JP2017031347A - Coating composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition capable of forming coated film excellent in antifouling property and slipping performance on a substrate such as a glass substrate and further excellent in storage stability and an article having the coated film obtained by using the composition.SOLUTION: There is provided a coating composition containing a silane compound (α) containing a poly(perfluoroalkylene ether) chain and a hydrolyzable group and alcohol (β) having an alkyl group having 1 to 10 carbon atoms and an article having the coated film of the coating composition on a substrate.SELECTED DRAWING: None

Description

  The present invention relates to a coating composition capable of forming a film having slipperiness and antifouling properties with excellent durability on a substrate such as a glass substrate. 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, the touch panel using the glass / glass combination has a very clear screen, and is also hard and weather resistant. It has excellent 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 human fingers during use, dirt derived from the human body such as fingerprints, sebum, and sweat tends to adhere to the touch panel. 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 has been adopted in which a fluorine-containing compound having both water repellency and oil repellency is coated on the outermost surface layer touched by a human finger. 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 modifying agent disclosed in Patent Document 1 has a problem that the stain is not sufficiently resistant to adhesion (antifouling property).

  In addition, among the touch panels, for example, a smartphone or tablet PC performs 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 coating composition that has a slip property and an antifouling property on a substrate, and that can provide a film having excellent durability. 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 a composition containing a silane compound containing a poly (perfluoroalkylene ether) chain and a hydrolyzable group and an alcohol having a specific range of alkyl groups has storage stability. As a result, even after long-term storage, when applied to various substrates typified by glass substrates, the resulting coatings are excellent in antifouling properties, slip properties and their durability. As a result, the present invention has been developed.

  That is, the present invention contains a silane compound (α) containing a poly (perfluoroalkylene ether) chain and a hydrolyzable group, and an alcohol (β) having an alkyl group having 1 to 10 carbon atoms. A coating composition characterized by the above is provided.

  Moreover, this invention provides the article | item characterized by having a film of the said coating composition on a base material.

  The coating composition of the present invention can suitably form a coating film on a substrate having slipperiness and antifouling property and excellent durability. Therefore, it is particularly useful for applications requiring antifouling properties and slipperiness such as touch panels. In addition, the coating composition of the present invention is less likely to generate insolubles over a long period of time and is excellent in storage stability.

FIG. 1 is an IR spectrum chart of the silane compound (α1) obtained in Synthesis Example 1. FIG. 2 is a chart of ¹ H-NMR spectrum of the silane compound (α1) obtained in Synthesis Example 1. FIG. 3 is a chart of ¹⁹ F-NMR spectrum of the silane compound (α1) obtained in Synthesis Example 1. 4 is a chart of ¹³ C-NMR spectrum of the silane compound (α1) obtained in Synthesis Example 1. FIG.

  The silane compound (α) used in the present invention contains a poly (perfluoroalkylene ether) chain and a hydrolyzable group. The inventors consider that the effect of using the silane compound (α) to obtain a film having slipperiness and antifouling properties and excellent durability is expressed as follows. ing. First, when the coating composition of the present invention is applied to the surface of a substrate represented by a glass substrate, the hydrolyzable group of the poly (perfluoroalkylene ether) chain-containing silane compound (α) is moisture in the air. To be hydroxylated. A dehydration condensation between the hydroxyl group and the hydroxyl group on the surface of the base material occurs, and a chemical bond is formed between the silane compound (α) and the base material. An excellent coating is obtained. Specifically, for example, a compound represented by the following general formula can be preferably exemplified.

〔式中、Ａはそれぞれ加水分解性基または非加水分解性基であり、式中、二つある（Ａ）_３の各々において、少なくとも一つのＡは加水分解性基である。Ｚ^１は２価の連結基である。ＰＦＰＥは、ポリ（パーフルオロアルキレンエーテル）鎖である。〕

[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 ¹ is a divalent linking group. PFPE is a poly (perfluoroalkylene ether) chain. ]

  Specific examples of the compound represented by the general formula (1) include, for example, compounds represented by the following formulas (1-1) to (1-6) and a compound represented by the following general formula (3). Etc. Also. Specific examples of the compound represented by the general formula (2) include compounds represented by the following formulas (2-1) to (2-6). In the formula, PFPE is a poly (perfluoroalkylene ether) chain.

  Further, specific examples of the compound represented by the general formula (2) include, for example, compounds represented by the following formulas (3) to (6) [hereinafter, these compounds are referred to as “poly (perfluoro Alkylene ether) chain-containing silane compound (ε) ”may be abbreviated.

[Wherein, r is an average of 5 to 100, R is a divalent linking group, R ¹ is an alkylene group having 1 to 6 carbon atoms, and X is a trivalent cycloaliphatic having 4 to 8 carbon atoms. It is a group. In the general formula (3) and the general formula (4), two Bs are organic groups or Si (A) ₃ , and at least one of the two Bs is Si (A) ₃ . A in the Si (A) ₃ is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. A in the general formulas (5) and (6) is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. ]

The compounds represented by the general formulas (1) to (6) have at least one Si (A) ₃ , and at least one A is a hydrolyzable group. By having such a silicon atom (reactive silyl group), the inventors speculate that the compounds represented by the general formulas (1) to (6) are covalently bonded to the substrate surface by the following reaction. doing. 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 substrate, the compounds represented by the general formulas (1) to (6) are formed by covalent bonds formed by these condensation reactions. The coating composition containing, is more firmly fixed to the surface of the substrate than the conventional invention product, and has antifouling properties exhibited by the poly (perfluoroalkylene ether) chain of the compounds represented by the general formulas (1) to (6) It is possible to form a film having excellent durability while having slipperiness.

  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; and a halogen such as chlorine. Among the hydrolyzable groups, an alkoxy group is preferable because it has a high hydrolysis rate and can form a coating with excellent durability while having both antifouling properties and slipperiness, and has 1 to 6 carbon atoms. Are more preferred, alkoxy groups having 1 to 3 carbon atoms are more preferred, methoxy groups and ethoxy groups are more preferred, and methoxy groups are most preferred.

  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. Among these, the hydrolysis rate can be increased by avoiding steric hindrance, and as a result, it is possible to form a film having excellent durability while having both antifouling properties and slip properties, so that alkyl having 1 to 3 carbon atoms can be formed. 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 coating composition capable of forming a film having more durability can be obtained. It is more preferable that all of 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.

  In the present invention, as the silane compound (α) containing a poly (perfluoroalkylene ether) chain and a hydrolyzable group, a film having more excellent antifouling properties and slipperiness can be suitably formed on an article. To the compound represented by the general formula (1) is more preferable. Among the compounds represented by the general formula (1), a compound represented by the following general formula (7) is more preferable.

〔式中、Ａはそれぞれ加水分解性基または非加水分解性基であり、式中、二つある（Ａ）_３の各々において、少なくとも一つのＡは加水分解性基である。Ｚは２価の連結基である。Ｙ^１及びＹ^２は、それぞれ直接結合または２価の連結基である。ＰＦＰＥは、ポリ（パーフルオロアルキレンエーテル）鎖を表す。〕で表される。

[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.

Z in the general formula (7) is a divalent linking group. Y ¹ and Y ² are each a direct bond or a divalent linking group. As a bivalent 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, 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 And alkylene groups such as a group, 3-octylene group, 2-propylpentylene group, 2,4,4-trimethylpentylene group and decaoctylene group.

  Z is preferably an alkylene group having 1 to 10 carbon atoms because synthesis is easy and a compound represented by the general formula (7) used in the present invention can be easily obtained. Are more preferable, an alkylene group of 1 to 3 is more preferable, and an n-propylene group is particularly preferable.

