JP2018016707A - Organopolysiloxane compound and coating composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organopolysiloxane compound that gives a cured product that can achieve all of hardness, crack resistance and impact resistance, and also has excellent curability and yellowing resistance.SOLUTION: An organopolysiloxane compound is composed of a hydrosilylation product of organopolysiloxane (a) and a hydrosilyl group-containing organic silicon compound (b). The (a) organopolysiloxane is a compound of formula (1): RRSiXO(where Ris an alkyl group or the like, Ris a carbon-carbon double bond-containing group, X is a hydroxy group or the like, a, b, c satisfy 0≤a≤1.5, 0.01≤b≤1, 0.5≤a+b≤1.8, 0.01≤c≤2.5, 1≤a+b+c≤3). The (b) hydrosilyl group-containing organic silicon compound is at least one compound selected from hydrosilyl siloxane having a phenylene group and hydrosilyl siloxane free of a phenylene group.SELECTED DRAWING: None

Description

  The present invention relates to an organopolysiloxane compound and a coating composition containing the organopolysiloxane compound, and more specifically, an organopolysiloxane having an alkoxysilyl group and / or silanol group in one molecule, and a specific hydrosilyl group-containing organosilicon. The present invention relates to an organopolysiloxane compound comprising a hydrosilylation reaction product with a compound, and a coating composition using the same.

Today, silicone resins are widely used in various fields because of their excellent properties such as water repellency, heat resistance, weather resistance, cold resistance, electrical insulation, chemical resistance, and safety to the body.
Among them, organopolysiloxane compounds having a three-dimensional cross-linking structure mainly composed of SiO ₂ units (Q units) and RSiO _1.5 units (T units) (R is an organic group such as an alkyl group or a phenyl group) are silicones. It is called a resin or a silicone alkoxy oligomer, and is widely used for paints, coating agents, bainters, etc. by utilizing its curability.

Among these, a liquid silicone alkoxy oligomer having an alkoxysilyl group as a cross-linking group is used as a main component of a solvent-free paint that is flammable and does not contain an organic solvent harmful to the human body (see Patent Document 1).
The alkoxysilyl group undergoes a crosslinking reaction at room temperature due to moisture in the air. Therefore, silicone alkoxy oligomers containing alkoxysilyl groups can form a siloxane network by reacting the alkoxysilyl groups at room temperature by blending a curing catalyst, making it easy to form a film with excellent heat resistance and weather resistance. Because it can be formed, it is used in a wide range of fields, from outdoor buildings to electronic components.
Further, as described above, the silicone alkoxy oligomer does not need to be heated for curing, and the paint using this as a main agent has an advantage that it can be applied on site.

However, such silicone resins and silicone alkoxy oligomers have the advantages of good curability and high surface hardness due to their three-dimensional cross-linking structure, while having high cross-linking density and flexibility and impact resistance. Insufficient, cracks may occur in the coating film over time after film formation or when external stress is applied.
In order to improve the flexibility and crack resistance, a method of incorporating a diorganosiloxane (R ₂ SiO _1.0 ) unit (D unit) at the time of synthesis of a silicone resin or a silicone alkoxy oligomer is employed. Since D units are randomly incorporated in the structure, it is necessary to add many D units to impart flexibility, and the excellent curability and surface hardness, which are the advantages of silicone resins, are reduced. There is a problem that.

  Further, in order to add the D unit to the silicone resin or silicone alkoxy oligomer in the form of a chain structure, even if an attempt is made to add a silicone oil having a chain structure of D unit, the silicone oil is not compatible with the silicone resin or the silicone alkoxy oligomer. Since it has poor solubility, it causes white turbidity and repellency of the coating film and cannot be added as expected.

Furthermore, a method of adding a silicone oil whose molecular ends are blocked with TEOS (Si (OEt) ₄ ) has also been proposed (see Non-Patent Document 1). In this case, however, the compatibility with silicone resins and silicone alkoxy oligomers is improved. It is not done, and causes the cloudiness and repelling of the coating film.

  In addition, flexibility can be improved by adding resins other than silicone, such as acrylic resin and epoxy resin, to silicone resin and silicone alkoxy oligomer, but these resins are generally used in terms of heat resistance, yellowing resistance and weather resistance. Since it is inferior to silicone, the heat resistance, yellowing resistance, weather resistance and the like of the paint obtained by adding these resins are lowered.

As materials that can solve the above problems, Patent Document 2 discloses a side-chain dimethyl type silicone oil compound containing a hydrosilyl group and having a D unit chain structure, and an olefin and an alkoxysilyl group in the side chain. It contains both a silicone alkoxy oligomer structure having an alkoxysilyl group in one molecule and a structure derived from a side chain dimethyl type silicone oil structure obtained by hydrosilylation reaction with a silicone alkoxy oligomer compound having both Organopolysiloxane compounds are disclosed.
Since the organopolysiloxane compound of Patent Document 2 is compatible with silicone resins and silicone alkoxy oligomers, it exhibits an effect when added as a crack resistance-imparting agent, but when cured alone. Insufficient hardness, it was difficult to use alone for paints and coatings.

Patent Document 3 discloses a side chain methyl / phenyl type silicone oil compound containing a hydrosilyl group and having a D unit chain structure, and a silicone alkoxy oligomer compound having both an olefin and an alkoxysilyl group in the side chain. An organopolysiloxane compound containing both a silicone alkoxy oligomer structure having an alkoxysilyl group in one molecule and a structure derived from a side chain methyl / phenyl type silicone oil structure obtained by hydrosilylation reaction of Yes.
The organopolysiloxane compound disclosed in Patent Document 3 has a relatively long chain and high molecular weight side chain methyl / phenyl silicone oil structure, and is therefore effective when added as a crack resistance imparting agent. However, in this case as well, when it is cured alone, the hardness is insufficient and it is difficult to use it alone for paints and coating agents.

Further, Patent Document 4 discloses a silicone comprising a T unit containing a phenyl group and an R ₃ SiO _0.5 unit (M unit) containing a vinyl group, having an olefin group in the side chain and no alkoxysilyl group. Organopolysiloxane having both a silicone resin structure not containing an alkoxysilyl group in one molecule and a structure derived from a hydrosilyl group-containing organosilicon compound, obtained by hydrosilylation reaction of a resin compound and a hydrosilyl group-containing organosilicon compound Siloxane compounds are disclosed.
Although the organopolysiloxane compound of Patent Document 4 has an olefin group in the side chain, it can be cured by a hydrosilylation reaction. However, heating is necessary for the curing, and it is like the above-mentioned silicone alkoxy oligomer. In addition, it was difficult to allow the crosslinking reaction to proceed at room temperature due to moisture in the air.
In addition, since all of these organopolysiloxane compounds are normal temperature solid compounds having a melting point of about 100 ° C., it is difficult to use the organopolysiloxane compound alone as a solventless coating agent at normal temperature. Since it contains many T units, it has a problem in terms of yellowing resistance.

Japanese Patent No. 2137192 Japanese Patent No. 3993373 Japanese Patent No. 5426613 International Publication No. 2015/194159

Polymeric Materia 1s Science and Engineering, 1998, Vol. 79,192

  The present invention has been made in view of the above circumstances, an organopolysiloxane compound capable of achieving both hardness, crack resistance and impact resistance, and providing a cured product having excellent curability and yellowing resistance, and It is an object of the present invention to provide a coating composition used.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a hydrosilylation reaction product of an organopolysiloxane having an alkoxysilyl group and / or silanol group in one molecule and a specific hydrosilyl group-containing organosilicon compound. It was found that an organopolysiloxane compound consisting of the above has excellent curability, can achieve both hardness, crack resistance and impact resistance, and gives a cured product excellent in yellowing resistance, thereby completing the present invention.

