JP7367864B2 - Coating agent composition, surface treatment agent containing the composition, and article surface treated with the surface treatment agent - Google Patents

Description

The present invention relates to a coating composition with excellent lipophilicity and scratch resistance, a surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent.

In recent years, the use of touch panels for displays, including mobile phones, has been accelerated. Since these devices are operated by touching them with fingers, dirt such as fingerprints adheres to them, making them unsightly. Therefore, in order to improve the appearance and visibility, the demand for technology that makes it difficult for fingerprints to stick to the surface of the display and technology that makes fingerprints less noticeable is increasing year by year, and it is necessary to develop materials that can meet these demands. desired.

Silane coupling agents are generally well known as surface modifiers for substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates. Silane coupling agents have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule, and this hydrolyzable silyl group is A self-condensation reaction occurs to form a film. The coating becomes a durable and strong coating due to the hydrolyzable silyl group chemically and physically bonding to the surface of glass, metal, or the like.

Therefore, by using a fluoropolyether group-containing polymer in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound, a composition that can form a coating having water and oil repellency, stain resistance, etc. on the surface of a substrate is developed. Many things have been disclosed (Patent Documents 1 to 6: Japanese Patent Application Publication No. 2008-534696, Japanese Patent Application Publication No. 2008-537557, Japanese Patent Application Publication No. 2012-072272, Japanese Patent Application Publication No. 2012-157856, Japanese Patent Application Publication No. 2013- 136833, JP 2015-199906).

However, although coating layers made using conventional fluoropolyether group-containing polymers have excellent dirt wiping properties due to their high water and oil repellency, the sebum contained in fingerprints is repelled by the surface, resulting in minute oil droplets. There was a problem in that fingerprints were easily noticeable due to the scattering of light.

Furthermore, a composition is also disclosed that uses a silane compound in which a hydrolyzable silyl group is introduced into a lipophilic compound, so that it can adhere to the surface of a base material and form a film having lipophilic properties on the surface of the base material. (Patent Document 7: Japanese Unexamined Patent Publication No. 2001-353808).
A composition containing a silane compound in which a hydrolyzable silyl group is introduced into the lipophilic compound can form a cured film with excellent lipophilicity, so that sebum scatters light when fingerprints etc. are attached. Fingerprints become less noticeable.

However, conventional coating agent compositions that can form cured films with excellent lipophilicity are worn out due to scratches during actual use, resulting in a decrease in lipophilicity, so they do not have satisfactory performance in practical use. do not have.

Special Publication No. 2008-534696 Special Publication No. 2008-537557 JP2012-072272A Japanese Patent Application Publication No. 2012-157856 Japanese Patent Application Publication No. 2013-136833 Japanese Patent Application Publication No. 2015-199906 Japanese Patent Application Publication No. 2001-353808

The present invention was made in view of the above circumstances, and includes a coating composition capable of forming a cured film with excellent lipophilicity and scratch resistance, a surface treatment agent containing the composition, and a surface treatment using the surface treatment agent. The purpose is to provide products that are

（式中、Ａは－Ｃ（＝Ｏ）ＯＲ¹、－Ｃ（＝Ｏ）ＮＲ¹ ₂、－Ｃ（＝Ｏ）ＳＲ¹又は－Ｐ（＝Ｏ）（ＯＲ¹）₂であり、Ｒ¹は独立に水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基であり、Ｙは独立に２価の有機基であり、Ｗは独立に炭素数１～４のアルキル基、フェニル基、水酸基又は加水分解性基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１～３の整数であり、ｑは１～３の整数である。）
（Ｂ）下記一般式（２）又は（３）で表される親油性基含有オルガノポリシロキサン化合物、

（式中、Ａ’は－Ｃ（＝Ｏ）ＯＲ¹、－Ｃ（＝Ｏ）ＮＲ¹ ₂、－Ｃ（＝Ｏ）ＳＲ¹又は－Ｐ（＝Ｏ）（ＯＲ¹）₂であり、Ｒ¹は上記と同じであり、Ｒ⁶は独立に水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基であり、Ｙ’は独立に２価の有機基であり、ｉは１～１９９の整数であり、ｊは１～２００の整数であり、ｊ／ｉ≧０．５であり、ｉ＋ｊ＝３～２０１であり、ｋは０～１１の整数であり、ｌは３～１２の整数であり、ｌ／ｋ≧０．５であり、ｋ＋ｌ＝３～１２であり、ｉ、ｊ、ｋ、ｌが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）As a result of intensive studies to solve the above object, the present inventors found that the following components (A) and (B) are contained as essential components, and the mass ratio of the components (A) and (B) is A coating agent composition within the range of 0.1<(A)/(B)<10 can form a cured film with excellent lipophilicity and scratch resistance, and can solve the problems of the prior art described above. They discovered this and came up with the present invention.
(A) a lipophilic group-containing (hydrolysable) organosiloxane compound represented by the following general formula (1) and/or a partial (hydrolysed) condensate thereof;

(In the formula, A is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ are independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, Y is independently a divalent organic group, and W is independently is an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X is independently a hydroxyl group or a hydrolyzable group , n is an integer from 1 to 3, and q is an integer from 1 to 3.)
(B) an organopolysiloxane compound containing a lipophilic group represented by the following general formula (2) or (3),

(In the formula, A' is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ is the same as above, R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and Y' is independently It is a divalent organic group, i is an integer from 1 to 199, j is an integer from 1 to 200, j/i≧0.5, i+j=3 to 201, and k is 0 to 200. is an integer of 11, l is an integer of 3 to 12, l/k≧0.5, k+l = 3 to 12, and is shown in parentheses with i, j, k, l Each repeating unit may be combined randomly.)

（式中、Ａは－Ｃ（＝Ｏ）ＯＲ¹、－Ｃ（＝Ｏ）ＮＲ¹ ₂、－Ｃ（＝Ｏ）ＳＲ¹又は－Ｐ（＝Ｏ）（ＯＲ¹）₂であり、Ｒ¹は独立に水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基であり、Ｙは独立に２価の有機基であり、Ｗは独立に炭素数１～４のアルキル基、フェニル基、水酸基又は加水分解性基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１～３の整数であり、ｑは１～３の整数である。）
で表される親油性基含有（加水分解性）オルガノシロキサン化合物及び／又はその部分（加水分解）縮合物と、
（Ｂ）下記一般式（２）又は（３）

（式中、Ａ’は－Ｃ（＝Ｏ）ＯＲ¹、－Ｃ（＝Ｏ）ＮＲ¹ ₂、－Ｃ（＝Ｏ）ＳＲ¹又は－Ｐ（＝Ｏ）（ＯＲ¹）₂であり、Ｒ¹は上記と同じであり、Ｒ⁶は独立に水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基であり、Ｙ’は独立に２価の有機基であり、ｉは１～１９９の整数であり、ｊは１～２００の整数であり、ｊ／ｉ≧０．５であり、ｉ＋ｊ＝３～２０１であり、ｋは０～１１の整数であり、ｌは３～１２の整数であり、ｌ／ｋ≧０．５であり、ｋ＋ｌ＝３～１２であり、ｉ、ｊ、ｋ、ｌが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
で表される親油性基含有オルガノポリシロキサン化合物と
を必須成分として含有し、（Ａ）成分と（Ｂ）成分の質量比が０．１＜（Ａ）／（Ｂ）＜１０の範囲内であるコーティング剤組成物。
２．
（Ａ）成分の一般式（１）で表される親油性基含有（加水分解性）オルガノシロキサン化合物において、Ｙが－Ｏ－、－Ｓ－、－ＮＲ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲ－、－ＯＣ（＝Ｏ）ＮＲ－（Ｒは炭素数１～４のアルキル基又はフェニル基である）、シルアルキレン基、シルアリーレン基、及びケイ素原子数２～１０個の直鎖状、分岐状又は環状の２価のオルガノポリシロキサン残基から選ばれる２価の基を含んでいてもよく、また炭素数６～２０のアリーレン基を含んでいてもよい炭素数２～３０のアルキレン基である１に記載のコーティング剤組成物。
３．
（Ａ）成分の一般式（１）で表される親油性基含有（加水分解性）オルガノシロキサン化合物において、Ｗがそれぞれ独立に、炭素数１～４のアルキル基、フェニル基、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシ置換アルコキシ基、炭素数１～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基、ハロゲン原子、オキシム基、イソシアネート基、及びシアネート基からなる群より選ばれるものである１又は２に記載のコーティング剤組成物。
４．
（Ａ）成分が、下記一般式（４）で表される親油性基含有（加水分解性）オルガノシロキサン化合物である１～３のいずれかに記載のコーティング剤組成物。

（式中、Ｒ²は炭素数１～２０のアルキル基、炭素数６～２０のアリール基又は炭素数７～２０のアラルキル基であり、Ｑは単結合、又はシルアルキレン基、シルアリーレン基、及びケイ素原子数２～１０個の直鎖状、分岐状もしくは環状の２価のオルガノポリシロキサン残基から選ばれる２価の基であり、ｍはそれぞれ独立に１～２０の整数であり、Ｘは独立に水酸基又は加水分解性基である。）
５．
（Ｂ）成分が、下記一般式（５）又は（６）で表されるオルガノポリシロキサンである１～４のいずれかに記載のコーティング剤組成物。

（式中、Ｙ²は独立に－Ｏ－、－Ｓ－、－ＮＲ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲ－、－ＯＣ（＝Ｏ）ＮＲ－（Ｒは炭素数１～４のアルキル基又はフェニル基である）、シルアルキレン基、シルアリーレン基、及びケイ素原子数２～１０個の直鎖状、分岐状又は環状の２価のオルガノポリシロキサン残基から選ばれる２価の基を含んでいてもよく、また炭素数６～２０のアリーレン基を含んでいてもよい炭素数２～３０のアルキレン基であり、Ｒ²、ｉ、ｊ、ｋ、ｌ、ｊ／ｉ、ｉ＋ｊ、ｌ／ｋ、ｋ＋ｌは上記と同じであり、ｉ、ｊ、ｋ、ｌが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
６．
１～５のいずれかに記載のコーティング剤組成物を含有する表面処理剤。
７．
更に、溶剤を含むものである６に記載の表面処理剤。
８．
更に、加水分解縮合触媒を含むものである６又は７に記載の表面処理剤。
９．
２５℃、相対湿度４０％におけるオレイン酸接触角が３０°以下の硬化被膜を与えるものである６～８のいずれかに記載の表面処理剤。
１０．
６～９のいずれかに記載の表面処理剤の硬化被膜を表面に有する物品。Accordingly, the present invention provides the following coating composition, a surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent.
1.
(A) General formula (1) below

(In the formula, A is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ are independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, Y is independently a divalent organic group, and W is independently is an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X is independently a hydroxyl group or a hydrolyzable group , n is an integer from 1 to 3, and q is an integer from 1 to 3.)
A lipophilic group-containing (hydrolysable) organosiloxane compound and/or a partial (hydrolysed) condensate thereof represented by;
(B) General formula (2) or (3) below

(In the formula, A' is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ is the same as above, R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and Y' is independently It is a divalent organic group, i is an integer from 1 to 199, j is an integer from 1 to 200, j/i≧0.5, i+j=3 to 201, and k is 0 to 200. is an integer of 11, l is an integer of 3 to 12, l/k≧0.5, k+l = 3 to 12, and is shown in parentheses with i, j, k, l Each repeating unit may be combined randomly.)
It contains a lipophilic group-containing organopolysiloxane compound represented by A certain coating composition.
2.
In the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the general formula (1) of component (A), Y is -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC(=O)NR- (R is an alkyl group having 1 to 4 carbon atoms or a phenyl group), sylalkylene group, sylarylene group, and a divalent group selected from linear, branched, or cyclic divalent organopolysiloxane residues having 2 to 10 silicon atoms, and arylene having 6 to 20 carbon atoms. 2. The coating agent composition according to 1, which is an alkylene group having 2 to 30 carbon atoms which may contain a group.
3.
In the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the general formula (1) of component (A), W each independently represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, or a carbon number From an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom, an oxime group, an isocyanate group, and a cyanate group. 3. The coating composition according to 1 or 2, which is selected from the group consisting of:
4.
4. The coating composition according to any one of 1 to 3, wherein the component (A) is a lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the following general formula (4).

