JP6780224B2 - Coating compositions and articles - Google Patents

Description

The present invention relates to a coating composition capable of forming a film having excellent slipperiness and antifouling property on a base material such as a glass base material. The present invention also relates to an article having a coating film obtained by using the coating composition.

In the touch panel, two transparent substrates made of glass, synthetic resin, or the like are arranged facing each other via a frame-shaped sealing material, and an input region made of a transparent conductive film or a plurality of electrodes is formed inside the frame-shaped sealing member. It is provided. Here, examples of the transparent base material 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 has hardness and weather resistance. Has excellent characteristics. Therefore, it can be suitably used for portable devices such as smartphones and tablet PCs used outdoors, and in-vehicle applications where a large temperature difference occurs.

Since the touch panel is touched by a human finger during use, stains derived from the human body such as fingerprints, sebum, and sweat are likely to adhere to the touch panel. When these stains adhere, they are difficult to remove, and they are conspicuous depending on the amount of light, which causes a problem of impairing visibility and aesthetics.

In order to solve this problem, a method is 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 comprising a compound having a silicon atom having a hydrolyzable group at one end and a perfluoroalkylene ether chain at the other end, and the like. An organic solvent solution (coating composition) containing a surface modifier is disclosed (see, for example, Patent Document 1). However, the surface modifier disclosed in Patent Document 1 has a problem that the stain has insufficient resistance to adhesion (antifouling property).

Further, among the touch panels, for example, in a smartphone or a tablet PC, an operation (swipe) of tracing (sliding) a fingertip or a pen tip is performed on the touch panel. In recent years, touch panel screens have been required to be smooth so that they do not feel caught in the fingertips or pen tips during this operation. However, the surface modifier disclosed in Patent Document 1 has a problem that the smoothness (slipperiness) is not sufficient.

Japanese Unexamined Patent Publication No. 2012-037896

An object of the present invention is to provide a coating composition which has slipperiness and antifouling property on a base material and can obtain a film having excellent durability thereof. Another object of the present invention is to provide an article having a coating film having excellent antifouling property and slipperiness.

As a result of diligent studies, the present inventors have found that the compound has a poly (perfluoroalkylene ether) chain, a urethane bond and a hydrolyzable silyl group, and urethane bonds are formed at both ends of the poly (perfluoroalkylene ether) chain. A coating composition which is arranged and further contains a compound in which the urethane bond and the hydrolyzable silyl group are close to each other and have hydrolyzable silyl groups at both ends of the compound is represented by a glass substrate. When applied to various substrates, the chemical bond between the compound having a hydrolyzable silyl group and the substrate is further promoted, and a film having durable antifouling property and slipperiness can be obtained. Further, they have found that further slipperiness can be imparted to the coating film by containing a fluorine compound having a poly (perfluoroalkylene ether) chain having a specific structure, and the present invention has been developed.

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

〔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。〕
で表されるポリ（パーフルオロアルキレンエーテル）鎖含有シラン化合物（α）と、下記一般式（２）
Ｒ^２−Ｒ^１−Ｒ^３ ・・・（２）
［式中、−Ｒ^１−は以下の式：
−（ＯＣ_４Ｆ_８）_ｗ−（ＯＣ_３Ｆ_６）_ｒ−（ＯＣ_２Ｆ_４）_ｓ−（ＯＣＦ_２）_ｔ−Ｏ−
（式中、ｒ、ｓ、ｔおよびｗはそれぞれ独立して０〜３００の整数であって、ｒ、ｓ、ｔおよびｗの和は少なくとも５であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）で表される基である。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、該炭化水素基は炭素原子と炭素原子との結合の間に−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。］
で表されるフッ素化合物（β）とを含有することを特徴とするコーティング組成物を提供するものである。

[In the formula, A is a hydrolyzable group or a non-hydrolyzable group, respectively, and in each of the two (A) _{3 in} the formula, at least one A is a hydrolyzable group. Z is a divalent linking group. Y ¹ and Y ² are direct-bonded or divalent linking groups, respectively. PFPE represents a poly (perfluoroalkylene ether) chain. ]
Poly (perfluoroalkylene ether) chain-containing silane compound (α) represented by and the following general formula (2)
R ^2- R ^1- R ³ ... (2)
[In the formula, -R ^1- is the following formula:
-(OC ₄ F ₈ ) _w- (OC ₃ F ₆ ) _r- (OC ₂ F ₄ ) _s- (OCF ₂ ) _t- O-
(In the equation, r, s, t and w are independently integers from 0 to 300, the sum of r, s, t and w is at least 5, and the existence of each repeating unit enclosed in parentheses. The order is arbitrary in the equation.). R ² and R ³ are monovalent hydrocarbon groups having 1 to 20 carbon atoms, and the hydrocarbon groups are -O-, -COO-, and -CONH- between carbon atoms and carbon atoms. , -OCONH- may have one or more linking groups, or even if some of the hydrogen atoms of the hydrocarbon group are substituted with -OH, -COOH, -OPO (OH) _2. Alternatively, it is a hydrocarbon group in which a part or all of the hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. ]
The present invention provides a coating composition comprising a fluorine compound (β) represented by.

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

The coating composition of the present invention can preferably form a film having excellent antifouling property and slipperiness on an article. Therefore, it is particularly useful for applications such as touch panels that require antifouling property and slipperiness.

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

The poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention has the following general formula (1).

〔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。

[In the formula, A is a hydrolyzable group or a non-hydrolyzable group, respectively, and in each of the two (A) _{3 in} the formula, at least one A is a hydrolyzable group. Z is a divalent linking group. Y ¹ and Y ² are direct bonds or divalent linking groups, respectively. PFPE represents a poly (perfluoroalkylene ether) chain. ] Is represented by.

The poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention has two Si (A) ₃ as represented by the general formula (1), and in each of (A) ₃ At least one A of is a hydrolyzable group. By having such a silicon atom (reactive silyl group), the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention is invented to be covalently bonded to the surface of the substrate by the following reaction. Those are guessing. One of the speculated reactions is to generate a silanol group by hydrolysis, and the silanol group is dehydrated and condensed with a hydroxyl group on the surface of various substrates, for example, a glass substrate, and shared on the surface of the substrate. It is a binding reaction. Another speculated reaction is a reaction in which the hydrolyzable group directly condenses with the hydroxyl group of the base material (dealcohol condensation when the hydrolyzable group is an alkoxy group) and covalently bonds to the surface of the base material. Since the product of the present invention can bond not only one end but also both ends to the base material, the poly (perfluoroalkylene ether) chain-containing silane compound used in the present invention by the covalent bond formed by these condensation reactions ( α) adheres more firmly to the surface of the base material than the conventional product, and can form a film having excellent durability while having both antifouling property and slipperiness exhibited by the poly (perfluoroalkylene ether) chain.

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; Alkoxyoxy groups such as propenyloxy group and isobutenyloxy group; imineoxy groups such as dimethylketoxim group, methylethylketoxim group, diethylketoxim group, cyclohexaneoxym group; methylamino group, ethylamino group, dimethylamino group, diethylamino Substituent amino groups such as groups; amide groups such as N-methylacetamide group and N-ethylamide group; substituted aminooxy groups such as dimethylaminooxy group and diethylaminooxy group; halogens such as chlorine and the like can be mentioned. Among the hydrolyzable groups, an alkoxy group is preferable because it has a high hydrolysis rate and can quickly form a film having both antifouling property and slipperiness and excellent durability, and has 1 to 6 carbon atoms. Alkoxy group is more preferable, alkoxy group having 1 to 3 carbon atoms is more preferable, methoxy group and ethoxy group are particularly preferable, and methoxy group is most preferable.

Examples of the non-hydrolyzable group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. And so on. Above all, the hydrolysis rate can be increased by avoiding steric hindrance, and as a result, a film having excellent durability while having both antifouling property and slipperiness can be formed quickly. Therefore, an alkyl having 1 to 3 carbon atoms can be formed. A group is preferable, and a methyl group is more preferable.

The number of hydrolyzable groups in (A) ₃ is at least one as described above, but two or more are preferable because a silane compound capable of forming a film having more excellent durability can be obtained. (A) It is more preferable that all A in ₃ are hydrolyzable groups. That is, those having no non-hydrolyzable group are most preferable.

When a plurality of hydrolyzable groups in (A) _{3 are present} , the hydrolyzable groups may be the same or different. Moreover, when it has a plurality of non-hydrolyzable groups, the non-hydrolyzable groups may be the same or different.

Z in the general formula (1) is a divalent linking group. Y ¹ and Y ² are direct-bonded or divalent linking groups, respectively. Examples of the divalent linking group include an alkylene group having 1 to 22 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a 2,2-dimethylpropylene group and a 2-methyl group. 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-pentylene group, 4-methylpentylene group, 4-methyl-2- Pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3-ethyl -3-Pentylene group, Heptylene group, 2-Heptylene group, 3-Heptylene group, 2-Methyl-2-hexylene group, 2-Methyl-3-hexylene group, 5-Methylhexylene group, 5-Methyl-2- Hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, 2-propylpentylene group, 2, Examples thereof include an alkylene group such as a 4,4-trimethylpentylene group and a decaoctylene group.

As the Z, an alkylene group having 1 to 10 carbon atoms is preferable because it is easy to synthesize and the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention can be easily obtained. The number 1 to 6 alkylene group is more preferable, the number 1 to 3 alkylene group is further preferable, and the n-propylene group is particularly preferable.

Further, Y ¹ and Y ² are preferably alkylene groups having 1 to 6 carbon atoms, respectively, because they are silane compounds having a high fluorine atom content and a film having more excellent antifouling properties, and carbon atoms are preferable. An alkylene group having 1 to 3 atoms is more preferable, and a methylene group is further preferable because it has excellent antifouling properties and is easily obtained industrially.

The two Zs in the general formula (1) may be the same or different. Further, the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention may be a mixture of modifiers having different Z's.

Y ¹ and Y ² in the general formula (1) may be the same or different. Further, the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention may be a mixture of modifiers having different Y ¹ and Y ² , respectively.

The poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention has a urethane bond in the skeleton. By having this urethane bond, the polarity of the silane compound (α) in the vicinity of the hydrolyzable groups at both ends is improved. As a result, the adhesiveness to the base material described later, preferably the glass base material, is improved, and the reaction with the surface of the base material proceeds efficiently. As a result, a film having durability and excellent antifouling property and slipperiness can be preferably formed on the article.

Specific examples of the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention are shown below. In the formula, PFPE represents a poly (perfluoroalkylene ether) chain.

The PFPE [poly (perfluoroalkylene ether) chain] contained in the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention includes, for example, a perfluoroalkylene group having 1 to 3 carbon atoms. Those having a structure in which oxygen atoms are alternately linked can be preferably mentioned. The perfluoroalkylene group having 1 to 3 carbon atoms may be of one type or a mixture of a plurality of types, and specifically, those represented by the following structural formula (P-1) are 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 above structural formula (P-1), X is a perfluoroalkylene group. All of the X may have the same structure, and a plurality of structures are randomly present or exist in a block shape. You may be doing it.)

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

Among these, the poly (perfluoroalkylene ether) chain has many oxygen atoms that serve as bending points that exhibit slipperiness, and there is no branched structure that inhibits the bending movement of the chain. Therefore, X is perfluoro. A methylene group and a perfluoroethylene group are preferable, and a group in which the perfluoromethylene group (a) and the perfluoroethylene group (b) coexist is particularly preferable, including the point that it is 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, and 3 /. 10 to 10/3 is more preferable.

As the silane compound (α) having a perfluoroalkylene group having 1 to 3 carbon atoms, for example, those represented by the following structural formulas 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。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。〕

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

The silane compound represented by the formula (1-2) has a perfluoroalkylene group having a short chain length and a number of carbon atoms of 1 to 3 existing between oxygen atoms and oxygen atoms. As described above, 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 are easily bent portions of the perfluoroalkylene group. As a result, a film having excellent slipperiness can be formed on the article. The n in the general formula (1) is more preferably 12 to 200, more preferably 20 to 150, further preferably 30 to 100, and particularly preferably 35 to 70.

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

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

〔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 poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention is, for example, the following general formula (α-1).

[In the formula, Y ¹ and Y ² are divalent linking groups, respectively. ] And 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。

[In the formula, 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. ] Can be preferably obtained by reacting with an 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, A in the general formula (α-2) are the same as those in the general formula (1).