（式中、Ｒ¹は、互いに独立して前記式（１）と同じ意味を表し、Ｙは、互いに独立して、酸素原子または炭素原子数１〜１０のアルキレン基を表し、ｋは、０〜１，０００の整数を表す。）
（ｂ２）下記一般式（３）で表されるヒドロシリル基含有有機ケイ素化合物

（式中、Ｒ¹は、互いに独立して、前記式（１）と同じ意味を表す。）
（ｂ３）平均構造式が下記一般式（４）で表されるヒドロシリル基含有有機ケイ素化合物

（式中、Ｒ¹は、互いに独立して、前記式（１）と同じ意味を表し、Ｒ³は、互いに独立して、Ｚで置換されていてもよい、炭素原子数６〜１４のアリール基または炭素原子数７〜１７のアラルキル基を表し、Ｚは、前記式（１）と同じ意味を表し、
ｍは、１〜５の整数を表し、ｎは、０〜５の整数を表すが、ｍ＋ｎは１〜５の整数を満たす。）
（ｂ４）下記一般式（５）で示されるヒドロシリル基含有有機ケイ素化合物

（式中、Ｒ³は、互いに独立して、前記式（４）と同じ意味を表す。）
（ｂ５）下記一般式（６）で示されるヒドロシリル基含有有機ケイ素化合物

（式中、Ｒ¹は、互いに独立して、前記式（１）と同じ意味を表し、ｐは、０〜３の整数を表し、ｑは、２〜５の整数を表すが、ｐ＋ｑは３〜６の整数を満たす。）
２． 前記（ｂ）ヒドロシリル基含有有機ケイ素化合物が、前記（ｂ１）、（ｂ３）および（ｂ４）から選ばれる１種または２種以上のヒドロシリル基含有有機ケイ素化合物を含む１のオルガノポリシロキサン化合物、
３． 前記（ｂ）ヒドロシリル基含有有機ケイ素化合物が、前記（ｂ１）のヒドロシリル基含有有機ケイ素化合物を含む２のオルガノポリシロキサン化合物、
４． 前記（ｂ１）のヒドロシリル基含有有機ケイ素化合物が、下記一般式（７）で示される３のオルガノポリシロキサン化合物、

５． 前記オルガノポリシロキサン（ａ）と前記ヒドロシリル基含有有機ケイ素化合物（ｂ）とを、ヒドロシリル化反応触媒の存在下、ヒドロシリル基含有有機ケイ素化合物（ｂ）のＳｉ−Ｈ基１モルに対して、オルガノポリシロキサン（ａ）のＳｉ原子に直結したアルケニル基が１〜１０モルとなる範囲でヒドロシリル化反応を行う１〜４のいずれかのオルガノポリシロキサン化合物の製造方法、
６． 前記オルガノポリシロキサン（ａ）と前記ヒドロシリル基含有有機ケイ素化合物（ｂ）とを、ヒドロシリル化反応触媒の存在下、ヒドロシリル基含有有機ケイ素化合物（ｂ）のＳｉ−Ｈ基１モルに対して、オルガノポリシロキサン（ａ）のＳｉ原子に直結したアルケニル基が２〜６モルとなる範囲でヒドロシリル化反応を行う５のオルガノポリシロキサン化合物の製造方法、
７． （Ａ）１〜４のいずれかのオルガノポリシロキサン化合物、および（Ｂ）硬化触媒
を含有するコーティング用組成物、
８． 前記（Ｂ）硬化触媒が、酸触媒、アミン化合物およびその塩、アミノアルキル基置換アルコキシシラン、並びにアルミ系、チタン系およびスズ系の有機金属触媒からなる群から選ばれる１種または２種以上である７のコーティング用組成物、
９． 前記（Ｂ）硬化触媒が、チタンを含有する有機金属触媒である７または８のコーティング用組成物、
１０． 溶剤の含有量が、１質量％以下である７〜９のいずれかのコーティング用組成物、
１１． ７〜１０のいずれかのコーティング用組成物を硬化させてなる硬化物品
を提供する。 That is, the present invention
1. An organopolysiloxane compound comprising a hydrosilylation reaction product of the following organopolysiloxane (a) and a hydrosilyl group-containing organosilicon compound (b):
(A) Organopolysiloxane represented by the average composition formula (1) and having at least one aliphatic unsaturated double bond in one molecule:
R ¹ _a R ² _b SiX _c O _{(4-abc) / 2} (1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 14 carbon atoms, an aryl group, or an aralkyl group, which may be substituted with Z, and Z represents a halogen atom, an amino group, Represents an epoxy group, thiirane group, mercapto group, iso (thio) cyanate group, succinic anhydride group, perfluoroalkyl group, polyether group or perfluoropolyether group,
R ² independently represents an aliphatic carbon-carbon double bond-containing group having 2 to 15 carbon atoms,
X independently represents a hydroxyl group, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms,
a, b and c are respectively 0 ≦ a ≦ 1.5, 0.01 ≦ b ≦ 1, 0.5 ≦ a + b ≦ 1.8, 0.01 ≦ c ≦ 2.5, and 1 ≦ a + b + c. It is a number satisfying ≦ 3. )
(B) One or more hydrosilyl group-containing organosilicon compounds selected from the following (b1) to (b5):
(B1) Hydrosilyl group-containing organosilicon compound whose average structural formula is represented by the following general formula (2)

(In the formula, R ¹ independently represents the same meaning as in the above formula (1), Y independently represents an oxygen atom or an alkylene group having 1 to 10 carbon atoms, and k represents 0 Represents an integer of ˜1,000.)
(B2) Hydrosilyl group-containing organosilicon compound represented by the following general formula (3)

(In the formula, R ^{1 s} independently of each other have the same meaning as the formula (1).)
(B3) Hydrosilyl group-containing organosilicon compound having an average structural formula represented by the following general formula (4)

(In the formula, R ¹ independently represents the same meaning as the formula (1), and R ³ independently represents an aryl having 6 to 14 carbon atoms which may be substituted with Z. Represents a group or an aralkyl group having 7 to 17 carbon atoms, Z represents the same meaning as the formula (1),
m represents an integer of 1 to 5, and n represents an integer of 0 to 5, but m + n satisfies an integer of 1 to 5. )
(B4) Hydrosilyl group-containing organosilicon compound represented by the following general formula (5)

(In the formula, R ³ independently represents the same meaning as in the formula (4).)
(B5) Hydrosilyl group-containing organosilicon compound represented by the following general formula (6)

(In the formula, R ¹ independently of each other represents the same meaning as in the above formula (1), p represents an integer of 0 to 3, q represents an integer of 2 to 5, and p + q represents 3) Meet an integer of ~ 6.)
2. 1 organopolysiloxane compound, wherein the (b) hydrosilyl group-containing organosilicon compound comprises one or more hydrosilyl group-containing organosilicon compounds selected from the above (b1), (b3) and (b4),
3. 2 organopolysiloxane compounds, wherein the (b) hydrosilyl group-containing organosilicon compound comprises the hydrosilyl group-containing organosilicon compound of (b1),
4). (B1) The hydrosilyl group-containing organosilicon compound is an organopolysiloxane compound of 3 represented by the following general formula (7):

5. The organopolysiloxane (a) and the hydrosilyl group-containing organosilicon compound (b) are combined with 1 mol of Si-H groups of the hydrosilyl group-containing organosilicon compound (b) in the presence of a hydrosilylation reaction catalyst. The method for producing an organopolysiloxane compound according to any one of 1 to 4, wherein the hydrosilylation reaction is performed in a range where the alkenyl group directly bonded to the Si atom of the polysiloxane (a) is 1 to 10 mol,
6). The organopolysiloxane (a) and the hydrosilyl group-containing organosilicon compound (b) are combined with 1 mol of Si-H groups of the hydrosilyl group-containing organosilicon compound (b) in the presence of a hydrosilylation reaction catalyst. 5. A method for producing an organopolysiloxane compound according to 5, wherein the hydrosilylation reaction is performed in a range where the alkenyl group directly bonded to the Si atom of the polysiloxane (a) is 2 to 6 mol,
7). (A) any one of the organopolysiloxane compounds 1 to 4 and (B) a coating composition containing a curing catalyst,
8). The (B) curing catalyst is one or more selected from the group consisting of acid catalysts, amine compounds and salts thereof, aminoalkyl group-substituted alkoxysilanes, and aluminum-based, titanium-based and tin-based organometallic catalysts. 7 coating compositions,
9. (B) The coating composition according to 7 or 8, wherein the curing catalyst is an organometallic catalyst containing titanium,
10. The coating composition according to any one of 7 to 9, wherein the solvent content is 1% by mass or less,
11. A cured article obtained by curing any of the coating compositions 7 to 10 is provided.

  Since the organopolysiloxane compound of the present invention contains both a structure derived from an organopolysiloxane having an alkoxysilyl group and / or silanol group in one molecule and a structure derived from a specific hydrosilyl group-containing organosilicon compound, In addition to excellent curability, when used as a coating composition, it is possible to achieve both hardness, crack resistance and impact resistance, which cannot be achieved with conventional silicone resins and silicone alkoxy oligomers, and is also resistant to yellowing. In addition, an excellent cured film can be obtained.

