TWI717417B - Coating composition - Google Patents

Abstract

(式中，Rf基係-(CF₂)_d-(OY)_e-O(CF₂)_d-之基，d為0~5，OY係選自OCF₂CF₂CF₂CF₂、OCF₂CF₂CF₂、OCF(CF₃)CF₂、OCF₂CF₂及OCF₂的1種或2種以上之基，e為5~200；A係末端為-CF₃基的1價含氟基，Q係2價烴基，X係水解性基，c為3~8)，相對於前述單末端水解性聚合物與前述兩末端水解性聚合物之合計莫耳，兩末端水解性聚合物之含有比例為超過0莫耳%且未達20莫耳%。 A coating agent composition comprising the single-terminal hydrolyzable polymer of formula (1) and the two-terminal hydrolyzable polymer of formula (2),

(In the formula, Rf base is -(CF ₂ ) _d -(OY) _e -O(CF ₂ ) _d -base, d is 0~5, OY is selected from OCF ₂ CF ₂ CF ₂ CF ₂ , OCF ₂ One or more groups of CF ₂ CF ₂ , OCF(CF ₃ )CF ₂ , OCF ₂ CF ₂ and OCF ₂ , e is 5 to 200; A is a monovalent fluorine-containing group with a -CF ₃ group at the end , Q is a divalent hydrocarbon group, X is a hydrolyzable group, c is 3-8), relative to the total mole of the aforementioned single-terminal hydrolyzable polymer and the aforementioned two-terminal hydrolyzable polymer, the content of the two-terminal hydrolyzable polymer The ratio is more than 0 mol% and less than 20 mol%.

With the composition of the present invention, excellent water and oil repellency, low dynamic friction, and scratch resistance can be imparted to the surface of the substrate in a short time.

Description

Coating composition

The present invention relates to a coating composition effective as a surface modifier for forming a layer that imparts functions such as antifouling and low friction (slidability) on the surface of various substrates, and the coating composition The surface treatment method of an article in which a hardened film of the composition is formed by treating the coating composition and the article using the coating composition.

Generally speaking, compounds containing perfluorooxyalkylene groups have very low surface free energy, and therefore have water and oil repellency, chemical resistance, lubricity, mold release, antifouling properties, and the like. Utilizing this property, it is widely used industrially as a water and oil repellent antifouling agent for paper, fiber, etc., a slip agent for magnetic recording media, an oil repellent for precision machinery, mold release agents, cosmetics, and protective films.

However, this property also means non-adhesion and non-adhesion to other substrates. Even if it can be coated on the surface of the substrate, it is difficult to make the film adhere to it.

On the other hand, as a material for bonding the surface of a substrate such as glass or cloth to an organic compound, a silane coupling agent is well known. Silane coupling agent contains amino group, epoxy group, (meth)acryloxy group, etc. in 1 molecule Monovalent hydrocarbon group with organic functional group and reactive silyl group (generally hydrolyzable silyl group such as alkoxysilyl group, etc.). Hydrolyzable silyl groups such as alkoxysilyl groups undergo a self-condensation reaction due to moisture (moisture) in the air to form siloxanes to form a film. At the same time, hydrolyzable silyl groups such as alkoxysilyl groups are chemically and physically bonded to the surface of glass or metal to form a durable and strong film. The silane coupling agent is widely used as a coating agent for the surface of various substrates by taking advantage of this property, and it is proposed to apply the compound of the silane coupling agent in order to impart the characteristics of perfluorooxyalkylene to the surface of the substrate.

In Patent Document 1, by coating a fluoroaminosilane compound represented by the following formula on glass, high water and oil repellency is achieved. However, this compound-based perfluoroalkylene chain is short and cannot sufficiently exhibit lubricity, mold releasability, and antifouling properties.

(In the formula, R ⁶ and R ⁷ are alkyl groups with 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 from 0 to 8, and i is 2 or 3).

In addition, 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 the main chain, and therefore the dirt wiping property or lubricity is insufficient.

(In the formula, X represents a hydrolyzable group, R ⁸ represents a monovalent hydrocarbon group, R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group, and R ⁹ represents an alkylene group into which an NH group can be inserted. j is an integer from 14 to 49, and k is 2. Or 3).

Patent Document 3 describes a perfluoropolyether-modified silane containing a linear perfluorooxyalkylene group represented by the following formula. Although the lens or anti-reflection film treated with the perfluoropolyether modified silane has excellent sliding properties, mold release properties, and abrasion resistance, the lubricity is insufficient because both ends are fixed to the substrate.

