KR102511340B1 - coating composition - Google Patents

Abstract

(Rf기는 -(CF2)_d-(OY)_e-O(CF₂)_d-의 기, d는 0∼5, OY는 OCF₂CF₂CF₂CF₂, OCF₂CF₂CF₂, OCF(CF₃)CF₂, OCF₂CF₂, OCF₂로부터 선택되는 1종 또는 2종 이상의 기, e는 5∼200. A는 말단이 -CF₃기인 1가 불소 함유기, Q는 2가 탄화수소기, X는 가수분해성 기, c는 3∼8)의 양말단 가수분해성 폴리머를 포함하고, 편말단 가수분해성 폴리머와 양말단 가수분해성 폴리머와의 합계 몰에 대한 양말단 가수분해성 폴리머의 함유 비율이 0몰%를 초과하고 20몰% 미만인 코팅제 조성물. 본 발명 조성물에 의하면, 기재 표면에 단시간에 우수한 발수발유성, 낮은 동마찰성, 또한 내찰상성을 부여할 수 있다.One-end hydrolysable polymer of formula (1) and formula (2)

(Rf is a group of -(CF2) _d -(OY) _e -O(CF ₂ ) _d -, d is 0 to 5, OY is OCF ₂ CF ₂ CF ₂ CF ₂ , OCF ₂ CF ₂ CF ₂ , OCF ( CF ₃ ) CF ₂ , OCF ₂ One or more groups selected from CF ₂ and OCF ₂ , e is 5 to 200. A is a monovalent fluorine-containing group having a terminal -CF ₃ group, Q is a divalent hydrocarbon group. , X is a hydrolyzable group, c is a hydrolyzable polymer at both ends of 3 to 8), and the content ratio of the hydrolyzable polymer at both ends to the total mole of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends is 0 greater than mol% and less than 20 mol% of the coating composition. According to the composition of the present invention, excellent water and oil repellency, low kinetic friction, and scratch resistance can be imparted to the surface of a substrate in a short time.

Description

coating composition

The present invention provides a coating composition effective as a surface modifier used to form a layer imparting functions such as antifouling and low friction (sliding) on the surface of various substrates, and a cured film of the composition treated with the coating composition to form a surface It relates to an article formed on and a method for treating the surface of an article using the coating composition.

In general, since the perfluorooxyalkylene group-containing compound has a very small surface free energy, it has water and oil repellency, chemical resistance, lubricity, release property, antifouling property and the like. Due to its properties, it is widely used industrially as a water and oil repellent and antifouling agent for paper and textiles, a lubricant for magnetic recording media, an oil repellent for precision equipment, a mold release agent, cosmetics, and protective films.

However, its properties mean that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the surface of the substrate, it is difficult to adhere the film.

On the other hand, a silane coupling agent is well known as a material for binding organic compounds to the surface of a substrate such as glass or cloth. The silane coupling agent has a monovalent hydrocarbon group containing an organic functional group such as an amino group, an epoxy group and a (meth)acryloxy group, and a reactive silyl group (usually a hydrolysable silyl group such as an alkoxysilyl group) in one molecule. A hydrolyzable silyl group such as an alkoxysilyl group undergoes a self-condensation reaction with moisture (moisture) in the air to form a siloxane and form a film. At the same time, a hydrolyzable silyl group such as an alkoxysilyl group is chemically and physically bonded to the surface of glass or metal to form a durable film. A silane coupling agent is widely used as a coating agent for the surface of various substrates by taking advantage of this property, and compounds in which the silane coupling agent is applied have been proposed in order to impart characteristics of a perfluorooxyalkylene group to the surface of a substrate.

In Patent Literature 1, high water and oil repellency is achieved by applying a fluoroaminosilane compound represented by the following formula to glass. However, this compound has a short perfluorooxyalkylene chain, and cannot sufficiently exhibit lubricity, release property, and antifouling properties.

(Wherein, R ⁶ , R ⁷ are alkyl groups having 1 to 4 carbon atoms, R ⁵ is CH ₂ CH ₂ CH ₂ or CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ , h is an integer of 0 to 8, i is 2 or 3.)

Further, Patent Document 2 describes a perfluoropolyether-modified aminosilane containing a branched long-chain perfluorooxyalkylene group represented by the following formula. Although this perfluoropolyether-modified aminosilane has high water and oil repellency, it has a branched structure in its main chain, so it has insufficient decontamination and lubricity.