Hereinafter, the present invention will be specifically described.
The organopolysiloxane compound according to the present invention comprises a hydrosilylation reaction product of the following organopolysiloxane (a) and the following hydrosilyl group-containing organosilicon compound (b).
(1) Organopolysiloxane (a)
The organopolysiloxane (a) is a compound represented by an average composition formula (1) and having at least one aliphatic unsaturated double bond in one molecule.
R ¹ _a R ² _b SiX _c O _{(4-abc) / 2} (1)

In the above formula (1), R ^{1 s} independently represent an alkyl group having 1 to 14 carbon atoms, an aryl group, or an aralkyl group that may be substituted with Z, and Z represents a halogen atom, Represents an amino group, an epoxy group, a thiirane group, a mercapto group, an iso (thio) cyanate group, a succinic anhydride group, a perfluoroalkyl group, a polyether group or a perfluoropolyether group, and R ² independently of each other, Represents an aliphatic carbon-carbon double bond-containing hydrocarbon group having 2 to 15 carbon atoms, and X is independently of each other a hydroxyl group, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, or a carbon atom. Represents an aryloxy group of formula 6 to 10, and a, b and c are 0 ≦ a ≦ 1.5, 0.01 ≦ b ≦ 1, 0.5 ≦ a + b ≦ 1.8, 0.01 ≦, respectively. c ≦ 2.5, and It is a number that satisfies 1 ≦ a + b + c ≦ 3.

In R ¹ , the alkyl group having 1 to 14 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n- Examples include butyl, i-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, octyl and decyl groups.
Specific examples of the aryl group include aryl groups having 6 to 14 carbon atoms such as phenyl and naphthyl groups.
Specific examples of the aralkyl group include aralkyl groups having 7 to 14 carbon atoms such as benzyl and phenylethyl groups.
In the above Z, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific examples of the polyether group include — (OCH ₂ ) _n —OR, — (OCH ₂ CH ₂ ) _n —OR, — (OCH (CH ₃ ) CH ₂ ) _n —OR (wherein n is An integer of 1 or more, R represents an alkyl group having 1 to 5 carbon atoms, and the like.
Specific examples of the perfluoropolyether group include — (OCF ₂ ) _n —OR ′, — (OCF ₂ CF ₂ ) _n —OR ′, — (OCF (CF ₃ ) CF ₂ ) _n —OR ′ (each formula In the formula, n represents an integer of 1 or more, and R ′ represents a perfluoroalkyl group having 1 to 5 carbon atoms.
Specific examples of the alkyl group having 1 to 14 carbon atoms substituted with Z include trifluoropropyl, 3-aminopropyl, 3-glycidoxypropyl, 3-mercaptopropyl group and the like.

Among these, considering the ease of acquisition and production, and the curability and weather resistance of the organopolysiloxane compound of the present invention, R ¹ is preferably a methyl group, an n-propyl group, or a phenyl group. Is more preferable.

R ² represents an aliphatic carbon-carbon double bond that is required in at least one molecule per molecule to cause the reaction between the organopolysiloxane (a) and the hydrosilyl group-containing organosilicon compound (b). More specifically, it is an aliphatic carbon-carbon double bond-containing group having 2 to 15 carbon atoms, independently of each other.
In the above R ² , specific examples of the carbon-carbon double bond-containing group having 2 to 15 carbon atoms are vinyl, n-1-propenyl, allyl, 1-methylethenyl, n-1-butenyl, n-2- Butenyl, n-3-butenyl, n-1-pentenyl, n-1-hexenyl, 2-cyclohexenyl, 3-cyclohexenyl, n-1-heptenyl, n-1-octenyl, n-1-nonenyl, n- 1-decenyl, 2-vinylcyclohexyl, 3-vinylcyclohexyl, 4-vinylcyclohexyl, 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl, 2-allylphenyl, 3-allylphenyl, 4-allylphenyl groups, etc. A carbon-carbon double bond-containing hydrocarbon group having 2 to 15 carbon atoms and containing a linear, branched, cyclic, or aromatic ring; 3- (meth) allyl Groups in which at least one carbon atom of the carbon-carbon double bond-containing hydrocarbon group such as a xylpropyl group is substituted with a heteroatom such as an oxygen atom; 2- (meth) acryloxyethyl, 3- (meth) acryloxy (Meth) acryloxyalkyl groups such as propyl group, 8- (meth) acryloxyoctyl, 11- (meth) acryloxyundecyl group and the like can be mentioned.

Among these, considering the ease of acquisition and production, reactivity with the hydrosilyl group, R ² is a straight chain having 2 to 10 carbon atoms such as vinyl group, 1-hexenyl group, 1-octenyl group and the like. A chain alkenyl group; an alkenyl group containing an aromatic ring having 6 to 12 carbon atoms such as 4-vinylphenyl group; 3- (meth) acryloxypropyl, 8- (meth) acryloxyoctyl, 11- (meth) acryl A (meth) acryloxyalkyl group such as a roxyundecyl group is preferred, a linear alkenyl group having 2 to 10 carbon atoms such as vinyl and 1-octenyl group is more preferred, and a vinyl group is even more preferred.

X is a group that contributes to curing of the obtained organopolysiloxane compound, and independently of each other, a hydroxyl group, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, or a group having 6 to 10 carbon atoms. It is a hydrolyzable group such as an aryloxy group.
Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, n-pentoxy, n-hexoxy, n-decoxy group and the like. It is done.
Specific examples of the aryloxy group having 6 to 10 carbon atoms include phenoxy, 1-naphthoxy, 2-naphthoxy group and the like.
Among these, in consideration of easiness of acquisition and production, curability of the organopolysiloxane compound of the present invention, coating film hardness, storage stability, etc., alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy groups Is preferable, an alkoxy group having 1 to 5 carbon atoms is more preferable, and a methoxy group is still more preferable.

  In consideration of enhancing the storage stability of the organopolysiloxane compound of the present invention, it is preferable that the content of hydroxyl groups in X is small. Specifically, the number of hydroxyl groups contained in the organopolysiloxane (a) is 3 % By mass or less is preferable, 1% by mass or less is more preferable, and 0.5% by mass or less is even more preferable.

In the average composition formula (1), the range of a indicating the number of R ¹ is 0 ≦ a ≦ 1.5, and when a> 1.5, the curability and coating film hardness of the organopolysiloxane compound of the present invention. Is lacking.
Further, the range of b indicating the number of R ² is 0.01 ≦ b ≦ 1, and when b <0.01, the reaction with the hydrosilyl group does not proceed sufficiently, and when b> 1, the organo group of the present invention is used. The curability and coating film hardness of the polysiloxane compound are insufficient.
The range of the total a + b of the organic groups (R ¹ + R ² ) is 0.5 ≦ a + b ≦ 1.8, and when a + b <0.5, the crack resistance of the coating film obtained from the organopolysiloxane compound of the present invention, When the impact resistance and flexibility are insufficient, and a + b> 1.8, the curability of the organopolysiloxane compound and the coating film hardness of the resulting coating film are insufficient.

Furthermore, the range of c indicating the number of X is 0.01 ≦ c ≦ 2.5. When c <0.01, the curability of the organopolysiloxane compound and the coating film hardness of the resulting coating film are insufficient. , C> 2.5, the resulting coating film has insufficient crack resistance, impact resistance and flexibility.
The total a + b + c of all substituents on Si in the average composition formula (1) is 1 ≦ a + b + c ≦ 3. When a + b + c <1, the organopolysiloxane (a) becomes high molecular weight and easily gels, and a + b + c> 3 Then, organopolysiloxane (a) becomes a low molecular weight body, and the resulting organopolysiloxane compound lacks crack resistance, impact resistance and flexibility.

  In order to achieve both hardness, crack resistance and impact resistance when the organopolysiloxane compound of the present invention is coated, the average degree of polymerization of the organopolysiloxane (a) is preferably 2 to 1,000. 5-200 is more preferable. If m is less than 2, cracking resistance, impact resistance and flexibility of the obtained organopolysiloxane compound may be insufficient. If m exceeds 1,000, production is difficult due to high molecular weight and easy gelation. And the reactivity with the hydrosilyl group-containing organosilicon compound (b) may be poor.

