JP6642324B2 - Organopolysiloxane compound and coating composition containing the same - Google Patents

Description

  The present invention relates to an organopolysiloxane compound and a coating composition containing the same. More specifically, the present invention relates to an organopolysiloxane having an alkoxysilyl group and / or a 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 body safety.
Among them, organopolysiloxane compounds having a three-dimensional cross-linked 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 in paints, coatings, binders, etc. by utilizing its curability.

Above all, a liquid silicone alkoxy oligomer having an alkoxysilyl group as a crosslinking group is used as a main component of a flammable, solvent-free paint containing no organic solvent harmful to the human body (see Patent Document 1).
The crosslinking reaction of the alkoxysilyl group proceeds at room temperature due to moisture in the air. Therefore, a silicone alkoxy oligomer containing an alkoxysilyl group can easily form a coating having excellent heat resistance and weather resistance because the alkoxysilyl group reacts at room temperature by forming a curing catalyst to form a siloxane network. 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 require heating for curing, and a paint using this product 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, but also have high flexibility and impact resistance due to their high cross-linking density. Insufficiently, 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) during the synthesis of a silicone resin or a silicone alkoxy oligomer has been adopted. However, since the D units are randomly incorporated into the structure, it is necessary to add many D units in order to impart flexibility, and the excellent curability and surface hardness, which are the advantages of the silicone resin, are reduced. There is a problem that it is.

  Further, in order to add D units 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 units, the silicone oil will not react with the silicone resin or silicone alkoxy oligomer. Poor solubility causes cloudiness and cissing of the coating film, and cannot be added as expected.

Furthermore, a method of adding a silicone oil whose molecular end is blocked with TEOS (Si (OEt) ₄ ) has been proposed (see Non-Patent Document 1), but also in this case, the compatibility with a silicone resin or a silicone alkoxy oligomer is improved. It is not applied, and causes cloudiness and cissing of the coating film.

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

As materials capable of solving the above problems, Patent Document 2 discloses a side chain dimethyl-type silicone oil compound containing a hydrosilyl group and having a chain structure of D units, and an olefin and an alkoxysilyl group in a side chain. Containing 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 subjecting a silicone alkoxy oligomer compound having both of the above to a hydrosilylation reaction. 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 it is cured alone. The hardness was insufficient, and it was difficult to use it alone for paints and coatings.

Further, Patent Document 3 discloses a side chain methyl / phenyl type silicone oil compound containing a hydrosilyl group and having a chain structure of D units, and a silicone alkoxy oligomer compound having both an olefin and an alkoxysilyl group in a side chain. Which contains 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, which is obtained by subjecting a compound to a hydrosilylation reaction. I have.
Since the organopolysiloxane compound of Patent Document 3 has a relatively long-chain, high-molecular-weight side chain methyl / phenyl type silicone oil structure, it is effective when added as a crack resistance imparting agent. However, in this case, too, when it was cured alone, the hardness was insufficient, and it was difficult to use it alone for paints and coatings.

Further, Patent Document 4 discloses a silicone comprising a phenyl group-containing T unit and a vinyl group-containing R ₃ SiO _0.5 unit (M unit) and having an olefin group in a side chain and no alkoxysilyl group. An organopoly obtained by subjecting a resin compound and a hydrosilyl group-containing organosilicon compound to a hydrosilylation reaction and having both a silicone resin structure containing no alkoxysilyl group in one molecule and a structure derived from the hydrosilyl group-containing organosilicon compound. Siloxane compounds are disclosed.
Although the organopolysiloxane compound of Patent Document 4 has an olefin group in a side chain, it can be cured by a hydrosilylation reaction. It was difficult to allow the crosslinking reaction to proceed at room temperature due to moisture in the air.
Further, since these organopolysiloxane compounds are all solid compounds at room temperature having a melting point of about 100 ° C., it is difficult to use them alone at room temperature as a solventless coating agent. Since a large number of T units are contained, there is a problem in yellowing resistance.

Japanese Patent No. 2137192 Japanese Patent No. 3993733 Japanese Patent No. 5426613 WO 2015/194159

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

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

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a hydrosilylation reaction product between an organopolysiloxane having an alkoxysilyl group and / or a silanol group in one molecule and a specific hydrosilyl group-containing organosilicon compound. The present inventors have found that an organopolysiloxane compound comprising a compound having excellent curability, at the same time having both hardness, crack resistance and impact resistance, and providing a cured product having excellent yellowing resistance, has completed 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) An 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)
(Wherein, 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, 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,
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 <3. )
(B) One or more hydrosilyl group-containing organosilicon compounds selected from the following (b1) to (b5):
(B1) a hydrosilyl group-containing organosilicon compound having an average structural formula represented by the following general formula (2)

(Wherein, R ¹ independently represents the same meaning as in the 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) a hydrosilyl group-containing organosilicon compound represented by the following general formula (3)

(In the formula, R ¹ independently represents the same meaning as in the formula (1).)
(B3) a hydrosilyl group-containing organosilicon compound having an average structural formula represented by the following general formula (4)

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

(Wherein, R ¹ independently of ^one another has 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 is 3 Satisfies the integer of ~ 6.)
2. (B) one organopolysiloxane compound containing one or more hydrosilyl group-containing organosilicon compounds selected from (b1), (b3) and (b4),
3. (B) two organopolysiloxane compounds comprising the hydrosilyl group-containing organosilicon compound of (b1),
4. The hydrosilyl group-containing organosilicon compound (b1) is an organopolysiloxane compound represented by the following general formula (7):