As the diol represented by the general formula (α-1), for example, the diol shown below can be exemplified.

Among the general formulas (α-1-1) and (α-1-2), the diols shown below 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, or a plurality of structures may be present at random or in a block shape. Is 6 to 300 in total.]

As the isocyanate represented by the general formula (α-2), for example, the isocyanate shown below can be exemplified.

Z in the isocyanate compounds represented by the formulas (α-2-1) to (α-2-12) is a poly (perfluoroalkylene ether) chain-containing silane compound which is easy to synthesize and is easily used in the present invention. Since (α) can be obtained, 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. preferable.

When reacting the diol represented by the general formula (α-1) with the isocyanate represented by the general formula (α-2), the OH group contained in the general formula (α-1) is 1 mol. The isocyanate represented by the general formula (α-2) is preferably charged in an amount of 0.5 to 1.5 mol, more preferably 0.9 to 1.1 mol. , 0.98 to 1.02 mol is most preferable.

In the reaction (urethaneization reaction) between 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) is generally used. 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 dilaurylate, dioctyltin dilaurylate, tin 2-ethylhexanoate and the like can be used. 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 even more preferably 0.02 to 0.2% by mass with respect to the entire reaction mixture. %. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably 30 to 120 ° C, more preferably 40 to 90 ° C.

When the reaction (urethaneization reaction) between the diol represented by the general formula (α-1) and the isocyanate represented by the general formula (α-2) is carried out, the reaction system may be a solvent-free system. A solvent system using a solvent such as acetone, methyl ethyl ketone, toluene, xylene, etc., which has no reactivity with the isocyanate group, or a fluorine-based solvent as the reaction solvent may be used.

The fluorine compound (β) used in the present invention has the following general formula (2).
R ^2- R ^1- R ³ ... (2)
[In the formula, -R ^1- is the following formula:
-(OC ₄ F ₈ ) _w- (OC ₃ F ₆ ) _r- (OC ₂ F ₄ ) _s- (OCF ₂ ) _t- O-
(In the equation, r, s, t and w are independently integers from 0 to 300, the sum of r, s, t and w is at least 5, and the existence of each repeating unit enclosed in parentheses. The order is arbitrary in the equation.). R ² and R ³ are monovalent hydrocarbon groups having 1 to 20 carbon atoms, and the hydrocarbon groups are -O-, -COO-, and -CONH- between carbon atoms and carbon atoms. , -OCONH- may have one or more linking groups, or even if some of the hydrogen atoms of the hydrocarbon group are substituted with -OH, -COOH, -OPO (OH) _2. Alternatively, it is a hydrocarbon group in which a part or all of the hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. ]
It is represented by. The fluorocompound (β) used in the present invention is a non-reactive fluoropolymer, which is also called a fluoropolymer. When referring to the number of carbon atoms of a hydrocarbon group in the present invention, the carbon atoms of "-COO-", "-CONH-", and "-COOH" are not included in the number.

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

As the fluorine compound represented by the general formula (2), for example, the following compounds can be preferably exemplified.

［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。］

[In the formula, r', s'and t'are integers from 1 to 200, respectively. R ² and R ³ are monovalent hydrocarbon groups having 1 to 20 carbon atoms, and the hydrocarbon group is one or more selected from -O-, -COO-, -CONH-, and -OCONH- on the way. It may have a linking group of, or a part of the hydrogen atom of the hydrocarbon group may be substituted with -OH, -COOH, -OPO (OH) ₂ , or the hydrogen of the hydrocarbon group. A hydrocarbon group in which some or all of the atoms may be substituted with fluorine atoms. ]

For R ² and R ³ in the general formula (2), for example, the following hydrocarbon groups can be exemplified.

In the compound represented by the general formula (2-1), r'is preferably in the range of 10 to 70, more preferably in the range of 20 to 65, and in the range of 35 to 60 because a film having excellent slipperiness can be obtained. Is particularly preferable.

In the compound represented by the general formula (2-2), s'is preferably in the range of 5 to 160 because a film having excellent slipperiness can be obtained. The 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 (2-3), r'is preferably in the range of 8 to 60 because a film having excellent slipperiness can be obtained. The t'is preferably in the range of 8 to 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 (2-4), r'is preferably in the range of 7 to 70, more preferably in the range of 10 to 60, and in the range of 20 to 50 because a film having excellent slipperiness can be obtained. Is particularly preferable.

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

The number average molecular weight of the fluorinated compound (β) used in the present invention is preferably 1,500 to 25,000, more preferably 3,000 to 17,000, because it provides a coating composition capable of obtaining a film having higher slipperiness. Preferably, 4,500 to 11,000 is particularly preferable.

In the present invention, the average molecular weight is an average value calculated from the integration ratio of the terminal structure and the repeating unit measured by ¹⁹ F-NMR.

The content of the compound (β) 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), which has high slipperiness and high slipperiness. It is preferable from the viewpoint of excellent durability of both slipperiness and antifouling property, 4 to 25 parts by mass is more preferable, and 6 to 16 parts by mass is particularly preferable. By containing the compound (α) and the compound (β) in the above range, the compound (α) reacts with the base material and firmly adheres to the surface of the base material, thereby exhibiting durability. It was invented that the compound (β) acts as a slippery developing component on the surface of the base material without reacting with the base material, and by imparting further slipperiness to the coating film, it has the effect of increasing the slipperiness and durability. Those are guessing.

The fluorine compound (β) used in the present invention can be obtained by a method for forming various perfluoropolyethers well known to those skilled in the art. Moreover, you may use a commercially available product.

Commercially available products that can be used as the fluorine compound (β) used in the present invention include, for example, Fomblin® Y series manufactured by Solvay Specialty Polymers, for example, Y04, Y06, Y15, Y25, Y45, YU700. YR, YPL1500, YR1800; Fluorine® M series, eg, M03, M07, M15, M30, M60, M100; Fluorine® Z series, eg, Z03, Z15, Z25, Z60; The Chemours Company. Krytox® GPL manufactured by, for example, GPL100, GPL101, GPL102, GPL103, GPL104, GPL105, GPL106, GPL107; Demnum® S-20, S-65, S-200 manufactured by Daikin Industries, Ltd., etc. Can be mentioned. Only one type of fluorine compound (β) may be used, or two or more types may be used in combination.

