TWI655226B - Coating composition and articles - Google Patents

Abstract

The present invention provides a surface modifier which can form a film excellent in antifouling property and smoothness on a substrate such as a glass substrate, a coating composition containing the surface modifier, and a film obtained by using the composition. Items.

A surface modifying agent represented by the following general formula (1), a coating composition containing the surface modifying agent and a solvent, and an article having a coating of the coating composition on a substrate:

Wherein A is a hydrolyzable group or a non-hydrolyzable group; wherein, in each of the two (A) ₃ , at least one of A is a hydrolyzable group; and X, Y ¹ and Y ² are each a link of two. Base; PFPE means poly(perfluoroalkylene ether) chain].

Description

Coating composition and articles

The present invention relates to a surface modifier capable of forming a film excellent in durability and excellent in antifouling property and smoothness on a substrate such as a glass substrate, and a coating composition containing the surface modifier. Further, the present invention relates to an article having a film obtained by using the coating composition.

In the touch panel, two transparent substrates including glass and synthetic resin are opposed to each other via a frame-shaped sheet, and an input including a transparent conductive film or a plurality of electrodes is provided inside the frame-shaped sheet member. region. Here, plastic, glass, etc. are mentioned as a transparent base material. Examples of the combination of the two transparent substrates include plastic (film), glass, and glass/glass. Among them, a touch panel using a combination of glass and glass has a feature that the screen is very clear and the weather resistance is excellent. Therefore, it can be applied to mobile devices such as smart phones and tablet computers that are used outdoors, and in-vehicle applications where a strong temperature difference occurs.

Since the touch panel is touched by a human finger during use, it is easy to adhere to stains from the human body such as fingerprints, sebum, and sweat. These stains are difficult to remove once they are attached, and are also apparent depending on the increase or decrease of light, and have problems that impair visibility and aesthetics.

In order to solve this problem, a method of applying a fluorine-containing compound having both water repellency and oil repellency to the outermost layer in contact with a human finger is employed. Specifically, for example, there is disclosed a surface modifier comprising a compound having a hydrazine atom having a hydrolyzable group at one end and a perfluoroalkylene ether chain at the terminal of the other side. An organic solvent solution (coating composition) containing the surface modifying agent is disclosed (for example, refer to Patent Document 1). However, the surface modifier disclosed in Patent Document 1 has a problem that the resistance to stain adhesion (antifouling property) is insufficient.

Further, among the touch panels, for example, a smart phone and a tablet computer perform a swipe of a fingertip and a pen tip on the touch panel. In recent years, when seeking to perform this operation on the touch panel screen, it is not felt that the fingertips and the nib are not smooth and smooth. However, the surface modifier disclosed in Patent Document 1 also has a problem that the smoothness (smoothness) is insufficient.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2012-037896

An object of the present invention is to provide a surface modifier and a coating composition which are excellent in durability and excellent in antifouling properties and smoothness. Further, another object of the present invention is to provide an article having a film excellent in antifouling property and smoothness.

As a result of intensive studies, the inventors of the present invention have found that the following compounds are used as surface modifiers which are excellent in antifouling properties and smoothness, and the present invention has been developed: the compound has poly(perfluoroalkylene) a compound having an ether) chain, a urethane bond, and a hydrolyzable decane, wherein a urethane bond is disposed at both ends of the poly(perfluoroalkylene ether) chain, and further, the urethane bond is The hydrolyzable decane is in a nearby position, and the compound has hydrolyzable decane at both ends.

That is, the present invention provides a surface modifying agent characterized by the following general formula (1):

Wherein A is a hydrolyzable group or a non-hydrolyzable group; wherein, in the two (A) ₃ , at least one of A is a hydrolyzable group; Z is a divalent linking group; Y ¹ and Y ² Each is a direct bond or a divalent linking group; PFPE means a poly(perfluoroalkylene ether) chain].

Further, the present invention provides a coating composition characterized by comprising the surface modifying agent and a solvent.

