Article having cured product of surface treatment agent containing polymer containing fluoropolyether group on surface

Abstract

Provided is an article which can be surface-treated with a surface treatment agent containing a fluorine-containing polyether-based polymer having a silanol group and / or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, said surface treatment agent being capable of forming a cured coating film having excellent water and oil repellency, wear resistance, and droplet slipping properties. The article has, on the surface thereof, a cured product of a surface treatment agent containing a polymer containing a fluorine-containing polyether group and / or a partial (hydrolysis) condensate thereof, the fluorine-containing polyether group polymer is a polymer having three silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a linear siloxane bond at one end in a molecule.

Description

TECHNICAL FIELD

[0001] The present application relates to an article having a cured product of a surface treatment agent containing a polymer having a fluorine-containing polyether group on the surface, and particularly, to an article having a cured product of a surface treatment agent containing a polymer having a fluorine-containing polyether group in which a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group is introduced to one side of the terminal of a fluorine-containing polyether group in a molecule having a fluorine-containing polyether group in the main chain via a linking group and / or a partial (hydrolyzed) condensate thereof on the surface. BACKGROUND

[0002] Generally, a compound having a fluorine-containing polyether group has water and oil repellency, chemical resistance, lubricity, mold releasability, stain resistance, and the like because the surface free energy thereof is very small. By utilizing the properties, it is widely used in industry for water and oil repellent stain resistance agents for paper, fibers, and the like, lubricants for magnetic recording media, oil repellents for precision machines, mold release agents, cosmetics, protective films, and the like. However, the properties also mean non-adhesion and non-cohesion to other substrates, and even if it can be applied to the surface of a substrate, it is difficult to make the coating film cohesive.

[0003] On the other hand, as a substance for bonding the surface of a substrate such as glass and cloth to an organic compound, a silane coupling agent is well known, and it is widely used as a coating agent for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxy silyl group) in one molecule. The hydrolyzable silyl group initiates a self-condensation reaction by moisture in the air or the like, and forms a coating film. The coating film is chemically and physically bonded to the surface of various substrates via the hydrolyzable silyl group, and thus a strong and durable coating film is formed.

[0004] Thus, a composition capable of forming a coating film which is easily cohesive to the surface of a substrate and has water and oil repellency, chemical resistance, lubricity, mold releasability, stain resistance, and the like on the surface of the substrate by using a fluorine-containing polyether group-containing polymer in which a hydrolyzable silyl group is introduced to the terminal of a fluorine-containing polyether group-containing compound is disclosed (Patent Documents 1 to 4).

[0005] Further, a substrate having a cured coating film such as a lens and an antireflection film, which is surface-treated with a composition containing a fluorine-containing polyether group-containing polymer having a siloxane bond of a linking group between a polymer residue (Rf) of a fluorine-containing oxyalkylene group in the main chain of a fluorine-containing polyether group-containing compound and a hydrolyzable silyl group at the terminal is disclosed, and the substrate is excellent in water repellency, and also good in resistance to cloth abrasion and resistance to paper abrasion (Patent Documents 5 and 6).

[0006] However, for a substrate having a cured film containing a cured film for a specific use such as a lens like a spectacle lens or an antireflection film, in addition to the water and oil repellency and the abrasion resistance, the paper abrasion resistance, the droplet removal property, that is, the droplet sliding property is also required to be good.

[0007] As one of the droplet sliding property indicators, there is a receding contact angle. The receding contact angle is a contact angle from a state in which the liquid is in equilibrium to a final state in which the liquid is not moved at an end point when the liquid is reduced. If the receding contact angle is a low value, it indicates that the force of the droplet adsorbed to the substrate is strong, and the droplet is difficult to move. On the other hand, the higher the receding contact angle, the weaker the adsorption force of the droplet to the substrate, that is, the higher the droplet sliding property.

[0008] Based on the above problems, it is necessary to develop an article that can balance the water and oil repellency, the abrasion resistance, and the droplet sliding property (receding contact angle).

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1 Japanese Patent Application Laid-Open No. 2012-072272

[0012] Patent Document 2 Japanese Patent Application Laid-Open No. 2012-157856

[0013] Patent Document 3 Japanese Patent Application Laid-Open No. 2013-136833

[0014] Patent Document 4 Japanese Patent Application Laid-Open No. 2015-199906

[0015] Patent Document 5 Japanese Patent No. 6531833

[0016] Patent Document 6 International Publication No. 2023 / 199768 SUMMARY

[0017] Problems to be Solved by the Invention

[0018] Therefore, an object of the present application is to provide an article having a cured product of a surface treatment agent on a surface, the surface treatment agent being capable of forming a cured film excellent in water and oil repellency, abrasion resistance, and droplet sliding property, and containing a fluorine-containing polyether group-containing polymer having a silanol group and / or a hydrolyzable silyl group and / or a partial (hydrolysis) condensate thereof.

[0019] Solution to Problem

[0020] As a result of intensive studies made by the present inventors in order to achieve the above object, it has been found that a surface treatment agent containing a fluorine-containing polyether group polymer and / or a partial (hydrolytic) condensate thereof having three silanol groups or hydrolyzable silyl groups bonded to hydrocarbon groups having a straight-chain siloxane bond at one end of the molecule is capable of forming a cured film which is excellent in water and oil repellency, abrasion resistance, and liquid droplet sliding-off property, thereby completing the present invention.

[0021] That is, it has been found that, as a result of having three hydrocarbon groups having a straight-chain siloxane bond and three terminal silanol groups or hydrolyzable silyl groups at one end of a fluorine-containing polyether group as a main chain, the straight-chain siloxane bonds in the hydrocarbon groups are concentrated in a close portion in the molecule, and the points of adhesion to the substrate are many, so that the abrasion resistance, particularly the cloth abrasion resistance and paper abrasion resistance, are further improved. In addition, as a result of being a single-end structure, the fluorine-containing polyether group is positioned on the side opposite to the points of adhesion to the substrate, so that the liquid droplet sliding-off property also becomes good, thereby completing the present invention.

[0022] That is, the present invention provides the following invention.

[0023] [1] An article which is an article having a cured product of a surface treatment agent containing a fluorine-containing polyether group polymer and / or a partial (hydrolytic) condensate thereof on a surface,

[0024] The fluorine-containing polyether group polymer is a polymer having three silanol groups or hydrolyzable silyl groups bonded to hydrocarbon groups having a straight-chain siloxane bond at one end of the molecule.

[0025] [2] The article according to [1], wherein

[0026] The straight-chain siloxane bond is a bond having 1 to 8 siloxane units.

[0027] [3] The article according to [1] or [2], wherein

[0028] The hydrocarbon group having a straight-chain siloxane bond is a group represented by the following formula (1).

[0029] [Chemical Formula 1]

[0030]

[0031] (In the formula, G is a methyl group, an ethyl group, or a phenyl group, M is a divalent hydrocarbon group which is a straight-chain or branched-chain group having 1 to 9 carbon atoms, b is a number of 3 to 4, and c is a number of 1 to 8.)