The coating composition of the present invention may contain a solvent (γ) containing a fluorine atom. Examples of the solvent (γ) containing a fluorine atom include hydrofluoroether, hydrofluorocarbon, perfluorocarbon, and fluorine-containing aromatic hydrocarbon. The solvent containing a fluorine atom may be linear, branched, or cyclic, or may contain a hetero atom. The number of carbon atoms of the solvent containing a fluorine atom is preferably 2 to 12, more preferably 4 to 10.

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 the} like can be mentioned. 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. Examples thereof include ₃ (CF ₂ ) ₄ CHF _2, CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ (CHF) ₂ CF ₂ CF ₃ .

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-butyl tetrahydrofuran) and the like.

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

Among the above-mentioned fluorine atom-containing solvents, C ₄ F ₉ C ₂ H ₅ , (CF ₃ ) ₂ CFCHFCHFCF ₃ , C ₆ F ₁₃ H, C ₆ F ₁₃ C ₂ H ₅ , C ₄ F ₉ OCH ₃ , C It is preferably at least one selected from the group consisting of 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 .

When a solvent (γ) containing a fluorine atom is contained, it is preferably contained in the coating composition of the present invention in an amount of 50 to 99.99% by mass, more preferably 90 to 99.98% by mass. It is more preferable to contain 99 to 99.95% by mass.

The coating composition of the present invention is a compound (Δ) that can be expected to act as a catalyst for promoting the hydrolysis of the silane compound (α), specifically, an amine compound, a carboxylic acid compound, a phosphoric acid compound, and a sulfone. A compound selected from the group consisting of an acid compound, a tin compound, a titanium compound and a zirconium compound may be mixed.

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

Examples of the carboxylic acid-based compound 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, heptanic acid and 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-based compound include phosphoric acid, metaphosphoric acid, phosphite, meta-phosphoric acid, hypophosphoric acid, hypophosphoric acid, and phosphoric acid derivatives; alkali metal salts of these phosphoric acid compounds. Alternatively, an ammonium salt or the like can be mentioned.

Examples of the sulfonic acid-based 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 diisopropoxytitanium bis (acetylacetonate), titanium tetra (acetylacetonate), dioctanoxytitanium dioctanete, diisopropoxytitanium bis (ethylacetacetate), tetraisopropyl titanate, and the like. Examples thereof include tetrabutyl titanate.

Examples of the zirconium compound include zirconium tetranormal butoxide.

When the compound (Δ) used in the present invention is mixed with the coating composition of the present invention, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and tin compounds can achieve both reactivity and stability. It is preferable because it becomes a coating composition.

When the compound (Δ) used in the present invention is mixed with the coating composition of the present invention, the content of the compound (Δ) is 0 with respect to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). 0.01 to 20 parts by mass is preferable, 0.05 to 10 parts by mass is more preferable, and 0.01 to 5 parts by mass is most preferable.

The coating composition of the present invention preferably further contains an alkyl alcohol (ε). By containing an alkyl alcohol, a coating composition having more excellent storage stability can be obtained.

As the alkyl alcohol (ε), an alcohol having an alkyl group having 1 to 10 carbon atoms can be preferably exemplified. Examples of alcohols having an alkyl group having 1 to 10 carbon atoms include methanol, ethanol, isopropanol, butanol and the like. Among them, alcohols having an alkyl group having 1 to 4 carbon atoms are preferable because a coating composition having more excellent storage stability can be obtained, and one or more alcohols selected from the group consisting of methanol, ethanol, isopropanol and butanol are more preferable. preferable.

The content of the alkyl alcohol (ε) is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). ..

The coating compositions of the present invention include the following general formulas (3) to (6).

[In the formula, 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 cyclic aliphatic group having 4 to 8 carbon atoms. It is a group. In the general formula (3) and the general formula (4), the 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 formula (5) and the general formula (6) is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. ]
A poly (perfluoroalkylene ether) chain-containing silane compound (ζ) represented by may be mixed. By mixing the silane compound (ζ), it can be expected to form a film having more excellent antifouling property and slipperiness.

The poly (perfluoroalkylene ether) chain-containing silane compound (ζ) has at least one Si (A) ₃ as represented by the general formulas (3) to (6), and each ( A) At least one A in ₃ is a hydrolyzable group. By having such a silicon atom (reactive silyl group), the poly (perfluoroalkylene ether) chain-containing silane compound (ε) is the same as the poly (perfluoroalkylene ether) chain-containing silane compound (α). The inventors speculate that it is covalently bonded to the surface of the base material by the action of. Due to the action of the poly (perfluoroalkylene ether) chain-containing silane compound (α) and the poly (perfluoroalkylene ether) chain-containing silane compound (ζ), the coating composition of the present invention has both antifouling property and slipperiness. It is possible to form a film having excellent durability.

In addition, the poly (perfluoroalkylene ether) chain-containing silane compound (ζ) has a large number of trifluoromethyl groups (CF ₃ groups). The _three CFs have a strong ability to reduce surface energy. Therefore, by containing the silane compound (ζ) having a large number of CF ₃ groups, the modifier of the present invention can be expected to exert the above-mentioned antifouling property more effectively.

Among the poly (perfluoroalkylene ether) chain-containing silane compounds (ζ) used in the present invention, the compound represented by the general formula (3) and the compound represented by the general formula (4) are represented by two Bs. At least one of them is Si (A) ₃ .

When one of the compounds represented by the general formula (3) and the compound B 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, a phenyl group and the like. The alkyl group may be further substituted with a part of a hydrogen atom or another atom or atomic group. Specifically, examples of the alkyl group in which a part or all of the hydrogen atom is replaced with another atom or atomic group include a partially fluorinated alkyl group and a perfluoroalkyl group. In the partially fluorinated alkyl group, the number of carbon atoms to which the fluorine atom is bonded is preferably 1 to 6. The number of carbon atoms of the perfluoroalkyl group is also preferably 1-6. By containing such a fluorinated alkyl group having a carbon atom number as B, further improvement in antifouling performance on the coating can be expected.