(In the formula, Rf is a divalent linear perfluoropolyether group, R is an alkyl or phenyl group with 1 to 4 carbon atoms, and X is a hydrolyzable group, l is 0-2, and m is between 1 and 5. Integer, a is 2 or 3).

Patent Document 4 describes a perfluoropolyether-modified silane represented by the following formula as a treatment agent for improving lubricity. However, since this compound does not have a fluorine-containing group at the terminal, it has poor water and oil repellency, low dynamic friction, and mold release properties.

(X ² Q) _β Rf(QZ ¹ A _α ) _{2- β}

(In the formula, Rf is a divalent perfluoroether residue-containing group, Q is a divalent organic group, Z ¹ and Z ² are organopolysiloxane residues, and A is a monovalent group with a terminal reactive silyl group Base, α is an integer from 1 to 8, β is a number greater than 0 and less than 2).

Patent Document 5 describes a surface treatment agent comprising a polymer composition containing a fluorooxyalkylene group, the composition system comprising: -(CF ₂ ) _d -(OC ₂ F ₄ ) _e (OCF ₂ ) _f -O (CF ₂ ) _d -A polymer containing a linear fluorooxyalkylene group with a hydrolyzable silyl group at one end as the main chain structure, and -(CF ₂ ) _d -(OC ₂ F ₄ ) _e (OCF ₂ ) _f -O(CF ₂ ) _d -is a polymer containing linear fluorooxyalkylene groups with hydrolyzable silyl groups at both ends as the main chain structure, and is relative to a single-end hydrolyzable polymer The total moles of the hydrolyzable polymer at both ends, the content of the hydrolyzable polymer at both ends is 0.1 mol% or more and less than 10 mol%; but wet coating such as spray coating, the heating time is short Under the conditions, the hardening is insufficient, and sufficient abrasion durability cannot be exerted.

Patent Document 6 describes that alkali resistance and acid resistance are improved by having a cyclic siloxane residue at the connection site, but on the other hand, the steel wool abrasion durability cannot achieve satisfactory performance.

Patent Document 7 describes that by introducing isopropenyl groups into the hydrolyzable silyl groups, it is possible to harden in a short time even in wet coating such as spray coating. However, there is also abrasion durability against steel wool. The performance cannot meet the requirements of recent years.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 58-167597

[Patent Document 2] JP 2000-143991 A

[Patent Document 3] JP 2003-238577 A

[Patent Document 4] JP 2007-297589 A

[Patent Document 5] JP 2012-072272 A

[Patent Document 6] JP 2014-084405 A

[Patent Document 7] JP 2014-077836 A

In recent years, coating manufacturers hope to provide a surface treatment material that can be cured in a short time after coating on a substrate to exhibit the above-mentioned surface characteristics (ie, excellent scratch resistance and low dynamic friction). Among the methods of coating the surface treatment agent on the substrate, there are dry coating methods such as vacuum evaporation and wet coating methods such as dip coating and spray coating.

The above-mentioned Patent Document 5 describes that the above-mentioned surface treatment agent whose polymer ends are trimethoxysilyl groups is coated on the surface of the substrate by vacuum evaporation, and then cured for 2 hours under an environment of 40°C and 80% humidity. This can provide a cured film with excellent scratch resistance and low dynamic friction. However, if the surface treatment agent is applied to the surface of the substrate by a wet coating method, there is a problem that a cured film having excellent surface characteristics cannot be obtained in the subsequent curing in a short time. This judgment is because when coating by vacuum evaporation, the SiO ₂ layer on the surface of the substrate can be cured in a short time to provide a cured film with excellent surface characteristics. However, when coating by wet coating method, the coating The SiO ₂ layer is not evaporated during cloth.

Therefore, the object of the present invention is to provide a coating agent composition that can provide a cured coating film with excellent surface characteristics, especially excellent wear durability and low dynamic friction, even if the curing time after coating is short, such as a wet coating method. Surface treatment methods for various articles on which a cured film of the composition is formed, and articles using the composition.

In order to solve the above-mentioned problems, the inventors intensively studied and found that when the polymer has 3 hydrolyzable silyl groups via 3 siloxane bonds at each end, the 3 hydrolyzable silyl groups are respectively bonded to The Si atom in the intermediate connection site, as shown in the general formula (1) and general formula (2), when each alkylene adjacent to each hydrolyzable silyl group has at least 3 carbon atoms, it can provide short-time curability The hardened film with excellent abrasion durability has finally completed the present invention. Furthermore, Patent Document 5 and Patent Document 7 do not clearly indicate that the structure of the present invention is included in the text and the examples.

