JP2017014452A - Surface modification agent, coating composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface modification agent and a coating composition capable of providing a coated film excellent in antifouling property and sliding property as well as durability thereof.SOLUTION: There is provided a surface modification agent containing a silane compound (α) represented by the formula (1), and a reaction product (β) of a compound having a poly(perfluoroalkylene ether) chain with a specific structure and a hydroxy group and monoisocyanate alkoxysilane. (1), where A is a hydrolyzable group or a non-hydrolyzable group, at least one of A is the hydrolyzable group, Z is a bivalent connecting group, Yand Yare direct bond or bivalent connecting group and PFPE is the poly(perfluoroalkylene ether) chain.SELECTED DRAWING: None

Description

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

  In the touch panel, two transparent substrates made of glass, synthetic resin, or the like are arranged to face each other via a frame-shaped sealing material, and an input region composed of a transparent conductive film or a plurality of electrodes is placed inside the frame-shaped sealing member. Is provided. Here, examples of the transparent substrate include plastic and glass. Examples of the combination of the two transparent substrates include plastic (film) / glass and glass / glass. Among them, a touch panel using a combination of glass / glass has a very clear screen, and hardness and weather resistance. 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 surface modifier and a coating composition that can provide a film having slipperiness and antifouling properties on a base material and 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 mixture containing a silane compound having a poly (perfluoroalkylene ether) chain, a urethane bond, a hydrolyzable silyl group, and a silane compound having a large number of trifluoromethyl groups is obtained. The present inventors have found that it is useful as a surface modifier capable of obtaining a coating film having excellent antifouling properties and slipperiness and good durability, and has led to the development of the present invention.

  That is, the present invention provides 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）〜（５）

[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. ]
A poly (perfluoroalkylene ether) chain-containing silane compound (α) represented by the following general formulas (2) to (5):

〔式中、ｒは平均５〜１００で、Ｒは二価の連結基で、Ｒ^１は炭素原子数１〜６のアルキレン基で、Ｘは炭素原子数４〜８の３価の環状脂肪族基である。一般式（２）および一般式（３）において、二つあるＢは有機基またはＳｉ（Ａ）_３であり二つあるＢの少なくとも一つはＳｉ（Ａ）_３である。該Ｓｉ（Ａ）_３中の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。一般式（４）および一般式（５）中の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からなる群から選ばれる一種以上の化合物（β）とを含有することを特徴とする表面改質剤を提供するものである。

[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 General Formula (2) and General Formula (3), two B are organic groups or Si (A) ₃ , and at least one of the two B 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 (4) and (5) is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. And a compound (β) selected from the group consisting of poly (perfluoroalkylene ether) chain-containing silane compounds represented by the formula:

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

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

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

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

  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。

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

The poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention has two Si (A) _{3 s} , as shown by the general formula (1), and in each (A) ₃ At least one of A 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 can be covalently bonded to the substrate surface by the following reaction. They speculate. One of the presumed reactions is the generation of silanol groups by hydrolysis, which dehydrates and condenses with hydroxyl groups on the surface of various substrates, for example, preferably glass substrates, and is shared on the substrate surface. It is a reaction that binds. Another presumed reaction is a reaction in which the hydrolyzable group directly condenses with the hydroxyl group of the substrate (dealcoholization condensation when the hydrolyzable group is an alkoxy group) and is covalently bonded to the substrate surface. Since the product of the present invention can bond not only one end but also both ends to the base material, the poly (perfluoroalkylene ether) chain-containing silane compound used in the present invention by a covalent bond formed by these condensation reactions ( The surface modifier containing α) adheres more firmly to the surface of the substrate than conventional products, and combines durability and anti-stain properties that the poly (perfluoroalkylene ether) chain of the surface modifier has. A film having excellent properties can be formed.

  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 preferable, an alkoxy group having 1 to 3 carbon atoms is more preferable, a methoxy group and an ethoxy group are particularly preferable, and a 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. 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 surface modifier capable of forming a film having more durability can be obtained. It is more preferable that all A in (A) ₃ are hydrolyzable groups. That is, those having no non-hydrolyzable group are most preferable.

