Patent Application
20240360324
The present invention relates to a surface treatment agent, an article, and a method for manufacturing an article.
It has been known that in order to impart water and oil repellency, an antifouling property, and the like to the surface of a substrate, a surface layer consisting of a condensate of a fluorine-containing ether compound is formed on the surface of the substrate through a surface treatment using a fluorine-containing ether compound having a fluoro-polyether chain and a reactive silyl group (Japanese Patent No. 5761305).
In recent years, it has been demanded that properties a surface layer formed by using a fluorine-containing ether compound is required to have should be further improved. For example, a touch panel or the like is repeatedly rubbed by fingers, so that it is desired to improve the friction resistance of a surface layer formed on a surface of a component which is rubbed by fingers, such as a touch panel, even further.
The inventors of the present application have evaluated surface layers formed by using a fluorine-containing ether compound such as those disclosed in Japanese Patent No. 5761305, and found that there is room for improvement in friction resistance of the surface layers.
Accordingly, an object of the present invention is to provide a surface treatment agent from which a surface layer having an excellent friction resistance can be formed, an article including such a surface layer, and a method for manufacturing such an article.
As a result of diligent examinations in regard to the above-described problem, the inventors of the present application have found that the use of a surface treatment agent containing a fluorine-containing ether compound and a metallic compound containing at least one metal element selected from the group consisting of elements in Groups 1 and 2 in the periodic table makes it possible to form a surface layer having an excellent friction resistance, and thereby made the present invention.
That is, the inventors of the present application have found that the above-described problem can be solved by the below-shown features.
[1] A surface treatment agent containing:
The above and other objects, features and advantages of the present disclosure will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not to be considered as limiting the present disclosure.
According to the present invention, it is possible to provide a surface treatment agent from which a surface layer having an excellent friction resistance can be formed, an article including such a surface layer, and a method for manufacturing such an article.
In this specification, a group represented by Formula (g1) may be expressed as a group (g1). Further, a compound represented by Formula (A1) may be expressed as Compound (A1). Compounds represented by other formulas are also expressed in a similar manner.
A fluoroalkyl group is a collective term for a perfluoroalkyl group and a partial fluoroalkyl group. A perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are replaced by fluorine atoms. Further, a partial fluoroalkyl group is an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom and which has at least one hydrogen atom. That is, a fluoroalkyl group is an alkyl group having at least one fluorine atom.
A “reactive silyl group” is a collective term for a hydrolytic silyl group and a silanol group (Si—OH), and the “hydrolytic silyl group” means a group that can form a silanol group through a hydrolysis reaction.
An “organic group” means a hydrocarbon group which may have a substituent and have a heteroatom or other bonds in a carbon chain.
The “hydrocarbon group” is a group consisting of a carbon atom(s) and a hydrogen atom(s) and is a group consisting of an aliphatic hydrocarbon group (e.g., as a divalent aliphatic hydrocarbon group, a linear alkylene group, a branched alkylene group, a cycloalkylene group or the like), an aromatic hydrocarbon group (e.g., as a divalent aromatic hydrocarbon group, a phenylene group or the like), and a combination thereof.
A “surface layer” means a layer formed on a substrate.
The “molecular weight” of a fluoro-polyether chain is a number-average molecular weight calculated by obtaining the number (average value) of oxyfluoro-alkylene units based on the end group, by 1H-NMR and 19F-NMR.
A symbol “-”, which indicates a range of numerical values, means that values in front of and behind this symbol are included in the range as lower and upper limits, respectively.
A surface treatment agent according to the present invention (hereinafter also referred to as “the surface treatment agent”) contains a fluorine-containing ether compound having a fluoro-polyether chain and a reactive silyl group, and a metallic compound containing at least one metal element selected from the group consisting of elements in Groups 1 excluding a hydrogen element and Group 2 in a periodic table (hereinafter also referred to as a “specific metal element”).
The surface treatment agent makes it possible to form a surface layer having an excellent friction resistance. The details of the reason for this feature are not elucidated, but it is inferred that this feature is obtained by the following reasons.
Carbonic acid generated by moisture and carbon dioxide present in the atmosphere may promote the hydrolysis of reactive silyl groups included in a fluorine-containing ether compound. If some of reactive silyl groups in a fluorine-containing ether compound contained in a surface treatment agent are consumed before the surface treatment agent is applied to a substrate, sufficient bonding between the substrate and the surface layer is not obtained when the surface treatment agent is applied to the substrate, thus causing a problem that the friction resistance of the surface layer is lowered.
Regarding this problem, in the surface treatment agent according to the present disclosure, the specific metal element contained in the metallic compound reacts with carbonic acid, thus making it possible to prevent reactive silyl groups in the fluorine-containing ether compound from being consumed by carbonic acid. It is inferred that as a result of the above, the friction resistance of the surface layer is improved.
A fluorine-containing ether compound has a fluoro-polyether chain and a reactive silyl group.
Since a fluorine-containing ether compound has a fluoro-polyether chain, a surface layer obtained by using the fluorine-containing ether compound has excellent water and oil repellency and an excellent fingerprint stain removal property.
A fluorine-containing ether compound has a reactive silyl group. Since the reactive silyl group is strongly chemically bonded to a substrate, an obtained surface layer has an excellent friction resistance.
A fluoro-polyether chain is a group having at least two oxyfluoro-alkylene units.
A fluoro-polyether chain may have a hydrogen atom. To achieve a more excellent friction resistance and a fingerprint stain removal property of the surface layer, the ratio of fluorine atoms in the fluoro-polyether chain represented by the below-shown Expression (I) is preferably 60% or higher, more preferably 80% or higher, and still more preferably substantially 100%, i.e., the fluoro-polyether chain is a perfluoro-polyether chain. When the amount of fluorine atoms is 60% or higher, the amount of fluorine in the fluoro-polyether chain is increased, so that the lubricity and the fingerprint removal property are further improved.
To achieve both the fingerprint stain removal property and the lubricity of the surface layer, the molecular weight of one fluoro-polyether chain is preferably 2,000-20,000, more preferably 2,500-15,000, and still more preferably 3,000-10,000. When the molecular weight of the fluoro-polyether chain is 2,000 or larger, the flexibility of the fluoro-polyether chain is improved and the amount of fluorine in the molecule is increased, so that the lubricity and the fingerprint removal property are improved even further. Meanwhile, when the molecular weight of the fluoro-polyether chain is 20,000 or smaller, the surface layer has a more excellent friction resistance.
The fluoro-polyether chain preferably has Structure (f1).
(ORf)y (f1)
Rf is a fluoro-alkylene group having a carbon number of 1-6. There are a plurality of fluoro-alkylene groups Rf, and they may be identical to each other or at least one of them is different from the others.
y is an integer of 2 or greater, and is preferably 2-200.
(ORf)y preferably has a structure represented by the below-shown Formula (f2).
-[(OGf1)m1(OGf2)m2(OGf3)m3(OGf4)m4(OGf5)m5(OGf6)m6]- (f2)
Note that the bonding order of (OGf1) to (OGf6) in Formula (f2) is arbitrary. In Formula (f2), m1 to m6 represent the numbers of (OGf1) to (OGf6), respectively, and do not represent the arrangement thereof. For example, (OG5)mm5 indicates that the number of (OGf5) is m5, and does not represent the block arrangement structure of (OGf5)m5. Similarly, the order of (OGf1) to (OGf6) in the description does not represent the bonding order of these units.
Further, each of the above-described fluoro-alkylene groups having carbon numbers 3-6 may be a linear fluoro-alkylene group, a branched fluoro-alkylene group, or a fluoro-alkylene group having a ring-structure.
Specific examples of Gf1 include —CF2— and —CHF—.
Specific examples of Gf2 include —CF2CF2—, —CHFCF2—, —CHFCHF—, —CH2CF2—, and —CH2CHF—.
