JPH10324749A - Epoxy group-bearing organopolysilsesquioxane and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy group-bearing organopolysilsesquioxane of high stability and high reactivity and its production process. SOLUTION: An organopolysilsesquioxane bearing whole side-chain mercapto groups in which the main chain terminuses are substituted with end-cap groups more than 75 mol.% and the whole side chains are organic groups having a mercapto group and the number-average molecular weight is 5×10<2> -1.5×10<4> is allowed to react with an epoxy group-bearing ethylenically unsaturated compound or with a combination thereof with an alkyl (meth)acrylate in the presence of a radical initiator to prepare the objective epoxy group-containing organopolysilsesquioxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an organopolysilsesquioxane containing an epoxy group and a method for producing the same.

[0002]

2. Description of the Related Art Ladder-shaped organopolysiloxanes represented by the general formula [-R (R ') SiO3 _{/ 2-} ] are commonly called ladder silicones, and their unique structures and performances have been noticed for a long time, and many studies have been made. Have been. Nakahama et al. Attempted to synthesize a ladder silicone having an organic group other than an alkyl group such as a methyl group and an aryl group such as a phenyl group as a side chain (R, R ′ in the above general formula) of the ladder silicone. Reported that ladder silicones having both vinyl or methacryloxypropyl groups and phenyl groups in the side chain were successfully synthesized (Polymer Preprints Japan, 29
73 (1980)).

A ladder silicone having an aralkyl group or a halogen-substituted derivative thereof in addition to the above-mentioned alkyl group, aryl group and alkenyl group as a side chain has been proposed (for example, Japanese Patent Application Laid-Open No. 50-111198). JP-A-3-20331). Further, γ of ladder silicone containing a methyl group or a phenyl group in a side chain
Photopolymerizable silicone compounds used for resists by reacting -methacryloxyalkyl trialkoxysilanes (JP-A-57-12057) or γ-methacryloxyalkyldimethylchlorosilane (JP-A-512057).
No. 9-217282), a ladder silicone having a side chain of a methyl group and a γ-methacryloxy group in a ratio of 5/1 has ω-
Ladder silicone containing a mercapto group reacted with dimercapto-modified dimethylpolysiloxane (JP-A-5-125)
192) and a graft-modified ladder silicone (JP-A-6-41307) in which a linear polysiloxane containing at least one unsaturated group or mercapto group per molecule is grafted to a side chain. Synthesis of a ladder silicone containing 12.5 to 20 mol% of the unsaturated group or mercapto group has been reported.

The side chain is preferably at least one organic group selected from an alkyl group having 1 to 3 carbon atoms and a substituted or unsubstituted phenyl group in addition to an unsaturated group or a mercapto group. The example illustrates a ladder silicone having a methyl group of 70 mol% or more. However, in this production method, since the reactivity of the silicone monomer having a methyl group (methyltriethoxysilane in the example) is very high, a ladder silicone in which a mercapto group is not actually introduced into a side chain occurs, and a more uniform ladder silicone occurs. It is difficult to obtain a ladder silicone having high reactivity.

On the other hand, as a method of introducing an epoxy group into the side chain of the ladder silicone, for example, a hydrolysis and condensation polymerization method of a trialkoxysilane monomer having an epoxy group can be easily conceived. In this method, ring opening of the epoxy group occurs and the target product cannot be easily obtained. For some reason, in some patent specifications, patent publications listing epoxy groups as types of functional groups in the side chain are scattered, but as specific examples, organopolysilyl having an epoxy group in the side chain. No synthetic examples of sesquioxane have been found so far.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organopolysilsesquioxane which is stable, does not cause gelation, and has a uniform and highly reactive epoxy group in a side chain. is there. Still another object of the present invention is to propose a method for efficiently producing the above-mentioned organopolysilsesquioxane.