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

The surface modifier and the coating composition of the present invention are suitable for forming a film having excellent antifouling properties and smoothness on an article. Therefore, it is particularly useful for applications such as touch panels that require antifouling properties and smoothness.

Fig. 1 is a graph showing the IR spectrum of the surface modifier (1) obtained in Example 1.

Fig. 2 is a chart showing the ¹ H-NMR spectrum of the surface modifier (1) obtained in Example 1.

Fig. 3 is a chart showing the ¹⁹ F-NMR spectrum of the surface modifier (1) obtained in Example 1.

[Formation for implementing the invention]

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; wherein, in the two (A) ₃ , at least one of A is a hydrolyzable group; Z is a divalent linking group; Y ¹ and Y ² Each is a direct bond or a divalent linking group; PFPE means a poly(perfluoroalkylene ether) chain].

The surface modifier of the present invention has two Si(A) ₃ as shown in the formula (1), and at least one of A in each of (A) ₃ is a hydrolyzable group. The inventors of the present invention have speculated that the surface modifier of the present invention is covalently bonded to the surface of the substrate by the following reaction by having such a ruthenium atom (reactive sulfhydryl group). One of the presumed reactions is to produce a sterol group by hydrolysis, which is dehydrated and condensed with a hydroxyl group having a surface of various substrates, for example, a glass substrate, etc., on the surface of the substrate. Covalent bond reaction. Another reaction is presumed to be a reaction in which a hydrolyzable group is directly condensed with a hydroxyl group of a substrate (a hydrolyzable group is a dealcoholization in the case of an alkoxy group), and a covalent bond is carried out on the surface of the substrate. The article of the present invention is not only a one-side end, but both ends can be bonded to the substrate, so that the surface modifier of the present invention is more invented than the conventional one by the covalent bond formed by the condensation reaction. The article adheres more firmly to the surface of the substrate, and can form a film having both antifouling property and smoothness and excellent durability; the antifouling property is derived from the poly(extension) of the surface modifier. Alkyl ether) chain.

Examples of the hydrolyzable group include an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group; an alkoxy-substituted alkoxy group such as a methoxyethoxy group; an ethoxy group and a propyloxy group. a decyloxy group such as a benzyl methoxy group; an alkenyloxy group such as an isopropenyloxy group or an isobutyleneoxy group; a dimethyl ketoximino group, a methyl ethyl ketoximino group, a diethyl ketoximino group, and a ring; An imine oxy group such as a keto oxime group; a substituted amine group such as a methylamino group, an ethylamino group, a dimethylamino group or a diethylamino group; an N-methylethylamino group, N-B a mercapto group such as a guanamine group; a substituted amino group such as a dimethylaminooxy group or a diethylaminooxy group; a halogen such as chlorine; Among the hydrolyzable groups, a film having excellent antifouling property and smoothness and excellent durability can be formed from a high degree of hydrolysis, and an alkoxy group is preferable, and a carbon number of 1 to 6 is more preferable. The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

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 aromatic group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. . Among them, the speed of hydrolysis can be accelerated from the steric obstacle, and the result can be quickly formed to have both antifouling properties and flatness. The film having excellent slip properties and durability is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

Although the number of the hydrolyzable groups in the above (A) ₃ is at least one as described above, it is preferably two or more, more preferably from the surface modifier for obtaining a film which is more excellent in durability. Both of A in both (A) ₃ are hydrolyzable groups. That is, it is preferably a non-hydrolyzable base.

When the (A) ₃ has a plurality of hydrolyzable groups, the hydrolyzable groups may be the same or different. Further, in the case of having a plurality of non-hydrolyzable groups, the non-hydrolyzable groups may be the same or different.