(2) Hydrosilyl group-containing organosilicon compound (b)
The hydrosilyl group-containing organosilicon compound (b) used in the present invention is one or more selected from the following (b1) to (b5).
(B1) Hydrosilyl group-containing organosilicon compound whose average structural formula is represented by the following general formula (2) (b2) Hydrosilyl group-containing organosilicon compound (b3) represented by the following general formula (3) Hydrosilyl group-containing organosilicon compound represented by the general formula (4) (b4) Hydrosilyl group-containing organosilicon compound represented by the following general formula (5) (b5) Hydrosilyl group-containing organosilicon represented by the following general formula (6) Compound

In the formulas (2) to (4) and (6), R ¹ independently represents the same meaning as in the above formula (1), and specific examples thereof are as described in the formula (1). However, in consideration of easiness of acquisition and production, curability and weather resistance of the organopolysiloxane compound of the present invention, in any of the formulas (2) to (4) and (6), R ¹ is , A methyl group, an n-propyl group, and a phenyl group are preferable, and a methyl group is more preferable.

In the formula (2), Y independently represents an oxygen atom or an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, trimethylene. , Propylene, tetramethylene, i-butylene, pentamethylene, isopentylene, cyclopentylene, hexamethylene, cyclohexylene, octamethylene, decamethylene group and the like.
Among these, considering the hardness, weather resistance and yellowing resistance of the cured coating obtained from the organopolysiloxane compound of the present invention, Y is preferably a methylene group, an ethylene group or an oxygen atom, more preferably an oxygen atom. .

In the formulas (4) and (5), R ³ independently of each other represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, which may be substituted with Z; Z represents the same meaning as in the above formula (1), and specific examples thereof are the same as those described above.
Specific examples of the aryl group having 6 to 14 carbon atoms include phenyl and naphthyl groups, and examples of the aralkyl group having 7 to 17 carbon atoms include benzyl and phenylethyl groups.
Among these, a phenyl group and a benzyl group are preferable, and a phenyl group is more preferable from the viewpoints of availability and production, hardness of a cured film obtained from the organopolysiloxane compound of the present invention, weather resistance, and yellowing resistance. preferable.

In the above formula (2), k represents an integer of 0 to 1,000. When k> 1,000, the crystallinity of the organopolysiloxane compound of the present invention is large, and it becomes difficult to form a coating without a solvent.
In consideration of enhancing the coating film hardness, crack resistance, impact resistance, flexibility, weather resistance, yellowing resistance and the like of the obtained organopolysiloxane compound of the present invention, k is from 0 to 100. An integer is preferable, an integer of 0 to 10 is preferable, and 0 is more preferable.

In said formula (4), m represents the integer of 1-5. When m <1, the side chain of the hydrosilyl group-containing organosilicon compound (b3) does not contain an aryl group or an aralkyl group, and the hardness, crack resistance, and resistance of the coating film produced from the resulting organopolysiloxane compound of the present invention Impact and flexibility are reduced. When m> 5, the hydrosilyl group-containing organosilicon compound (b3) has a long chain and a high molecular weight, and since the aryl group and aralkyl group have a high content, the coating film produced from the resulting organopolysiloxane compound of the present invention Hardness, weather resistance and yellowing resistance are reduced.
In consideration of enhancing the hardness, crack resistance, impact resistance, flexibility, weather resistance and yellowing resistance of the coating film prepared from the organopolysiloxane compound of the present invention, m is an integer of 1 to 2 Is preferable, and 1 is more preferable.
n represents an integer of 0 to 5. When n> 5, the hydrosilyl group content in one molecule of the hydrosilyl group-containing organosilicon compound (b3) is increased. As a result, the resulting organopolysiloxane compound of the present invention has a high crosslinking density. Cracked resistance, impact resistance, and flexibility of the cured film to be reduced.
Considering the coating film hardness, crack resistance, impact resistance, flexibility and the like of the organopolysiloxane compound of the present invention, n is preferably an integer of 0 to 2, more preferably 0.
Further, m + n satisfies an integer of 1-5. When m + n <1, the side chain of the hydrosilyl group-containing organosilicon compound (b3) does not contain an aryl group or an aralkyl group, and the hardness, crack resistance, impact resistance of the coating film produced from the resulting organopolysiloxane compound, Flexibility is reduced. When m + n> 5, the hydrosilyl group-containing organosilicon compound (b3) has a long chain and a high molecular weight, and the aryl group and aralkyl group have a high content, or the hydrosilyl group-containing organosilicon compound (b3) in one molecule Since the hydrosilyl group content is increased, the hardness, crack resistance, impact resistance, flexibility, weather resistance and yellowing resistance of the coating film prepared from the resulting organopolysiloxane compound of the present invention are lowered.
In view of further increasing the hardness, crack resistance, impact resistance, flexibility, weather resistance, and yellowing resistance of the coating film prepared from the organopolysiloxane compound of the present invention, m + n is from 1 to 3. An integer is preferable, and 1 is more preferable.
In particular, in the above formula (4), m is preferably an integer of 1 to 2, n is an integer of 0 to 2, and m + n is preferably an integer of 1 to 3, and m is 1 and n is more preferably 0.

In said formula (6), p represents the integer of 0-3. When p> 3, since the hydrosilyl group-containing organosilicon compound (b5) has a high molecular weight, the hardness of the coating film produced from the resulting organopolysiloxane compound of the present invention decreases. In consideration of further increasing the hardness of the coating film produced from the organopolysiloxane compound of the present invention, p is preferably an integer of 0-2.
q represents an integer of 2 to 5. When q <2, since the hydrosilyl group content in one molecule of the hydrosilyl group-containing organosilicon compound (b5) is small, the resulting organopolysiloxane compound of the present invention has a low crosslinking density, and the coating film hardness produced therefrom Decreases. When q> 5, the hydrosilyl group-containing organosilicon compound (b5) has a high molecular weight, or the hydrosilyl group content in one molecule of the hydrosilyl group-containing organosilicon compound (b5) is large. The hardness, crack resistance, impact resistance and flexibility of the coating film prepared from the polysiloxane compound are lowered. From the viewpoint of improving the hardness, crack resistance, impact resistance, flexibility and the like of the coating film produced from the organopolysiloxane compound of the present invention, q is preferably an integer of 2 to 4.
Furthermore, p + q satisfies an integer of 3-6. When p + q <3, the storage stability of the resulting organopolysiloxane compound of the present invention decreases, and the crack resistance, impact resistance, and flexibility of the coating film produced therefrom decrease. When p + q> 6, the hydrosilyl group-containing organosilicon compound (b5) has a high molecular weight, so that the coating film hardness produced from the resulting organopolysiloxane compound of the present invention decreases. P + q is an integer of 4 to 5 from the viewpoint of ease of raw material acquisition and compound production, coating film hardness, crack resistance, impact resistance, flexibility and the like produced from the resulting organopolysiloxane compound of the present invention Is preferable, and 4 is more preferable.
In particular, in formula (6), p is preferably an integer of 0 to 2, q is an integer of 2 to 4, and p + q is an integer of 4 to 5, p is 2 and q is 2 or p is 0 and q is 4. More preferred.

In the organopolysiloxane compound of the present invention, the hydrosilyl group-containing organosilicon compound (b) constituting the organopolysiloxane compound is any one or more of the hydrosilyl group-containing organosilicon compounds (b1), (b3), and (b4) described above. When it contains, the obtained organopolysiloxane compound exhibits better coating film hardness, crack resistance, impact resistance, flexibility, curability, weather resistance and yellowing resistance.
In particular, it is preferable to include (b1). In the general formula (2), when R ¹ is a methyl group, Y is an oxygen atom, and k is 0, the obtained organopolysiloxane compound is A particularly good coating film is given.
That is, when the hydrosilyl group-containing organosilicon compound (b) is a hydrosilyl group-containing organosilicon compound represented by the following general formula (7), the obtained organopolysiloxane compound has particularly good coating film hardness, It exhibits crack resistance, impact resistance, flexibility, curability, weather resistance and yellowing resistance.

The number of silicon atoms in the organopolysiloxane compound of the present invention is not particularly limited, but is preferably 5 to 2,000, and more preferably 10 to 400.
Further, in the organopolysiloxane compound of the present invention, among the substituents bonded to silicon atoms other than X, 80 mol% or more is a methyl group. It is preferable from the viewpoint of crack resistance, impact resistance, flexibility, weather resistance and yellowing resistance.

The organopolysiloxane compound of the present invention can be used as a main component of a solvent-free paint, and is liquid in the range of 20 to 50 ° C. from the viewpoint of good workability when applied to the surface of a substrate. It is preferable that
The viscosity of the organopolysiloxane compound is preferably in the range of 1 to 50,000 mm ² / s at 25 ° C., more preferably in the range of 10 to 5,000 mm ² / s, from the viewpoint of workability at the time of application. The range of 50 to 1,000 mm ² / s is even more preferable. The viscosity in the present invention is a value measured with a B-type rotational viscometer.