[0007]

Means for Solving the Problems The present inventors have intensively studied to obtain an organopolysilsesquioxane which is stable, does not cause gelation, and has a uniform and highly reactive epoxy group in the side chain. As a result, the organopolysilsesquioxane having a specific molecular weight, and the main chain terminal group is substituted with an endcap group, and having a specific functional group on all side chains, and an epoxy group-containing compound, or further, The present inventors have found that the above object can be achieved by an addition reaction product of the compound and an alkyl (meth) acrylate compound, and have completed the present invention.

That is, the first of the present invention is 5 × 10 ^{2 to} 1.5.
An organopolysilsesquioxane having a number average molecular weight of × 10 ⁴ , a main chain terminal group substituted by an end cap group of 75 mol% or more, and all side chains being a mercapto group; An epoxy group-containing organopolysilsesquioxane characterized by comprising an addition reaction product with a compound. The second aspect of the present invention is 5 × 10 ² to
It has a number average molecular weight of 1.5 × 10 ⁴ and has a main chain terminal group of 7
An addition reaction product of an organopolysilsesquioxane substituted with 5 mol% or more of endcap groups and having all side chains being a mercapto group, an epoxy group-containing ethylenically unsaturated compound, and an alkyl (meth) acrylate. It is an organopolysilsesquioxane containing an epoxy group, characterized in that: The third aspect of the present invention is 5 × 10 ² -1.
An organopolysilsesquioxane having a number average molecular weight of 5 × 10 ⁴ , wherein the main chain terminal group is substituted by at least 75 mol% by an endcap group, and all side chains are mercapto groups,
A process for producing an epoxy group-containing organopolysilsesquioxane, comprising subjecting an epoxy group-containing ethylenically unsaturated compound to a Michael addition reaction in the presence of a radical initiator. A fourth aspect of the present invention is 5 × 10 ^{2 to} 1.5 × 10 ^4.
An organopolysilsesquioxane having a number-average molecular weight of at least 75 mol% of the main chain terminal group substituted by an endcap group and all side chains being a mercapto group, and an epoxy group-containing ethylenically unsaturated compound (a )) And alkyl (meth) acrylate (b) in a molar ratio of (a)
/ (B) = 99/1 to 1/99 in a Michael addition reaction in the presence of a radical initiator, which is a process for producing an epoxy group-containing organopolysilsesquioxane.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, "(meth) acryl-" means "acryl and / or methacryl-". The organopolysilsesquioxane containing all side chain mercapto groups used as a raw material in the present invention is a ladder silicone having m repeating "silsesquioxanes" represented by the following formula [1].

[0010]

Embedded image (Wherein, R ¹ and R ² are each an organic group containing a mercapto group, 75 mol% or more of OR ^{3 to} OR ⁶ is an end cap group, the remainder is a hydroxyl group and / or an alkoxy group, and m is a natural number. Represent)

The side chains R ¹ and R ^{2 in the} silsesquioxane unit represented by the above formula [1] are represented by the general formula HS
R ⁷ - (wherein, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms) and an organic group containing a mercapto group represented by. Examples of the divalent hydrocarbon group represented by R ⁷ include an ethylene group, a propylene group, and a trimethylene group.

The organopolysilsesquioxane containing all side chain mercapto groups represented by the formula [1] has a main chain terminal group OR
³ 75% or more ～OR ⁶ is replaced by the end-capping group, the remainder being hydroxyl and / or alkoxy groups. The end-capping group is exemplified silyloxy group, in alkoxy group -OR ⁸ (wherein, R ⁸ is 1 to carbon atoms
6, preferably 1 to 3 alkyl groups).

The silyl group constituting the silyloxy group is represented by the following formula [2].

Embedded image (In the formula, R ⁹ , R ¹⁰ , and R ¹¹ represent a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms and may be the same or different.)

The proportion of the main chain terminal group substituted by the end cap group is, for example, ¹ H, ¹³ C and ²⁹ Si-NM.
It can be calculated by calculating the total number of hydroxyl groups and alkoxy groups remaining in the main chain terminal groups from the peak intensities of the NMR curves obtained by the R measurement. Generation can be prevented and excellent storage stability can be imparted.

