WO2015115522A1

WO2015115522A1 - Surface modifier, coating composition, and article

Info

Publication number: WO2015115522A1
Application number: PCT/JP2015/052464
Authority: WO
Inventors: 知代尾崎; 鈴木　秀也
Original assignee: Dic株式会社
Priority date: 2014-01-31
Filing date: 2015-01-29
Publication date: 2015-08-06
Also published as: KR102338699B1; CN105940077A; TWI655226B; TW201538566A; KR20160114583A; JPWO2015115522A1; JP5846466B1; CN105940077B

Abstract

With the objective of providing a surface modifier that is capable of forming a coating which has excellent antifouling and slippage properties on a base material such as a glass base material, a coating composition which comprises the surface modifier, and an article with a coating obtained using the composition, the present invention provides the surface modifier represented by general formula (1). [In the formula, A is each a hydrolyzable group or a non-hydrolyzable group, and in the formula, out of each of the two (A)₃, at least one A is a hydrolyzable group. X, Y¹, and Y² are each a divalent linking group. PFPE is a poly(perfluoroalkylene ether) chain.]

Description

Surface modifier, coating composition and article

The present invention relates to a surface modifier capable of forming a film having excellent durability and anti-slip properties on a substrate such as a glass substrate, and a coating composition containing 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 arranged to face each other via a frame-shaped sealing material, and an input region composed of a transparent conductive film or a plurality of electrodes is placed inside the frame-shaped sealing member. Is provided. Here, examples of the transparent substrate include plastic and glass. Examples of the combination of the two transparent substrates include plastic (film) / glass and glass / glass. Among them, a touch panel using the glass / glass combination has a very clear screen and excellent weather resistance. Has characteristics. Therefore, it can be suitably used for portable devices such as smartphones and tablet PCs used outdoors and in-vehicle applications in which a severe temperature difference occurs.

Since the touch panel is touched by a human finger during use, dirt derived from the human body such as fingerprints, sebum, and sweat is likely to adhere. These stains are difficult to remove when attached, and they are conspicuous depending on the amount of light, etc., and thus there is a problem that visibility and aesthetics are impaired.

In order to solve this problem, a technique of coating a fluorine-containing compound having both water repellency and oil repellency on the outermost surface layer touched by a human finger is employed. Specifically, for example, a surface modifier containing a compound having a hydrolyzable silicon atom at one end and a perfluoroalkylene ether chain at the other end, and An organic solvent solution (coating composition) containing a surface modifier is disclosed (for example, see Patent Document 1). However, the surface modifier disclosed in Patent Document 1 has a problem that the resistance to dirt (antifouling property) is not sufficient.

Also, among the touch panels, for example, smartphones and tablet PCs perform an operation (swipe) for tracing (sliding) a fingertip or a pen tip on the touch panel. In recent years, the touch panel screen is required to be smooth so that the fingertip and the pen tip do not get caught during this operation. However, the surface modifier disclosed in Patent Document 1 has a problem that the smoothness (slidability) is not sufficient.

JP 2012-037896 A

An object of the present invention is to provide a surface modifier and a coating composition that can provide a film having excellent durability and antifouling properties and slipperiness. Moreover, the subject of this invention is also providing the articles | goods which have a film excellent in antifouling property and slipperiness.

As a result of intensive studies, the present inventors have found that the compound has a poly (perfluoroalkylene ether) chain, a urethane bond, and a hydrolyzable silane, and urethane bonds are arranged at both ends of the poly (perfluoroalkylene ether) chain. Furthermore, the compound having the hydrolyzable silane at both ends of the compound, in which the urethane bond and the hydrolyzable silane are in the vicinity, is a surface modifier that provides a film having excellent antifouling properties and slipperiness. As a result, the present invention was developed.

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

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and in each of the two (A) ₃ , at least one A is a hydrolyzable group. Z is a divalent linking group. Y ¹ and Y ² are each a direct bond or a divalent linking group. PFPE represents a poly (perfluoroalkylene ether) chain. ]
The surface modifier characterized by these is provided.

The present invention also provides a coating composition comprising the surface modifier and a solvent.

Furthermore, the present invention provides an article characterized by having a coating of the coating composition on a substrate.