(In the formula, R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and Q is a single bond, or a sylalkylene group, a sylarylene group, and a divalent group selected from linear, branched, or cyclic divalent organopolysiloxane residues having 2 to 10 silicon atoms, m is each independently an integer of 1 to 20, and are independently hydroxyl groups or hydrolyzable groups.)
5.
5. The coating composition according to any one of 1 to 4, wherein component (B) is an organopolysiloxane represented by the following general formula (5) or (6).

(In the formula, Y ² is independently -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC( =O)NR- (R is an alkyl group having 1 to 4 carbon atoms or a phenyl group), a sylalkylene group, a sylarylene group, and a linear, branched or cyclic 2 group having 2 to 10 silicon atoms. is an alkylene group having 2 to 30 carbon atoms which may contain a divalent group selected from valent organopolysiloxane residues and may also contain an arylene group having 6 to 20 carbon atoms, and R ² , i, j, k, l, j/i, i+j, l/k, k+l are the same as above, and each repeating unit shown in parentheses with i, j, k, l is randomly combined. (You can leave it there.)
6.
A surface treatment agent containing the coating composition according to any one of 1 to 5.
7.
6. The surface treatment agent according to 6, which further contains a solvent.
8.
8. The surface treatment agent according to 6 or 7, further comprising a hydrolysis condensation catalyst.
9.
9. The surface treatment agent according to any one of 6 to 8, which provides a cured film having an oleic acid contact angle of 30° or less at 25° C. and 40% relative humidity.
10.
10. An article having a cured film of the surface treatment agent according to any one of 6 to 9 on its surface.

The coating composition of the present invention comprises a specific organosiloxane compound containing a lipophilic group and a hydroxyl group or a hydrolyzable silyl group and/or a partial (hydrolyzed) condensate thereof, and a specific organosiloxane compound containing a lipophilic group. It contains a mixture containing a polysiloxane compound in a specific proportion, and the cured film coated on the surface of the base material with a surface treatment agent containing the composition is resistant to scratches when fingerprints are attached. The sebum contained in the fingerprint can be wetted and spread onto the substrate. Moreover, since the coating agent composition contains an organopolysiloxane compound with excellent lubricity, friction is reduced and a cured film with excellent scratch resistance can be provided. As a result, an article having a cured film surface-treated with a surface treatment agent containing the coating agent composition has excellent lipophilicity and scratch resistance.

The coating agent composition of the present invention comprises a specific lipophilic group-containing (hydrolyzable) organosiloxane compound containing a hydroxyl group or a hydrolyzable group and a lipophilic group and/or a partial (hydrolyzed) condensate thereof (hereinafter referred to as , component (A)) and a specific organopolysiloxane compound containing a lipophilic group (hereinafter referred to as component (B)) as essential components, and the mass of component (A) and component (B). It is characterized in that the ratio is within the range of 0.1<(A)/(B)<10.

The present inventors have developed a lipophilic group-containing (hydrolyzable) organosiloxane compound as a component (A) that exhibits adhesion to a base material, and a lipophilic group-containing component as a component (B) that exhibits surface lubricity. It has been found that when an organopolysiloxane compound is blended, the coating composition can form a cured film with excellent lipophilicity and scratch resistance.

（式中、Ａは－Ｃ（＝Ｏ）ＯＲ¹、－Ｃ（＝Ｏ）ＮＲ¹ ₂、－Ｃ（＝Ｏ）ＳＲ¹又は－Ｐ（＝Ｏ）（ＯＲ¹）₂であり、Ｒ¹は独立に水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基であり、Ｙは独立に２価の有機基であり、Ｗは独立に炭素数１～４のアルキル基、フェニル基、水酸基又は加水分解性基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１～３の整数であり、ｑは１～３の整数である。）The lipophilic group-containing (hydrolysable) organosiloxane compound of component (A), which is the first essential component in the coating composition of the present invention, is represented by the following general formula (1). It may be a partial (hydrolysis) condensate or a mixture of one or more thereof.

(In the formula, A is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ are independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, Y is independently a divalent organic group, and W is independently is an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X is independently a hydroxyl group or a hydrolyzable group , n is an integer from 1 to 3, and q is an integer from 1 to 3.)

In the above formula (1), A is an ester or carboxylic acid represented by -C(=O)OR ¹ , an amide represented by -C(=O)NR ¹ ₂ , or an amide represented by -C(=O)SR ¹ It is either a thioester or a thioacid, or a phosphonic acid ester or a phosphonic acid represented by -P(=O)(OR ¹ ) ₂ , and is a lipophilic terminal group in the present invention.

Here, R ¹ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and the alkyl group is linear, branched, It may be either cyclic or a combination thereof. Preferably it is a linear alkyl group having 1 to 8 carbon atoms, more preferably a linear alkyl group having 2 to 4 carbon atoms.
Specifically, ^R1 includes a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group. , octadecyl group, isopropyl group, isobutyl group, tert-butyl group, neopentyl group, thexyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclohexylmethyl group, norbornyl group, decahydronaphthyl group, adamantyl group, adamantylmethyl group, etc. Examples include alkyl groups such as phenyl, tolyl, and naphthyl groups, and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups. R ¹ is preferably a methyl group, ethyl group, butyl group, or octyl group.

Examples of A include those shown below.

In the above formula (1), W is an alkyl group having 1 to 4 carbon atoms, which may be different from each other, a phenyl group, a hydroxyl group, or a hydrolyzable group. Such W includes alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and carbon atoms having 1 to 10 carbon atoms such as phenyl group, hydroxyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, and butoxy group. alkoxy groups, alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy groups and methoxyethoxy groups, acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups, and alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy groups. , halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, oxime group, isocyanate group, and cyanate group. Among them, methyl group, methoxy group, ethoxy group, isopropenoxy group, and chlorine atom are preferred.

In the above formula (1), X is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of such X include alkoxy groups having 1 to 10 carbon atoms such as hydroxyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, and 2 to 10 carbon atoms such as methoxymethoxy group and methoxyethoxy group. Alkoxy-substituted alkoxy groups, acyloxy groups with 1 to 10 carbon atoms such as acetoxy groups, alkenyloxy groups with 2 to 10 carbon atoms such as isopropenoxy groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, oxime groups , isocyanate group, cyanate group, etc. Among them, methoxy group, ethoxy group, isopropenoxy group, and chlorine atom are preferred.

In the above formula (1), R is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, or phenyl group. group, of which methyl group is preferred.

In the above formula (1), Y is independently a divalent organic group, -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C( =O)NR-, -OC(=O)NR- (R is the same as above), sylalkylene group, sylarylene group, and linear, branched or cyclic divalent group having 2 to 10 silicon atoms An alkylene group having 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms, which may contain a divalent group selected from the organopolysiloxane residues of is preferable, and more preferably a divalent group represented by the following formula (7).

In the above formula (7), R ³ independently represents a divalent hydrocarbon group, specifically an alkylene group having 1 to 30 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, etc. Examples include alkylene groups having 7 to 30 carbon atoms, including arylene groups having 6 to 20 carbon atoms such as phenylene groups, and preferably alkylene groups having 2 to 20 carbon atoms.

In the above formula (7), Z is a single bond, or -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR- , -OC(=O)NR-, a sylalkylene group, a sylarylene group, and a linear, branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms. It is a divalent group selected from the group, and R is the same as above.

（式中、Ｒ⁴はメチル基、エチル基、プロピル基、ブチル基等の炭素数１～４のアルキル基、フェニル基等の炭素数６～１０のアリール基であり、Ｒ⁴は同一でも異なっていてもよい。Ｒ⁵は炭素数１～１２のアルキレン基、フェニレン基等の炭素数６～１２のアリーレン基である。）Here, as the sylalkylene group and the sylarylene group, those shown below can be exemplified.

(In the formula, R ⁴ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or an aryl group having 6 to 10 carbon atoms such as a phenyl group, and R ⁴ may be the same or different. (R ⁵ is an arylene group having 6 to 12 carbon atoms such as an alkylene group having 1 to 12 carbon atoms or a phenylene group.)

（式中、Ｒ⁴は上記と同じである。ｇは１～９、好ましくは１～４の整数であり、ｈは１～８、好ましくは１～３の整数である。）Further, as the linear, branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, the following can be exemplified.

(In the formula, R ⁴ is the same as above. g is an integer of 1 to 9, preferably 1 to 4, and h is an integer of 1 to 8, preferably 1 to 3.)

In the above formula (7), a is 0 or 1.

Specific examples of Y include the following groups.

In the above formula (1), n is an integer of 1 to 3, q is an integer of 1 to 3, preferably n is 2 or 3, q is 2 or 3, more preferably n is 3, q is 3.

Examples of the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1) include those represented by the following formula.

（式中、Ｒ²は炭素数１～２０のアルキル基、炭素数６～２０のアリール基又は炭素数７～２０のアラルキル基であり、Ｑは単結合、又はシルアルキレン基、シルアリーレン基、及びケイ素原子数２～１０個の直鎖状、分岐状もしくは環状の２価のオルガノポリシロキサン残基から選ばれる２価の基であり、ｍはそれぞれ独立に１～２０、好ましくは２～１０の整数であり、Ｘは上記と同じである。）The lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1) is more preferably one represented by the following general formula (4).

(In the formula, R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and Q is a single bond, or a sylalkylene group, a sylarylene group, and a divalent group selected from linear, branched, or cyclic divalent organopolysiloxane residues having 2 to 10 silicon atoms, and m is each independently 1 to 20, preferably 2 to 10. is an integer, and X is the same as above.)

In the above formula (4), R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably a linear group having 1 to 8 carbon atoms. is an alkyl group.
Specifically, ^R2 includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group. , isopropyl group, isobutyl group, tert-butyl group, neopentyl group, thexyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclohexylmethyl group, norbornyl group, decahydronaphthyl group, adamantyl group, adamantylmethyl group, etc. , aryl groups such as phenyl group, tolyl group, and naphthyl group, and aralkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group. R ² is preferably a methyl group, ethyl group, butyl group, or octyl group.

In the above formula (4), Q is a single bond, a sylalkylene group, a sylarylene group, or a linear, branched, or cyclic divalent organ with 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms. It is a divalent group selected from polysiloxane residues.

Here, the sylalkylene group, sylarylene group, linear, branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, is represented by the above-mentioned formula (7 ) as sylalkylene group, sylarylene group, or linear, branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms in Z. An example similar to this can be given.

Examples of the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (4) include those represented by the following formula.