The number average molecular weight of the organopolysilsesquioxane containing mercapto groups in all side chains of the present invention is 5 × 10 ^2.
１．５1.5 × 10 ⁴ , and m in equation [1] is a numerical value corresponding to this value. It is difficult to form a silsesquioxane structure having a number average molecular weight of less than 5 × 10 ² , and if the number average molecular weight exceeds 1.5 × 10 ⁴ , the compatibility with general-purpose solvents becomes insufficient. The number average molecular weight is measured by gel permeation chromatography (abbreviated as GPC), which is already widely used as a general measuring method, using polystyrene as a standard substance.

The epoxy group-containing organopolysilsesquioxane of the present invention is obtained by reacting the all-chain mercapto group-containing organopolysilsesquioxane represented by the above formula [1] with an epoxy group-containing ethylenically unsaturated compound. It is an addition reactant. This addition reactant is obtained, for example, by a Michael addition reaction between a side chain —SH group and an ethylenically unsaturated double bond in the presence of a radical initiator.

Examples of the epoxy group-containing ethylenically unsaturated compound include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate,
Allyl glycidyl ether and the like are exemplified.

The first epoxy group-containing organopolysilsesquioxane of the present invention is represented by the following formula [3].

Embedded image (Wherein OR ^{3 to} OR ⁶ are the same as described above, and R ¹² and R ¹³ are each an organic group formed by an addition reaction between an organic group having a mercapto group and an epoxy group-containing ethylenically unsaturated compound, m is a natural number.)

Further, the second epoxy group-containing organopolysilsesquioxane of the present invention comprises an alloside chain mercapto group-containing organopolysilsesquioxane represented by the above formula [1] and an epoxy group-containing ethylenic compound. It is an addition reaction product with an unsaturated compound and an alkyl (meth) acrylate. These addition reactants can be easily obtained by, for example, a Michael addition reaction between a side chain —SH group and an ethylenically unsaturated double bond in the presence of a radical initiator. The usage ratio of the epoxy group-containing ethylenically unsaturated compound (a) and the alkyl (meth) acrylate (b) may be arbitrarily determined, and (a) / (b) may be determined according to the required amount of epoxy group.

The alkyl (meth) acrylate used in the present invention is represented by the following formula [4].

Embedded image (Wherein, R ¹⁴ is hydrogen or a methyl group, R ¹⁵ is carbon number 1 to
20 alkyl groups. )

The second epoxy group-containing organopolysilsesquioxane of the present invention is represented by the following formula [5].

Embedded image (Wherein, OR ^{3 to} OR ⁶ are the same as described above, and R ¹⁶ and R ¹⁷ are the addition of an organic group having a mercapto group to an epoxy group-containing ethylenically unsaturated compound and an alkyl (meth) acrylate, respectively) An organic group generated by the reaction, and m is a natural number.)

The organopolysilsesquioxane containing all side chain mercapto groups used in the present invention can be produced by hydrolyzing a mercapto group-containing trialkoxysilane or a mercapto group-containing trihalosilane as a raw material and subjecting it to condensation polymerization. it can. Examples of the mercapto group-containing trialkoxysilane used in producing the all side chain mercapto group-containing organopolysilsesquioxane include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and mercapto group-containing trihalo. Examples of the silane include γ-mercaptopropyltrichlorosilane. The organopolysilsesquioxane containing all side chain mercapto groups is composed of 1 to 8 moles of water and 0.005 to 0.05 mole of 1 mole of the corresponding raw material monomer. By hydrolysis and polycondensation in the presence of an acid catalyst described above, removing the salt formed after neutralization with alkali, and further end-capping the main chain terminal.

