JPH10101801A - Hydroxyl group-containing polyorganosilsesquioxane and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stable hydroxyl group-containing polyorganosilsesquioxane excellent in reactivity and to provide a method for its production. SOLUTION: A polyorganosilsesquioxane containing mercapto groups in the whole side chains, comprising >=75% of end groups of a main chain replaced with an end cap group and the whole side chains which are mercapto group- containing organic groups, having 500-10,000 number -average molecular weight is reacted with a hydroxyl group unsaturated compound or a mixture of the hydroxyl group-containing unsaturated compound (a) and a (meth)acrylic acid ester (b) in the presence of a radical initiator and subjected to addition reaction to produce a hydroxyl group-containing polyorganosilsesquioxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydroxyl-containing polyorganosilsesquioxane and a method for producing the same.

[0002]

2. Description of the Related Art A ladder-shaped polyorganosiloxane represented by the general formula [-R (R ') SiO3 _{/ 2-} ] is generally called a ladder silicone, and its unique structure and performance have been noticed and studied for a long time. Was. Nakahama et al. Attempted to synthesize a ladder silicone having a side chain other than an alkyl group such as a methyl group or an aryl group such as a phenyl group as the side chain (R or R ') of the ladder silicone, Report on the successful synthesis of ladder silicones having phenyl and methacryloxypropyl groups (Polymer Pr.
eprints Japan, 29, 73 (1980)).

A ladder silicone having an aralkyl group or a halogen-substituted derivative group thereof in addition to the above-mentioned alkyl group, aryl group and alkenyl group as a side chain has been proposed (for example, JP-A-50-111198, Kaihei 3
-20331). Further, a γ-methacryloxyalkyl trialkoxysilane (Japanese Unexamined Patent Publication No.
7-12057) or a photopolymerizable silicone compound used for a resist or the like by reacting with γ-methacryloxyalkyldimethylchlorosilane (JP-A-59-213272), wherein the side chain is a methyl group or a γ-methacryloxy group. Is 5/1 ladder silicone (number average molecular weight 4,5)
00) with a ω-dimercapto-modified dimethylpolysiloxane and a ladder silicone containing a mercapto group (Japanese Patent Application Laid-Open No. 5-125192), and a linear polymer containing at least one unsaturated group or mercapto group per molecule in the side chain. A graft-modified ladder silicone obtained by grafting siloxane (JP-A-6-41307) has been proposed, and the 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 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. Is 70% by mol or more. However, even with this production method, a ladder silicone in which a mercapto group is not actually introduced into a side chain is statistically produced with a probability of several% to several tens%. Difficult to obtain.

On the other hand, in the report by Nakahama et al., Polyorganosilsesquioxane having a hydroxyl group or an alkoxyl group at the terminal has a high reactivity of a functional group such as a hydroxyl group or an alkoxyl group at the terminal, resulting in gelation. And it was stated that synthesis was not possible.

Further, in order to provide a high reactivity, a hydroxyl group-containing trialkoxysilane, a hydroxyl group-containing trichlorosilane, or the like is used as a raw material for synthesizing a ladder silicone having a hydroxyl group in a side chain. In addition to being stable, an alcohol exchange reaction proceeds during the polycondensation reaction and gelation is likely to occur, so that it is difficult to synthesize a target substance having excellent stability and having no gel.

Therefore, a hydroxyl group-containing polyorganosilsesquioxane which is stable in itself, does not cause gelation, and has high reactivity with other compounds such as an isocyanate compound, cannot be obtained.

[0008]

The first object of the present invention is to provide a highly reactive hydroxyl-containing polyorganosilsesquioxane which is stable, does not cause gelation, and has a hydroxyl group in a side chain. To provide. A second object of the present invention is to provide a hydroxyl-containing polyorganosilsesquioxane which is stable, does not cause gelation and the like, has high reactivity, and is capable of adjusting the number of hydroxyl groups. Another object of the present invention is to propose an efficient method for producing the above polyorganosilsesquioxane.