As a method for preparing the lipophilic group-containing (hydrolysable) organosiloxane compound represented by the above formula (1), especially the lipophilic group-containing (hydrolysable) organosiloxane compound in which R is a methyl group, for example, Examples of methods include:
A siloxane compound (organohydrogensiloxane compound) each having A in the above formula (1) and a plurality of SiH groups (hydrogen atoms bonded to silicon atoms) at the molecular chain end is heated at 40 to 120°C, preferably 60 to 100°C. The mixture is heated and stirred, preferably at a temperature of about 80° C., and a toluene solution of a hydrosilylation reaction catalyst, such as a chloroplatinic acid/vinyl siloxane complex, is added. Subsequently, a silane compound having a hydrolyzable silyl group and an olefin moiety (for example, an alkenyl group) at the end of the molecular chain is added dropwise at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C. , 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably about 3 hours. Moreover, when carrying out the reaction, it may be diluted with an organic solvent.

（式中、Ａ、Ｙ、Ｗ、ｑは上記と同じである。）Here, examples of the siloxane compound (organohydrogensiloxane compound) each having A in the above formula (1) and a plurality of SiH groups at the molecular chain end include a siloxane compound represented by the following general formula (8). .

(In the formula, A, Y, W, and q are the same as above.)

（式中、Ｒ²、Ｗ、ｍ、ｑは上記と同じである。ｍ’は２～２０、好ましくは２～１０の整数であり、Ｑ’はシルアルキレン基、シルアリーレン基、及びケイ素原子数２～１０個の直鎖状、分岐状もしくは環状の２価のオルガノポリシロキサン残基から選ばれる２価の基である。）Specific examples of the siloxane compound represented by formula (8) include organohydrogensiloxane compounds represented by the following general formulas (a) to (h).

(In the formula, R ² , W, m, and q are the same as above. m' is an integer of 2 to 20, preferably 2 to 10, and Q' is a sylalkylene group, a sylarylene group, and a silicon atom. It is a divalent group selected from several 2 to 10 linear, branched, or cyclic divalent organopolysiloxane residues.)

Specific examples of the organohydrogensiloxane compound represented by formula (a) include those shown below.

Specific examples of the organohydrogensiloxane compound represented by formula (b) include those shown below.

Specific examples of the organohydrogensiloxane compound represented by formula (c) include those shown below.

Specific examples of the organohydrogensiloxane compound represented by formula (d) include those shown below.

Specific examples of the organohydrogensiloxane compound represented by formula (e) include those shown below.

Specific examples of the organohydrogensiloxane compound represented by formula (f) include those shown below.

Specific examples of the organohydrogensiloxane compound represented by formula (g) include those shown below.

Specific examples of the organohydrogensiloxane compound represented by formula (h) include those shown below.

As a method for preparing organohydrogensiloxane compounds represented by the above formula (8), especially formulas (a) to (h), each has A in the above formula (1) and a hydrolyzable silyl group at the molecular chain end. The silane or siloxane compound is stirred at a temperature of -20 to 40°C, preferably -10 to 20°C, more preferably 0 to 10°C, and tetramethyldisiloxane (1,3-dihydro-1,1,3,3 -Tetraorganodisiloxane (1,3-dihydro-1,1,3,3-tetraorganodisiloxane) such as -tetramethyldisiloxane) and a cohydrolysis reaction catalyst, such as hydrochloric acid or sulfuric acid, are added dropwise to -20~ Aging is carried out at a temperature of 40°C, preferably -10 to 20°C, more preferably 0 to 10°C, for 10 minutes to 12 hours, preferably 1 to 6 hours. Moreover, when carrying out the reaction, it may be diluted with an organic solvent.

（式中、Ａ、Ｙ、Ｗ、ｑは上記と同じである。）Here, as the silane or siloxane compound having A in the above formula (1) and a hydrolyzable silyl group at the molecular chain end, a silane or siloxane compound represented by the following general formula (9) can be exemplified.

(In the formula, A, Y, W, and q are the same as above.)

Specific examples of the silane or siloxane compound represented by formula (9) include those shown below.

A silane or siloxane compound having A in formula (1) above and a hydrolyzable silyl group at the molecular chain terminal represented by formula (9), particularly in formula (9), where Y is a sylalkylene group, a sylarylene group, The method for preparing a silane or siloxane compound, which is an alkylene group containing a divalent group selected from linear, branched or cyclic divalent organopolysiloxane residues having 2 to 10 silicon atoms, includes A compound having two SiH groups at the chain end, for example, 1,4-bis(dimethylsilyl)benzene, is heated and stirred at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, A hydrosilylation reaction catalyst, such as a toluene solution of chloroplatinic acid/vinyl siloxane complex, is added. Subsequently, a compound having A in formula (1) above and an olefin moiety (e.g., an alkenyl group) at the molecular chain end is slowly added dropwise over a period of time to 40 to 120°C, preferably 60 to 100°C, more preferably is aged at a temperature of about 80° C. for 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably about 3 hours, so that A in the above formula (1) and a terminal SiH group are respectively present at the molecular chain ends. Silane or siloxane compounds can be obtained. Moreover, when carrying out the reaction, it may be diluted with an organic solvent.
Subsequently, the silane or siloxane compound obtained above having A in formula (1) above and a terminal SiH group at the molecular chain end, respectively, is heated at 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C. The mixture is heated and stirred at a temperature, and a toluene solution of a hydrosilylation reaction catalyst, such as a chloroplatinic acid/vinyl siloxane complex, is added. Subsequently, a silane compound having a hydrolyzable silyl group and an olefin moiety (for example, an alkenyl group) at the end of the molecular chain is added dropwise at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C. , 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably 3 to 6 hours. Moreover, when carrying out the reaction, it may be diluted with an organic solvent.

Here, specific examples of the compound having two SiH groups at the end of the molecular chain include those shown below.

Further, specific examples of compounds having A in the above formula (1) and an olefin moiety at the end of the molecular chain include those shown below.

The amount of the compound having A in the above formula (1) and an olefin moiety at the end of the molecular chain is 0.05 to 0.5 equivalent per equivalent of the compound having two SiH groups at the end of the molecular chain, and more. Preferably, it can be used in an amount of 0.1 to 0.4 equivalent, more preferably 0.2 equivalent.

In the preparation of the silane or siloxane compound represented by the above formula (9), the hydrosilylation reaction catalyst may include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefin, aldehyde, vinyl siloxane, Examples include complexes with acetylene alcohols and the like, and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds.

The amount of the hydrosilylation reaction catalyst used in the reaction between a compound having two SiH groups at the molecular chain end and a compound having A in formula (1) above and an olefin moiety at the molecular chain end is determined by From 0.1 to 100 ppm in terms of transition metal (mass), based on the total mass of the compound having two SiH groups and the compound having A in formula (1) above and an olefin moiety at the end of the molecular chain, respectively. It is preferably used in an amount of 0.2 to 50 ppm.

An organic solvent may be used to prepare the silane or siloxane compound represented by the above formula (9). Examples of the organic solvents used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.) and hydrocarbon solvents (petroleum benzene, toluene, xylene, etc.). Among these, toluene is particularly preferred.

The amount of organic solvent used in the reaction between a compound having two SiH groups at the molecular chain end and a compound having A in the above formula (1) and an olefin moiety at the molecular chain end is as follows: It can be used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably about 100 parts by weight, per 100 parts by weight of the compound having A and an olefin moiety in (1).

Subsequently, the reaction is stopped and the organic solvent is distilled off to obtain a silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the end of the molecular chain.

In the preparation of the silane or siloxane compound represented by the above formula (9), the following silane compounds having a hydrolyzable silyl group and an olefin moiety (e.g., alkenyl group) at the end of the molecular chain are used. I can give examples.

The amount of the silane compound having a hydrolyzable silyl group and an olefin moiety at the end of the molecular chain is as follows: 1. It can be used in an amount of 1 to 5 equivalents, more preferably 1.1 to 2.5 equivalents.

In the preparation of the silane or siloxane compound represented by the above formula (9), the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain end obtained above, and The amount of the hydrosilylation reaction catalyst used in the reaction with the silane compound having a hydrolyzable silyl group and an olefin moiety is determined by the amount of the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain end, respectively. and 0.1 to 100 ppm, more preferably 0.2 to 50 ppm in terms of transition metal (mass), relative to the total mass of the silane compound having a hydrolyzable silyl group and an olefin moiety at the end of the molecular chain. Use in quantity.

In the preparation of the silane or siloxane compound represented by the above formula (9), the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain end obtained above, and When using an organic solvent for the reaction with a silane compound having a hydrolyzable silyl group and an olefinic moiety, the amount of organic solvent used is determined by the amount of A in the above formula (1) and the terminal SiH group at the molecular chain end obtained above. It can be used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and more preferably about 100 parts by weight, per 100 parts by weight of the silane or siloxane compound, respectively.

Subsequently, by stopping the reaction and distilling off the organic solvent and unreacted components, the silane or siloxane compound represented by the above formula (9), particularly in formula (9), Y is a sylalkylene group, a sylarylene group, etc. A silane or siloxane compound which is an alkylene group containing a divalent group selected from a linear, branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms can be obtained. .

In addition, a silane or siloxane compound having A in formula (1) above and a hydrolyzable silyl group at the molecular chain terminal represented by formula (9), particularly a silane or siloxane compound in which Y is an alkylene group in formula (9), As a method for preparing a siloxane compound, the above-mentioned compound having A in formula (1) and an olefin moiety (for example, an alkenyl group) at the molecular chain end is heated at 40 to 120°C, preferably at 60 to 100°C, more preferably at 60 to 100°C. The mixture is heated and stirred at a temperature of about 80° C., and a toluene solution of a hydrosilylation reaction catalyst, such as a chloroplatinic acid/vinyl siloxane complex, is added. Subsequently, a silane compound having a hydrolyzable silyl group and a SiH group at the molecular chain ends is slowly added dropwise over a period of time at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C. , by aging for 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably 1 to 3 hours, the silane or siloxane compound having A in the above formula (1) and a hydrolyzable silyl group, especially the formula ( In 9), a silane or siloxane compound in which Y is an alkylene group can be obtained. Moreover, when carrying out the reaction, it may be diluted with an organic solvent.

Here, specific examples of the silane compound having a hydrolyzable silyl group and a SiH group at the molecular chain terminals include those shown below.

The amount of the compound having A in the above formula (1) and an olefin moiety (for example, an alkenyl group) at the molecular chain end is based on 1 equivalent of the silane compound having a hydrolyzable silyl group and an SiH group at the molecular chain end. It can be used in an amount of 0.2 to 1 equivalent, more preferably 0.4 to 1 equivalent.

In the above formula (9), in the preparation of a silane or siloxane compound in which Y is an alkylene group, the same hydrosilylation reaction catalysts as those mentioned above can be exemplified. With respect to the total mass of the compound having each of A and an olefin moiety in the above formula (1) and the silane compound having a hydrolyzable silyl group and an SiH group at the end of the molecular chain, 0. It is used in an amount of 1 to 100 ppm, more preferably 0.2 to 50 ppm.

In the above formula (9), when an organic solvent is used in the preparation of the silane or siloxane compound in which Y is an alkylene group, the same organic solvents as mentioned above can be exemplified, and the amount of the organic solvent used is It can be used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and more preferably about 100 parts by weight, per 100 parts by weight of a compound having A in formula (1) and an olefin moiety at the terminal.

In the preparation of organohydrogensiloxane compounds represented by the above formula (8), especially formulas (a) to (h), A in the above formula (1) and hydrolysis at the molecular chain end represented by the formula (9). The amount of the silane or siloxane compound each having a functional silyl group to be used is 0.2 to 0.6 equivalents, more preferably 0.3 to 0.5 equivalents, and still more preferably 0.2 to 0.6 equivalents, more preferably 0.3 to 0.5 equivalents, and still more preferably 0.2 to 0.6 equivalents, more preferably 0.3 to 0.5 equivalents, and even more preferably 0.2 to 0.6 equivalents, more preferably 0.3 to 0.5 equivalents, and even more preferably 0.2 to 0.6 equivalents, more preferably 0.3 to 0.5 equivalents, and even more preferably 0.2 to 0.6 equivalents to 1 equivalent of tetraorganodisiloxane. 4 to 0.5 equivalents can be used.