In the hydrolysis and polycondensation, if the amount of water used is less than 1 mol, the hydrolysis does not proceed sufficiently and it is difficult to obtain the desired molecular weight. An exothermic reaction occurs, which makes the control of the reaction difficult and undesirably causes the product to easily gel.
The amount of the acid catalyst used in the hydrolysis and polycondensation is 0.005 to 0.05 times mol per mol of the raw material monomer. When the amount of the acid catalyst is less than 0.005 mol, the rate of hydrolysis and condensation polymerization becomes extremely slow and inefficient, and it is difficult to obtain the target molecular weight. Not only does a rapid reaction occur, which makes reaction control difficult, and irregular three-dimensional polycondensation occurs, so that not only the highly ordered ladder structure aimed at by the present invention cannot be obtained, but also gelation of the product. Is more likely to occur. Examples of the acid catalyst to be used include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid and oxalic acid.

The reaction conditions are not particularly limited, but generally the reaction temperature is usually 0 to 100 ° C., and the reaction time is about 1 to 24 hours. In order to carry out the reaction more efficiently and to increase the regularity of the ladder structure, the first hydrolysis reaction is carried out at a relatively low temperature such as 0 to 20 ° C. for about 0.5 to 1 hour, and subsequently at 40 to 100 ° C. Preferably 60-8
It is desirable to carry out the reaction at 0 ° C. for 1 to 10 hours.

The polycondensation reaction is stopped by neutralizing the reaction solution with an alkali, and the resulting salt is removed by filtration or washing with water or a combination of both. If necessary, prior to the desalting operation, if the coexisting water is sufficiently removed, a solvent having an azeotropic property with the water, for example, alcohols such as ethyl alcohol, esters such as ethyl acetate and butyl acetate, A distillation operation may be performed by adding an aromatic hydrocarbon such as xylene or toluene. Examples of the alkali used in the present invention include metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic amine compounds such as n-butylamine and triethylamine.

Subsequently, the hydroxyl group and / or the alkoxy group at the terminal of the main chain of the organopolysilsesquioxane containing all side chain mercapto groups obtained by the above method are subjected to a silylation reaction using a monofunctional silylating agent. Thereby, at least 75 mol% or more of the main chain terminal is substituted with an end cap group.

When the substitution of the end of the main chain with an end cap group is less than 75 mol% on average, the stability of the organopolysilsesquioxane containing all side chain mercapto groups is low, gelation is liable to occur, and furthermore, epoxy resin It is not preferable because gelation easily occurs at the time of addition reaction with a group-containing ethylenically unsaturated compound or the like.

The silylation reaction is carried out by adding the following silylating agent to an organopolysilsesquioxane solution containing all side chain mercapto groups. The silylating agent may be one containing no halosilane and hardly affected by excess water used for hydrolysis, or one itself hydrolyzed in an acidic atmosphere to become a silylating agent.

As the silylating agent, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol,
Compounds such as hexamethyldisiloxane, hexaethyldisiloxane, acetyltriphenylsilane, ethoxytriphenylsilane, trimethylmethoxysilane, triethylmethoxysilane, and triethylethoxysilane are exemplified.

In a preferred embodiment of the present invention, trimethylsilylation can be carried out by reacting trimethylsilanol with all the side chain mercapto group-containing organopolysilsesquioxane as a raw material. It is also effective to react the organopolysilsesquioxane under acidic conditions with hexamethyldisiloxane as a silylating agent. As reaction conditions in this case, hexamethyldisiloxane is used in a slightly excessive amount from a predetermined amount, and as a solvent, for example, a small amount of ethyl alcohol is used, and 50 to 100
The temperature is selected from 1 to 8 hours at a temperature of ° C, but is not necessarily limited to these reaction conditions.

In a preferred embodiment of the present invention, when a mercapto group-containing trialkoxysilane is hydrolyzed and polycondensed as a solvent in the step of replacing the main chain terminal group with an endcap group (silylation reaction), By-product alcohols (preferably methyl alcohol, ethyl alcohol or a mixture thereof) can be used.