[0032] [4] The article according to any one of [1] to [3], wherein

[0033] The fluorine-containing polyether group is a group represented by the following formula (2).

[0034] [Chemical Formula 2]

[0035]

[0036] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is a number from 1 to 6, p, q, r, s, t, u, and v are each a number from 0 to 450, p + q + r + s + t + u + v is a number satisfying 10 to 450, and each of the repeating units shown within the parentheses marked with p, q, r, s, t, u, and v is linear or branched, and the order of arrangement is arbitrary.)

[0037] [5] The fluoropolyether group-containing polymer according to any one of [1] to [4] is a polymer represented by the following formula (3).

[0038] [Chemical Formula 3]

[0039]

[0040] (In the formula, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom, the end of which is CF3- or CF2H-, Rf is a fluoropolyether group represented by the following formula (2), G is a methyl group, an ethyl group, or a phenyl group, M is a linear or branched divalent hydrocarbon group having a carbon atom number of 1 to 9, R is independently an alkyl group having a carbon atom number of 1 to 4 or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is a number from 2 to 3, b is a number from 3 to 4, and c is a number from 1 to 8.

[0041] [Chemical Formula 4]

[0042]

[0043] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is a number from 1 to 6, p, q, r, s, t, u, and v are each a number from 0 to 450, p + q + r + s + t + u + v is a number satisfying 10 to 450, and each of the repeating units shown within the parentheses marked with p, q, r, s, t, u, and v is linear or branched, and the order of arrangement is arbitrary.)

[0044] [6] The article according to [5], wherein,

[0045] In formula (3), X is any one selected from the group consisting of a hydroxyl group, an alkoxy group having a carbon atom number of 1 to 10, an alkoxy-substituted alkoxy group having a carbon atom number of 2 to 10, an acyloxy group having a carbon atom number of 2 to 10, an alkenyloxy group having a carbon atom number of 2 to 10, and a halogen group.

[0046] [7] The article according to [5] or [6], wherein,

[0047] In formula (3), G is a methyl group or a phenyl group.

[0048] [8] The article according to any one of [5] to [7], wherein

[0049] In formula (3), c is a number from 1 to 3.

[0050] [9] The article according to any one of [5] to [8], wherein

[0051] In formula (3), M is a linear or branched divalent hydrocarbon group having a carbon atom number of 1 to 3.

[0052]

[10] The article according to any one of [5] to [9], wherein

[0053] The fluorine-containing polyether group-containing polymer represented by formula (3) is a polymer of any one of the following formulae.

[0054] [Chemical Formula 5]

[0055]

[0056] (In the formula, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom and whose terminal is CF3- or CF2H-, pi is a number from 5 to 440, qi is a number from 5 to 250, pi + qi is a number satisfying 20 to 450, and the arrangement order of each repeating unit shown within the parentheses marked with pi and qi is arbitrary.)

[0057]

[11] The article according to any one of [1] to

[10] , wherein

[0058] The surface treatment agent further contains a fluorine-containing polyether group-containing polymer represented by the following formula (4) and / or a partial (hydrolysis) condensate thereof.

[0059] [Chemical Formula 6]

[0060]

[0061] (In the formula, V is a monovalent hydrocarbon group or a hydrogen atom, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom and whose terminal is CF3- or CF2H-, Rf is a fluorine polyether group represented by the following formula (2), G is a methyl group, an ethyl group, or a phenyl group, M is a linear or branched divalent hydrocarbon group having a carbon atom number of 1 to 9, R is independently an alkyl group having a carbon atom number of 1 to 4 or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is a number from 2 to 3, b is a number from 3 to 4, c is a number from 1 to 8,

[0062] [Chemical Formula 7]

[0063]

[0064] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is a number from 1 to 6, p, q, r, s, t, u, v are each a number from 0 to 450, p+q+r+s+t+u+v is a number satisfying 10 to 450, and the arrangement order of each repeating unit shown in the parentheses marked with p, q, r, s, t, u, v is arbitrary.)

[0065]

[12] . The article according to any one of [1] to

[11] , wherein

[0066] The surface treatment agent further comprises a fluorine-containing polyether group-containing polymer represented by the following formula (5).

[0067] [Chemical Formula 8]

[0068] RF-Rf'-RF (5)

[0069] (In the formula, the two terminal Rfs are independently a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom having CF3- or CF2H- at the terminal, and Rf' is a fluorine polyether group represented by the following formula (2)'.

[0070] [Chemical Formula 9]

[0071]

[0072] (In the formula, p, q, r, s are each a number from 0 to 450, p+q+r+s is a number satisfying 10 to 450, p+q is a number satisfying 20 to 450, and the arrangement order of each repeating unit shown in the parentheses marked with p, q, r, s is arbitrary.)

[0073] 13. The article according to any one of [1] to

[12] , wherein

[0074] The surface treatment agent is for spray coating or vacuum evaporation.

[0075] 14. The article according to any one of [1] to

[13] , wherein

[0076] The article is a glass substrate, a film substrate, or a plastic substrate.

[0077] 15. The article according to

[14] , wherein

[0078] The article is a resin product having a SiO2 surface treated by plasma.

[0079] 16. The article according to

[14] , wherein

[0080] The article is a spectacle lens.

[0081] Effects of the Invention

[0082] The water and oil repellency, abrasion resistance, and liquid droplet sliding-off property of the article of the present application having a cured product of the surface treatment agent on the surface are excellent. Specific implementation method

[0083] Hereinafter, the present application will be described in detail.

[0084] The article of the present application is an article having a cured product of a surface treatment agent containing a fluorine-containing polyether group-containing polymer and / or a partial (hydrolytic) condensate thereof on the surface, the fluorine-containing polyether group-containing polymer having 3 silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a straight-chain siloxane bond at one side end in the molecule. Hereinafter, the fluorine-containing polyether group-containing polymer will be referred to as "fluorine-containing polyether group-containing polymer (A)". Furthermore, in the present specification, the silanol group means a group having a silicon atom and at least one hydroxyl group bonded to the silicon atom.

[0085] In the present application, the number average molecular weight (Mn) of the fluorine-containing polyether group-containing polymer (A) and / or a partial (hydrolytic) condensate thereof or the surface treatment agent containing the silanol group or the hydrolyzable silyl group can be measured by gel permeation chromatography (GPC) or 19 Characteristic peak intensity ratio calculation by F-NMR analysis. In GPC, a fluorine-based solvent can be used as an elution solvent.

[0086] In addition, in the present application, the "partial (hydrolytic) condensate" of the fluorine-containing polyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group means a polymer obtained by partially condensing a hydroxyl group of the fluorine-containing polyether group-containing polymer (A) having a silanol group or a hydrolyzable group of the fluorine-containing polyether group-containing polymer (A) having a hydrolyzable silyl group, which is partially hydrolyzed in advance by a known method.

[0087] In the hydrocarbon group having a straight-chain siloxane bond of the fluorine-containing polyether group-containing polymer (A), the straight-chain siloxane bond preferably has 1 to 8 siloxane units, more preferably 1 to 3 siloxane units.