Specific examples of Gf3 include —CF2CF2CF2—, —CF2CHFCF2—, —CF2CH2CF2—, —CHFCF2CF2—, —CHFCHFCF2—, —CHFCHFCHF—, —CHFCH2CF2—, —CH2CF2CF2—, —CH2CHFCF2—, —CH2CH2CF2—, —CH2CF2CHF—, —CH2CHFCHF—, —CH2CH2CHF—, —CF(CF3)—CF2—, —CF(CHF2)—CF2—, —CF(CH2F)—CF2—, —CF(CH3)—CF2—, —CF(CF3)—CHF—, —CF(CHF2)—CHF—, —CF(CH2F)—CHF—, —CF(CH3)—CHF—, —CF(CF3)—CH2—, —CF(CHF2)—CH2—, —CF(CH2F)—CH2—, —CF(CH3)—CH2—, —CH(CF3)—CF2—, —CH(CHF2)—CF2—, —CH(CH2F)—CF2—, —CH(CH3)—CF2—, —CH(CF3)—CHF—, —CH(CHF2)—CHF—, —CH(CH2F)—CHF—, —CH(CH3)—CHF—, —CH(CF3)—CH2—, —CH(CHF2)—CH2—, and —CH(CH2F)—CH2—. Specific examples of Gf4 include —CF2CF2CF2CF2—, —CHFCF2CF2CF2—, —CH2CF2CF2CF2—, —CF2CHFCF2CF2—, —CHFCHFCF2CF2—, —CH2CHFCF2CF2—, —CF2CH2CF2CF2—, —CHFCH2CF2CF2—, —CH2CH2CF2CF2—, —CHFCF2CHFCF2—, —CH2CF2CHFCF2—, —CF2CHFCHFCF2—, —CHFCHFCHFCF2—, —CH2CHFCHFCF2—, —CF2CH2CHFCF2—, —CHFCH2CHFCF2—, —CH2CH2CHFCF2—, —CF2CH2CH2CF2—, —CHFCH2CH2CF2—, —CH2CH2CH2CF2—, —CHFCH2CH2CHF—, —CH2CH2CH2CHF—, and -cycloC4F6—.
Specific examples of Gf5 include —CF2CF2CF2CF2CF2—, —CHFCF2CF2CF2CF2—, —CH2CHFCF2CF2CF2—, —CF2CHFCF2CF2CF2—, —CHFCHFCF2CF2CF2—, —CF2CH2CF2CF2CF2—, —CHFCH2CF2CF2CF2—, —CH2CH2CF2CF2CF2—, —CF2CF2CHFCF2CF2—, —CHFCF2CHFCF2CF2—, —CH2CF2CHFCF2CF2—, —CH2CF2CF2CF2CH2—, and -cycloC5F8—.
Specific examples of Gf6 include —CF2CF2CF2CF2CF2CF2—, —CF2CF2CHFCHFCF2CF2—, —CHFCF2CF2CF2CF2CF2—, —CHFCHFCHFCHFCHFCHF—, —CHFCF2CF2CF2CF2CH2—, —CH2CF2CF2CF2CF2CH2—, and -cycloC6F10—.
Note that -cycloC4F6— refers to a perfluoro-cyclobutanediyl group, and its specific example include a perfluoro-cyclobutane-1,2-diyl group. -cycloC5F8— refers to a perfluoro-cyclopentanediyl group, and its specific examples include a perfluoro-cyclopentane-1,3-diyl group. -cycloC6F10 refers to a perfluoro-cyclohexanediyl group, and its specific examples include a perfluoro-cyclohexane-1,4-diyl group.
To achieve more excellent water and oil repellency, a friction resistance, and a fingerprint stain removal property, (ORf)y preferably has, in particular, one of structures represented by the below-shown Formulas (f3) to (f5). Further, to achieve a more excellent alkali resistance, (ORf)y more preferably has a structure represented by the below-shown Formula (f3), and still more preferably has a structure expressed as (OCF2)m1·(OCF2CF2)m2.
(OGf1)m1·(OGf2)m2 (f3)
(OGf2)m2·(OGf4)m4 (f4)
(OGf3)m3 (f5)
Note that symbols in Formulas (f3) to (f5) are similar to those in the above-show Formula (f2).
In Formulas (f3) and (f4), the bonding order of (OGf1) and (OGf2), and that of (OGf2) and (OGf4) are arbitrary. For example, in Formula (G2), (OGf1) and (OG12) may be alternately arranged, and (OGf1) and (OGf1) may be arranged in each block or randomly arranged. The same applies to Formula (f5).
In Formula (f3), m1 is preferably 1-30 and more preferably 1-20. Further, m2 is preferably 1-30 and more preferably 1-20.
In Formula (f4), m2 is preferably 1-30 and more preferably 1-20. Further, m4 is preferably 1-30 and more preferably 1-20.
In Formula (f5), m3 is preferably 1-30 and more preferably 1-20.
To achieve more excellent water and oil repellency and a fingerprint removal property, the ratio of fluorine atoms in the fluoro-polyether chain (ORf)y, i.e., the ratio [{Number of fluorine atoms/(Number of fluorine atoms+number of hydrogen atoms)}×100(%)], is preferably 60% or higher, more preferably 70% or higher, and still more preferably 80% or higher.
Further, in view of the friction resistance, the molecular weight of the part of the fluoro-polyether chain (ORf)y is preferably 2,000-20,000, more preferably 2,500-15,000, and still more preferably 3,000-10,000.
The reactive silyl group is preferably a group (g1).
—SiRa1z1Ra23-z (g1)
When Ra1 is a hydroxyl group, it constitutes a silanol (Si—OH) group together with an Si atom. Further, the hydrolytic group is a group that becomes a hydroxyl group (i.e., a silanol group) through a hydrolysis reaction. The silanol group further forms a Si—O—Si bond through an intermolecular reaction. Further, the silanol group forms a chemical bond (substrate (or underlayer)-O—Si) through a dehydration condensation reaction with a hydroxyl group (substrate (or underlayer)-OH) present on the surface of the substrate (or underlayer). Since the fluorine-containing ether compound has at least one group (g1), it has an excellent friction resistance after the surface layer is formed.
Examples of hydrolytic groups of Ra1 include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (—NCO). As the alkoxy group, an alkoxy group having a carbon number of 1-4 is preferred. As the acyl group, an acyl group having a carbon number of 1-6 is preferred. As the acyloxy group, an acyloxy group having a carbon number of 1-6 is preferred.
For the ease of the manufacturing of a fluorine-containing ether compound, Ra1 is preferably, in particular, an alkoxy group having a carbon number of 1-4 or a halogen atom. To improve the storage stability of the fluorine-containing ether compound and to prevent gas from being emitted outside during the reaction, the alkoxy group in Ra1 is preferably, in particular, an alkoxy group having a carbon number of 1-4. Further, in view of the storage stability over a long time, the alkoxy group in Ra1 is, preferably, an ethoxy group, and to reduce the hydrolysis reaction time, the alkoxy group in Ra1 is preferably a methoxy group. As the halogen atom, in particular, a chlorine atom is preferred.
Examples of the non-hydrolytic group of Ra2 include a hydrogen atom and a monovalent hydrocarbon group and the like. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group. Further, for the ease of the manufacturing or the like, an alkyl group is preferred. Further, for the ease of the manufacturing or the like, the carbon number of the hydrocarbon group is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
z1 may be an integer of 1-3. In view of the adhesion to the substrate (or underlayer), z1 is preferably 2 or 3, and more preferably 3.
Specific examples of the group (g1) include —Si(OCH3)3, —SiCH3(OCH3)2, —Si(OCH2CH3)3, —SiCl3, —Si(OCOCH3)3, and —Si(NCO)3. For the ease of the handling in the manufacturing, the group (g1) is preferably —Si(OCH3)3.
Note that when there are a plurality of groups (g1) in one molecule, the plurality of groups (g1) may be identical to each other or at least one of them is different from the others.
In the fluorine-containing ether compound, the above-described fluoro-polyether chain and the above-described group (g1) are bonded to each other directly or through a linking group. Examples of the linking group include an organic group having a valency of 2 or higher.
The number of fluoro-polyether chains in one molecule in the fluorine-containing ether compound may be one, or may be two or more. For the ease of synthesis or the like, the number of fluoro-polyether chains in one molecule is preferably 1-20, more preferably 1-10, and still more preferably 1-4.
Further, the number of groups (g1) in one molecule of the fluorine-containing ether compound may be one, or may be two or more. To improve both the friction resistance and the water and oil repellency or the like, the number of groups (g1) is preferably 1-32, more preferably 1-18, and still more preferably 2-12.