(3) Production Method of Organopolysiloxane Compound The organopolysiloxane compound of the present invention comprises a carbon-carbon double bond contained in the organopolysiloxane (a), a molecular end of the hydrosilyl group-containing organosilicon compound (b), and a side chain. Or a hydrosilylation reaction with a hydrosilyl group contained in both.
The organopolysiloxane compound of the present invention obtained by this reaction has a form in which a structure derived from an organopolysiloxane (a) having a hydrolyzable group and a structure derived from a hydrosilyl group-containing organosilicon compound (b) are combined. Have.

In general, in a hydrosilylation reaction, a simple metal such as Ni, Rh, Pd, or Pt, a compound thereof, or a complex thereof is used as a hydrosilylation reaction catalyst.
In the hydrosilylation reaction for producing the organopolysiloxane compound of the present invention, a complex having platinum (Pt) and / or platinum (Pt) as the central metal, which is a known hydrosilylation reaction catalyst, having an oxidation number of II or 0 It is preferred to use the compound as a catalyst.
Specific examples thereof include chloroplatinic acid (H ₂ PtCl ₆ .6H ₂ O), alcohol solution of chloroplatinic acid, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, and Toluene or xylene solution of compound neutralized complex, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum-alumina, Examples thereof include a supported catalyst such as platinum-silica. Among these, zero-valent platinum complexes are preferable from the viewpoints of catalytic activity, addition site selectivity, and easy handling with homogeneous catalysts, and platinum-1,3-divinyl-1,1,3,3 is preferable. -A toluene or xylene solution of tetramethyldisiloxane complex is more preferred.

  In the present invention, the amount of the hydrosilylation reaction catalyst used is not particularly limited as long as the catalyst effect is manifested. However, the catalyst effect to be exhibited, the economical efficiency such as the cost, and the coloring of the product are prevented. Considering this, the range of 0.1 to 1,000 ppm in terms of metal elements is preferable with respect to the entire reaction system.

  The hydrosilylation reaction proceeds even without solvent, but a solvent can also be used. Specific examples of usable solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, xylene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane; ethyl acetate, butyl acetate, etc. Ester solvents; aprotic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon solvents such as dichloromethane and chloroform, and the like. You may mix and use a seed | species or more.

The reaction temperature in the hydrosilylation reaction is not particularly limited, and heating from 0 ° C. can be adopted, but 0 to 200 ° C. is preferable. Further, in order to obtain an appropriate reaction rate, the reaction is performed under heating. From such a viewpoint, 40 to 110 ° C is more preferable, and 40 to 90 ° C is even more preferable.
Also, the reaction time is not particularly limited and is usually about 1 to 60 hours, preferably 1 to 30 hours, and more preferably 1 to 20 hours.

(4) Coating composition The coating composition of this invention contains the (A) organopolysiloxane compound and (B) curing catalyst which were mentioned above.
Since the coating composition of the present invention contains the above-described organopolysiloxane compound of the present invention, when this is used to coat a solid substrate, compared to the case of using a conventional organopolysiloxane compound, Due to the structure of the organopolysiloxane compound of the present invention, the hardness, crack resistance, impact resistance and yellowing resistance of the cured coating are improved.

On the other hand, the curing catalyst (B) is a component that promotes the reaction in which the hydrolyzable group contained in the (A) organopolysiloxane compound is hydrolyzed and condensed with moisture in the air, and accelerates the curing of the coating composition. Yes, added to cure efficiently.
The addition amount of the curing catalyst (B) is not particularly limited, but the cured rate is adjusted to an appropriate range to produce a cured film having desired physical properties, and the workability at the time of application is improved. Taking into account the economics associated with the addition, the amount is preferably 0.01-50 parts by weight, more preferably 0.05-10 parts by weight, and 0.1-5 parts by weight with respect to 100 parts by weight of component (A). Even more preferred.

The curing catalyst (B) is not particularly limited as long as it is a curing catalyst used for curing a general moisture condensation curable composition. Specific examples thereof include acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid; alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium alkoxide, potassium alkoxide; NH ₃ ; ethylamine, diethylamine, triethylamine, hexyl Amine compounds such as amine, dodecylamine phosphate, diazabicycloundecene, diazabicyclononene, 1,1,3,3-tetramethylguanidine and salts thereof; dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, Alkyl tin ester compounds such as dibutyltin dioctoate and dioctyltin dioctoate; tetraisopropoxytitanium, tetran-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) ) Titanic acid esters such as titanium and titanium isopropoxyoctylene glycol, and titanium chelate compounds and partial hydrolysates thereof; zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexo Ate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, aluminum trihydroxide, aluminum alcoholate, aluminum acylate, salt of aluminum acylate, aluminosyloxy compound, di-n- Organometallic compounds such as aluminum chelate compounds such as butoxy (ethyl acetoacetate) aluminum; 3-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, bis [3- (trimethoxysilane) L) propyl] amine, aminoalkyl group-substituted alkoxysilanes such as N, N-bis- [3- (trimethoxysilyl) propyl] ethylenediamine; quaternary ammonium salts such as benzyltriethylammonium acetate; potassium acetate, sodium acetate, Lower fatty acid salts of alkali metals such as lithium oxalate; Dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; Tetramethylguanidylpropyltrimethoxysilane, Tetramethylguanidylpropylmethyldimethoxysilane, Tetramethylguanidyl Silanes and siloxanes containing guanidyl groups such as propyltris (trimethylsiloxy) silane; N, N, N ′, N ′, N ″, N ″ -hexamethyl-N ′ ″-[3- (trimethoxysilyl ) Propi - phosphoryl, such as silanes and siloxanes containing phosphazene base such as Mi Dick triamide and the like, which may be used singly or may be used in combination of two or more thereof.

  Among these, since it is more excellent in reactivity, acid catalysts, amine compounds and salts thereof, aminoalkyl group-substituted alkoxysilanes, aluminum alcoholates, aluminum acylates, salts of aluminum acylates, aluminosyloxy compounds, aluminum chelate compounds, etc. One or more selected from titanium-based organometallic catalysts such as aluminum-based organometallic catalysts, titanate esters, titanium chelate compounds and partial hydrolysates thereof, and tin-based organometallic catalysts such as alkyl tin ester compounds Preferably, a titanium-based organometallic catalyst containing titanium is more preferable, tetraisopropoxy titanium, tetra n-butoxy titanium and partial hydrolysates thereof are more preferable, and tetra n-butoxy titanium is most preferable.

  Depending on the purpose of use, the viscosity of the coating composition of the present invention is adjusted to improve workability, the curability of the composition, the hardness of the resulting coating film, the flexibility, etc. A silane compound optionally containing an alkoxysilyl group, a silicone alkoxy oligomer having an alkoxysilyl group and / or a silanol group in a molecule, and one or more compounds selected from silicone resins (A ) Component organopolysiloxane compound may be mixed separately.

Furthermore, the coating composition of the present invention is preferably in a solvent-free form that does not substantially contain an organic solvent (in many cases, harmful to humans and has flammability). It is also possible to add a solvent from
Here, “substantially” means that the solvent contained in the composition is 1% by mass or less, particularly 0.1% by mass or less.
Specific examples of the solvent that can be used include the same solvents as those used in the production of the (A) organopolysiloxane compound.
In addition, as a solvent, what is not the component added intentionally in the composition for coatings including the reaction solvent which could not be removed completely by distillation under reduced pressure is included.

  The coating composition of the present invention contains various additives such as an adhesion improver, an inorganic and organic ultraviolet absorber, a storage stability improver, a plasticizer, a filler, and a pigment depending on the purpose of use. Can be added.

The coating composition of the present invention described above is applied to the surface of a solid substrate and cured to form a coating layer, whereby a coated solid substrate that is a cured article is obtained.
The coating method is not particularly limited, and specific examples thereof can be appropriately selected from known methods such as spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating.
The solid substrate is not particularly limited, and specific examples thereof include epoxy resins, phenol resins, polycarbonates and polycarbonate blends, acrylic resins such as poly (methyl methacrylate), poly (ethylene terephthalate), and poly (butylene terephthalate). ), Polyester resins such as unsaturated polyester resins, polyamide resins, polyimide resins, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride resins, polystyrene resins, blends of polystyrene and polyphenylene ether, cellulose Organic polymer substrate such as acetate butyrate and polyethylene resin, metal substrate such as steel plate, paint coated surface, glass, ceramic, concrete, slate plate, textile, wood, stone, tile (Hollow) Inorganic fillers such as silica, titania, zirconia, and alumina, glass cloth including glass fiber, glass fiber products such as glass tape, glass mat, glass paper, etc. Although not particularly limited, the coating composition of the present invention can be particularly suitably used for coating steel sheets and glass.