5. The organopolysiloxane (a) and the hydrosilyl group-containing organosilicon compound (b) are reacted with the organosilicon compound (b) in the presence of a hydrosilylation reaction catalyst, based on 1 mol of the Si—H group of the hydrosilyl group-containing organosilicon compound (b). A method for producing an organopolysiloxane compound according to any one of 1 to 4, 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 1 to 10 mol;
6. The organopolysiloxane (a) and the hydrosilyl group-containing organosilicon compound (b) are reacted with the organosilicon compound (b) in the presence of a hydrosilylation reaction catalyst, based on 1 mol of the Si—H group of the hydrosilyl group-containing organosilicon compound (b). 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) a coating composition containing any of the organopolysiloxane compounds of (1) to (4), and (B) a curing catalyst;
8. The curing catalyst (B) is one or more selected from the group consisting of an acid catalyst, an amine compound and a salt thereof, an aminoalkyl-substituted alkoxysilane, and an aluminum-based, titanium-based, and tin-based organometallic catalyst. Certain coating compositions of 7,
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 content of the solvent is 1% by mass or less,
11. A cured article obtained by curing any one of the coating compositions of 7 to 10.

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

Hereinafter, the present invention will be described specifically.
The organopolysiloxane compound according to the present invention comprises a hydrosilylation 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 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 above formula (1), 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 is a halogen atom, amino group, an epoxy group, thiirane group, a mercapto group, iso (thio) cyanate groups, succinic anhydride groups, perfluoroalkyl groups, polyether groups or perfluoropolyether group, R ^2, independently of one another, X represents an aliphatic carbon-carbon double bond-containing hydrocarbon group having 2 to 15 carbon atoms, and Xs are each independently a hydroxyl group, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, or a carbon atom. Represents an aryloxy group of the formulas 6 to 10, wherein 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 It is a number that satisfies 1 ≦ a + b + c ≦ 3.

In the above 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 and n- Butyl, i-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl group and the like.
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.
Examples of polyether _{groups, - (OCH 2) n -OR} , - (OCH 2 CH 2) n -OR, - (OCH (CH 3) CH 2) n -OR ( in each formula, n is An integer of 1 or more, and R represents an alkyl group having 1 to 5 carbon atoms.) Group.
Specific examples of the perfluoropolyether _{group, - (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.) Group.
Specific examples of the alkyl group having 1 to 14 carbon atoms substituted with Z include a trifluoropropyl, 3-aminopropyl, 3-glycidoxypropyl, 3-mercaptopropyl group and the like.

Among them, R ¹ is preferably a methyl group, an n-propyl group, or a phenyl group in consideration of easiness of acquisition and production, and the curability and weather resistance of the organopolysiloxane compound of the present invention. Is more preferred.

R ² represents an aliphatic carbon-carbon double bond required for at least one in one molecule to react the organopolysiloxane (a) with the hydrosilyl group-containing organosilicon compound (b). And more specifically, independently of each other, an aliphatic carbon-carbon double bond-containing group having 2 to 15 carbon atoms.
In the above R ² , specific examples of the carbon-carbon double bond-containing group having 2 to 15 carbon atoms include 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 group, etc. A C2-C15 straight-chain, branched, cyclic or aromatic ring-containing hydrocarbon group containing a carbon-carbon double bond; 3- (meth) allyl A group in which at least one carbon atom of the above-mentioned hydrocarbon group containing a carbon-carbon double bond such as a xypropyl group is substituted by a hetero atom such as an oxygen atom; 2- (meth) acryloxyethyl, 3- (meth) acryloxy Examples include (meth) acryloxyalkyl groups such as propyl group, 8- (meth) acryloxyoctyl, and 11- (meth) acryloxyundecyl group.

Among them, R ² is a straight-chain having 2 to 10 carbon atoms such as a vinyl group, a 1-hexenyl group, and a 1-octenyl group in consideration of availability and production, reactivity with a hydrosilyl group, and the like. Chain alkenyl group; 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 (Meth) acryloxyalkyl groups such as roxyundecyl group are preferred, linear alkenyl groups having 2 to 10 carbon atoms such as vinyl and 1-octenyl group are more preferred, and vinyl group is even more preferred.

X is a group contributing to the curing of the obtained organopolysiloxane compound, and independently of each other, is a hydroxyl group, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, or an alkoxy 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. Can be
Specific examples of the aryloxy group having 6 to 10 carbon atoms include a phenoxy, 1-naphthoxy, and 2-naphthoxy group.
Among them, alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy groups are considered in view of easiness of acquisition and production and curability, coating film hardness and storage stability of the organopolysiloxane compound of the present invention. 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 the hydroxyl group in X is small. Specifically, the hydroxyl group contained in the organopolysiloxane (a) is 3%. It is preferably at most 1 mass%, more preferably at most 1 mass%, even more preferably at most 0.5 mass%.