(Wherein, X is a hydrolysable group, R ⁸ is a monovalent hydrocarbon group, R ¹⁰ is a hydrogen atom or a monovalent hydrocarbon group, and R ⁹ is an alkylene group which may be passed through an NH group. j is an integer of 14 to 49; k is 2 or 3.)

Patent Document 3 describes a perfluoropolyether-modified silane containing a linear perfluorooxyalkylene group represented by the following formula. Lenses and antireflection films treated with this perfluoropolyether-modified silane are excellent in sliding properties, releasability, and abrasion resistance, but have insufficient lubricity because both ends are fixed to the base material.

(Wherein, Rf is a divalent straight-chain perfluoropolyether group, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is a hydrolysable group, l is 0 to 2, m is an integer of 1 to 5, and a is 2 or 3.)

Patent Document 4 describes a perfluoropolyether-modified silane represented by the following formula as a treatment agent with improved lubricity. However, since this compound did not have a fluorine-containing group at the terminal, it was inferior in water and oil repellency, low dynamic friction property, and releasability.

(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 group having a terminal reactive silyl group. α is an integer from 1 to 8, and β is a number greater than 0 and less than 2.)

Patent Document 5 is a linear fluorooxy having -(CF ₂ ) _d -(OC ₂ F ₄ ) _e (OCF ₂ ) _f -O(CF ₂ ) _d - as a main chain structure and having a hydrolyzable silyl group at one end. A polymer containing an alkylene group, -(CF ₂ )d-(OC ₂ F ₄ ) _e (OCF ₂ ) _f -O(CF ₂ ) _d - as a main chain structure, and a linear fluorocarbon having a hydrolyzable silyl group at both ends. A composition containing a hydroxyalkylene group-containing polymer, wherein the content of the hydrolysable polymer at both ends is 0.1% by mol or more and less than 10% by mol, based on the total number of moles of the hydrolysable polymer at one end and the hydrolysable polymer at both ends. Although a surface treatment agent containing a polymer composition is described, sufficient wear durability cannot be exhibited due to insufficient curing under conditions of short heating time, such as in wet coating such as spray coating.

Patent Literature 6 describes that alkali resistance and acid resistance are improved by having a cyclic siloxane residue at the connecting portion, but on the other hand, regarding steel wool abrasion durability, satisfactory performance has not been reached.

Patent Document 7 describes that by introducing an isopropenoxy group to a site of a hydrolyzable silyl group, curing is possible in a short time even in wet coating such as spray coating, but this also satisfies the recently required level for steel wool abrasion durability. performance was not reached.

Japanese Unexamined Patent Publication No. 58-167597 Japanese Unexamined Patent Publication No. 2000-143991 Japanese Unexamined Patent Publication No. 2003-238577 Japanese Unexamined Patent Publication No. 2007-297589 Japanese Unexamined Patent Publication No. 2012-072272 Japanese Unexamined Patent Publication No. 2014-084405 Japanese Unexamined Patent Publication No. 2014-077836

Recently, there has been a demand from a coating manufacturer to provide a surface treatment material capable of exhibiting the above-described surface properties (ie, excellent scratch resistance and low dynamic friction) by curing in a short time after being applied to a substrate. Methods for applying the surface treatment agent to the substrate include a dry coating method such as vacuum deposition and a wet coating method such as dipping coating and spray coating.

In Patent Document 5, the surface treatment agent having a trimethoxysilyl group at the end of the polymer is applied to the surface of the substrate by vacuum deposition, and then cured for 2 hours in an atmosphere of 40 ° C. and 80% humidity, resulting in excellent scratch resistance and low copper. It describes being able to provide a cured coating having frictional properties. However, when this surface treatment agent was applied to the surface of the substrate by a wet coating method, a cured coating having excellent surface properties could not be obtained by curing in a short time thereafter. This is because in the case of coating by vacuum deposition, since the SiO ₂ layer on the surface of the substrate is deposited, it is possible to provide a cured film having excellent surface properties by curing in a short time, but in the case of coating by the wet coating method, during coating It is thought that this is because the SiO ₂ layer is not deposited on.

