JP2014077836A - Surface treatment method and surface-treated object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured coating film which has excellent surface characteristics, in particular, excellent scratch resistance and low dynamic friction property in spite of short setting time after coating, by wet coating method.SOLUTION: A surface treatment method for a substrate is provided. A surface-treatment agent includes fluorooxyalkylene group containing polymer composition and/or partial hydrolytic condensate of the fluorooxyalkylene group containing polymer composition. The fluorooxyalkylene group containing polymer composition includes straight-chain fluorooxyalkylene group containing polymer having isopropenoxysilyl group at one terminal and straight-chain fluorooxyalkylene group containing polymer having isopropenoxysilyl group at both terminals (hereinafter referred to as both terminals hydrolytic polymer), in which both terminals hydrolytic polymer has a content of less than 10 mol% (not 0 mol%) with respect to a total molar amount of the straight-chain fluorooxyalkylene group containing polymers. Further, an object whose surface is treated by the surface treatment method is provided.

Description

  The present invention relates to a substrate surface treatment method including a step of applying a surface treatment agent to a substrate by a wet coating method and then curing the substrate. In detail, the surface that can provide a cured film that has high curability after application to a base material and has excellent adhesion, water / oil repellency, low dynamic friction, and scratch resistance even when cured in a short time. The present invention relates to a surface treatment method using a treatment agent, and an article treated with the surface treatment agent.

  In recent years, there has been an increasing demand for technology that makes it difficult to attach fingerprints to the surface of a display to improve the appearance and visibility, and technology that makes it easier to remove dirt, and the development of materials that can meet these requirements has been developed year after year. It is desired. In particular, since the surface of the touch panel display is likely to be contaminated with fingerprints, it is desirable that the water / oil repellent layer coated on the surface of the touch panel display has a low dynamic friction coefficient from the viewpoint of scratch resistance and fingerprint wiping. Accordingly, development of a water / oil repellent layer having excellent scratch resistance and a low dynamic friction coefficient is required, and various surface treatment agents for providing such a water / oil repellent layer have been developed.

（式中、Ｒ^２、Ｒ^３は炭素数１〜４のアルキル基、Ｒ^１は−ＣＨ_２ＣＨ_２ＣＨ_２−又は−ＣＨ_２ＣＨ_２ＮＨＣＨ_２ＣＨ_２ＣＨ_２−、ｈは０〜８の整数、ｉは２又は３である） Patent Document 1 describes a fluoroaminosilane compound represented by the following formula, and realizes high water and oil repellency for glass. However, the compound has a short perfluorooxyalkylene chain and cannot provide sufficient lubricity, releasability and antifouling properties.

Wherein R ² and R ³ are alkyl groups having 1 to 4 carbon atoms, R ¹ is —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ —, and h is 0 to 8. Integer, i is 2 or 3)

（式中、Ｘは加水分解性基、Ｒ^４は一価炭化水素基、Ｒ^６は水素原子又は一価炭化水素基、Ｒ^５はＮＨ基を介在してもよいアルキレン基を示す。ｊは１４〜４９の整数、ｋは２又は３である） Patent Document 2 describes a perfluoropolyether-modified aminosilane containing a branched long-chain perfluorooxyalkylene group represented by the following formula. The perfluoropolyether-modified aminosilane has a high water and oil repellency angle, but has a branched structure in the main chain, so that the dirt wiping property and lubricity are not sufficient.

(In the formula, X represents a hydrolyzable group, R ⁴ represents a monovalent hydrocarbon group, R ⁶ represents a hydrogen atom or a monovalent hydrocarbon group, and R ⁵ represents an alkylene group which may intervene an NH group. J represents An integer of 14 to 49, k is 2 or 3)

（式中、Ｒｆは二価の直鎖型パーフルオロポリエーテル基、Ｒは炭素数１〜４のアルキル基又はフェニル基、Ｘは加水分解性基、ｌは０〜２の整数、ｍは１〜５の整数、ａは２又は３である） Patent Document 3 describes a perfluoropolyether-modified silane containing a linear perfluorooxyalkylene group represented by the following formula. The lens or antireflection film treated with the perfluoropolyether-modified silane is excellent in slipperiness, releasability, and wear resistance, but has insufficient lubricity because both ends are fixed to the substrate.