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

Z in the general formula (1) is a divalent linking group. Y ¹ and Y ² are each a direct bond or a divalent linking group. 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 it is easy to synthesize and can easily obtain the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention. An alkylene group of 1 to 6 is 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 surface modifier that provides a film with more excellent antifouling properties is obtained. An alkylene group having 1 to 3 carbon atoms is more preferable, and a methylene group is more preferable because it is excellent in antifouling property and easily obtained industrially.

  Two Zs in the general formula (1) may be the same or different. In addition, the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention may be a mixture of modifiers each having a different Z.

Y ¹ and Y ² in the general formula (1) may be the same or different. Further, the 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 surface modifier of the present invention improves the polarity in the vicinity of the hydrolyzable groups at both ends. As a result, the adhesion to a substrate described later, preferably a glass substrate, is improved, and the reaction with the substrate surface proceeds efficiently. As a result, a film having durability and excellent antifouling properties and slipperiness can be suitably formed on the article.

  Specific examples of the 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.

  Examples of the PFPE [poly (perfluoroalkylene ether) chain] of the poly (perfluoroalkylene ether) chain-containing silane compound (α) used in the present invention include, for example, a perfluoroalkylene group having 1 to 3 carbon atoms and an oxygen atom. The thing which has the structure which connected alternately can be mentioned preferably. 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, X is a perfluoroalkylene group. All of X may have the same structure, or a plurality of structures may be present randomly or in a block form. .)

  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 the point that the perfluoromethylene group (a) and the perfluoroethylene group (b) coexist is particularly preferable including the point that it 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.

  Preferred examples of the silane compound (α) having a perfluoroalkylene group having 1 to 3 carbon atoms 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 (1-1) has a perfluoroalkylene group having 1 to 3 carbon atoms. Thus, by having a short chain | strand, it becomes a flexible frame | skeleton, As a result, the film excellent in slip property can be formed on an article | item. As for n in General formula (1), 12-200 are more preferable, 20-150 are more preferable, 30-100 are still more preferable, and 35-70 are especially preferable.

  As a silane compound represented by said (1-1), 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. The range of 60 to 450 is more preferable, the range of 90 to 300 is still more preferable, and the range of 100 to 200 is particularly preferable.

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

〔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）

[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。

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

Y ¹ , Y ² , PFPE in the general formula (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) is easy to synthesize and contains a poly (perfluoroalkylene ether) chain-containing silane compound that 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 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. The reaction temperature is preferably 30 to 120 ° C, more preferably 40 to 90.

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, It is ° C. of acetone, methyl ethyl ketone, toluene, xylene or the like that has no reactivity with an isocyanate group.
A solvent system using a solvent or a fluorine-based solvent as a reaction solvent may be used.

  The poly (perfluoroalkylene ether) chain-containing silane compound (β) used in the present invention has the following general formulas (2) to (5).

〔式中、ｒは平均５〜１００で、Ｒは二価の連結基で、Ｒ^１は炭素原子数１〜６のアルキレン基で、Ｘは炭素原子数４〜８の３価の環状脂肪族基である。一般式（２）および一般式（３）において、二つあるＢは有機基またはＳｉ（Ａ）_３であり二つあるＢの少なくとも一つはＳｉ（Ａ）_３である。該Ｓｉ（Ａ）_３中の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。一般式（４）および一般式（５）中の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からなる群から選ばれる一種以上の化合物（β）とを含有する。

[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 General Formula (2) and General Formula (3), two B are organic groups or Si (A) ₃ , and at least one of the two B 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 (4) and (5) is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. And one or more compounds (β) selected from the group consisting of poly (perfluoroalkylene ether) chain-containing silane compounds represented by the formula:

The poly (perfluoroalkylene ether) chain-containing silane compound (β) used in the present invention has at least one Si (A) ₃ as represented by the general formulas (2) to (5), and At least one A in each (A) ₃ is a hydrolyzable group. By having such a silicon atom (reactive silyl group), the poly (perfluoroalkylene ether) chain-containing silane compound (β) used in the present invention is the poly (perfluoroalkylene ether) chain-containing silane compound (α The inventors presume that it is covalently bonded to the surface of the substrate by the same action as in (1). Due to the action of the poly (perfluoroalkylene ether) chain-containing silane compound (α) and the poly (perfluoroalkylene ether) chain-containing silane compound (β), the surface modifier of the present invention has antifouling properties and slip properties. However, a film excellent in durability can be formed.