Therefore, the present invention provides a coating agent composition capable of providing a cured coating having excellent surface properties, in particular, excellent abrasion durability and low dynamic friction even if the curing time after application is short, such as in a wet coating method, and a cured coating of the composition. It is an object of the present invention to provide various formed articles and a method for treating the surface of articles using this composition.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that, as represented by the general formulas (1) and (2), each end via three siloxane bonds via the Si atom of the connecting site on the way. has three hydrolyzable silyl groups, and when each alkylene group adjacent to each hydrolyzable group has three or more carbon atoms, it has been found that a cured coating excellent in short-time curability and abrasion durability can be provided, and the present invention It has been achieved. In addition, in Patent Document 5 and Patent Document 7, the structure of the present invention is not specified in the text and examples.

That is, the present invention relates to the following coating agent composition and various articles having a surface treated with the coating composition (surface modifier) (that is, having a cured film of the coating composition on the surface), and a surface treatment method of the article using the coating composition is to provide

[One]

The following general formula (1)

(In the formula, the Rf group is a group represented by -(CF ₂ ) _d -(OY) _e -O(CF ₂ ) _d -, d is each independently an integer of 0 or 1 to 5, and OY is OCF ₂ CF ₂ CF ₂ CF ₂ , OCF ₂ CF ₂ CF ₂ , OCF(CF ₃ )CF ₂ , OCF ₂ CF ₂ and OCF ₂ , which is one or two or more groups selected from the group consisting of random or block arrangement. and e is an integer of 5 to 200. A is a monovalent fluorine-containing group having a terminal -CF ₃ group, Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond, and X is a hydrolysable group , and c is an integer from 3 to 8.)

A polymer containing a linear fluorooxyalkylene group represented by (hereinafter referred to as a hydrolyzable polymer at one end) and the following general formula (2)

(In the formula, Rf, Q, X, c are the same as in formula (1) above.)

A polymer containing a linear fluorooxyalkylene group represented by (hereinafter referred to as a hydrolyzable polymer at both ends), wherein the hydrolyzable polymer at both ends relative to the total mole of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends A coating agent composition characterized in that the content ratio of exceeds 0 mol% and is less than 20 mol%.

[2]

Also, the following formula (3)

A-Rf-A (3)

(In the formula, Rf and A are as described above.)

It contains a fluorooxyalkylene group-containing polymer (hereinafter referred to as a non-functional polymer) represented by and further hydrolysable at one end with respect to the total mole of the hydrolysable polymer at one end, the hydrolysable polymer at both ends and the non-functional polymer The coating agent composition according to [1], wherein the polymer content is 65 mol% or more and less than 100 mol%, and the content of the hydrolyzable polymer at both ends is more than 0 mol% and less than 20 mol%.

[3]

[2] The coating composition according to [2], wherein the content of the non-functional polymer relative to the total mole of the one-end hydrolyzable polymer, the both-end hydrolyzable polymer, and the non-functional polymer is greater than 0 mol% and less than 30 mol%.

[4]

The coating composition according to any one of [1] to [3] further containing a fluorine-based solvent.

[5]

In general formula (1) and general formula (2), the coating agent composition in any one of [1]-[4] where the divalent hydrocarbon group Q is a group represented by the following formula.

-CH ₂ OCH ₂ CH ₂ CH ₂ -

(However, the left end is connected to the Rf group, and the right end is connected to Si.)

[6]

In formulas (1) and (2), the hydrolyzable group X is any one of [1] to [5], which is at least one group selected from a methoxy group, an ethoxy group, an isopropenoxy group, and an acetoxy group. The coating agent composition described in one.

[7]

An article having on its surface a cured film of the coating agent composition according to any one of [1] to [6].

[8]

An optical article having on its surface a cured film of the coating agent composition according to any one of [1] to [6].

[9]

A touch panel having a cured film of the coating agent composition according to any one of [1] to [6] on the surface.

[10]

An antireflection film having on its surface a cured film of the coating agent composition according to any one of [1] to [6].

[11]

A SiO ₂ treated glass having on its surface a cured film of the coating agent composition according to any one of [1] to [6].

[12]

A tempered glass having on its surface a cured film of the coating agent composition according to any one of [1] to [6].

[13]

A quartz substrate having on its surface a cured film of the coating agent composition according to any one of [1] to [6].

[14]

A method for treating the surface of an article, comprising a step of treating the surface of the article by a dry coating method or a wet coating method using the coating agent composition according to any one of [1] to [6].

The coating composition (surface modifier) of the present invention can impart excellent water and oil repellency, low dynamic friction, and scratch resistance to the surface of a substrate in a short time by a dry coating method and a wet coating method. Even if it is short, the above performance can be exhibited.