[0088] In the fluorine-containing polyether group-containing polymer (A), the hydrocarbon group having a straight-chain siloxane bond preferably has a straight-chain siloxane bond in the middle of the hydrocarbon group, more preferably is a hydrocarbon group represented by the following formula (1).

[0089] [Chemical Formula 10]

[0090]

[0091] (In the formula, G is a methyl group, an ethyl group, or a phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, b is a number of 3 to 4, and c is a number of 1 to 8.)

[0092] In formula (1), c, which represents the number of connections of siloxane units, is a number of 1 to 8, preferably a number of 1 to 3. If c exceeds 8, the distance from the polyfluoro ether group of the main chain to the silanol group or hydrolyzable silyl group at the end becomes large, which can cause curing to become difficult, and in addition, since the fluorine content in the polymer decreases, it can not be possible to obtain sufficient water repellency.

[0093] In formula (1), G is a methyl group, an ethyl group, or a phenyl group, preferably a methyl group or a phenyl group, more preferably a methyl group.

[0094] In formula (1), M is a linear or branched divalent hydrocarbon group having a carbon atom number of 1 to 9, preferably a carbon atom number of 1 to 4, more preferably a carbon atom number of 1 to 3, and specifically, methylene, ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propylene), and the like can be exemplified.

[0095] As a preferred M, for example, the following groups can be exemplified.

[0096] [Chemical Formula 11]

[0097] -CH2-

[0098] -CH2CH2-

[0099]

[0100] -CH2CH2CH2-

[0101] -CH2CH2CH2CH2-

[0102] As the hydrocarbon group represented by formula (1), specifically, the following can be exemplified.

[0103] [Chemical Formula 12]

[0104]

[0105] In the fluorine-containing polyether group-containing polymer (A), the fluorine polyether group is preferably a group represented by the following formula (2).

[0106] [Chemical Formula 13]

[0107]

[0108] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is a number of 1 to 6, p, q, r, s, t, u, and v are each a number of 0 to 450, p + q + r + s + t + u + v is a number satisfying 10 to 450, and the arrangement order of each of the repeating units shown within the parentheses marked with p, q, r, s, t, u, and v is arbitrary.

[0109] Note that the order of arrangement of each repeating unit in the entire present specification is arbitrary, and the bonding of each repeating unit can be any one of alternating, random, and block.

[0110] In formula (2), W is a fluoroalkylene group (fluoroalkylenegroup) containing 1 or more hydrogen atoms, and examples include a fluoroalkylene group in which 1 or 2 fluorine atoms are substituted with hydrogen atoms among each perfluoroalkylene group such as -CF2-, -C2F4-, -C3F6-, -C4F8-, -C5F10-, -C6F12-, and the like. 10 12 group

[0111] In formula (2), d is independently 1 to 6, preferably 1 to 3, and more preferably 1 or 2, for each unit.

[0112] In formula (2), p, q, r, s, t, u, and v are each a number from 0 to 450. Preferably, p is a number from 5 to 440, q is a number from 5 to 250, r is a number from 0 to 180, s is a number from 0 to 100, t is a number from 0 to 100, u is a number from 0 to 100, and v is a number from 0 to 100. p + q + r + s + t + u + v is a number satisfying 10 to 450, and preferably a number satisfying 20 to 200. If p + q + r + s + t + u + v is less than the above upper limit value, adhesion and curability are good, and if p + q + r + s + t + u + v is greater than the above lower limit value, the characteristics of the fluoroether group can be sufficiently exhibited. Each unit can be linear or branched. In addition, the order of arrangement of each repeating unit shown in the parentheses marked with p, q, r, s, t, u, and v is arbitrary.

[0113] The number average molecular weight of the fluoroether group is preferably a polymer of 1000 to 50000, and more preferably 2000 to 20000, wherein the number average molecular weight (Mn) can be calculated by the method.

[0114] As the fluoroether group, specifically, the following fluoroether groups can be exemplified.

[0115] [Chemical Formula 14]

[0116]

[0117] [Chemical Formula 15]

[0118] -C2F4O(CF2O) p′ (CF2CF2O) q′ C2F4-

[0119] ​​​- C2F4O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ C2F4-

[0120] (in the formula, p', q', r', s', t', u' are each a number of 1 or more, the upper limit of which is the same as the upper limit of p, q, r, s, t, u described above, and the total of these p', q', r', s', t', u' is a number of 20 to 450. r2', r3' are each a number of 1 or more, and the total of r2', r3' is a number of 35 to 180. The arrangement order of each repeating unit shown within the parentheses marked with p', q', r', s', t', u' is arbitrary.)

[0121] The fluorine-containing polyether group-containing polymer (A) is preferably a polymer represented by the following formula (3).

[0122] [Chemical Formula 16]

[0123]

[0124] (in the formula, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom and whose terminal is CF3- or CF2H-, Rf is a divalent fluorine polyether group represented by the formula (2), G is a methyl group, an ethyl group, or a phenyl group, M is a divalent hydrocarbon group which is a straight chain or a branched chain and whose carbon atom number is 1 to 9, R is independently an alkyl group whose carbon atom number is 1 to 4 or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is a number of 2 to 3, b is a number of 3 to 4, and c is a number of 1 to 8.)

[0125] In the formula (3), RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom and whose terminal is CF3- or CF2H-. The carbon atom number of the monovalent fluorine-containing hydrocarbon group is preferably 1 to 3, and examples thereof include CF3O-, CF3CF2O, CF2H-, CF2HCF2-, CF3CF2CF2O-, and the like.

[0126] In the formula (3), Rf is a divalent fluorine polyether group represented by the formula (2), and the specific examples and the preferable range thereof are described in the description of the formula (2).

[0127] In the formula (3), G, M, b, and c are the same as those of the formula (1), and the specific examples and the preferable range thereof are described in the description of the formula (1).

[0128] In the formula (3), R is an alkyl group whose carbon atom number is 1 to 4 or a phenyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and the like, among which a methyl group and an ethyl group are preferable.

[0129] In formula (3), a is 2 or 3, but from the viewpoints of reactivity and adhesion to a substrate, a is preferably 3.

[0130] As the fluorine-containing polyether group-containing polymer represented by formula (3), a polymer represented by the following formula can be exemplified.

[0131] [Chemical Formula 17]

[0132]

[0133] (In the formula, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom having a terminal of CF3- or CF2H-, pi is a number of 5 to 440, qi is a number of 5 to 250, pi + qi is a number satisfying 20 to 450, and the arrangement order of each repeating unit shown within the parentheses marked with pi and qi is arbitrary.)

[0134] As the method for producing the fluorine-containing polyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), a method exemplified by, for example, the following method can be exemplified.