In addition, 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 coating composition that provides a more excellent antifouling property is obtained. An alkylene group having 1 to 3 carbon atoms is more preferable, and a methylene group is more preferable in terms of excellent antifouling property and industrially easily obtained.

  Two Z in the general formula (7) may be the same or different. The compound represented by the general formula (7) may be a mixture of modifiers having different Zs.

Y ¹ and Y ² in the compound represented by the general formula (7) may be the same or different. The compound represented by the general formula (7) may be a mixture of modifiers having different Y ¹ and Y ² .

  The compound represented by the general formula (7) has a urethane bond in the skeleton. By having this urethane bond, the polarity of the compound represented by the general formula (7) in the vicinity of the hydrolyzable groups at both ends is improved. 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 silane compound represented by the general formula (7) are shown below. In the formula, PFPE represents a poly (perfluoroalkylene ether) chain.

  Preferred examples of the PFPE [poly (perfluoroalkylene ether) chain] include those having a structure in which perfluoroalkylene groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The perfluoroalkylene group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds. Specifically, those represented by the following structural formula (P-1) may be used. Can be mentioned.

（上記構造式（Ｐ−１）中、Ｘはパーフルオロアルキレン基である。該Ｘはその全てが同一構造のものであっても良いし、また、複数の構造がランダムにまたはブロック状に存在していても良い。）

(In the structural formula (P-1), X is a perfluoroalkylene group. All of X may have the same structure, or a plurality of structures are present randomly or in a block form. You may do it.)

  Examples of X include 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 (a) and a perfluoroethylene group (b) 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. 10 to 10/3 is more preferable.

  Among the silane compounds represented by the general formula (7), examples of the silane compound having a perfluoroalkylene group having 1 to 3 carbon atoms preferably include those represented by the following structural formula.

〔式中、Ａはそれぞれ加水分解性基または非加水分解性基であり、式中、二つある（Ａ）_３の各々において、少なくとも一つのＡは加水分解性基である。Ｘはその全てが同一構造のものであっても良いし、また、複数の構造がランダムにまたはブロック状に存在していても良い炭素原子数１〜３のパーフルオロアルキレン基である。Ｚは炭素原子数１〜６のアルキレン基である。Ｙ^１及びＹ^２はそれぞれ炭素原子数１〜３のアルキレン基である。ｎは合計で６〜３００である。〕

[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 may be 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 silane compound represented by the formula (7-2) has an oxygen atom and a perfluoroalkylene group having 1 to 3 carbon atoms and a short chain length present between the oxygen atoms. Thus, in addition to having a perfluoroalkylene group having a short chain length, the silane compound (α) becomes a flexible skeleton by increasing the proportion of oxygen atoms that easily bend the perfluoroalkylene group. As a result, it is possible to form a film having excellent slipperiness on the article. 12-200 are more preferable, as for n in general formula general formula (7-2), 20-150 are more preferable, 30-100 are still more preferable, and 35-70 are especially preferable.

  As a silane compound represented by said (7-2), what is represented by a following formula can be illustrated, for example.

  The poly (perfluoroalkylene ether) chain preferably has a total number of fluorine atoms in the range of 30 to 600 in one poly (perfluoroalkylene ether) chain from the viewpoint of excellent dirt wiping property and slipperiness. More preferably, the range is 60 to 450, more preferably 90 to 300, and particularly preferably 100 to 200.

〔式中、Ｙ^１及びＹ^２はそれぞれ２価の連結基である。〕で表されるジオールと、下記一般式（α―２） The silane compound represented by the general formula (7) is, for example, the following general formula (α-1)

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

〔式中、Ａは加水分解性基または非加水分解性基であり、少なくとも一つのＡは加水分解性基である。Ｚは２価の連結基である。〕で表されるイソシアネートとを反応させることにより好ましく得ることができる。具体的には、本発明のシラン化合物（α）は、一般式（α―１）で表されるジオールと一般式（α―２）で表されるイソシアネートを原料とする化合物である。

[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. Specifically, the silane compound (α) of the present invention is a compound using a diol represented by the general formula (α-1) and an isocyanate represented by the general formula (α-2) as raw materials.

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

  Examples of the diol represented by the general formula (α-1) include the diols shown below.

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

（Ｘはその全てが同一構造のものであっても良いし、また、複数の構造がランダムにまたはブロック状に存在していても良い炭素原子数１〜３のパーフルオロアルキレン基である。ｎは合計で６〜３００である。〕

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

  As isocyanate represented by the said general formula ((alpha) -2), the isocyanate etc. which are shown below can be illustrated, for example.

  Z in the isocyanate compounds represented by the formulas (α-2-1) to (α-2-12) can be easily synthesized, and a silane compound represented by the general formula (7) can be easily obtained. Therefore, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 3 carbon atoms is further preferable, and an n-propylene group is particularly preferable.

  When the diol represented by the general formula (α-1) is reacted with the isocyanate represented by the general formula (α-2), 1 mol of the OH group contained in the general formula (α-1) is reacted. The isocyanate represented by the general formula (α-2) is preferably charged so as to be 0.5 to 1.5 mol, more preferably 0.9 to 1.1 mol. It is most preferable to prepare such that the amount is 0.98 to 1.02 mol.

  In the reaction (urethanization reaction) of the diol represented by the general formula (α-1) and the isocyanate represented by the general formula (α-2), the diol represented by the general formula (α-1) In order to promote the reaction with the isocyanate represented by the formula (α-2), for example, tertiary amines such as triethylamine and benzyldimethylamine, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, etc. It can be carried out using a tin compound 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, 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. Moreover, 30-120 degreeC of reaction temperature is preferable, More preferably, it is 40-90 degreeC.

  When performing the reaction (urethanization reaction) between the diol represented by the general formula (α-1) and the isocyanate represented by the general formula (α-2), the reaction system may be a solventless system, A solvent system using a solvent such as acetone, methyl ethyl ketone, toluene, xylene or the like, which is not reactive with an isocyanate group, or a fluorine-based solvent as a reaction solvent may be used.

  The alcohol (β) used in the coating composition of the present invention has an alkyl group having 1 to 10 carbon atoms. By containing the alcohol (β), a coating composition having excellent storage stability can be obtained. The said silane compound ((alpha)) has a property which is easy to produce | generate an insoluble matter by advancing the hydrolysis condensation reaction resulting from the reaction with the water | moisture content in air in storage. In the present invention, the coexistence of the silane compound (α) and the alcohol (β) causes the alcohol (β) to suppress the reaction between the silane compound (α) and moisture, and as a result, the coating of the present invention. The present inventors presume that the agent becomes a coating composition having excellent storage stability.

  Examples of the alcohol (β) include methanol, ethanol, isopropanol, butanol, hexanol and the like. Among them, an alcohol having an alkyl group having 1 to 4 carbon atoms is preferable because a coating composition having more excellent storage stability is obtained, and one or more alcohols selected from the group consisting of methanol, ethanol, isopropanol, and butanol are more preferable. preferable.

  As specific examples of the compound represented by the general formula (2), the compounds represented by the general formulas (3) to (6) will be described. [As described above, these compounds may be abbreviated as “poly (perfluoroalkylene ether) chain-containing silane compounds (ε)”].

The compound represented by the general formula (3) to the general formula (6) has at least one Si (A) ₃ , and at least one A in each (A) ₃ is a hydrolyzable group. It is. By having such a silicon atom (reactive silyl group), the compound represented by the general formula (3) to the general formula (6) is a base material by the same action as the compound represented by the general formula (1). As a result, the coating composition of the present invention can form a film excellent in durability while having both antifouling property and slipperiness.