(Mode for implementing the invention)

The coating composition of the present invention is a hydrolyzable polymer at one end represented by the following general formula (1) and

Both ends hydrolyzable polymer represented by the following general formula (2)

Including, the content ratio of the hydrolyzable polymer at both ends to the total mole of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends is greater than 0 mol% and less than 20 mol%, preferably 0.1 to 18 mol %, more preferably 0.5 to 15 mol%, still more preferably 1 to 10 mol% (i.e., the sum of the two components of the one-end hydrolysable polymer and the both-end hydrolysable polymer) The content ratio of the hydrolyzable polymer at one end to mole is 80 mol% or more and less than 100 mol%, preferably 82 to 99.9 mol%, more preferably 85 to 99.5 mol%, still more preferably 90 to 99 mol%. It is a coating agent composition characterized in that).

In the above general formula (1), A is a monovalent fluorine-containing group, preferably a 1 to 6 linear or branched perfluoroalkyl group having a terminal -CF ₃ group, specifically, a trifluoromethyl group. , Pentafluoroethyl group, heptafluoropropyl group, 1- (trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, nonafluorobutyl group, 1,1-di (trifluoromethyl ) -2,2,2-trifluoroethyl group, undecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptatecafluorooctyl group and the like, among which preferred is a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, and a tridecafluorohexyl group, particularly preferably a trifluoromethyl group and a pentafluoro They are an ethyl group and a heptafluoropropyl group.

In Formulas (1) and (2), the Rf group is a group represented by -(CF ₂ ) _d -(OY) _e -O(CF ₂ ) _d -, and d is each independently 0 or 1 OCF ₂ CF ₂ CF ₂ CF ₂ , OCF ₂ CF ₂ CF ₂ , OCF(CF ₃ )CF ₂ , OCF ₂ CF 2 and OCF 2 selected from the group consisting of OCF 2 CF 2 CF 2 CF ₂ and OCF ₂ . These are the above groups, and the arrangement order may be random or block, and e is an integer of 5 to 200.

In the above general formulas (1) and (2), Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond, and examples thereof include the following groups (each example below In , the left end is connected to the Rf group, and the right end is connected to Si).

In the general formulas (1) and (2), c is an integer of 3 to 8, preferably an integer of 3 to 6.

In the general formula (1) and general formula (2), X is a hydrolysable group, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a trifluoromethoxy group, and a trifluoro Halogenated alkoxy groups such as oxy groups and trichloroethoxy groups, alkoxy groups such as methoxyethoxy groups, substituted alkoxy groups, acyloxy groups such as acetoxy groups, propionyloxy groups and benzoyloxy groups, and isopropenyloxy. Alkenyloxy groups such as isobutenyloxy groups, ketoxime groups such as dimethyl ketoxime groups, methylethyl ketoxime groups, and diethyl ketoxime groups, imineoxy groups such as cyclohexane oxime groups, methylamino groups, ethylamino groups, dimethylamino groups, Substituted amino groups such as diethylamino group, amide groups such as N-methylacetamide group and N-ethylamide group, substituted aminooxy groups such as dimethylaminooxy group and diethylaminooxy group, halogen groups such as chlorine atom etc. can be mentioned. Among examples of X, a methoxy group, an ethoxy group, a trifluoroethoxy group, an acetoxy group, an isopropenyloxy group, a chlorine atom, a dimethyl ketoxime group, and a methylethyl ketoxime group are preferable, and a methoxy group and an ethoxy group , an isopropenyloxy group is particularly preferred. X can be included in the hydrolyzable polymer of the present invention as one type or in combination of two or more types.

The coating agent composition of the present invention (hereinafter also referred to as a fluorooxyalkylene group-containing polymer composition) has the following formula (3)

A-Rf-A (3)

(In the formula, Rf and A are as described in formulas (1) and (2) above.)

A fluorooxyalkylene group-containing polymer represented by (hereinafter, referred to as a non-functional polymer) may be contained.

When the fluorooxyalkylene group-containing polymer used in the present invention contains the above non-functional polymer, the above-mentioned one-end hydrolyzable polymer, both ends hydrolyzable polymer, and the non-functional polymer for the total mole of the three components The ratio of the hydrolyzable polymer at one end is 65 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and less than 100 mol%, and the ratio of the hydrolyzable polymer at both ends is 0 mol%. It is preferable that it exceeds 20 mol%, preferably 0.1 to 18 mol%, and more preferably 1 to 10 mol%. It is preferable that the proportion of the non-functional polymer is greater than 0 mol% and less than 30 mol%, preferably 1 to 25 mol%, and more preferably 5 to 20 mol%.