The poly (perfluoroalkylene ether) chain-containing silane compound (β) used in the present invention has a large number of trifluoromethyl groups (CF ₃ groups). The CF ₃ group has a strong ability to reduce the surface energy. Therefore, by containing this silane compound (β) having a large number of CF ₃ groups, the modifier of the present invention can more effectively exhibit the antifouling property.

Among the poly (perfluoroalkylene ether) chain-containing silane compounds (β) used in the present invention, the compound represented by the general formula (2) and the compound represented by the general formula (3) are represented by two Bs. And at least one of them is the Si (A) ₃ .

When one of B of the compound represented by the general formula (2) and the compound represented by the general formula (3) 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.

  Examples of the hydrolyzable group possessed by the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (2) to the general formula (5) include a poly (perfluoroalkylene ether) chain used in the present invention. The hydrolyzable group which the containing silane compound (α) has can be preferably mentioned. The hydrolyzable group possessed by the poly (perfluoroalkylene ether) chain-containing silane compound (β) represented by the general formula (2) to the general formula (5) has a high hydrolysis rate, and is quickly antifouling and slippery. An alkoxy group is preferable because it can form a film having excellent durability while having excellent properties, an alkoxy group having 1 to 6 carbon atoms is more preferable, an alkoxy group having 1 to 3 carbon atoms is more preferable, and methoxy And ethoxy groups are particularly preferred.

  Examples of the non-hydrolyzable group possessed by the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (2) to the general formula (5) include poly (perfluoroalkylene ether) used in the present invention. Preferred examples include non-hydrolyzable groups that the chain-containing silane compound (α) can have.

The number of hydrolyzable groups in (A) _{3 of the} poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (2) to the general formula (5) is at least one as described above. However, two or more are preferable because a surface modifier capable of forming a film having higher durability can be obtained, and it is more preferable that all of A in the 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 formula (2) to the general formula (5) has a plurality of hydrolyzable groups in (A) ₃ , the hydrolyzable group is They 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.

R in the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (2) to the general formula (5) is 5 to 100 on average. Since r is a surface modifier that provides a film having excellent antifouling properties as the content of CF ₃ groups increases, it is preferably 8 to 80 on average and more preferably 10 to 60 on average.

  R in the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (2) to the general formula (5) is a divalent linking group. R is, for example, the following (R-1) or (R-2)

Wherein 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 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 materials for producing the silane compound (β) used in the present invention can be stably obtained, and groups such as a glass substrate can be obtained. (R-1-1), (R-1-3), (R-) because a surface modifier capable of forming a film having excellent durability and anti-slip properties on the material can be obtained. 1-4), (R-2-5), (R-2-6), and a structure represented by (R-2-8) are preferable, and (R-1-3) and (R-1-4) are preferable. ) Is more preferable.

  X in the silane compound represented by the general formula (3) and the silane compound represented by the general formula (5) is a trivalent cyclic aliphatic group having 4 to 8 carbon atoms. Preferred examples of the cycloaliphatic group include a cyclohexyl ring.

  Specific examples of the poly (perfluoroalkylene ether) chain-containing silane compound (β) used in the present invention are shown below.

In the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (2) and the poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (3) 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 (β-1) below

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

(In the formula, r is an average of 5 to 100.)
And the following general formula (β-2) or general formula (β-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（β―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 (β-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（β−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 (β-4) represented by Manufacturing method including.

In the poly (perfluoroalkylene ether) chain-containing silane compound represented by general formula (2) or general formula (3) used in the present invention, one of B is Si (A) ₃ and the other of B is Si ( A) A compound that is an organic group other than ₃ can be obtained by the following production method.

  Production method 2: Carboxylic acid (β-1) represented by the general formula (β-1) and the following general formula (β-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（β―４）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（β―４）で表されるイソシアネート化合物（β―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 (β-4) 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 (β-4) represented by the general formula (β-4).