In the above average composition formula (1), the range of a representing the number of R ¹ is 0 ≦ a ≦ 1.5, and when a> 1.5, the curability and the coating film hardness of the organopolysiloxane compound of the present invention are obtained. Run out.
The range of b, which represents the number of R ² , is 0.01 ≦ b ≦ 1, and when b <0.01, the reaction with the hydrosilyl group does not sufficiently proceed. The curability and coating film hardness of the polysiloxane compound are insufficient.
The range of the sum 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 can be improved. When a + b> 1.8, the impact resistance and flexibility are insufficient, and the curability of the organopolysiloxane compound and the hardness of the coating film obtained are insufficient.

Further, 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 hardness of the obtained coating film are insufficient. , C> 2.5, the resulting coating film has insufficient crack resistance, impact resistance and flexibility.
The sum a + b + c of all the substituents on Si in the average composition formula (1) is 1 ≦ a + b + c ≦ 3. When a + b + c <1, the organopolysiloxane (a) has a high molecular weight and is easily gelled, and a + b + c> 3 In this case, the organopolysiloxane (a) has a low molecular weight, and the resulting organopolysiloxane compound lacks crack resistance, impact resistance and flexibility.

  Further, in order to achieve both hardness, crack resistance and impact resistance when the organopolysiloxane compound of the present invention is formed into a coating film, the average degree of polymerization of the organopolysiloxane (a) is preferably from 2 to 1,000. , 5 to 200 are more preferred. If m is less than 2, crack resistance, impact resistance and flexibility of the obtained organopolysiloxane compound may be insufficient, and if m is more than 1,000, production becomes 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 having an average structural formula represented by the following general formula (2) (b2) Hydrosilyl group-containing organosilicon compound represented by the following general formula (3) (b3) 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 of each other has the same meaning as in the above formula (1), and specific examples thereof are as described in the formula (1). However, in consideration of the easiness of acquisition and production and the curability and weather resistance of the organopolysiloxane compound of the present invention, in any of 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, and specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene and trimethylene. Propylene, tetramethylene, i-butylene, pentamethylene, isopentylene, cyclopentylene, hexamethylene, cyclohexylene, octamethylene, decamethylene and the like.
Among these, in consideration of the hardness, weather resistance, yellowing resistance, and the like of the cured film obtained from the organopolysiloxane compound of the present invention, Y is preferably a methylene group, an ethylene group, or an oxygen atom, and more preferably an oxygen atom. .

In the formulas (4) and (5), R ³ represents, independently of each other, 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; The Z has the same meaning as in the above formula (1), and specific examples thereof include the same as above.
Specific examples of the aryl group having 6 to 14 carbon atoms include phenyl and naphthyl groups, and aralkyl groups having 7 to 17 carbon atoms include benzyl and phenylethyl groups.
Among them, phenyl group and benzyl group are preferable, and phenyl group is more preferable, from the viewpoint of easiness of acquisition and production, and hardness, weather resistance and yellowing resistance of the cured film obtained from the organopolysiloxane compound of the present invention. preferable.

In the above formula (2), k represents an integer of 0 to 1,000. When k> 1,000, the organopolysiloxane compound of the present invention has high crystallinity, making it difficult to form a coating film without a solvent.
In consideration of increasing the coating film hardness, crack resistance, impact resistance, flexibility, weather resistance and yellowing resistance 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 the above formula (4), m represents an integer of 1 to 5. When m <1, the side chain of the hydrosilyl group-containing organosilicon compound (b3) does not contain an aryl group and an aralkyl group, and the hardness, crack resistance, and anti-cracking property of the resulting coating film formed from the organopolysiloxane compound of the present invention are obtained. 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 the aryl group and the aralkyl group have a high content. Therefore, a coating film formed from the organopolysiloxane compound of the present invention obtained. The hardness, weather resistance and yellowing resistance of the powder are reduced.
In consideration of 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 is an integer of 1 to 2. Is preferable, and 1 is more preferable.
n represents the integer of 0-5. When n> 5, the content of the hydrosilyl group in one molecule of the hydrosilyl group-containing organosilicon compound (b3) increases, so that the obtained organopolysiloxane compound of the present invention has a high crosslink density, and is thus prepared from the organopolysiloxane compound. Crack resistance, impact resistance, and flexibility of the cured film to be produced are reduced.
In consideration of 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, and more preferably 0.
Further, m + n satisfies an integer of 1 to 5. When m + n <1, the side chain of the hydrosilyl group-containing organosilicon compound (b3) does not contain an aryl group and an aralkyl group, and the hardness, crack resistance and impact resistance of a coating film formed from the obtained organopolysiloxane compound are high. 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 the aralkyl group have a high content, or the hydrosilyl group-containing organosilicon compound (b3) in one molecule Since the content of the hydrosilyl group is increased, the hardness, crack resistance, impact resistance, flexibility, weather resistance, and yellowing resistance of a coating film formed from the organopolysiloxane compound of the present invention are reduced.
In consideration of enhancing the hardness, crack resistance, impact resistance, flexibility, weather resistance and yellowing resistance of the coating film formed from the organopolysiloxane compound of the present invention, m + n is preferably from 1 to 3. An integer is preferred, and 1 is more preferred.
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 an integer of 1 to 3, and m is preferably 1 and n is more preferably 0.