Z in the above formula (1) is a divalent linking group. Y ¹ and Y ² are a direct bond or a divalent bond group, respectively. The divalent linking group may, for example, be an alkylene group having 1 to 22 carbon atoms. Examples of the alkylene group include a methylene group, an ethylidene group, a n-propyl group, an exo-propyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, and 2,2. - dimethyl-propyl, 2-methylbutylene, 2-methyl-2-butylene, 3-methylbutylene, 3-methyl-2-butylene, pentyl, 2-extended pentyl, 3-exetylpentyl, 3-dimethyl-2-butylene, 3,3-dimethylbutylene, 3,3-dimethyl-2-butylene, 2 -ethyl butyl, hexyl, 2-exetyl, 3-extended hexyl, 2-methyl-amyl, 2-methyl-2-amylpentyl, 2-methyl-3-amylpentyl, 3 -methyl-amyl, 3-methyl-2-amylpentyl, 3-methyl-3-amylpentyl, 4-methyl-amylpentyl, 4-methyl-2-amylpentyl, 2, 2-Dimethyl-3-exopentyl, 2,3-dimethyl-3-endopenyl, 2,4-dimethyl-3-amylpentyl, 4,4-dimethyl-2- Ethyl, 3-ethyl-3-etylpentyl, heptanoyl, 2-exetyl, 3-heptyl, 2-methyl-2-exexyl, 2-methyl-3-exetyl , 5-methylhexyl, 5-methyl-2-extended hexyl, 2-ethylhexyl, 6-methyl-2-exetylene, 4-methyl-3-etylene, octyl, 2-extension octyl, 3-extension octyl, 2 - an extended alkyl group such as a propyl amyl group, a 2,4,4-trimethylamyl pentyl group or a decaoctylene group.

As the Z, the surface modifier of the present invention can be easily obtained from the synthesis, and is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. Further preferably, it is an alkyl group of 1 to 3, and particularly preferably a propyl group.

Further, as Y ¹ and Y ² , a surface modifier which has a high content of fluorine atoms and is excellent in antifouling property is preferably an alkylene having 1 to 6 carbon atoms. The base is more preferably an alkylene group having 1 to 3 carbon atoms, and is excellent in antifouling property and industrially easy to obtain, and is preferably a methylene group.

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

The surface modifier of the present invention has a urethane bond in the skeleton. By having the urethane bond, the surface modifier of the present invention has an increased polarity in the vicinity of the hydrolyzable group at both ends. As a result, it is preferable that the adhesion to the substrate described below is good, and the reaction with the surface of the substrate is efficiently performed. As a result, it is suitable for forming a film which is excellent in durability and excellent in antifouling property and smoothness.

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

The PFPE [poly(perfluoroalkylene ether) chain] which is a surface modifier of the present invention preferably has, for example, a carbon number. A structure in which a perfluoroalkyl group of 1 to 3 is bonded to an oxygen atom. The perfluoroalkyl group having 1 to 3 carbon atoms may be a mixture of a plurality of kinds, and specific examples thereof include those represented by the following structural formula 1.

(In the above structural formula 1, X is a perfluoroalkylene group; the X may be all of the same structure, or a plurality of structures may be present randomly or in blocks).

As the X, for example, the structure shown below can be mentioned.

-CF ₂ - a

-CF ₂ CF ₂ - b

-CF ₂ CF ₂ CF ₂ - e

Among these, from the poly(perfluoroalkylene ether) chain, there are many branching structures which are oxygen atoms which exhibit smoothness bending points and which do not hinder the bending motion of the chain, and X is preferably all The fluoromethylene group and the perfluoro-extended ethyl group are particularly preferably those in which the perfluoromethylene group and the perfluoroextended ethyl group coexist. Also, the perfluoromethylene (a) and the whole When the fluorine-extended ethyl group (b) coexists, the ratio (a/b) (number ratio) is preferably from 1/10 to 10/1.

The surface modifier having the perfluoroalkylene group having 1 to 3 carbon atoms is preferably represented, for example, by the following structural formula.

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

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, it becomes a soft skeleton, and as a result, a film excellent in smoothness can be formed on an article. The n in the formula (1) is preferably from 12 to 200, more preferably from 30 to 150, still more preferably from 50 to 120.