When the coating composition of the present invention is brought into contact with moisture in the atmosphere, the hydrolysis condensation reaction of the (A) organopolysiloxane compound proceeds and the curing reaction starts. As an indicator of moisture in the atmosphere, any humidity of 10 to 100% RH may be used. Humidity in the air is sufficient, but generally, the higher the humidity, the faster the hydrolysis proceeds. May be added.
The curing reaction temperature and time can be appropriately changed according to factors such as the substrate used, the moisture concentration, the catalyst concentration, and the type of hydrolyzable group. Usually, it is about 5 minutes to 1 week within a range not exceeding the heat resistance temperature of the substrate to be used.
Since the coating composition of the present invention is cured well at room temperature, even when room temperature curing is indispensable for on-site construction or the like, there is no stickiness (tack) on the coating film surface in minutes to hours, Although it is excellent in workability, the heat treatment may be performed within a range not exceeding the heat-resistant temperature of the substrate.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these Examples.
In the following, the viscosity of each product is a value measured at 25 ° C. with a B-type rotational viscometer, and the molecular weight is toluene, as a solvent, using a GPC (gel permeation chromatograph) apparatus manufactured by Tosoh Corporation. It is a weight average molecular weight (hereinafter referred to as Mw) in terms of polystyrene determined by GPC measurement using RI as a vessel.
The average silicone composition was calculated from the integrated value of the detection spectra in ¹ H-NMR and b ²⁹ Si-NMR using a 300 MHz-NMR measuring apparatus manufactured by JEOL Ltd.
The content (mass%) of the silanolic hydroxyl group contained in each product was determined from the amount of methane gas generated when a Grignard reagent (methyl magnesium iodide) was allowed to act on each product.
In the following average silicone composition, Me represents a side chain methyl group, Vi represents a side chain vinyl group, and Ph represents a side chain phenyl group.

[1] Synthesis of organopolysiloxane compound [Synthesis Example 1] Synthesis of organopolysiloxane (a1) Into a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, methyltrimethoxysilane 1, 158 g and 198 g of vinylmethyldimethoxysilane were added, and 188 g of 0.05N hydrochloric acid was added dropwise at 25 ° C. with stirring, followed by hydrolysis and condensation at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off the byproduct methanol at normal pressure and then filtered to obtain 850 g of organopolysiloxane (a1). The resulting organopolysiloxane (a1) is a colorless transparent liquid, having a viscosity of 45 mm ² / s, an average composition of Me _1.00 Vi _0.14 SiO _1.13 (OCH ₃ ) _0.60 , Mw 1,740, and a silanolic hydroxyl group content of 0.1. It was mass%.

[Synthesis Example 2] Synthesis of organopolysiloxane (a2) Into a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, were charged 1,090 g of methyltrimethoxysilane and 264 g of vinylmethyldimethoxysilane. While stirring, 151 g of 0.05N hydrochloric acid was added dropwise at 25 ° C., followed by hydrolysis and condensation at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off the by-product methanol at normal pressure and then filtered to obtain 920 g of organopolysiloxane (a2). The obtained organopolysiloxane (a2) is a colorless transparent liquid, having a viscosity of 35 mm ² / s, an average composition of Me _1.00 Vi _0.19 SiO _0.73 (OCH ₃ ) _1.35 , Mw 550, and a silanolic hydroxyl group content of 0.5% by mass. Met.

[Synthesis Example 3] Synthesis of organopolysiloxane (a3) A 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 1,342 g of methyltrimethoxysilane and 20 g of vinylmethyldimethoxysilane. While stirring, 225 g of 0.05N hydrochloric acid was added dropwise at 25 ° C., followed by hydrolysis and condensation at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off the by-product methanol at normal pressure and then filtered to obtain 743 g of organopolysiloxane (a3). The resulting organopolysiloxane (a3) is a colorless and transparent liquid having a viscosity of 80 mm ² / s, an average composition of Me _1.00 Vi _0.01 SiO _1.27 (OCH ₃ ) _0.45 , Mw 8,200, and a silanolic hydroxyl group content of 0.2. It was mass%.

[Comparative Synthesis Example 1] Synthesis of organopolysiloxane (a4) Into a 2 L separable flask equipped with a stirrer, a reflux condenser and a thermometer, 954 g of methyltrimethoxysilane and 361 g of dimethyldimethoxysilane were charged and stirred at 25 ° C. Then, 190 g of 0.05N hydrochloric acid was added dropwise, and hydrolytic condensation was performed at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off the by-product methanol at normal pressure and then filtered to obtain 790 g of organopolysiloxane (a4). The obtained organopolysiloxane (a4) is a colorless transparent liquid, has a viscosity of 75 mm ² / s, an average composition of Me _1.28 SiO _1.07 (OCH ₃ ) _0.58 , Mw = 1,900, and a silanolic hydroxyl group content of 0 It was 5% by mass. This organopolysiloxane (a4) has a structure in which methylsiloxane units (T units) and dimethylsiloxane units (D units) are randomly incorporated in the average silicone composition.

[Comparative Synthesis Example 2] Synthesis of organopolysiloxane (a5) Into a 2 L separable flask equipped with a stirrer, a reflux condenser and a thermometer, 1,905 g of methyltrimethoxysilane was charged and stirred at 25 ° C. .05N-hydrochloric acid (180 g) was added dropwise, followed by hydrolysis and condensation at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off the by-product methanol at normal pressure and then filtered to obtain 875 g of organopolysiloxane (a5). The obtained organopolysiloxane (a5) was a colorless and transparent liquid, and had a viscosity of 285 mm ² / s, an average composition of Me _1.00 SiO _1.03 (OCH ₃ ) _0.94 and Mw of 1,500. This organopolysiloxane (a5) has a silicone average composition consisting only of methylsiloxane units (T units).

[Comparative Synthesis Example 3] Synthesis of organopolysiloxane (a6) 95 L of methyltrimethoxysilane and 734 g of dimethoxydiphenylsilane were charged into a 2 L separable flask equipped with a stirrer, a reflux condenser and a thermometer. 190 g of 0.05N-hydrochloric acid was added dropwise at ° C, followed by hydrolysis and condensation at 70 ° C for 2 hours. This was heated to 120 ° C. to distill off the byproduct methanol at normal pressure and then filtered to obtain 1,227 g of organopolysiloxane (a6). The obtained organopolysiloxane (a6) is a colorless and transparent liquid, and has a viscosity of 80 mm ² / s, an average composition of Me _0.43 Ph _0.86 SiO _0.73 (OCH ₃ ) _1.25 , Mw 900, and a silanolic hydroxyl group content of 0.3% by mass. Met. This organopolysiloxane (a6) has a structure in which methylsiloxane units (T units) and diphenylsiloxane units ( ^DΦ units) are randomly incorporated in the average silicone composition.

[2] Synthesis of organopolysiloxane compound [Example 1-1] Synthesis of organopolysiloxane compound (A1) In a 200 mL separable flask equipped with a stirrer, reflux condenser and thermometer, organopolysiloxane (a1) 150 g and 5.7 g of a hydrosilyl group-containing organosilicon compound represented by the following formula (8) were placed and mixed with stirring. Then, when heated to an internal temperature of 80 ° C., a toluene solution of platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of platinum complex with respect to the whole solution (platinum Conversion)) 0.96 g was added. After completion of the addition, the hydrosilylation reaction was performed while heating to an internal temperature of 80 ° C., and the reaction solution was aged for 8 hours, and then the disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Then, vacuum distillation (80 degreeC, 5 mmHg) was implemented for 1 hour, and the corresponding organopolysiloxane compound (A1) 152g was obtained by filtering. The obtained organopolysiloxane compound (A1) was a colorless transparent liquid having a viscosity of 121 mm ² / s.