Note that when there are a plurality of fluoro-polyether chains, the plurality of fluoro-polyether chains may be identical to each other or at least one of them is different from the others. Further, when there are a plurality of groups (g1), the plurality of groups (g1) may be identical to each other or at least one of them is different from the others.
The fluorine-containing ether compound may be any fluorine-containing ether compound that meets the above-described structure. For the ease of synthesis, the ease of handling of compounds, and the like, the fluorine-containing ether compound is preferably a compound represented by the below-shown Formula (A1), (A2) or (A3).
[Rf1—(ORf11)y1—O—R1]j-L1-(R11-T11)x1 (A1)
(T31-R31)x3-L3-R3—(ORf12)y2—O—R2-L2-(R21-T21)x2 (A2)
Q1[—(ORf13)y3—O—R4-L4-(R41-T41)x4]r1 (A3)
The structure of each of compounds will be described hereinafter. Symbols assigned to similar structures indicate similar structures, and they may be referred to each other as appropriate.
Compound (A1) has a structure represented by the below-shown Formula (A1).
[Rf1—(ORf11)y1—O—R1]j-L1-(R11-T11)x1 (A1)
Note that the symbols in Formula (A1) are as described above.
Ra1 is a fluoro-alkyl group having a carbon number of 1-20. This fluoro-alkyl group may be linear and may have a branch and/or a ring structure. In view of the friction resistance, the fluoro-alkyl group is preferably a linear fluoro-alkyl group. Further, for the ease of synthesis or the like, the carbon number of the fluoro-alkyl group is preferably 1-6 and more preferably 1-3.
Rf11 and y1 of (ORf11)y1 are similar to Rf and y in the above-shown Formula (f1), respectively, and their preferred aspects are also similar.
R1 is an alkylene group or a fluoro-alkylene group. The alkylene group and the fluoro-alkylene group in R1 may be linear and may have a branch and/or a ring structure. For the ease of synthesis or the like, it is preferably a linear or branched alkylene group or a fluoro-alkylene group, and more preferably an alkylene group or a fluoro-alkylene group having a methyl group or a fluoro-methyl group as a linear chain or a branch. The carbon number of R1 is preferably 1-6 and more preferably 1-3. Note that when L1 is a single bond, R1 bonds to Ra1. In this case, it is assumed that the carbon atom bonded to Ra1 in R1 is bonded to at least one fluorine atom or a fluoro-alkyl group.
j represents the number of [Rf1—(ORf11)y1—O—R1] in one molecule, and may be an integer of 1 or greater, preferably 1-20, more preferably 1-10, and still more preferably 1-4.
R11 is an alkylene group in which an atom bonded to L1 may be an ethereal oxygen atom or an alkylene group which may have an ethereal oxygen atom between carbon-carbon atoms.
The alkylene group in R11 may be linear and may have a branch and/or a ring structure. Based on the fact that Compound (A1) is more likely to be densely disposed when the surface layer is formed, it is preferably an alkylene group having a methyl group as a linear chain or a branch, and more preferably a linear alkylene group.
Specifically, R11 can be expressed by the below-shown Formula (g2).
*—(O)a1—(Rg2O)a2—Rg2—** (g2)
When a1 is 0, the atom having the bonding hand * is a carbon atom, whereas when a1 is 1, the atom having the bonding hand * is an oxygen atom. In Compound (A1), a1 can be either 0 or 1, and may be selected as appropriate in view of synthesis or the like.
a2 is the number of repetitions of Rg2O, and in view of the durability or the like as the surface layer, is preferably 0-6, more preferable 0-3, and still more preferably 0-1.
To achieve, as the surface layer, more excellent water and oil repellency and a fingerprint stain removal property and to achieve excellent durability such as a friction resistance, R11 is more preferably a group represented by the below-shown Formula (g3).
*—(O)a1—Rg3—** (g3)
The alkylene group in Rg3 may be linear and may have a branch and/or a ring structure. Based on the fact that Compound (A1) is more likely to be densely disposed when the surface layer is formed, it is preferably a linear alkylene group. Further, the carbon number of Rg3 may be one or greater, preferably 1-18, more preferably 1-12, and still more preferably 1-6.
T11 is —SiRa11z11Ra3z11, and Ra11, Ra12, and z11 are similar to Ra1, Ra2, and z1, respectively, constituting the above-described group (g1). Further, their preferred aspects are also similar.
x1 represents the number of R11-T11 in one molecule, and may be an integer of 1 or greater, preferably 1-32, more preferably 1-18, and still more preferably 2-12.
L1 is a single bond, or a group having a valency of j+x1 which may have N, O, S, Si and may have a branch point. Atoms bonded to R1 and R11 are independent of each other, and each of them is N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O). Note that the atoms bonded to R1 and R11 may be the atoms of the same element or those of different elements.
When L1 is a single bond, R1 and R11 in Formula (A1) are directly bonded to each other, and Compound (A1) is represented by the below-shown Formula (A11).
Rf1—(ORf11)y1—O—R1—R11-T11 (A1′)
Note that the symbols in Formula (A1′) are similar to those in Formula (A1).
When L1 is a group having a valency of 3 or higher, L1 has at least one branch point (hereinafter also referred to as a “branch point P1”) selected from the group consisting of C, N, Si, a ring structure, and an organo-polysiloxane residue having a valency of (j+x1).
When N is the branch point P1, the branch point P1 is expressed, for example, as *—N(—**)2 or (*—)2N—**. Note that * is the bonding hand on the R1 side, and ** is the bonding hand on the R11 side.
When C is the branch point P1, the branch point P1 is expressed, for example, as *—C(—**)3, (*—)2C(—**)2, (*—)3C—**, *—CR29(—**)2, or (*—)2CR29—**. Note that * is a bonding hand on the R1 side, and ** is a bonding hand on the R11 side. Further, R29 is a monovalent group, and its examples include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.
When Si is the branch point P1, the branch point P1 is expressed, for example, as *—Si(—**)3, (*—)2Si(—**)2, (*—)3Si—**, *—SiR29(—**)2, or (*—)2SiR29—** Note that * is a bonding hand on the R1 side, and ** is a bonding hand on the R11 side. Further, R29 is a monovalent group, and its examples include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.
For the ease of the manufacturing of a fluorine-containing ether compound and to achieve a more excellent friction resistance, light stability, and a chemical resistance of the surface layer, the ring structure constituting the branch point P1 is preferably one selected from the group consisting of a 3-8 membered aliphatic ring, a 3-8 membered aromatic ring, a 3-8 membered hetero ring, and a fused ring consisting of two or more of these rings, and more preferably a ring structure listed in the below-shown formulas. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may include an ethereal oxygen atom between carbon-carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, and an oxo group (═O).
Examples of the organo-polysiloxane residue constituting the branch point P1 include the below-shown groups. Note that R25 in the below-shown formulas is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The carbon number of each of the alkyl group and the alkoxy group of R25 is preferably 1-10 and more preferably 1.
L1 having a valency of 2 or higher may have at least one bond (hereinafter also referred to as a “bond B1”) selected from the group consisting of —C(O)N(R26)—, —N(R26)C(O)—, —C(O)O—, —OC(O)—, —C(O)—, —O—, —N(R26)—, —S—, —OC(O)O—, —NHC(O)O—, —OC(O)NH—, —NHC(O)N(R26)—, —SO2N(R26)—, —N(R26)SO2—, —Si(R26)2—, —OSi(R26)2—, —Si(CH3)2—Ph—Si(CH3)2—, and a divalent organo-polysiloxane residue.
Note that R26 is a hydrogen atom, or an alkyl group or a phenyl group having a carbon number of 1-6, and Ph is a phenylene group. For the ease of the manufacturing of a fluorine-containing ether compound, the carbon number of the alkyl group of R26 is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
The divalent organo-polysiloxane residue is, for example, a group represented by the below-shown formula. Note that R27 in the below-shown formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The carbon number of each of the alkyl group and the alkoxy group of R27 is preferably 1-10 and more preferably 1.
For the ease of the manufacturing of a fluorine-containing ether compound, the bond B1 is preferably at least one bond selected from the group consisting of —C(O)NR26—, —N(R26)C(O)—, —C(O)—, and —NR26—, and to achieve more excellent light stability and a chemical resistance of the surface layer, more preferably —C(O)NR26—, —N(R26) C(O)—, or —C(O)—.