(Wherein Rf is a divalent linear perfluoropolyether group, R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group, l is an integer of 0 to 2, and m is 1) An integer of ~ 5, a is 2 or 3)

Patent Document 4 describes a perfluoropolyether-modified silane represented by the following formula as a treatment agent having improved lubricity. However, since this compound does not have a fluorine-containing group at the terminal, it is inferior in water / oil repellency, low dynamic friction, and releasability.
[Chemical formula 4]
(Z ² Q) _β Rf (QZ ¹ A _α ) _2-β
(Wherein Rf is a group containing a divalent perfluoroether residue, Q is a divalent organic group, Z ¹ and Z ² are organopolysiloxane residues, and A is a monovalent having a terminal reactive silyl group. A represents an integer of 1 to 8, and β is a number greater than 0 and less than 2.

Patent Document 5 describes a linear chain having — (CF ₂ ) _d — (OC ₂ F ₄ ) _e (OCF ₂ ) _f —O (CF ₂ ) _d — as a main chain structure and a hydrolyzable silyl group at one end. and Jo fluorooxyalkylene group-containing _{polymer, - (CF 2) d -} (OC 2 F 4) e (OCF 2) f -O (CF 2) d - was a main chain structure, hydrolyzable silyl groups at both ends The content of the hydrolyzable polymer at both ends with respect to the total mole of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends is 0. A surface treatment agent containing a fluorooxyalkylene group-containing polymer composition characterized by being 1 mol% or more and less than 10 mol% is described.

JP 58-167597 A JP 2000-143991 A JP 2003-238777 A JP 2007-297589 A JP 2012-72272 A

  2. Description of the Related Art In recent years, coating manufacturers have desired to provide surface treatment materials that can be cured in a short time after being applied to a substrate and exhibit the above-described surface characteristics (that is, excellent scratch resistance and low dynamic friction properties). . Methods for applying the surface treatment agent to the substrate include dry coating methods such as vacuum deposition and wet coating methods such as dip coating and spray coating.

The above-mentioned patent document 5 is excellent by applying the surface treatment agent having a trimethoxysilyl group at the end of the polymer to the substrate surface by vacuum vapor deposition, and then curing for 2 hours in an atmosphere of 40 ° C. and 80% humidity. Further, it is described that a cured film having scratch resistance and low dynamic friction can be provided. However, when the surface treatment agent is applied to the surface of the substrate by a wet coating method, a problem has arisen in that a cured film having excellent surface properties cannot be obtained by subsequent short-time curing. This is because when the coating is performed by vacuum deposition, it is possible to provide a cured film having excellent surface characteristics by short-time curing because the SiO ₂ layer on the substrate surface is deposited. This is probably because the SiO ₂ layer is not deposited during coating.

  Therefore, the present invention is a surface treatment method for a substrate including a step of applying a surface treatment agent to the substrate by a wet coating method. Even if the curing time after application is short, excellent surface characteristics, particularly excellent Another object of the present invention is to provide a surface treatment method for a substrate, which can provide a cured film having scratch resistance and low dynamic friction.

  As a result of intensive studies to solve the above problems, the present inventors have expressed a linear fluorooxyalkylene group-containing polymer represented by the following formula (1) and having an isopropenoxysilyl group at one end, and the following formula ( 2), a fluorooxyalkylene group-containing polymer composition and / or the fluorooxyalkylene containing a linear fluorooxyalkylene group-containing polymer having isopropenoxysilyl groups at both ends in a specific blending ratio By using a surface treatment agent containing a partially hydrolyzed condensate of a group-containing polymer composition, a cured film having excellent scratch resistance and low dynamic friction can be provided by short-time curing after application by a wet coating method. The present inventors have found that this can be done and have come to achieve the present invention.