[0135] The fluorine-containing polyether group-containing polymer having an alkenyl group is dissolved in a solvent, for example, in a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having an SiH group and a silanol group or a hydrolyzable silyl group (a halogenated silyl group, an alkoxy silyl group, etc.) and a linear siloxane bond is mixed, and in the presence of a hydrosilation reaction catalyst such as a 2-ethylhexanol solution of chloroplatinic acid, and also in the presence of an acid catalyst such as acetic acid, aging is performed at a temperature condition of preferably 40 to 120°C, more preferably 60 to 100°C, further preferably about 80°C, for preferably 1 to 96 hours, more preferably 30 to 50 hours, further preferably about 40 hours. Note that, in the organosilicon compound having an SiH group and a silanol group or a hydrolyzable silyl group and a linear siloxane bond, and in the case where an organosilicon compound having a halogen atom as a hydrolyzable silyl group is used, the substituent (halogen atom) on the silyl group can also be converted into an alkoxy group or the like such as a methoxy group or the like as another hydrolyzable group thereafter.

[0136] In the production of the fluorine-containing polyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), as the fluorine-containing polyether group-containing polymer having an alkenyl group, a fluorine-containing polyether group-containing polymer represented by the following formula (3A) can be exemplified.

[0137] [Chemical Formula 18]

[0138]

[0139] (In the formula, RF, Rf are the same as in formula (3), and b' is a number of 1 to 2.)

[0140] As the polymer having a fluorochemical polyether group represented by formula (3A) having an alkenyl group, for example, the following polymer can be exemplified.

[0141] [Chemical Formula 19]

[0142]

[0143] (In the formula, RF is CF3O or CF3CF2O, pi is a number of 5 to 440, qi is a number of 5 to 250, pi + qi is a number satisfying 20 to 450, and the arrangement order of each repeating unit shown within the parentheses marked with pi and qi is arbitrary.)

[0144] In the production of the polymer having a silanol group or a hydrolyzable silyl group-containing fluorochemical polyether group represented by formula (3), the amount of use of the organosilicon compound at the time of causing the polymer having a fluorochemical polyether group having an alkenyl group to react with the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group and a linear siloxane bond is preferably 1 to 30 equivalents, more preferably 8 to 24 equivalents, and further preferably about 16 equivalents of the SiH group in the organosilicon compound per 1 equivalent of the olefin site (alkenyl group) in the fluorochemical polyether group-containing polymer.

[0145] Note that, in the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group and a linear siloxane bond in the molecule, in the case where an organosilicon compound having a halogen atom as a hydrolyzable silyl group is used, thereafter, the substituent (halogen atom) on the silyl group can be converted into an alkoxy group or the like such as a methoxy group or the like as another hydrolyzable group, and as a reagent that can be used at the time of converting the substituent (halogen atom) on the silyl group into another hydrolyzable group, for example, an alcohol having a carbon atom number of 1 to 10 such as methanol, ethanol, propanol, isopropanol, butanol, or the like can be exemplified.

[0146] The amount of use of the reagent is preferably 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and further preferably 65 parts by mass, with respect to 100 parts by mass of the addition reaction product of the polymer having a fluorochemical polyether group having an alkenyl group and the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (halogenated silyl group and alkoxy silyl group, etc.) and a linear siloxane bond in the molecule.

[0147] In the production of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by Formula (3), as the solvent, for example, a fluorine-based solvent can be exemplified. As the fluorine-based solvent, 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, perfluorobutyl methyl ether, perfluoroisobutyl methyl ether, perfluorobutyl ethyl ether, perfluoroisobutyl ethyl ether, a hydrofluoroether (HFE)-based solvent (manufactured by 3M Company, trade name: Novec series), a perfluoro-based solvent (manufactured by 3M Company, trade name: Fluorinert series) composed of a completely fluorinated compound, and the like can be exemplified.

[0148] The amount of the solvent used is preferably 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 100 parts by mass, with respect to 100 parts by mass of the polymer having a fluoropolyether group with an alkenyl group.

[0149] In the production of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by Formula (3), as the hydrosilylation reaction catalyst, for example, platinum black, chloroplatinic acid, an alcohol-modified product of chloroplatinic acid, a complex of chloroplatinic acid with an olefin, an aldehyde, a vinylsiloxane, an alkyne alcohol, or the like, and the like, a platinum group metal-based catalyst such as tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, and the like can be exemplified. A platinum compound such as a vinylsiloxane complex compound is preferable.

[0150] The amount of the hydrosilylation reaction catalyst used is preferably an amount that becomes 0.01 to 100 ppm, and more preferably an amount that becomes 0.1 to 50 ppm, in terms of transition metal (mass), with respect to the mass of the fluoropolyether group-containing polymer having an alkenyl group and an alkynyl group at the molecular chain terminal.

[0151] For example, in the case where a compound represented by the following formula is used as the fluoropolyether group-containing polymer having an alkenyl group,

[0152] [Chemical Formula 20]

[0153]

[0154] (p1 / q1 = 0.96, p1 / q1 = 47)

[0155] In the case where 1,1,3,3-tetramethyldisiloxane is used as the organosilicon compound having an SiH group and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula can be obtained.

[0156] [Chemical Formula 21]

[0157]

[0158] (p1 / q1 = 0.96, p1 + q1 = 47)

[0159] In the present application, the surface treatment agent includes a fluorine-containing polyether group-containing polymer (A) and / or a partial (hydrolytic) condensate thereof. The surface treatment agent can include, as a main component, only the fluorine-containing polyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group as described above, or can include an unreacted raw material or a reaction intermediate before the fluorine-containing polyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group is introduced with a terminal silanol group or a terminal hydrolyzable silyl group. In addition, the surface treatment agent can include a partial (hydrolytic) condensate obtained by condensing a hydroxyl group of the fluorine-containing polyether group-containing polymer (A) or a terminal hydrolyzable silyl group of the fluorine-containing polyether group-containing polymer (A) which is partially hydrolyzed in advance by a known method.

[0160] In addition to the fluorine-containing polyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolytic) condensate thereof as a main component, the surface treatment agent can include a fluorine-containing polyether group-containing polymer (B) represented by the following formula (4) and / or a partial (hydrolytic) condensate thereof.

[0161] [Chemical Formula 22]

[0162]

[0163] (In the formula, V is a hydrogen atom or a monovalent hydrocarbon group, and RF, Rf, G, M, R, X, a, b, and d are the same as described in the formula (3).)

[0164] In the formula (4), V is a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group is linear or branched, and the number of carbon atoms is preferably 1 to 4. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, and the like can be exemplified.

[0165] In the formula (4), RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom and has a terminal CF3- or CF2H-, and the specific examples and the preferable range thereof are described in the formula (3).

[0166] In the formula (4), Rf is a divalent fluorine-containing polyether group represented by the formula (2), and the specific examples and the preferable range thereof are described in the formula (2) and the formula (3) including the formula (2).

[0167] In formula (4), G is a methyl group, an ethyl group, or a phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is a number from 2 to 3, b is a number from 3 to 4, and c is a number from 1 to 8. Specific examples and preferred ranges thereof are described above in the description of formula (3).

[0168] As the fluorine-containing polyether group-containing polymer (B) represented by formula (4), the following polymer can be exemplified.

[0169] [Chemical Formula 23]

[0170]

[0171] (In the formula, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom having a terminal CF3- or CF2H-, pi is a number from 0 to 450, qi is a number from 0 to 450, pi + qi is a number satisfying 10 to 450, and the arrangement order of each repeating unit shown in the parentheses marked with pi and qi is arbitrary.)