As the divalent L1, the atoms bonded to R1 and Ra1 are independent of each other, and each of them is N, O, S, Si, or a carbon atom having an oxo group (═O). That is, each of the atoms adjacent to R1 and R11 is a constituent element of the bond B1. Specific examples of the divalent L1 include a single bond and at least one bond B1 (e.g., *—B1—** and *—B1—R28—B1—**). Note that R28 is a single bond or a divalent organic group. Further, * is a bonding hand on the R1 side, and ** is a bonding hand on the R11 side.
Regarding L1 having a valency of 3 or higher, the atoms bonded to R1 and R11 are independent of each other, and each of them is N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O). That is, each of atoms adjacent to R1 and R11 is a constituent element of the bond B1 or the branch point P1. Specific examples of L1 having a valency of 3 or higher include at least one branch point P1 (e.g., {(*—)jP1(—**)x1} or {(*—)jP1—R28—P1(—**)x1}) and a combination of at least one branch point P1 and at least one bond B1 (e.g., {*—B1—R28—P1(—**)x1} or {*—B1—R28—P1(—R28—B1—**)x1}). Note that R28 is a single bond or a divalent organic group. Further, * is a bonding hand on the R1 side, and ** is a bonding hand on the R11 side.
Examples of the divalent organic group in the above-described R28 include hydrocarbon groups such as a divalent aliphatic hydrocarbon group (such as an alkylene group and a cycloalkylene group), a divalent aromatic hydrocarbon group (such as a phenylene group). Further, the divalent organic group may have a bond B1 between carbon-carbon atoms of the hydrocarbon group. The carbon number of the divalent organic group is preferably 1-10, more preferably 1-6, and still more preferably 1-4.
For the ease of the manufacturing of a fluorine-containing ether compound, the above-described L1 is preferably a group represented by one of the below-shown Formulas (L1) to (L7).
(-A1-)d5C(Re2)4-d5-d6(-Q22-)d6 (L2)
(-A2-)d7N(-Q23-)3-d7 (L3)
(-A3-)d8Z1(-Q24-)d9 (L4)
(-A2-)d10Si(Re3)4-d10-d11(-Q25-)d11 (L5)
-A1-Q26 (L6)
-A1-CH(-Q22-)—Si(Re3)3-d12(-Q25-)d12 (L7)
Note that in Formulas (L1) to (L7), the A1, A2 or A3 side is connected to R1 of Formula (A1), and the Q22, Q23, Q24, Q25 or Q26 side is connected to R11.
Note that A1 is a single bond, —B3—, —B3—R30—, or —B3—R30—B2—; R30 is an alkylene group or a group having —C(O)NRe6, —C(O)—, —NRe6—, or —O— between carbon-carbon atoms of an alkylene group having a carbon number of 2 or greater; B2 is —C(O)NRe6—, —C(O)—, —NRe6—, or —O—; and B3 is —C(O)NRe6, —C(O)—, or —NRe6—;
Note that when there are a plurality of A1, the plurality of A1 may be identical to each other or at least one of them is different from the others. The same applies to A2, A3, Q22, Q23, Q24, Q25, Re1, Re2 and Re3.
Further, each of d1+d3, d5, d7, d8, and d10 is j, and each of d2+d4, d6, 3-d7, d9, d11, and 1+d12 is x1.
For the ease of the manufacturing of a fluorine-containing ether compound and to achieve a more excellent friction resistance, light stability, and a chemical resistance of the surface layer, the carbon number of the alkylene group of R30 is preferably 1-10, more preferably 1-6, and still more preferably 1-4. Meanwhile, the lower limit value of the carbon number of the alkylene group in the case where the alkylene group has a specific bond between carbon-carbon atoms is 2.
Examples of the ring structure in Z1 include the above-described ring structure, and its preferred aspects are also similar to those of the above-described ring structure.
For the ease of the manufacturing of a fluorine-containing ether compound, the carbon number of the alkyl group of Re1, Re2 or Re3 is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
For the ease of the manufacturing of Compound 1, the carbon number of the alkyl group part of the acyloxy group of Re2 is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
For the ease of the manufacturing of a fluorine-containing ether compound and to achieve a more excellent friction resistance and a fingerprint stain removal property of the surface layer, the carbon number of d9 is preferably 2-6, more preferably 2-4, and still more preferably 2 or 3.
Examples of other forms of the above-described L11 include groups represented by the below-shown Formulas (L11) to (L17).
(-A1-)d5C(Re2)4-d5-d6(-Q22-G)d6 (L12)
(-A2-)d7N(-Q23-G)3-d7 (L13)
(-A3-)d8Z1(-Q24-G)d9 (L14)
(-A2-)d10Si(Re3)4-d10-d11(Q25-G)d11 (L15)
-A1-Q26-G (L16)
-A1-CH(-Q22-)—Si(Re3)3-d12(-Q25-G)d12 (L17)
Note that in Formulas (L11) to (L17), the A1, A2 or A3 side is connected to R1 of Formula (A1), and the Q22, Q23, Q24, Q25 or Q26 side is connected to R11. G is the below-shown group (G21), and two or more G in L1 may be identical to each other or at least one of them is different from the others. Symbols other than G are similar to those in Formulas (L11) to (L17).
—Si(R21)3-k(-Q3-)k (G21)
Note that in Formula (G21), the Si side is connected to Q22, Q23, Q24, Q25 or Q26, and the Q3 side is connected to R11. R21 is an alkyl group. Q3 is a single bond, or —R31—B3—. R31 is an alkylene group, or a group having —C(O)NR32—, —C(O)—, —NR32—, or —O— between carbon-carbon atoms of an alkylene group having a carbon number of two or greater, or is —(OSi(R22)2)p11—O—, in which the two or more Q3 may be identical to each other or at least one of them is different from the others. k is 2 or 3. R32 is a hydrogen atom, an alkyl group or a phenyl group having a carbon number of 1-6. R22 is an alkyl group, a phenyl group, or an alkoxy group, and the two R22 may be identical to each other or at least one of them is different from the others. p11 is an integer of 0-5. When p11 is two or greater, the two or more (OSi(R22)2) may be identical to each other or at least one of them is different from the others.
For the ease of the manufacturing of a fluorine-containing ether compound and to achieve a more excellent friction resistance, light stability, and a chemical resistance of the surface layer, the carbon number of the alkylene group of Q3 is preferably 1-10, more preferably 1-6, and still more preferably 1-4. Meanwhile, the lower limit value of the carbon number of the alkylene group in the case where the alkylene group has a specific bond between carbon-carbon atoms is two.
For the ease of the manufacturing of a fluorine-containing ether compound, the carbon number of the alkyl group of R21 is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
For the ease of the manufacturing of a fluorine-containing ether compound, the carbon number of the alkyl group of R22 is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
To improve the storage stability of the fluorine-containing ether compound, the carbon number of the alkoxy group of R22 is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
p11 is preferably 0 or 1.
Examples of Compound (A1) include those shown below. Note that Rf is [Rf1—(ORf1)y1—O—R1].
Compound (A2) has a structure represented by the below-shown Formula (A2).
(T31-R31)x3-L3-R3—(ORf12)y2—O—R2-L2-(R21-T21)x2 (A2)
Note that the symbols in Formula (A2) are as described above.
Rf12 and (ORf12)y2 are similar to the above-described Rf11, and (ORf11)y1, respectively, and their preferred aspects are also similar.
R2 and R3 are independent of each other and each of them is similar to the above-described R1. Further, their preferred aspects are also similar.
Each of R21 and R31 is similar to the above-described R11, and their preferred aspects are also similar. However, for R21, the phrase “bonded to L1” is changed to “bonded to L2” in the description below, and for R31, it is changed to “bonded to L3” in the description below. Further, for R21, the phrase “bonded to T11” is changed to “bonded to T21” in the description below, and for R31, it is changed to “bonded to T31” in the description below. Note that when L2 is a single bond, R21 is directly bonded to R2. Further, when L3 is a single bond, R31 is directly bonded to R3.
T21 and T31 are independent of each other, and each of them is —SiRa21z21Ra223-z21. Further, Ra21, Ra22 and z21 are similar to Ra1, Ra2 and z1, respectively, constituting the above-described group (g1), and their preferred aspects are also similar.