In the above formula (6), p represents an integer of 0 to 3. When p> 3, the hydrosilyl group-containing organosilicon compound (b5) has a high molecular weight, so that the hardness of the coating film produced from the obtained organopolysiloxane compound of the present invention is reduced. In consideration of further increasing the hardness of a coating film formed from the organopolysiloxane compound of the present invention, p is preferably an integer of 0 to 2.
q represents an integer of 2 to 5. When q <2, the content of the hydrosilyl group in one molecule of the hydrosilyl group-containing organosilicon compound (b5) becomes small, so that the obtained organopolysiloxane compound of the present invention has a low crosslinking density, and the coating film hardness produced therefrom Decrease. When q> 5, the hydrosilyl group-containing organosilicon compound (b5) has a high molecular weight or the hydrosilyl group-containing organosilicon compound (b5) has a large hydrosilyl group content in one molecule. The hardness, crack resistance, impact resistance, and flexibility of the coating film formed from the polysiloxane compound are reduced. From the viewpoint of improving the hardness, crack resistance, impact resistance, flexibility, and the like of the coating film formed from the organopolysiloxane compound of the present invention, q is preferably an integer of 2 to 4.
Further, p + q satisfies an integer of 3 to 6. When p + q <3, the storage stability of the obtained organopolysiloxane compound of the present invention decreases, and the crack resistance, impact resistance, and flexibility of a coating film produced therefrom decrease. When p + q> 6, since the hydrosilyl group-containing organosilicon compound (b5) has a high molecular weight, the hardness of the coating film produced from the obtained organopolysiloxane compound of the present invention is reduced. From the viewpoints of easiness of raw material acquisition and compound production, and the hardness, crack resistance, impact resistance, flexibility, and the like of a coating film formed from the obtained organopolysiloxane compound of the present invention, p + q is an integer of 4 to 5. Is preferred, and 4 is more preferred.
In particular, in the 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 at least one of the above-described hydrosilyl group-containing organosilicon compounds (b1), (b3), and (b4). In the case of containing, 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 contain (b1). In the above general formula (2), when R ¹ is a methyl group, Y is an oxygen atom, and k is 0, the resulting organopolysiloxane compound Gives particularly good coatings.
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 a 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, it is preferable that 80 mol% or more of the substituents bonded to silicon atoms other than X is a methyl group. It is suitable from the viewpoints 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 has a good working property when applied to the surface of a base material. It is preferred that
Further, 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 coating. , 50 to 1,000 mm ² / s. The viscosity in the present invention is a value measured by 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 terminal 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 structure in which a structure derived from an organopolysiloxane having a hydrolyzable group (a) and a structure derived from a hydrosilyl group-containing organosilicon compound (b) are bonded. Have.

Generally, in the hydrosilylation reaction, a simple metal such as Ni, Rh, Pd, and Pt, a compound thereof, or a complex thereof is used as a catalyst for the hydrosilylation reaction.
In the hydrosilylation reaction for producing the organopolysiloxane compound of the present invention, platinum (Pt) having an oxidation number of II or 0 and / or a complex containing platinum (Pt) as a central metal, which is a known hydrosilylation reaction catalyst, is used. It is preferred to use the compound as a catalyst.
Specific examples thereof include chloroplatinic acid _{(H 2 PtCl 6 · 6H 2} O), an alcohol solution of chloroplatinic acid, a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex and this A solution of a compound obtained by neutralizing the complex in toluene or xylene, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum-alumina, Supported catalysts such as platinum-silica are exemplified. Among these, a zero-valent platinum complex is preferable from the viewpoints of catalytic activity, addition regioselectivity, and easy handling with a homogeneous catalyst, and platinum-1,3-divinyl-1,1,3,3. More preferred is a toluene or xylene solution of the tetramethyldisiloxane complex.

  In the present invention, the amount of the hydrosilylation reaction catalyst used is not particularly limited as long as the catalytic effect is exhibited, but the catalytic effect to be exhibited and the economical efficiency such as cost, and further, the coloring of the product is prevented. Taking this into consideration, the range is preferably 0.1 to 1,000 ppm in terms of metal element with respect to the entire reaction system.

  The above hydrosilylation reaction proceeds without a 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 and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like. Ester solvents; aprotic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon solvents such as dichloromethane, chloroform and the like. Mixtures of more than one species may be used.

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

(4) Coating composition The coating composition of the present invention contains the above-mentioned (A) organopolysiloxane compound and (B) a curing catalyst.
Since the coating composition of the present invention contains the above-described organopolysiloxane compound of the present invention, when a solid substrate is coated with the composition, a coating composition of the present invention is compared with 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 film are improved.