[0172] The use amount in compounding the fluorine-containing polyether group-containing polymer (B) represented by formula (4) and / or a partial (hydrolysis) condensate thereof is not particularly limited, and it is preferably in a range of 50% by mass or less, more preferably in a range of 0.1 to 50% by mass, and further preferably in a range of 10 to 40% by mass, with respect to the mass of the fluorine-containing polyether group-containing polymer (A) and / or a partial hydrolysis condensate thereof. The fluorine-containing polyether group-containing polymer (B) represented by formula (4) has a low viscosity compared to the fluorine-containing polyether group-containing polymer (A), and is good in handleability, and thus, from the viewpoint of considering the scale-up of production, it is preferable to include the fluorine-containing polyether group-containing polymer (B) represented by formula (4) to the extent that the effects of the present application are not impaired. If the content of the fluorine-containing polyether group-containing polymer (B) in the surface treatment agent is too much, it can be possible to cause a problem in adhesion.

[0173] In addition to the fluorine-containing polyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolysis) condensate thereof as a main component, the surface treatment agent can include a fluorine-containing polyether group-containing polymer (C) represented by the following formula (5).

[0174] [Chemical Formula 24]

[0175] RF-Rf'-RF (5)

[0176] (In the formula, the two terminal RF's are independently a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom having a terminal CF3- or CF2H-, and Rf' is a fluorine-containing polyether group represented by the following formula (2)'.

[0177] [Chemical Formula 25]

[0178]

[0179] (In the formula, p, q, r, s are each a number from 0 to 450, p + q + r + s is a number satisfying 10 to 450, p + q is a number satisfying 20 to 450, and the arrangement order of each repeating unit shown in the parentheses marked with p, q, r, s is arbitrary.)

[0180] In formula (5), RFis a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom, and the end of which is CF3- or CF2H-, and is the same as RFof formula (3). Specific examples and the description of the preferable range of RFmay be referred to the description of RFin formula (3).

[0181] In formula (5), Rf' is a divalent fluorine-containing polyether group represented by formula (2)', in which formula (2)', p, q, r, s are each a number from 0 to 450. Preferably, p is a number from 5 to 440, q is a number from 5 to 250, r is a number from 0 to 180, and s is a number from 0 to 100. p + q + r + s is a number satisfying 10 to 450, and preferably a number satisfying 20 to 200. p + q is a number satisfying 20 to 450, and preferably a number satisfying 20 to 200.

[0182] As the polymer (C) of the fluorine-containing polyether group represented by formula (5), polymers shown in the following can be exemplified.

[0183] [Chemical Formula 26]

[0184] CF3-O-(CF2O) p′ (CF2CF2O) q′ -CF3

[0185] CF3-O-(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ -CF3

[0186] CF3-O-(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ -CF3

[0187] CF3-O-(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ -CF3

[0188] (In the formula, p', q', r', s', and the total of these are the same as p, q, r, s of formula (2)'. The arrangement order of each repeating unit shown within the parentheses marked with p, q, r, s is arbitrary.)

[0189] The use amount in the case of compounding the non-functional polymer represented by formula (5) is not particularly limited, and is preferably in the range of 50 mass% or less, more preferably 0.1 to 50 mass%, further preferably 10 to 40 mass%, relative to the mass of the fluorine-containing polyether group-containing polymer (A) and / or the partial hydrolytic condensate thereof. By compounding the fluorine-containing polyether group-containing polymer (C) represented by formula (5), it is expected to improve properties such as water and oil repellency from the fluorine polyether group, but on the other hand, if the above range is exceeded, sometimes problems of adhesion can occur.

[0190] In the surface treatment agent used in the present application, the number average molecular weight of the composition containing the fluorine-containing polyether group-containing polymer (A) and / or the partial (hydrolytic) condensate thereof, or containing the fluorine-containing polyether group-containing polymer (A), further containing the fluorine-containing polyether group-containing polymer (B) and / or the partial (hydrolytic) condensate thereof and / or the fluorine-containing polyether group-containing polymer (C) is preferably in the range of 1000 to 50000, more preferably 2000 to 20000, further preferably 2500 to 10000, particularly preferably 3000 to 8000.

[0191] In the surface treatment agent, a hydrolytic condensation catalyst such as an organic tin compound (dibutyltin oxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), an inorganic acid (hydrochloric acid, sulfuric acid, etc.) can also be added as needed. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferable.

[0192] The addition amount of the hydrolytic condensation catalyst is a catalytic amount, and generally, relative to 100 parts by mass of the fluorine-containing polyether group-containing polymer (A) and / or the partial (hydrolytic) condensate thereof, it is 5 parts by mass or less, preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 parts by mass.

[0193] The surface treatment agent can also contain an appropriate solvent. As such a solvent, fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, hexafluoropropylene trimer, etc.); fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.); fluorine-modified ether solvents (methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran, etc.), methyl perfluoroheptene ether; 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropyl methyl ether); fluorine-modified alkyl amine solvents (perfluorotributyl amine, perfluorotripentyl amine, etc.), hydrocarbon solvents (ligroin, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, from the viewpoints of solubility and wettability, etc., solvents that have been fluorine-modified are preferred, and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran, etc.), perfluorotributyl amine, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, tridecafluorooctane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether are particularly preferred.

[0194] The solvent can also be a mixture of two or more of the above, and is preferably one that uniformly dissolves the fluorine-containing polyether group-containing polymer (A) and the partial (hydrolytic) condensate thereof. Note that the appropriate concentration of the fluorine-containing polyether group-containing polymer (A) and the partial (hydrolytic) condensate thereof that is dissolved in the solvent varies depending on the treatment method, but as long as it is an amount that is easy to measure, in the case of direct coating, the appropriate concentration of the condensate is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total of the solvent and the fluorine-containing polyether group-containing polymer (A) and the partial (hydrolytic) condensate thereof, and in the case of vapor deposition treatment, the appropriate concentration of the condensate is preferably 1 to 100 parts by mass, more preferably 3 to 30 parts by mass, relative to 100 parts by mass of the total of the solvent and the fluorine-containing polyether group-containing polymer (A) and the partial (hydrolytic) condensate thereof.

[0195] The method for producing the surface treatment agent used in the present application is not particularly limited, and examples include a method in which, after adding the polymer components in a container, the mixture is diluted with a diluent solvent, and then mixed well using a stirrer or a shaker, or a method in which, after diluting and mixing the respective polymer components to a prescribed concentration, the dilute solutions are further mixed with each other (using a stirrer or a shaker in these mixings), etc. Here, the polymer components must be the fluorine-containing polyether group-containing polymer (A) and / or the partial (hydrolytic) condensate thereof that contains a silanol group or a hydrolyzable silyl group, and in addition, the fluorine-containing polyether group-containing polymer (B) represented by formula (4) and / or the partial (hydrolytic) condensate thereof or the fluorine-containing polyether group-containing polymer (C) represented by formula (5) can also be used as the polymer components.