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

FIG. 1 is an IR spectrum chart of the surface modifier (1) obtained in Example 1. FIG. 2 is a chart of ¹ H-NMR spectrum of the surface modifier (1) obtained in Example 1. FIG. 3 is a chart of ¹⁹ F-NMR spectrum of the surface modifier (1) obtained in Example 1.

The surface modifier of the present invention is represented by the following general formula (1)

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and in each of the two (A) ₃ , at least one A is a hydrolyzable group. Z is a divalent linking group. Y ¹ and Y ² are each a direct bond or a divalent linking group. PFPE represents a poly (perfluoroalkylene ether) chain. ] Is represented.

The surface modifier of the present invention has two Si (A) ₃ as shown by the general formula (1), and at least one A in each (A) ₃ is a hydrolyzable group. is there. The inventors speculate that by having such a silicon atom (reactive silyl group), the surface modifier of the present invention is covalently bonded to the substrate surface by the following reaction. One of the presumed reactions is the generation of silanol groups by hydrolysis, which dehydrates and condenses with hydroxyl groups on the surface of various substrates, for example, preferably glass substrates, and is shared on the substrate surface. It is a reaction that binds. Another presumed reaction is a reaction in which the hydrolyzable group directly condenses with the hydroxyl group of the substrate (dealcoholization condensation when the hydrolyzable group is an alkoxy group) and is covalently bonded to the substrate surface. Since the product of the present invention can bond not only one end but also both ends to the base material, the surface modifier of the present invention is formed on the surface of the base material more than the conventional product due to the covalent bond formed by these condensation reactions. It is possible to form a film having excellent durability while having both the antifouling property and the slip property exhibited by the poly (perfluoroalkylene ether) chain of the surface modifier.

Examples of the hydrolyzable group include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; an alkoxy group-substituted alkoxy group such as a methoxyethoxy group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; Alkenyloxy groups such as propenyloxy group and isobutenyloxy group; Imineoxy groups such as dimethylketoxime group, methylethylketoxime group, diethylketoxime group and cyclohexaneoxime group; methylamino group, ethylamino group, dimethylamino group, diethylamino group A substituted amino group such as a group; an amide group such as an N-methylacetamide group and an N-ethylamide group; a substituted aminooxy group such as a dimethylaminooxy group and a diethylaminooxy group; a halogen such as chlorine and the like. Among the hydrolyzable groups, an alkoxy group is preferable because it has a high hydrolysis rate and can form a coating having excellent durability while having both antifouling properties and slip properties, and has 1 to 6 carbon atoms. Are more preferable, alkoxy groups having 1 to 3 carbon atoms are more preferable, and methoxy group and 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, and an aralkyl group having 7 to 20 carbon atoms. Etc. Above all, steric hindrance can be avoided and the hydrolysis rate can be increased. As a result, it is possible to quickly form a film having excellent anti-staining properties and sliding properties, and having excellent durability. Group is preferred, and a methyl group is more preferred.

The number of hydrolyzable groups in the (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 durability can be obtained. It is more preferable that all A in (A) ₃ are hydrolyzable groups. That is, those having no non-hydrolyzable group are most preferable.

In the case of having a plurality of hydrolyzable groups in (A) ₃ , the hydrolyzable groups may be the same or different. Moreover, also when it has two or more non-hydrolyzable groups, this non-hydrolyzable group may be the same and may differ.

Z in the general formula (1) is a divalent linking group. Y ¹ and Y ² are each a direct bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 22 carbon atoms. 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, and 2-methyl. Butylene 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-pen Len 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, alkylene group such as 3-octylene group, 2-propylpentylene group, 2,4,4-trimethylpentylene group, decaoctylene group and the like.

Z is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, since synthesis is easy and the surface modifier of the present invention can be easily obtained. 1-3 alkylene groups are more preferred, and n-propylene groups are particularly preferred.

Moreover, as Y ¹ and Y ² , an alkylene group having 1 to 6 carbon atoms is preferable because the content of fluorine atoms is high and a surface modifier that can provide a film with more excellent antifouling properties can be obtained. An alkylene group having 1 to 3 carbon atoms is more preferable for each, and a methylene group is still more preferable because it is excellent in antifouling property and is easily obtained industrially.