On the other hand, the curing catalyst (B) is a component that promotes a reaction in which the hydrolyzable group contained in the organopolysiloxane compound (A) is hydrolyzed and condensed with moisture in the air, and promotes curing of the coating composition. Yes, added for efficient curing.
The addition amount of the curing catalyst (B) is not particularly limited, but the curing rate is adjusted to an appropriate range to produce a cured film having desired physical properties, and to improve the workability during application. Considering the economics involved in the addition, the amount is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the 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, and methanesulfonic acid; alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium alkoxide, and potassium alkoxide; NH ₃ ; ethylamine, diethylamine, triethylamine, and hexyl. Amine compounds such as amines, 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, tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetonate) ) Titanate such as titanium and titanium isopropoxyoctylene glycol, and titanium chelate compounds and partial hydrolysates thereof; zinc naphthenate, zinc stearate, zinc-2-ethyloctoate, iron-2-ethylhexo Ethate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, aluminum trihydroxide, aluminum alcoholate, aluminum acylate, salt of aluminum acylate, aluminosiloxy compound, di-n- Organometallic compounds such as aluminum chelate compounds such as butoxy (ethylacetoacetate) aluminum; 3-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, bis [3- (trimethoxysilane) L) propyl] amine, N, N-bis- [3- (trimethoxysilyl) propyl] ethylenediamine and the like; alkoxyalkyl-substituted alkoxysilanes; 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 a guanidyl group 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 they are more excellent in reactivity, acid catalysts, amine compounds and salts thereof, aminoalkyl group-substituted alkoxysilanes, aluminum alcoholates, aluminum acylates, salts of aluminum acylates, aluminosiloxy compounds, aluminum chelate compounds and the like One or more selected from a titanium-based organometallic catalyst such as an aluminum-based organometallic catalyst, a titanate ester, a titanium chelate compound and a partial hydrolyzate thereof, and a tin-based organometallic catalyst such as an alkyltin ester compound. Preferably, a titanium-containing organometallic catalyst containing titanium is more preferable, and tetraisopropoxytitanium, tetra-n-butoxytitanium and a partial hydrolyzate thereof are further more preferable, and tetra-n-butoxytitanium is most preferable.

  Further, for the purpose of adjusting the viscosity of the coating composition of the present invention to improve workability, and for the purpose of adjusting the curability of the composition, the hardness of the obtained coating film, the flexibility, etc., depending on the intended use. 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, The components may be mixed separately from the organopolysiloxane compound.

Furthermore, the coating composition of the present invention is preferably in a solvent-free form that does not substantially contain an organic solvent (often harmful to humans and has flammability). Can be used by adding a solvent.
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 organopolysiloxane compound (A).
Note that the solvent also includes a solvent that is not a component intentionally added to the coating composition, such as a reaction solvent that could not be completely removed by distillation under reduced pressure.

  The coating composition of the present invention may contain 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 above-described coating composition of the present invention is applied to the surface of a solid substrate and cured to form a coating layer, whereby a coated solid substrate as a cured article is obtained.
The application 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, phenolic resins, polycarbonates and polycarbonate blends, acrylic resins such as poly (methyl methacrylate), poly (ethylene terephthalate), and poly (butylene terephthalate). ), Polyester resin such as unsaturated polyester resin, polyamide resin, polyimide resin, acrylonitrile-styrene copolymer, styrene-acrylonitrile-butadiene copolymer, polyvinyl chloride resin, polystyrene resin, blend of polystyrene and polyphenylene ether, cellulose Organic polymer base such as acetate butyrate and polyethylene resin, metal base 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, and glass fiber products such as glass cloth, glass tape, glass mat, and glass paper, and the like. 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 comes into contact with moisture in the atmosphere, the hydrolysis-condensation reaction of the organopolysiloxane compound (A) proceeds, and the curing reaction starts. As an index of moisture in the atmosphere, any humidity of 10 to 100% RH may be used, and moisture in the air is sufficient. However, in general, the higher the humidity, the faster the hydrolysis proceeds. May be added.
The curing reaction temperature and time can be appropriately changed depending on factors such as the substrate used, the water concentration, the catalyst concentration, and the type of the hydrolyzable group. Usually, it is about 5 minutes to 1 week within a range not exceeding the heat resistant temperature of the base material used.
Since the coating composition of the present invention cures well even at room temperature, especially when room temperature curing is indispensable for on-site construction or the like, stickiness (tack) on the coating film surface is eliminated in several minutes to several hours, Although excellent in workability, heat treatment may be performed within a range not exceeding the heat resistance temperature of the base material.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the following, the viscosity of each product is a value measured at 25 ° C. using a B-type rotational viscometer, and the molecular weight is determined by using a GPC (gel permeation chromatograph) apparatus manufactured by Tosoh Corporation, using toluene as a solvent, detecting Weight average molecular weight (hereinafter Mw) in terms of polystyrene determined by GPC measurement using RI as an analyzer.
The average silicone composition was calculated from the integrated value of the detected spectrum in ¹ H-NMR and b ²⁹ Si-NMR using a 300 MHz-NMR measuring apparatus manufactured by JEOL Ltd.
The content (% by mass) of the silanol hydroxyl group contained in each product was determined from the amount of methane gas generated when a Grignard reagent (methylmagnesium iodide) was allowed to act on each product.
In the following silicone average 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) In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, methyltrimethoxysilane 1 was added. 158 g of vinylmethyldimethoxysilane and 198 g of vinylmethyldimethoxysilane were charged, and under stirring, 188 g of 0.05 N 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 by-product methanol at normal pressure, and then filtered to obtain 850 g of organopolysiloxane (a1). The obtained organopolysiloxane (a1) is a colorless and transparent liquid, having a viscosity of 45 mm ² / s, an average composition Me _1.00 Vi _0.14 SiO _1.13 (OCH ₃ ) _0.60 , a Mw of 1,740, and a silanolic hydroxyl group content of 0.1. % By mass.