[Example 1-2] Synthesis of organopolysiloxane compound (A2) In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 150 g of organopolysiloxane (a2), represented by the above formula (8) 5.7 g of a hydrosilyl group-containing organosilicon compound was placed and mixed with stirring. Then, when heated to an internal temperature of 80 ° C., a toluene solution of platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of platinum complex with respect to the whole solution (platinum Conversion)) 0.96 g was added. After completion of the addition, the hydrosilylation reaction was performed while heating to an internal temperature of 80 ° C., and the reaction solution was aged for 8 hours, and then the disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Then, vacuum distillation (80 degreeC, 5 mmHg) was implemented for 1 hour, and the corresponding organopolysiloxane compound (A2) 154g was obtained by filtering. The obtained organopolysiloxane compound (A2) was a colorless transparent liquid having a viscosity of 110 mm ² / s.

[Example 1-3] Synthesis of organopolysiloxane compound (A3) In a 200 mL separable flask equipped with a stirrer, reflux condenser and thermometer, 150 g of organopolysiloxane (a3), represented by the above formula (8) The hydrosilyl group-containing organosilicon compound (0.9 g) was placed and mixed with stirring. Then, when heated to an internal temperature of 80 ° C., a toluene solution of platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of platinum complex with respect to the whole solution (platinum Conversion)) 0.96 g was added. After completion of the addition, the hydrosilylation reaction was performed while heating to an internal temperature of 80 ° C., and the reaction solution was aged for 8 hours, and then the disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Then, vacuum distillation (80 degreeC, 5 mmHg) was implemented for 1 hour, and the corresponding organopolysiloxane compound (A3) 146g was obtained by filtering. The obtained organopolysiloxane compound (A3) was a colorless transparent liquid having a viscosity of 193 mm ² / s.

[Example 1-4] Synthesis of organopolysiloxane compound (A4) In place of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), the hydrosilyl group-containing organic represented by the following average structural formula (9) The reaction was conducted in the same procedure as in Example 1-1 except that 67 g of the silicon compound was used, and 210 g of the corresponding organopolysiloxane compound (A4) was obtained. The obtained organopolysiloxane compound (A4) was a colorless transparent liquid having a viscosity of 624 mm ² / s.

[Example 1-5] Synthesis of organopolysiloxane compound (A5) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), the hydrosilyl group-containing organic represented by the following average structural formula (10) The reaction was conducted in the same procedure as in Example 1-1 except that 71 g of the silicon compound was used, and 215 g of the corresponding organopolysiloxane compound (A5) was obtained. The obtained organopolysiloxane compound (A5) was a colorless transparent liquid having a viscosity of 517 mm ² / s.

[Example 6] Synthesis of organopolysiloxane compound (A6) In place of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), 5 g of a hydrosilyl group-containing organosilicon compound represented by the following formula (11) was used. Except for the use, the reaction was carried out in the same procedure as in Example 1-1 to obtain 150 g of the corresponding organopolysiloxane compound (A6). The obtained organopolysiloxane compound (A6) was a colorless transparent liquid having a viscosity of 425 mm ² / s.

[Example 1-7] Synthesis of organopolysiloxane compound (A7) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), the hydrosilyl group-containing organic represented by the following average structural formula (12) The reaction was conducted in the same procedure as in Example 1-1 except that 10 g of the silicon compound was used, and 156 g of the corresponding organopolysiloxane compound (A7) was obtained. The obtained organopolysiloxane compound (A7) was a colorless transparent liquid having a viscosity of 156 mm ² / s.

[Example 1-8] Synthesis of organopolysiloxane compound (A8) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), a hydrosilyl group-containing organosilicon compound represented by the following formula (13) The reaction was conducted in the same procedure as in Example 1-1 except that 5.5 g was used, to obtain 152 g of the corresponding organopolysiloxane compound (A8). The obtained organopolysiloxane compound (A8) was a colorless transparent liquid having a viscosity of 124 mm ² / s.

[Example 1-9] Synthesis of organopolysiloxane compound (A9) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), the hydrosilyl group-containing organic represented by the following average structural formula (14) The reaction was conducted in the same procedure as in Example 1-1 except that 9.7 g of the silicon compound was used, and 154 g of the corresponding organopolysiloxane compound (A9) was obtained. The resulting organopolysiloxane compound (A9) was a colorless transparent liquid having a viscosity of 158 mm ² / s.

[Example 1-10] Synthesis of organopolysiloxane compound (A10) In place of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), a hydrosilyl group-containing organosilicon compound represented by the following formula (15) The reaction was conducted in the same procedure as in Example 1-1 except that 3.6 g was used, to obtain 149 g of the corresponding organopolysiloxane compound (A10). The obtained organopolysiloxane compound (A10) was a colorless transparent liquid having a viscosity of 373 mm ² / s.

[Comparative Example 1-1] Synthesis of organopolysiloxane compound (A11) In place of 150 g of organopolysiloxane (a1), 150 g of vinyltrimethoxysilane was used, and the hydrosilyl group-containing organosilicon represented by the above formula (8) The reaction was conducted in the same procedure as in Example 1-1 except that 229 g of the compound was used, and 375 g of the corresponding organopolysiloxane compound (A11) was obtained. The obtained organopolysiloxane compound (A11) was a white solid.

Comparative Example 1-2 Synthesis of Organopolysiloxane Compound (A12) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), a hydrosilyl group-containing organosilicon compound represented by the following formula (16) Except for using 4 g, the reaction was performed in the same procedure as in Example 1-1 to obtain 149 g of the corresponding organopolysiloxane compound (A12). The obtained organopolysiloxane compound (A12) was a colorless transparent liquid having a viscosity of 100 mm ² / s.

[Comparative Example 1-3] Synthesis of organopolysiloxane compound (A13) In place of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), the hydrosilyl group-containing organic represented by the following average structural formula (17) The reaction was conducted in the same procedure as in Example 1-1 except that 90.4 g of the silicon compound was used, and 235 g of the corresponding organopolysiloxane compound (A13) was obtained. The obtained organopolysiloxane compound (A13) was a colorless transparent liquid having a viscosity of 305 mm ² / s.

Comparative Example 1-4 Synthesis of Organopolysiloxane Compound (A14) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), the hydrosilyl group whose average structural formula is represented by the following formula (18) The reaction was conducted in the same procedure as in Example 1-1 except that 39.2 g of the containing organosilicon compound was used, to obtain 184 g of the corresponding organopolysiloxane compound (A14). The obtained organopolysiloxane compound (A14) was a colorless transparent liquid having a viscosity of 430 mm ² / s.

[Comparative Example 1-5] Synthesis of organopolysiloxane compound (A15) In a separable flask equipped with a stirrer, reflux condenser and thermometer, 150 g of toluene, average structural formula (C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 ] 58.6 mass% toluene of organopolysiloxane (Mw = 1,560, silanolic hydroxyl group content 4.1 mass%) represented by _0.25 205 g of the solution and 9.8 g of a hydrosilyl group-containing organosilicon compound represented by the above formula (8) were placed and mixed with stirring. Then, when heated to an internal temperature of 80 ° C., a toluene solution of platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of platinum complex with respect to the whole solution (platinum Conversion)) 1.65 g was added. After completion of the addition, the hydrosilylation reaction was performed while heating to an internal temperature of 80 ° C., and the reaction solution was aged for 8 hours, and then the disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Then, vacuum distillation (80 degreeC, 5 mmHg) was performed for 1 hour, and 117 g of corresponding organopolysiloxane compounds (A15) were obtained by cooling to 25 degreeC. The obtained organopolysiloxane compound (A2) was a white solid.

[Comparative Example 1-6] Synthesis of Organopolysiloxane Compound (A16) In place of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), the hydrosilyl group-containing organosilicon compound represented by the above formula (12) Except for using 2 g, the reaction was performed in the same procedure as in Comparative Example 1-5 to obtain 124 g of the corresponding organopolysiloxane compound (A16). The obtained organopolysiloxane compound (A16) was a white solid.

[3] Preparation of coating composition and cured film [Example 2-1]
100 parts by mass of the organopolysiloxane compound (A1) obtained in Example 1-1 above and 5 parts by mass of tetra-n-butoxytitanium as a curing catalyst are uniformly mixed using a stirrer to form a coating composition. Was prepared.
The resulting coating composition was subjected to bar coater No. 5 under air at 25 ° C. and 50% RH. 14 was applied to a glass plate or polished steel plate, and dried and cured for 1 day in air at 25 ° C. and 50% RH to produce a cured coating.