The two Zs in the general formula (1) may be the same or different. The surface modifier of the present invention may be a mixture of modifiers having different Zs.

Y ¹ and Y ² in the general formula (1) may be the same or different. The surface modifier of the present invention may be a mixture of modifiers having different Y ¹ and Y ² .

The surface modifier of the present invention has a urethane bond in the skeleton. By having this urethane bond, the surface modifier of the present invention improves the polarity in the vicinity of the hydrolyzable groups at both ends. As a result, the adhesion to a substrate described later, preferably a glass substrate, is improved, and the reaction with the substrate surface proceeds efficiently. As a result, a film having durability and excellent antifouling properties and slipperiness can be suitably formed 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.

As the PFPE [poly (perfluoroalkylene ether) chain] of the surface modifier of the present invention, for example, those having a structure in which perfluoroalkylene groups having 1 to 3 carbon atoms and oxygen atoms are alternately linked are preferable. Can be mentioned. The perfluoroalkylene group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds. Specific examples include those represented by the following structural formula 1.

(In the above structural formula 1, X is a perfluoroalkylene group. All of X may have the same structure, or a plurality of structures may be present randomly or in a block form. good.)

Examples of X include, for example, the structures shown below.

Among these, the poly (perfluoroalkylene ether) chain has a large number of oxygen atoms that serve as bending points that exhibit slipperiness, and there is no branched structure that inhibits the bending movement of the chain. A methylene group and a perfluoroethylene group are preferable, and a compound in which a perfluoromethylene group and a perfluoroethylene group coexist is particularly preferable, including a point that can be easily obtained industrially. When the perfluoromethylene group (a) and the perfluoroethylene group (b) coexist, the abundance ratio (a / b) (number ratio) is preferably 1/10 to 10/1.

Preferred examples of the surface modifier having a perfluoroalkylene group having 1 to 3 carbon atoms include those represented by the following structural formula.

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and in each of the two (A) ₃ , at least one A is a hydrolyzable group. X may be all of the same structure, or a perfluoroalkylene group having 1 to 3 carbon atoms in which a plurality of structures may be present randomly or in a 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. Thus, by having a short chain | strand, it becomes a flexible frame | skeleton, As a result, the film excellent in slip property can be formed on an article | item. In the general formula (1), n is more preferably 12 to 200, more preferably 30 to 150, and further preferably 50 to 120.

Examples of the surface modifier represented by the above (1-2-1) include those represented by the following formula.

The poly (perfluoroalkylene ether) chain preferably has a total of 18 to 600 fluorine atoms contained in one poly (perfluoroalkylene ether) chain from the viewpoint of excellent dirt wiping property and slipperiness. The range of 90 to 450 is more preferable, and the range of 150 to 360 is particularly preferable.

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

[Wherein Y ¹ and Y ² are each a divalent linking group. And a diol represented by the following general formula (3)

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

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

Examples of the diol represented by the general formula (2) include the diols shown below.

Of the above general formulas (2-1) and (2-2), the following diols are preferred.

(X is a perfluoroalkylene group having 1 to 3 carbon atoms, all of which may have the same structure or a plurality of structures may be present randomly or in a block form. Is a total of 6 to 300.]

Examples of the isocyanate represented by the general formula (3) include the isocyanates shown below.

Z in the isocyanate compounds represented by the above formulas (3-1) to (3-12) is easy to synthesize, and the surface modifier of the present invention can be easily obtained. An alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 3 carbon atoms is 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 general formula (3) is added to 1 mol of the OH group contained in the general formula (2). ) Is preferably charged so as to be 0.5 to 1.5 mol, more preferably 0.9 to 1.1 mol, and 0.98 to 1.02 Most preferably, it is charged so as to be a mole.

In the reaction of the diol represented by the general formula (2) and the isocyanate represented by the general formula (3) (urethanization reaction), the diol represented by the general formula (2) and the general formula (3) are used. In order to promote the reaction with the isocyanate produced, for example, a tertiary amine such as triethylamine or benzyldimethylamine, a tin compound such as dibutyltin dilaurate, dioctyltin dilaurate or tin 2-ethylhexanoate is used as a catalyst. be able to.