[Synthesis Example 2] Synthesis of organopolysiloxane (a2) 1,090 g of methyltrimethoxysilane and 264 g of vinylmethyldimethoxysilane were charged into a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. Under stirring, 151 g of 0.05 N hydrochloric acid was added dropwise at 25 ° C, and the mixture was hydrolyzed and condensed at 70 ° C for 2 hours. This was heated to 120 ° C. to distill off by-product methanol at normal pressure, and then filtered to obtain 920 g of organopolysiloxane (a2). The obtained organopolysiloxane (a2) is a colorless and 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 content of silanolic hydroxyl group of 0.5% by mass. Met.

Synthesis Example 3 Synthesis of Organopolysiloxane (a3) 1,342 g of methyltrimethoxysilane and 20 g of vinylmethyldimethoxysilane were charged into a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. Under stirring, 225 g of 0.05 N hydrochloric acid was added dropwise at 25 ° C., and the mixture was hydrolyzed and condensed at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off by-product methanol at normal pressure, and then filtered to obtain 743 g of organopolysiloxane (a3). The obtained 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 of 8,200, and a silanolic hydroxyl group content of 0.2. % By mass.

[Comparative Synthesis Example 1] Synthesis of organopolysiloxane (a4) 954 g of methyltrimethoxysilane and 361 g of dimethyldimethoxysilane were charged into a 2 L separable flask equipped with a stirrer, a reflux condenser and a thermometer, and stirred at 25 ° C. Then, 190 g of 0.05N-hydrochloric acid was added dropwise, followed by hydrolysis and condensation at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off by-product methanol at normal pressure, and then filtered to obtain 790 g of organopolysiloxane (a4). The obtained organopolysiloxane (a4) is a colorless and transparent liquid, having 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 silanol-containing hydroxyl group content of 0. It was 0.5% by mass. The organopolysiloxane (a4) has a structure in which a methylsiloxane unit (T unit) and a dimethylsiloxane unit (D unit) are randomly incorporated in an average silicone composition.

[Comparative Synthesis Example 2] Synthesis of organopolysiloxane (a5) In 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 under 0 ° C. 180 g of 0.05N-hydrochloric acid was added dropwise and hydrolyzed and condensed at 70 ° C. for 2 hours. This was heated to 120 ° C. to distill off 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, 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) 954 g 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, and stirred under 25 g. 190 g of 0.05 N hydrochloric acid was added dropwise at 70 ° C, and the mixture was hydrolyzed and condensed at 70 ° C for 2 hours. This was heated to 120 ° C. to distill off by-product 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 having a viscosity of 80 mm ² / s, an average composition 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 a methylsiloxane unit (T unit) and a diphenylsiloxane unit ( ^DΦ unit) are randomly incorporated in an average silicone composition.

[2] Synthesis of organopolysiloxane compound [Example 1-1] Synthesis of organopolysiloxane compound (A1) Organopolysiloxane (a1) was placed in a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer. 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 the internal temperature was raised to 80 ° C. by heating, the toluene solution of the platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of the platinum complex relative to the whole solution (platinum) 0.96 g) was added. After completion of the addition, the hydrosilylation reaction was carried out while heating to an internal temperature of 80 ° C., and after aging the reaction solution for 8 hours, disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Thereafter, distillation under reduced pressure (80 ° C., 5 mmHg) was performed for 1 hour, and filtration was performed to obtain 152 g of the corresponding organopolysiloxane compound (A1). 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) was prepared by the above formula (8). Then, 5.7 g of the hydrosilyl group-containing organosilicon compound to be used was placed and mixed with stirring. Then, when the internal temperature was raised to 80 ° C. by heating, the toluene solution of the platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of the platinum complex relative to the whole solution (platinum) 0.96 g) was added. After completion of the addition, the hydrosilylation reaction was carried out while heating to an internal temperature of 80 ° C., and after aging the reaction solution for 8 hours, disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Thereafter, distillation under reduced pressure (80 ° C., 5 mmHg) was performed for 1 hour, and the mixture was filtered to obtain 154 g of the corresponding organopolysiloxane compound (A2). The obtained organopolysiloxane compound (A2) was a colorless and 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, a reflux condenser and a thermometer, 150 g of organopolysiloxane (a3) was prepared by the above formula (8). Then, 0.9 g of the hydrosilyl group-containing organosilicon compound to be used was placed and mixed with stirring. Then, when the internal temperature was raised to 80 ° C. by heating, the toluene solution of the platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of the platinum complex relative to the whole solution (platinum) 0.96 g) was added. After completion of the addition, the hydrosilylation reaction was carried out while heating to an internal temperature of 80 ° C., and after aging the reaction solution for 8 hours, disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Thereafter, distillation under reduced pressure (80 ° C., 5 mmHg) was performed for 1 hour, and the mixture was filtered to obtain 146 g of the corresponding organopolysiloxane compound (A3). 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) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), a hydrosilyl group-containing organic compound represented by the following average structural formula (9) The reaction was carried out in the same manner as in Example 1-1, except that 67 g of the silicon compound was used, to obtain 210 g of the corresponding organopolysiloxane compound (A4). 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), a hydrosilyl group-containing organic compound represented by the following average structural formula (10) The reaction was carried out in the same manner as in Example 1-1, except that 71 g of the silicon compound was used, to obtain 215 g of the corresponding organopolysiloxane compound (A5). 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) Instead 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 using, 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), a hydrosilyl group-containing organic compound represented by the following average structural formula (12) The reaction was carried out in the same manner as in Example 1-1, except that 10 g of the silicon compound was used, to obtain 156 g of the corresponding organopolysiloxane compound (A7). 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 carried out in the same manner 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 and 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), a hydrosilyl group-containing organic compound represented by the following average structural formula (14) The reaction was carried out in the same manner as in Example 1-1, except that 9.7 g of the silicon compound was used, to obtain 154 g of the corresponding organopolysiloxane compound (A9). The obtained organopolysiloxane compound (A9) was a colorless transparent liquid having a viscosity of 158 mm ² / s.