  The poly (perfluoroalkylene ether) chain-containing silane compound represented by the general formula (4) or the general formula (5) used in the present invention can be obtained, for example, by the first step of the production method 1.

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

  Preferred examples of the epoxysilane compound (β-2) and the epoxysilane compound (β-3) include the compounds shown below.

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

  As said isocyanate compound ((beta) -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 (β-4-1) to (α-4-12) is easy to synthesize and contains a poly (perfluoroalkylene ether) chain-containing silane that is easily used in the present invention. Since a compound (β) 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 preferable. Particularly preferred.

  Since the isocyanate compound (β-4) is a surface modifier that is excellent in reactivity and provides a highly durable coating, (β-4-1), (β-4-2), and (β- One or more compounds selected from the group consisting of 4-3) are preferred, and (β-4-1) and (β-4-2) are more preferred. The isocyanate compound (β-4) may be used alone or in combination of two or more.

  As said epoxy compound ((beta) -5), the following compound can be illustrated preferably, for example.

  Among the epoxy compounds (β-5), (β-5-1) or (β-5-2) is preferable, and (β-5-2) is more preferable in order to obtain a coating film having excellent antifouling properties. . An epoxy compound ((beta) -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 in which 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 is used 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 (β-1) and the epoxysilane compound [(β-2), (β-3)] is the carboxyl group of the carboxylic acid (β-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 (β-4) is the same as that of the hydroxyl group of the reaction product and the isocyanate compound (β-4). 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 the production method 2, the reaction ratio between the carboxylic acid (β-1) and the epoxy compound (β-5) is the same as the carboxyl group of the carboxylic acid (β-1) and the epoxy group of the epoxy compound. The ratio in which the equivalent ratio (carboxyl group / epoxy group) is 0.5 to 1.5 is preferable, the ratio in which 0.9 to 1.1 is more preferable, and the ratio in which 0.98 to 1.02 is most preferable. 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 production method 2, the reaction ratio between the reaction product having a secondary hydroxyl group derived from an epoxy group and the isocyanate compound (β-4) is the same as that of the hydroxyl group and isocyanate compound (β-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.

  The content ratio of the poly (perfluoroalkylene ether) chain-containing silane compound (α) and the poly (perfluoroalkylene ether) chain-containing silane compound (β) in the surface modifier of the present invention maintains slipperiness. Since the antifouling performance can be improved, the poly (perfluoroalkylene ether) chain-containing silane compound (β) 0.01 to 100 per 1 part by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). Mass parts are preferred, 0.05 to 20 parts by mass are more preferred, and 0.1 to 2 parts by mass are even more preferred.

  The coating composition of the present invention contains the surface modifier of the present invention and a solvent. The solvent is not particularly limited as long as it dissolves the surface modifier. Alcohols, ethers, ketones, aromatic hydrocarbons, esters, paraffinic hydrocarbons and the like are preferable, and in particular, a solvent containing a fluorine atom is preferably used because it can dissolve the surface modifier of the present invention well. can do. One type of solvent may be used, or two or more types may be mixed and used.

  Examples of the solvent containing a fluorine atom include hydrofluoroether, hydrofluorocarbon, perfluorocarbon, fluorine-containing aromatic hydrocarbon, perfluoropolyether compound, and the like. 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, C ₄ F ₉ C ₂ H ₅ , (CF ₃ ) ₂ CFCHFCHFCF ₃ , C ₆ F ₁₃ H, C ₆ F ₁₃ C ₂ H ₅ , C ₄ F ₉ OCH ₃ , C _{4 F 9 OC 2 H 5,} C 2 F 5 CF (OCH 3) C 3 F 7 and is preferably _HCF is 2 _CF 2 _OCH 2 _CF 1 or more _{to 3} selected from the group consisting of.

  As the content of the surface modifier in the coating composition of the present invention, a coating containing the surface modifier can be uniformly formed, and the surface modifier and the substrate such as glass react well. Therefore, 0.001 to 50 mass% is preferable, 0.01 to 10 mass% is more preferable, and 0.05 to 1 mass% is still more preferable.

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

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

  As the shape of the substrate used in the present invention, various shapes can be used. Especially, a sheet-like thing can be used conveniently. The thickness of a sheet-like base material can illustrate the thing of the range of 5 micrometers-10 mm, for example.