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

The poly(perfluoroalkylene ether) chain is preferably in the range of 18 to 600 in total of fluorine atoms contained in one poly(perfluoroalkylene ether) chain, in terms of excellent stain removal property and smoothness. It is preferably in the range of 90 to 450, and particularly preferably in the range of 150 to 360.

The surface modifier of the present invention is preferably obtained by reacting a diol represented by the following formula (2) with an isocyanate represented by the following formula (3).

HO-Y ¹ -PFPE-Y ² -OH▪▪▪▪(2)

[wherein, Y ¹ and Y ² are each a divalent linking group].

OCN-Z-Si(A) ₃ ▪▪▪▪(3)

[In the formula, A is a hydrolyzable group or a non-hydrolyzable group; at least one of A is a hydrolyzable group; and Z is a divalent linking group].

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

The diol represented by the above formula (2) is exemplified by, for example, a diol represented by the following.

HO-CH ₂ -PFPE-CH ₂ -OH (2-1)

HO-CH ₂ CH ₂ -PFPE-CH ₂ CH ₂ -OH (2-2)

Among the above formulae (2-1) and (2-2), a diol represented by the following is preferably exemplified.

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

The isocyanate represented by the above formula (3) is, for example, an isocyanate represented by the following.

OCN-Z-Si(OCH ₃ ) ₃ ▪▪▪▪(3-1)

OCN-Z-Si(OC ₂ H ₅ ) ₃ ▪▪▪▪(3-2)

OCN-Z-Si(OC ₃ H ₇ ) ₃ ▪▪▪▪(3-3)

OCN-Z-Si(OC ₄ H ₉ ) ₃ ▪▪▪▪(3-4)

OCN-Z-SiCH ₃ (OCH ₃ ) ₂ ▪▪▪▪(3-5)

OCN-Z-SiCH ₃ (OC ₂ H ₅ ) ₂ ▪▪▪▪(3-6)

OCN-Z-SiCH ₃ (OC ₃ H ₇ ) ₂ ▪▪▪▪(3-7)

OCN-Z-SiCH ₃ (OC ₄ H ₉ ) ₂ ▪▪▪▪(3-8)

OCN-Z-Si(CH ₃ ) ₂ (OCH ₃ )▪▪▪▪(3-9)

OCN-Z-Si(CH ₃ ) ₂ (OC ₂ H ₅ )▪▪▪▪(3-10)

OCN-Z-Si(CH ₃ ) ₂ (OC ₃ H ₇ )▪▪▪▪(3-11)

Z in the isocyanate compound represented by the formulae (3-1) to (3-12) is preferably one having a carbon number of from 1 to 10, since it is easy to synthesize and can easily obtain the surface modifier of the present invention. The alkyl group is more preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a forward stretching propyl group.

When the diol represented by the formula (2) is reacted with the isocyanate represented by the formula (3), it is contained in the formula (2) with respect to 1 mol. It is preferred to incorporate the isocyanate represented by the formula (3) in an amount of 0.5 to 1.5 moles, and to form it in a manner of 0.9 to 1.1 moles to be more preferably 0.98 to 1.02. The way the ear is placed is optimal.

In the reaction (a urethanation reaction) of the diol represented by the formula (2) and the isocyanate represented by the formula (3), in order to promote the diol and the benzene represented by the formula (2) The reaction of the isocyanate represented by the formula (3) may be, for example, a tertiary amine such as triethylamine or Benzyl Dimethyl Amine, dibutyltin dilaurate or dilauric acid. A tin compound such as Dioctyltin Dilaurate or tin 2-ethylhexanoate is used as a catalyst.

The amount of the catalyst added is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.0% by mass, even more preferably 0.02 to 0.2% by mass based on the entire reaction mixture. The reaction time is preferably from 1 to 10 hours. Further, the reaction temperature is preferably from 30 to 120 ° C, more preferably from 40 to 90 ° C.