（式中、Ｒｆ基は−（ＣＦ_２）_ｄ−（ＯＣ_２Ｆ_４）_ｅ（ＯＣＦ_２）_ｆ−Ｏ（ＣＦ_２）_ｄ−であり、Ａは末端が−ＣＦ_３基である１価のフッ素含有基であり、Ｑは２価の有機基であり、Ｚはシロキサン結合を有する２〜８価のオルガノポリシロキサン残基であり、Ｒは炭素数１〜４のアルキル基またはフェニル基であり、Ｘはイソプロペノキシ基であり、ａは２又は３、ｂは１〜７の整数、ｃは２〜５の整数であり、ｄはそれぞれ独立に０または１〜５の整数、ｅは０〜８０の整数、ｆは０〜８０の整数であり、かつ、ｅ＋ｆ＝５〜１００の整数であり、繰り返し単位はランダムに結合されていてよい）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、片末端加水分解性ポリマーと称す）と、
下記式（２）

（式中、Ｒｆ、Ｑ、Ｚ、Ｒ、Ｘ、ａ、ｂ、ｃは上記式（１）と同じである）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、両末端加水分解性ポリマーと称す）
を含み、前記片末端加水分解性ポリマーと前記両末端加水分解性ポリマーとの合計モルに対する両末端加水分解性ポリマーの含有量が１０モル％未満（但し、０モル％ではない）であることを特徴とする、表面処理方法、及び該方法で処理された表面を有する物品を提供する。 That is, the present invention is a substrate surface treatment method including a step of applying a surface treatment agent to a substrate by a wet coating method and then curing the substrate,
The surface treatment agent contains a fluorooxyalkylene group-containing polymer composition and / or a partial hydrolysis condensate of the fluorooxyalkylene group-containing polymer composition,
The fluorooxyalkylene group-containing polymer composition has the following formula (1)

(In the formula, the Rf group is — (CF ₂ ) _d — (OC ₂ F ₄ ) _e (OCF ₂ ) _f —O (CF ₂ ) _d —, and A is a monovalent group whose terminal is a —CF ₃ group A fluorine-containing group, Q is a divalent organic group, Z is a divalent to octavalent organopolysiloxane residue having a siloxane bond, and R is an alkyl group having 1 to 4 carbon atoms or a phenyl group , X is an isopropenoxy group, a is 2 or 3, b is an integer of 1-7, c is an integer of 2-5, d is independently an integer of 0 or 1-5, e is 0-80 And f is an integer of 0 to 80, and e + f is an integer of 5 to 100, and the repeating units may be combined randomly)
A linear fluorooxyalkylene group-containing polymer represented by (hereinafter referred to as a single-end hydrolyzable polymer),
Following formula (2)

(In the formula, Rf, Q, Z, R, X, a, b, and c are the same as the above formula (1)).
A linear fluorooxyalkylene group-containing polymer represented by (hereinafter referred to as a hydrolyzable polymer at both ends)
And the content of the hydrolyzable polymer at both ends relative to the total moles of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends is less than 10 mol% (but not 0 mol%). Provided are a surface treatment method and an article having a surface treated by the method.

  According to the present invention, in a substrate surface treatment method including a step of applying a surface treatment agent to a substrate by a wet coating method, the surface of various articles has excellent water and oil repellency and low dynamic friction properties by curing in a short time. In addition, scratch resistance can be imparted.

  In the method of the present invention, the surface treatment agent contains a fluorooxyalkylene group-containing polymer composition and / or a partial hydrolysis condensate of the fluorooxyalkylene group-containing polymer composition. The present invention relates to a terminal hydrolyzable polymer and a terminal hydrolyzable group (group represented by X in the formulas (1) and (2)) of the one terminal hydrolyzable polymer and the both terminal hydrolyzable polymer contained in the fluorooxyalkylene group-containing polymer composition ) Are all isopropenoxy groups. Thus, in a surface treatment method for a substrate including a step of applying a surface treatment agent to the substrate by a wet coating method, a cured film having excellent scratch resistance and low dynamic friction can be provided by curing in a short time. Can do.