That is, the present invention provides the following coating agent composition and a surface treated with the coating agent composition (surface modifier) (ie, a cured film having the coating agent composition on the surface) Surface treatment methods for various articles and articles using the coating composition.

[1] A coating agent composition characterized by comprising a linear fluorooxyalkylene-containing polymer represented by the following general formula (1) (hereinafter referred to as a single-terminal hydrolyzable polymer) and the following general formula (1) A polymer containing linear fluorooxyalkylene groups represented by formula (2) (hereinafter referred to as a two-terminal hydrolyzable polymer),

(In the formula, Rf group is represented by -(CF ₂ ) _d -(OY) _e -O(CF ₂ ) _d -, d is each independently 0 or an integer of 1~5, OY is selected from 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 are a group of one or more groups, the order of arrangement can be random Or block, e is an integer of 5 to 200; A is a monovalent fluorine-containing group with a -CF ₃ group at the end, Q is a divalent hydrocarbon group with 2 to 6 carbons that may contain an ether bond, and X is a hydrolyzable group, c is an integer from 3 to 8);

(In the formula, Rf, Q, X, and c are the same as the above formula (1)); relative to the total mole of the aforementioned single-terminal hydrolyzable polymer and the aforementioned two-terminal hydrolyzable polymer, the ratio of the two-terminal hydrolyzable polymer The content ratio exceeds 0 mol% and does not reach 20 mol%.

[2] The coating composition as described in [1], which further contains a fluorooxyalkylene group-containing polymer represented by the following formula (3) (hereinafter referred to as non-functional polymer), A-Rf- A (3)

(In the formula, Rf and A are the same as those described above); and, compared to the one-terminal hydrolyzable polymer The total mole of the compound and the non-functional polymer, the content of the hydrolyzable polymer at one end is 65 mole% or more and less than 100 mole%, and the content of the hydrolyzable polymer at both ends is more than 0 mole Ear% and less than 20 mol%.

[3] The coating composition according to [2], wherein the content ratio of the non-functional polymer relative to the total mole of the single-terminal hydrolyzable polymer, the two-terminal hydrolyzable polymer and the non-functional polymer It is more than 0 mol% and less than 30 mol%.

[4] The coating agent composition according to any one of [1] to [3], which further contains a fluorine-based solvent.

[5] The coating composition according to any one of [1] to [4], wherein in the general formula (1) and the general formula (2), the divalent hydrocarbon group Q is represented by the following formula Group, -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] The coating composition according to any one of [1] to [5], wherein in the general formula (1) and the general formula (2), the hydrolyzable group X is selected from the group consisting of methoxy and ethyl At least one group of an oxy group, an isopropenoxy group, and an acetoxy group.

[7] An article having a cured film of the coating composition described in any one of [1] to [6] on the surface.

[8] An optical article having a cured film of the coating composition described in any one of [1] to [6] on the surface.

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

[10] An anti-reflection film having a cured film of the coating composition described in any one of [1] to [6] on the surface.

[11] A SiO ₂ treated glass having a cured film of the coating composition described in any one of [1] to [6] on the surface.

[12] A strengthened glass having a cured film of the coating composition described in any one of [1] to [6] on the surface.

[13] A quartz substrate having a cured film of the coating composition described in any one of [1] to [6] on the surface.

[14] A method for surface treatment of an article, comprising the step of using the coating composition as described in any one of [1] to [6] to treat the surface of the article by a dry coating method or a wet coating method .

The coating composition (surface modifier) of the present invention can provide excellent water and oil repellency, low dynamic friction and scratch resistance to the surface of the substrate in a short time by dry coating method and wet coating method , Especially even in the wet coating method, the curing time is short, and the above performance can also be exerted.

[The form of implementing the invention]

The coating composition of the present invention comprises a single-terminal hydrolyzable polymer represented by the following general formula (1)) and a two-terminal hydrolyzable polymer represented by the following general formula (2),

Relative to the total mole of the aforementioned single-terminal hydrolyzable polymer and the aforementioned two-terminal hydrolyzable polymer, the content of the two-terminal hydrolyzable polymer is more than 0 mol% and less than 20 mol%, preferably 0.1~ 18 mol%, more preferably 0.5-15 mol%, particularly preferably 1-10 mol% (that is, a coating composition characterized by the fact that relative to the aforementioned single-terminal hydrolyzable polymer and the aforementioned two-terminal The total mole of the two components of the hydrolyzable polymer, the content of the single-end hydrolyzable polymer is 80 mole% or more and less than 100 mole%, preferably 82~99.9 mole%, more preferably 85~ 99.5 mol%, particularly preferably 90~99 mol%).