In general formula (3) to formula (6), having a large number of trifluoromethyl group (CF ₃ group). The CF ₃ group has a strong ability to reduce the surface energy. Therefore, by having a large number of CF ₃ groups, the silane compounds represented by the general formulas (3) to (6) can more effectively exhibit antifouling properties.

The compound represented by the general formula (3) and the compound represented by the general formula (4) have two groups represented by B, and at least one is the Si (A) ₃ .

When one of B of the compound represented by the general formula (3) and the compound represented by the general formula (4) is Si (A) ₃ , the other B is an organic group other than Si (A) _3. . Examples of the organic group include an alkyl group, an alkenyl group, and a phenyl group. In the alkyl group, some or all of the hydrogen atoms may be substituted with other atoms or atomic groups. Specific examples of the alkyl group in which some or all of the hydrogen atoms are substituted with other atoms or atomic groups include a partially fluorinated alkyl group and a perfluoroalkyl group. In the partially fluorinated alkyl group, the number of carbon atoms to which fluorine atoms are bonded is preferably 1-6. The number of carbon atoms in the perfluoroalkyl group is also preferably 1-6. By containing such a fluorinated alkyl group having the number of carbon atoms as B, further improvement in antifouling performance to the coating can be expected.

R in the silane compound represented by the general formula (3) to the general formula (6) is 5 to 100 on average. r is preferably 8 to 80 on average and more preferably 10 to 60 on average because a coating composition that provides a film with excellent antifouling properties can be obtained as the content of CF ₃ groups increases.

  R in the silane compound represented by the general formulas (3) to (6) is a divalent linking group. The R is, for example, the following (R-1)

（式中、Ｒ^２およびＲ^４はそれぞれ炭素原子数１〜５のアルキレン基であり、Ｒ^３は直接結合または炭素原子数１〜６のアルキレン基である）
で表される構造を好ましく例示できる。

(Wherein R ² and R ⁴ are each an alkylene group having 1 to 5 carbon atoms, and R ³ is a direct bond or an alkylene group having 1 to 6 carbon atoms)
The structure represented by can be illustrated preferably.

  Specific examples of the structure represented by (R-1) are shown below.

  Specific examples of the structure represented by (R-2) are shown below.

  Among the structures represented by the above (R-1) and (R-2), the raw material for producing the silane compound (ε) used in the present invention can be stably obtained, and a group such as a glass substrate can be obtained. (R-1-1), (R-1-3), (R-1) because a coating composition capable of forming a film having excellent durability and anti-slip properties on the material can be obtained. -4), (R-2-1), (R-2-2), and a structure represented by (R-2-4) are preferable, and (R-1-3) and (R-1-4) The structure represented by is more preferable.

  As described above, X represented by the general formulas (4) and (6) is a trivalent cyclic aliphatic group having 4 to 8 carbon atoms. As the cycloaliphatic group, for example, a cyclohexane ring can be preferably exemplified.

  Specific examples of the silane compounds represented by the general formulas (3) to (6) are shown below.

In the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (3) and the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (4) used in the present invention, both B are The compound of Si (A) ₃ can be obtained, for example, by the following production method.

  Production Method 1: General Formula (ε-1)

（式中、ｒは平均５〜１００である。）
で表されるカルボン酸（ε―１）と、下記一般式（ε−２）または一般式（ε−３）

(In the formula, r is an average of 5 to 100.)
And the following general formula (ε-2) or general formula (ε-3)

（式中Ｒはそれぞれ二価の連結基である。Ａは加水分解性基または非加水分解性基であり、そのうちの少なくとも一つは加水分解性基である。）で表されるエポシキシラン化合物とを反応させて、エポキシ基由来の２級水酸基を有する反応物を得る第一工程と、該反応物と下記一般式（ε―４）

(Wherein R is a divalent linking group, A is a hydrolyzable group or a non-hydrolyzable group, at least one of which is a hydrolyzable group) To obtain a reaction product having a secondary hydroxyl group derived from an epoxy group, the reaction product and the following general formula (ε-4)

（Ｒ^１は炭素原子数１〜６のアルキレン基である。Ａは加水分解性基または非加水分解性基である。）で表されるイソシアネート化合物（ε−４）とを反応させる第二工程を含む製法。

(R ¹ is an alkylene group having 1 to 6 carbon atoms. A is a hydrolyzable group or a non-hydrolyzable group.) The second step of reacting with an isocyanate compound (ε-4) represented by Manufacturing method including.

In the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (5) and the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (6), one of B Is a Si (A) ₃ and the other B is an organic group other than Si (A) ₃ can be obtained by the following production method.

  Production method 2: Carboxylic acid (ε-1) represented by the general formula (ε-1) and the following general formula (ε-5)

（式中Ｒは二価の連結基である。Ｇは有機基である）で表されるエポキシ化合物（ε―５）とを反応させて、エポキシ由来の２級水酸基を有する反応物を得る第一工程と、該反応物と前記一般式（ε―４）で表されるイソシアネート化合物（ε―４）とを反応させる第二工程とを含む製法。

(Wherein R is a divalent linking group, G is an organic group) is reacted with an epoxy compound (ε-5) to obtain a reaction product having a secondary hydroxyl group derived from epoxy. A process comprising one step and a second step of reacting the reactant with the isocyanate compound (ε-4) represented by the general formula (ε-4).

  The poly (perfluoroalkylene ether) chain-containing silane compound represented by general formula (5) or general formula (6) used in the present invention can be obtained, for example, by the first step of the production method 1.

  R in the carboxylic acid (ε-1) is preferably 8 to 80 on average and more preferably 10 to 60 because a coating composition exhibiting high antifouling performance can be obtained. Carboxylic acid (ε-1) may be used alone or in combination of two or more.

  Preferred examples of the epoxy silane compound (ε-2) and the epoxy silane compound (ε-3) include the compounds shown below.

  Since the epoxy silane compound (ε-2) and the epoxy silane compound (ε-3) are easily available industrially, the (ε-2-1), (ε-2-2), (ε-3) -1) and one or more compounds selected from the group consisting of (ε-3-2) are preferable, and (ε-2-1) and (ε-2-2) are more preferable. The epoxy silane compound (ε-2) and the epoxy silane compound (ε-3) may be used alone or in combination of two or more.

  As said isocyanate compound ((epsilon) -4), the compound etc. which are shown below can be illustrated preferably, for example.

(Wherein R ¹ is an alkylene group having 1 to 6 carbon atoms)

R ¹ in the isocyanate compounds represented by the above formulas (ε-4-1) to (ε-4-12) is easy to synthesize, and can easily be synthesized with the poly (perfluoroalkylene ether) chain-containing silane compound (ε Is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably an n-propylene group.

  Since the isocyanate compound (ε-4) is a coating composition with excellent reactivity and a highly durable film, (ε-4-1), (ε-4-2) and (ε-4) -3) is preferably one or more compounds selected from the group consisting of (ε-4-1) and (ε-4-2). The isocyanate compound (ε-4) may be used alone or in combination of two or more.

  As the epoxy compound (ε-5), for example, the following compounds can be preferably exemplified.

  Among the epoxy compounds (ε-5), the above (ε-5-1) or (ε-5-2) is preferable, and (ε-5-2) is more preferable in order to obtain a coating film having excellent antifouling properties. . An epoxy compound ((epsilon) -5) may be used independently and may use 2 or more types together.