  In the fluorooxyalkylene group-containing polymer composition, the content of the hydrolyzable polymer at both ends relative to the total mole of the hydrolyzable polymer at both ends and the hydrolyzable polymer at both ends is less than 10 mol% (however, at 0 mol%) Not more), preferably 0.1 to 9.8 mol%, more preferably 1 to 9 mol%, more preferably 1 to 5 mol%. The surface treating agent of the present invention can form a film having excellent scratch resistance when the content of the hydrolyzable polymer at both ends is within the above range.

The surface treatment agent of the present invention, the fluorooxyalkylene group-containing polymer _- and a main chain structure _{- (CF 2) d - (} OC 2 F 4) e (OCF 2) f -O (CF 2) d By doing so, a film having a low dynamic friction coefficient can be formed. In the above formula, d is independently an integer of 0 or 1 to 5, e is an integer of 0 to 80, f is an integer of 0 to 80, and e + f is an integer of 5 to 100, and the repeating unit is They may be combined randomly. e + f is preferably 10 to 80, more preferably 15 to 60. If e + f is larger than the upper limit, adhesion and curability may be deteriorated. If e + f is smaller than the lower limit, the characteristics of the fluorooxyalkylene group cannot be exhibited sufficiently.

In the above formula (1), A is a monovalent fluorine-containing group whose terminal is a —CF ₃ group, preferably a linear perfluoro group having 1 to 6 carbon atoms, and among them, a CF ₃ group is preferable.

  In said formula (1) and (2), R is a C1-C4 alkyl group or a phenyl group, and a methyl group is suitable especially. a is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to a substrate. b is an integer of 1 to 7, preferably 1 to 3, and c is an integer of 2 to 5, preferably 2 to 3.

In the above formulas (1) and (2), Q is a linking group of Rf group and Z group. Preferably, it is a C2-C12 hydrocarbon group which may contain one or more bonds selected from the group consisting of amide bonds, ether bonds, ester bonds, or vinyl bonds. For example, the following groups are mentioned.

In the above formulas (1) and (2), Z is a 2 to 8 valent, preferably 2 to 4 valent organopolysiloxane residue having a siloxane bond, and has 2 to 13 silicon atoms, preferably a silicon atom. It is a linear or cyclic organopolysiloxane residue of several to five. However, it may contain a silalkylene structure in which two silicon atoms are bonded by an alkylene group, that is, Si— (CH ₂ ) _n —Si (wherein n is an integer of 2 to 6). The fluorooxyalkylene group-containing polymer composition of the present invention can provide a coating excellent in abrasion resistance and scratch resistance by having a siloxane bond in the molecule.

The organopolysiloxane residue preferably has an alkyl group or phenyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The alkylene group in the silalkylene bond may be an alkylene group having 2 to 6, preferably 2 to 4 carbon atoms. Examples of such Z include those shown below.

（式中、Ｒｆ及びＡは前記式（１）及び（２）のために記載したものと同じ）
で表されるフルオロオキシアルキレン基含有ポリマー（以下、無官能性ポリマーと称す）を含有していてもよい。 The fluorooxyalkylene group-containing polymer composition used in the present invention further comprises the following formula (3):

(Wherein Rf and A are the same as those described for formulas (1) and (2) above)
The polymer may contain a fluorooxyalkylene group-containing polymer represented by (hereinafter referred to as a non-functional polymer).

  When the fluorooxyalkylene group-containing polymer used in the present invention contains the non-functional polymer, the one-terminal hydrolyzable polymer, the bi-terminal hydrolyzable polymer, and the total moles of the non-functional polymer described above The proportion of one-end hydrolyzable polymer is 80 mol% or more, preferably 85 mol% or more, more preferably 90 mol% or more (however, not 100 mol%), and the proportion of both-end hydrolyzable polymers is Desirably, it is less than 10 mol% (but not 0 mol%), preferably 0.1 to 9.8 mol%, more preferably 1 to 9 mol%, and more preferably 1 to 5 mol%. The proportion of the non-functional polymer should be less than 20 mol%, preferably 1 to 15 mol%, more preferably 5 to 10 mol%.