In the preparation of organohydrogensiloxane compounds represented by the above formula (8), especially formulas (a) to (h), an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.) is used as a cohydrolysis reaction catalyst. , organic titanium compounds (tetra n-butyl titanate, etc.), organic acids (acetic acid, methanesulfonic acid, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.). Among these, hydrochloric acid and sulfuric acid are preferred.
The amount of co-hydrolysis reaction catalyst to be used is 1 to 5 equivalents, more preferably 2 to 5 equivalents, per equivalent of the silane or siloxane compound having A in formula (1) above and a hydrolyzable silyl group at the molecular chain end, respectively. 4 equivalents, more preferably 2 to 3 equivalents can be used.

An organic solvent may be used to prepare the organohydrogensiloxane compounds represented by the above formula (8), particularly formulas (a) to (h). The organic solvents used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and fluorine solvents (perfluorohexane, 1,4-bis(trihydrofuran, etc.)). (fluoromethyl)benzene, etc.). Among these, toluene and 1,4-bis(trifluoromethyl)benzene are particularly preferred.
The amount of the organic solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, per 100 parts by mass of the silane or siloxane compound having A in the above formula (1) and a hydrolyzable silyl group at the molecular chain end, respectively. part can be used.

Subsequently, the reaction is stopped and the organic solvent is distilled off to obtain organohydrogensiloxane compounds represented by the above formula (8), particularly formulas (a) to (h).

In the preparation of the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by formula (1), specific silane compounds each having a hydrolyzable silyl group and an olefin moiety (e.g., alkenyl group) at the end of the molecular chain are used. Specifically, the following can be exemplified.

The amount of the silane compound each having a hydrolyzable silyl group and an olefin moiety at the molecular chain end is 1 equivalent of the organohydrogensiloxane compound having A in formula (1) above and a plurality of SiH groups at the molecular chain end, respectively. It can be used in an amount of 3 to 5 equivalents, more preferably 3.5 to 4.5 equivalents, even more preferably 4 to 4.3 equivalents.

In the preparation of the lipophilic group-containing (hydrolysable) organosiloxane compound represented by the above formula (1), the hydrosilylation reaction catalyst includes platinum black, chloroplatinic acid, an alcohol-modified product of chloroplatinic acid, and chloroplatinic acid. and complexes with olefins, aldehydes, vinyl siloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds.
The amount of the hydrosilylation reaction catalyst used is an organohydrogensiloxane compound having A in formula (1) above and a plurality of SiH groups at the molecular chain end, and a hydrolyzable silyl group and an olefin moiety at the molecular chain end, respectively. It is used in an amount of 0.1 to 100 ppm, more preferably 0.2 to 50 ppm in terms of transition metal (mass), based on the total mass of the silane compounds.

An organic solvent may be used to prepare the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1). Examples of the organic solvents used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.) and hydrocarbon solvents (petroleum benzene, toluene, xylene, etc.). Among these, toluene is particularly preferred.
The amount of the organic solvent to be used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, per 100 parts by mass of the organohydrogensiloxane compound each having A in the above formula (1) and a plurality of SiH groups at the molecular chain end. Parts by weight, more preferably about 100 parts by weight, can be used.

Subsequently, the reaction is stopped and the organic solvent and unreacted components are distilled off to obtain the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1).

を使用し、分子鎖末端に加水分解性シリル基とオレフィン部位をそれぞれ有するシラン化合物として、下記式で表される化合物

を使用した場合には、下記式で表されるシロキサン化合物が得られる。

For example, as an organohydrogensiloxane compound having A in the above formula (1) and a plurality of SiH groups at the end of the molecular chain, a compound represented by the following formula:

A compound represented by the following formula as a silane compound having a hydrolyzable silyl group and an olefin moiety at the end of the molecular chain.

When used, a siloxane compound represented by the following formula is obtained.

The lipophilic group-containing (hydrolysable) organosiloxane compound represented by the general formula (1) obtained by the above reaction is subjected to purification and isolation operations such as concentration, column purification, distillation, and extraction, and also subjected to reaction. The solution can be used as it is as a mixture containing the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the general formula (1), or it can be further diluted with an organic solvent or the like.

Component (A) is a lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1), or the terminal hydrolyzable group of the siloxane compound is partially hydrolyzed in advance by a known method. It may also contain a partial (hydrolysis) condensate obtained by condensing decomposed hydroxyl groups.

（式中、Ａ’は－Ｃ（＝Ｏ）ＯＲ¹、－Ｃ（＝Ｏ）ＮＲ¹ ₂、－Ｃ（＝Ｏ）ＳＲ¹又は－Ｐ（＝Ｏ）（ＯＲ¹）₂であり、Ｒ¹は上記と同じであり、Ｒ⁶は独立に水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基であり、Ｙ’は独立に２価の有機基であり、ｉは１～１９９の整数であり、ｊは１～２００の整数であり、ｊ／ｉ≧０．５であり、ｉ＋ｊ＝３～２０１であり、ｋは０～１１の整数であり、ｌは３～１２の整数であり、ｌ／ｋ≧０．５であり、ｋ＋ｌ＝３～１２であり、ｉ、ｊ、ｋ、ｌが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）The lipophilic group-containing organopolysiloxane compound (B), which is the second essential component in the coating composition of the present invention, is represented by the following general formula (2) or (3), and is one type. Alternatively, a mixture of two or more types may be used.

(In the formula, A' is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ is the same as above, R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and Y' is independently It is a divalent organic group, i is an integer from 1 to 199, j is an integer from 1 to 200, j/i≧0.5, i+j=3 to 201, and k is 0 to 200. is an integer of 11, l is an integer of 3 to 12, l/k≧0.5, k+l = 3 to 12, and is shown in parentheses with i, j, k, l Each repeating unit may be combined randomly.)

In the above formula (2) or (3), A' is an ester or carboxylic acid represented by -C(=O)OR ¹ , an amide represented by -C(=O)NR ¹ ₂ , or -C(=O) It is either a thioester or thioacid represented by SR ¹ or a phosphonic acid ester or phosphonic acid represented by -P(=O)(OR ¹ ) ₂ , and is a lipophilic group in the present invention.

Here, R ¹ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and the alkyl group is linear, branched, It may be either cyclic or a combination thereof. Preferably it is a linear alkyl group having 1 to 8 carbon atoms, more preferably a linear alkyl group having 2 to 4 carbon atoms.
Specifically, ^R1 includes a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group. , octadecyl group, isopropyl group, isobutyl group, tert-butyl group, neopentyl group, thexyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclohexylmethyl group, norbornyl group, decahydronaphthyl group, adamantyl group, adamantylmethyl group, etc. Examples include alkyl groups such as phenyl, tolyl, and naphthyl groups, and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups. R ¹ is preferably a methyl group, ethyl group, butyl group, or octyl group.

Examples of A' include those shown below.

In the above formula (2) or (3), R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms; It may be linear, branched, or cyclic, or a combination thereof.
Specifically, R ⁶ includes a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group. , octadecyl group, isopropyl group, isobutyl group, tert-butyl group, neopentyl group, thexyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclohexylmethyl group, norbornyl group, decahydronaphthyl group, adamantyl group, adamantylmethyl group, etc. Examples include alkyl groups such as phenyl, tolyl, and naphthyl groups, and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups. R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms, more preferably a linear alkyl group having 1 to 15 carbon atoms.

In the above formula (2) or (3), Y' is a divalent organic group, -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, It may contain a divalent group selected from -C(=O)NR- and -OC(=O)NR- (R is the same as above), and may also contain an arylene group having 6 to 20 carbon atoms. An optional alkylene group having 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms, is preferable.

Specific examples of Y' include the following groups.

Y' is preferably a divalent organic group having 2 to 30 carbon atoms, particularly preferably an alkylene group having 2 to 20 carbon atoms.

In the above formula (2), i is an integer from 1 to 199, j is an integer from 1 to 200, j/i≧0.5, and i+j=3 to 201. Preferably, i is an integer from 1 to 99, j is an integer from 1 to 100, j/i≧0.75, and i+j=3 to 101. Particularly preferably, i is an integer from 1 to 49, j is an integer from 1 to 50, j/i≧1, and i+j=3 to 51.

When j/i is within the above range, the coating composition containing the organopolysiloxane compound has excellent lipophilicity and scratch resistance. On the other hand, if it is smaller than the above, the lipophilicity of the organopolysiloxane compound will decrease.

When i+j is within the above range, the coating composition containing the organopolysiloxane compound has excellent lubricity and leveling properties. On the other hand, if it is larger than the above, the viscosity of the organopolysiloxane compound increases and the leveling property decreases.

In the above formula (3), k is an integer from 0 to 11, l is an integer from 3 to 12, l/k≧0.5, and k+l=3 to 12. Preferably, k is an integer from 0 to 7, l is an integer from 1 to 8, l/k≧0.75, and k+l=3 to 8. Particularly preferably, k is an integer from 0 to 5, l is an integer from 1 to 6, l/k≧1, and k+l=3 to 6.

When l/k is within the above range, the coating composition containing the organopolysiloxane compound has excellent lipophilicity and scratch resistance. On the other hand, if it is smaller than the above, the lipophilicity of the organopolysiloxane compound will decrease.

When k+l is within the above range, the coating composition containing the organopolysiloxane compound has excellent lubricity and leveling properties. On the other hand, if it is larger than the above, the viscosity of the organopolysiloxane compound increases and the leveling property decreases.

Examples of the organopolysiloxane compound represented by the above formula (2) include those represented by the following formula.

Examples of the organopolysiloxane compound represented by the above formula (3) include those represented by the following formula.

（式中、Ｙ²は独立に－Ｏ－、－Ｓ－、－ＮＲ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲ－、－ＯＣ（＝Ｏ）ＮＲ－（Ｒは炭素数１～４のアルキル基又はフェニル基である）、シルアルキレン基、シルアリーレン基、及びケイ素原子数２～１０個の直鎖状、分岐状又は環状の２価のオルガノポリシロキサン残基から選ばれる２価の基を含んでいてもよく、また炭素数６～２０のアリーレン基を含んでいてもよい炭素数２～３０のアルキレン基であり、Ｒ²、ｉ、ｊ、ｋ、ｌ、ｊ／ｉ、ｉ＋ｊ、ｌ／ｋ、ｋ＋ｌは上記と同じであり、ｉ、ｊ、ｋ、ｌが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）The organopolysiloxane compound represented by the above formula (2) or (3) is more preferably an organopolysiloxane represented by the following general formula (5) or (6).

(In the formula, Y ² is independently -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC( =O)NR- (R is an alkyl group having 1 to 4 carbon atoms or a phenyl group), a sylalkylene group, a sylarylene group, and a linear, branched or cyclic 2 group having 2 to 10 silicon atoms. is an alkylene group having 2 to 30 carbon atoms which may contain a divalent group selected from valent organopolysiloxane residues and may also contain an arylene group having 6 to 20 carbon atoms, and R ² , i, j, k, l, j/i, i+j, l/k, k+l are the same as above, and each repeating unit shown in parentheses with i, j, k, l is randomly combined. (You can leave it there.)

