substrate surface, and the article of the present disclosure is produced. The surface-treating layer thus obtained has 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. Furthermore, this surface-treating layer may have not only high friction durability and surface lubricity, but also have, depending on the compositional features of the composition, surface-treating agent, or curable composition to be used, water-repellency, oil-repellency, antifouling property (for example, preventing fouling including fingerprints and the like from adhering), and the like, and may be suitably used as a functional thin film.
The dynamic friction coefficient of the film formed from the surface-treating composition of the present invention is preferably 0.85 or less, more preferably 0.80 or less, and still more preferably 0.77 or less. By keeping the dynamic friction coefficient low, the coating film can be made to have better tactile sensations.
The above dynamic friction coefficient can be measured using a friction measuring machine (“Tribomaster TL201 Ts”, manufactured by Trinity-Lab Inc.) and the like with a tactile contactor as the friction block, a load of 20 gf, and a scanning speed of 10 mm/sec.
The range of static contact angle of water of the film formed from the surface-treating composition of the present invention is preferably 111 degrees or more, more preferably 112 degrees or more, and still more preferably 113 degrees or more. By increasing the contact angle, the coating film can be made to have more excellent antifouling property.
The above contact angle can be measured at a drop volume of 2 μL using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.).
The present disclosure further relates to an optical material having the above 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 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® discs, DVD discs, CD-Rs, and MOs; and optical fibers.
In one embodiment, examples of the article having a surface-treating layer obtained according to the present disclosure include a light detection and ranging (LiDAR) cover member, a sensor member, an instrument panel cover member, an automobile interior member, and the like, and in particular, these members for automobiles.
The thickness of the surface-treating layer is not limited. The thickness of the surface-treating layer in the case of an optical member is in the range of 0.1 to 30 μm, preferably 0.5 to 20 μm, from the viewpoint of optical performance, surface lubricity, friction durability, and antifouling property.
The article obtained by using the composition, surface-treating agent, or curable composition of the present disclosure has been described in detail above. The application of the composition, surface-treating agent, or curable composition of the present disclosure, the method for using the same, the method for producing an article, and the like are not limited to those exemplified above.
The present disclosure includes the following embodiments.
(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3RFa6)d—(OC2F4)e—(OCF2)f—
—(OC3F6)d—(OC2F4)e— (f1)
—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f2)
—(R6—R7)g— (f3)
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f4)
(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f5)
Hereinafter, the present disclosure will be described by way of Examples, but the present disclosure is not intended to be limited to the following Examples. In the Examples, all chemical formulas shown below indicate average compositional features, and the occurrence order of repeating units (such as (OCF2CF2CF2), (OCF2CF2), and (OCF2)) constituting perfluoropolyether is not limited.
1. Synthesis of Perfluoropolyether-Containing Chain Transfer Agent
Synthesis of Chain Transfer Agent (A-1)
To a flask were added 0.505 g of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl] propanoic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.019 g of 4-dimethylaminopyridine (DMAP) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.293 g of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5.0 g of an alcohol containing perfluoropolyether represented by CF3CF2CF2(OCF2CF2CF2)nOCF2CF2CH2OH (average value of n≈25) (manufactured by Daikin Industries, Ltd.), 13 mL of ASAHIKLIN AK-225 (manufactured by AGC Inc.) was added, and the mixture was stirred at room temperature to conduct the reaction. After stirring overnight, the reaction solution was washed with saturated aqueous sodium bicarbonate and brine. The organic layer was separated, concentrated, and dropped into methanol to give 4.56 g of a yellow oily target product (A-1).
2. Synthesis of PFPE Block Polymers Having an Epoxy Group
(1) Synthesis of PFPE Block Polymer (P-1) Having an Epoxy Group
Into a reaction vessel were added 1.0 g of the chain transfer agent (A-1), 0.23 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) (manufactured by Mitsubishi Chemical Corporation), and 12 mg of N,N′-azobis(isobutyronitrile) (AIBN) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and the mixture was dissolved in 2.9 mL of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was heated at 75° C. for 17 hours, and the reaction solution was added dropwise to hexane to precipitate and recover a block polymer (P-1). From NMR measurement, the polymerization degree of 4HBAGE was calculated to be 5.
