KR102338699B1 - Surface modifier, coating composition, and article - Google Patents

Abstract

〔식 중, A는 각각 가수분해성기 또는 비가수분해성기이고, 식 중, 2개 있는 (A)₃의 각각에 있어서, 적어도 1개의 A는 가수분해성기이다. X, Y¹ 및 Y²는 각각 2가의 연결기이다. PFPE는, 폴리(퍼플루오로알킬렌에테르)쇄를 나타낸다〕으로 표시되는 표면개질제를 제공한다.The present invention relates to a surface modifier capable of forming a film excellent in antifouling properties and slipperiness on a substrate such as a glass substrate, a coating composition comprising the surface modifier, and an article having a film obtained by using the composition For the purpose of providing, the following general formula (1)

[In the formula, A is a hydrolysable group or a non-hydrolysable group, respectively, in the formula, in each of two (A) ₃ , at least one A is a hydrolysable group. X, Y ¹ and Y ² are each a divalent linking group. PFPE represents a poly(perfluoroalkylene ether) chain].

Description

Surface modifiers, coating compositions and articles {SURFACE MODIFIER, COATING COMPOSITION, AND ARTICLE}

The present invention relates to a surface modifier capable of forming a film having excellent durability and excellent antifouling properties and sliding properties on a substrate such as a glass substrate, and a coating composition comprising the surface modifier. The present invention also relates to an article having a film obtained by using the coating composition.

In the touch panel, two transparent substrates made of glass, synthetic resin, or the like are disposed to face each other through a frame-shaped sealing material, and an input region composed of a transparent conductive film or a plurality of electrodes is provided inside the frame-shaped sealing member. Here, plastics, glass, etc. are mentioned as a transparent base material. The combination of the two transparent substrates includes, for example, plastic (film)/glass and glass/glass. Among them, the touch panel using the glass/glass combination has a very clear screen and excellent weather resistance. have characteristics. Therefore, it can be suitably used for portable devices, such as a smart phone and tablet PC used outdoors, and an in-vehicle use in which an intense temperature difference generate|occur|produces.

Since the touch panel is in contact with a human finger during use, contamination derived from the human body, such as fingerprints, sebum, and sweat, is easily attached. When these stains adhere, they are difficult to come off, and since they are conspicuous depending on the amount of light or the like, there is a problem of impairing visibility or aesthetics.

In order to solve this problem, a method has been taken in which a fluorine-containing compound having both water repellency and oil repellency is coated on the outermost layer touched by a human finger. Specifically, for example, a surface modifier comprising a compound having a silicon atom having a hydrolyzable group at one end and a perfluoroalkylene ether chain at the other end, and the surface modifier The organic solvent solution (coating composition) containing is disclosed (for example, refer patent document 1). However, in the surface modifier disclosed in Patent Document 1, there is a problem in that the resistance (antifouling property) to the adhesion of the stain is insufficient.

In addition, among the touch panels, for example, in a smartphone or a tablet PC, an operation (swiping) of tracing (sliding) a finger tip or a pen tip is performed on the touch panel. In recent years, the smoothness which does not feel the pinch of a fingertip or a pen tip at the time of this operation is calculated|required by a touchscreen screen. However, in the surface modifier disclosed in Patent Document 1, there is a problem that the above-described smoothness (slidability) is not sufficient.

Japanese Patent Laid-Open No. 2012-037896

An object of the present invention is to provide a surface modifier and a coating composition from which a film having excellent durability and excellent antifouling properties and sliding properties is obtained. Another object of the present invention is to provide an article having a film excellent in antifouling properties and sliding properties.

As a result of intensive studies, the present inventors have found that it is a compound having a poly(perfluoroalkylene ether) chain, a urethane bond, and a hydrolyzable silane, and a urethane bond is disposed at both terminals of the poly(perfluoroalkylene ether) chain In addition, it was found that a compound having a hydrolyzable silane at both ends of the compound, in which the urethane bond and the hydrolysable silane are located in the vicinity, is useful as a surface modifier for obtaining a film excellent in antifouling properties and slipperiness, etc. The present invention has been developed.