In the above formula (5) or (6), Y ² is independently -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O )NR-, -OC(=O)NR- (R is the same as above), a sylalkylene group, a sylarylene group, and a linear, branched or cyclic divalent organo group having 2 to 10 silicon atoms. It is an alkylene group having 2 to 30 carbon atoms which may contain a divalent group selected from polysiloxane residues, and which may also contain an arylene group having 6 to 20 carbon atoms.

Specific examples of Y ² include the following groups.

Y ² is preferably a divalent organic group having 2 to 30 carbon atoms, particularly preferably an alkylene group having 2 to 20 carbon atoms.

In the above formula (5) or (6), R ² , i, j, k, l, j/i, i+j, l/k, and k+l are the same as above.

Examples of the organopolysiloxane compound represented by the above formula (5) include those represented by the following formula.

Examples of the organopolysiloxane compound represented by the above formula (5) include those represented by the following formula.

Examples of the method for preparing the organopolysiloxane compound represented by the above formula (2) or (3) include the following methods.
Heating an organopolysiloxane compound (organohydrogenpolysiloxane compound) having multiple SiH groups (hydrogen atoms bonded to silicon atoms) at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C. Stir and add a toluene solution of a hydrosilylation reaction catalyst, such as a chloroplatinic acid/vinyl siloxane complex. Subsequently, a compound having A' in the above formula (2) or (3) and an olefin moiety (for example, an alkenyl group) is added dropwise to the molecular chain terminal, and the mixture is heated at 40 to 120°C, preferably 60 to 100°C, more preferably Aging is performed at a temperature of about 80° C. for 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably about 3 hours. Moreover, when carrying out the reaction, it may be diluted with an organic solvent.

（式中、Ｒ⁶、ｉ、ｊ、ｋ、ｌ、ｊ／ｉ、ｉ＋ｊ、ｌ／ｋ、ｋ＋ｌは上記と同じである。）Here, as an organopolysiloxane compound (organohydrogenpolysiloxane compound) having a plurality of SiH groups (hydrogen atoms bonded to silicon atoms), a siloxane compound represented by the following general formula (10) or (11) is used. I can give an example.

(In the formula, R ⁶ , i, j, k, l, j/i, i+j, l/k, k+l are the same as above.)

Specifically, the organopolysiloxane compound (organohydrogenpolysiloxane compound) having a plurality of SiH groups (hydrogen atoms bonded to silicon atoms) represented by formula (10) or (11) is represented by the following formula. Examples include compounds where

Further, specific examples of compounds having A' in the above formula (2) or (3) and an olefin moiety (for example, an alkenyl group) at the end of the molecular chain include those shown below.

The usage amount of the compound having A' in the above formula (2) or (3) and an olefin moiety (for example, an alkenyl group) at the molecular chain end is determined by the amount of the compound having A' in the above formula (2) or (3), respectively, It can be used in an amount of 0.5 to 5 equivalents, more preferably 0.75 to 3 equivalents, and still more preferably 1 to 1.5 equivalents, per equivalent of SiH group possessed by the polysiloxane compound.

In the preparation of the organopolysiloxane compound represented by the above formula (2) or (3), the hydrosilylation reaction catalyst includes platinum black, chloroplatinic acid, an alcohol-modified product of chloroplatinic acid, chloroplatinic acid and olefin, aldehyde. , vinylsiloxane, complexes with acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds.

An organopolysiloxane compound having multiple SiH groups (hydrogen atoms bonded to silicon atoms) and a compound having A' in the above formula (2) or (3) and an olefin moiety (e.g., alkenyl group) at the molecular chain end, respectively. The amount of the hydrosilylation reaction catalyst used in the reaction with the organopolysiloxane compound having multiple SiH groups (hydrogen atoms bonded to silicon atoms) and A in the above formula (2) or (3) at the molecular chain end Used in an amount of 0.1 to 1,000 ppm, more preferably 0.2 to 500 ppm in transition metal terms (mass), based on the total mass of ' and the compound having an olefin moiety (e.g., alkenyl group). do.

An organic solvent may be used to prepare the organopolysiloxane compound represented by the above formula (2) or (3). Examples of the organic solvents used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.) and hydrocarbon solvents (petroleum benzene, toluene, xylene, etc.). Among these, toluene is particularly preferred.

An organopolysiloxane compound having multiple SiH groups (hydrogen atoms bonded to silicon atoms) and a compound having A' in the above formula (2) or (3) and an olefin moiety (e.g., alkenyl group) at the molecular chain end, respectively. The amount of the organic solvent used in the reaction is 10 to 3,000 parts by mass, preferably 50 to 3,000 parts by mass, per 100 parts by mass of the organopolysiloxane compound having multiple SiH groups (hydrogen atoms bonded to silicon atoms). 1,000 parts by weight, more preferably about 100 to 500 parts by weight can be used.

Subsequently, the reaction is stopped and the organic solvent is distilled off to obtain the organopolysiloxane compound represented by the above formula (2) or (3).

を使用し、分子鎖末端に上記式（２）又は（３）におけるＡ’とオレフィン部位（例えば、アルケニル基）をそれぞれ有する化合物として、下記式で表される化合物

を使用した場合には、下記式で表されるオルガノポリシロキサン化合物が得られる。

For example, as an organopolysiloxane compound having multiple SiH groups (hydrogen atoms bonded to silicon atoms), a compound represented by the following formula

A compound represented by the following formula as a compound having A' in the above formula (2) or (3) and an olefin moiety (e.g., alkenyl group) at the molecular chain terminal, respectively.

When used, an organopolysiloxane compound represented by the following formula is obtained.

The organopolysiloxane compound represented by the general formula (2) or (3) obtained by the above reaction is purified by purification and isolation operations such as concentration, column purification, distillation, and extraction, and the reaction solution is directly used in the general public. It can also be used as a mixture containing the organopolysiloxane compound represented by formula (2) or (3), or after being further diluted with an organic solvent or the like.

Component (B) represented by general formula (2) or (3) may be a single component or a mixture of multiple compounds that meet the above definition, and in the case of a mixture, the content of the compound that corresponds to component (B). What is necessary is just to calculate the sum total as content of (B) component.

The coating agent composition of the present invention contains the component (A) and the component (B) in a predetermined ratio, that is, the mass ratio of the component (A) to the component (B) is 0.1<(A)/(B). )<10, preferably 0.5<(A)/(B)<10, more preferably 1≦(A)/(B)≦9. If component (A), which ensures lipophilicity, is too small, the cured film exhibits oil repellency, and the sebum contained in fingerprints will be repelled by the surface, making the fingerprints noticeable, and component (B), which ensures lubricity, will be too small. If it is too high, the scratch resistance will decrease.

The present invention further provides a surface treatment agent containing the above coating composition.
The surface treatment agent may contain a suitable solvent. Such solvents include alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), Examples include ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, alcohol solvents and ether solvents are preferable in terms of solubility and wettability, with propylene glycol monomethyl ether and dibutyl ether being particularly preferable.

Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the above (A) component and (B) component. The optimal concentration of the total mass of components (A) and (B) to be dissolved in the solvent varies depending on the treatment method, and may be an amount that is easy to weigh, but when directly coating, the solvent and (A) , 0.01 to 10 parts by mass (0.01 to 10% by mass), especially 0.05 to 5 parts by mass (0.05 parts by mass) per 100 parts by mass of the mixture of components (B) (coating composition). 5% by mass), and in the case of vapor deposition treatment, 1 to 100 parts by mass ( (1 to 100% by mass), particularly preferably 3 to 30 parts by mass (3 to 30% by mass), and in the case of wet treatment, a mixture of the solvent and components (A) and (B) (coating agent composition) It is preferably 0.01 to 10 parts by weight (0.01 to 10 parts by weight), particularly 0.05 to 1 part by weight (0.05 to 1% by weight), based on a total of 100 parts by weight.

Surface treatment agents include hydrolysis condensation catalysts, such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra n-butyl titanate, etc.), organic acids (acetic acid, methanesulfonic acid, etc.) , inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, etc. are particularly preferred.
When adding a hydrolysis condensation catalyst, the amount added is preferably 0.1 to 150 parts by mass, particularly 25 parts by mass, based on 100 parts by mass of the mixture of components (A) and (B) (coating composition). The amount is preferably 125 parts by weight, more preferably 50 to 110 parts by weight.

The surface treatment agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. In addition, the curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), the curing temperature is 25 to 200°C, especially 25 to 150°C for 15 minutes to 36 hours, especially 30°C. Preferably, the time is from minutes to 24 hours. It may be cured under humid conditions. Furthermore, when applying by vapor deposition, the temperature is preferably in the range of 20 to 200°C. It may be cured under humid conditions. The thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. In addition, for example, in spray coating, if the material is diluted in an organic solvent to which water has been added in advance and subjected to hydrolysis, that is, to generate Si--OH, then spray coating is performed, resulting in faster curing after coating.

The surface treatment agent of the present invention preferably has a contact angle with respect to oleic acid of 30° or less, more preferably 30° or less at 25° C. and 40% relative humidity, as measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). A cured film having an angle of 25° or less can be formed. Therefore, when sebum is attached, the contact angle is small, visibility is low, and fingerprints are not noticeable.

The surface treatment agent of the present invention can form a cured film with excellent scratch resistance that does not leave visible scratches on the substrate even when abraded by steel wool.

The substrate treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the base material. In particular, it can be suitably used as a surface treatment agent for SiO ₂ -treated glass or film.

Articles treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, Examples include optical articles such as sunglasses, medical equipment such as gastrocameras, copying machines, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. The surface treatment agent of the present invention makes it difficult to see fingerprints and sebum attached to the article, and is particularly useful as a lipophilic layer for touch panel displays, antireflection films, and the like.

Hereinafter, the present invention will be explained in more detail by showing synthesis examples, working examples, and comparative examples, but the present invention is not limited by the following examples.

で示される化合物を１２．１ｇ得た。[Synthesis example 1]
10.0 g (4.71×10 ^-2 mol) of ethyl undecenoate placed in a reaction vessel was heated to 80°C. Subsequently, 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone) was added, and then 8.6 g (7.0 g) of trimethoxysilane was added. 06×10 ⁻² mol) was added dropwise over 3 hours, and the mixture was heated and stirred at 80° C. for 1 hour. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (A) is obtained.

12.1g of the compound shown was obtained.

^1H -NMR
δ0.8(-(CH ₂ ) ₇ CH ₂ -Si(OCH ₃ ) ₃ )2H
δ1.2-1.4(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )17H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-Si(OC H ₃ ) ₃ )9H
δ4.1(-OC H ₂ CH ₃ )2H

で表される化合物５．０ｇ（１．５×１０^-2ｍｏｌ）を滴下し、０℃で６時間熟成した。その後、分液操作により下層を回収し、溶剤及び未反応物を減圧留去することで、下記式（Ｂ）

で示される生成物を５．８ｇ得た。A mixture of 4.5 g (3.4 x 10 ^-2 mol) of tetramethyldisiloxane, 3.6 g of 12N hydrochloric acid aqueous solution, and 2.5 g of 1,4-bis(trifluoromethyl)benzene placed in a reaction vessel was heated to 0°C. Cooled to . Subsequently, the following formula (A) obtained above

5.0 g (1.5 x 10 ^-2 mol) of the compound represented by was added dropwise, and the mixture was aged at 0°C for 6 hours. Thereafter, the lower layer is collected by a liquid separation operation, and the solvent and unreacted substances are distilled off under reduced pressure, so that the following formula (B) can be obtained.