  You may perform reaction in the said manufacturing method 1-manufacturing method 2 in presence of an organic solvent as needed. The organic solvent is not particularly limited as long as it dissolves the compound as a raw material. Further, a solvent system using a solvent such as acetone, methyl ethyl ketone, toluene, xylene or the like inert to an isocyanate group or a fluorine-based solvent as a reaction solvent may be used.

Examples of the fluorine-based solvent include fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis (trifluoromethyl) benzene and trifluorotoluene; carbon numbers of 3 to 3 such as perfluorohexane and perfluoromethylcyclohexane. 12 perfluorocarbon solvents; 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4,5,5,6 hydrofluorocarbon based solvents such as _{6-tridecafluoro-octane; 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, Hydrofluoroether solvents such as Fomblin, Galden (Solvay), Demnam (Daikin Kogyo), Krytox (Kemers), etc. It can be preferably exemplified ether-based compounds.

  In the first step of production method 1, the reaction ratio between the carboxylic acid (ε-1) and the epoxysilane compound [(ε-2), (ε-3)] is the carboxyl group of the carboxylic acid (ε-1). And the epoxy group of the epoxy silane compound have an equivalent ratio (carboxyl group / epoxy group) of preferably 0.5 to 1.5, more preferably 0.9 to 1.1. A ratio of 98 to 1.02 is most preferred.

  The reaction temperature of the 1st process of the said manufacturing method 1 is 50-150 degreeC normally. Moreover, reaction time is 1 to 10 hours normally.

  In the second step of the production method 1, the reaction ratio between the reaction product having a secondary hydroxyl group derived from an epoxy group and the isocyanate compound (ε-4) is the same as that of the hydroxyl group and isocyanate compound (ε-4) of the reaction product. The ratio with which the equivalent ratio with the group (hydroxyl group / isocyanate group) is 0.5 to 1.5 is preferable, the ratio with 0.9 to 1.1 is more preferable, and 0.98 to 1.02 is preferable. The ratio is most preferred.

  The reaction temperature in the second step of the production method 1 is usually 30 to 120 ° C. Moreover, reaction time is 1 to 10 hours normally.

  In the first step of production method 2, the reaction ratio between the carboxylic acid (ε-1) and the epoxy compound (ε-5) is such that the carboxyl group of the carboxylic acid (ε-1) and the epoxy compound (ε-5) are The ratio in which the equivalent ratio (carboxyl group / epoxy group) with the epoxy group is 0.5 to 1.5 is preferable, the ratio 0.9 to 1.1 is more preferable, and 0.98 to 1.02 The ratio is most preferable.

  The reaction temperature in the first step of production method 2 is usually 50 to 150 ° C. Moreover, reaction time is 1 to 10 hours normally.

  In the second step of the production method 2, the reaction ratio between the reaction product having a secondary hydroxyl group derived from an epoxy group and the isocyanate compound (ε-4) is the isocyanate content of the hydroxyl group and isocyanate compound (ε-4) of the reaction product. The ratio with which the equivalent ratio with the group (hydroxyl group / isocyanate group) is 0.5 to 1.5 is preferable, the ratio with 0.9 to 1.1 is more preferable, and 0.98 to 1.02 is preferable. The ratio is most preferred.

  The reaction temperature in the second step of the production method 2 is usually 30 to 120 ° C. Moreover, reaction time is 1 to 10 hours normally.

  In the present invention, as the silane compound (α), a compound represented by the general formula (1) and a compound represented by the general formulas (3) to (6) [poly (perfluoroalkylene ether) chain-containing silane It is preferable because a coating composition capable of forming a film having excellent antifouling properties and slip properties can be obtained by using in combination with one or more compounds selected from the group consisting of the compounds (ε)]. When the silane compound represented by the general formula (1) and the silane compound (ε) are used in combination, a poly (perfluoroalkylene ether) chain is used with respect to 1 part by mass of the silane compound represented by the general formula (1). The contained silane compound (ε) is preferably 0.01 to 100 parts by mass, more preferably 0.05 to 20 parts by mass, and still more preferably 0.1 to 2 parts by mass.

  The content of the alkyl alcohol (β) in the coating composition of the present invention is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass in the coating composition. More preferably, it is 1-10 mass%.

  In addition, the content of the alkyl alcohol (β) in the coating composition of the present invention is 0.1 to 500 parts by mass with respect to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). Preferably, 1-100 mass parts is more preferable, and 5-50 mass parts is still more preferable.

  The coating composition of the present invention may further contain a catalyst that promotes hydrolysis of alkoxysilane [alkoxysilane hydrolysis catalyst (γ)]. By containing an alkoxysilane hydrolysis catalyst (γ), a coating having more durability, antifouling properties and slipperiness can be obtained, and a coating composition having excellent storage stability can be obtained.

  The alkoxysilane hydrolysis catalyst (γ) is one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, phosphoric acid compounds, sulfonic acid compounds, tin compounds, titanium compounds and zirconium compounds. However, it is excellent in storage stability because hydrolysis of the hydrolyzable group and dehydration condensation of the generated hydroxyl group do not occur during storage in the coating composition, and when the coating composition of the present invention is applied to the substrate Efficiently hydrolyzes hydrolyzable groups and dehydrates and condenses with hydroxyl groups on the substrate. As a result, a film having excellent durability, antifouling properties and slipperiness is obtained, and storage stability is improved. It is preferable because an excellent coating composition can be obtained.

  Examples of the amine compound include methylamine, ethylamine, triethylamine, tributylamine, trihexylamine, trioctylamine, dimethylaminoethanol, diethylaminoethanol, dibutylaminoethanol, dimethylaminopropanol, dimethyldecylamine, dodecyldimethylamine, Examples include methyldiethanolamine, ethyldiethanolamine, butyldiethanolamine, ethylenediamine, tetramethylethylenediamine, and hexamethylenediamine. In addition, cyclic amines such as aniline, pyridine, pyridine ethanol, aminopyridine, N, N-dimethyl-4-aminopyridine and the like can also be exemplified as amine compounds.

  Examples of the carboxylic acid compounds include formic acid, glacial acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, benzoic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid. Nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, glycolic acid, perfluorobutyric acid and the like.

  Examples of the phosphoric acid compound include phosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, hypophosphoric acid, hypophosphorous acid, and phosphoric acid derivatives; alkali metal salts of these phosphoric acid compounds Or ammonium salt etc. are mentioned.

  Examples of the sulfonic acid compound include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like.

  Examples of the tin compound include dibutyltin diacetate, bis (acetoxydibutyltin) oxide, bis (lauroxydibutyltin) oxide, dibutyltin bisacetylacetonate, dibutyltin bismaleic acid monobutyl ester, and dioctyl bismaleic acid monobutyl ester. Can be mentioned.

  Examples of the titanium compound include diisopropoxy titanium bis (acetylacetonate), titanium tetra (acetylacetonate), dioctanoxy titanium dioctanoate, diisopropoxy titanium bis (ethyl acetoacetate), tetraisopropyl titanate, Examples include tetrabutyl titanate.

  Examples of the zirconium compound include zirconium tetranormal butoxide.

  Among the alkoxysilane hydrolysis catalysts (γ), one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and tin compounds become a coating composition having both reactivity and stability. preferable.

  The content of the alkoxysilane hydrolysis catalyst (γ) is preferably 0.01 to 20 parts by mass, and 0.05 to 10 parts by mass with respect to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). Part is more preferable, and 0.1 to 5 parts by mass is most preferable.