The epoxy group-containing ethylenically unsaturated compound to be subjected to the addition reaction with the all-chain mercapto group-containing organopolysilsesquioxane is as described above.
As the alkyl (meth) acrylate (b),
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, iso-butyl acrylate, 2-ethylhexyl acrylate, iso-decyl acrylate, lauryl acrylate, tri-decyl acrylate, stearyl acrylate, cyclohexyl acrylate, iso acrylate
-Boronyl, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, iso-decyl methacrylate, lauryl methacrylate, tri-decyl methacrylate, stearyl methacrylate, methacrylic Examples thereof include cyclohexyl acid and iso-boronyl methacrylate. These may be used alone or in combination of two or more. Among them, methyl acrylate, ethyl acrylate,
Preferred are n-butyl acrylate, methyl methacrylate, and n-butyl methacrylate.

The first epoxy group-containing organopolysilsesquioxane of the present invention comprises the above-mentioned all-chain mercapto group-containing organopolysilsesquioxane and the epoxy group-containing ethylenically unsaturated compound in the presence of a radical initiator. It can be produced by reacting the following. The second epoxy group-containing organopolysilsesquioxane is composed of the all-side-chain mercapto group-containing organopolysilsesquioxane and the epoxy group-containing ethylenically unsaturated compound (a) and the alkyl (meth) acrylate (b) ) In a molar ratio of (a) / (b) = 99/1 to 1/99 in the presence of a radical initiator. In the above, the proportion of the organopolysilsesquioxane containing all side chain mercapto groups and the mixture of the above (a) or (a) and (b) is in the range of about ± 30% based on the equivalent weight in the reaction of both. It is good.

Examples of the radical initiator include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azobisisobutyronitrile, dimethyl 2,2'-azobis ( An azo compound such as 2-methylpropionate) is used. The addition reaction is preferably performed in an organic solvent, such as methyl alcohol, ethyl alcohol,
Examples include alcohols such as 2-propanol, acid esters such as ethyl acetate and n-butyl acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, and 4-methyl-2-pentanone. The amount of the radical initiator used is the amount of the epoxy group-containing ethylenically unsaturated compound or the epoxy group-containing ethylenically unsaturated compound to be reacted with all the side chain mercapto group-containing organopolysilsesquioxane and the alkyl (meth) acrylate. It is 0.0001 to 0.5 times mol, preferably 0.01 to 0.1 times mol for the mixture.

In the addition reaction, first, an organopolysilsesquioxane containing all side-chain mercapto groups is dissolved in an organic solvent, and an epoxy group-containing ethylenically unsaturated compound or an epoxy group-containing ethylene The method of dropping a mixture of the unsaturated compound and the alkyl (meth) acrylate and the radical initiator little by little is preferable. The reaction conditions in this case are generally 5
The reaction is carried out at a reaction temperature of 0 to 100 ° C. for 1 to 8 hours. The reaction is appropriately selected depending on the type of the unsaturated compound used, the reaction solvent, the initiator and the like.

The first and second epoxy group-containing organopolysilsesquioxanes of the present invention are very stable because the end of the main chain is substituted by at least 75 mol% of an end cap group. Since it has an epoxy group, it has good reactivity with polyvalent carboxylic acid-containing compounds, for example, maleic acid, fumaric acid, itaconic acid, and the like, and is useful as various coating materials by applying this fact.