  The fluorooxyalkylene group-containing polymer composition can be produced, for example, by the following steps (i) to (iv).

(I) a fluorooxyalkylene group-containing polymer having a carboxylic acid group at one end (hereinafter referred to as a one-end carboxylic acid polymer) by partially fluorinating the end of a perfluorooxy compound having a carboxylic acid at both ends; A mixture containing a fluorooxyalkylene group-containing polymer having carboxylic acid groups at both ends (hereinafter referred to as both-end carboxylic acid polymer) is produced. In the reaction, the introduction rate of the terminal —CF ₃ group can be appropriately adjusted by adjusting the amount of fluorine gas to be supplied and controlling the fluorination. The mixture obtained in this step may contain a fluorooxyalkylene group-containing polymer having no carboxylic acid group at the terminal (hereinafter referred to as a non-functional polymer).

  (Ii) A mixture containing a carboxylic acid polymer at one end and a carboxylic acid polymer at both ends is subjected to an adsorption treatment and / or a molecular distillation treatment, and contains a fluorooxyalkylene group-containing polymer having a carboxylic acid group at one end in a high concentration. A polymer composition is obtained. The method of adsorption treatment and / or molecular distillation treatment may follow a known method. By this step, it is possible to adjust the content ratio of the hydrolyzable polymer at both ends with respect to the total mole of the hydrolyzable polymer at both ends and the hydrolyzable polymer at both ends.

(Iii) A group having an aliphatic unsaturated group at the terminal is introduced into the terminal carboxylic acid group in the polymer composition via an amide bond, an ether bond, an ester bond, or a vinyl bond. The introduction method may follow a known method. For example, first, the terminal carboxylic acid group-containing polymer composition is subjected to reduction using a metal hydride or catalytic hydrogenation using a noble metal catalyst to obtain a terminal hydroxyl group-containing polymer composition shown below (wherein The Rf ¹ group is — (OC ₂ F ₄ ) _e (OCF ₂ ) _f O—, where e and f are as described above.

Next, an aliphatic unsaturated group is introduced into the terminal hydroxyl group of the polymer obtained above. The introduction of the aliphatic unsaturated group into the terminal hydroxyl group may be performed according to a known method. By this step, as shown below, a terminal aliphatic unsaturated group-containing polymer composition having an alkenyl group such as an allyl group introduced therein is produced (wherein Rf ¹ is as described above).

  (Iv) Next, an organosilicon compound having a large number of SiH groups in the terminal aliphatic unsaturated group of the polymer, for example, an organosilicon compound having 2 to 8 SiH groups, is subjected to an addition reaction. The polymer obtained by the reaction has many SiH groups remaining in the molecule. Next, an organosilicon compound having an aliphatic unsaturated group at one end and an isopropenoxy group at the other end is added to the remaining SiH group. The addition reaction may be performed under known reaction conditions, and may be performed in the presence of an addition reaction catalyst such as a platinum group compound. Through this step, the fluorooxyalkylene group-containing polymer composition of the present invention can be obtained.

  In the surface treatment agent of the present invention, the partial hydrolysis-condensation product of the fluorooxyalkylene group-containing polymer composition is a partial isopropenoxy group of the polymer of the fluorooxyalkylene group-containing polymer composition obtained by a known method in advance. It is obtained by hydrolyzing and condensing.

  If necessary, the surface treatment agent of the present invention includes a hydrolysis-condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetran-butyl titanate, etc.), an organic acid, etc. (Acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid and the like are particularly desirable. The addition amount may be a catalyst amount. Usually, it is 0.01-5 mass parts with respect to 100 mass parts of fluorooxyalkylene group containing polymer compositions and / or its partial hydrolysis-condensation product, especially 0.1-1 mass part.

  The surface treating agent of the present invention may further contain a solvent. Examples of the solvent include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, 1,3 trifluoromethyl). Benzene), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.) And hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, a fluorine-modified solvent (that is, a fluorine solvent) is desirable in terms of solubility and wettability. In particular, m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are preferable.