[0196] The article of the present application is manufactured by surface treatment with the surface treatment agent described above. The method for manufacturing the article of the present application is not particularly limited, but has, for example, a step of applying the surface treatment agent to a substrate of the article and a step of curing the surface treatment agent.

[0197] In the step of applying the surface treatment agent to the substrate of the article, the surface treatment agent can be applied to the substrate by a known method such as brushing, dipping, spraying, vapor deposition treatment, and the like. Spraying and vacuum vapor deposition are preferable. The heating method at the time of vapor deposition treatment can use either of a resistance heating method and an electron beam heating method, but is not particularly limited.

[0198] In the step of curing the surface treatment agent, the curing temperature thereof varies depending on the curing method, and, for example, in the case of direct coating (brushing, dipping, spraying, and the like), it is preferable to heat at 25 to 200°C, particularly at 25 to 150°C, for 30 minutes to 36 hours, particularly for 1 to 18 hours. In addition, in the case of application by vapor deposition treatment, it is preferable to be in the range of 20 to 200°C. In addition, it can also be cured under a humidified condition. The film thickness of the cured film can be appropriately selected depending on the kind of the substrate, and is usually 0.1 to 100 nm, particularly 1 to 20 nm. In addition, for example, in spraying, if diluted in a fluorine-based solvent to which moisture is added in advance and hydrolyzed, that is, after Si-OH is generated, spraying is performed, then the curing after coating is fast.

[0199] The substrate of the article is not particularly limited, and can be various materials such as paper, cloth, metals and metal oxides thereof, glass, plastic, ceramic, quartz, and the like. Among them, glass substrates, film substrates, and plastic substrates are preferable. The surface treatment agent for the present application can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for glass or a film on which SiO2 is treated, and a surface treatment agent for a resin product having a surface of SiO2 treated by plasma.

[0200] As the article treated with the surface treatment agent, there can be exemplified a car navigation system, a cellular phone, a smart phone, a digital camera, a digital video camera, a PDA, a portable audio player, a car audio, a game machine, a spectacle lens, a camera lens, a lens filter, a pair of sunglasses, a gastroscope, and the like for medical use; an optical article such as a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, an anti-reflection film, and the like. The surface treatment agent used in the present application can prevent the attachment of fingerprints and sebum to the article, and can impart scratch resistance, and thus is particularly useful as a water and oil repellent layer for a lens, a touch panel display, an anti-reflection film, and the like.

[0201] In addition, the surface treatment agent used in the present application, by surface treatment of an article using the surface treatment agent, functions as an antifouling paint for sanitary articles such as a bathtub, a washstand; an antifouling paint for glass windows or tempered glass, a headlamp cover, and the like of an automobile, an electric train, an aircraft, and the like; a water / oil repellent paint for an exterior wall building material; an oil stain-resistant paint for a kitchen building material; an antifouling and anti-poster / anti-graffiti paint for a telephone booth; a paint for preventing the attachment of fingerprints for an artwork and the like; a paint for preventing the attachment of fingerprints for an optical disc, a DVD, and the like. In addition, the fluorine-containing polyether group-containing polymer (A) and / or a partial (hydrolyzed) condensate thereof contained in the surface treatment agent also functions as a mold release agent or a paint additive for a mold; a resin modifier, a flowability modifier or a dispersibility modifier for an inorganic filler; a lubricity improver for a tape, a film, and the like.

[0202] In particular, the cured film obtained by the surface treatment agent used in the present application is capable of imparting excellent water / oil repellency, droplet sliding properties, and abrasion resistance. [Examples]

[0203] Hereinafter, a synthesis example, examples, and comparative examples are shown, and the present application is explained in more detail, but the present application is not limited by the following examples. In addition, in the following general formula, each of the repeating units shown in parentheses marked with pi and qi is a unit that is randomly linked.

[0204] [Synthesis Example 1]

[0205] Referring to Japanese Patent No. 6524955, a compound represented by the following formula (A) was prepared.

[0206] [Chemical Formula 27]

[0207]

[0208] (p1 / q1 = 0.96, p1 + q1 = 47)

[0209] 10 g of a compound represented by formula (A), 10 g of 1,3-bis(trifluoromethyl)benzene, 3.0 g of a compound represented by the following formula (B)

[0210] [Chemical Formula 28]

[0211]

[0212] 5.8 x 10 -3 g (as a Pt monomer, containing 1.8 x 10 -8mol) chloroplatinic acid / vinylsiloxane complex solution was mixed, and stirred at 80°C for 24 hours. After that, the solvent and unreacted substance were distilled off under reduced pressure, and 9 g of a liquid product was obtained. The obtained product was confirmed by1H-NMR to be the following compound (C). 1 H-NMR was confirmed to be the following compound (C).

[0213] [Chemical Formula 29]

[0214]

[0215] (p1 / q1 = 0.96, p1 + q1 = 47)

[0216] [Synthesis Example 2]

[0217] 10 g of a compound represented by the following formula (A), 10 g of 1,3-bis(trifluoromethyl)benzene, 3.8 g of a compound represented by the following formula (D)

[0218] [Chemical Formula 30]

[0219]

[0220] and 5.8 x 10 -3 g (as a Pt monomer, containing 1.8 x 10 -8 mol) chloroplatinic acid / vinylsiloxane complex solution was mixed, and stirred at 80°C for 24 hours. After that, the solvent and unreacted substance were distilled off under reduced pressure, and 9 g of a liquid product was obtained. The obtained product was confirmed by1H-NMR to be the following compound (C). 1 H-NMR was confirmed to be the following compound (C).

[0221] [Chemical Formula 31]

[0222]

[0223] (p1 / q1 = 0.96, p1 + q1 = 47)

[0224] [Synthesis Example 3]

[0225] Referring to Japanese Patent No. 6524955, a compound represented by the following formula (F) was prepared.

[0226] [Chemical Formula 32]

[0227]

[0228] (p1 / q1 = 0.96, p1 + q1 = 68)

[0229] A mixture of 10 g of a compound represented by the formula (F), 10 g of 1,3-bis(trifluoromethyl)benzene, 2.7 g of a compound represented by the formula (B), and 4.9 x 10 -3 g (as a Pt monomer, containing 1.4 x 10 -8 mol) of a chloroplatinic acid / vinylsiloxane complex solution in toluene was mixed, and stirred at 80°C for 24 hours. After that, the solvent and unreacted materials were distilled off under reduced pressure, to thereby obtain 9 g of a liquid product. The obtained product was confirmed by1H-NMR to be a compound (G) represented by the following formula. 1

[0230] [Chemical Formula 33]

[0231]

[0232] (p1 / q1 = 0.96, p1 + q1 = 68)

[0233] [Synthesis Example 4]

[0234] A mixture of 10 g of a compound represented by the formula (A), 10 g of 1,3-bis(trifluoromethyl)benzene, 3.0 g of a mixture of two compounds represented by the following formula (H)

[0235] [Chemical Formula 34]

[0236]

[0237] and 5.8 x 10 -3 g (as a Pt monomer, containing 1.8 x 10 -8 mol) of a chloroplatinic acid / vinylsiloxane complex solution in toluene was mixed, and stirred at 80°C for 24 hours. After that, the solvent and unreacted materials were distilled off under reduced pressure, to thereby obtain 9 g of a liquid product. The obtained product was confirmed by1H-NMR to be a mixture of two compounds represented by the following formula (I) (hereinafter, referred to as a compound (I)). 1

[0238] [Chemical Formula 35]

[0239]

[0240] (p1 / q1 = 0.96, p1 + q1 = 47)

[0241] [Synthesis Example 5]

[0242] Referring to Japanese Patent No. 6531833, a compound represented by the following formula (J) was prepared.