In the above general formula (1), A is a monovalent fluorine-containing group whose terminal is a -CF ₃ group, preferably a linear or branched perfluoroalkyl group of 1 to 6, specifically three Fluoromethyl, pentafluoroethyl, heptafluoropropyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, nonafluorobutyl, 1,1-bis(trifluoromethyl) Yl)-2,2,2-trifluoroethyl, undecafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptafluorooctyl, etc., among which trifluoromethyl and pentafluoroethyl are preferred Group, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorohexyl, particularly preferably trifluoromethyl, pentafluoroethyl, and heptafluoropropyl.

In the above general formula (1) and general formula (2), the Rf group is represented by -(CF ₂ ) _d -(OY) _e -O(CF ₂ ) _d -, and d is each independently 0 or 1 an integer of 5 ~, OY selected from the group consisting of _{OCF 2 CF 2 CF 2 CF 2} , OCF 2 CF 2 CF 2, OCF (CF 3) CF 2, OCF 2 CF 2 OCF ₂ and formed by a group of one or two For more than one base, the arrangement order can be random or block, and e is an integer from 5 to 200.

In the above general formula (1) and general formula (2), Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond. Examples include the following groups (in the following examples, the left end It is connected to the Rf group, and the right end is connected to S).

In the above general formula (1) and general formula (2), c is an integer of 3-8, preferably an integer of 3-6.

In the above general formula (1) and general formula (2), the X-based hydrolyzable group includes, for example, alkoxy such as methoxy, ethoxy, and propoxy, trifluoromethoxy, trifluoro Halogenated alkoxy such as ethoxy and trichloroethoxy, alkoxy substituted alkoxy such as methoxyethoxy, acetyloxy, propionyloxy, benzyloxy, etc. Alkenyloxy group, isopropenyloxy group, isobutenoxy group, etc., dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, etc., ketoxime group, cyclohexane oxime group, etc. Substituted amino groups such as iminooxy, methylamino, ethylamino, dimethylamino, diethylamino, etc., N-methyl acetylamino, Amino groups such as N-ethylamino groups, substituted amine groups such as dimethylaminooxy and diethylaminooxy groups, halogen groups such as chlorine atoms, etc. In the example of X, methoxy group, ethoxy group, trifluoroethoxy group, acetoxy group, isopropenoxy group, chlorine atom, dimethyl ketoxime group, methyl ethyl ketoxime group are preferred. , Particularly preferred are methoxy, ethoxy, and isopropenoxy. The X series can be contained in the hydrolyzable polymer of the present invention as one type or a combination of two or more types.

The coating composition of the present invention (hereinafter, also referred to as a fluorooxyalkylene-containing polymer composition) may further contain a fluorooxyalkylene-containing polymer represented by the following formula (3) (hereinafter referred to as Non-functional polymer), A-Rf-A (3)

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

When the fluorooxyalkylene-containing polymer used in the present invention contains the aforementioned non-functional polymer, it is relative to the aforementioned single-terminal hydrolyzable polymer, two-terminal hydrolyzable polymer and the three-component non-functional polymer The total moles, the ratio of the single-end hydrolyzable polymer is 65 mole% or more, preferably 70 mole% or more, more preferably 80 mole% or more, and less than 100 mole%, and both ends are hydrolyzed The proportion of the sexual polymer is more than 0 mol% and less than 20 mol%, preferably 0.1-18 mol%, more preferably 1-10 mol%. The proportion of the non-functional polymer is preferably more than 0 mol% and less than 30 mol%, preferably 1-25 mol%, and more preferably 5-20 mol%.

The above-mentioned fluorooxyalkylene-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 a carboxylic acid at both ends, to produce a fluorooxyalkylene-containing polymer having a carboxylic acid group at one end (hereinafter referred to as single-end A mixture of a carboxylic acid polymer) and a fluorooxyalkylene group-containing polymer having a carboxylic acid group at both ends (hereinafter referred to as a two-terminal carboxylic acid polymer). In this partial fluorination reaction, the introduction rate of terminal -CF ₃ groups can be appropriately adjusted by adjusting the amount of fluorine gas supplied and controlling fluorination. The mixture obtained in this step may also contain a fluorooxyalkylene group-containing polymer (hereinafter referred to as a non-functional polymer) that does not have a carboxylic acid group at the terminal.