  Examples of the method for forming a coating film of the coating composition of the present invention on the substrate include various methods, and a method of drying after applying the coating composition on the substrate. Examples of the method of applying the coating composition on the substrate include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and vapor deposition.

  After coating the coating composition on the substrate, the solvent in the composition is removed by various methods to form a film. For example, the drying may be carried out by allowing to stand at room temperature and drying, or may be allowed to stand and dry in a warmed atmosphere. When drying in a warmed atmosphere, the temperature of the atmosphere is usually 30. It is -200 degreeC, Preferably it is 50-180 degreeC.

  The film thickness of the film 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 surface modifier and coating composition of the present invention can form a film having excellent antifouling properties and slipperiness on the surface of an article. Utilizing such excellent effects, the surface modifying agent or coating composition of the present invention allows the fingertip to directly touch the screen, and to perform an operation (swipe) for tracing (sliding) the screen with the fingertip or the pen tip. It can be 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 surface modifier, < ¹ > H-NMR spectrum, < ¹⁹ > F-NMR spectrum, and < ¹³ > C-NMR spectrum are as follows.

[IR spectrum measurement conditions]
Apparatus: “Nicolet 380” manufactured by Thermo Electron
Measuring method: KBr method

[Measurement conditions for ¹ H-NMR spectrum, ¹⁹ F-NMR spectrum and 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)

（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。ｎは平均４１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, with an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups per molecule, and an average of 126 fluorine atoms. N is an average of 41.)
45.3 g of a diol having a poly (perfluoroalkylene ether) chain represented by: 4.7 g of 3-isocyanatopropyltrimethoxysilane, and 0.025 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 such that the solvent content in the obtained reaction product was 80%. 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 (1) is used in the present invention. A solvent solution containing (α-1) was obtained. Here, 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 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 (β)]
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 30.45 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)

44.0 g of carboxylic acid represented by the formula, 1.67 g of γ-glycidoxypropyltriethoxysilane and 0.137 g of triphenylphosphine as a reaction catalyst were added, and stirring was started under a nitrogen stream, After warming, the reaction was performed for about 6 hours to obtain a reaction product.

The reaction product was diluted with C ₄ F ₉ OC ₂ H ₅ such that the solvent content in the obtained reaction product was 80%. 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 (4) is used in the present invention. A solvent solution containing (β1) was obtained. Here, in the silane compound (β1), in the general formula (4), r is an average of 43, (—R—) is (—CH ₂ OCH ₂ CH ₂ CH ₂ —), and A is an ethoxy group.

In addition, the chart figure of IR spectrum of a silane compound ((beta) 1) is shown in FIG. 5, and the chart figure of a < ¹ > H-NMR spectrum is shown in FIG.

Synthesis example 3 (same as above)
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 30.28 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)

44.0 g of carboxylic acid represented by the formula, 1.42 g of γ-glycidoxypropyltrimethoxysilane and 0.136 g of triphenylphosphine as a reaction catalyst were added, and stirring was started under a nitrogen stream. After warming, the reaction was performed for about 6 hours to obtain a reaction product.

The reaction product was diluted with C ₄ F ₉ OC ₂ H ₅ such that the solvent content in the obtained reaction product was 80%. 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 (4) is used in the present invention. A solvent solution containing (β2) was obtained. Here, in the silane compound (β2), in the general formula (4), r is 43 on average, (—R—) is (—CH ₂ OCH ₂ CH ₂ CH ₂ —), and A is a methoxy group.

Synthesis example 4 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 27.49 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)

39.0 g of carboxylic acid represented by the following formula

2.24 g of the epoxy compound represented by the above formula and 0.123 g of triphenylphosphine as a reaction catalyst were added, stirring was started under a nitrogen stream, and the mixture was heated to 105 ° C. and reacted for about 5 hours. Thereafter, the temperature was lowered to 50 ° C., 15.10 g of C ₄ F ₉ OC ₂ H ₅ , 1.35 g of 3-isocyanatopropyltriethoxysilane, and 0.026 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 such that the solvent content in the obtained reaction product was 80%. 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 (2) is used in the present invention. A solvent solution containing (β3) was obtained. Here, in the general formula (2), the silane compound (β3) has an average of 43, (—R—) is (—CH ₂ OCH ₂ CH ₂ —), and (—R ¹ —) is (— CH ₂ CH ₂ CH ₂ —), one of the two B is Si (OC ₂ H ₅ ) ₃ and the other is C ₆ F ₁₃ .