5.8g of the product shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )18H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ1.2-1.5(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )17H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ4.1(-OC H ₂ CH ₃ )2H
δ4.7(-Si-H)3H

で表される化合物５．０ｇ（１．１×１０^-2ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液５．０×１０^-3ｇ（Ｐｔ単体として１．５×１０^-8ｍｏｌを含有）を添加した後、アリルトリメトキシシラン７．３ｇ（４．５×１０^-2ｍｏｌ）を滴下し、８０℃にて３時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｃ）

で示される生成物（親油性基含有加水分解性オルガノシロキサン化合物１）を８．８ｇ得た。The following formula (B) obtained above was placed in a reaction container.

5.0 g (1.1×10 ^-2 mol) of the compound represented by was heated to 80°C. Subsequently, 5.0 x 10 ^-3 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 1.5 x 10 ^-8 mol as Pt alone) was added, and then 7.3 g (4 mol of allyltrimethoxysilane) was added. .5×10 ⁻² mol) was added dropwise thereto, and the mixture was heated and stirred at 80° C. for 3 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (C) is obtained.

8.8 g of the product (lipophilic group-containing hydrolyzable organosiloxane compound 1) was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )18H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ0.6-0.8 (-SiCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ , -SiCH 2 _{CH 2} CH ₂ -Si(OCH ₃ ) ₃ ) 12H
δ1.2-1.4(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )17H
δ1.5(-SiCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ )6H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-SiCH ₂ CH ₂ CH ₂ -Si(OC H ₃ ) ₃ )27H
δ4.1(-OC H ₂ CH ₃ )2H

で示される生成物を４．１ｇ得た。[Synthesis example 2]
10.0 g (4.34×10 ^-2 mol) of 1,8-bis(dimethylsilyl)octane placed in a reaction vessel was heated to 80°C. Subsequently, 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone) was added, and then 1.9 g (8. 95×10 ⁻³ mol) was added dropwise over 3 hours, and the mixture was heated and stirred at 80° C. for 1 hour. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (D) is obtained.

4.1 g of the product shown was obtained.

^1H -NMR
δ0.2-0.4(-Si-C H ₃ )12H
δ0.7(-C H ₂ -Si-)6H
δ1.2-1.5(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )29H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ4.1(-OC H ₂ CH ₃ )2H
δ4.4(-Si-H)1H

で表される化合物４．０ｇ（９．０３×１０^-3ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-2ｇ（Ｐｔ単体として０．３×１０^-7ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン２．９ｇ（１．２６×１０^-2ｍｏｌ）を滴下し、８０℃にて３時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｅ）

で示される化合物を５．０ｇ得た。The following formula (D) obtained above was placed in a reaction container.

4.0 g (9.03×10 ^-3 mol) of the compound represented by was heated to 80°C. Subsequently, 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone) was added, and 2.0 g of 7-octenyltrimethoxysilane was added. 9 g (1.26×10 ⁻² mol) was added dropwise, and the mixture was heated and stirred at 80° C. for 3 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (E) is obtained.

5.0g of the compound shown was obtained.

^1H -NMR
δ0.2(-Si-C H ₃ )12H
δ0.6(-C H ₂ -Si-,)8H
δ0.7(-C H ₂ -Si(OCH ₃ ) ₃ )2H
δ1.2-1.4 (-(C H ₂ ) ₇ -, -(C H ₂ ) ₆ -, -OCH ₂ C H ₃ )43H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-SiCH ₂ (CH ₂ ) ₆ CH ₂ -Si(OC H ₃ ) ₃ ) 9H
δ4.1(-OC H ₂ CH ₃ )2H

で表される化合物４．０ｇ（５．９２×１０^-3ｍｏｌ）を滴下し、０℃で６時間熟成した。その後、分液操作により下層を回収し、溶剤及び未反応物を減圧留去することで、下記式（Ｆ）

で示される生成物を３．３ｇ得た。A mixture of 1.8 g (1.36 x 10 ^-2 mol) of tetramethyldisiloxane, 1.5 g of 12N hydrochloric acid aqueous solution, and 5.0 g of 1,4-bis(trifluoromethyl)benzene placed in a reaction vessel was heated to 0°C. Cooled to . Next, the following formula (E) obtained above

4.0 g (5.92×10 ^-3 mol) of the compound represented by was added dropwise to the mixture, and the mixture was aged at 0° C. for 6 hours. After that, the lower layer is collected by a liquid separation operation, and the solvent and unreacted substances are distilled off under reduced pressure, so that the following formula (F) is obtained.

3.3g of the product shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ0.7-0.8(-Si-C H ₂ -)8H
δ1.2-1.5 (-(C H ₂ ) ₇ -, -OCH ₂ C H _{3 ,} -Si-CH ₂ (C H ₂ ) ₆ CH ₂ -Si-)41H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ4.1(-OC H ₂ CH ₃ )2H
δ4.7(-Si-H)3H

で表される化合物２．０ｇ（２．４８×１０^-3ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液５．０×１０^-3ｇ（Ｐｔ単体として１．５×１０^-8ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン２．４ｇ（１．０４×１０^-2ｍｏｌ）を滴下し、８０℃にて３時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｇ）

で示される生成物（親油性基含有加水分解性オルガノシロキサン化合物２）を３．８ｇ得た。The following formula (F) obtained above was placed in the reaction vessel.

2.0 g (2.48 x 10 ^-3 mol) of the compound represented by was heated to 80°C. Subsequently, after adding 5.0 x 10 ^-3 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 1.5 x 10 ^-8 mol as Pt alone), 7-octenyltrimethoxysilane 2. 4 g (1.04 x 10 ^-2 mol) was added dropwise, and the mixture was heated and stirred at 80°C for 3 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (G) is obtained.

3.8 g of the product (lipophilic group-containing hydrolyzable organosiloxane compound 2) shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ0.6-0.8 (-Si-C H ₂ -, - ₆ C H ₂ -Si(OCH ₃ ) ₃ ) 20H
δ1.2-1.4 (-(C H ₂ ) ₆ -, -(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )29H
δ1.5(-SiCH ₂ (CH 2 ) ₆ CH ₂ -Si ₍ OCH ₃ ) ₃ )36H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-SiCH ₂ CH ₂ CH ₂ -Si(OC H ₃ ) ₃ )27H
δ4.1(-OC H ₂ CH ₃ )2H

で示される生成物を１６．４ｇ得た。[Synthesis example 3]
31.6 g (2.35 x 10 ^-1 mol) of tetramethyldisiloxane placed in a reaction vessel was heated to 80°C. Subsequently, after adding 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone), 10.0 g of ethyl undecenoate (4. 71×10 ⁻² mol) was added dropwise over 3 hours, and the mixture was heated and stirred at 80° C. for 1 hour. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (H) is obtained.

16.4 g of the product shown was obtained.

^1H -NMR
δ0.2-0.4(-Si-C H ₃ )12H
δ0.7(-(CH ₂ ) ₇ CH ₂ -Si-)2H
δ1.2-1.5(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )17H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ4.1(-OC H ₂ CH ₃ )2H
δ4.4(-Si-H)1H

で表される化合物１０．０ｇ（２．８８×１０^-2ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-2ｇ（Ｐｔ単体として０．３×１０^-7ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン９．４ｇ（４．０４×１０^-2ｍｏｌ）を滴下し、８０℃にて３時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｉ）

で示される化合物を１５．１ｇ得た。The following formula (H) obtained above was placed in the reaction container.

10.0 g (2.88×10 ^-2 mol) of the compound represented by was heated to 80°C. Subsequently, after adding 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone), 9.0 g of 7-octenyltrimethoxysilane was added. 4 g (4.04 x 10 ^-2 mol) was added dropwise, and the mixture was heated and stirred at 80°C for 3 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (I) is obtained.

15.1g of the compound shown was obtained.

^1H -NMR
δ0.2-0.3(-Si-C H ₃ )12H
δ0.7(-(CH ₂ ) ₇ CH 2 -Si-, -SiC H ₂ (CH ₂ ) ₆ CH ₂ -Si(OCH _{3 ) 3} )4H
δ0.8(-SiCH ₂ (CH ₂ ) ₆ CH ₂ -Si(OCH ₃ ) ₃ )2H
δ1.2-1.4 (-(C H ₂ ) ₇ -, -SiCH ₂ (C H ₂ ) ₆ CH ₂ -Si(OCH ₃ ) ₃ , -OCH ₂ C H ₃ )29H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-SiCH ₂ (CH ₂ ) ₆ CH ₂ -Si(OC H ₃ ) ₃ ) 9H
δ4.1(-OC H ₂ CH ₃ )2H

で表される化合物１０．０ｇ（１．７×１０^-2ｍｏｌ）を滴下し、０℃で６時間熟成した。その後、分液操作により下層を回収し、溶剤及び未反応物を減圧留去することで、下記式（Ｊ）

で示される生成物を８．６ｇ得た。A mixture of 5.1 g (3.8 x 10 ^-2 mol) of tetramethyldisiloxane, 4.1 g of 12N hydrochloric acid solution, and 5.0 g of 1,4-bis(trifluoromethyl)benzene placed in a reaction vessel was heated to 0°C. Cooled to . Subsequently, the following formula (I) obtained above

10.0 g (1.7×10 ^-2 mol) of the compound represented by was added dropwise to the mixture, and the mixture was aged at 0° C. for 6 hours. After that, the lower layer is collected by a liquid separation operation, and the solvent and unreacted substances are distilled off under reduced pressure, so that the following formula (J) can be obtained.

8.6 g of the product shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5-0.6(-O-Si(CH ₃ ) ₂ -C H ₂ -)6H
δ1.2-1.5 (-(C H ₂ ) ₇ -, -OCH ₂ C H _{3 ,} -Si-CH ₂ (C H ₂ ) ₆ CH ₂ -Si-)29H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ4.1(-OC H ₂ CH ₃ )2H
δ4.7(-Si-H)3H

で表される化合物５．０ｇ（７．０×１０^-3ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液５．０×１０^-3ｇ（Ｐｔ単体として１．５×１０^-8ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン６．５ｇ（２．８×１０^-2ｍｏｌ）を滴下し、８０℃にて３時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｋ）

で示される生成物（親油性基含有加水分解性オルガノシロキサン化合物３）を７．６ｇ得た。The following formula (J) obtained above was placed in the reaction vessel.

5.0 g (7.0×10 ^-3 mol) of the compound represented by was heated to 80°C. Subsequently, after adding 5.0 x 10 ^-3 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 1.5 x 10 ^-8 mol as Pt alone), 7-octenyltrimethoxysilane 6. 5 g (2.8 x 10 ^-2 mol) was added dropwise, and the mixture was heated and stirred at 80°C for 3 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (K) is obtained.

7.6 g of the product (lipophilic group-containing hydrolyzable organosiloxane compound 3) shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5-0.7(-O-Si(CH ₃ ) ₂ -C H ₂ -, -SiCH ₂ (C H ₂ ) ₆ C H ₂ -Si(OCH ₃ ) ₃ , -SiC H ₂ (C H ₂ ) _{6CH 2} -Si(OCH ₃ ) ₃ ) 18H
δ1.2-1.4(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )17H
δ1.5(-SiCH ₂ (CH 2 ) ₆ CH ₂ -Si ₍ OCH ₃ ) ₃ )36H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-SiCH ₂ CH ₂ CH ₂ -Si(OC H ₃ ) ₃ )27H
δ4.1(-OC H ₂ CH ₃ )2H

で示される生成物を１８．０ｇ得た。[Synthesis example 4]
45.7 g (2.35×10 ^-1 mol) of 1,4-bis(dimethylsilyl)benzene placed in a reaction vessel was heated to 80°C. Subsequently, after adding 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone), 10.0 g of ethyl undecenoate (4. 71×10 ⁻² mol) was added dropwise over 3 hours, and the mixture was heated and stirred at 80° C. for 1 hour. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (L) is obtained.