[0243] [Chemical Formula 36]

[0244] ​​

[0245] (p1 / q1 = 0.96, p1 + q1 = 47)

[0246] [Synthesis Example 6]

[0247] International Publication No. 2023 / 199768 prepared a compound represented by the following formula (K) and (L).

[0248] [Chemical Formula 37]

[0249]

[0250] (Formula (K): p1 / q1 = 0.96, p1 + q1 = 47 Formula (L): p1 / q1 = 0.96, p1 + q1 = 68) [Synthesis Example 7]

[0251] Referring to Japanese Patent No. 6524955, a compound represented by the following formula (M) was prepared.

[0252] [Chemical Formula 38]

[0253]

[0254] (p1 / q1 = 0.96, p1 + q1 = 47)

[0255] In addition to the above-mentioned Synthesis Examples 1 to 7, a compound represented by the following formula (N) was prepared.

[0256] [Chemical Formula 39]

[0257] CF3O-(CF2O) p3 -(C2F4O) q3 -CF3 (N)

[0258] (p3 / q3 = 0.89, p3 + q3 = 43)

[0259] When dilution was performed, the following solvents were used.

[0260] Novec 7300 (manufactured by 3M Company, methyl perfluorohexyl ether)

[0261] Novec 7200 (manufactured by 3M Company, ethyl perfluorobutyl ether)

[0262] Asahi Krin AC-6000 (manufactured by AGC, tridecafluorooctane)

[0263] Hexafluoropropylene trimer (manufactured by Fuji Photo Film and Otsuka Pharmaceutical Co., Ltd.)

[0264] Opteon SF 10 (manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd., perfluoroheptenyl methyl ether)

[0265] Hexafluoroisopropyl Methyl Ether, (HFIPM), (manufactured by Tokyo Chemical Industry Co., Ltd., Japan)

[0266] [Examples 1 to 6, Comparative Examples 1 to 4]

[0267] Using the compounds obtained in the above synthesis examples, surface treatment agents were prepared in combinations of the compounds and solvents shown in Table 1, with the compounds being diluted to 20 mass% with the solvents.

[0268] [Table 1]

[0269]

[0270] Preparation of a surface treatment agent and formation of a cured film

[0271] Using the surface treatment agents prepared in Examples 1 to 6 and Comparative Examples 1 to 4, the speed of the water contact angle rise was measured immediately after the cured coating film was produced. Each of the surface treatment agents was vacuum-deposited (deposition conditions: pressure: 3.0 x 10 -2 Pa, heating temperature: 700°C) on an AR-treated plastic lens (size: 80 mmφ) having a SiO2layer on the surface, and the sample was removed from the apparatus and allowed to cure for 12 hours in an atmosphere of 25°C, 50% humidity, to form a cured coating film having a film thickness of 10 nm.

[0272] Evaluation of water and oil repellency

[0273] [Measurement of initial water contact angle]

[0274] Using a contact angle meter (Drop Master, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the cured coating film with respect to water (water repellency) was measured for the lens on which the cured coating film had been formed as produced above (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The results (initial water contact angle) are shown in Table 2.

[0275] Evaluation of dynamic water contact angle

[0276] [Measurement of receding water contact angle]

[0277] Using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.), the dynamic contact angle of the cured coating film with respect to water (droplet: 5 μl, liquid speed: 0.5 μL / s, temperature: 25°C, relative humidity: 40%) was measured for the lens having the cured coating film formed thereon, which was produced as described above, using the expansion / contraction method. The results (receding water contact angle) are shown in Table 2.

[0278] Evaluation of durability

[0279] [Measurement of paper abrasion resistance]

[0280] For the lens having the cured coating film formed thereon, which was produced as described above, the contact angle of the cured coating film with respect to water (water repellency) after rubbing under the following conditions was measured using a rubbing tester (manufactured by Shinwa Science Co., Ltd.), as described above, and the paper abrasion resistance was evaluated. The test environmental conditions were 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 2. The decrease in the water contact angle after abrasion was less than 3° compared to the initial water contact angle, and the abrasion resistance was excellent.

[0281] Paper: Dusper (manufactured by Oji Data Systems Corporation)

[0282] Contact area: 1 cm 2

[0283] Moving distance (one way): 40 mm

[0284] Moving speed: 4800 mm / minute

[0285] Load: 1 kg / 1 cm 2

[0286] Number of abrasions: 30,000 times

[0287] [Table 2]

[0288]

[0289] (Examples 7 to 11, Comparative Examples 5 to 7)

[0290] Using the compounds obtained in the above Synthesis Examples, surface treatment agents were prepared using the combinations of compounds and solvents shown in Table 3, by diluting the compounds with the solvents so that the compounds became 0.1 mass%.

[0291] [Table 3]

[0292]

[0293] Preparation of a surface treatment agent and formation of a cured film

[0294] Using the surface treatment agent prepared in Examples 7 to 11 and Comparative Examples 5 to 7, cured films were prepared. The surface treatment agent was sprayed on the surface of a chemical tempered glass (manufactured by Corning, Gorilla V) cleaned by plasma treatment using a spray device (manufactured by T&K Corp., NST-51). Thereafter, the cured film was cured for 12 hours in an atmosphere of 25°C and 50% relative humidity to form a cured film having a thickness of 10 nm, thereby obtaining a test piece.

[0295] Evaluation of water and oil repellency

[0296] [Measurement of initial water contact angle]

[0297] The contact angle meter (Drop Master, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of the cured film with respect to water (water repellency) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%) for the glass on which the cured film had been formed as prepared above. The results (initial water contact angle) are shown in Table 4.

[0298] Evaluation of dynamic water contact angle

[0299] [Measurement of receding water contact angle]

[0300] The contact angle meter (Drop Master, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the dynamic contact angle of the cured film with respect to water (droplet: 5 μl, liquid speed: 0.5 μL / s, temperature: 25°C, relative humidity: 40%) for the glass on which the cured film had been formed as prepared above, according to the method (expansion / contraction method) described in ISO 19043 part 6. The results (receding water contact angle) are shown in Table 4.

[0301] Evaluation of durability

[0302] [Measurement of paper abrasion resistance]

[0303] The contact angle of the cured film with respect to water (water repellency) after rubbing under the following conditions was measured for the glass on which the cured film had been formed as prepared above, using a friction tester (manufactured by Shinto Scientific Co., Ltd.), in the same manner as described above, and the paper abrasion resistance was evaluated. The test environment conditions were 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 4. The decrease in the water contact angle after abrasion was less than 3° compared to the initial water contact angle, and the abrasion resistance was excellent.