The coating composition of the present invention further includes the following general formula (8)
R ² -R ¹ -R ³ (8)
[Wherein, -R ¹ -represents the following formula:
_{- (OC 4 F 8) w} - (OC 3 F 6) r - (OC 2 F 4) s - (OCF 2) t -O-
Wherein r, s, t and w are each independently an integer of 0 to 300, and the sum of r, s, t and w is at least 5, and the presence of each repeating unit in parentheses The order is arbitrary in the formula.) R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is -O-, -COO-, -CONH- between the bonds between carbon atoms. , —OCONH— may have one or more linking groups, or a part of hydrogen atoms of the hydrocarbon group may be substituted with —OH, —COOH, —OPO (OH) _2. The hydrocarbon group may be a hydrocarbon group in which part or all of the hydrogen atoms of the hydrocarbon group may be substituted with fluorine atoms. ]
The fluorine compound ((DELTA)) represented by these can be contained. By containing a fluorine compound (Δ), it is possible to provide a coating composition that can provide a film having excellent durability and antifouling properties and slipperiness. The fluorine compound (Δ) is a non-reactive fluorine-containing polymer also called fluorine-containing oil. In the present invention, when referring to the number of carbon atoms of a hydrocarbon group, carbon atoms of “—COO—”, “—CONH—”, and “—COOH” are not included in the number.

R ² and R ³ in the general formula (8) of the fluorine compound (Δ) used in the present invention can provide a film having excellent slipperiness, so that even if some or all of the hydrogen atoms are substituted with fluorine atoms. A good alkyl group having 1 to 4 carbon atoms is preferable, and since a film having excellent antifouling property in addition to slipperiness is obtained, an alkyl group having 1 to 4 carbon atoms in which all of the hydrogen atoms are substituted with fluorine atoms Is more preferable. This is because, since R ² and R ³ have a structure similar to R ¹ in the general formula (8), the molecular chain becomes flexible and the structure has excellent water and oil repellency. The inventors speculate that a film with better properties can be obtained.

  As a fluorine compound represented by the said General formula (8), the following compound can be illustrated preferably, for example.

［式中、ｒ’、ｓ’およびｔ’はそれぞれ１〜２００の整数である。Ｒ^２およびＲ^３は、炭素原子数１〜２０の１価の炭化水素基であり、該炭化水素基は途中に−Ｏ−、−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯＮＨ−から選ばれる一種以上の連結基を有していても良いし、該炭化水素基の水素原子の一部が−ＯＨ、−ＣＯＯＨ、−ＯＰＯ（ＯＨ）_２で置換されていても良いし、該炭化水素基の水素原子の一部または全部がフッ素原子で置換されていても良い炭化水素基である。］

[Wherein, r ′, s ′ and t ′ each represent an integer of 1 to 200. R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is one or more selected from —O—, —COO—, —CONH—, and —OCONH— along the way. Or a part of hydrogen atoms of the hydrocarbon group may be substituted with —OH, —COOH, —OPO (OH) ₂ , or hydrogen of the hydrocarbon group It is a hydrocarbon group in which some or all of the atoms may be substituted with fluorine atoms. ]

Examples of R ² and R ³ in the general formula (8) include the following hydrocarbon groups.

  In the compound represented by the general formula (8-1), r ′ is preferably in the range of 10 to 70, more preferably in the range of 20 to 65, and more preferably in the range of 35 to 60 because a film excellent in slipperiness is obtained. Is particularly preferred.

  In the compound represented by the general formula (8-2), s ′ is preferably in the range of 5 to 160 because a film excellent in slipperiness can be obtained. t 'is preferably in the range of 5 to 160. The total of s ′ and t ′ is preferably in the range of 20 to 220, more preferably in the range of 30 to 180, and more preferably in the range of 50 to 120.

  In the compound represented by the general formula (8-3), r ′ is preferably in the range of 8 to 60 because a film excellent in slipperiness can be obtained. t 'is preferably in the range of 8-60. The total of r 'and t' is preferably in the range of 8 to 60, more preferably in the range of 15 to 50, and particularly preferably in the range of 25 to 45.

  In the compound represented by the general formula (8-4), r ′ is preferably in the range of 7 to 70, more preferably in the range of 10 to 60, and more preferably in the range of 20 to 50 because a film excellent in slipperiness is obtained. Is particularly preferred.

  Among the compounds represented by the general formulas (8-1) to (8-4), since a film having more excellent slip properties can be obtained, the compound represented by the general formula (8-2) is more preferable. preferable. This is because the repeating structure of the compound represented by the general formula (8-2) has no branched structure in the molecular chain, and the perfluoroalkylene group sandwiched between oxygen atoms has a short chain. This is based on the inventors' assumption that the skeleton is flexible.

  The number average molecular weight of the fluorine compound (Δ) used in the present invention is preferably from 1,500 to 25,000, more preferably from 3,000 to 17,000 because a coating composition having a higher sliding property can be obtained. Preferably, 4,500 to 11,000 is particularly preferable.

In the present invention, the number average molecular weight of the fluorine compound (Δ) is an average value calculated from the terminal structure and the integration ratio of the repeating units measured by ¹⁹ F-NMR.
0144

  The content of the compound (Δ) in the coating composition of the present invention is 2 to 50 parts by mass with respect to 10 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α), and high slipperiness, and From the point which is excellent in both durability of slipperiness and antifouling property, 4-25 mass parts is more preferable, and 6-16 mass parts is especially preferable. By containing the compound (α) and the compound (Δ) in the above range, the compound (α) reacts with the base material to firmly adhere to the surface of the base material, thereby expressing durability. The compound (Δ) acts as a slipping expression component on the surface of the base material without reacting with the base material, and imparts further slipping property to the coating, thereby increasing the slipping property and increasing the durability. They speculate.

  The fluorine compound (Δ) used in the present invention can be obtained by synthetic methods for forming various perfluoropolyethers well known to those skilled in the art. Moreover, you may use a commercial item. Examples of the commercially available products include Fomblin (registered trademark) Y series manufactured by Solvay Specialty Polymers, for example, Y04, Y06, Y15, Y25, Y45, YU700, YR, YPL1500, YR1800; Fomblin (registered trademark) M Series, such as M03, M07, M15, M30, M60, M100; Fomblin® Z series, such as Z03, Z15, Z25, Z60; Krytox® GPL manufactured by Kemers, such as GPL100, GPL101, GPL102, GPL103, GPL104, GPL105, GPL106, GPL107; Daikin Industries, Ltd. demnum (trademark) S-20, S-65, S-200 etc. are mentioned. Only one type of fluorine compound (Δ) may be used, or two or more types may be used in combination.

  The coating composition of this invention can also mix the solvent containing a fluorine atom. Examples of the solvent containing a fluorine atom include hydrofluoroether, hydrofluorocarbon, perfluorocarbon, fluorine-containing aromatic hydrocarbon, and perfluoropolyether compound. The solvent containing a fluorine atom may be linear, branched or cyclic, and may contain a hetero atom. Moreover, 2-12 are preferable and, as for the carbon atom number of the solvent containing a fluorine atom, 4-10 are more preferable.

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.

  Examples of the fluorine-containing aromatic hydrocarbon include 1,3-bis (trifluoromethyl) benzene and trifluorotoluene.

  Examples of the perfluoropolyether compound include Fomblin, Galden (manufactured by Solvay), Demnam (manufactured by Daikin Industries), Krytox (manufactured by Chemers), and the like.

Among the solvents containing fluorine atoms used in the present invention, C ₄ F ₉ C ₂ H ₅ , (CF ₃ ) ₂ CFCHFCHFCCF ₃ , because the silane compound (α) has good solubility and is easy to obtain a uniform composition. _{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 _HCF 2 _CF 2 OCH One or more solvents selected from the group consisting of ₂ CF ₃ are preferred. The coating composition of the present invention preferably contains 50 to 99.99% by mass, more preferably 90 to 99.98% by mass, and even more preferably 99 to 99.95% by mass. .