Synthesis example 5 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 27.49 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)

39.0 g of carboxylic acid represented by the following formula

で表されるエポキシ化合物２．２４ｇと、反応触媒としてトリフェニルフォスフィン０．１２３ｇを加え、窒素気流下で攪拌を開始し、１０５℃に加温後、約５時間反応させた。その後、５０℃まで降温し、Ｃ_４Ｆ_９ＯＣ_２Ｈ_５ １４．８７ｇと、３−イソシアナトプロピルトリメトキシシラン１．１２ｇと、ウレタン化触媒としてオクチル酸スズ０．０２６ｇを加え、窒素気流下で攪拌を開始し、７０℃で約４時間反応させ、反応物を得た。

2.24 g of the epoxy compound represented by the above formula and 0.123 g of triphenylphosphine as a reaction catalyst were added, stirring was started under a nitrogen stream, and the mixture was heated to 105 ° C. and reacted for about 5 hours. Thereafter, the temperature was lowered to 50 ° C., 14.87 g of C ₄ F ₉ OC ₂ H _5, 1.12 g of 3-isocyanatopropyltrimethoxysilane and 0.026 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 such that the solvent content in the obtained reaction product was 80%. 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 (2) is used in the present invention. A solvent solution containing (β4) was obtained. Here, in the silane compound (β4), in the general formula (2), r is an average of 43, (—R—) is (—CH ₂ OCH ₂ CH ₂ —), and (—R ¹ —) is (— CH ₂ CH ₂ CH ₂ —), one of the two B is Si (OCH ₃ ) ₃ and the other is C ₆ F ₁₃ .

Synthesis example 6 (same as above)
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 such that the solvent content in the obtained reaction product was 80%. 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 (2) is used in the present invention. A solvent solution containing (β5) was obtained. Here, in the silane compound (β5), in the general formula (2), 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 .

Synthesis example 7 (same as above)
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。）
で表されるカルボン酸８７．６ｇと、γ−グリシドキシプロピルトリエトキシシラン３．３３ｇと、反応触媒としてトリフェニルフォスフィン０．２７３ｇを加え、窒素気流下で攪拌を開始し、１０５℃に加温後、約５時間反応させた。その後、５０℃まで降温し、Ｃ_４Ｆ_９ＯＣ_２Ｈ_５ ３２．８２ｇと、３−イソシアナトプロピルトリメトキシシラン２．５１ｇと、ウレタン化触媒としてオクチル酸スズ０．０４７ｇを加え、窒素気流下で攪拌を開始し、７０℃で約４時間反応させ、反応物を得た。

(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., 32.82 g of C ₄ F ₉ OC ₂ H ₅ , 2.51 g of 3-isocyanatopropyltrimethoxysilane, 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 such that the solvent content in the obtained reaction product was 80%. 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 (2) is used in the present invention. A solvent solution containing (β6) was obtained. Here, in the silane compound (β6), in the general formula (2), r is an average of 43, (—R—) is (—CH ₂ OCH ₂ CH ₂ CH ₂ —), and (—R ¹ —) is (—CH ₂ CH ₂ CH ₂ —), one of the two B is Si (OC ₂ H ₅ ) ₃ and the other is Si (OCH ₃ ) ₃ .

Example 1 (Preparation of surface modifiers, coating compositions and articles)
The solvent solution containing the silane compound (α-1) and the solvent solution containing the silane compound (β-1) were mixed in an equal amount in terms of mass to obtain a solvent solution containing the surface modifier (1) of the present invention. . A solvent solution containing the surface modifier (1) was diluted with C ₄ F ₉ OC ₂ H ₅ to obtain a solution [coating composition (1)] having a surface modifier content of 0.1%. . 50 ml of the coating composition (1) was spray-coated with a spray gun on a 7 × 15 cm glass substrate whose surface was treated with ozone. After coating, the glass substrate coated with the coating composition (1) 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 1.