When the reaction of the diol represented by the formula (2) with the isocyanate represented by the formula (3) (a urethanation reaction) is carried out, the reaction system may be a solventless system or may be an isocyanate group. A solvent system of a solvent such as inert acetone, methyl ethyl ketone, toluene, xylene or the like or a fluorine-based solvent as a reaction solvent.

The coating composition of the present invention is characterized by comprising the surface modifying agent of the present invention and a solvent. As the solvent, a solvent containing a fluorine atom is preferably used from the surface modifier which can satisfactorily dissolve the present invention.

Examples of the solvent containing a fluorine atom include hydrofluoroether, hydrofluorocarbon, and perfluorocarbon. The solvent of the fluorine-containing atom may be any of a linear chain, a branched form, and a cyclic form, and may contain a hetero atom. Further, the solvent of the fluorine-containing atom preferably has 2 to 12 carbon atoms, more preferably 4 to 10 carbon atoms.

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 , and HCF ₂ CF _{2 .} OCH ₂ CF ₃ and so on. 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 , and 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 or the like.

Examples of the perfluorocarbon compound 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 , and 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-butyl) Tetrahydrofuran).

Among the fluorine atom-containing solvents, it is preferably selected from the group consisting of 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 1 or more of the group of ₉ OCH ₃ , C ₄ 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 .

A coating film containing a surface modifying agent can be uniformly formed, and a film having excellent durability can be formed by a good reaction between the surface modifying agent and a substrate such as glass, and is used as a coating composition of the present invention. The content of the surface modifier is preferably from 0.01 to 50% by mass, more preferably from 0.02 to 10% by mass, even more preferably from 0.05 to 1% by mass.

The article of the present invention is characterized in that it has a film of the coating composition of the present invention on a substrate. Examples of the substrate include inorganic substrates such as glass; acrylic resins, polycarbonate resins, polyester resins, polybutylene terephthalate resins, polypropylene resins, polyamide resins, and polyamic acid. An organic substrate such as an ester resin, a polyvinyl chloride resin or a polyvinyl fluoride resin.

The substrate to be used in the present invention is a film which is excellent in antifouling property and smoothness and which is excellent in antifouling property and smoothness, and which is excellent in antifouling property and smoothness, can be formed from the surface-modifying agent of the coating composition of the present invention. A glass substrate is preferred.

As the shape of the substrate used in the present invention, various shapes can be used. Among them, it can be applied to the sheet. The thickness of the sheet-like base material can be, for example, a range of 5 μm to 800 μm.

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

The surface modifier and the coating composition of the present invention can form a film having excellent antifouling properties and smoothness on the surface of the article. By using such an excellent effect, the surface modifier and the coating composition of the present invention are particularly suitable for use in a smart phone for forming a finger swipe with a fingertip or a pen tip to directly contact a screen with a fingertip or a pen tip. And the film on the outermost surface of the tablet screen.

[Examples]

The invention is illustrated in more detail below by reference to specific examples. In the example, if not stated, "parts" and "%" are quality benchmarks. Further, the IR spectrum, ¹ H-NMR spectrum and ¹⁹ F-NMR spectrum of the obtained surface modifier were measured as follows.

[IR spectrum measurement conditions]

Device: "FT/IR-6100" manufactured by JASCO Corporation

Measuring method: KBr method

[Measurement conditions of ¹ H-NMR spectrum and ¹⁹ F-NMR spectrum]

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

Solvent: deuterated chloroform

Example 1 (Modulation of Surface Modifier)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a drip device, 88.9 g of a diol having a poly(perfluoroalkylene ether) chain represented by the following formula (2-1-1) was placed and used. 0.05 g of tin octylate of the urethanization catalyst was stirred under a nitrogen gas stream, and 11.1 g of 3-isocyanatopropyltriethoxydecane was dropped over 15 minutes while maintaining the temperature at 60 °C. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 2 hours, whereby the diol was reacted with 3-isocyanatopropyltriethoxysilane to obtain a reactant. Thereafter, the reactant was subjected to IR spectrum measurement to confirm the disappearance of the isocyanate group in the reactant. The obtained reactant was filtered and purified using a PTFE filter having a pore size of 0.2 μm to obtain a surface modifier (1) of the present invention represented by the formula (1). Here, the surface modifier (1), in the formula (1), A is an ethoxy group; Z is a n-propyl group; Y ¹ and Y ² are methylene groups.