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

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

(ii) a mixture comprising a single-terminal carboxylic acid polymer and both-terminal carboxylic acid polymers is subjected to adsorption treatment and/or molecular distillation treatment, which basically contains a high concentration of a fluorooxyalkylene group-containing polymer having a carboxylic acid group at one terminal. obtains a three-component polymer composition. The method of adsorption treatment and/or molecular distillation treatment may be according to a known method. In this step, the content ratio of the hydrolyzable polymer at both ends to the total mole of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends can be adjusted.

(iii) A terminal carboxylic acid group in this three-component polymer composition is modified, and a group having an aliphatic unsaturated group is introduced at the terminal. The introduction method may be according to a known method. For example, first, the three-component polymer composition containing a terminal carboxylic acid group is subjected to reduction using a metal hydride or catalytic hydrogenation using a noble metal catalyst, and the three-component system containing a terminal hydroxyl group (methylol group) shown below is obtained. It is set as a polymer composition (in formula, Rf group is as above).

Next, an aliphatic unsaturated group is introduced into the terminal hydroxyl group of the three-component polymer composition obtained above. Introduction of the aliphatic unsaturated group into the terminal hydroxyl group may be performed according to a known method. This step produces a three-component polymer composition containing a terminal aliphatic unsaturated group into which an alkenyl group such as an allyl group is introduced at the terminal, as shown below.

(iv) Next, an organosilicon compound having one SiH group and three hydrolysable groups, such as trimethoxysilane, is subjected to a hydrosilylation addition reaction to the terminal aliphatic unsaturated groups of the three-component polymer composition. 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. By this step, a three-component polymer composition having a hydrolyzable silyl group at the terminal as shown below is produced.

(v) Next, tetramethyldisiloxane (1,3-dihydro-1,1,3,3-tetramethyldisiloxane) is added to the hydrolyzable silyl group of the three-component polymer composition in the presence of hydrochloric acid or sulfuric acid. By decomposition, a three-component polymer composition having three SiH groups at the terminals as shown below is produced. The method of cohydrolysis may follow a known method.

(vi) Next, an organosilicon compound having an aliphatic unsaturated group at one end and a hydrolyzable silyl group at the other end is subjected to an addition reaction to the SiH group in the three-component polymer composition. 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 as a three-component polymer composition.

The one-end and both-end hydrolyzable polymers used in the coating composition of the present invention each have a number average molecular weight in terms of polystyrene determined by gel permeation chromatography of preferably 500 or more and 40,000 or less, particularly preferably 1,000 or more and 30,000 or less, More preferably, it is preferable to use what is in the range of 1,000 or more and 20,000 or less. If the number average molecular weight is less than 500, water and oil repellency and antifouling properties, which are characteristics of a fluorooxyalkylene group, may not be sufficiently exhibited. There may be cases of deterioration.

The number average molecular weight referred to in the present invention refers to the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) measured under the following conditions (the same applies hereinafter).

[Measuring conditions]

Developing solvent: Hydrochlorofluorocarbon (HCFC)-225

Flow rate: 1 mL/min.

Detector: Evaporative Light Scattering Detector

Column: Two TSKgel Multipore HXL-M 7.8 mmφ×30 cm manufactured by Tosoh Corporation were used.

Column temperature: 35°C

Sample injection amount: 100 μL (HCFC-225 solution with a concentration of 0.3% by mass)

The coating composition of the present invention may also contain a solvent or diluent. Examples of such solvents or diluents include alcohols (ethanol, isopropyl alcohol, etc.), hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.), ester solvents (ethyl acetate, isopropyl acetate, acetic acid butyl, etc.), ether-based solvents (diethyl ether, isopropyl ether, etc.), ketone-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and polar It is preferable to use a solvent, and isopropyl alcohol and methyl isobutyl ketone are particularly preferable from the viewpoints of solubility, wettability and safety. Fluorinated solvents (perfluoro solvents) are also preferably used, examples of which include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, etc.), fluorinated aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.), Fluorinated ether solvents [methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, etc. ], and among them, fluorinated ether-based solvents are preferably used in terms of solubility, wettability, and the like.