Examples of the hydrolyzable group contained in the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formulas (3) to (6) include the poly (perfluoroalkylene ether) chain used in the present invention. The hydrolyzable group contained in the contained silane compound (α) can be preferably mentioned. The hydrolyzable group of the poly (perfluoroalkylene ether) chain-containing silane compound (ζ) represented by the general formulas (3) to (6) has a high hydrolysis rate, and has rapid antifouling property and slippage. An alkoxy group is preferable because a film having both properties and excellent durability can be formed, an alkoxy group having 1 to 6 carbon atoms is more preferable, an alkoxy group having 1 to 3 carbon atoms is further preferable, and methoxy. Groups and ethoxy groups are particularly preferable.

Examples of the non-hydrolyzable group contained in the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formulas (3) to (6) include the poly (perfluoroalkylene ether) used in the present invention. The non-hydrolyzable group that the chain-containing silane compound (α) can have can be preferably mentioned.

The number of hydrolyzable groups in (A) _{3 of the} poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formulas (3) to (6) is at least one as described above. However, two or more are preferable because a coating composition capable of forming a film having more excellent durability can be obtained, and it is more preferable that all A in the above two (A) ₃ are hydrolyzable groups. That is, those having no non-hydrolyzable group are most preferable.

When the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formulas (3) to (6) has a plurality of hydrolyzable groups in (A) ₃ , the hydrolyzable group is used. It may be the same or different. Moreover, when it has a plurality of non-hydrolyzable groups, the non-hydrolyzable groups may be the same or different.

The average r in the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formulas (3) to (6) is 5 to 100. The value of r is preferably 8 to 80 on average, and more preferably 10 to 60 on average, because the coating composition obtains a film having excellent antifouling property as the content of ₃ CF groups increases.

R in the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formulas (3) to (6) is a divalent linking group. The R is, for example, the following (R-1) or (R-2).

（式中、Ｒ^２は炭素原子数１〜３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り、Ｒ^４は炭素原子数１〜５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。

(In the formula, R ² is an alkylene group having 1 to 3 carbon atoms, R ³ is a direct bond or an alkylene group having 1 to 6 carbon atoms, and R ⁴ is an alkylene group having 1 to 5 carbon atoms. is there)
The structure represented by is preferably exemplified.

A specific example of the structure represented by (R-1) is shown below.

A specific example of the structure represented by (R-2) is shown below.

Among the structures represented by (R-1) and (R-2), the raw material for producing the silane compound (β) used in the present invention can be stably obtained, and the base such as a glass substrate can be obtained stably. Since a coating composition capable of forming a film having excellent antifouling properties and excellent slipperiness on the material can be obtained (R-1-1), (R-1-3), (R-1). -4), (R-2-1), (R-2-2), (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 (6) and (8) is a trivalent cyclic aliphatic group having 4 to 8 carbon atoms. As the cyclic aliphatic group, for example, a cyclohexane ring can be preferably exemplified.

Specific examples of the poly (perfluoroalkylene ether) chain-containing silane compound (ζ) that may be used in the coating composition of the present invention are shown below.

In both 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, B is used. The compound of Si (A) ₃ can be obtained, for example, by the following production method.

Manufacturing method 1: The following general formula (ζ-1)

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

(In the formula, r is 5 to 100 on average.)
Carboxylic acid (ζ-1) represented by and the following general formula (ζ-2) or general formula (ζ-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。）で表されるエポキシ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（ζ―４）

(In the formula, R is a divalent linking group, respectively. A is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group.) An epoxysilane compound represented by In the first step of reacting with and to obtain a reactant having a secondary hydroxyl group derived from an epoxy group, and the reactant and the following general formula (ζ-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（ζ−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 (ζ-4) represented by the group. Manufacturing method including.

One of B 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. in There Si _{(a) 3,} the other B is an organic group other than Si _{(a) 3} compound can be obtained by the process described below.

Production method 2: Carboxylic acid (ζ-1) represented by the general formula (ζ-1) and the following general formula (ζ-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（ζ―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（ζ―４）で表されるイソシアネート化合物（ζ―４）とを反応させる第二工程とを含む製法。

A reaction product having a secondary hydroxyl group derived from epoxy is obtained by reacting with an epoxy compound (ζ-5) represented by (R is a divalent linking group and G is an organic group in the formula). A production method comprising one step and a second step of reacting the reactant with the isocyanate compound (ζ-4) represented by the general formula (ζ-4).

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

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

As the epoxy silane compound (ζ-2) and the epoxy silane compound (ζ-3), for example, the compounds shown below can be preferably exemplified.

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

As the isocyanate compound (ζ-4), for example, the compounds shown below can be preferably exemplified.

(In the formula, R ¹ is an alkylene group having 1 to 6 carbon atoms)

R ¹ in the isocyanate compounds represented by the formulas (ζ-4-1) to (ζ-4-12) is a poly (perfluoroalkylene ether) that is easy to synthesize and can be easily used in the present invention. Since a chain-containing silane compound (ζ) can be obtained, 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 n− A propylene group is particularly preferred.

Since the isocyanate compound (ζ-4) is a coating composition capable of obtaining a highly reactive and highly durable film, (ζ-4-1), (ζ-4-2) and (ζ-4). One or more compounds selected from the group consisting of -3) are preferable, and (ζ-4-1) and (ζ-4-2) are more preferable. The isocyanate compound (ζ-4) may be used alone or in combination of two or more.

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

Among the epoxy compounds (ζ-5), the above (ζ-5-1) or (ζ-5-2) is preferable, and (ζ-5-2) is more preferable in order to obtain a coating film having excellent antifouling property. .. The epoxy compound (ζ-5) may be used alone or in combination of two or more.

The reactions in the above-mentioned production methods 1 and 2 may be carried out in the presence of an organic solvent, if necessary. The organic solvent is not particularly limited as long as it dissolves the above compound as a raw material. Further, a solvent system using a solvent such as acetone, methyl ethyl ketone, toluene, xylene, etc., which has no reactivity with the isocyanate group, or a fluorine-based solvent as the 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; and having 3 to 3 carbon atoms such as perfluorohexane and perfluoromethylcyclohexane. Twelve perfluorocarbon-based solvents; 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,5,5,6 Hydrofluorocarbon-based solvents such as 6-tridecafluorooctane; 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-based solvents such as Fombulin, Garden (manufactured by Solvay), Demnum (manufactured by Daikin Industries), Kleitox (manufactured by Chemers) and the like can be preferably exemplified.