(ii) The mixture containing the single-terminal carboxylic acid polymer and the two-terminal carboxylic acid polymer is subjected to adsorption treatment and/or molecular distillation treatment to obtain a high concentration of a fluorooxyalkylene-containing alkyl group having a carboxylic acid group at one end The polymer is basically a 3-component polymer composition. The method of adsorption treatment and/or molecular distillation treatment can be in accordance with well-known methods. By this step, the content ratio 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 can be adjusted.

(iii) The terminal carboxylic acid group in the three-component polymer composition is modified, and a group having an aliphatic unsaturated group at the terminal is introduced. The introduction method can follow a well-known method. For example, first, the three-component polymer composition containing the terminal carboxylic acid group is fed to reduction using a metal hydride or contact hydrogenation using a noble metal catalyst to form a terminal hydroxyl group (hydroxymethyl) as shown below: The three-component polymer composition (wherein, the Rf group is the same as the above).

[Chemical 9] CF ₃ -Rf-CH ₂ OH HOH ₂ C-Rf-CH ₂ OHCF ₃ -Rf-CF ₃

Next, an aliphatic unsaturated group is introduced into the terminal hydroxyl group of the three-component polymer composition obtained above. The introduction system of the aliphatic unsaturated group to the terminal hydroxyl group can be performed according to a well-known method. Through this step, a terminal aliphatic unsaturated group-containing three-component polymer composition having an alkenyl group such as an allyl group introduced into the terminal is produced as shown below.

[Chemical 10] CF ₃ -Rf-CH ₂ OCH ₂ CH=CH ₂ CH ₂ =CHCH ₂ OCH ₂ -Rf-CH ₂ OCH ₂ CH=CH ₂ CF ₃ -Rf-CF ₃

(iv) Next, an organosilicon compound having 1 SiH group and 3 hydrolyzable groups at the terminal aliphatic unsaturated group of the aforementioned 3-component polymer composition, such as trimethoxysilane, is subjected to hydrosilylation addition reaction. The addition reaction system can be carried out under well-known reaction conditions, and the addition reaction catalyst can be carried out in the presence of a platinum group compound, for example. Through this step, a three-component polymer composition having a hydrolyzable silyl group at the terminal as shown below is produced.

[Chem. 11] CF ₃ -Rf-CH ₂ O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (CH ₃ O) ₃ Si(CH ₂ ) ₃ OCH ₂ -Rf-CH ₂ O(CH ₂ ) ₃ Si( OCH ₃ ) ₃ CF ₃ -Rf-CF ₃

(v) Next, the composition of the above-mentioned 3-component polymer The hydrolyzable silyl group of the substance makes tetramethyldisiloxane (1,3-dihydro-1,1,3,3-tetramethyldisiloxane) co-hydrolyzed in the presence of hydrochloric acid or sulfuric acid to produce as follows The polymer composition of a 3-component system with 3 SiH groups at the end is described. The method of cohydrolysis can be according to well-known methods.

(vi) Next, an organosilicon compound having an aliphatic unsaturated group at one end and a hydrolyzable silyl group at the other end is added to the SiH group in the aforementioned 3-component polymer composition. The addition reaction system can be carried out under well-known reaction conditions, and the addition reaction catalyst can be carried out in the presence of a platinum group compound, for example. Through this step, the fluorooxyalkylene-containing polymer composition of the present invention can be obtained as a three-component polymer composition.

The single-end and both-end hydrolyzable polymers used in the coating composition of the present invention are preferably based on the number average molecular weight of polystyrene conversion obtained by gel permeation chromatography, preferably 500 or more 40,000 Below, it is particularly preferably 1,000 to 30,000, and more preferably 1,000 to 20,000. When the number average molecular weight is less than 500, there are water and oil repellency, antifouling properties, etc. that cannot fully exhibit the characteristics of the fluorooxyalkylene group. In the case of more than 40,000, the concentration of terminal functional groups If the degree becomes too small, the reactivity or adhesion with the substrate may decrease.

The number average molecular weight mentioned 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 below).

[Measurement conditions]

Developing solvent: Hydrochlorofluorocarbon (HCFC)-225

Flow rate: 1mL/min.