[0009]

The present invention relates to the following hydroxyl-containing polyorganosilsesquioxane and a method for producing the same. (1) An organic group in which the main chain terminal group is substituted by an end cap group by 75% or more, all side chains are mercapto group-containing organic groups, and the number average molecular weight is 500 to 10,000, An organosilsesquioxane,
A hydroxyl group-containing polyorganosilsesquioxane comprising an addition reaction product with a hydroxyl group-containing unsaturated compound. (2) All side chain mercapto group-containing poly (organic group) having 75% or more of main chain terminal groups substituted by an end cap group, all side chains being an organic group containing a mercapto group, and having a number average molecular weight of 500 to 10,000. An organosilsesquioxane,
A hydroxyl-containing polyorganosilsesquioxane comprising an addition reaction product with a hydroxyl-containing unsaturated compound and a (meth) acrylate. (3) The hydroxyl-containing polyorganosilsesquioxane according to the above (1) or (2), wherein the hydroxyl-containing unsaturated compound is a hydroxyalkyl (meth) acrylate. (4) The (meth) acrylate compound is methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
At least one selected from the group consisting of butyl acrylate
The hydroxyl-containing polyorganosilsesquioxane according to the above (1), which is a seed. (5) All side chain mercapto group-containing poly (organic groups) in which the main chain terminal group is substituted by 75% or more of an end cap group, all side chains are mercapto group-containing organic groups, and the number average molecular weight is 500 to 10,000. A method for producing a hydroxyl-containing polyorganosilsesquioxane, comprising reacting an organosilsesquioxane with a hydroxyl-containing unsaturated compound in the presence of a radical initiator. (6) All side-chain mercapto group-containing poly (organic groups) in which the main chain terminal group is substituted by 75% or more of endcap groups, all side chains are mercapto group-containing organic groups, and the number average molecular weight is 500 to 10,000. The molar ratio (a) / (b) = 99 / of the organosilsesquioxane to the hydroxyl group-containing unsaturated compound (a) and the (meth) acrylate (b)
A method for producing a hydroxyl-containing polyorganosilsesquioxane, comprising reacting a mixture of 1 to 1/99 in the presence of a radical initiator.

In the present invention, "(meth) acryl" means "acryl and / or methacryl".

The polyorganosilsesquioxane containing all side chain mercapto groups used as a raw material in the present invention has a silsesquioxane unit of m as shown by the following formula [1].
It is a ladder silicone having a repeating structure.

[0012]

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

As the side chains R ¹ and R ² in the silsesquioxane unit represented by the above formula [1], HSR ⁷ — (where R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms) And an organic group containing a mercapto group. Examples of the divalent hydrocarbon group represented by R ⁷ include an ethylene group and a trimethylene group.

The polyorganosilsesquioxane containing all side chain mercapto groups represented by the formula [1] has a main chain terminal group OR
^{3 ~OR 6} is replaced by an end-capping group average of 75% or more, the balance has a hydroxyl group and / or alkoxy groups. Examples of the end cap group include a silyloxy group. Alkoxy group -OR ⁸ (In the formula, R ⁸ is 1 to 6 carbon atoms, preferably 1 to 3 alkyl group.)
And the group represented by

The silyl group constituting the silyloxy group includes a group 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 percentage of the main chain terminal groups to be substituted can be clearly determined by calculating the total number of remaining hydroxyl groups and alkoxy groups of the main chain terminal groups, for example, from peaks of ¹ H, ¹³ C and ²⁹ Si-NMR. Become. By setting the substitution to 75% or more on average, gel generation upon reaction with an unsaturated compound is prevented, and storage stability is maintained.

The number average molecular weight of the polyorganosilsesquioxane containing all side chain mercapto groups of the present invention is from 500 to 1
0000, and m in equation [1] is a number corresponding to this value. It is difficult to form a ladder structure having a number average molecular weight of less than 500, and if it exceeds 10,000, compatibility with general-purpose solvents is insufficient. The number average molecular weight is measured by gel permeation chromatography (GPC)
The method is carried out using styrene as a standard substance.

The first hydroxyl group-containing polyorganosilsesquioxane of the present invention is obtained by an addition reaction of the all-side-chain mercapto group-containing polyorganosilsesquioxane represented by the above formula [1] with a hydroxyl group-containing unsaturated compound. Things. This addition reaction is a Michael addition reaction, in which the polymerizable unsaturated bond of the hydroxyl-containing unsaturated compound is opened, and a reaction product added to the mercapto group of the polyorganosilsesquioxane is obtained. The ratio of the polyorganosilsesquioxane and the hydroxyl group-containing unsaturated compound is preferably a ratio of 1 equivalent of the polymerizable unsaturated groups of the hydroxyl group-containing unsaturated compound to 1 equivalent of the mercapto group of the polyorganosilsesquioxane. However, if necessary, it may be less than 1 equivalent of a polymerizable unsaturated group.

Examples of the hydroxyl-containing unsaturated compound include, for example, hydroxyl-containing (meth) acrylates represented by the following formulas [3a] to [3c].

Embedded image (In the formula, R ¹² is hydrogen or a methyl group, and n is an integer of 2 to 10, preferably 2 to 4.)