18.0 g of the product shown was obtained.

^1H -NMR
δ0.2-0.4(-Si-C H ₃ )12H
δ0.7(-(CH ₂ ) ₇ CH ₂ -Si-)2H
δ1.2-1.5(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )17H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ4.1(-OC H ₂ CH ₃ )2H
δ4.4(-Si-H)1H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で表される化合物１０．０ｇ（２．４６×１０^-2ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-2ｇ（Ｐｔ単体として０．３×１０^-7ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン９．１０ｇ（３．９４×１０^-2ｍｏｌ）を滴下し、８０℃にて４時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｍ）

で示される化合物を１４．０ｇ得た。The following formula (L) obtained above was placed in the reaction container.

10.0 g (2.46×10 ^-2 mol) of the compound represented by was heated to 80°C. Subsequently, after adding 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone), 9.0 g of 7-octenyltrimethoxysilane was added. 10 g (3.94×10 ⁻² mol) was added dropwise to the mixture, and the mixture was heated and stirred at 80° C. for 4 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (M) is obtained.

14.0g of the compound shown was obtained.

^1H -NMR
δ0.2(-Si-C H ₃ )12H
δ0.6(-SiC H ₂ (CH ₂ ) ₆ CH ₂ -Si(OCH ₃ ) ₃ )4H
δ0.7(-(CH ₂ ) ₇ CH ₂ -Si-, -SiCH ₂ (CH ₂ ) ₆ CH ₂ -Si(OCH ₃ ) ₃ )2H
δ1.2-1.4 (-(C H ₂ ) ₇ -, -(C H ₂ ) ₆ -, -OCH ₂ C H ₃ )31H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-SiCH ₂ (CH ₂ ) ₆ CH ₂ -Si(OC H ₃ ) ₃ ) 9H
δ4.1(-OC H ₂ CH ₃ )2H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で表される化合物７．０ｇ（１．１×１０^-2ｍｏｌ）を滴下し、０℃で６時間熟成した。その後、分液操作により下層を回収し、溶剤及び未反応物を減圧留去することで、下記式（Ｎ）

で示される生成物を５．６ｇ得た。A mixture of 3.3 g (2.5 x 10 ^-2 mol) of tetramethyldisiloxane, 2.6 g of 12N hydrochloric acid aqueous solution, and 3.5 g of 1,4-bis(trifluoromethyl)benzene placed in a reaction vessel was heated to 0°C. Cooled to . Subsequently, the following formula (M) obtained above

7.0 g (1.1×10 ^-2 mol) of the compound represented by was added dropwise to the mixture, and the mixture was aged at 0° C. for 6 hours. After that, the lower layer is collected by a liquid separation operation, and the solvent and unreacted substances are distilled off under reduced pressure, so that the following formula (N) can be obtained.

5.6g of the product shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ0.7-0.8(-C ₆ H ₄ -Si-C H ₂ -)4H
δ1.2-1.5 (-(C H ₂ ) ₇ -, -OCH ₂ C H _{3 ,} -Si-CH ₂ (C H ₂ ) ₆ CH ₂ -Si-)29H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ4.1(-OC H ₂ CH ₃ )2H
δ4.7(-Si-H)3H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で表される化合物１．８ｇ（２．３×１０^-3ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液２．０×１０^-3ｇ（Ｐｔ単体として６．０×１０^-9ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン２．３ｇ（９．８×１０^-3ｍｏｌ）を滴下し、８０℃にて３時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｏ）

で示される生成物（親油性基含有加水分解性オルガノシロキサン化合物４）を２．７ｇ得た。The following formula (N) obtained above was placed in the reaction vessel.

1.8 g (2.3×10 ^-3 mol) of the compound represented by was heated to 80°C. Subsequently, 2.0 x 10 ^-3 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 6.0 x 10 ^-9 mol as Pt alone) was added, and 2.0 x 10 -3 g of 7-octenyltrimethoxysilane was added. 3 g (9.8×10 ⁻³ mol) was added dropwise, and the mixture was heated and stirred at 80° C. for 3 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (O) is obtained.

2.7 g of the product (lipophilic group-containing hydrolyzable organosiloxane compound 4) shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ0.6-0.8 (-C ₆ H ₄ -Si-C H ₂ -, -SiCH ₂ (C H ₂ ) ₆ C H ₂ -Si(OCH ₃ ) ₃ , -SiC H ₂ (C H ₂ ) _{6CH 2} -Si(OCH ₃ ) ₃ ) 16H
δ1.2-1.4(-(C H ₂ ) ₇ -, -OCH ₂ C H ₃ )17H
δ1.5(-SiCH ₂ (CH 2 ) ₆ CH ₂ -Si ₍ OCH ₃ ) ₃ )36H
δ1.6(-OOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-OOC-C H ₂ -)2H
δ3.5(-SiCH ₂ CH ₂ CH ₂ -Si(OC H ₃ ) ₃ )27H
δ4.1(-OC H ₂ CH ₃ )2H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で示される化合物１０．０ｇ（４．１８×１０^-2ｍｏｌ）を３時間かけて滴下し、８０℃にて６時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｑ）

で示される生成物を１７．１ｇ得た。[Synthesis example 5]
40.6 g (2.09×10 ^-1 mol) of 1,4-bis(dimethylsilyl)benzene placed in a reaction vessel was heated to 80°C. Subsequently, after adding 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone), the following formula (P) was added.

10.0 g (4.18×10 ^-2 mol) of the compound represented by was added dropwise over 3 hours, and the mixture was heated and stirred at 80° C. for 6 hours. Then, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (Q) is obtained.

17.1g of the product shown was obtained.

^1H -NMR
δ0.2-0.4(-Si-C H ₃ )12H
δ0.7(-(CH ₂ ) ₇ CH ₂ -Si-)2H
δ1.0-1.2(-N(CH ₂ CH ₃ ) ₂ )6H
δ1.2-1.5(-(C H ₂ ) ₇ -)14H
δ1.6 (-NOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-NOC-C H ₂ -)2H
δ3.2-3.4(-N(C H ₂ CH ₃ ) ₂ ) 4H
δ4.4(-Si-H)1H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で表される化合物１０．０ｇ（２．３１×１０^-2ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-2ｇ（Ｐｔ単体として０．３×１０^-7ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン７．５ｇ（３．２３×１０^-2ｍｏｌ）を滴下し、８０℃にて６時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｒ）

で示される化合物を１２．６ｇ得た。The following formula (Q) obtained above was placed in the reaction container.

10.0 g (2.31×10 ^-2 mol) of the compound represented by was heated to 80°C. Subsequently, 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone) was added, and then 7-octenyltrimethoxysilane 7. 5 g (3.23×10 ⁻² mol) was added dropwise, and the mixture was heated and stirred at 80° C. for 6 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (R) is obtained.

12.6g of the compound shown was obtained.

^1H -NMR
δ0.2-0.3(-Si-C H ₃ )12H
δ0.7(-(CH ₂ ) ₇ CH 2 -Si-, -SiC H ₂ CH ₂ CH ₂ -Si( _{OCH 3} ) ₃ ) 4H
δ0.8(-SiCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ )2H
δ1.0-1.2(-N(CH ₂ CH ₃ ) ₂ )6H
δ1.2-1.4(-(C H ₂ ) ₇ -)14H
δ1.5(-SiCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ )2H
δ1.6 (-NOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-NOC-C H ₂ -)2H
δ3.2-3.4(-N(C H ₂ CH ₃ ) ₂ ) 4H
δ3.5(-SiCH ₂ CH ₂ CH ₂ -Si(OC H ₃ ) ₃ ) 9H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で表される化合物１０．０ｇ（１．５×１０^-2ｍｏｌ）を滴下し、０℃で６時間熟成した。その後、分液操作により下層を回収し、溶剤及び未反応物を減圧留去することで、下記式（Ｓ）

で示される生成物を８．６ｇ得た。A mixture of 4.5 g (3.4 x 10 ^-2 mol) of tetramethyldisiloxane, 3.6 g of 12N hydrochloric acid solution, and 5.0 g of 1,4-bis(trifluoromethyl)benzene placed in a reaction vessel was heated to 0°C. Cooled to . Subsequently, the following formula (R) obtained above

10.0 g (1.5×10 ^-2 mol) of the compound represented by was added dropwise to the mixture, and the mixture was aged at 0° C. for 6 hours. Thereafter, the lower layer is collected by a liquid separation operation, and the solvent and unreacted substances are distilled off under reduced pressure, so that the following formula (S) is obtained.

8.6 g of the product shown was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ0.7-0.8(-C ₆ H ₄ -Si-C H ₂ -)4H
δ1.0-1.2(-N(CH ₂ CH ₃ ) ₂ )6H
δ1.2-1.5(-(C H ₂ ) ₇ -, -Si-CH ₂ (C H ₂ ) ₆ CH ₂ -Si-)26H
δ1.6 (-NOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-NOC-C H ₂ -)2H
δ3.2-3.4(-N(C H ₂ CH ₃ ) ₂ ) 4H
δ4.7(-Si-H)3H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で表される化合物５．０ｇ（６．３×１０^-3ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液５．０×１０^-3ｇ（Ｐｔ単体として１．５×１０^-8ｍｏｌを含有）を添加した後、７－オクテニルトリメトキシシラン５．９ｇ（２．５×１０^-2ｍｏｌ）を滴下し、８０℃にて３時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、下記式（Ｔ）

で示される生成物（親油性基含有加水分解性オルガノシロキサン化合物５）を８．１ｇ得た。The following formula (S) obtained above was placed in the reaction container.

5.0 g (6.3×10 ^-3 mol) of the compound represented by was heated to 80°C. Subsequently, after adding 5.0 x 10 ^-3 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 1.5 x 10 ^-8 mol as Pt alone), 5.0 g of 7-octenyltrimethoxysilane was added. 9 g (2.5×10 ⁻² mol) was added dropwise, and the mixture was heated and stirred at 80° C. for 3 hours. Then, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (T) is obtained.

8.1 g of the product (lipophilic group-containing hydrolyzable organosiloxane compound 5) represented by was obtained.

^1H -NMR
δ0.1-0.2(-Si-C H ₃ )30H
δ0.5(-(CH ₂ ) ₇ CH ₂ -Si(O-Si(CH ₃ ) ₂ -) ₃ )2H
δ0.6-0.8(-C ₆ H ₄ -Si-C H ₂ -, -SiCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ , -SiC H ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ) 16H
δ1.0-1.2(-N(CH ₂ CH ₃ ) ₂ )6H
δ1.2-1.4(-(C H ₂ ) ₇ -, -Si-CH ₂ (C H ₂ ) ₆ CH ₂ -Si-)26H
δ1.5(-SiCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ )6H
δ1.6 (-NOC-CH ₂ CH ₂ (CH ₂ ) ₇ CH ₂ -Si-)2H
δ2.3(-NOC-C H ₂ -)2H
δ3.2-3.4(-N(C H ₂ CH ₃ ) ₂ ) 4H
δ3.5(-SiCH ₂ CH ₂ CH ₂ -Si(OC H ₃ ) ₃ )27H
δ7.5(-Si-C ₆ H ₄ -Si-)4H

で表される化合物１０．０ｇ（ＳｉＨ量１．２４×１０^-1ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-1ｇ（Ｐｔ単体として０．３×１０^-6ｍｏｌを含有）を添加した後、ウンデセン酸エチル３９．６ｇ（１．８７×１０^-1ｍｏｌ）を滴下し、８０℃にて４時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、平均構造として下記式（Ｖ）

で示されるオルガノポリシロキサン化合物６を３１．０ｇ得た。[Synthesis example 6]
The average structure placed in the reaction container is the following formula (U)

10.0 g of the compound represented by (SiH amount: 1.24×10 ⁻¹ mol) was heated to 80° C. Subsequently, 1.0 x 10 ^-1 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 -6 mol as Pt alone) was added, and then 39.6 g (1.0 x 10 ^-6 mol of Pt alone) of ethyl undecenoate was added. 87×10 ⁻¹ mol) was added dropwise thereto, and the mixture was heated and stirred at 80° C. for 4 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (V) is obtained as an average structure.