That is, the present invention, the following general formula (1)

[In the formula, A is a hydrolysable group or a non-hydrolysable group, respectively, in the formula, in each of two (A) ₃ , at least one A is a hydrolysable group. Z is a divalent linking group. Y ¹ and Y ² each represent a direct bond or a divalent linking group. PFPE represents a poly(perfluoroalkylene ether) chain]

It is to provide a surface modifier characterized in that represented by.

In addition, the present invention provides a coating composition comprising the surface modifier and the solvent.

In addition, the present invention provides an article characterized in that it has a film of the coating composition on a substrate.

The surface modifier or coating composition of the present invention can suitably form a film excellent in antifouling properties and slippage properties on an article. Therefore, it is particularly useful for applications requiring antifouling properties and sliding properties such as touch panels.

[Fig. 1] A chart of the IR spectrum of the surface modifier (1) obtained in Example 1. [Fig.
^{[Fig. 2] A chart of 1} H-NMR spectrum of the surface modifier (1) obtained in Example 1. [Fig.
^{[Fig. 3] A chart of 19} F-NMR spectrum of the surface modifier (1) obtained in Example 1. [Fig.

The surface modifier of the present invention has the following general formula (1)

[In the formula, A is a hydrolysable group or a non-hydrolysable group, respectively, in the formula, in each of two (A) ₃ , at least one A is a hydrolysable group. Z is a divalent linking group. Y ¹ and Y ² each represent a direct bond or a divalent linking group. PFPE represents a poly(perfluoroalkylene ether) chain].

The surface modifier of the present invention has two Si(A) ₃ , and, further, at least one A of each (A) ₃ is a hydrolysable group as represented by the general formula (1). By having such a silicon atom (reactive silyl group), the inventors speculate that the surface modifier of the present invention is covalently bonded to the surface of the substrate by the following reaction. One of the presumed reactions is hydrolysis to generate a silanol group, and the silanol group is dehydrated and condensed with hydroxyl groups on the surface of various substrates, preferably glass substrates, to be shared on the substrate surface. It is a binding reaction. Another presumed reaction is a reaction in which a hydrolyzable group is directly condensed with a hydroxyl group of a base material (in case the hydrolyzable group is an alkoxy group, dealcoholization condensation), and is covalently bonded to the base material surface. Since both ends of the product of the present invention can be bonded to the substrate at both ends, the surface modifier of the present invention adheres more strongly to the surface of the substrate than the conventional product by the covalent bond formed by their condensation reaction, and the surface modifier It is possible to form a film having excellent durability while having both antifouling properties and sliding properties exhibited by the poly(perfluoroalkylene ether) chain of .

As said hydrolysable group, For example, alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group; Alkoxy group-substituted alkoxy groups, such as a methoxyethoxy group; Acyloxy groups, such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; alkenyloxy groups such as isopropenyloxy group and isobutenyloxy group; imineoxy groups such as a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, and a cyclohexanoxime group; Substituted amino groups, such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group; amide groups such as N-methylacetamide group and N-ethylamide group; Substituted aminooxy groups, such as a dimethylaminooxy group and a diethylaminooxy group; Halogen, such as chlorine, etc. are mentioned. Among the hydrolysable groups, an alkoxy group is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable, since the rate of hydrolysis is high and a coating film having excellent durability while having both antifouling properties and sliding properties can be formed quickly. An alkoxy group having 1 to 3 atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

Examples of the non-hydrolyzable group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. can be heard Among them, an alkyl group having 1 to 3 carbon atoms is preferable because it is possible to avoid steric hindrance and to speed up the hydrolysis rate, and as a result, a film having excellent durability while having both antifouling properties and sliding properties can be formed quickly, A methyl group is more preferable.

The number of hydrolysable groups in (A) ₃ is at least one as described above, but two or more are preferable because a surface modifier capable of forming a film having more excellent durability is obtained, and A in (A) _{3 having two} It is more preferable that all are hydrolysable groups. That is, it is most preferable that there is no non-hydrolyzable group.