(X is a perfluoromethylene group and a perfluoroethyl group, and an average of 21 perfluoromethylene groups per molecule, and an average of 21 perfluoroextended ethyl groups, and the number of fluorine atoms is 126).

Further, the spectrum of the IR spectrum of the surface modifier (1) is shown in Fig. ¹ , the spectrum of the ¹ H-NMR spectrum is shown in Fig. 2, and the spectrum of the ¹⁹ F-NMR spectrum is shown in Fig. 3.

Example 2 (ibid.)

45.3 g of a diol having a poly(perfluoroalkylene ether) chain represented by the above formula (2-1-1) was placed in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a drip device. 0.025 g of tin octoate of the urethanization catalyst was stirred under a nitrogen gas stream, and while maintaining 60 ° C, 4.7 g of 3-isocyanatopropyltriethoxysilane was dropped over 15 minutes. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 2 hours, whereby the diol was reacted with 3-isocyanatopropyltriethoxysilane to obtain a reactant. Thereafter, the reactant was subjected to IR spectrum measurement to confirm the disappearance of the isocyanate group in the reactant. The obtained reactant was filtered and purified using a PTFE filter having a pore size of 0.2 μm to obtain a surface modifier (2) of the present invention represented by the formula (1). Here, the surface modifier (2), in the formula (1), A is a methoxy group; Z is a n-propyl group; and Y ¹ and Y ² are methylene groups. X in the formula (2-1-1) is a perfluoromethylene group and a perfluoroexetyl group, and an average of 21 perfluoromethylene groups per molecule, and an average of 21 perfluoroextended ethyl groups. The number of fluorine atoms averaged 126.

Example 3 (ibid.)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a drip device, 54.99 g of a diol having a poly(perfluoroalkylene ether) chain represented by the above formula (2-1-1), 40 g, was placed. The fluorine-containing solvent C ₄ F ₉ OC ₂ H ₅ and 0.03 g of tin octylate as a urethanization catalyst, and stirring was started under a nitrogen gas stream, while maintaining the temperature at 50 ° C, it took 15 minutes to drip 5.01 g. 3-isocyanatopropyltriethoxydecane. After completion of the dropwise addition, the mixture was stirred at 50 ° C for 18 hours to thereby react the diol with 3-isocyanatopropyltriethoxysilane to obtain a reactant. Thereafter, the reactant was subjected to IR spectrum measurement to confirm the disappearance of the isocyanate group in the reactant. The obtained reactant 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 formula (1). Here, the surface modifier (3), in the formula (1), A is an ethoxy group; Z is a n-propyl group; and Y ¹ and Y ² are methylene groups. X in the formula (2-1-1) is a perfluoromethylene group and a perfluoroexetyl group, and an average of 30 perfluoromethylene groups per molecule, and an average of 30 perfluoroextended ethyl groups. The number of fluorine atoms averages 180.

Example 4 (ibid.)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a drip device, 55.79 g of a diol having a poly(perfluoroalkylene ether) chain represented by the above formula (2-1-1), 40 g, was placed. The fluorine-containing solvent C ₄ F ₉ OC ₂ H ₅ and 0.03 g of tin octylate as a urethanization catalyst, and stirring was started under a nitrogen gas stream, while keeping the temperature at 50 ° C, it took 4 minutes to drip 4.12 g. 3-isocyanatopropyltriethoxydecane. After completion of the dropwise addition, the mixture was stirred at 50 ° C for 18 hours to thereby react the diol with 3-isocyanatopropyltriethoxysilane to obtain a reactant. Thereafter, the reactant was subjected to IR spectrum measurement to confirm the disappearance of the isocyanate group in the reactant. The obtained reactant 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 (4) of the present invention represented by the formula (1). Here, the surface modifier (4), in the formula (1), A is a methoxy group; Z is a n-propyl group; Y ¹ and Y ² are methylene groups.