The addition amount of the catalyst is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.02 to 0.2% by mass with respect to the entire reaction mixture. %. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably 30 to 120 ° C, more preferably 40 to 90 ° C.

When the reaction of the diol represented by the general formula (2) and the isocyanate represented by the general formula (3) (urethanization reaction) is performed, the reaction system may be a solvent-free system, and the isocyanate group may not be used. A solvent system using a solvent such as active acetone, methyl ethyl ketone, toluene, xylene, or a fluorine-based solvent as a reaction solvent may be used.

The coating composition of the present invention contains the surface modifier of the present invention and a solvent. As the solvent, a solvent containing a fluorine atom can be preferably used because it can dissolve the surface modifier of the present invention well.

Examples of the solvent containing a fluorine atom include hydrofluoroether, hydrofluorocarbon, perfluorocarbon, and the like. The solvent containing a fluorine atom may be linear, branched or cyclic, and may contain a hetero atom. The number of carbon atoms in the solvent containing fluorine atoms is preferably 2 to 12, more preferably 4 to 10.

As the hydrofluoroether, for _{_{_{_{example, 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 CF 2 OCH ₂ CF ₃ and the like. 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 CF ₂ CH 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 , and C _11. Examples thereof include F ₂₄ , C ₁₂ F ₂₆ , (C ₄ F ₉ ) ₃ N, perfluoro (1,2-dimethylcyclobutane), perfluoro (methylcyclohexane), perfluoro (2-butyltetrahydrofuran) and the like.

Among the solvents containing fluorine atoms, 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 F 9 OC 2 H 5,}}}} C 2 F 5 CF (OCH 3) C 3 F 7 and is preferably _HCF is 2 _CF 2 _OCH 2 _CF 1 or more _{to 3} selected from the group consisting of.

As the content of the surface modifier in the coating composition of the present invention, a coating containing the surface modifier can be uniformly formed, and the surface modifier and the substrate such as glass react well. Therefore, 0.01 to 50% by mass is preferable, 0.02 to 10% by mass is more preferable, and 0.05 to 1% by mass is even more preferable.

The article of the present invention is characterized by having a coating of the coating composition of the present invention on a substrate. Examples of the substrate include inorganic substrates such as glass; organic substrates such as acrylic resin, polycarbonate resin, polyester resin, polybutylene terephthalate resin, polypropylene resin, polyamide resin, polyurethane resin, polyvinyl chloride resin, and polyvinyl fluoride resin. Etc.

As the base material used in the present invention, the surface modifier in the coating composition of the present invention reacts satisfactorily to form a film having excellent antifouling property and slipperiness and durability on the base material. Therefore, a glass substrate is preferable.

As the shape of the substrate used in the present invention, various shapes can be used. Especially, a sheet-like thing can be used conveniently. Examples of the thickness of the sheet-like base material include those in the range of 5 μm to 800 μm.

Various methods can be used as a method for forming the coating composition of the present invention on the substrate. Specific examples include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and vapor deposition.

The surface modifier and coating composition of the present invention can form a film having excellent antifouling properties and slipperiness on the surface of an article. Utilizing such excellent effects, the surface modifying agent or coating composition of the present invention allows the fingertip to directly touch the screen, and to perform an operation (swipe) for tracing (sliding) the screen with the fingertip or the pen tip. It can be particularly preferably used for film formation on the outermost surface of the screen of a smartphone or tablet PC to be performed.

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

[IR spectrum measurement conditions]
Equipment: “FT / IR-6100” manufactured by JASCO Corporation
Measuring method: KBr method

[Measurement conditions for ¹ H-NMR spectrum and ¹⁹ F-NMR spectrum]
Equipment: “JNM-ECA500” manufactured by JEOL Ltd.
Solvent: deuterated chloroform

Example 1 (Preparation of surface modifier)
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 88.9 g of a diol having a poly (perfluoroalkylene ether) chain represented by the following formula (2-1-1) and a urethanization catalyst 0.05 g of tin octylate was charged, stirring was started under a nitrogen stream, and 11.1 g of 3-isocyanatopropyltriethoxysilane was added dropwise over 15 minutes while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, further heated to 80 ° C. and stirred for 2 hours to react the diol with 3-isocyanatopropyltriethoxysilane to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss | disappearance of the isocyanate group in a reaction material was confirmed. The obtained reaction product was purified by filtration using a PTFE filter having a pore size of 0.2 μm to obtain the 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, and Y ¹ and Y ² are methylene groups.