When it has two or more hydrolysable groups in said (A) ₃ , the said hydrolysable group may be the same or different. In addition, even when it has two or more non-hydrolysable groups, the said non-hydrolysable group may be the same or different.

Z in the said General formula (1) is a bivalent coupling group. Y ¹ and Y ² each represent a direct bond or a divalent linking group. As a divalent coupling group, a C1-C22 alkylene group etc. are mentioned, for example. Examples of the alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, 2 -Methylbutylene group, 2-methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group , 3,3-dimethylbutylene group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2- Methyl-2-pentylene group, 2-methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene group, 4-methyl- 2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3 -Ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexylene group, 5- Methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, 2-propylpentyl group Alkylene groups, such as a ren group, a 2,4, 4- trimethylpentylene group, and a decaoctylene group, etc. are mentioned.

As Z, since synthesis is easy and the surface modifier of the present invention can be obtained simply, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and a group of 1 to 3 carbon atoms is preferable. An alkylene group is more preferable, and an n-propylene group is particularly preferable.

In addition, as Y ¹ and Y ² , since the content of fluorine atoms is increased and it becomes a surface modifier for obtaining a film having more excellent antifouling properties, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 1 to 3 carbon atoms, respectively. A group is more preferable, and a methylene group is more preferable, respectively, from the point which is excellent in antifouling property and is easy to obtain industrially.

In the general formula (1), two Zs may be the same or different. In addition, the surface modifier of the present invention may be a mixture of modifiers each having a different Z.

^{Y 1} and Y ² in the general formula (1) may be the same or different. Further, the surface modifier of the present invention may be a mixture of modifiers ^{each having Y 1} and Y ^{2 different from each other.}

The surface modifier of the present invention has a urethane bond in its skeleton. By having this urethane bond, the polarity of the surface modifier of the present invention in the vicinity of the hydrolyzable groups at both terminals is improved. As a result, adhesion with the base material mentioned later, Preferably, a glass base material becomes favorable, and reaction with the base material surface advances efficiently. As a result, it is possible to suitably form a film having durability and excellent in antifouling properties and sliding properties on the article.

Specific examples of the surface modifier of the present invention are shown below. In the formula, PFPE represents a poly(perfluoroalkylene ether) chain.

The PFPE [poly(perfluoroalkylene ether) chain] possessed by the surface modifier of the present invention preferably has a structure in which perfluoroalkylene groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. can be heard The number of perfluoroalkylene groups having 1 to 3 carbon atoms may be one or a mixture of multiple types may be used, and specifically, those represented by the following Structural Formula 1 are exemplified.

(In Structural Formula 1, X is a perfluoroalkylene group. All of the Xs may have the same structure, and a plurality of structures may exist randomly or in block form)

As said X, the structure etc. shown below can be illustrated, for example.

Among these, the poly(perfluoroalkylene ether) chain has a large number of oxygen atoms serving as bending points that exhibit sliding properties, and there is no share structure that inhibits the bending motion of the chain, so X is purple. A luoromethylene group and a perfluoroethylene group are preferable, and it is particularly preferable that a perfluoromethylene group and a perfluoroethylene group coexist, including a point that is easy to obtain industrially. Moreover, when the said perfluoromethylene group and a perfluoroethylene group (b) coexist, the abundance ratio (a/b) (ratio of the number) is preferably 1/10 - 10/1.

As the surface modifier having a perfluoroalkylene group having 1 to 3 carbon atoms, those represented by the following structural formula are preferably exemplified.