X in the formula (2-1-1) is a perfluoromethylene group and a perfluoroexetyl group, and an average of 30 perfluoromethylene groups per molecule, and an average of 30 perfluoroextended ethyl groups are present. The number of fluorine atoms averages 180.

Example 5 (Preparation of coating composition and articles)

The surface modifying agent (1) was added to C ₄ F ₉ OC ₂ H ₅ in 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 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 coating of a coating composition on the surface of the glass plate.

Using the obtained article (1), the durability of water-repellent oil repellency, smoothness, anti-fouling adhesion, and anti-fouling adhesion on the surface of the article was evaluated according to the following method. The evaluation results are shown in Table 1.

<Evaluation method of water repellency on the surface of articles>

The evaluation was carried out by measuring the contact angle of water and n-dodecane. For the measurement of the contact angle, a contact angle measuring device ("MODEL CA-W150" manufactured by Kyowa Interface Science Co., Ltd.) was used. The higher the contact angle, the better the water repellency.

<Method for evaluating the smoothness of the surface of the article>

Using a surface measuring machine ("HEIDON-14D" manufactured by Shinto Scientific Co., Ltd.), after fixing the article (1) to the sample stage and confirming the level, the probe was placed on the sample to a load of 100 g and a tensile speed of 0.3 m. The measurement was performed under the conditions of /min, and the dynamic friction coefficient was obtained. The lower the dynamic friction coefficient, the more excellent the smoothness.

<Evaluation method of anti-stain adhesion on the surface of articles>

An oily signature pen (Felt-tip pen) (a large black pen made by Sixi Chemical Industry Co., Ltd.) was streaked on the surface of the article (1), and the adhesion state of the black ink was visually observed. In addition, the evaluation criteria are as follows. The evaluation results were in the order of A>B>C>D.

A: Black ink is gathered into beads.

B: The ink is not aggregated into a bead shape, and a linear shrinkage is produced, and the line width is less than 50% of the width of the pen tip of the pen.

C: The ink is not aggregated into a bead shape, and a linear shrinkage is produced, and the line width is 50% or more and less than 100% of the width of the pen tip of the signature pen.

D: The ink does not aggregate at all, but can be smoothly drawn on the surface.

<Evaluation method of durability against stain adhesion>

In the above-mentioned "method for evaluating the anti-fouling property of the surface of the article", after the oily pen ink is wiped off, the evaluation test of the anti-fouling property of the surface of the article is again performed until the aggregation is not performed (to the evaluation of the above evaluation as "D"). ), the test for the antifouling adhesion of the surface of the article was evaluated several times. The evaluation results were in the order of A>B>C>D.

A: The antifouling adhesion test can be repeated 10 times or more.

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

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

D: The anti-fouling adhesion test could not be repeated at one time.

Examples 6-8 (ibid.)

Paint compositions (2) to (4) and articles (2) to (4) were obtained in the same manner as in Example 5 except that the surface modifiers shown in Table 1 were used. In the same manner as in Example 5, evaluation of water repellency, smoothness, and stain resistance was performed. The evaluation results are shown in Table 1.

Comparative Example 1 (Comparison of comparative paint composition and comparative control article)

In addition to the 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) described in Synthesis Example 1 of JP-A-2012-037896 ₃ ) ₃ ] [Comparative control surface modifier (1 ' )], in place of the surface modifier (1), a comparative control paint composition (1 ' ) and a comparative control article were obtained in the same manner as in Example 5. (1 ' ). In the same manner as in Example 5, the evaluation of the durability of water repellency, smoothness, antifouling adhesion, and antifouling adhesion was performed. The evaluation results are shown in Table 1.