  Two or more kinds of the above-mentioned solvents may be mixed, and it is preferable to uniformly dissolve the fluorooxyalkylene group-containing polymer composition and the partially hydrolyzed condensate thereof. The optimum concentration of the fluorooxyalkylene group-containing polymer composition dissolved in the solvent and the partially hydrolyzed condensate thereof may be appropriately adjusted according to the treatment method, but is 0.01 to 10% by weight, particularly 0.05. It is preferably ˜5% by weight.

  This invention provides the surface treatment method of a base material including the process of apply | coating the said surface treating agent to a base material by the wet coating method. Examples of the wet coating method include dip, spray, spin coating, blade coating, and the like. The method of the present invention is particularly suitable for use in dip coating and spray coating. A method for applying a surface treatment agent to a substrate using the wet coating method, for example, an apparatus to be used may follow a conventionally known method.

  The method of the present invention includes a step of curing the surface treatment agent after the coating step by the wet coating method. When the wet coating method is used, the curing time of the surface treatment agent is usually 12 to 24 hours. In the method of the present invention, the curing time may be 6 hours or less, particularly 1 to 4 hours, and further 1 to 3 hours. The method of the present invention provides a cured film having excellent surface characteristics, in particular, excellent low dynamic friction and scratch resistance, even with such a short-time curing, by using the surface treatment agent. can do.

  In the method of the present invention, the curing temperature of the surface treatment agent is desirably a temperature in the range of room temperature to 100 ° C, and particularly a temperature in the range of 50 to 80 ° C. Curing is preferably carried out under humidification in order to promote the reaction, and in particular, it is preferably carried out under humidity in the range of 60 to 90% RH. The film thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 0.1 nm to 100 nm, particularly 1 to 20 nm.

The substrate to be surface-treated by the method of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, and quartz. The method of the present invention can impart water and oil repellency, low dynamic friction and scratch resistance to the surface of the substrate. In particular, it can be suitably used as a method for treating the surface of a glass or quartz substrate treated with SiO ₂ .

  Articles to be used for the method of the present invention include car navigation, mobile phone, digital camera, digital video camera, PDA, portable audio player, car audio, game device, spectacle lens, camera lens, lens filter, sunglasses, Optical articles such as medical devices such as stomach cameras, copying machines, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, antireflection films, and the like. By performing the surface treatment using the method of the present invention, it is possible to prevent fingerprints and sebum from adhering to the surface of the article, and to further provide damage prevention. The treatment method of the present invention is particularly useful for providing a water / oil repellent layer on a touch panel display, an antireflection film or the like.

  In addition, the method of the present invention comprises a water-repellent and antifouling coating on sanitary products such as bathtubs and washstands; an antifouling coating on window glass or tempered glass for automobiles, trains, aircraft, etc., headlamp covers, etc. Water-repellent and antifouling coating for building materials; Coating for preventing oil stains on kitchen building materials; Water-repellent, antifouling and paper on phone boxes, anti-graffiti coatings; Water-repellent and anti-fingerprint coating for artworks Coating for preventing adhesion of fingerprints to compact discs, DVDs, etc .; It can be suitably used in various processes such as application of a release agent to a mold for nanoimprinting.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）

Fluorooxyalkylene group-containing polymer composition The fluorooxyalkylene group-containing polymer composition used in Example 1 was
(1a) One-end hydrolyzable polymer represented by the following formula (4), wherein X ₁ is a group represented by the following formula (a), and X ₂ is a fluorine atom: 91 mol%,
(1b) Both terminal hydrolyzable polymers represented by the following formula (4), wherein X ₁ and X ₂ are both groups represented by the following formula (a): 1 mol%, and (1c) Non-functional polymer in which X ₁ and X ₂ are both fluorine atoms: 8 mol%
It is the composition which consists of.

(P / q = 0.9, p + q≈45)

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）

The fluorooxyalkylene group-containing polymer composition used in Example 2 is
(2a) One-end hydrolyzable polymer represented by the following formula (5), wherein X ₁ is a group represented by the following formula (b), and X ₂ is a fluorine atom: 91 mol%,
(2b) Both terminal hydrolyzable polymers represented by the following formula (5), wherein both X ₁ and X ₂ are groups represented by the following formula (b): 1 mol%, and (2c) the following formula (5 Non-functional polymer in which X ₁ and X ₂ are both fluorine atoms: 8 mol%
It is the composition which consists of.