<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) 1000 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) 1000 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.

Examples 2 to 7 (same as above)
Coating compositions (2) to (7) and articles (2) to (7) in the same manner as in Example 5 except that the silane compound (α) and the silane compound (β) were blended at the blending ratio shown in Table 1. Got. In the same manner as in Example 1, water repellency, slipperiness and water repellency durability were evaluated. The evaluation results are shown in Table 1.

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

Claims (19)

The following general formula (1)

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and in each of the two (A) ₃ , at least one A is a hydrolyzable group. Z is a divalent linking group. Y ¹ and Y ² are each a direct bond or a divalent linking group. PFPE represents a poly (perfluoroalkylene ether) chain. ]
A poly (perfluoroalkylene ether) chain-containing silane compound (α) represented by the following general formulas (2) to (5):

[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 General Formula (2) and General Formula (3), two B are organic groups or Si (A) ₃ , and at least one of the two B 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 (4) and (5) is a hydrolyzable group or a non-hydrolyzable group, and at least one of them is a hydrolyzable group. And a compound (β) selected from the group consisting of a poly (perfluoroalkylene ether) chain-containing silane compound represented by the formula: The surface modifier according to claim ¹ , wherein Z in the general formula (1) is an alkylene group having 1 to 10 carbon atoms, and Y ¹ and Y ² are each an alkylene group having 1 to 6 carbon atoms. .   The surface modifier according to claim 1, wherein the hydrolyzable group in the general formula (1) is an alkoxy group having 1 to 6 carbon atoms.   The surface modifier according to claim 1, wherein the hydrolyzable group in the general formula (1) is a methoxy group or an ethoxy group, Z is an n-propylene group, and Y1 and Y2 are methylene groups. The poly (perfluoroalkylene ether) chain-containing silane compound (α) is represented by the following general formula (1-1)

[Wherein, A is a hydrolyzable group or a non-hydrolyzable group, and in each of the two (A) ₃ , at least one A is a hydrolyzable group. X may be all of the same structure, or 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 surface modifier according to claim 1, which is a compound represented by the formula:   6. The surface modifier according to claim 5, wherein the perfluoroalkylene group having 1 to 3 carbon atoms is a perfluoromethylene group or a perfluoroethylene group. The two is (A) A in ₃ are all a hydrolyzable group, with the hydrolyzable group is a methoxy group or an ethoxy group, Z is in each n- propylene, Y ¹ and Y ² is a methylene group The surface modifier according to claim 5, wherein n is 12 to 200. R in the poly (perfluoroalkylene ether) chain-containing silane compound (β) is the following (R-1) or (R-2)

Wherein 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 surface modifier according to claim 1, which is represented by: The surface modifier according to claim ¹ , wherein R ¹ in the general formula (2) or the general formula (3) is a propylene group. The surface modifier according to claim 8, wherein R ² is a methylene group, R ³ is an ethylene group or an n-propylene group, and R ⁴ is a methylene group or an n-butylene group.   The surface modifying agent according to claim 1, wherein the hydrolyzable group of the compound (β) is an alkoxy group having 1 to 6 carbon atoms.   The surface modifier according to claim 1, wherein all A in the compound (β) are hydrolyzable groups, and the hydrolyzable groups are methoxy groups or ethoxy groups.   The surface modifier according to claim 1, wherein r in the compound (β) is 5 to 100.   The content of the poly (perfluoroalkylene ether) chain-containing silane compound (β) is 0.05 to 20 parts by mass with respect to 1 part by mass of the poly (perfluoroalkylene ether) chain-containing silane compound (α). The surface modifier according to 1.   A coating composition comprising the surface modifier of any one of claims 1 to 14 and a solvent.   The coating composition according to claim 15, wherein the solvent is a fluorine atom-containing solvent.   The coating composition according to claim 15 or 16, wherein the content of the surface modifier is 0.001 to 50 mass%.   An article comprising a coating of the coating composition according to any one of claims 15 to 17 on a substrate.   The article of claim 18, wherein the substrate is a glass substrate.

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