  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 substrate used in the present invention, the silane compound in the coating composition of the present invention reacts satisfactorily, and a coating film having excellent antifouling property and slipperiness and durability can be formed on the substrate. 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. The thickness of a sheet-like base material can illustrate the thing of the range of 5 micrometers-10 mm, for example.

  Various methods can be used as a method of 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 coating composition of the present invention can form a film having excellent antifouling properties and slipperiness on the article surface. 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 preferably used for forming a film on the outermost surface of the screen of a smartphone or tablet PC to be performed. Moreover, it can use preferably also for antifouling uses, such as lenses, such as a camera and glasses, the glass surface used for a motor vehicle or a house, and an exhibition panel.

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. In addition, the measurement conditions of IR spectrum of the obtained silane compound, < ¹ > H-NMR spectrum, < ¹⁹ > F-NMR spectrum, and < ¹³ > C-NMR spectrum are as follows.

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

[Measurement conditions for ¹ H-NMR spectrum, ¹ H-NMR spectrum, ¹⁹ F-NMR spectrum, ¹³ C-NMR spectrum]
Apparatus: “JNM-ECA500” manufactured by JEOL Ltd.
Solvent: DMSO-d6

Synthesis Example 1 [Synthesis of poly (perfluoroalkylene ether) chain-containing silane compound (α)]
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 66.67 g of hydrofluoroether (C ₄ F ₉ OC ₂ H ₅ ) and the following formula (α-1-1-1)

（Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均２１個、パーフルオロエチレン基が平均２１個存在するものであり、フッ素原子の数が平均１２６である。）
で表されるポリ（パーフルオロアルキレンエーテル）鎖を有するジオール４５．３ｇと、３−イソシアナトプロピルトリメトキシシラン４．７ｇと、ウレタン化触媒としてオクチル酸スズ０．０１５ｇを仕込み、窒素気流下で攪拌を開始し、６０℃に加温後、ＩＲ測定によりイソシアネート基の消失が確認されるまで約３時間反応させ、反応物を得た。

(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.)
45.3 g of a diol having a poly (perfluoroalkylene ether) chain represented by: 4.7 g of 3-isocyanatopropyltrimethoxysilane and 0.015 g of tin octylate as a urethanization catalyst, Stirring was started, and the mixture was heated to 60 ° C. and reacted for about 3 hours until the disappearance of the isocyanate group was confirmed by IR measurement to obtain a reaction product.

The reaction product was diluted with C ₄ F ₉ OC ₂ H ₅ so that the solvent content in the obtained reaction product was 70%. The diluted reaction product is purified by filtration using a polytetrafluoroethylene (PTFE) filter having a pore size of 1 μm, and the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (7) is used in the present invention. A solvent solution containing (α1) was obtained. Here, in the silane compound (α1), in the general formula (7), A is an ethoxy group, Z is an n-propylene group, and Y ¹ and Y ² are methylene groups.

The chart of the IR spectrum of the silane compound (α1) is shown in FIG. 1, the chart of the ¹ H-NMR spectrum is shown in FIG. 2, the chart of the ¹⁹ F-NMR spectrum is shown in FIG. 3, and the ¹³ C-NMR spectrum is shown. A chart is shown in FIG.

Synthesis Example 2 [Synthesis of poly (perfluoroalkylene ether) chain-containing silane compound (ε)]
In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 60.62 g of 1,3-bis (trifluoromethyl) benzene and the following formula

（式中、ｒは平均４３である。）

(Wherein r is 43 on average)

87.6 g of carboxylic acid represented by the formula, 3.33 g of γ-glycidoxypropyltriethoxysilane and 0.273 g of triphenylphosphine as a reaction catalyst are added, and stirring is started under a nitrogen stream, After warming, the reaction was allowed to proceed for about 5 hours. Thereafter, the temperature was lowered to 50 ° C., 33.33 g of C ₄ F ₉ OC ₂ H _5, 3.02 g of 3-isocyanatopropyltriethoxysilane, and 0.047 g of tin octylate as a urethanization catalyst were added, Stirring was started and the reaction was carried out at 70 ° C. for about 4 hours to obtain a reaction product.

The reaction product was diluted with C ₄ F ₉ OC ₂ H ₅ so that the solvent content in the obtained reaction product was 70%. The diluted reaction product is purified by filtration using a polytetrafluoroethylene (PTFE) filter having a pore size of 1 μm, and the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (3) is used in the present invention. A solvent solution containing (ε1) was obtained. Here, in the silane compound (ε1), in the general formula (3), r is an average of 43, (—R—) is (—CH ₂ OCH ₂ CH ₂ CH ₂ —), and (—R ¹ —) is In (—CH ₂ CH ₂ CH ₂ —), B is Si (OC ₂ H ₅ ) ₃ .

Example 1 (Preparation of coating compositions and articles)
A solvent solution containing the silane compound (α1) was mixed with 20 g, 5 g of methanol and 1 g of 2- (dimethylamino) ethanol in terms of film forming components (solid content) to obtain a mixed solution. Further, C ₄ F ₉ OC ₂ H ₅ which is a fluorine atom-containing solvent is added to this mixed solution so that the content of the silane compound (α1) is 20 wt% in terms of film forming component (solid content), An inventive coating composition (1-1) was obtained.

The storage stability of the coating composition (1-1) was evaluated according to the following method. The evaluation results are shown in Table 1.
<Method for evaluating storage stability>
The coating composition (1-1) is allowed to stand in a dryer adjusted to an atmosphere of 38 ° C., put in, visually observed after 1 day, 60 days and 90 days, and in accordance with the following criteria: evaluated.
○: Insoluble matter cannot be confirmed in the composition.
X: Insoluble matter can be confirmed in the composition.

In the evaluation of storage stability, the content of the silane compound (α1) was 0 in terms of film forming component (solid content) using a composition that was allowed to stand for 90 days in a drier adjusted to an atmosphere of 38 ° C. It was added _C 4 _F 9 _OC 2 _{H 5} is a fluorine atom-containing solvents such that .1wt%, to give a coating composition of the present invention (1-2).

  50 ml of the coating composition (1-2) was spray-coated on a 7 × 15 cm glass substrate treated with UV ozone with a spray gun. After the coating, the glass substrate coated with the coating composition (1-2) was allowed to stand for 30 minutes in an environment of 150 ° C. to obtain an article (1) having a coating composition coating.

  Using the obtained article (1), the surface of the article was evaluated for water repellency, slipperiness, durability of water repellency and durability of slipperiness according to the following methods. The evaluation results are shown in Table 2.

<Method for evaluating water repellency of article surface>
Evaluation was made by measuring the contact angle of water. 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 repellency (excellent antifouling property).

<Evaluation method of slipperiness of article surface>
Using a surface property measuring instrument (“Tribogear TYPE-38” 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 load at 500 g. Measurement was performed under the condition of a pulling speed of 0.3 m / min to obtain a dynamic friction coefficient. The lower the coefficient of dynamic friction, the better the slipperiness.

<Method for evaluating water repellency durability>
Using a reciprocating wear tester TYPE: 30S manufactured by Shinto Kagaku Co., with the indenter (1 cm x 1 cm indenter), steel wool # 0000 manufactured by Bonstar Sales Co., Ltd. is attached, and a load of 1 kg is applied. By reciprocating (1) 3000 times, the surface of the article (1) was rubbed with steel wool. Thereafter, the contact angle of water was measured in the same manner as in <Method for evaluating water repellency of article surface>. The lower the contact angle of water before and after rubbing the surface with steel wool, the better the durability.