(2) Synthesis of PFPE Block Polymer (P-2) Having an Epoxy group
In the same manner as in Synthesis Example 2, a block polymer (P-2) having a polymerization degree of 4HBAGE of 10 was synthesized by changing the charging amount of 4HBAGE to 0.46 g.
3. Synthesis of PFPE Block Polymers Having a (Meth)Acrylic Group
(1) Synthesis of PFPE Block Polymer (P-3) Having a Hydroxyl Group
Into a reaction vessel were added 1.3 g of (A-1), 0.18 g of 2-hydroxyethyl acrylate (HEA) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 15.5 mg of AIBN, and the mixture was dissolved in 2.1 mL of 1,3-bis (trifluoromethyl)benzene. Polymerization was carried out by heating at 70° C. for 22.5 hours to obtain a solution of a block polymer (P-3). From NMR measurement, the polymerization degree of HEA was calculated to be 5.
(2) Synthesis of PFPE Block Polymer (P-4) Having an Acrylic Group
1.1 equivalents of Karenz AOI (manufactured by Showa Denko K.K.) and 0.01 equivalents of dibutyltin dilaurate (DBTDL) (manufactured by Tokyo Chemical Industry Co., Ltd.) with respect to the HEA unit in the polymer (P-3) were added to the reaction solution of (1), and the mixture was stirred at 40° C. for 2 hours. After it was confirmed by NMR measurement that 100% of the hydroxyl groups had reacted, the reaction solution was added dropwise to methanol to precipitate and recover a block polymer (P-4) having an acrylic group.
(3) Synthesis of PFPE Block Polymer (P-5) Having a Methacrylic Group
In the same manner as in (2) of Synthesis Example 5, a block polymer (P-5) having a methacrylic group was synthesized, except that Karenz AOI was changed to Karenz MOI (manufactured by Showa Denko K.K.).
4. Synthesis of PFPE Compound (P-6) Having an Acrylic Group
In a 1 L four-neck flask equipped with a dropping funnel, a condenser, a thermometer, and a stirrer, Sumidur® N3300 (manufactured by Sumika Bayer Urethane Co., Ltd., NCO group content: 21.8%, 36.6 g) was dissolved in ASAHIKLIN AK-225 (219.4 g), dibutyltin dilaurate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 0.30 g) was added, a solution in which an alcohol containing perfluoropolyether represented by the average compositional features: CF3CF2CF2O(CF2CF2CF2O)14CF2CF2CH2OH (60.0 g) was dissolved in ASAHIKLIN AK-225 (60.0 g) was added dropwise while stirring at 40° C. under nitrogen gas stream, and the mixture was stirred. HEA (19.6 g) was added dropwise and the mixture was stirred. It was confirmed by IR that absorption of NCO had been completely eliminated. 0.05 g of dibutylhydroxytoluene was added and the solvent was completely removed, and a PFPE compound (P-6) having an acrylic group was synthesized.
5. Synthesis of PFPE Block Polymer (P-7) Having an Epoxy Group
Into a reaction vessel were added 1.0 g of the chain transfer agent (A-1), 0.20 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) (manufactured by Mitsubishi Chemical Corporation), 0.10 g of n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 12 mg of N,N′-azobis(isobutyronitrile) (AIBN) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and the mixture was dissolved in 3.1 mL of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was heated at 75° C. for 20 hours, and the reaction solution was added dropwise to hexane to precipitate and recover a block polymer (P-7). It was confirmed by NMR measurement that four 4HBAGE units and three n-butyl acrylate units had been introduced into one molecule of the block polymer.
5. Coating Liquid Preparation and Coating Film Preparation
(1) Epoxy Coatings
CELLOXIDE 2021P (manufactured by Daicel Corporation) was dissolved in MIBK as a matrix-forming epoxy compound, and the PFPE block polymers (P-1), (P-2), and (P-7) synthesized in Synthesis Examples 2 and 3 were added to the solution so that the concentration of the PFPE block polymers based on the solid of the epoxy compound was 1% in terms of the solid concentration respectively. Furthermore, the silicone compounds (S-1) to (S-9) were added in the combinations and in the amounts added (based on the matrix-forming compound) shown in Table 1 below in terms of the solid concentration based on the solid of the epoxy compound respectively, thereby preparing epoxy compound solutions of 50% by mass (Examples 1 to 9, 18 to 21, and Comparative Examples 4 to 7). In addition, a solution in which only the silicone compound (S-2) was added without adding any PFPE block polymer (Comparative Example 1), and solutions in which only the PFPE block polymer (P-1) or (P-2) was added without adding any silicone compound (Comparative Examples 2 and 3) were also prepared. Furthermore, a thermal acid generator, San-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) was added in an amount of 3% by mass based on the solid of the epoxy compound to obtain coating agents. A PET substrate was coated with the coating agents using a bar coater and heated under conditions of 90° C. for 2 hours to obtain cured films.