[In the formula, A is a hydrolysable group or a non-hydrolysable group, respectively, in the formula, in each of two (A) ₃ , at least one A is a hydrolysable group. X is a perfluoroalkylene group having 1 to 3 carbon atoms in which all of them may have the same structure, and a plurality of structures may exist in random or block form. Z is an alkylene group having 1 to 6 carbon atoms. Y ¹ and Y ² are each an alkylene group having 1 to 3 carbon atoms. n is 6 to 300 in total]

The surface modifier represented by the formula (1-2-1) has a perfluoroalkylene group having 1 to 3 carbon atoms. As described above, by having a short chain, it becomes a flexible skeleton, and as a result, a film excellent in slidability can be formed on an article. 12-200 are more preferable, as for n in General formula (1), 30-150 are more preferable, 50-120 are still more preferable.

As the surface modifier represented by the above (1-2-1), for example, those represented by the following formula can be exemplified.

In the poly(perfluoroalkylene ether) chain, the total number of fluorine atoms contained in one poly(perfluoroalkylene ether) chain is in the range of 18 to 600, in terms of excellent stain removal and sliding properties. Preferably, it is in the range of 90-450, more preferably, it is in the range of 150-360.

The surface modifier of the present invention is, for example, the following general formula (2)

A diol represented by [wherein, Y ¹ and Y ² are each a divalent linking group], and the following general formula (3)

[Wherein, A is a hydrolysable group or a non-hydrolysable group, and at least one A is a hydrolysable group. Z is a divalent linking group.] It can obtain preferably by making the isocyanate represented by it.

^{Y 1} , Y ² , PFPE in the general formula (2), and Z and A in the general formula (3) are the same as in the general formula (1).

As diol represented by the said General formula (2), the diol etc. shown below can be illustrated, for example.

Among the general formulas (2-1) and (2-2), diols shown below can be preferably exemplified.

(X is a perfluoroalkylene group having 1 to 3 carbon atoms, all of which may have the same structure, and a plurality of structures may exist in random or block form. n is 6 to 300 in total to be〕

As isocyanate represented by the said General formula (3), the isocyanate etc. shown below can be illustrated, for example.

Z in the isocyanate compound represented by the above formulas (3-1) to (3-12) is preferably an alkylene group having 1 to 10 carbon atoms because synthesis is easy and the surface modifier of the present invention can be obtained simply, An alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 3 carbon atoms is still more preferable, and an n-propylene group is particularly preferable.

When the diol represented by the general formula (2) is reacted with the isocyanate represented by the general formula (3), the isocyanate represented by the general formula (3) with respect to 1 mol of the OH group contained in the general formula (2). It is preferable to add so that it may be 0.5 to 1.5 mol, more preferably so that it may be 0.9 to 1.1 mol, and it is most preferable to add so that it may be 0.98 to 1.02 mol.

In the reaction (urethanation reaction) of the diol represented by the general formula (2) and the isocyanate represented by the general formula (3), the diol represented by the general formula (2) and the diol represented by the general formula (3) In order to accelerate the reaction with isocyanate, for example, tertiary amines such as triethylamine and benzyldimethylamine, dibutyltin dilaurylate, dioctyltin dilaurylate, 2-ethylhexanoate tin, etc. of tin compound as a catalyst.

As for the addition amount of the said catalyst, 0.001-5.0 mass % is preferable with respect to the whole reaction mixture, More preferably, it is 0.01-1.0 mass %, More preferably, it is 0.02-0.2 mass %. The reaction time is preferably 1 to 10 hours. Moreover, as for reaction temperature, 30-120 degreeC is preferable, More preferably, it is 40-90 degreeC.

When performing the reaction (urethanation reaction) of the diol represented by the general formula (2) and the isocyanate represented by the general formula (3), the reaction system may be a solvent-free system, and acetone, methyl ethyl ketone, and toluene that are inactive to the isocyanate group , a solvent such as xylene or a fluorine-based solvent may be used as the reaction solvent.

The coating composition of the present invention contains the surface modifier of the present invention and a solvent. As said solvent, since the solvent containing a fluorine atom can melt|dissolve the surface modifier of this invention favorably, it can be used preferably.

Examples of the fluorine atom-containing solvent include hydrofluoroether, hydrofluorocarbon and perfluorocarbon. The solvent containing a fluorine atom may be linear, branched, or cyclic any, and may contain a hetero atom. Moreover, 2-12 are preferable and, as for carbon atom number of the solvent containing a fluorine atom, 4-10 are more preferable.