In addition, the said solvent may be used individually by 1 type, or may mix and use 2 or more types, and it is preferable to use what dissolves the said component uniformly anyway.

The amount of the solvent used is not particularly limited, and the optimum concentration differs depending on the treatment method. For vapor deposition applications, it is generally preferred to use an amount such that the solid content in the coating composition is 1 to 80% by mass, particularly 5 to 50% by mass. In the case of spray coating or dipping coating, it is preferable to use an amount such that the solid content in the composition is 0.05 to 20.0% by mass, particularly 0.1 to 1.0% by mass. In addition, solid content means the mass of a non-volatile component.

When the coating agent composition requires a fast curing rate, a curing catalyst may be added as needed. Examples of curing catalysts include organic titanic acid esters, organic titanium chelate compounds, organic aluminum compounds, organic zirconium compounds, organic tin compounds, metal salts of organic carboxylic acids, amine compounds and salts thereof, quaternary ammonium compounds, and lower fatty acid salts of alkali metals. , dialkylhydroxyamines, organosilicon compounds containing a guanidyl group, inorganic acids, perfluorocarboxylic acids, perfluoroalcohols, and the like, and perfluorocarboxylic acids are preferably used.

The addition amount of the curing catalyst is the catalytic amount, and the fluorine-containing organosilane compound according to the present invention, its partial hydrolyzate or its partial hydrolysis condensate (i.e., one-end and both-end hydrolyzable polymers and their partial hydrolysates and partial hydrolysis products) according to the present invention. Total amount of decomposition/condensation product (total amount of polymer components)) 0.05 to 5 parts by mass, preferably 0.1 to 1 part by mass, per 100 parts by mass.

As a method of applying the coating composition of the present invention obtained in this way to a substrate as a surface modifier, there are known methods such as wet coating methods such as brush coating, dipping, and spraying, and dry coating methods such as vapor deposition.

The optimum temperature for the treatment of the applied coating composition (surface modifier) varies depending on the coating method, but, for example, in the case of spray coating or dipping, the range of 10 to 100°C is preferable. As the treatment humidity, it is preferable to perform under humidification from the viewpoint of accelerating the reaction.

The curing time of conventional surface modifiers is usually 12 to 24 hours. In contrast, in the method of the present invention, the curing time may be 6 hours or less, particularly 1 to 4 hours, and more preferably 1 to 3 hours. The method of the present invention, by using the surface modifier, can provide a cured film having excellent surface properties, particularly excellent low dynamic friction and scratch resistance even after curing in such a short time. In addition, it is preferable to appropriately optimize the treatment conditions according to the substrate, the curing catalyst, and the like.

The base material treated with the coating composition 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 coating composition of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface modifier for chemically strengthened glass, SiO ₂ treated glass or film.

The film thickness of the cured film of the coating composition formed on the surface of the various substrates or articles is appropriately selected depending on the type of substrate, but is preferably 1 to 100 nm, more preferably 3 to 20 nm.

The obtained film has water and oil repellency and high water activity, and is excellent in durability such as heat resistance, chemical resistance, and UV resistance compared to conventional products. These properties are often exposed to water or ultraviolet rays and are effective in applications where maintenance is not easy, or where grease, fingerprints, cosmetics, sunscreen cream, human or animal excrement, oil, etc. are easily adhered. For example, , window glass or tempered glass of automobiles, trams, ships, aircraft, high-rise buildings, etc., headlamp covers, outdoor products, telephone boxes, large outdoor displays, hygiene products such as bathtubs and washbasins, cosmetic tools, building materials for kitchens, Coatings for imparting anti-fingerprint adhesion to water tanks, works of art, and the like, and the like are exemplified. In addition, it is also useful as an anti-fingerprint coating for compact discs and DVDs, as a release agent for molds, as a paint additive, or as a resin modifier. In addition, car navigation devices, cell phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio devices, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as Wi-Fi cameras, copiers, PCs, LCD monitors , optical articles such as organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. Since the surface modifier of the present invention can prevent fingerprints and sebum from adhering to the article and impart scratch resistance, it is particularly useful as a water and oil repellent layer for touch panel displays and antireflection films.

Example

Hereinafter, Examples and Comparative Examples are presented to explain the present invention in detail, but the present invention is not limited to the following Examples.

Fluorooxyalkylene group-containing polymer composition

The following four types of polymer compositions were prepared.