[0304] Paper: Dusper (manufactured by Oji Data Systems Corp.)

[0305] Contact area: 1 cm 2

[0306] Moving distance (one way): 40 mm

[0307] Moving speed: 4800 mm / min

[0308] Load: 1 kg / 1 cm 2

[0309] Wear number: 20000 times

[0310] [Table 4]

[0311]

[0312] From the above results, it was confirmed that in Comparative Examples 1 to 2 and 5, the receding water contact angle was greatly lower than 105°, and the water sliding property was low. In addition, it was also confirmed that in Comparative Examples 3 and 6, the water contact angle after wear was decreased by 5° or more compared to the initial water contact angle, and the paper wear was decreased. In Comparative Examples 4 and 7, the water sliding property was good, and the water contact angle after wear did not significantly decrease, but compared to the examples, there was a tendency to be poor. On the other hand, in Examples 1 to 11, compounds (C), (E), (G), and (I) which are fluorine-containing polyether-based polymers containing 3 hydrolyzable silyl groups and 3 linear siloxane bonds were used. The article obtained by using the composition containing these compounds as a surface treatment agent was able to obtain a high receding water contact angle and a good result in paper wear durability.

Claims

1. An article which is an article having a cured product of a surface treatment agent containing a fluorine-containing polyether group-containing polymer and / or a partial (hydrolytic) condensate thereof on a surface, the fluorine-containing polyether group-containing polymer is a polymer having 3 silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a straight-chain siloxane bond at the terminal of one side in a molecule.

2. The article according to claim 1, wherein the straight-chain siloxane bond is a bond having 1 to 8 siloxane units.

3. The article according to claim 1, wherein the hydrocarbon group having a straight-chain siloxane bond is a group represented by the following formula (1), [Chemical Formula 1] -Si- (CH2)b- (Si) - (CH2)b- G M (1) in the formula, G is a methyl group, an ethyl group or a phenyl group, M is a divalent hydrocarbon group having a linear chain or a branched chain with a carbon atom number of 1 to 9, b is a number of 3 to 4, and c is a number of 1 to 8.

4. The article according to claim 1, wherein the fluorine-containing polyether group is a group represented by the following formula (2), [Chemical Formula 2] -Si- (CH2)b- (Si) - (CH2)b- G M (2) in the formula, W is a fluoroalkylene group containing 1 or more hydrogen atoms, d is a number of 1 to 6, p, q, r, s, t, u, v are each a number of 0 to 450, p + q + r + s + t + u + v is a number satisfying 10 to 450, and each of the repeating units shown in the parentheses marked with p, q, r, s, t, u, v is linear or branched, and the arrangement order thereof is arbitrary.

5. The article according to claim 4, wherein the fluorine-containing polyether group-containing polymer is a polymer represented by the following formula (3), [Chemical Formula 3] -Si- (CH2)b- (Si) - (CH2)b- G M (3) in the formula, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom with a terminal of CF3- or CF2H-, Rf is a fluorine-containing polyether group represented by the following formula (2), G is a methyl group, an ethyl group or a phenyl group, M is a divalent hydrocarbon group having a linear chain or a branched chain with a carbon atom number of 1 to 9, R is independently an alkyl group or a phenyl group with a carbon atom number of 1 to 4, X is independently a hydroxyl group or a hydrolyzable group, a is a number of 2 to 3, b is a number of 3 to 4, and c is a number of 1 to 8, [Chemical Formula 4] -Si- (CH2)b- (Si) - (CH2)b- G M (4) in the formula, W is a fluoroalkylene group containing 1 or more hydrogen atoms, d is a number of 1 to 6, p, q, r, s, t, u, v are each a number of 0 to 450, p + q + r + s + t + u + v is a number satisfying 10 to 450, and each of the repeating units shown in the parentheses marked with p, q, r, s, t, u, v is linear or branched, and the arrangement order thereof is arbitrary.

6. The article according to claim 5, wherein in formula (3), X is any one selected from the group consisting of a hydroxyl group, an alkoxy group with a carbon atom number of 1 to 10, an alkoxy-substituted alkoxy group with a carbon atom number of 2 to 10, an acyloxy group with a carbon atom number of 2 to 10, an alkenyloxy group with a carbon atom number of 2 to 10, and a halogen group.

7. The article according to claim 5, wherein in formula (3), G is a methyl group or a phenyl group.

8. The article according to claim 5, wherein in formula (3), c is a number of 1 to 3.

9. The article according to claim 5, wherein in formula (3), M is a divalent hydrocarbon group having a linear chain or a branched chain with a carbon atom number of 1 to 3.

10. The article according to claim 5, wherein The fluorine-containing polyether group-containing polymer represented by formula (3) is any one of the polymers represented by the following formula, [Chemical Formula 5] In the formula, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom having a terminal of CF3- or CF2H-, pi is a number of 5 to 440, qi is a number of 5 to 250, pi + qi is a number satisfying 20 to 450, and the arrangement order of each repeating unit shown within the parentheses marked with pi and qi is arbitrary.

11. The article according to any one of claims 1 to 10, wherein The surface treatment agent further contains a fluorine-containing polyether group-containing polymer represented by the following formula (4) and / or a partial (hydrolytic) condensate thereof, [Chemical Formula 6] In the formula, V is a monovalent hydrocarbon group or a hydrogen atom, RF is a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom having a terminal of CF3- or CF2H-, Rf is a fluorine polyether group represented by the following formula (2), G is a methyl group, an ethyl group or a phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is a number of 2 to 3, b is a number of 3 to 4, and c is a number of 1 to 8, [Chemical Formula 7] In the formula, W is a fluorine alkylene group containing 1 or more hydrogen atoms, d is a number of 1 to 6, p, q, r, s, t, u, v are respectively a number of 0 to 450, p + q + r + s + t + u + v is a number satisfying 10 to 450, and each repeating unit shown within the parentheses marked with p, q, r, s, t, u, v is linear or branched, and the arrangement order thereof is arbitrary.

12. The article according to any one of claims 1 to 10, wherein The surface treatment agent further contains a fluorine-containing polyether group-containing polymer represented by the following formula (5), [Chemical Formula 8] RF-Rf'-RF (5) In the formula, the two terminal RF's are independently a fluorine atom, or a monovalent fluorine-containing hydrocarbon group which can contain an oxygen atom having a terminal of CF3- or CF2H-, and Rf' is a fluorine polyether group represented by the following formula (2)', [Chemical Formula 9] In the formula, p, q, r, s are respectively a number of 0 to 450, p + q + r + s is a number satisfying 10 to 450, p + q is a number satisfying 20 to 450, and the arrangement order of each repeating unit shown within the parentheses marked with p, q, r, s is arbitrary.

13. The article according to any one of claims 1 to 10, wherein The surface treatment agent is for spray coating or vacuum evaporation.

14. The article according to any one of claims 1 to 10, wherein The article is a glass substrate, a film substrate or a plastic substrate.

15. The article according to claim 14, wherein The article is a resin product having a SiO2 surface treated by plasma.

16. The article according to claim 14, wherein The article is a spectacle lens.

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