Examples of the hydrofluoroether include C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ , HCF ₂ and the like can be mentioned CF ₂ OCH ₂ CF _3. Examples of the hydrofluorocarbon include C ₄ F ₉ C ₂ H ₅ , (CF ₃ ) ₂ CFCHFCHFCF ₃ , C ₆ F ₁₃ H, C ₆ F ₁₃ C ₂ H ₅ , C ₈ F ₁₇ C ₂ H ₅ , CF ₃ (CF ₂ ) ₄ CHF ₂ , CF ₃ CH ₂ CFCH ₃ , CF ₃ (CHF) ₂ CF ₂ CF ₃ , and the like.

Examples of the perfluorocarbon include C ₃ F ₈ , C ₄ F ₁₀ , C ₅ F ₁₂ , C ₆ F ₁₄ , C ₇ F ₁₆ , C ₈ F ₁₈ , C ₉ F ₂₀ , C ₁₀ F _{22 .} , C ₁₁ F ₂₄ , C ₁₂ F ₂₆ , (C ₄ F ₉ ) ₃ N, perfluoro(1,2-dimethylcyclobutane), perfluoro(methylcyclohexane), perfluoro(2-butyltetra hydrofuran) and the like.

Among the solvents containing a fluorine atom, C ₄ F ₉ C ₂ H ₅ , (CF ₃ ) ₂ CFCHFCHFCF ₃ , C ₆ F ₁₃ H, C ₆ F ₁₃ C ₂ H ₅ , C ₄ F ₉ OCH ₃ , C ₄ It is preferable that at least one selected from the group consisting of F ₉ OC ₂ H ₅ , C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ and HCF ₂ CF ₂ OCH ₂ CF _{3 .}

As the content rate of the surface modifier in the coating composition of the present invention, a coating containing the surface modifier can be uniformly formed, and a coating having excellent durability can be formed by reacting favorably with the surface modifier and a substrate such as glass. Therefore, 0.01-50 mass % is preferable, 0.02-10 mass % is more preferable, 0.05-1 mass % is still more preferable.

The article of the present invention is characterized in that it has a coating of the coating composition of the present invention on a substrate. As said base material, Inorganic base materials, such as glass; and organic base materials such as acrylic resin, polycarbonate resin, polyester resin, polybutylene terephthalate resin, polypropylene resin, polyamide resin, polyurethane resin, polyvinyl chloride resin, and polyvinyl fluoride resin.

As the substrate used in the present invention, a glass substrate is preferable because the surface modifier in the coating composition of the present invention reacts favorably, and a film having excellent antifouling properties and slipperiness and durability can be formed on the substrate.

As a shape of the base material used by this invention, the thing of various shapes can be used. Especially, a sheet-like thing can use it suitably. As for the thickness of a sheet-like base material, the thing of the range of 5 micrometers - 800 micrometers can be illustrated, for example.

As a method of forming the film of the coating composition of this invention on the said base material, various methods can be used. Specifically, for example, a dip coating method, a spin coating method, a flow coating method, a spray coating method, a roll coating method, a gravure coating method, a vapor deposition method, etc. can be illustrated.

The surface modifier or coating composition of the present invention can form a film excellent in antifouling properties and sliding properties on the surface of an article. Utilizing such excellent effects, the surface modifier or coating composition of the present invention is a smart device that directly contacts the screen with a fingertip, and performs an operation (swiping) of tracing (sliding) the screen with a fingertip or pen tip It can be used especially suitably for the film formation of the outermost surface of the screen of a phone or tablet PC.

(Example)

Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, unless otherwise specified, "parts" and "%" are based on mass. In addition, the measurement conditions of the IR spectrum, ¹ H-NMR spectrum, and ¹⁹ F-NMR spectrum of the obtained surface modifier are as follows.

[IR spectrum measurement conditions]

Device: "FT/IR-6100" manufactured by Nippon Funko Co., Ltd.