[Polymer composition 1]... (Composition of the present invention)

Equation (4)

(p/q=0.9, p+q≒45. In addition, although (OCF ₂ CF ₂ CF ₂ ) units and (OCF ₂ CF ₂ CF ₂ CF ₂ ) units are included in the polymer, since they are trace amounts, formula (4) not added to the notation of),

(1a): Hydrolyzable polymer at one end in which X ¹ in the formula (4) is a group represented by the following formula (a), and X ² is a fluorine atom: 83 mol%,

(1b): Hydrolyzable polymer at both ends of a group in which X ¹ and X ² in the above formula (4) are represented by the following formula (a): 8 mol%,

(1c): Non-functional polymer in which both X ¹ and X ² in the formula (4) are fluorine atoms: 9 mol%

Polymer composition consisting of.

[Polymer composition 2]... (Composition of the present invention)

In the above formula (4),

(2a): Hydrolyzable polymer at one end in which X ¹ in the above formula (4) is a group represented by the following formula (b), and X ² is a fluorine atom: 83 mol%,

(2b): Hydrolyzable polymer at both ends of a group in which X ¹ and X ² in the above formula (4) are represented by the following formula (b): 8 mol%,

(2c): Non-functional polymer in which both X ¹ and X ² in the formula (4) are fluorine atoms: 9 mol%

Polymer composition consisting of.

[Polymer composition 3]... (Composition for comparison)

In the above formula (4),

(3a): Hydrolyzable polymer at one end in which X ¹ in the formula (4) is a group represented by the following formula (c), and X ² is a fluorine atom: 83 mol%,

(3b): Hydrolyzable polymer at both ends of a group in which X ¹ and X ² in the above formula (4) are represented by the following formula (c): 8 mol%,

(3c): Non-functional polymer in which both X ¹ and X ² in the formula (4) are fluorine atoms: 9 mol%

Polymer composition consisting of.

[Polymer composition 4]... (Composition for comparison)

In the above formula (4),

(4a): Hydrolyzable polymer at one end in which X ¹ in the above formula (4) is a group represented by the following formula (d), and X ² is a fluorine atom: 83 mol%,

(4b): Hydrolyzable polymer at both ends of a group in which X ¹ and X ² in the above formula (4) are represented by the following formula (d): 8 mol%,

(4c): Non-functional polymer in which both X ¹ and X ² in the formula (4) are fluorine atoms: 9 mol%

Polymer composition consisting of.

[Preparation of Coating Composition]

The above polymer compositions 1 to 4 were diluted and dissolved to a concentration of 0.08% by mass with a fluorine-based solvent Novec7 (registered trademark) 200 (manufactured by 3M; ethyl perfluorobutyl ether) dehydrated to a water content of 10 ppm or less to obtain a coating composition prepared

[Formation of Cured Film on Glass Substrate]

After cleaning the surface of the chemically strengthened glass (50 mm × 100 mm, Gorilla 3 manufactured by Corning) by plasma treatment (Ar: 10 cc, O ₂ : 80 cc, output: 250 W, time: 30 seconds), each of the above coating compositions It was spray-coated with a spray coating device (NST-51, manufactured by T&K Co., Ltd.), and cured for 1 hour in an atmosphere of 80°C and 80% humidity to form a cured film having a thickness of 7 to 8 nm.

[Evaluation of water and oil repellency]

The contact angle of the cured film to water (water repellency) and the contact angle to oleic acid (oil repellency) were measured using a contact angle meter Drop Master (manufactured by Kyowa Kaimen Chemical Co., Ltd.).

[Measurement of dynamic friction coefficient]

The dynamic friction coefficient for Bemcot (manufactured by Asahi Kasei Co., Ltd.) was measured under the following conditions using a surface tester 14FW (manufactured by Shinto Kagaku Co., Ltd.).

Contact Area: 35mm×35mm

Load: 200g

[Evaluation of abrasion durability]

Using a rubbing tester (manufactured by Shinto Chemical Co., Ltd.), the surface of the cured film was rubbed with steel wool under the following conditions. Every 3,000 times of rubbing, the water contact angle of the surface of the cured film after rubbing was measured, and the number of times of friction at which the water contact angle of the cured film could maintain 100° or more was measured, and the number of wear durability was determined. At this time, the water contact angle was measured using a contact angle meter Drop Master (manufactured by Kyowa Kaimen Chemical Co., Ltd.). The test environment conditions are 25 ° C. and 40% humidity.