In the first step of the above-mentioned production method 1, the reaction ratio of the carboxylic acid (ζ-1) and the epoxysilane compound [(ζ-2), (ζ-3)] is the carboxyl group of the carboxylic acid (ζ-1). The ratio of the equivalent ratio (carboxyl group / epoxy group) of the epoxy silane compound to the epoxy group is preferably 0.5 to 1.5, more preferably 0.9 to 1.1, and 0. The ratio of 98 to 1.02 is most preferable.

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

In the second step of the above-mentioned production method 1, the reaction ratio between the reactant having a secondary hydroxyl group derived from an epoxy group and the isocyanate compound (ζ-4) is the isocyanate contained in the hydroxyl group of the reactant and the isocyanate compound (ζ-4). The ratio of the equivalent ratio to the group (hydroxyl group / isocyanate group) is preferably 0.5 to 1.5, more preferably 0.9 to 1.1, and 0.98 to 1.02. The ratio is the most preferable.

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

In the first step of the above-mentioned production method 2, the reaction ratio of the carboxylic acid (ζ-1) and the epoxy compound (ζ-5) is the carboxyl group of the carboxylic acid (ζ-1) and the epoxy group of the epoxy compound. The ratio of the equivalent ratio (carboxyl group / epoxy group) is preferably 0.5 to 1.5, more preferably 0.9 to 1.1, and most preferably 0.98 to 1.02. preferable.

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

In the second step of the above-mentioned production method 2, the reaction ratio between the reactant having a secondary hydroxyl group derived from an epoxy group and the isocyanate compound (ζ-4) is the isocyanate contained in the hydroxyl group of the reactant and the isocyanate compound (ζ-4). The ratio of the equivalent ratio to the group (hydroxyl group / isocyanate group) is preferably 0.5 to 1.5, more preferably 0.9 to 1.1, and 0.98 to 1.02. The ratio is the most preferable.

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

The mixing ratio of the poly (perfluoroalkylene ether) chain-containing silane compound (ζ) with the coating composition of the present invention is expected to improve the antifouling performance without impairing the durability. 0.01 to 100 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (β) is preferable with respect to 1 part by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α), and 0.05 to 20 parts by mass. Parts are more preferable, and 0.1 to 2 parts by mass is further preferable.

The article of the present invention is characterized by having a coating film of the coating composition of the present invention on a substrate. The base material includes an inorganic base material such as glass; an organic base material such as acrylic resin, polycarbonate resin, polyester resin, polybutylene terephthalate resin, polypropylene resin, polyamide resin, polyurethane resin, polyvinyl chloride resin, and polyvinyl fluoride resin. And so on.

As the base material used in the present invention, the silane compound (α) in the coating composition of the present invention reacts well, and a film having excellent antifouling property and slipperiness and durability is formed on the base material. A glass base material is preferable because it can be used.

As the shape of the base material used in the present invention, various shapes can be used. Among them, a sheet-shaped one can be preferably used. The thickness of the sheet-shaped base material can be exemplified, for example, in the range of 5 μm to 10 mm.

As a method for forming a film of the coating composition of the present invention on the base material, various methods can be used, and a method of applying the coating composition on the base material and then drying can be exemplified. Examples of the method of applying the coating composition on the base material 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.

After applying the coating composition on the base material, the solvent in the composition is removed by various methods to form a film. For drying, for example, it may be allowed to stand at room temperature for drying, or it may be allowed to stand in a warmed atmosphere for drying. When drying in a warmed atmosphere, the temperature of the atmosphere is usually 30. It is about 200 ° C., preferably 50 to 180 ° C.

The film thickness of the article of the present invention is usually 1 to 100 nm, preferably 5 to 50 nm, for example, when it is the outermost film that protects the screen of a smartphone or tablet PC.

The coating composition of the present invention can form a film having excellent antifouling property and slipperiness on the surface of an article. Utilizing such an excellent effect, in the coating composition of the present invention, a smartphone or tablet PC in which the fingertip directly contacts the screen and the screen is traced (sliding) with the fingertip or pen tip (swipe). It can be preferably used for forming a film on the outermost surface of the screen. Further, it can be preferably used for antifouling applications such as lenses such as cameras and eyeglasses, glass surfaces used in automobiles and houses, and exhibition panels.

The present invention will be described in more detail below with reference to specific examples. In the example, "part" and "%" are based on mass unless otherwise specified. The measurement conditions of the IR spectrum, ¹ H-NMR spectrum, ¹ H-NMR spectrum, ¹⁹ F-NMR spectrum, and ¹³ C-NMR spectrum of the obtained silane compound are as follows.

[IR spectrum measurement conditions]
Equipment: "FT / IR-6100" manufactured by JASCO Corporation
Measurement method: KBr method

[ ¹ H-NMR spectrum, ¹ H-NMR spectrum, ¹⁹ F-NMR spectrum, ¹³ C-NMR spectrum measurement conditions]
Equipment: "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 cooling tube, and a dropping device, 66.67 g of hydrofluoroether (C ₄ F ₉ OC ₂ H ₅ ) and the following formula (α-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０．０２５ｇ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, and each molecule has an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups, and the average number of fluorine atoms is 126. is there.)
45.3 g of a diol having a poly (perfluoroalkylene ether) chain represented by (perfluoroalkylene ether), 4.7 g of 3-isocyanatopropyltrimethoxysilane, and 0.025 g of tin octylate as a urethanization catalyst were charged under a nitrogen stream. Stirring was started, the mixture was heated to 60 ° C., and then 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 content of the solvent in the obtained reaction product was 80%. This diluted reaction product is filtered and purified using a filter made of polytetrafluoroethylene (PTFE) having a pore size of 1 μm, and the poly (perfluoroalkylene ether) chain-containing silane compound used in the present invention represented by the general formula (1) is used. A solvent solution containing (α-1) was obtained. Here, in the silane compound (α1), in the general formula (1), A is an ethoxy group, Z is an n-propylene group, and Y ¹ and Y ² are methylene groups.