Measurement method: KBr method

[ ¹ H-NMR spectrum, ¹⁹ F-NMR spectrum measurement conditions]

Device: "JNM-ECA500" manufactured by Nippon Denshi Co., Ltd.

Solvent: deuterated chloroform

Example 1 (Preparation of surface modifier)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dripping device, 88.9 g of a diol having a poly(perfluoroalkylene ether) chain represented by the following formula (2-1-1) and a urethanation catalyst 0.05 g of tin thilate was thrown in, stirring was started under nitrogen stream, and 11.1 g of 3-isocyanatopropyl triethoxysilane was dripped over 15 minutes, maintaining 60 degreeC. After completion of dripping, after stirring at 60 degreeC for 1 hour, the said diol and 3-isocyanatopropyltriethoxysilane were made to react by raising the temperature further to 80 degreeC and stirring for 2 hours, and the reaction material was obtained. Then, IR spectrum measurement was performed about this reaction material, and the loss|disappearance of the isocyanate group in the reaction material was confirmed. The obtained reactant was purified by filtration using a PTFE filter having a pore diameter of 0.2 µm to obtain a surface modifier (1) of the present invention represented by the general formula (1). Here, in the surface modifier (1), in the general formula (1), A is an ethoxy group, Z is an n-propylene group, Y ¹ , Y ² is a methylene group.

(X is a perfluoromethylene group and a perfluoroethylene group, an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups exist per molecule, and the average number of fluorine atoms is 126)

Moreover, the chart diagram of the IR spectrum of the surface modifier (1) is shown in FIG. 1, the chart diagram of the ¹ H-NMR spectrum is shown in FIG. 2, and the chart diagram of the ¹⁹ F-NMR spectrum is shown in FIG.

Example 2 (same above)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dripping device, 45.3 g of a diol having a poly (perfluoroalkylene ether) chain represented by the formula (2-1-1) and a urethanation catalyst were added 0.025 g of tin thilate was put, stirring was started under nitrogen stream, and 4.7 g of 3-isocyanatopropyl trimethoxysilane was dripped over 15 minutes, maintaining 60 degreeC. After completion of the dropwise addition, the mixture was stirred at 60°C for 1 hour, then heated to 80°C and stirred for 2 hours to make the diol and 3-isocyanatopropyltrimethoxysilane react to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss|disappearance of the isocyanate group in the reaction material was confirmed. The obtained reactant was purified by filtration using a PTFE filter having a pore diameter of 0.2 µm to obtain a surface modifier (2) of the present invention represented by the general formula (1). Here, in the surface modifier (2), in the general formula (1), A is a methoxy group, Z is an n-propylene group, Y ¹ , Y ² is a methylene group. X in formula (2-1-1) is a perfluoromethylene group and a perfluoroethylene group, and per molecule, an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups exist per molecule, and fluorine The average number of atoms is 126.

Example 3 (Frostbite)

54.99 g of a diol having a poly (perfluoroalkylene ether) chain represented by the above formula (2-1-1) and a fluorinated solvent C _{4 in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device} F ₉ OC ₂ H ₅ 40 g and 0.03 g of tin octylate as a urethanization catalyst were put, stirring was started under a nitrogen stream, and 5.01 g of 3-isocyanatopropyl triethoxysilane was dripped over 15 minutes, maintaining 50 degreeC. After completion of the dropwise addition, the diol and 3-isocyanatopropyltriethoxysilane were reacted with stirring at 50°C for 18 hours to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss|disappearance of the isocyanate group in the reaction material was confirmed. The obtained reaction product was filtered and purified using a PTFE filter having a pore size of 0.2 µm to obtain a fluorinated solvent solution of the surface modifier (3) of the present invention represented by the general formula (1). Here, in the surface modifier (3), in the general formula (1), A is an ethoxy group, Z is an n-propylene group, Y ¹ , Y ² is a methylene group. X in the formula (2-1-1) is a perfluoromethylene group and a perfluoroethylene group, and an average of 30 perfluoromethylene groups and an average of 30 perfluoroethylene groups exist per molecule, and fluorine The average number of atoms is 180.