[Examples 2-2 to 2-10 and Comparative Examples 2-1 to 2-10]
The organopolysiloxane compound (A1) of Example 2-1 was replaced with the organopolysiloxane compounds (A2) to (A10) obtained in Examples 1-2 to 1-10 and Comparative Examples 1-1 to 1-6. Organopolysiloxane compounds (A11) to (A16) obtained, organopolysiloxanes (a4) to (a6) obtained in Comparative Synthesis Examples 1 to 3, and organopolysiloxane (a1) obtained in Synthesis Example 1 A coating composition and a cured film were prepared in the same manner as in Example 2-1, except that each was changed to.

[Example 2-11]
The coating composition and curing were carried out in the same manner as in Example 2-1, except that 5 parts by mass of di-n-butoxy (ethylacetoacetate) aluminum was used as a curing catalyst instead of 5 parts by mass of tetra-n-butoxytitanium. A coating was prepared.

The following evaluation was implemented about the cured film produced in the said Examples 2-1 to 2-11 and Comparative Examples 2-1-10. The results are also shown in Tables 1 and 2.
[Finger touch drying time]
The test piece obtained by applying the coating composition to the glass plate by the above application method is left in air at 25 ° C. and 50% RH, and moisture curing proceeds, so that the applied surface can be pressed with a finger. The time (minutes) until the coating film did not adhere to the finger was shown. It shows that sclerosis | hardenability is so favorable that a value is small.
[Crack resistance]
The test piece in which the cured film was formed on the glass plate by the above coating method was visually observed for the presence or absence of cracks (cracks) in the cured film when heat-treated in an oven at 150 ° C. for 2 hours.
When no crack was observed, it was evaluated as “◯” as having excellent crack resistance. When one crack was observed, it was evaluated as “Δ”. When two or more cracks were observed, it was evaluated as “x”.
〔Pencil hardness〕
A test piece in which a cured film was formed on a glass plate by the above coating method was measured by applying a load of 750 g by a method according to the pencil scratch test described in JIS K 5600, and the result was shown.
(Impact resistance)
Using a DuPont drop impact tester described in JIS K 5600, a test piece with a hardened film formed on the polished steel plate by the above application method is sandwiched between the shooting mold and the cradle, and from a certain height A 500 g weight was dropped, and the presence or absence of cracks and peeling of the test piece due to impact deformation was observed with the naked eye. At that time, the drop height (cm) at the stage where abnormalities such as cracks and peeling were observed on the coating film surface was shown. Larger values indicate better impact resistance.
(Yellowing resistance)
A UV irradiation test was carried out for 2 weeks using a germicidal lamp in air at 25 ° C. and 50% RH on the test piece having a cured film formed on the glass plate by the above coating method. The degree of yellowing of the cured film at that time was evaluated by ΔYI (yellowing degree = change width of yellowing degree YI) using a color difference meter described in JIS K 7373. Smaller values indicate better yellowing resistance.

As shown in Tables 1 and 2, curing produced in Examples 2-1 to 2-11 using the organopolysiloxane compounds (A1) to (A10) obtained in Examples 1-1 to 1-10. It can be seen that the film has both hardness, crack resistance and impact resistance as well as excellent curability and yellowing resistance as compared with the cured film prepared in each Comparative Example.
On the other hand, the cured coatings produced in Comparative Examples 2-1 to 2-4 and 2-7 to 2-10 cannot realize both the hardness and the crack resistance and the impact resistance, and the curability, Some coating properties such as yellowing resistance are insufficient.
In Comparative Examples 2-5 and 2-6, the obtained organopolysiloxane compounds (A15) and (A16) were solidified and could not be coated.

  As explained above, the organopolysiloxane compound of the present invention is excellent in curability and has both hardness, crack resistance and impact resistance, which has been difficult with conventional silicone resins and silicone alkoxy oligomers. A cured film excellent in yellowing resistance can be obtained.

Claims (11)

An organopolysiloxane compound comprising a hydrosilylation reaction product of the following organopolysiloxane (a) and a hydrosilyl group-containing organosilicon compound (b).
(A) Organopolysiloxane represented by the average composition formula (1) and having at least one aliphatic unsaturated double bond in one molecule:
R ¹ _a R ² _b SiX _c O _{(4-abc) / 2} (1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 14 carbon atoms, an aryl group, or an aralkyl group, which may be substituted with Z, and Z represents a halogen atom, an amino group, Represents an epoxy group, thiirane group, mercapto group, iso (thio) cyanate group, succinic anhydride group, perfluoroalkyl group, polyether group or perfluoropolyether group,
R ² independently represents an aliphatic carbon-carbon double bond-containing group having 2 to 15 carbon atoms,
X independently represents a hydroxyl group, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms,
a, b and c are respectively 0 ≦ a ≦ 1.5, 0.01 ≦ b ≦ 1, 0.5 ≦ a + b ≦ 1.8, 0.01 ≦ c ≦ 2.5, and 1 ≦ a + b + c. It is a number satisfying ≦ 3. )
(B) One or more hydrosilyl group-containing organosilicon compounds selected from the following (b1) to (b5):
(B1) Hydrosilyl group-containing organosilicon compound whose average structural formula is represented by the following general formula (2)

(Wherein, R ¹ independently represents the same meaning as in the above formula (1), Y independently represents an oxygen atom or an alkylene group having 1 to 10 carbon atoms, and k is Represents an integer of 0 to 1,000.)
(B2) Hydrosilyl group-containing organosilicon compound represented by the following general formula (3)

(In the formula, R ^{1 s} independently of each other have the same meaning as the formula (1).)
(B3) Hydrosilyl group-containing organosilicon compound having an average structural formula represented by the following general formula (4)

(In the formula, R ¹ independently represents the same meaning as the formula (1), and R ³ independently represents an aryl having 6 to 14 carbon atoms which may be substituted with Z. Represents a group or an aralkyl group having 7 to 17 carbon atoms, Z represents the same meaning as the formula (1),
m represents an integer of 1 to 5, and n represents an integer of 0 to 5, but m + n satisfies an integer of 1 to 5. )
(B4) Hydrosilyl group-containing organosilicon compound represented by the following general formula (5)

(In the formula, R ³ independently represents the same meaning as in the formula (4).)
(B5) Hydrosilyl group-containing organosilicon compound represented by the following general formula (6)

(In the formula, R ¹ independently of each other represents the same meaning as in the above formula (1), p represents an integer of 0 to 3, q represents an integer of 2 to 5, and p + q represents 3) Meet an integer of ~ 6.)   The organopolysiloxane according to claim 1, wherein the (b) hydrosilyl group-containing organosilicon compound contains one or more hydrosilyl group-containing organosilicon compounds selected from the above (b1), (b3) and (b4). Compound.   The organopolysiloxane compound according to claim 2, wherein the (b) hydrosilyl group-containing organosilicon compound comprises the hydrosilyl group-containing organosilicon compound (b1). The organopolysiloxane compound according to claim 3, wherein the hydrosilyl group-containing organosilicon compound (b1) is represented by the following general formula (7).

  The organopolysiloxane (a) and the hydrosilyl group-containing organosilicon compound (b) are combined with 1 mol of Si-H groups of the hydrosilyl group-containing organosilicon compound (b) in the presence of a hydrosilylation reaction catalyst. The method for producing an organopolysiloxane compound according to any one of claims 1 to 4, wherein the hydrosilylation reaction is carried out within a range where the alkenyl group directly bonded to the Si atom of the polysiloxane (a) is 1 to 10 mol.   The organopolysiloxane (a) and the hydrosilyl group-containing organosilicon compound (b) are combined with 1 mol of Si-H groups of the hydrosilyl group-containing organosilicon compound (b) in the presence of a hydrosilylation reaction catalyst. 6. The method for producing an organopolysiloxane compound according to claim 5, wherein the hydrosilylation reaction is carried out in a range where the alkenyl group directly bonded to the Si atom of the polysiloxane (a) is 2 to 6 mol. (A) The coating composition containing the organopolysiloxane compound according to any one of claims 1 to 4 and (B) a curing catalyst.   The (B) curing catalyst is one or more selected from the group consisting of acid catalysts, amine compounds and salts thereof, aminoalkyl group-substituted alkoxysilanes, and aluminum-based, titanium-based and tin-based organometallic catalysts. The coating composition according to claim 7.   The coating composition according to claim 7 or 8, wherein the (B) curing catalyst is an organometallic catalyst containing titanium.   Content of a solvent is 1 mass% or less, The composition for coating of any one of Claims 7-9.   A cured article obtained by curing the coating composition according to any one of claims 7 to 10.