31.0 g of organopolysiloxane compound 6 represented by the formula was obtained.

^1H -NMR
δ0.2(-Si-C H ₃ )42H
δ0.6(-SiC H ₂ -)16H
δ1.2-1.6(-(C H ₂ ) ₈ -, -OCH ₂ C H ₃ )152H
δ2.3(-OOC-C H ₂ -)16H
δ4.1 (-OC H ₂ CH ₃ ) 16H

で表される化合物１０．０ｇ（ＳｉＨ量１．５５×１０^-1ｍｏｌ）を８０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-1ｇ（Ｐｔ単体として０．３×１０^-6ｍｏｌを含有）を添加した後、ウンデセン酸エチル４９．５ｇ（２．３３×１０^-1ｍｏｌ）を滴下し、８０℃にて４時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、平均構造として下記式（Ｘ）

で示されるオルガノポリシロキサン化合物７を３４．０ｇ得た。[Synthesis example 7]
The average structure in the reaction container is the following formula (W)

10.0 g of the compound represented by (SiH amount: 1.55×10 ⁻¹ mol) was heated to 80° C. Subsequently, 1.0 x 10 ^-1 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-6 mol as Pt alone) was added, and then 49.5 g (2. 33×10 ⁻¹ mol) was added dropwise thereto, and the mixture was heated and stirred at 80° C. for 4 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (X) is obtained as an average structure.

34.0g of organopolysiloxane compound 7 shown by was obtained.

^1H -NMR
δ0.2(-Si-C H ₃ )123H
δ0.6(-SiC H ₂ -)76H
δ1.2-1.6 (-(C H ₂ ) ₈ -, -OCH ₂ C H ₃ )722H
δ2.3(-OOC-C H ₂ -)76H
δ4.1(-OC H ₂ CH ₃ )76H

で表される化合物１０．０ｇ（ＳｉＨ量１．６６×１０^-1ｍｏｌ）を７０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-1ｇ（Ｐｔ単体として０．３×１０^-6ｍｏｌを含有）を添加した後、ウンデセン酸エチル５３．２ｇ（２．４９×１０^-1ｍｏｌ）を滴下し、７０℃にて４時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、平均構造として下記式（Ｚ）

で示されるオルガノポリシロキサン化合物８を４１．２ｇ得た。[Synthesis example 8]
The following formula (Y) was placed in a reaction container.

10.0 g of the compound represented by (SiH amount: 1.66×10 ^-1 mol) was heated to 70°C. Subsequently, 1.0 x 10 ^-1 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-6 mol as Pt alone) was added, and then 53.2 g (2. 49×10 ⁻¹ mol) was added dropwise thereto, and the mixture was heated and stirred at 70° C. for 4 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (Z) is obtained as an average structure.

41.2g of organopolysiloxane compound 8 represented by the formula was obtained.

^1H -NMR
δ0.2(-Si-C H ₃ )12H
δ0.6(-SiC H ₂ -)8H
δ1.2-1.6 (-(C H ₂ ) ₈ -, -OCH ₂ C H ₃ )76H
δ2.3(-OOC-C H ₂ -)8H
δ4.1 (-OC H ₂ CH ₃ )8H

で表される化合物１０．０ｇ（ＳｉＨ量６．１６×１０^-2ｍｏｌ）を７０℃まで加熱した。続いて、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-2ｇ（Ｐｔ単体として０．３×１０^-7ｍｏｌを含有）を添加した後、ウンデセン酸エチル１９．６ｇ（９．２４×１０^-2ｍｏｌ）を滴下し、７０℃にて４時間加熱撹拌した。その後、溶剤及び未反応物を減圧留去することで、平均構造として下記式（ＡＢ）

で示されるオルガノポリシロキサン化合物９を２０．４ｇ得た。[Synthesis example 9]
The following formula (AA) was placed in a reaction container.

10.0 g of the compound represented by (6.16×10 ^-2 mol of SiH) was heated to 70°C. Subsequently, 1.0 x 10 ^-2 g of a toluene solution of chloroplatinic acid/vinyl siloxane complex (containing 0.3 x 10 ^-7 mol as Pt alone) was added, and then 19.6 g (9. 24×10 ⁻² mol) was added dropwise thereto, and the mixture was heated and stirred at 70° C. for 4 hours. Thereafter, by distilling off the solvent and unreacted substances under reduced pressure, the following formula (AB) is obtained as an average structure.

20.4 g of organopolysiloxane compound 9 represented by the formula was obtained.

^1H -NMR
δ0.2(-Si-C H ₃ )12H
δ0.6(-SiC H ₂ -)8H
δ1.2-1.6 (-(C H ₂ ) ₈ -, -C H ₂ C H ₃ , -OCH ₂ C H ₃ )48H
δ2.3(-OOC-C H ₂ -)4H
δ4.1(-OC H ₂ CH ₃ )4H

[Examples 1 to 10, Comparative Examples 1 to 3]
Table 1 shows compounds 1 to 5 as lipophilic group-containing (hydrolyzable) organosiloxane compounds (component (A)), compounds 6 to 9 as lipophilic group-containing organopolysiloxane compounds (component (B)), 2 and dissolved in propylene glycol monomethyl ether to prepare a 0.2% by mass solution to prepare a surface treatment agent. Thereafter, it was spray coated onto Corning's Gorilla glass and cured at 40° C. and 80% RH for 12 hours to produce a cured film with a thickness of about 5 nm.

[Evaluation of fingerprint visibility]
Sebum was applied to the glass on which the cured film prepared above was formed under a load of 1 kg, and its visibility was visually evaluated in the following four stages. The results are shown in Tables 1 and 2.
4: Fingerprints are barely visible 3: Fingerprints are slightly visible 2: Fingerprints are thin but clearly visible 1: Fingerprints are clearly visible

[Evaluation of lipophilicity]
The contact angle of the cured film with respect to oleic acid (oleic acid contact angle) was measured using a contact angle meter Drop Master (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) for the glass on which the cured film prepared above was formed (droplet: 2 μl, temperature: 25° C., humidity (RH): 40%, measurement time: 40 seconds). The results are shown in Tables 1 and 2.

[Evaluation of scratch resistance]
The glass with the hardened film produced above was rubbed 50 times under the following conditions using a rubbing tester (manufactured by Shinto Kagakusha), and the presence or absence of scratches on the surface was visually confirmed. This was repeated until it was completed, and the scratch resistance was evaluated. The more times it takes to see scratches, the higher the scratch resistance, and the fewer the number of times it takes to see scratches, the lower the scratch resistance. The test environmental conditions were 25° C. and 40% humidity. Tables 1 and 2 show the number of wears (number of times of steel wool resistance) when scratches were visually confirmed.
Steel wool abrasion resistance
Steel wool: BONSTAR #0000 (manufactured by Nippon Steel Wool Co., Ltd.)
Contact area: 10mmφ
Travel distance (one way): 40mm
Traveling speed: 3,200mm/min Load: 1.5kg/cm

Examples showed excellent low visibility of fingerprints, lipophilicity, and scratch resistance. On the other hand, Comparative Example 1 containing only the lipophilic group-containing (hydrolyzable) organosiloxane compound (component (A)) exhibited low scratch resistance. Moreover, Comparative Example 2 containing only the lipophilic group-containing organopolysiloxane compound (component (B)) showed low lipophilicity. Furthermore, Comparative Example 3, in which the amount of the lipophilic group-containing organopolysiloxane compound (component (B)) was smaller than the predetermined amount, showed insufficient scratch resistance.

Claims (10)

(A) General formula (1) below

(In the formula, A is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ are independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, Y is independently a divalent organic group, and W is independently is an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X is independently a hydroxyl group or a hydrolyzable group , n is an integer from 1 to 3, and q is an integer from 1 to 3.)
A lipophilic group-containing (hydrolysable) organosiloxane compound and/or a partial (hydrolysed) condensate thereof represented by;
(B) General formula (2) or (3) below

(In the formula, A' is -C(=O)OR ¹ , -C(=O)NR ¹ ₂ , -C(=O)SR ¹ or -P(=O)(OR ¹ ) ₂ , and R ¹ is the same as above, R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and Y' is independently It is a divalent organic group, i is an integer from 1 to 199, j is an integer from 1 to 200, j/i≧0.5, i+j=3 to 201, and k is 0 to 200. is an integer of 11, l is an integer of 3 to 12, l/k≧0.5, k+l = 3 to 12, and is shown in parentheses with i, j, k, l Each repeating unit may be combined randomly.)
It contains a lipophilic group-containing organopolysiloxane compound represented by A certain coating composition. In the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the general formula (1) of component (A), Y is -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC(=O)NR- (R is an alkyl group having 1 to 4 carbon atoms or a phenyl group), sylalkylene group, sylarylene group, and a divalent group selected from linear, branched, or cyclic divalent organopolysiloxane residues having 2 to 10 silicon atoms, and arylene having 6 to 20 carbon atoms. The coating agent composition according to claim 1, which is an alkylene group having 2 to 30 carbon atoms which may contain a group. In the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the general formula (1) of component (A), W each independently represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, or a carbon number From an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom, an oxime group, an isocyanate group, and a cyanate group. The coating agent composition according to claim 1 or 2, which is selected from the group consisting of: The coating composition according to any one of claims 1 to 3, wherein component (A) is a lipophilic group-containing (hydrolysable) organosiloxane compound represented by the following general formula (4).

(In the formula, R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and Q is a single bond, or a sylalkylene group, a sylarylene group, and a divalent group selected from linear, branched, or cyclic divalent organopolysiloxane residues having 2 to 10 silicon atoms, m is each independently an integer of 1 to 20, and are independently hydroxyl groups or hydrolyzable groups.) The coating composition according to any one of claims 1 to 4, wherein component (B) is an organopolysiloxane represented by the following general formula (5) or (6).

(In the formula, Y ² is independently -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC( =O)NR- (R is an alkyl group having 1 to 4 carbon atoms or a phenyl group), a sylalkylene group, a sylarylene group, and a linear, branched or cyclic 2 group having 2 to 10 silicon atoms. is an alkylene group having 2 to 30 carbon atoms which may contain a divalent group selected from valent organopolysiloxane residues and may also contain an arylene group having 6 to 20 carbon atoms, and R ² , i, j, k, l, j/i, i+j, l/k, k+l are the same as above, and each repeating unit shown in parentheses with i, j, k, l is randomly combined. (You can leave it there.) A surface treatment agent containing the coating composition according to any one of claims 1 to 5. The surface treatment agent according to claim 6, further comprising a solvent. The surface treatment agent according to claim 6 or 7, further comprising a hydrolysis condensation catalyst. The surface treatment agent according to any one of claims 6 to 8, which provides a cured film having an oleic acid contact angle of 30° or less at 25° C. and 40% relative humidity. An article having a cured film of the surface treatment agent according to any one of claims 6 to 9 on its surface.