(X is a perfluoromethylene group and a perfluoroethylene group, with an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups per molecule, and an average of 126 fluorine atoms. is there.)

FIG. 1 shows a chart of the IR spectrum of the surface modifier (1), FIG. 2 shows a chart of the ¹ H-NMR spectrum, and FIG. 3 shows a chart of the ¹⁹ F-NMR spectrum.

Example 2 (same as above)
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 45.3 g of a diol having a poly (perfluoroalkylene ether) chain represented by the above formula (2-1-1) and a urethanization catalyst 0.025 g of tin octylate was charged, stirring was started under a nitrogen stream, and 4.7 g of 3-isocyanatopropyltrimethoxysilane was added dropwise over 15 minutes while maintaining 60 ° C. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, further heated to 80 ° C. and stirred for 2 hours to react the diol with 3-isocyanatopropyltrimethoxysilane to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss | disappearance of the isocyanate group in a reaction material was confirmed. The obtained reaction product was purified by filtration using a PTFE filter having a pore size of 0.2 μm to obtain the 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, and Y ¹ and Y ² are methylene groups. X in the formula (2-1-1) is a perfluoromethylene group and a perfluoroethylene group, and an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups exist per molecule. The average number of fluorine atoms is 126.

Example 3 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 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 ₄₀ F of ₄ F ₉ OC ₂ H ₅ and 0.03 g of tin octylate as a urethanization catalyst were charged, stirring was started under a nitrogen stream, and 5.01 g of 3-isocyanatopropyltriethoxysilane was maintained for 15 minutes while maintaining 50 ° C. It was dripped over. After completion of the dropwise addition, the diol was reacted with 3-isocyanatopropyltriethoxysilane by 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 a 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 fluorine-containing 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, and Y ¹ and Y ² are methylene groups. 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 are present per molecule. The average number of fluorine atoms is 180.

Example 4 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, 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 ₄₀ F of ₄ F ₉ OC ₂ H ₅ and 0.03 g of tin octylate as a urethanization catalyst were charged, stirring was started under a nitrogen stream, and 4.12 g of 3-isocyanatopropyltrimethoxysilane was maintained for 15 minutes while maintaining 50 ° C. It was dripped over. After completion of the dropwise addition, the diol was reacted with 3-isocyanatopropyltrimethoxysilane by 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 a reaction material was confirmed. The obtained reaction product was purified by filtration using a PTFE filter having a pore size of 0.2 μm to obtain a fluorine-containing 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, and Y ¹ and Y ² are methylene groups. 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 are present per molecule. The average number of fluorine 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 which is a fluorine atom-containing solvent so as to have 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 of the coating composition (1), and the glass plate was dried at 90% humidity and 60 ° C. for 1 hour to obtain an article (1) having a coating composition coating on the glass plate surface.

Using the obtained article (1), the durability of water / oil repellency, slipping, dirt adhesion prevention and dirt adhesion prevention on the article surface was evaluated according to the following method. The evaluation results are shown in Table 1.

<Evaluation method of water and oil repellency on article surface>
Evaluation was made by measuring the contact angles of water and n-dodecane. The contact angle was measured using a contact angle measuring device (“MODEL CA-W150” manufactured by Kyowa Interface Science Co., Ltd.). The higher the contact angle, the better the water and oil repellency.

<Evaluation method of slipperiness of article surface>
Using a surface property measuring instrument (“HEIDON-14D” manufactured by Shinto Kagaku Co., Ltd.), fix the article (1) on the sample table and check the level, then set the probe on the sample and pull it with a load of 100 g. The dynamic friction coefficient was determined by measuring at a speed of 0.3 m / min, and the lower the dynamic friction coefficient, the better the sliding property.