[0037]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Production Examples, Examples, Comparative Examples, and Application Examples, but the present invention is not limited to these. In addition, each physical property value in an example was measured according to the following method. (1) Number average molecular weight: GPC method (2) Adhesion: Cross-cut method based on JIS K5400 method (mesh number: 100)

Production Example 1 Production of Organopolysilsesquioxane Containing All Side-Chain Mercapto Groups A nitrogen gas was introduced into a 500 ml glass flask equipped with a thermometer, stirrer, reflux condenser and tubes for introducing raw materials, reagents and nitrogen. 196.34 g (1,000 mmol) of γ-mercaptopropyltrimethoxysilane in purified water 5
4.06 g (3,000 mmol) were charged and the mixture was cooled to 5 ° C. Then, 3.6% hydrochloric acid aqueous solution 1
After 0.13 g (10 mmol) was added dropwise to the mixture over 30 minutes, the mixture was kept at 10 ° C. for 60 minutes. Subsequently, the mixture was heated in a warm water bath to 70 ° C., and the hydrolysis and condensation reaction was carried out for 3 hours under a nitrogen stream, and then 65 g (400 mmol) of hexamethyldisiloxane was added to carry out the silylation reaction. (Endcapping of main chain terminal)
After a period of time, the obtained reaction solution was cooled to 40 ° C. Next, the reaction solution was neutralized with an aqueous solution of potassium hydroxide and allowed to stand at room temperature for 12 hours. Further, the lower layer separated into two layers was extracted, and n-butyl acetate was added.
Distillation at 40 ° C. under a vacuum of mHg to remove 240 g of solvent, again adding 200 g of n-butyl acetate,
Stir for 1 hour. The obtained reaction solution was filtered through a 0.8 μm filter, and a colorless and transparent n-butyl acetate solution of an organopolysilsesquioxane containing all side-chain mercapto groups 9
00 g were obtained. The number average molecular weight of the polymer determined by the GPC method was 1,200, and ¹ H, ¹³ C and ²⁹ Si—N
The total number of hydroxyl groups and / or alkoxy groups at the terminal of the main chain determined by MR measurement was 20 mol% of the terminal groups of the main chain, and the stability at room temperature was excellent, and no gelation was observed even after 2 weeks of aging. .

In the thus obtained organopolysilsesquioxane containing all side chain mercapto groups, R ¹ and R ² in the above formula [1] are γ-mercaptopropyl groups, OR ³ to
It was confirmed that 20 mol% of OR ⁶ was a ladder silicone having a methoxy group, the rest being a trimethylsilyloxy group, and m = 3.6.

Example 1 Using the organopolysilsesquioxane containing all side chain mercapto groups produced in Production Example 1, an epoxy group-containing organopolysiloxane obtained from an addition reaction product of this with an epoxy group-containing ethylenically unsaturated compound. Polysilsesquioxane was produced by the following method. Organopolysilsesquioxane 50 containing all side chain mercapto groups produced in Production Example 1 under a nitrogen stream in a 500 ml glass flask equipped with a thermometer, a stirrer, a reflux condenser and an inlet tube for raw materials, reagents and nitrogen. 0.0 g (41.5 mmol) and ethyl alcohol 170 were charged, and the mixture was heated to 70 ° C. while stirring. Then, glycidyl methacrylate 40.4
g (284.2 mmol), 2.65 g of dimethyl 2,2'-azovir (2-methylpropionate) (11.
47 mmol) and 40 g of ethyl alcohol were preliminarily mixed, added dropwise to a solution of the above mixture over 60 minutes, and then subjected to an addition reaction at 70 ° C. for 3 hours. The obtained reaction solution was cooled to 40 ° C., and then the reaction solution was cooled to 200 ° C.
distilled at 40 mm C. to remove 200 g of solvent,
84.7 g of a colorless and transparent liquid was obtained.

The obtained epoxy group-containing organopolysilsesquioxane has a number average molecular weight of 2100, and the mercapto group reacts quantitatively with glycidyl methacrylate. According to ¹ H-NMR analysis, the unreacted mercapto group Was less than 5% of all side chains. In the epoxy group-containing organopolysilsesquioxane, OR ^{3 to} OR ⁶ in the above formula [5] are 20 mol% of a methoxy group and the remainder is a trimethylsilyloxy group, and R ¹⁶ and R ¹⁷ are represented by the following formulas [ 6], and m = 3.6.