Detector: Evaporative light scattering detector

Column: TSKgel Multipore HXL-M manufactured by Tosoh Corporation

×30cm 使用2支 7.8mm

×30cm use 2

Column temperature: 35℃

Sample injection volume: 100μL (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, isopropanol, etc.), hydrocarbon solvents (petroleum ether, mineral spirits, toluene, xylene, etc.), ester solvents (ethyl acetate, acetic acid, etc.) Isopropyl ester, butyl acetate, etc.), ether solvents (diethyl ether, isopropyl ether, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), preferably Use polar solvents such as alcohols, esters, ethers, ketones, etc., in terms of solubility, wettability, safety, etc., isopropyl alcohol and methyl isobutyl ketone are particularly preferred. It is also preferable to use a fluorine-based solvent (perfluorinated solvent). As examples, fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, etc.), fluorinated aromatic hydrocarbon solvents (hexafluorom-xylene, trifluoromethyl) Fluoromethylbenzene Etc.), fluorinated ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl Ether etc.] Among them, fluorinated ether-based solvents are preferably used in terms of solubility and wettability.

In addition, the above-mentioned solvent system may be used individually by 1 type, and may mix and use 2 or more types, and it is preferable to use the one which dissolves the said component uniformly.

The amount of solvent used is not particularly limited, and the most suitable concentration varies depending on the treatment method. In the vapor deposition application, it is generally preferable to use an amount such that the solid content in the coating composition becomes 1 to 80% by mass, especially 5 to 50% by mass. In the case of spray coating or dip coating, it is preferable to use an amount such that the solid content in the composition becomes 0.05 to 20.0% by mass, especially 0.1 to 1.0% by mass. Furthermore, the amount of solid content means the mass of non-volatile content.

When a fast curing speed is required for the coating composition composition, a curing catalyst may be added as needed. Examples of hardening catalysts include organic titanates, organic titanium chelate compounds, organic aluminum compounds, organic zirconium compounds, organic tin compounds, metal salts of organic carboxylic acids, amine compounds and their salts, and quaternary ammonium compounds , Lower fatty acid salts of alkali metals, dialkylhydroxylamines, guanidine group-containing organosilicon compounds, inorganic acids, perfluorocarboxylic acids, perfluoroalcohols, etc., preferably perfluorocarboxylic acids are used.

The addition amount of the hardening catalyst is a catalytic amount, relative to the fluorine-containing organosilane compound of the present invention, its partial hydrolyzate or their partial hydrolyzed condensate (ie, single-terminal and two-terminal hydrolyzable polymers and these parts The total amount of hydrolyzate and partial hydrolysis condensate (total polymer components Amount) 100 parts by mass, preferably 0.05-5 parts by mass, particularly preferably 0.01-1 parts by mass.

As a method of applying the coating composition of the present invention thus obtained as a surface modifier to a substrate, there are wet coating methods such as brush coating, dipping, spraying, or vapor deposition treatment. Well-known methods such as dry coating method.

The treatment temperature of the applied coating composition (surface modifier) depends on the application method and the most suitable temperature is different. For example, when spray coating or dipping, it is preferably in the range of 10-100°C. It is advisable for the treatment humidity to be carried out under humidification to promote 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, especially 1 to 4 hours, and further 1 to 3 hours. The method of the present invention uses the above-mentioned surface modifier to provide a cured film having excellent surface properties, particularly excellent low dynamic friction and scratch resistance even after such a short time of curing. Furthermore, the above-mentioned treatment conditions should be appropriately optimized in accordance with the base material, curing catalyst, and the like.

The substrate system treated with the coating agent composition is not particularly limited, and can be various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. The coating composition system of the present invention can impart water and oil repellency to the aforementioned substrate. In particular, it can be suitably used as a surface modifier for chemically strengthened glass, SiO ₂ treated glass or thin film.

The thickness of the cured film of the coating composition formed on the surface of the various substrates or articles mentioned above depends on the type of substrate and is appropriately selected. However, it is preferably 1-100 nm, more preferably 3-20 nm.

The resulting film has water and oil repellency and high water slidability, and has superior durability compared to conventional products in heat resistance, chemical resistance, and UV resistance. Such characteristics are effective for uses that are exposed to water or ultraviolet rays and are not easy to maintain, or uses that are easy to adhere to such as grease or fingerprints, cosmetics, sunscreen lotions, human or animal excrement, and oil. Examples include automobiles, Window glass or tempered glass for trains, ships, aircrafts, high-rise buildings, etc., headlamp shades, outdoor products, telephone booths, large outdoor displays, bathroom products such as baths, washstands, cosmetics, kitchen materials, sinks, and art Provide coating to prevent fingerprint adhesion. In addition, it is also useful as a coating for preventing fingerprint adhesion of CDs, DVDs, etc., mold release agents or paint additives, and resin modifiers. In addition, medical applications such as car navigation devices, mobile phones, digital cameras, digital cameras, PDAs, portable audio players, car audios, game consoles, spectacle lenses, camera lenses, filters, sunglasses, gastroscopes, etc. Optical articles such as machines, photocopiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, etc. Since the surface modifier of the present invention can prevent fingerprints and sebum from adhering to the aforementioned articles, and can impart damage resistance, it is particularly useful as a water and oil repellent layer for touch panel displays, anti-reflection films, etc.