<Evaluation method of antifouling property on article surface>
A line was drawn on the surface of the article (1) with an oil-based felt pen (Magic ink large black, manufactured by Teranishi Chemical Co., Ltd.), and the adhesion state of the black ink was visually observed. The evaluation criteria are as follows. The evaluation results are good in the order of A>B>C> D.
A: Black ink repels.
B: The ink does not repel, the linear repelling occurs, and the line width is less than 50% of the width of the pen tip of the felt pen.
C: The ink did not repel, the line repelled, and the line width was 50% or more and less than 100% of the width of the pen tip of the felt pen.
D: The ink can be drawn cleanly on the surface without repelling at all.

<Durability evaluation method for dirt adhesion prevention>
In the above “evaluation method of anti-smudge property on article surface”, after wiping off the magic, the evaluation test for anti-smudge property on the article surface is performed again until it does not repel (until it is evaluated as “D” in the above evaluation). ) It was evaluated how many times the surface of the article could be tested to prevent soil adhesion. The evaluation results are good in the order of A>B>C> D.
A: The soil adhesion prevention test can be repeated 10 times or more.
B: The soil adhesion prevention test can be repeated 5 to 9 times.
C: The soil adhesion prevention test can be repeated 1 to 4 times.
D: The soil adhesion prevention test cannot be repeated by one.

Examples 6 to 8 (same as above)
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, the water and oil repellency, the slip property, and the antifouling property were evaluated. The evaluation results are shown in Table 1.

Comparative Example 1 (Preparation of Comparative Coating Composition and Comparative Article)
Instead of the surface modifier (1), the surface modifier [CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₁₁ OCF ₂ CF ₂ CH ₂ OCH ₂ described in Synthesis Example 1 of JP2012-037896A CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] [surface modifier for comparison control (1 ′)], except that a comparative coating composition (1 ′) and comparison control were used in the same manner as in Example 5. Article (1 ') was obtained. In the same manner as in Example 5, evaluation of durability of water / oil repellency, slipperiness, stain adhesion prevention property and stain adhesion prevention property was evaluated. The evaluation results are shown in Table 1.

Claims

The following general formula (1)

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and in each of the two (A) 3 , at least one A is a hydrolyzable group. Z is a divalent linking group. Y 1 and Y 2 are each a direct bond or a divalent linking group. PFPE represents a poly (perfluoroalkylene ether) chain. ]
The surface modifier characterized by these.
2. The surface modifier according to claim 1 , wherein Z in the general formula (1) is an alkylene group having 1 to 10 carbon atoms, and Y 1 and Y 2 are each an alkylene group having 1 to 6 carbon atoms. .
The surface modifier according to claim 1, wherein the hydrolyzable group is an alkoxy group having 1 to 6 carbon atoms.
The surface modifier according to claim 1, wherein the hydrolyzable group is a methoxy group or an ethoxy group, Z is an n-propylene group, and Y1 and Y2 are methylene groups.
The following general formula (1-2-1)

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and in each of the two (A) 3 , at least one A is a hydrolyzable group. X may be all of the same structure, or a perfluoroalkylene group having 1 to 3 carbon atoms in which a plurality of structures may be present randomly or in a 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 of Claim 1 represented by these.
The surface modifier according to claim 5, wherein the perfluoroalkylene group having 1 to 3 carbon atoms is a perfluoromethylene group or a perfluoroethylene group.
The two is (A) A in 3 are all a hydrolyzable group, with the hydrolyzable group is a methoxy group or an ethoxy group, Z is in each n- propylene, in Y1 and Y2 is methylene group, The surface modifier according to claim 6, wherein n is 12 to 150.
The following general formula (2)

[Y 1 and Y 2 are each a direct bond or a divalent linking group. And a diol represented by the following general formula (3)

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and at least one A is a hydrolyzable group. Z is a divalent linking group. The surface modifier of Claim 1 obtained by making it react with the isocyanate represented by this.
A coating composition comprising the surface modifier according to any one of claims 1 to 8 and a solvent.
The coating composition according to claim 9, wherein the solvent is a fluorine atom-containing solvent.
The coating composition according to claim 9 or 10, wherein the content of the surface modifier is 0.01 to 50% by mass.
12. An article comprising a coating of the coating composition according to any one of claims 9 to 11 on a substrate.
The article according to claim 12, wherein the substrate is a glass substrate.