Further, x2 and x3 are independent of each other, and each of them is similar to x1. Further, their preferred aspects are also similar.
L2 and L3 are independent of each other, and each of them is similar to the case of the above-described L1 where j is set to 1.
For example, when L2 and L3 are single bonds, Compound (A2) is represented by the below-shown Formula (A2′).
T31-R31—R3—(ORf12)y2—O—R2-L2-R21-T21 (A2′)
Note that the symbols in Formula (A2′) are similar to those in Formula (A2).
When L2 or L3 is a group having a valency of 3 or higher, L2 or L3 has at least one branch point (hereinafter also referred to as a “branch point P2”) selected from the group consisting of C, N, Si, a ring structure, and an organo-polysiloxane residue having a valency of (1+x2) or (1+x3).
When N is the branch point P2, the branch point P2 is expressed, for example, as *—N(—**)2. Note that * is the bonding hand on the R2 or R3 side, and ** is the bonding hand on the R21 or R31 side.
When C is the branch point P2, the branch point P2 is expressed, for example, as *—C(—**)3 or *—CR29(—**)2 Note that * is a bonding hand on the R2 or R3 side, and ** is a bonding hand on the R21 or R31 side. Further, R29 is a monovalent group, and its examples include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.
When Si is the branch point P2, the branch point P2 is expressed, for example, as *—Si(—**)3 or *—SiR29(—**)2. Note that * is a bonding hand on the R2 or R3 side, and ** is a bonding hand on the R21 or R31 side. Further, R29 is a monovalent group, and its examples include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.
The ring structure constituting the branch point P2 and the organo-polysiloxane residue are similar to those of the above-described branch point P1, and their preferred aspects are also similar.
Further, L2 or L3 having a valency of 2 or higher is independent of each other, and each of them may have the above-described bond B1. The aspects of the bond B1 are as described above, and its preferred aspects are also similar.
Regarding the divalent L2 or L3, the atoms bonded to R2 and R21 or R3 and R31 are independent of each other, and each of them is N, O, S, Si, or a carbon atom having an oxo group (═O). That is, each of the atoms adjacent to R2 and R21, or R3 and R31 is a constituent element of the bond B1. Specific examples of the divalent L2 or L3 include a single bond and at least one bond B1 (e.g., *—B1—** and *—B1—R28—B1—**). Note that R28 is a single bond or a divalent organic group. Further, * is a bonding hand on the R2 or R3 side, and * * is a bonding hand on the R21 or R31 side.
Regarding L2 or L3 having a valency of 3 or higher, the atoms bonded to R2 and R21, or R3 and R31 are independent of each other, and each of them is N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O). That is, each of the atoms adjacent to R2 and R21, or R3 and R31 is a constituent element of the bond B1 or the branch point P2. Specific examples of L2 or L3 having a valency of 3 or higher include at least one branch point P2 (e.g., {*-p2 (-* *)x} or {*—P2—R28—P2 (—* *)x}) and a combination of at least one branch point P2 and at least one bond B1 (e.g., {*—B1—R28—P2(—**)x} or {*—B1—R28—P2(—R28—B1—**)x}. Note that for L2, x is x2, and for L3, x is x3. R28 is a single bond or a divalent organic group. Further, * is a bonding hand on the R2 or R3 side, and ** is a bonding hand on the R21 or R31 side.
The aspects of the above-described bond R28 are as described above, and its preferred aspects are also similar.
For the ease of the manufacturing of a fluorine-containing ether compound, each of the above-described L2 or L3 is preferably a group represented by one of the below-shown Formulas (L21) to (L27).
-A1-C(Re2)4-d6(-Q22-)d6 (L22)
-A2-N(-Q23-)2 (L23)
-A3-Z1(-Q24-)d9 (L24)
-A2-Si(Re3)4-d11(-Q25-)d11 (L25)
-A1-Q26- (L26)
-A1-CH(-Q22-)—Si(Re3)3-d12(-Q25-)d12 (L27)
Note that in Formulas (L21) to (L27), the A1, A2 or A3 side is connected to R2 or R3, and the Q22, Q23, Q24, Q25 or Q26 side is connected to R21 or R31.
Note that A1, A2, A3, Q11, Q22, Q23, Q24, Q25, Q26, Re1, Re2Re3 and Re6 are similar to those in the description of the above-described L1, and their preferred aspects are also similar.
Note that each of d2+d4, d6, d9, d11, and 1+d12 is x2 or x3. For the ease of the manufacturing of a fluorine-containing ether compound and to achieve a more excellent friction resistance and a fingerprint stain removal property of the surface layer, d9 is preferably 2-6, more preferably 2-4, and still more preferably 2 or 3.
Examples of other forms of the above-described L2 or L3 include groups represented by the below-shown Formulas (L31) to (L37).
-A1-C(Re2)4_d6(-Q22-G)d6 (L32)
-A2-N(-Q23-G)2 (L33)
-A3-Z1(-Q24-G)d9 (L34)
-A2-Si(Re3)4-d11(-Q25-G)d11 (L35)
-A1-Q26-G (L36)
-A1-CH(-Q22-)—Si(Re3)3-d12(-Q25-G)d12 (L37)
Note that in Formulas (L31) to (L37), the A1, A2 or A3 side is connected to R2 or R3, and the Q22, Q23, Q24, Q25 or Q26 side is connected to R21 or R31. G is the above-described group (G21), and its preferred aspects are also similar. Symbols other than G are similar to those in Formulas (L21) to (L27), and their preferred aspects are also similar.
Examples of Compound (A2) include those shown below. Note that Qf is —R3—(ORf12)y2—O—R2—.
Compound (A3) has a structure represented by the below-shown Formula (A3).
Q1[—(ORf13)y3—O—R4-L4-(R41-T41)x4]r1 (A3)
Note that the symbols in Formula (A3) are as described above.
Rf13 and (ORf13)y3 are similar to the above-described Rf11 and (ORf11)y1, respectively, and their preferred aspects are also similar.
R4 is similar to the above-described R1, and its preferred aspects are also similar.
R41 is similar to the above-described R11, and its preferred aspects are also similar. However, “bonded to L1” is changed to “bonded to L4” in the description below. Further, “bonded to T11” is changed to “bonded to T41” in the description below. Note that when L4 is a single bond, R41 directly bonded to R4.
T41 is —SiRa41z41Ra423-z41, and Ra41, Ra42, and z41 are similar to Ra1, Ra2, and z1, respectively, constituting the above-described group (g1). Further, their preferred aspects are also similar.
x4 is similar to x1, and its preferred aspects are also similar.
L4 is similar to L2 or L3, and its preferred aspects are also similar.
Q1 is a group having a valency of r1 and having a branch point, and r1 is 3 or 4.
Examples of the branch point P3 constituting Q1 include N, C, Si and a ring structure. The number of branch points P3 may be one, or may be two or more.
When N is the branch point P3, the branch point P1 is expressed, for example, as N(—*)3 or NR29(—*)2.
When C is the branch point P3, the branch point P3 is expressed, for example, as C(—*)4, CR29(—*)3, or C(R29)2(—*)2.
When Si is the branch point P3, the branch point P3 is expressed, for example, as Si(—*)4, SiR29(—*)3, or Si(R29)2(—*)2. Note that * is the bonding hand on the OR13 side, and R29 is a monovalent group. Examples of R29 include a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoro-alkyl group, and a fluoro-polyether chain or the like having no R41-T41.
Examples of the ring structure constituting the branch point P3 include those of the branch point P1, and examples of the substituent of the ring structure include, in addition to the above-described substituents, a fluorine atom, a fluoro-alkyl group, and a fluoro-polyether chain having no R41-T41.
For the ease of the manufacturing of a fluorine-containing ether compound, the above-described Q1 is preferably a group represented by one of the below-shown Formulas (Q1) to (Q8).
C(-A11-)d23(Re12)4-d23 (Q2)
N(-A12-)3 (Q3)
Z1(-A13-)d24 (Q4)
Si(-A12-)d25(Re13)4-d25 (Q5)
CH(-A11-)2—Si(Re13)3-d26(-A11-)d26 (Q6)
Note that in Formulas (Q1) to (Q8), A11, A12 or A13 is connected to (ORf13).