<Slip durability evaluation method>
Using a reciprocating wear tester TYPE: 30S manufactured by Shinto Kagaku Co., with the indenter (1 cm x 1 cm indenter), steel wool # 0000 manufactured by Bonstar Sales Co., Ltd. is attached, and a load of 1 kg is applied. By reciprocating (1) 3000 times, the surface of the article (1) was rubbed with steel wool. Thereafter, the dynamic friction coefficient was determined in the same manner as in the above <Method for evaluating the slipperiness of the article surface>. The smaller the increase in the coefficient of dynamic friction before and after rubbing the surface with steel wool, the better the durability.

Example 2 (same as above)
A coating composition (2-1) was obtained in the same manner as in Example 1 except that 5 g of ethanol was used instead of 5 g of methanol. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Moreover, the coating composition (2-2) was obtained using the composition left to stand for 90 days in the dryer adjusted to the atmosphere of 38 degreeC similarly to Example 1, and article | item (2) using this Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 3 (same as above)
A coating composition (3-1) was obtained in the same manner as in Example 1 except that 5 g of isopropyl alcohol was used instead of 5 g of methanol. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. In addition, a coating composition (3-2) was obtained using a composition that was allowed to stand for 90 days in a drier adjusted to an atmosphere of 38 ° C. in the same manner as in Example 1, and an article (3) was obtained using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 4 (same as above)
A coating composition (4-1) was obtained in the same manner as in Example 1 except that 5 g of n-butanol was used instead of 5 g of methanol. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Moreover, the coating composition (4-2) was obtained using the composition left to stand for 90 days in the dryer adjusted to the atmosphere of 38 degreeC similarly to Example 1, and article | item (4) was obtained using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 5 (same as above)
A solvent solution containing the silane compound (α1) was mixed with 20 g and 5 g of isopropyl alcohol in terms of film forming components (solid content) to obtain a mixed solution. Further, C ₄ F ₉ OC ₂ H ₅ which is a fluorine atom-containing solvent is added to this mixed solution so that the content of the silane compound (α1) is 20 wt% in terms of film forming component (solid content), An inventive coating composition (5-1) was obtained. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. In addition, a coating composition (5-2) was obtained using a composition that was allowed to stand for 90 days in a drier adjusted to an atmosphere of 38 ° C. in the same manner as in Example 1, and an article (5) was obtained using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 6 (same as above)
10 g of a solvent solution containing a silane compound (α1) in terms of film-forming components (solid content), Fomblin (registered trademark) M15 manufactured by Solvay Specialty Polymers [number average molecular weight 9,700. In the general formula (8-2), R ² and R ³ are CF ₃ , and s ′ and t ′ are arbitrary integers that give the number average molecular weight 9,700. 10 g, 5 g of isopropyl alcohol and 1 g of 2- (dimethylamino) ethanol were mixed to obtain a mixed solution. Furthermore, C ₄ F ₉ OC ₂ H, which is a fluorine atom-containing solvent, is added so that the total content of the silane compound (α1) and fomblin M15 in the mixed solution is 20 wt% in terms of film forming components (in terms of solid content). ₅ was added to obtain a coating composition (6-1) of the present invention. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

In the evaluation of storage stability, the total content of the silane compound (α1) and fomblin M15 was converted into a film forming component using a composition that was allowed to stand for 90 days in a dryer adjusted to an atmosphere of 38 ° C. C ₄ F ₉ OC ₂ H ₅ which is a fluorine atom-containing solvent is added so as to be 0.1 wt% (in terms of solid content) to obtain the coating composition (6-2) of the present invention. Article (6) was obtained. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 7 (same as above)
A solvent solution containing the silane compound (α1) was mixed with 10 g of a film forming component (solid content), 10 g of Fomblin (registered trademark) M15 manufactured by Solvay Specialty Polymers, and 5 g of isopropyl alcohol to obtain a mixed solution. Furthermore, C ₄ F ₉ OC ₂ H, which is a fluorine atom-containing solvent, is added so that the total content of the silane compound (α1) and fomblin M15 in the mixed solution is 20 wt% in terms of film forming components (in terms of solid content). ₅ was added to obtain a coating composition (7-1) of the present invention. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Moreover, the coating composition (7-2) was obtained using the composition left to stand for 90 days in the dryer adjusted to the atmosphere of 38 degreeC similarly to Example 1, and article | item (7) was used using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 8 (same as above)
10 g of the solvent solution containing the silane compound (α1) in terms of film forming component (solid content), 10 g of the solvent solution containing the silane compound (ε1) in terms of film forming component (solid content), 5 g of isopropyl alcohol and 2- 1 g of (dimethylamino) ethanol was mixed to obtain a mixed solution. Furthermore, C ₄ F ₉ OC _2, which is a fluorine atom-containing solvent, so that the total content of the silane compound (α1) and the silane compound (ε1) is 20 wt% in terms of film forming components (solid content) in the mixed solution. It was added H _5, to give a coating composition of the present invention (8-1). The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

In the evaluation of storage stability, the total content of the silane compound (α1) and the silane compound (ε1) was formed using a composition that was allowed to stand for 90 days in a dryer adjusted to an atmosphere of 38 ° C. C ₄ F ₉ OC ₂ H ₅ which is a fluorine atom-containing solvent is added so as to be 0.1 wt% in terms of components (solid content) to obtain the coating composition (8-2) of the present invention. Used to obtain article (8). In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 9 (same as above)
10 g of the solvent solution containing the silane compound (α1) in terms of film-forming components (solid content), 10 g of the solvent solution containing the silane compound (ε1) in terms of film-forming components (solid content) and 5 g of isopropyl alcohol are mixed. A mixed solution was obtained. Furthermore, C ₄ F ₉ OC, which is a fluorine atom-containing solvent, so that the total content of the silane compound (α1) and the silane compound (ε1) is 20 wt% in terms of film forming components (solid content) in the mixed solution. ₂ H ₅ was added to obtain a coating composition (9-1) of the present invention. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Also, a coating composition (9-2) was obtained using a composition that was allowed to stand for 90 days in a drier adjusted to an atmosphere of 38 ° C. in the same manner as in Example 1, and an article (9) was obtained using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 10 (same as above)
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 [hereinafter abbreviated as silane compound (α2). ] 20 g, 5 g of methanol, and 1 g of 2- (dimethylamino) ethanol were mixed with a solvent (C ₄ F ₉ OC ₂ H ₅ ) solution containing Further, C ₄ F ₉ OC ₂ H ₅ which is a fluorine atom-containing solvent is added to this mixed solution so that the content of the silane compound (α2) is 20 wt% in terms of film forming component (solid content). An inventive coating composition (10-1) was obtained. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Moreover, the coating composition (10-2) was obtained using the composition left to stand for 90 days in the dryer adjusted to the atmosphere of 38 degreeC similarly to Example 1, and article | item (10) using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 11 (same as above)
A coating composition (11-1) was obtained in the same manner as in Example 10 except that 5 g of isopropyl alcohol was used instead of 5 g of methanol. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. In addition, a coating composition (11-2) was obtained using a composition that was allowed to stand for 90 days in a dryer adjusted to an atmosphere of 38 ° C. in the same manner as in Example 1, and the article (11) was obtained using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Example 12 (same as above)
A solvent solution containing the silane compound (α2) was mixed with 20 g and 5 g of isopropyl alcohol in terms of film forming components (solid content) to obtain a mixed solution. Further, C ₄ F ₉ OC ₂ H ₅ which is a fluorine atom-containing solvent is added to this mixed solution so that the content of the silane compound (α2) is 20 wt% in terms of film forming component (solid content). An inventive coating composition (12-1) was obtained. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Moreover, the coating composition (12-2) was obtained using the composition left to stand for 90 days in the dryer adjusted to the atmosphere of 38 degreeC similarly to Example 1, and article | item (12) was obtained using this. Got. In the same manner as in Example 1, water repellency, slipperiness, durability of water repellency and durability of slipperiness of the article surface were evaluated. The evaluation results are shown in Table 2.