Example 4 (Frostbite)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 55.79 g of a diol having a poly(perfluoroalkylene ether) chain represented by the above formula (2-1-1) and a fluorinated solvent C ₄ F ₉ OC ₂ H ₅ 40 g and 0.03 g of tin octylate as a urethanization catalyst were put, stirring was started under a nitrogen stream, and 4.12 g of 3-isocyanatopropyl trimethoxysilane was dripped over 15 minutes, maintaining 50 degreeC. After completion of dripping, the said diol and 3-isocyanatopropyl trimethoxysilane were made to react by stirring at 50 degreeC for 18 hours, and the reaction material was obtained. Then, IR spectrum measurement was performed about this reaction material, and the loss|disappearance of the isocyanate group in the reaction material was confirmed. The obtained reaction product was filtered and purified using a PTFE filter having a pore size of 0.2 µm to obtain a fluorinated solvent solution of the surface modifier (4) of the present invention represented by the general formula (1). Here, in the surface modifier (4), in the general formula (1), A is a methoxy group, Z is an n-propylene group, Y ¹ , Y ² is a methylene group. X in the formula (2-1-1) is a perfluoromethylene group and a perfluoroethylene group, and an average of 30 perfluoromethylene groups and an average of 30 perfluoroethylene groups exist per molecule, and fluorine The average number of atoms is 180.

Example 5 (Preparation of Coating Compositions and Articles)

_{The surface modifier (1) was added to C 4} F ₉ OC ₂ H ₅ as a fluorine atom-containing solvent at a concentration of 0.1% to obtain a coating composition (1) of the present invention. The washed glass substrate was immersed in the coating composition (1) for 1 minute. After 1 minute, the glass plate was taken out from the coating composition (1), and the glass plate was dried at a humidity of 90% and 60°C for 1 hour to obtain an article (1) having a film of the coating composition on the surface of the glass plate.

Using the obtained article (1), durability evaluation of water and oil repellency, slippery property, stain-preventing property and stain-preventing property of the surface of the article was performed according to the following method. An evaluation result is shown in 1st table|surface.

<Evaluation method for water and oil repellency of the surface of an article>

It was evaluated by measuring the contact angle of water and n-dodecane. For the measurement of the contact angle, a contact angle measuring apparatus (“MODEL CA-W150” manufactured by Kyowa Chemicals Co., Ltd.) was used. The higher the contact angle, the better the water and oil repellency.

<Evaluation method of the slipperiness of the article surface>

Using a surface property measuring instrument (“HEIDON-14D” manufactured by Shinto Chemical Co., Ltd.), fix the article 1 on the sample stand and check the level, then set the probe on the sample, and under a load of 100 g, the tensile rate Measurement was performed under the condition of 0.3 m/min to determine the coefficient of kinetic friction, the lower the coefficient of kinetic friction, the better the sliding properties.

<Evaluation method for anti-fouling properties on the surface of articles>

A line was drawn on the surface of the article 1 with an oil-based felt-tip pen (magic ink large black made by Terranish Chemicals Co., Ltd.), and the adhesion state of the black ink was visually observed. In addition, evaluation criteria are as follows. The evaluation result is good in the order of A>B>C>D.

A : Black ink splatters in the form of beads

B: Ink does not splatter in the form of beads, and splashes in a linear form occur, and the line width is less than 50% of the width of the tip of the felt-tip pen.

C: Ink did not splatter in a bead-like shape, and linear spatter occurred, and the line width was not less than 50% and less than 100% of the width of the tip of the felt-tip pen.

D : Ink does not splash at all and is beautifully drawn on the surface

<Method for evaluating the durability of anti-fouling properties>

In the above "Method for evaluating the anti-fouling property of an article surface", after wiping off the magic, an evaluation test of the anti-fouling property of the article surface is performed again until there is no splash (when evaluated as "D" in the evaluation above) Until), it was evaluated how many times the surface of the article can be tested for anti-fouling properties. The evaluation result is good in the order of A>B>C>D.