Note that A11 is a single bond, —R40—, or —B13—R40—; R40 is an alkylene group, a fluoro-alkylene group, or a group having —C(O)NRe17—, —C(O)—, —NRe17— or —O— between carbon-carbon atoms of an alkylene group or a fluoro-alkylene group having a carbon number of 2 or greater; and B13 is —C(O)NRe6—, —C(O)—, —NRe6— or —O—;
Note that when there are a plurality of A11, the plurality of A11 may be identical to each other or at least one of them is different from the others. The same applies to A12, A13, Re11, Re12 and Re13.
For the ease of the manufacturing of a fluorine-containing ether compound and to achieve a more excellent friction resistance, light stability, and a chemical resistance of the surface layer, the carbon number of the alkylene group or the fluoro-alkylene group of R40 is preferably 1-10, more preferably 1-6, and still more preferably 1-4. Meanwhile, the lower limit value of the carbon number of the alkylene group in the case where the alkylene group has a specific bond between carbon-carbon atoms is 2.
Examples of the ring structure in Z1 include the above-described ring structure, and its preferred aspects are also similar to those of the above-described ring structure.
In Re11, Re12, Re13, Re14, Re15, and Re16, for the ease of the manufacturing of a fluorine-containing ether compound, the carbon number of the alkyl group or the fluoro-alkylene group is preferably 1-6, more preferably 1-3, and still more preferably 1-2.
Examples of Compound (A3) include those shown below. Note that Rf3 is (ORf13)y3—O—R4.
The content of the fluorine-containing ether compound is preferably 0.01-50 mass %, more preferably 0.03-40 mass %, and still more preferably 0.05-30 mass % based on the total mass of the surface treatment agent. When the content of the fluorine-containing ether compound is in the above-described range, the surface layer is excellent in water and oil repellency, friction resistance, fingerprint stain removal property, lubricity, and appearance.
The surface treatment agent according to the present disclosure contains a metallic compound containing a specific metal element(s). The specific metal element means, as described above, at least one metal element selected from the group consisting of elements in Groups 1 excluding a hydrogen element and Group 2 in a periodic table.
Specific examples of specific metal elements include lithium (Li), sodium (Na), potassium (K), rubicium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). The metallic compound may contain only one specific metal element or may contain two or more specific metal elements.
In particular, to achieve a more excellent friction resistance of the surface layer, the metallic compound preferably contains at least one metal element selected from the group consisting of Li, Na, K, Rb, Be, Mg, Ca, and Sr, more preferably at least one metal element selected from the group consisting of Li, Na, K, Mg, and Ca, and still more preferably at least one metal element selected from the group consisting of Na, K, Mg, and Ca.
The metallic compound is a compound containing a specific metal element(s) and another element(s), and specific examples of other elements include an oxide containing a specific metal element, a salt containing a specific metal element, a complex containing a specific metal element, and a metal alkoxide containing a specific metal element. In particular, to achieve a more excellent friction resistance of the surface layer, the metallic compound preferably contains an oxide containing a specific metal element, a salt containing a specific metal element, or a metal alkoxide containing a specific metal element, more preferably an oxide containing a specific metal element, a carbonate or hydrogencarbonate containing a specific metal element, or a metal alkoxide containing a specific metal element, and in particular, still more preferably an alkoxide of an alkali metal, an alkoxide of an alkaline earth metal, a carbonate of an alkali metal, a hydrogencarbonate of an alkali metal, a carbonate of an alkaline earth metal, or an oxide of an alkaline earth metal.
The alkoxy group contained in the metal alkoxide containing a specific metal element is preferably an alkoxy group having a carbon number of 1-4, and more preferably an alkoxy group having a carbon number of 1-2.
Specific examples of the metallic compound include lithium methoxide, lithium ethoxide, lithium carbonate, lithium hydrogencarbonate, sodium methoxide, sodium ethoxide, sodium carbonate, sodium hydrogencarbonate, potassium methoxide, potassium ethoxide, potassium carbonate, potassium hydrogencarbonate, magnesium methoxide, magnesium ethoxide, magnesium oxide, magnesium carbonate, calcium methoxide, calcium ethoxide, calcium oxide, and calcium carbonate.
The content of the metallic compound is preferably 0.01 mass ppm (1.0×10−6 mass %) to 10 mass %, more preferably 0.05 mass ppm to mass %, and still more preferably 0.1 mass ppm to 1 mass % based on the total mass of the surface treatment agent. When the content of the metallic compound is 0.01 mass ppm or more, the surface layer has a more excellent friction resistance. When the content of the metallic compound is 10 mass % or less, the surface layer has more excellent water and oil repellency.
The content of the metallic compound is preferably 0.00001-10 mass parts, more preferably 0.00005-5 mass parts, and still more preferably 0.0001-1 mass parts based on 100 mass parts of the fluorine-containing ether compound contained in the surface treatment agent. When the content of the metallic compound is 0.00001 mass parts or more, the surface layer has a more excellent friction resistance. When the content of the metallic compound is 10 mass parts or less, the surface layer has more excellent water and oil repellency.
The surface treatment agent according to the present disclosure may contain components other than the fluorine-containing ether compound and the metallic compound (hereinafter also referred to as “other components”).
Specific examples of other components include fluorine-containing compounds other than the above-described fluorine-containing ether compound, at least one of the below-shown impurities, and liquid mediums.
Examples of other fluorine-containing compounds include fluorine-containing compounds that are generated as by-products during the manufacturing process of the above-described fluorine-containing ether compound (hereinafter also referred to as “by-product fluorine-containing compounds”) and known fluorine-containing compounds used for purposes similar to that of the above-described fluorine-containing ether compound.
As the other fluorine-containing compounds, a compound that is unlikely to deteriorate the properties of the above-described fluorine-containing ether compound is preferred.
To make the fluorine-containing ether compound fully exhibit its properties, the content of other fluorine-containing compounds is preferably less than 70 mass %, more preferably less than 50 mass %, still more preferably less than 20 mass %, particularly preferably less than 10 mass %, and most preferably less than 5 mass % based on the total mass of the surface treatment agent.
Examples of by-product fluorine-containing compounds include fluorine-containing compounds or the like that are not reacted during the synthesis of the fluorine-containing ether compound. In the case where the composition according to the present disclosure contains a by-product fluorine-containing compound, it is possible to simplify a purification process for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound.
Examples of known fluorine-containing compounds include those disclosed in the below-listed literatures.
Further, examples of commercially available products of fluorine-containing compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., SURECO (Registered Trademark) AF series such as SURECO 2101S manufactured by AGC Inc., and OPTOOL (Registered Trademark) DSX, OPTOOL (Registered Trademark) AES, OPTOOL (Registered Trademark) UF503, OPTOOL (Registered Trademark) UD509 manufactured by Daikin Industries, Ltd.
When the surface treatment agent contains another fluorine-containing compound(s), the content of the other fluorine-containing compound(s) in the surface treatment agent is preferably 60 mass % or less, more preferably 30 mass % or less, and still more preferably 10 mass % or less based on the total content of the above-described fluorine-containing ether compound and the other fluorine-containing compound(s).
The total content of the above-described fluorine-containing ether compound and the other fluorine-containing compound(s) in the surface treatment agent is preferably 0.01 mass % or more and more preferably 0.03 mass % or more.
When the content of the above-described fluorine-containing ether compound and the other fluorine-containing compound(s) is within the above-described range, the surface layer is excellent in water and oil repellency, friction resistance, fingerprint stain removal property, lubricity, and appearance.
When the surface treatment agent contains a liquid medium, the surface treatment agent can be used as a coating liquid. The coating liquid may be any type of liquid such as a solution or a dispersion liquid.
As the liquid medium, an organic solvent is preferred. The organic solvent may be a fluorine-based organic solvent or a non-fluorine-based organic solvent, or may contain both solvents.
Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoro-alkyl ethers, fluorinated alkylamines, and fluoro-alcohols.
As the fluorinated alkane, a compound having a carbon number of 4-8 is preferred. Examples of commercially available products include C6F13H (Manufactured by AGC Inc., Asahi Clin (Registered Trademark) AC-2000), C6F13C2H5 (Manufactured by AGC Inc., Asahi Clin (Registered Trademark) AC-6000), and C2F5CHFCHFCF3 (Manufactured by The Chemours Company, Bartrell (Registered Trademark) XF).