Claims (13)

A coating composition comprising a coating composition of a surface modifying agent represented by the following general formula (1) and a solvent, wherein the content of the surface modifying agent in the coating composition is 0.05 to 1% by mass , Wherein A is a hydrolyzable group or a non-hydrolyzable group; wherein, in the two (A) ₃ , at least one of A is a hydrolyzable group; Z is a divalent linking group; Y ¹ and Y ² Each is a direct bond or a divalent linking group; PFPE is a poly(perfluoroalkylene ether) chain, and the perfluoroalkylene group of the poly(perfluoroalkylene ether) chain is perfluoromethylene and perfluorinated Ethyl, the poly(perfluoroalkylene ether) chain has an average of 21 to 30 perfluoromethylene groups with an average of 21 to 30 perfluoroextended ethyl groups. The coating composition of claim 1, wherein Z in the 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 coating composition of claim 1, wherein the hydrolyzable group is an alkoxy group having 1 to 6 carbon atoms. The coating composition of claim 1, wherein the hydrolyzable group is a methoxy group or an ethoxy group; Z is a n-propyl group, and Y ¹ and Y ² are methylene groups. The coating composition of claim 1, wherein the surface modifying agent is represented by the following formula (1-2-1), Wherein A is a hydrolyzable group or a non-hydrolyzable group, respectively; wherein, in the two (A) ₃ , at least one of A is a hydrolyzable group; and X is a group which can exist randomly or in a block form. Fluoromethylene and perfluoroethyl; n is an average of 41 to 59; Z is an alkylene group having 1 to 6 carbon atoms; and Y ¹ and Y ² are each an alkyl group having 1 to 3 carbon atoms. The coating composition of claim 5, wherein the A in the two (A) ₃ are all hydrolyzable groups; the hydrolyzable group is a methoxy group or an ethoxy group, and Z is a n-propyl group, Y ¹ and Y ² is a methylene group. The coating composition of claim 1, wherein the PFPE chain is a poly(perfluoroalkylene ether) chain, and the perfluoroalkylene group of the poly(perfluoroalkylene ether) chain is perfluoromethylene and perfluoroethylene Ethyl, the poly(perfluoroalkylene ether) chain has an average of 21 perfluoromethylene groups with an average of 21 perfluoroextended ethyl groups. The coating composition of claim 1, wherein the PFPE chain is a poly(perfluoroalkylene ether) chain, and the perfluoroalkylene group of the poly(perfluoroalkylene ether) chain is perfluoromethylene and perfluoroethylene Ethyl, the poly(perfluoroalkylene ether) chain has an average of 30 perfluoromethylene groups with an average of 30 perfluoroextended ethyl groups. The coating composition of claim 5, wherein n in the formula (1-2-1) is an average of 41 or an average of 59. The coating composition of claim 1, wherein the surface modifying agent is a raw material represented by the following formula (2) and an isocyanate represented by the following formula (3), HO-Y ¹ -PFPE -Y ² -OH‧‧‧‧‧(2)[Y ¹ and Y ² are direct bonding or divalent linking groups, respectively, PFPE is a poly(perfluoroalkylene ether) chain, and the poly(perfluoroalkylene) The perfluoroalkylene group of the ether) chain is a perfluoromethylene group and a perfluoroethylidene group, and the poly(perfluoroalkylene ether) chain has an average of 21 to 30 perfluoromethylene groups, and an average of 21 to 30 full Fluorine-extended ethyl]; OCN-Z-Si(A) ₃ ‧‧‧‧‧(3) [wherein A is a hydrolyzable group or a non-hydrolyzable group; at least one A is a hydrolyzable group; Z is 2 The link of the price]. The coating composition according to any one of claims 1 to 10, wherein the solvent is a fluorine atom-containing solvent. An article characterized by having a film of a coating composition according to any one of claims 1 to 11 on a substrate. The article of claim 12, wherein the substrate is a glass substrate.