A: The test of anti-fouling properties can be repeated 10 times or more.

B: The anti-fouling test can be repeated 5 to 9 times.

C: The test of anti-fouling properties can be repeated 1 to 4 times.

D: The test of anti-fouling properties cannot be repeated even once.

Examples 6 to 8 (same statue)

Coating compositions (2) to (4) and articles (2) to (4) were obtained in the same manner as in Example 5 except that the surface modifier shown in Table 1 was used. In the same manner as in Example 5, water and oil repellency, slipping properties, and antifouling properties were evaluated. An evaluation result is shown in 1st table|surface.

Comparative Example 1 (Preparation of Comparative Control Coating Composition and Comparative Control Article)

Surface modifier [CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₁₁ OCF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si ( OCH ₃ ) ₃ ] [Surface modifier for comparison (1')] was used in the same manner as in Example 5, to obtain a coating composition for comparison (1') and article for comparison (1'). In the same manner as in Example 5, evaluation of durability of water and oil repellency, slipping property, staining prevention property and staining prevention property was evaluated. An evaluation result is shown in 1st table|surface.

[Table 1]

Claims (13)

The following general formula (1)

[In the formula, A is a hydrolysable group or a non-hydrolysable group, respectively, in the formula, in each of two (A) ₃ , at least one A is a hydrolysable group. Z is a divalent linking group. Y ¹ and Y ² each represent a direct bond or a methylene group. PFPE is a poly(perfluoroalkylene ether) chain, and the perfluoroalkylene group of the poly(perfluoroalkylene ether) chain is a perfluoromethylene group and a perfluoroethylene group]
A surface modifier, characterized in that represented by. According to claim 1,
A surface modifier wherein Z in the general formula (1) is an alkylene group having 1 to 10 carbon atoms, and Y ¹ and Y ² are a methylene group. According to claim 1,
A surface modifier wherein the hydrolyzable group is an alkoxy group having 1 to 6 carbon atoms. According to claim 1,
The hydrolyzable group is a methoxy group or an ethoxy group, Z is each n-propylene group, Y ¹ And Y ^{2 A} surface modifier wherein Y 1 and Y 2 are methylene groups. According to claim 1,
The following general formula (1-2-1)

[In the formula, A is a hydrolysable group or a non-hydrolysable group, respectively, in the formula, in each of two (A) ₃ , at least one A is a hydrolysable group. X is a perfluoromethylene group and a perfluoroethylene group which may exist in random or block form. Z is an alkylene group having 1 to 6 carbon atoms. Y ¹ and Y ² are methylene groups. n is 6 to 300 in total]
A surface modifier represented by . delete 6. The method of claim 5,
A surface modifier wherein both A in (A) ₃ above are a hydrolysable group, the hydrolyzable group is a methoxy group or an ethoxy group, each Z is an n-propylene group, and n is 12 to 150. According to claim 1,
The following general formula (2)

[Y ¹ and Y ² are each a direct bond or a methylene group. PFPE is a poly(perfluoroalkylene ether) chain, and the perfluoroalkylene group in the poly(perfluoroalkylene ether) chain is a perfluoromethylene group and a perfluoroethylene group] And, the following general formula (3)

[Wherein, A is a hydrolysable group or a non-hydrolysable group, and at least one A is a hydrolysable group. Z is a divalent linking group], a surface modifier obtained by reacting the isocyanate represented by A coating composition comprising the surface modifier according to any one of claims 1 to 5, 7 and 8 and a solvent. 10. The method of claim 9,
The coating composition wherein the solvent is a fluorine atom-containing solvent. 10. The method of claim 9,
A coating composition wherein the content of the surface modifier is 0.01 to 50% by mass. An article characterized in that it has a film of the coating composition according to claim 9 on a substrate. 13. The method of claim 12,
An article wherein the substrate is a glass substrate.

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