(2) Acrylic Coatings
BEAMSET 575CB (manufactured by Arakawa Chemical Industries, Ltd.) was dissolved in MIBK as a composition comprising a matrix-forming acrylic compound, and the PFPE block polymers (P-4) and (P-5) synthesized in Synthesis Examples 5 and 6 were added to the solution so that the concentration of the PFPE copolymer based on the resin solid of BEAMSET 575CB was 1% in terms of the solid concentration respectively. Furthermore, the silicone compounds (S-1), (S-4), and (S-6) were added in the combinations and in the amounts added (based on the matrix-forming compound) shown in Table 2 below in terms of the solid concentration based on the resin solid of BEAMSET 575CB respectively, thereby obtaining coating compositions of 50% by mass (Examples 10 to 17, and Comparative Examples 10, 11, 13, and 14). In addition, a coating agent in which only the silicone compound (S-4) was added without adding any PFPE block polymer (Comparative Example 8), coating agents in which only the PFPE block polymer (P-4) or (P-5) was added without adding any silicone compound (Comparative Examples 9 and 12), and coating agents in which the PFPE compound (P-6) having an acrylic group synthesized in Comparative Synthesis Example 1 was added in place of the PFPE block polymer (Comparative Examples 15 and 16) were also prepared. A PET substrate was coated with the coating compositions using a bar coater, dried under conditions of 70° C. for 10 minutes, and irradiated with ultraviolet rays to obtain cured films. A belt conveyor type ultraviolet irradiation device was used for the ultraviolet irradiation, and the dose was set to 600 mJ/cm2.
Silicone Compounds
For the above Examples and Comparative Examples, miscibility, coating film appearance, contact angle, and surface lubricity were evaluated as follows. The results are shown in Table 3 (epoxy coatings) and Table 4 (acrylic coatings) below.
6. Evaluation of Miscibility
For the coating solutions prepared in 5 above, the solution state was visually confirmed. The evaluation criteria were as follows.
7. Coating Film Appearance
The cured films prepared in 5 above were visually observed. The evaluation criteria were as follows.
8. Evaluation of Contact Angle
For the cured films prepared in 5 above, the static contact angle of water was measured using 2 μL of liquid using a contact angle meter (“DropMaster” manufactured by Kyowa Interface Science Co., Ltd.). The measurement was not performed for those with NG coating film appearance.
9. Evaluation of Surface Lubricity
For the cured films prepared in 5 above, the static friction coefficient and dynamic friction coefficient were measured using a friction measuring machine (“Tribomaster TL201 Ts”, manufactured by Trinity-Lab Inc.) with a tactile contactor as the friction block, a load of 20 gf, and a scanning speed of 10 mm/sec. The measurement was not performed for those with NG coating film appearance.
As described above, the compositions comprising fluoropolyether group-containing polymers (P-1 to P-5 and P-7) and siloxane polymers (S-1, S-2, S-4, and S-6 to S-9), which fall within the range of the present invention, were confirmed to have high miscibility, good coating film appearance, and both a large contact angle to water of 113 degrees or more and high lubricity.
The surface-treating agent of the present disclosure can be suitably utilized to form a surface-treating layer on the surface of a variety of substrates, in particular optical members for which transparency is required.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-030453 | Feb 2021 | JP | national |
This application is a Rule 53(b) Continuation of International Application No. PCT/JP2022/008033 filed Feb. 25, 2022, which claims priority from Japanese Patent Application No. 2021-030453 filed Feb. 26, 2021, the respective disclosures of all of the above of which are incorporated herein by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2022/008033 | Feb 2022 | US |
| Child | 18456091 | US |