Embedded image

Example 2 Using the organopolysilsesquioxane containing all side chain mercapto groups produced in Production Example 1, a mixture comprising an ethylenically unsaturated compound containing an epoxy group and an alkyl (meth) acrylate was used. The organopolysilsesquioxane containing an epoxy group obtained from the addition reaction product of was prepared by the following method. 500m equipped with a thermometer, stirrer, reflux condenser and feed pipes for raw materials, reagents and nitrogen
10.0 g (41.5 mmol) of the organopolysilsesquioxane containing all side chain mercapto groups produced in Production Example 1 and 162 g of ethyl alcohol in a 1 l glass flask under a nitrogen stream, and the mixture was stirred with stirring. At 70 ° C
Warmed up. Then, glycidyl methacrylate 1
2.1 g (85.1 mmol), methyl methacrylate 20.0 g (199.8 mmol), dimethyl 2,
2'-azobis (2-methylpropionate) 2.65
g (11.47 mmol) and ethyl alcohol 3
4 g was mixed in advance, and the mixture was added dropwise to a solution of the above mixture over 60 minutes, followed by addition reaction at 70 ° C. for 3 hours. After cooling the obtained reaction liquid to 40 ° C., the reaction liquid was distilled at 200 mmHg and 40 ° C. to remove 210 g of the solvent to obtain 81.5 g of a colorless and transparent liquid.

[0043] The number average molecular weight of the epoxy group-containing organopolysilsesquioxane is 2000, also, a mercapto group reacts quantitatively with glycidyl methacrylate and methyl methacrylate, the unreacted According to ¹ H-NMR analysis Mercapto groups accounted for less than 5% of all side chains. Further, the epoxy group-containing organopolysilsesquioxane is such that OR ^{3 to} OR ⁶ in the above formula [5] are such that 20 mol% is a methoxy group and the rest is a trimethylsilyloxy group;
R ¹⁶ and R ¹⁷ are a group represented by the above formula [6] and a group represented by the following formula [7], and their ratio is [6] / [7] =
29/71 (molar ratio), and m = 3.6.

[0044]

Embedded image

Example 3 The reaction was carried out in the same manner as in Example 2 except that the charge ratio of glycidyl methacrylate to methyl methacrylate was changed to 5/5 (molar ratio), and an epoxy group-containing organopolysiloxane having a number average molecular weight of 1800 was used. Rusesquioxane was obtained. The mercapto group reacted quantitatively with glycidyl methacrylate and methyl methacrylate. According to ¹ H-NMR analysis, the unreacted mercapto group was less than 5% of all side chains. Further, in the epoxy group-containing organopolysilsesquioxane, OR ^{3 to} OR ⁶ in the above formula [5] are such that 20 mol% is a methoxy group and the rest is a trimethylsilyloxy group;
¹⁶ and R ¹⁷ are groups represented by the above formulas [6] and [7], the ratio of which is [6] / [7] = 49/51 (molar ratio)
And m = 3.6.

Example 4 A reaction was carried out in the same manner as in Example 2 except that the charge ratio of glycidyl methacrylate to methyl methacrylate was changed to 3/7 (molar ratio), and an epoxy group-containing organopolysiloxane having a number average molecular weight of 1600 was used. Rusesquioxane was obtained. The mercapto group reacted quantitatively with glycidyl methacrylate and methyl methacrylate. According to ¹ H-NMR analysis, the unreacted mercapto group was less than 5% of all side chains. Further, in the epoxy group-containing organopolysilsesquioxane, OR ^{3 to} OR ⁶ in the above formula [5] are such that 20 mol% is a methoxy group and the rest is a trimethylsilyloxy group;
¹⁶ and R ¹⁷ are groups represented by the above formulas [6] and [7], and their ratio is [6] / [7] = 28/72 (molar ratio)
And m = 3.6. Table 3 shows the ¹ H-NMR analysis results of the epoxy group-containing organopolysilsesquioxane.