[Example]

Below, examples and comparative examples are shown, and more specifically, the present invention is not limited by the following examples.

Polymer composition containing fluorooxyalkylene

The following four types of polymer compositions were prepared.

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

In the following formula (4)

[Chemical 13] X ¹ -CF ₂ -(OCF ₂ ) _p (OCF ₂ CF ₂ ) _q -OCF ₂ -X ² (4)

(p/q=0.9, p+q≒45. In addition, the polymer contains (OCF ₂ CF ₂ CF ₂ ) units and (OCF ₂ CF ₂ CF ₂ CF ₂ ) units, but they are not added to In the description of chemical formula (4)), from (1a): the above-mentioned formula (4) X ¹ is a group represented by the following formula (a) and X ² is a fluorine atom single-terminal hydrolyzable polymer: 83 mol %, (1b): X ¹ and X ^{2 of the} aforementioned formula (4) are both terminal hydrolyzable polymers represented by the following formula (a): 8 mol%, (1c): the aforementioned formula (4) X ¹ and X ² are non-functional polymers with fluorine atoms: a polymer composition composed of 9 mol%.

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

In the aforementioned formula (4), (2a): The single-terminal hydrolyzable polymer in which X ¹ of the aforementioned formula (4) is a group represented by the following formula (b) and X ² is a fluorine atom: 83 mol%, (2b): X ¹ and X ^{2 of the} aforementioned formula (4) are both terminal hydrolyzable polymers represented by the following formula (b): 8 mol%, (2c): X of the aforementioned formula (4) ^1. X ^{2 is} a non-functional polymer with fluorine atoms: a polymer composition composed of 9 mol%.

[Polymer composition 3]...(comparative composition)

In the aforementioned formula (4), from (3a): the aforementioned formula (4) X ¹ is a group represented by the following formula (c) and X ² is a fluorine atom single-terminal hydrolyzable polymer: 83 mol%, (3b): X ¹ and X ^{2 of the} aforementioned formula (4) are both terminal hydrolyzable polymers represented by the following formula (c): 8 mol%, (3c): X of the aforementioned formula (4) ^1. X ^{2 is} a non-functional polymer with fluorine atoms: a polymer composition composed of 9 mol%.

[Polymer composition 4]...(comparative composition)

In the aforementioned formula (4), from (4a): the aforementioned formula (4) X ¹ is a group represented by the following formula (d) and X ² is a fluorine atom single-terminal hydrolyzable polymer: 83 mol%, (4b): X ¹ and X ^{2 of the} aforementioned formula (4) are both terminally hydrolyzable polymers represented by the following formula (d): 8 mol%, (4c): X of the aforementioned formula (4) ^1. X ^{2 is} a non-functional polymer with fluorine atoms: a polymer composition composed of 9 mol%.

[Preparation of coating composition]

Use the fluorine-based solvent Novec7 (registered trademark) 200 (manufactured by 3M Company; ethyl perfluorobutyl ether), which has been dehydrated to a moisture content of 10 ppm or less, to dilute and dissolve the above polymer composition 1 to 4 to a concentration of 0.08 mass %, and prepare the coating composition.

[Form a hardened film on the glass substrate]

After cleaning the surface of chemically strengthened glass (50mm×100mm, Gorilla3 manufactured by Corning) with plasma treatment (Ar: 10cc, O ₂ : 80cc, output: 250W, time: 30 seconds), spray coating An apparatus (manufactured by T&K Co., Ltd., NST-51) spray-coated each of the above-mentioned coating agent compositions, and cured for 1 hour in an environment of 80° C. and a humidity of 80% to form a cured film with a thickness of 7 to 8 nm.

[Evaluation of water and oil repellency]

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

[Measurement of Dynamic Friction Coefficient]

Using a surface tester 14FW (manufactured by Shinto Scientific Co., Ltd.), the coefficient of dynamic friction with respect to Bemcot (manufactured by Asahi Kasei Co., Ltd.) was measured under the following conditions.