Specific examples of fluorinated aromatic compounds include hexafluoro-benzene, trifluoro-methylbenzene, perfluoro-toluene, and bis(trifluoro-methyl)benzene. As the fluoro-alkyl ether, a compound having a carbon number of 4-12 is preferred. Examples of commercially available products include CF3CH2OCF2CF2H (Manufactured by AGC Inc., Asahi Clin (Registered Trademark) AE-3000), C4F9OCH3 (Manufactured by 3M, Noveck (Registered Trademark) 7100), C4F9OC2H5 (Manufactured by 3M, Noveck (Registered Trademark) 7200), and C2F5CF(OCH3) C3F7 (Manufactured by 3M, Noveck (Registered Trademark) 7300).
Specific examples of fluorinated alkylamines include perfluoro-tripropylamine and perfluoro-tributylamine.
Specific examples of fluoro-alcohols include 2,2,3,3-tetrafluoro-propanol, 2,2,2-trifluoro-ethanol, and hexafluoro-isopropanol.
Preferred examples of non-fluorine-based organic solvents include a compound consisting of only hydrogen atoms and carbon atoms, and a compound consisting of hydrogen atoms, carbon atoms, and oxygen atoms. Further, its examples include a hydrocarbon organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, an ether-based organic solvent, and an ester-based organic solvent.
When the surface treatment agent contains a liquid medium, the surface treatment agent preferably contains 60-99.999 mass % of the liquid medium, more preferably 85-99.99 mass % of the liquid medium, and still more preferably 90-99.9 mass % of the liquid medium.
The surface treatment agent may further contain a known additive(s) such as an acid catalyst or a basic catalysts that promotes the hydrolysis and the condensation reaction of the hydrolytic silyl group.
The content of additives is preferably 10 mass % or less and more preferably 1 mass % or less based on the total mass of the surface treatment agent.
An article according to the present invention preferably includes a substrate and a surface layer disposed on the substrate, and has an underlayer between the substrate and the surface layer.
The surface layer is a layer formed from the above-described surface treatment agent and contains a condensate of the above-described fluorine-containing ether compound.
The material and shape of the substrate may be selected as appropriate according to the use or the like of the article. Examples of materials for the substrate include glass, resins, sapphire, metals, ceramics, stone, and composite materials thereof. The glass may be chemically reinforced. In particular, examples of substrates required to be water- and oil-repellent include substrates for touch panels, substrates for displays, and substrates from which housings of electronic apparatuses are formed. Substrates for touch panels and substrates for displays are transparent or translucent. “Transparent or translucent” means that a visible-light transmittance when light is incident at right angles according to JIS R3106:1998 (ISO 9050:1990) is 25% or higher. As the material for the substrate for a touch panel, glass or a transparent resin is preferred.
The substrate may be one of which a surface on which an underlayer is provided has been subjected to a surface treatment such as a corona discharge treatment, a plasma treatment, and a plasma graft polymerization treatment. The surface, which has been subjected to the surface treatment, has a more excellent adhesive property between the substrate and the underlayer, and as a result, the friction resistance of the surface layer is improved even further. To achieve a more excellent friction resistance of the surface layer, the surface treatment may be preferably a corona discharge treatment or a plasma treatment.
The underlayer is preferably a layer containing an oxide containing silicon (preferably, silicon oxide), and may contain other elements. When the underlayer contains silicon oxide, the reactive silyl group of the above-described fluorine-containing ether compound is dehydrated and condensed, and an Si—O—Si bond is thereby formed between the substrate and the underlayer, so that s surface layer having an excellent friction resistance is formed.
The content of the silicon oxide in the underlayer is preferably 65 mass % or more, more preferably 80 mass % or more, still more preferably 85 mass % or more, and particularly preferably 90 mass % or more. When the content of the silicon oxide is equal to or higher than the lower limit value, the Si—O—Si bond is sufficiently formed in the underlayer, so that mechanical properties of the underlayer are sufficiently ensured. The content of the silicon oxide corresponds to the remnant, i.e., what is obtained by excluding the sum total of the total content of the other elements (in the case of the oxide, the oxide equivalent amount) from the mass of the underlayer.
In view of the durability of the surface layer, the oxide in the underlayer preferably further contains at least one element selected from the group consisting of alkali metal elements, alkali earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bond between the underlayer and the fluorine-containing ether compound is strengthened, so that the friction resistance is improved.
The thickness of the underlayer is preferably 1-200 nm and still more preferably 2-20 nm. When the thickness of the underlayer is equal to or larger than the lower limit value, the effect of improving the adhesive property obtained by the underlayer is more likely to be sufficiently obtained. When the thickness of the underlayer is equal to or shorter than the upper limit value, the friction resistance of the underlayer itself increases. Examples of methods for measuring the thickness of an underlayer include the observation of a cross section of the underlayer by an electron microscope (such as SEM and TEM) and methods using an optical interference film thickness meter, a spectroscopic ellipsometer, a step gauge, or the like.
Examples of methods for forming an underlayer include a method in which a vapor-deposition material having a desired composition of an underlayer is vapor-deposited (i.e., is evaporated and deposited) on the surface of a substrate.
An example of the vapor-deposition method is a vacuum vapor-deposition method.
The vacuum vapor-deposition method is a method in which a vapor-deposition material is evaporated in a vacuum tank and the evaporated vapor-deposition material is made to adhere onto the surface of a substrate.
The temperature of the vapor-deposition (e.g., when a vacuum vapor-deposition apparatus is used, the temperature of a boat in which a vapor-deposition material is put) is preferably 100-3,000° C. and more preferably 500-3,000° C.
The pressure of the vapor-deposition (e.g., when a vacuum vapor-deposition apparatus is used, the absolute pressure in a tank in which a vapor-deposition material is put) is preferably 1 Pa or lower and more preferably 0.1 Pa or lower.
When an underlayer is formed by using a vapor-deposition material, one deposition material may be used or two or more deposition materials containing different elements may be used.
Examples of methods for evaporating a vapor-deposition material include a resistance heating method in which a vapor-deposition material is melted and evaporated on a resistance heating boat made of metal having a high melting point and an electron-gun method in which the surface of a vapor-deposition material is melted and evaporated by irradiating the vapor-deposition material with an electron beam and thereby directly heating the vapor-deposition material. As the method for evaporating a vapor-deposition material, the electron-gun method is preferred because a vapor-deposition material can locally heated, so that even a substance having a high melting point can be evaporated. Further, temperatures are low in places where the electron beam is not incident, so there is no risk of the reaction with the container and the contamination with impurities. As the vapor-deposition material used for the electron gun method, a molten granular material or a sintered body is preferred because they are less likely to scatter even when an air flow occurs.
The surface layer includes a condensate of the above-described fluorine-containing ether compound. The condensate of the fluorine-containing ether compound includes a structure in which a silanol group (Si—OH) is formed through a hydrolysis reaction of a hydrolytic silyl group contained in the fluorine-containing ether compound, and an Si—O—Si bond is formed through an intermolecular condensation reaction of the silanol group, and a structure in which an Si—O—Si bond is formed through a condensation reaction of a silanol group contained in the fluorine-containing ether compound with a silanol group or an Si-OM group (note that M is an alkali metal element) present on the surface of the substrate or the underlayer. Further, the surface layer may also contain a condensate of a fluorine-containing compound other than the fluorine-containing ether compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state in which some or all of reactive silyl groups contained the fluorine-containing compound have undergone a condensation reaction.
The thickness of the surface layer is preferably 1-100 nm and more preferably 1-50 nm. When the thickness of the surface layer is equal to or larger than the lower limit value, the effect by the surface layer can be sufficiently obtained. When the thickness of the surface layer is equal to or smaller than the upper limit value, the use efficiency is high.
The thickness of the surface layer is a thickness obtained (measured) by an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the oscillation cycle of an interference pattern of a reflected X-ray obtained by an X-ray reflectivity method using an X-ray diffractometer for thin film analysis.
The article is preferably a touch panel. In this case, the surface layer is preferably formed on the surface of a member constituting the surface of the touch panel which is touched by fingers.
The method for manufacturing an article is a method for forming a surface layer on a substrate by a dry- or wet-coating method by using the surface treatment agent according to the present disclosure.