(P / q = 0.9, p + q≈45)

  In Comparative Examples 1 and 2, a fluorooxyalkylene group-containing polymer composition whose terminal is a trimethoxysilyl group as described in Examples of JP2012-72272A was used.

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） The fluorooxyalkylene group-containing polymer composition used in Comparative Example 1 is composed of 91 mol% of a one-end hydrolyzable polymer represented by the following formula (3a) and a both-end hydrolyzable polymer represented by the following formula (3b). 1 mol% and 8 mol% of a non-functional polymer represented by the following formula (3c) (same as the composition used in Example 1 described in JP2012-72272A).

(P / q = 0.9, p + q≈45)

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）

The fluorooxyalkylene group-containing polymer composition used in Comparative Example 2 is
(4a) One-end hydrolyzable polymer represented by the following formula (6), wherein X ₁ is a group represented by the following formula (c), and X ₂ is a fluorine atom: 91 mol%,
(4b) Both terminal hydrolyzable polymers represented by the following formula (6), wherein X ₁ and X ₂ are both groups represented by the following formula (c): 1 mol%, and (4c) the following formula (6 Non-functional polymer in which X ₁ and X ₂ are both fluorine atoms: 8 mol%
It is the composition which consists of.

(P / q = 0.9, p + q≈45)

Preparation of surface treatment agent A surface treatment agent was prepared by dissolving each of the above-mentioned fluorooxyalkylene group-containing polymer compositions in m-xylene hexafluoride so as to have a concentration of 0.3 wt%.

[Examples 1 and 2 and Comparative Examples 1 and 2]
A glass (Gorilla manufactured by Corning) with 10 nm of SiO ₂ treated on the outermost surface of the substrate was washed with a neutral detergent, and then ultrasonically washed with isopropanol for 10 minutes and dried (hereinafter referred to as a glass test piece). ). Each said surface treating agent with a density | concentration of 0.3 wt% was put into the glass container, respectively, and the said glass test piece was immersed in each surface treating agent for 30 second, and pulled up at the speed of 200 mm / min. Thereafter, each test piece was placed in a constant temperature and humidity chamber at 80 ° C./80% RH for 1 hour to cure the surface treatment agent to form a cured film.

  The surface physical properties of the cured film formed on the surface of the glass test piece were evaluated by the following methods. The results are shown in Table 1.

[Evaluation of water and oil repellency]
Using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the cured coating with water and the contact angle with oleic acid were measured.

[Measurement of dynamic friction coefficient]
The dynamic friction coefficient with respect to Bencott (made by Asahi Kasei Co., Ltd.) was measured using the surface property tester 14FW (made by Shinto Kagaku Co.) under the following conditions.
Contact area: 35mm x 35mm
Load: 200g

[Evaluation of wear resistance]
Using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.), the surface of the cured coating was rubbed with steel wool under the following conditions. Each time the surface was rubbed 1000 times, the water contact angle on the surface of the cured coating after rubbing was measured, and the number of rubs that allowed the water contact angle of the cured coating to be maintained at 100 ° or more was measured to determine the number of wear durability. The water contact angle was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). The test environmental conditions are 25 ° C. and humidity 40%.
Steel wool: BONSTAR # 0000 (manufactured by Nippon Steel Wool Co., Ltd.)
Travel distance (one way) 30mm
Movement speed 1800mm / min Load: 1kg / cm ²

  As shown in Table 1, in a method using a surface treatment agent containing a fluorooxyalkylene group-containing polymer composition whose terminal is a trimethoxysilyl group, as described in Examples of JP2012-72272A, After the coating process by the wet coating method, a cured film having sufficient scratch resistance cannot be obtained by short-time curing. On the other hand, the method of the present invention using the surface treatment agent containing the fluorooxyalkylene group-containing polymer composition whose terminal is an isopropenoxysilyl group has excellent scratch resistance even when the curing time is short. A coating can be provided.