Contact area: 35mm×35mm

Load: 200g

[Evaluation of Abrasion Durability]

Using a friction tester (manufactured by Shinto Scientific Co.), under the following conditions, wipe the surface of the hardened film with steel wool. Every 3000 wipes, measure the water contact angle of the hardened film surface after wiping, and measure the number of wipes that the water contact angle of the hardened film can be kept above 100°, which is regarded as abrasion durability times number. The measurement of the water contact angle was performed using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). The above-mentioned test environmental conditions are 25°C and 40% humidity.

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

Moving distance (one way) 30mm

Moving speed 1,800mm/min

Load: 1kg/cm ²

In addition, the evaluation system is an average number of times performed at N=8.

The cured films formed using the polymer compositions 1 and 2 were regarded as Examples 1 and 2, and the cured films formed using the polymer compositions 3 and 4 were regarded as Comparative Examples 1 and 2. The evaluation results are shown in Table 1.

As shown in Table 1, when the polymer composition of the present invention is used to form a cured film, it exhibits excellent abrasion durability. On the other hand, when the carbon number of the alkylene group adjacent to the hydrolyzable silyl group is 2 (Comparative Example 1), sufficient abrasion durability is not exhibited. Comparative Example 2 having a cyclic silicone structure is the structure described in Japanese Patent Application Publication No. 2014-084405 and Japanese Patent Application Publication No. 2014-077836, but these are also more durable than this. The embodiment is poor.

Claims (13)

A coating agent composition characterized by comprising a linear fluorooxyalkylene-containing polymer represented by the following general formula (1) (hereinafter referred to as a single-terminal hydrolyzable polymer) and the following general formula (2) ) Represents a polymer containing linear fluorooxyalkylene groups (hereinafter referred to as a two-terminal hydrolyzable polymer),

(In the formula, Rf group is represented by -(CF ₂ ) _d -(OY) _e -O(CF ₂ ) _d -, d is each independently 0 or an integer of 1~5, OY is selected from 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 are a group of one or more groups, the order of arrangement can be random Or block, e is an integer from 5 to 200; A is a monovalent fluorine-containing group with -CF ₃ at the end, Q is a divalent hydrocarbon group with 2 to 6 carbons that may contain ether bonds, and X is selected from alkoxy Hydrolyzable group of at least one of alkoxy group, halogenated alkoxy group, alkoxy-substituted alkoxy group, acyloxy group, alkenoxy group, ketoxime group and halogen group, c is an integer of 3-8);

(In the formula, Rf, Q, X, and c are the same as the above formula (1)); relative to the total mole of the aforementioned single-terminal hydrolyzable polymer and the aforementioned two-terminal hydrolyzable polymer, the ratio of the two-terminal hydrolyzable polymer The content ratio exceeds 0 mol% and does not reach 20 mol%. The coating agent composition of claim 1, which further contains a fluorooxyalkylene-containing polymer represented by the following formula (3) (hereinafter referred to as non-functional Polymer), A-Rf-A (3) (where Rf and A are the same as the above); and, relative to the total of a single-terminal hydrolyzable polymer, two-terminal hydrolyzable polymer and a non-functional polymer In mol, the content of the hydrolyzable polymer at one end 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%. Such as the coating composition of claim 2, wherein the content ratio of the non-functional polymer is more than 0 mole relative to the total mole of the single-terminal hydrolyzable polymer, the two-terminal hydrolyzable polymer and the non-functional polymer Ear% and less than 30 mol%. The coating agent composition according to any one of claims 1 to 3, which further contains a fluorine-based solvent. The coating agent composition according to any one of claims 1 to 3, wherein in the general formula (1) and the general formula (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 coating agent composition of any one of claims 1 to 3, wherein in the general formula (1) and the general formula (2), the hydrolyzable group X is selected from the group consisting of methoxy, ethoxy, and isopropoxy At least one group of acetyl group and acetoxy group. An optical article having a hardened coating film of the coating composition according to any one of claims 1 to 6 on the surface. A touch panel having a hardened film of the coating composition composition according to any one of claims 1 to 6 on the surface. An anti-reflection film having a cured coating film of the coating composition composition of any one of claims 1 to 6 on the surface. A SiO ₂ treated glass having a hardened coating film of the coating composition composition of any one of claims 1 to 6 on the surface. A strengthened glass having a hardened film of the coating composition composition according to any one of claims 1 to 6 on the surface. A quartz substrate having a cured coating film of the coating composition composition according to any one of claims 1 to 6 on the surface. A method for surface treatment of an article, which comprises the step of treating the surface of the article by a dry coating method or a wet coating method using the coating composition composition of any one of claims 1 to 6.