Steel wool: BONSTAR #0000 (manufactured by Nippon Steel Wool Co., Ltd.)

Travel distance (one way) 30mm

Moving speed 1,800mm/min

Load: 1 kg/cm ²

In addition, evaluation was made into the average number of times performed by N=8.

Cured films formed using Polymer Compositions 1 and 2 were used as Examples 1 and 2, and Comparative Examples 1 and 2 were cured films formed using Polymer Compositions 3 and 4. Table 1 shows the evaluation results.

As shown in Table 1, when a cured film is formed using the polymer composition of the present invention, excellent abrasion durability is exhibited. On the other hand, when the alkylene group adjacent to the hydrolyzable silyl group has two carbon atoms (Comparative Example 1), sufficient abrasion durability is not expressed. Comparative Example 2 having a cyclic siloxane structure is a structure described in Japanese Patent Application Laid-Open No. 2014-084405 and Japanese Patent Application Laid-open No. 2014-077836, but these are also inferior in abrasion durability compared to this Example.

Claims (14)

The following general formula (1)

(In the formula, the Rf group is a group represented by -(CF ₂ ) _d -(OY) _e -O(CF ₂ ) _d -, d is each independently an integer of 0 or 1 to 5, and OY is OCF ₂ CF ₂ CF ₂ CF ₂ , OCF ₂ CF ₂ CF ₂ , OCF(CF ₃ )CF ₂ , OCF ₂ CF ₂ and OCF ₂ , which is one or two or more groups selected from the group consisting of random or block arrangement. and e is an integer of 5 to 200. A is a monovalent fluorine-containing group having a terminal -CF ₃ group, Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond, and X is a hydrolyzable group , and c is an integer from 3 to 8.)
A linear fluorooxyalkylene group-containing polymer represented by (hereinafter referred to as a single-end hydrolysable polymer), and the following general formula (2)

(In the formula, Rf, Q, X, c are the same as in formula (1) above.)
Hydrolyzability at both ends with respect to the total mole of the hydrolysable polymer at one end and the hydrolysable polymer at both ends, including a linear fluorooxyalkylene group-containing polymer (hereinafter referred to as a hydrolysable polymer at both ends) represented by A coating agent composition characterized in that the polymer content is greater than 0 mol% and less than 20 mol%. According to claim 1,
Equation (3)
A-Rf-A (3)
(In the formula, Rf and A are as described above.)
It further contains a fluorooxyalkylene group-containing polymer (hereinafter referred to as a non-functional polymer) represented by and further hydrolysable at one end with respect to the total moles of the hydrolysable polymer at one end, the hydrolysable polymer at both ends and the non-functional polymer A coating composition characterized in that the polymer content is 65 mol% or more and less than 100 mol%, and the content of the hydrolyzable polymer at both ends is more than 0 mol% and less than 20 mol%. The coating composition according to claim 2, wherein the content of the non-functional polymer relative to the total mole of the hydrolyzable polymer at one end, the hydrolyzable polymer at both ends, and the non-functional polymer is greater than 0 mol% and less than 30 mol%. . The coating composition according to claim 1, further comprising a fluorine-based solvent. The coating agent composition according to claim 1, wherein in the general formulas (1) and (2), the divalent hydrocarbon group Q is a group represented by the following formula.
-CH ₂ OCH ₂ CH ₂ CH ₂ -
(However, the left end is connected to the Rf group, and the right end is connected to Si.) The method according to claim 1, characterized in that the hydrolyzable group X in the general formula (1) and general formula (2) is at least one group selected from a methoxy group, an ethoxy group, an isopropenoxy group and an acetoxy group. coating composition. An article having a cured film of the coating agent composition according to any one of claims 1 to 6 on its surface. An optical article having on its surface a cured film of the coating agent composition according to any one of claims 1 to 6. The touch panel which has the cured film of the coating agent composition in any one of Claims 1-6 on the surface. An antireflection film having on its surface a cured coating of the coating agent composition according to any one of claims 1 to 6. The _SiO2 treated glass which has on the surface the cured film of the coating agent composition of any one of Claims 1-6. A tempered glass having on its surface a cured film of the coating agent composition according to any one of claims 1 to 6. A quartz substrate having on its surface a cured film of the coating agent composition according to any one of claims 1 to 6. A method for treating the surface of an article, comprising a step of treating the surface of the article by a dry coating method or a wet coating method using the coating composition according to any one of claims 1 to 6.