APPLICATION EXAMPLES 1 to 4 A composition was prepared by uniformly mixing the epoxy group-containing organopolysilsesquioxane resin obtained in Examples 1 to 4 at the mixing ratio shown in Table 1 below. Was applied to a 1.0 mm thick aluminum substrate (JIS A1050P) so as to have a dry coating thickness of 20 μm,
For 20 minutes. About the obtained coating film
According to the adhesion test method of IS K5400 Section 8.5,
The adhesion was evaluated by a grid test. Table 2 shows the results.

[0048]

[Table 1]

[0049]

[Table 2] * Appearance observation; good: almost no turbidity, good transparency very good: no turbidity, very good transparency ** 100/100; number of peeled pieces = 0 out of 100 squares (good adhesion)

[0050]

[Table 3]

[0051]

According to the first organopolysilsesquioxane containing an epoxy group of the present invention, the end of the main chain is substituted by at least 75 mol% with an end cap group, and the epoxy group is present on the side chain. It is stable, hardly causes gelation, and has high reactivity, and can be reacted with a compound such as a polyvalent carboxylic acid.

In the second organopolysilsesquioxane containing an epoxy group of the present invention, the terminal of the main chain is substituted by an end cap group of 75 mol% or more, and the epoxy group and the epoxy group are not present in the side chain. Since the compound is added, the compound is excellent in stability and has high reactivity, can adjust the content of the epoxy group, and can increase compatibility with other resins and solvents.

The method for producing the epoxy group-containing organopolysilsesquioxane of the present invention comprises the steps of preparing an organopolysilsesquioxane containing all side chain mercapto groups and an ethylenically unsaturated compound containing an epoxy group, or an ethylenically unsaturated compound containing an epoxy group. By reacting the compound with the alkyl (meth) acrylate, the first and second epoxy group-containing organopolysilsesquioxanes as described above can be produced relatively easily and efficiently.

Claims (5)

[Claims] 1. A 5 × has 10 ² to 1.5 × 10 number-average molecular weight of ^4, the main chain terminal groups is replaced by an end-capping group or 75 mol%, organopolysilane total side chain is mercapto group An epoxy group-containing organopolysilsesquioxane comprising an addition reaction product of rusesquioxane and an epoxy group-containing ethylenically unsaturated compound. 2. A 5 × has 10 ² to 1.5 × 10 number-average molecular weight of ^4, the main chain terminal groups is replaced by an end-capping group or 75 mol%, organopolysilane total side chain is mercapto group An epoxy group-containing organopolysilsesquioxane comprising an addition reaction product of rusesquioxane, an epoxy group-containing ethylenically unsaturated compound and an alkyl (meth) acrylate. 3. An epoxy group-containing ethylenically unsaturated compound is glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate,
The epoxy group-containing organopolysilsesquioxane according to claim 1 or 2, which is 3,4-epoxy methacrylate or allyl glycidyl ether. ^4. An organopolysiloxane having a number average molecular weight of 5 × 10 ^{2 to} 1.5 × 10 ⁴ , wherein the main chain terminal group is substituted by at least 75 mol% by an endcap group, and all side chains are mercapto groups. A process for producing an epoxy group-containing organopolysilsesquioxane, which comprises subjecting Rusesquioxane to a Michael addition reaction with an epoxy group-containing ethylenically unsaturated compound in the presence of a radical initiator. 5. A having a number average molecular weight of ^{5 × 10 2 ~1.5 × 10 4} , the main chain terminal groups is replaced by an end-capping group or 75 mol%, organopolysilane total side chain is mercapto group (A) / (b) = molar ratio of sesquioxane, ethylenically unsaturated compound containing epoxy group (a) and alkyl (meth) acrylate (b) =
A process for producing an epoxy group-containing organopolysilsesquioxane, comprising subjecting a mixture of 99/1 to 1/99 to a Michael addition reaction in the presence of a radical initiator.