According to the method of the present invention, in the substrate surface treatment method including the step of applying a surface treatment agent to the substrate by a wet coating method, even if the curing time of the surface treatment agent is short, water and oil repellency, low dynamic friction Can provide a cured film excellent in heat resistance, abrasion resistance, particularly scratch resistance (steel wool durability). Therefore, the surface treatment method of the present invention can be suitably used in the surface treatment process of a substrate using a wet coating method such as dip coating or spray coating. In particular, the surface treatment method of the present invention is useful as a method of forming a water / oil repellent layer on the surface of an optical article such as a touch panel display or an antireflection film.

Claims (13)

A surface treatment method for a substrate including a step of applying a surface treatment agent to the substrate by a wet coating method and then curing the substrate,
The surface treatment agent contains a fluorooxyalkylene group-containing polymer composition and / or a partial hydrolysis condensate of the fluorooxyalkylene group-containing polymer composition,
The fluorooxyalkylene group-containing polymer composition has the following formula (1)

(In the formula, the Rf group is — (CF ₂ ) _d — (OC ₂ F ₄ ) _e (OCF ₂ ) _f —O (CF ₂ ) _d —, and A is a monovalent group whose terminal is a —CF ₃ group A fluorine-containing group, Q is a divalent organic group, Z is a divalent to octavalent organopolysiloxane residue having a siloxane bond, and R is an alkyl group having 1 to 4 carbon atoms or a phenyl group , X is an isopropenoxy group, a is 2 or 3, b is an integer of 1-7, c is an integer of 2-5, d is independently an integer of 0 or 1-5, e is 0-80 And f is an integer of 0 to 80, and e + f is an integer of 5 to 100, and the repeating units may be combined randomly)
A linear fluorooxyalkylene group-containing polymer represented by (hereinafter referred to as a single-end hydrolyzable polymer),
Following formula (2)

(In the formula, Rf, Q, Z, R, X, a, b, and c are the same as the above formula (1)).
A linear fluorooxyalkylene group-containing polymer represented by (hereinafter referred to as a hydrolyzable polymer at both ends)
And the content of the hydrolyzable polymer at both ends relative to the total moles of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends is less than 10 mol% (but not 0 mol%). A surface treatment method that is characterized. The fluorooxyalkylene group-containing polymer composition further comprises the following formula (3)

(Wherein Rf and A are the same as above)
A piece containing a fluorooxyalkylene group-containing polymer represented by the formula (hereinafter referred to as a non-functional polymer), and a piece with respect to the total mole of the one-end hydrolyzable polymer, the two-end hydrolyzable polymer, and the non-functional polymer. The proportion of the terminal hydrolyzable polymer is 80 mol% or more (however, not 100 mol%), and the proportion of both terminal hydrolyzable polymers is less than 10 mol% (but not 0 mol%). The surface treatment method according to claim 1.   The surface treatment method according to claim 1, wherein the surface treatment agent further contains a fluorine solvent.   The ratio of the non-functional polymer to the total of the one-end hydrolyzable polymer, the both-end hydrolyzable polymer, and the non-functional polymer is less than 20 mol% (but not 0 mol%). The surface treatment method as described.   The surface treatment method according to any one of claims 1 to 4, wherein Z is a linear or cyclic organopolysiloxane residue having 2 to 5 silicon atoms.   Q is a C2-C12 hydrocarbon group which may contain one or more bonds selected from the group consisting of an amide bond, an ether bond, an ester bond, and a vinyl bond. The surface treatment method according to 1.   An article having a surface treated by the method of any one of claims 1-6.   An optical article having a surface treated by the method of any one of claims 1-6.   A touch panel having a surface treated by the method according to claim 1.   The antireflection film which has the surface processed by the method of any one of Claims 1-6. A glass treated with SiO ₂ having a surface treated with the method according to claim 1.   Tempered glass which has the surface processed by the method of any one of Claims 1-6. A quartz substrate having a surface treated by the method according to claim 1.