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

Example 1 (Preparation of coating composition and article)
5 parts of a solvent solution containing a silane compound (α-1) in terms of solid content and Fomblin (registered trademark) M03 manufactured by Solvay Specialty Polymers [number average molecular weight 3,900. In Rf is CF ₃ in the general formula (2-2), Rf 'is CF _3, s' and t' is an arbitrary integer which gives the number average molecular weight 3,900. ] 5 parts were mixed to obtain a mixture (coating composition). A fluorine-based solvent [the hydrofluoroether (C ₄ F ₉ OC ₂ H ₅ )] was added to this coating composition so that the solvent concentration was 99.9% to obtain a diluted coating composition (1). It was. 50 ml of the coating composition (1) was spray-coated with a spray gun on a 7 × 15 cm glass substrate obtained by treating the coating composition (1) with ozone. After coating, the glass substrate coated with the coating composition (1) was allowed to stand in an environment of 150 ° C. for 30 minutes to obtain an article (1) having a coating film of the coating composition.

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

<Evaluation method of water repellency on the surface of articles>
It was evaluated 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 (the better the antifouling property).

<Evaluation method for slipperiness on the surface of articles>
Using a surface measuring machine (“Tribo Gear 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 it with 500 g. The measurement was performed under the condition of a tensile speed of 0.3 m / min, and the coefficient of dynamic friction was determined. The lower the coefficient of dynamic friction, the better the slipperiness.

<Evaluation method of water repellency durability>
Using the reciprocating wear tester TYPE: 30S manufactured by Shinto Kagaku Co., Ltd., steel wool # 0000 manufactured by Bonstar Sales Co., Ltd. was attached to the indenter (1 cm x 1 cm indenter) of this, and the article was loaded with 1 kg. By reciprocating (1) 3000 times, the surface of the article (1) was rubbed with steel wool. Then, the contact angle of water was measured in the same manner as in the above <Method for evaluating water repellency on the surface of an article>. The smaller the decrease in the contact angle of water before and after rubbing the surface with steel wool, the better the durability.

<Evaluation method of slipperiness durability>
Using the reciprocating wear tester TYPE: 30S manufactured by Shinto Kagaku Co., Ltd., steel wool # 0000 manufactured by Bonstar Sales Co., Ltd. was attached to the indenter (1 cm x 1 cm indenter) of this, and the article was loaded with 1 kg. By reciprocating (1) 3000 times, the surface of the article (1) was rubbed with steel wool. After that, the coefficient of kinetic friction 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)
Instead of using Fomblin® M03 manufactured by Solvay Specialty Polymers, Fomblin® M07 [number average molecular weight 5,400. In the general formula (2-2), Rf is CF ₃ , Rf'is F, and s'and t'are arbitrary integers giving an average molecular weight of 5,400 on the left. ] Was used, and a diluted coating composition (2) and an article (2) using the same were obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 3 (same as above)
Instead of using Fomblin® M03 manufactured by Solvay Specialty Polymers, Fomblin® M15 [number average molecular weight 9,700. In the general formula (2-2), Rf is CF ₃ , Rf'is CF ₃ , and s'and t'are arbitrary integers giving the average molecular weight of 9,700 on the left. ] Was used, and a diluted coating composition (3) and an article (3) using the same were obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 4 (same as above)
Instead of using Fomblin® M03 manufactured by Solvay Specialty Polymers, Fomblin® M30 [number average molecular weight 16,000. In Rf is CF ₃ in the general formula (2-2), Rf 'is CF _3, s' and t' is an arbitrary integer giving the left average molecular weight of 16,000. ] Was used, and a diluted coating composition (4) and an article (4) using the same were obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 5 (same as above)
Instead of using Fomblin® M03 manufactured by Solvay Specialty Polymers, KrytoX® GPL107 manufactured by The Chemours [number average molecular weight 7,500. In the Rf in the general formula _{(2-3) CF 2 CF 2 CF} 3, Rf ' is CF _3, s' is an arbitrary integer giving the left average molecular weight of 7,500. ] Was used, and a diluted coating composition (5) and an article (5) using the same were obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 6 (same as above)
A mixture (coating composition) was obtained by mixing 8 parts of a solvent solution containing a silane compound (α-1) in terms of solid content with 2 parts of Fombulin (registered trademark) M15. A fluorine-based solvent [the hydrofluoroether (C ₄ F ₉ OC ₂ H ₅ )] was added to this coating composition so that the solvent concentration was 99.9% to obtain a diluted coating composition (6). It was. 50 ml of the coating composition (1) was spray-coated with a spray gun on a 7 × 15 cm glass substrate obtained by treating the coating composition (6) with ozone. After coating, the glass substrate coated with the coating composition (6) was allowed to stand in an environment of 150 ° C. for 30 minutes to obtain an article (6) having a coating film of the coating composition. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 7 (same as above)
Similar to Example 6 except that a solvent solution containing a silane compound (α-1) was mixed with 7 parts in terms of solid content and 3 parts of Fomblin (registered trademark) M15 to obtain a mixture (coating composition). And then. A diluted coating composition (7) and an article (7) using the same were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 8 (same as above)
Same as Example 6 except that a solvent solution containing a silane compound (α-1) was mixed with 6 parts in terms of solid content and 4 parts of Fomblin (registered trademark) M15 to obtain a mixture (coating composition). And then. A diluted coating composition (8) and an article (8) using the same were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 9 (same as above)
Same as Example 6 except that a solvent solution containing a silane compound (α-1) was mixed with 4 parts in terms of solid content and 6 parts of Fomblin (registered trademark) M15 to obtain a mixture (coating composition). And then. A diluted coating composition (9) and an article (9) using the same were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 10 (same as above)
Same as in Example 6 except that 3 parts of a solvent solution containing a silane compound (α-1) in terms of solid content and 7 parts of Fombulin (registered trademark) M157 were mixed to obtain a mixture (coating composition). And then. A diluted coating composition (10) and an article (10) using the same were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 11 (same as above)
Same as in Example 6 except that 2 parts of a solvent solution containing a silane compound (α-1) in terms of solid content and 8 parts of Fomblin (registered trademark) M158 were mixed to obtain a mixture (coating composition). And then. A diluted coating composition (11) and an article (11) using the same were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 12 (same as above)
The same as in Example 1 except that a solvent solution containing a silane compound (α-1) was mixed with 7 parts in terms of solid content and 3 parts of KrytoX (registered trademark) GPL107 to obtain a mixture (coating composition). hand. A diluted coating composition (12) and an article (12) using the same were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Example 13 (same as above)
Six parts of a solvent solution containing a silane compound (α-1) in terms of solid content and a compound in which Rf and Rf'are both CF ₂ CH ₂ OH in the general formula (2-2) [number average molecular weight 4,000] .. In the general formula (2-2), s'is 21 and t'is 21. ] The same as in Example 1 except that 4 parts were mixed to obtain a mixture (coating composition). A diluted coating composition (13) and an article (13) using the same were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 1 (Preparation of coating composition for comparative control and article for comparative control)
Silane compound described in Synthesis Example 1 of JP-A-2012-037896 [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 ] [ A fluorinated solvent [the hydrofluoroether (C ₄ F ₉ OC ₂ H ₅ )] was added to the silane compound (α'-1)] so that the solvent concentration was 99.9%, and the mixture was diluted for comparison and control. A coating composition (1') was obtained. An article (1') having a coating film of a comparative coating composition was obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed, and the evaluation results are shown in Table 1.