[Example 1-10] Synthesis of organopolysiloxane compound (A10) 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 (15) The reaction was carried out in the same manner 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 a hydrosilyl group-containing organosilicon represented by the above formula (8) was used. The reaction was carried out in the same manner as in Example 1-1, except that 229 g of the compound was used, to obtain 375 g of the corresponding organopolysiloxane compound (A11). 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) The reaction was carried out in the same manner as in Example 1-1, except that 4 g was used, 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) Instead of the hydrosilyl group-containing organosilicon compound represented by the above formula (8), a hydrosilyl group-containing organic compound represented by the following average structural formula (17) The reaction was carried out in the same manner as in Example 1-1, except that 90.4 g of the silicon compound was used, to obtain 235 g of the corresponding organopolysiloxane compound (A13). The obtained organopolysiloxane compound (A13) was a colorless and transparent liquid having a viscosity of 305 mm ² / s.

[Comparative Example 1-4] Synthesis of organopolysiloxane compound (A14) A hydrosilyl group having an average structural formula represented by the following formula (18) instead of the hydrosilyl group-containing organosilicon compound represented by the formula (8) The reaction was carried out in the same manner as in Example 1-1, except that 39.2 g of the contained 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] organopolysiloxane compound (A15) Synthesis stirrer, to a separable flask equipped with a reflux condenser and a thermometer, toluene 150 g, average structural formula _{(C 6 H 5 SiO 3/2)} 0.75 [(CH ₃ ) ₂ (CH ₂ ＣＨCH) SiO _1/2 ] 58.6% by mass of an organopolysiloxane (Mw = 1,560, silanolic hydroxyl group content 4.1% by mass) represented by _0.25 205 g of the solution and 9.8 g of the hydrosilyl group-containing organosilicon compound represented by the above formula (8) were placed and mixed with stirring. Then, when the internal temperature was raised to 80 ° C. by heating, the toluene solution of the platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0), 0.5% by mass of the platinum complex relative to the whole solution (platinum) 1.65 g) were added. After completion of the addition, the hydrosilylation reaction was carried out while heating to an internal temperature of 80 ° C., and after aging the reaction solution for 8 hours, disappearance of the hydrosilyl group was confirmed by IR analysis of the reaction solution and measurement of the amount of hydrogen gas generated. . Thereafter, distillation under reduced pressure (80 ° C., 5 mmHg) was performed for 1 hour, and the mixture was cooled to 25 ° C. to obtain 117 g of the corresponding organopolysiloxane compound (A15). 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), a hydrosilyl group-containing organosilicon compound represented by the above formula (12) The reaction was carried out in the same manner as in Comparative Example 1-5, except that 2 g was used, 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 and 5 parts by mass of tetra-n-butoxytitanium as a curing catalyst are uniformly mixed using a stirrer, and a coating composition is obtained. Was prepared.
The obtained coating composition was treated with a bar coater No. 25 in air at 25 ° C. and 50% RH. Using No. 14, the composition was applied to a glass plate or a polished steel plate, and dried and cured at 25 ° C. and 50% RH for 1 day to form a cured film.

[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. The obtained organopolysiloxane compounds (A11) to (A16), the organopolysiloxanes (a4) to (a6) obtained in Comparative Synthesis Examples 1 to 3, and the organopolysiloxane (a1) obtained in Synthesis Example 1. The coating composition and the cured film were prepared in the same manner as in Example 2-1 except that the respective components were changed.

[Example 2-11]
Except for using 5 parts by mass of di-n-butoxy (ethylacetoacetate) aluminum instead of 5 parts by mass of tetra-n-butoxytitanium, the coating composition and curing were performed in the same manner as in Example 2-1. A coating was prepared.

The following evaluations were performed on the cured films produced in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 10 described above. The results are shown in Tables 1 and 2.
(Touch dry time)
A test piece obtained by applying the coating composition to a glass plate by the above-mentioned application method is left in the air at 25 ° C. and 50% RH, and the moisture hardening proceeds, so that the application surface can be pressed with a finger. The time (minute) until the coating film did not adhere to the finger was shown. The smaller the value, the better the curability.
[Crack resistance]
The test piece obtained by forming a cured film on a glass plate by the above-mentioned coating method was subjected to heat treatment in a 150 ° C. oven for 2 hours, and the presence or absence of cracks in the cured film was visually observed.
When no crack was observed, it was evaluated as “「 ”as having excellent crack resistance. When one crack was observed, it was evaluated as “△”. When two or more cracks were observed, the evaluation was "x".
〔Pencil hardness〕
A test piece having a cured film formed on a glass plate by the above coating method was measured by applying a load of 750 g according to a pencil scratch test described in JIS K 5600, and the results were shown.
(Shock resistance)
A test piece obtained by forming a cured coating on a polished steel plate by the above-mentioned coating method is sandwiched between a shooting die and a pedestal using a Dupont-type drop impact tester described in JIS K 5600. A 500 g weight was dropped, and the presence or absence of cracking and peeling of the test piece due to impact deformation was visually observed. At this time, the drop height (cm) at the stage where abnormalities such as cracks and peeling were observed on the coating film surface was shown. The larger the value, the better the impact resistance.
(Yellowing resistance)
A UV irradiation test was performed on the test piece having a cured film formed on a glass plate by the above-mentioned coating method using a germicidal lamp at 25 ° C. and 50% RH for 2 weeks. At this time, the degree of yellowing of the cured film was evaluated by ΔYI (yellowing degree = change width of yellowness YI) using a color difference meter described in JIS K 7373. The smaller the value, the better the yellowing resistance.