Comparative Example 1 (Preparation of Comparative Coating Composition and Comparative Article)
A comparative coating composition (1′-1) was obtained in the same manner as in Example 10 except that 5 g of methanol was not used. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. In the evaluation of storage stability, a comparative coating composition (1 ′) was used in the same manner as in Example 1 except that the comparative composition was allowed to stand for 90 days in a dryer adjusted to an atmosphere of 38 ° C. -2) was obtained. However, since the comparative coating composition (1′-2) was still insoluble, it could not be applied by spraying, resulting in water repellency, slipperiness, durability of water repellency and durability of slipperiness. Could not be evaluated.

Comparative Example 2 (same as above)
A comparative coating composition (2′-1) was obtained in the same manner as in Example 10 except that 5 g of methanol and 2- (dimethylamino) ethanol were not used. The storage stability was evaluated in the same manner as in Example 1, and the results are shown in Table 1. In the evaluation of storage stability, a comparative coating composition (2 ′) was used in the same manner as in Example 1 except that the comparative composition was allowed to stand for 90 days in a dryer adjusted to an atmosphere of 38 ° C. -2) was obtained. However, since the comparative coating composition (2′-2) was still insoluble, it could not be applied by spraying, resulting in water repellency, slipperiness, durability of water repellency and durability of slipperiness. Could not be evaluated.

  Footnotes in Table 1: In Comparative Examples 1 and 2, since insoluble materials existed in the composition, spray coating was not possible. As a result, water repellency, slipperiness, durability of water repellency and slipperiness Durability cannot be evaluated.

  Table 3 shows the composition ratio (in terms of mass, unit: g) of the raw materials in the solutions (mixed solutions) used when obtaining the coating compositions in Examples 1 to 12 and Comparative Examples 1 and 2.

Footnotes in Table 3 M15: Fomblin (registered trademark) M15 manufactured by Solvay Specialty Polymers

Claims (24)

  A coating composition comprising a silane compound (α) containing a poly (perfluoroalkylene ether) chain and a hydrolyzable group, and an alcohol (β) having an alkyl group having 1 to 10 carbon atoms. object. The silane compound (α) is represented by the following general formula (1) or (2)

[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 ¹ is a divalent linking group. PFPE is a poly (perfluoroalkylene ether) chain. ]
The coating composition according to claim 1, which is a compound represented by the formula: The silane compound (α) is represented by the following general formula (7)

[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 coating composition according to claim 1, which is a compound represented by the formula: The coating composition according to claim 3, wherein Z in the general formula (7) 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 according to claim 1, wherein the hydrolyzable group is an alkoxy group having 1 to 6 carbon atoms. The coating composition according to claim 3, wherein the hydrolyzable group is a methoxy group or an ethoxy group, Z is an n-propylene group, and Y ¹ and Y ² are methylene groups. The silane compound (α) is represented by the following general formula (7-2)

[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 may be 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 coating composition of Claim 3 represented by these.   The coating composition according to claim 7, wherein the C1-C3 perfluoroalkylene group 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, Y ¹ and Y ² is a methylene group The coating composition according to claim 7, wherein n is 12 to 200. The poly (perfluoroalkylene ether) chain-containing silane compound (α) is represented by the following general formula (α-1)

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

[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 coating composition according to claim 1, which is a compound using an isocyanate represented by the formula:   The coating composition according to claim 1, wherein the alcohol (β) is an alcohol having an alkyl group having 1 to 4 carbon atoms.   The coating composition according to claim 11, wherein the alcohol (β) is one or more alcohols selected from the group consisting of methanol, ethanol, isopropyl alcohol, and butanol.   The coating composition according to claim 1, wherein the content of the alkyl alcohol (β) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α).   The coating composition according to claim 1, further comprising an alkoxysilane hydrolysis catalyst (γ).   The alkoxysilane hydrolysis catalyst (γ) is one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, phosphoric acid compounds, sulfonic acid compounds, tin compounds, titanium compounds and zirconium compounds. The coating composition according to claim 14.   The coating composition according to claim 14, wherein the alkoxysilane hydrolysis catalyst (γ) is one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds tin compounds, and titanium compounds.   The coating composition according to claim 14, wherein the content of the alkoxysilane hydrolysis catalyst (γ) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). object. Furthermore, the following general formula (8)
R ² -R ¹ -R ³ (8)
[Wherein, -R ¹ -represents the following formula:
_{- (OC 4 F 8) w} - (OC 3 F 6) r - (OC 2 F 4) s - (OCF 2) t -O-
Wherein r, s, t and w are each independently an integer of 0 to 300, and the sum of r, s, t and w is at least 5, and the presence of each repeating unit in parentheses The order is arbitrary in the formula.) R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is -O-, -COO-, -CONH- between the bonds between carbon atoms. , —OCONH— may have one or more linking groups, or a part of hydrogen atoms of the hydrocarbon group may be substituted with —OH, —COOH, —OPO (OH) _2. The hydrocarbon group may be a hydrocarbon group in which part or all of the hydrogen atoms of the hydrocarbon group may be substituted with fluorine atoms. ]
The coating composition of Claim 1 containing the fluorine compound ((DELTA)) represented by these. The fluorine compound (Δ) is represented by the following general formulas (8-1), (8-2), (8-3) and (8-3).

[Wherein, r ′, s ′ and t ′ each represent an integer of 1 to 200. R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is -O-, -COO-, -CONH- between the bonds between carbon atoms. , —OCONH— may have one or more linking groups, or a part of hydrogen atoms of the hydrocarbon group may be substituted with —OH, —COOH, —OPO (OH) _2. The hydrocarbon group may be a hydrocarbon group in which part or all of the hydrogen atoms of the hydrocarbon group may be substituted with fluorine atoms. ]
The coating composition according to claim 18, which is one or more compounds selected from the group consisting of:   The coating composition according to claim 18, wherein the compound (Δ) has a number average molecular weight of 1,500 to 25,000.   The coating composition according to claim 18, wherein the content of the compound (Δ) is 2 to 50 parts by mass with respect to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). As the silane compound (α), a compound represented by the following general formula (1) and the following general formula (3) to general formula (8):

[Wherein, r is an average of 5 to 100, R is a divalent linking group, R ¹ is an alkylene group having 1 to 6 carbon atoms, and X is a trivalent cycloaliphatic having 4 to 8 carbon atoms. It is a group. In the general formula (3) and the general formula (4), two Bs are organic groups or Si (A) ₃ , and at least one of the two Bs is Si (A) ₃ . A in the Si (A) ₃ is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. A in the general formulas (5) and (6) is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. The coating composition of Claim 1 containing 1 or more types of compounds ((epsilon)) chosen from the group which consists of a poly (perfluoroalkylene ether) chain | strand containing silane compound represented by these.   An article having a coating of the coating composition according to any one of claims 1 to 22 on a substrate.   24. The article of claim 23, wherein the substrate is a glass substrate.

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