Claims (11)

An article having a coating of a coating composition on a base material.
The coating composition comprises a poly (perfluoroalkylene ether) chain-containing silane compound (α) represented by the following general formula (1-2) and a fluorine compound (β) represented by the following general formula (2). Contains,
The content of the compound (β) is 4 to 25 parts by mass with respect to 10 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α).
An article having a coating thickness of 1 to 100 nm.

[In the formula, A is a hydrolyzable group or a non-hydrolyzable group, respectively, and in each of the two (A) _{3 in} the formula, at least one A is a hydrolyzable group.
X is a perfluoromethylene group or a perfluoroethylene group in which a plurality of structures may be present at random or in a block shape, and the perfluoroemethylene group and the perfluoroethylene group coexist.
Z is an alkylene group having 1 to 6 carbon atoms.
Y ¹ and Y ² are alkylene groups having 1 to 3 carbon atoms, respectively.
n is 6 to 300 in total. ]
R ^2- R ^1- R ³ ... (2)
[In the formula, -R ^1- is the following formula:
-(OC ₄ F ₈ ) _w- (OC ₃ F ₆ ) _r- (OC ₂ F ₄ ) _s- (OCF ₂ ) _t- O-
(In the equation, r, s, t and w are independently integers from 0 to 300, the sum of r, s, t and w is at least 5, and the existence of each repeating unit enclosed in parentheses. The order is arbitrary in the equation.). R ² and R ³ are monovalent hydrocarbon groups having 1 to 20 carbon atoms, and the hydrocarbon groups are -O-, -COO-, and -CONH- between carbon atoms and carbon atoms. , -OCONH- may have one or more linking groups, or even if some of the hydrogen atoms of the hydrocarbon group are substituted with -OH, -COOH, -OPO (OH) _2. Alternatively, it is a hydrocarbon group in which a part or all of the hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. ] The article according to claim 1, wherein the hydrolyzable group is an alkoxy group having 1 to 6 carbon atoms. The article according to claim 1, 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. All of A in the two (A) ₃ are hydrolyzable groups, 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 article according to claim 1, wherein n is 12 to 150. The poly (perfluoroalkylene ether) chain-containing silane compound (α) has the following general formula (α-1).

The diol represented by and the following general formula (α-2)

[In the formula, A is a hydrolyzable group or a non-hydrolyzable group, and at least one A is a hydrolyzable group. Z is an alkylene group having 1 to 6 carbon atoms. ], The article according to claim 1, which is a compound made from an isocyanate represented by. The fluorine compound (β) has the following general formulas (2-1), (2-2), (2-3) and (2-4).

[In the formula, r', s'and t'are integers from 1 to 200, respectively. R ² and R ³ are monovalent hydrocarbon groups having 1 to 20 carbon atoms, and the hydrocarbon groups are -O-, -COO-, and -CONH- between carbon atoms and carbon atoms. , -OCONH- may have one or more linking groups, or even if some of the hydrogen atoms of the hydrocarbon group are substituted with -OH, -COOH, -OPO (OH) _2. Alternatively, it is a hydrocarbon group in which a part or all of the hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. ]
The article according to claim 1, which is one or more compounds selected from the group consisting of. The article according to claim 1, wherein the compound (β) has a number average molecular weight of 1,500 to 25,000. The article according to any one of claims 1 to 7 , wherein the base material is a glass base material. The article according to any one of claims 1 to 8 , which is a touch panel. A coating containing a poly (perfluoroalkylene ether) chain-containing silane compound (α) represented by the following general formula (1-2), a fluorine compound (β) represented by the following general formula (2), and a solvent. In the composition, the content of the compound (β) in the coating composition is 4 to 25 parts by mass with respect to 10 parts by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). After applying the coating composition on the substrate,
A method for producing an article that is dried at 50 to 200 ° C. to form a film on a substrate.

[In the formula, A is a hydrolyzable group or a non-hydrolyzable group, respectively, and in each of the two (A) _{3 in} the formula, at least one A is a hydrolyzable group.
X is a perfluoromethylene group or a perfluoroethylene group in which a plurality of structures may be present at random or in a block shape, and the perfluoroemethylene group and the perfluoroethylene group coexist.
Z is an alkylene group having 1 to 6 carbon atoms.
Y ¹ and Y ² are alkylene groups having 1 to 3 carbon atoms, respectively.
n is 6 to 300 in total. ]
R ^2- R ^1- R ³ ... (2)
[In the formula, -R ^1- is the following formula:
-(OC ₄ F ₈ ) _w- (OC ₃ F ₆ ) _r- (OC ₂ F ₄ ) _s- (OCF ₂ ) _t- O-
(In the equation, r, s, t and w are independently integers from 0 to 300, the sum of r, s, t and w is at least 5, and the existence of each repeating unit enclosed in parentheses. The order is arbitrary in the equation.). R ² and R ³ are monovalent hydrocarbon groups having 1 to 20 carbon atoms, and the hydrocarbon groups are -O-, -COO-, and -CONH- between carbon atoms and carbon atoms. , -OCONH- may have one or more linking groups, or even if some of the hydrogen atoms of the hydrocarbon group are substituted with -OH, -COOH, -OPO (OH) _2. Alternatively, it is a hydrocarbon group in which a part or all of the hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. ] The method for producing an article according to claim 10 , wherein the base material is a glass base material.

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