As shown in Tables 1 and 2, curing prepared 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, and is excellent in curability and yellowing resistance as compared with the cured film produced in each comparative example.
On the other hand, the cured films produced in Comparative Examples 2-1 to 2-4 and 2-7 to 2-10 cannot realize both hardness, crack resistance and impact resistance, and have curability, Some film properties such as yellowing resistance are also insufficient.
In Comparative Examples 2-5 and 2-6, the obtained organopolysiloxane compounds (A15) and (A16) were solidified and could not be formed into a coating film.

  As described above, the organopolysiloxane compound of the present invention is excellent in curability, and has a balance between hardness, crack resistance and impact resistance, which has been difficult with conventional silicone resins and silicone alkoxy oligomers. And a cured film having excellent yellowing resistance can be obtained.

Claims (12)

An organopolysiloxane compound comprising a hydrosilylation reaction product of the following siloxane compound (a) and a hydrosilyl group-containing organosilicon compound (b).
(A) A siloxane compound 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)
(Wherein, 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, 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,
R ² independently represents an aliphatic carbon-carbon double bond-containing group having 2 to 15 carbon atoms;
Xs each independently represent 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 (however, X is not only a hydroxyl group; .),
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 ≤ 2.54 . )
(B) One or more hydrosilyl group-containing organosilicon compounds selected from the following (b1) to (b5):
(B1) a hydrosilyl group-containing organosilicon compound having an average structural formula represented by the following general formula (2)

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

(In the formula, R ¹ independently represents the same meaning as in the formula (1).)
(B3) a hydrosilyl group-containing organosilicon compound having an average structural formula represented by the following general formula (4)

(Wherein, R ¹ independently represents the same meaning as in the formula (1), and R ³ independently represents an aryl having 6 to 14 carbon atoms which may be substituted by Z.) Represents a group or an aralkyl group having 7 to 17 carbon atoms, Z represents the same meaning as in the above formula (1),
m represents an integer of 1 to 5, n represents an integer of 0 to 4, and m + n satisfies the integer of 1 to 5. )
(B4) a 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) a hydrosilyl group-containing organosilicon compound represented by the following general formula (6)

(Wherein, R ¹ independently of ^one another has 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 is 3 Satisfies the integer of ~ 6.)   The organopolysiloxane compound according to claim 1, wherein X is a combination of a hydroxyl group and an alkoxy group having 1 to 10 carbon atoms.   The organo according to claim 1 or 2, wherein the (b) hydrosilyl group-containing organosilicon compound includes one or more hydrosilyl group-containing organosilicon compounds selected from (b1), (b3) and (b4). Polysiloxane compounds.   The organopolysiloxane compound according to claim 3, wherein the (b) hydrosilyl group-containing organosilicon compound includes the (b1) hydrosilyl group-containing organosilicon compound. The organopolysiloxane compound according to claim 4, wherein the hydrosilyl group-containing organosilicon compound (b1) is represented by the following general formula (7).

The siloxane compound (a) and the hydrosilyl group-containing organosilicon compound (b) are reacted with the siloxane compound in the presence of a hydrosilylation reaction catalyst with respect to 1 mol of the Si—H group of the hydrosilyl group-containing organosilicon compound (b) . The method for producing an organopolysiloxane compound according to any one of claims 1 to 5, wherein the hydrosilylation reaction is performed within a range of 1 to 10 mol of the alkenyl group directly bonded to the Si atom in (a). The siloxane compound (a) and the hydrosilyl group-containing organosilicon compound (b) are reacted with the siloxane compound in the presence of a hydrosilylation reaction catalyst with respect to 1 mol of the Si—H group of the hydrosilyl group-containing organosilicon compound (b) . 7. The method for producing an organopolysiloxane compound according to claim 6, wherein the hydrosilylation reaction is carried out in the range of 2 to 6 mol of the alkenyl group directly bonded to the Si atom in (a). A coating composition comprising (A) the organopolysiloxane compound according to any one of claims 1 to 5 and (B) a curing catalyst.   The curing catalyst (B) is one or more selected from the group consisting of an acid catalyst, an amine compound and a salt thereof, an aminoalkyl-substituted alkoxysilane, and an aluminum-based, titanium-based, and tin-based organometallic catalyst. The coating composition according to claim 8, wherein   The coating composition according to claim 8 or 9, wherein the (B) curing catalyst is an organometallic catalyst containing titanium.   The coating composition according to any one of claims 8 to 10, wherein the content of the solvent is 1% by mass or less.   A cured article obtained by curing the coating composition according to any one of claims 8 to 11.