When the surface treatment agent does not contain a liquid medium, the surface treatment agent can be used as it is in the dry-coating method. Examples of the dry-coating method include vacuum vapor-deposition, CVD, and sputtering. The vacuum vapor-deposition method can be suitably used because it suppresses the decomposition of the fluorine-containing ether compound and the apparatus is simple.
For the vacuum vapor-deposition, a pellet-like substance in which a fluorine-containing ether compound and a metallic compound are supported in a metal porous body made of a metal material such as iron or steel may be used. The pellet-like material in which the fluorine-containing ether compound and the metallic compound are supported can be manufactured by impregnating a metal porous body with the surface treatment agent containing a liquid medium, and drying the metal porous body and thereby removing the liquid medium therefrom.
When the surface treatment agent contains a liquid medium, the surface treatment agent can be suitably used in a wet-coating method. Examples of the wet-coating method include a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a dip coating method, a die coating method, an inkjet method, a flow coating method, a roll coating method, a casting method, a Langmuir-Blodgett method, and a gravure coating method.
In order to improve the friction resistance of the surface layer, if necessary, an operation to promote the reaction of the fluorine-containing ether compound with the substrate (or underlayer) may be performed. Examples of such an operation include heating, humidification, and light irradiation. For example, it is possible, by heating the substrate including a surface layer formed thereon in an atmosphere containing moisture, to promote reactions such as a hydrolysis reaction of a hydrolytic group, a reaction between a hydroxyl group or the like on the surface of a substrate and a silanol group, and the generation of a siloxane bond through a condensation reaction of a silanol group.
After the surface treatment, if necessary, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed. Its specific examples include a method for pouring a solvent over a surface layer and a method for wiping off such compounds with a cloth soaked with a solvent.
The present invention will be described hereinafter in a more detailed manner by using examples. Examples 1 to 13 are examples according to the present disclosure, and Examples 14 to 17 are comparative examples. Note that the present invention is not limited to these examples. Note that the amount of each component in the tables described later indicates a value expressed by mass.
A fluorine-containing ether compound X1 was obtained in a manner similar to a method disclosed in Example 11 of International Patent Publication No. WO2017/038830.
CF3—(OCF2CF2OCF2CF2CF2CF2)n(OCF2CF2)—OCF2CF2CF2—C(O)NH—CH2—C[CH2CH2CH2—Si(OCH3)3]3 (X1)
In the formula, an average value of n was 13, and the number-average molecular weight of the fluorine-containing ether compound X1 was 5,400.
A control compound 1 disclosed in Japanese Unexamined Patent Application Publication No. 2019-131807 was used as a fluorine-containing ether compound X2.
CF3CF2CF2(OCF2CF2CF2)30OCF2CF2CONHCH2C[CH2CH2CH2Si(O CH3)3]3 (X2)
A control compound 2 disclosed in Japanese Unexamined Patent Application Publication No. 2019-131807 was used as a fluorine-containing ether compound X3.
CF3(OCF2CF2)22(OCF2)23OCF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3 (X3)
Perfluoro-polyether group-containing silane compound (0) disclosed in Japanese Unexamined Patent Application Publication No. 2014-218639 was used as a fluorine-containing ether compound X4.
CF3(OCF2CF2)15(OCF2)16OCF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 (X4)
The fluorine-containing ether compound X1 and C4F9OC2H5 (Noveck-7200: product name, manufactured by 3M), which was used as a liquid medium, were mixed, and a solution containing 10 mass % of the fluorine-containing ether compound was thereby obtained.
30 g of the obtained solution was mixed with 0.03 g of diethoxymagnesium (manufactured by Kojundo Chemical Lab. Co., Ltd.), which was used as a metallic compound, and a surface treatment agent 1 was thereby obtained.
Surface treatment agents 2 to 13 were obtained in a manner similar to that of the preparation of the surface treatment agent 1 except that at least one of the type of the fluorine-containing ether compound, the type of the metallic compound, and the amount of the added metallic compound was changed as shown in Table 1.
The metallic compounds listed in Table 1 are roughly described below.
Surface treatment agents 14 to 17 were obtained in a manner similar to that of the preparation of the surface treatment agent 1 except that the fluorine-containing ether compound shown in Table 1 was used and no metallic compound was added.
Each of the surface treatment agents obtained as described above was vacuum vapor-deposited on a glass substrate (Dragontrail (Registered Trademark), manufactured by AGC Inc., 50 mm×50 mm, 0.5 mm thick). Specifically, each of the surface treatment agents 1 to 17 (0.5 g) was charged into a resistance heating boat in a vacuum vapor-deposition apparatus (manufactured by ULVAC, VTR 350M), and the vacuum vapor-deposition apparatus was evacuated to a pressure of 3.0×10−3 Pa or lower. Next, a silicon dioxide film having a thickness of 5 nm was formed on the above-described glass substrate, and the resistance heating boat was heated, so that a film was formed on the glass. Next, the glass with the vapor-deposition film formed thereon was left undisturbed for 30 minutes under an atmosphere of a temperature of 150° C., and then left undisturbed to be cooled to a room temperature, so that a surface layer was formed on the substrate. As a result, glass substrates each including a surface layer formed thereon according to Examples 1 to 17 (surface treatment agents 1 to 17) were obtained.
The evaluation samples according to Examples 1 to 17 were horizontally positioned, and the surfaces of the surface layers of them were brought into contact with the below-shown friction element (the contact surface had a circular shape having a diameter of 1 cm). Then, a load of 5 N was applied on each of them. After that, the friction element was reciprocated at a speed of 40 mm/sec while keeping the application of the load. After the friction element was reciprocated 10,000 times, the static contact angle of water was measured.
As the static contact angle of water, a drop of 2 μL pure water was deposited on the surface layer, and the contact angle with respect to the water was measured by using a contact angle meter (Kyowa Interface Science Co., Ltd.: Automatic contact angle meter DropMaster 701). As the static contact angle of water, an arithmetic average value of five different points was recorded.
The evaluation criteria were as follows, and results are shown in Table 2.
The surface (diameter 1 cm) of the below-shown silicone rubber processed article was covered with cotton soaked with artificial sweat having the below-shown composition, and the obtained article was used as a friction element.
An O-ring made of PTFE (polytetrafluoroethylene) and having a diameter of 1 cm was placed on the surface layer of each of the evaluation samples according to Examples 1, 11, 12, 13, 14, 15, 16 and 17, and an 8N aqueous sodium hydroxide solution was dropped inside the above-described O-ring, so that the surface of the surface layer was brought into contact with the aqueous sodium hydroxide solution. Five hours after the contact with the aqueous sodium hydroxide solution, the aqueous sodium hydroxide solution was wiped off, washed with pure water and ethanol, and then the contact angle with respect to water was measured.
Note that the contact angle with respect to water was measured in a manner similar to that of the friction resistance test. The evaluation criteria were as follows, and results are shown in Table 3.
As shown in Table 2, it was confirmed that the use of a surface treatment agent containing a fluorine-containing ether compound and a metallic compound containing a specific metal element makes it possible to form a surface layer having an excellent friction resistance (Examples 1 to 13).
Further, as shown in Table 3, it was confirmed that the use of a surface treatment agent containing a fluorine-containing ether compound having a structure expressed as (OCF2)m1·(OCF2CF2)m2 and a metallic compound containing a specific metal element makes it possible to form a surface layer having an excellent alkali resistance (Examples 12 and 13).
According to the present invention, it is possible to provide a surface treatment agent that makes it possible to form a surface layer having an excellent friction resistance and a water- and oil-repellent property on a surface of various articles, and to provide an article including such a surface layer. As an example, the article is useful for an optical article, a touch panel, an antireflection film, antireflection glass, SiO2-treated glass, tempered glass, sapphire glass, a quartz substrate, a mold metal, and the like.
From the disclosure thus described, it will be obvious that the embodiments of the disclosure may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the disclosure, and all such modifications as would be obvious to one skilled in the art are intended for inclusion within the scope of the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-002477 | Jan 2022 | JP | national |
This application is based upon and claims the benefit of priority from Japanese patent application 2022-2477, filed on Jan. 11, 2022, and PCT application No. PCT/JP2022/048308 filed on Dec. 27, 2022, the disclosure of which is incorporated herein in its entirety by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2022/048308 | Dec 2022 | WO |
| Child | 18766013 | US |