The first hydroxyl group-containing polyorganosilsesquioxane of the present invention is represented by the following formula [4].

Embedded image (Wherein, OR ^{3 to} OR ⁶ represent the same as described above, and R ¹³ and R ¹⁴ each represent an organic group formed by an addition reaction between an organic group having a mercapto group and a hydroxyl group-containing unsaturated compound;
m is a natural number. )

The second hydroxyl group-containing polyorganosilsesquioxane of the present invention comprises a polyorganosilsesquioxane having all the side chain mercapto groups represented by the above formula [1], the hydroxyl group-containing unsaturated compound and It is an addition reaction product with a (meth) acrylic acid ester. This addition reaction is a Michael addition reaction in which the polymerizable unsaturated group of the hydroxyl group-containing unsaturated compound is opened to obtain a reaction product added to the mercapto group of the polyorganosilsesquioxane. The ratio of the polyorganosilsesquioxane, the hydroxyl group-containing unsaturated compound and the (meth) acrylate is based on 1 equivalent of the mercapto group of the polyorganosilsesquioxane.
It is preferable to use one equivalent of the polymerizable unsaturated group of the hydroxyl group-containing unsaturated compound and the (meth) acrylate, but it may be less than one equivalent of the polymerizable unsaturated group if necessary. The ratio of the hydroxyl group-containing unsaturated compound and the (meth) acrylic acid ester can be arbitrarily determined, but is 6/4 to 8 in molar ratio.
/ 2, preferably 6.5 / 3.5 to 7.5 / 2.5.

Examples of the hydroxyl group-containing unsaturated compound include (meth) acrylic esters of the above formulas [3a] to [3c]. The (meth) acrylic acid ester is represented by the following formula [5].

[0023]

Embedded image (Wherein, R ¹⁵ is hydrogen or a methyl group, and R ¹⁶ is C 1 -C 1
6, preferably 1-4 alkyl groups. )

The second hydroxyl group-containing polyorganosilsesquioxane of the present invention is represented by the following formula [6].

Embedded image [OR ^{3 to} OR ⁶ are the same as those described above, and R ¹⁷ and R ¹⁸ are each obtained by subjecting an organic group having a mercapto group to a hydroxyl group-containing unsaturated compound or an unsaturated group of a (meth) acrylate ester by a Michael-type addition reaction. It represents an organic group to be generated, and m represents a natural number. ]

The compound of the formula [1] in which a hydroxyl group-containing unsaturated compound is added to all mercapto groups of a mercapto group-containing polyorganosilsesquioxane is a compound having hydroxyl groups in all side chains, and the number of reaction points increases. Although the compatibility with other resins and solvents deteriorates, the addition of the (meth) acrylate to the mercapto group-containing polyorganosilsesquioxane together with the unsaturated compound reduces the number of hydroxyl groups in the side chain. As compared with the case where the (meth) acrylic acid ester is not added, the compatibility with a resin such as an acrylic copolymer resin and a solvent is excellent, and the generation of cloudiness is prevented.

The polyorganosilsesquioxane containing all side chain mercapto groups used in the present invention can be produced by hydrolyzing a mercapto group-containing trialkoxysilane as a raw material and subjecting it to polycondensation.

The mercapto group-containing trialkoxysilane used for producing the polyorganosilsesquioxane containing all side chain mercapto groups includes γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercapto Propyltrichlorosilane and the like.

All the side chain mercapto group-containing polyorganosilsesquioxanes are obtained by adding 1 to 8 moles of water and 1 mole of mercapto group-containing trialkoxysilane to the total number of moles of the corresponding raw material mercapto group-containing trialkoxysilane. It can be produced by hydrolysis and polycondensation in the presence of a 0.005 to 0.05-fold molar amount of an acid catalyst to remove water and salts.

The amount of water used for hydrolysis and condensation polymerization is 1
If the molar ratio is less than 2 times, hydrolysis does not proceed sufficiently and storage stability is insufficient. If the amount of water exceeds 8 times, the polycondensation reaction occurs rapidly and gelation easily occurs.

The amount of the acid catalyst used in the hydrolysis and polycondensation depends on the amount of the raw material mercapto group-containing trialkoxysilane 1
It is 0.005 to 0.05 times mol per mol. If the amount of the acid catalyst used is less than 0.005 mol, hydrolysis and polycondensation become extremely slow, resulting in inefficiency and insufficient storage stability. When the amount of the acid catalyst exceeds 0.05 mol, an irregular three-dimensional polycondensation reaction occurs, and not only a ladder structure having a high regularity as the object of the present invention cannot be obtained, but also Gelation occurs. Examples of the acid catalyst used include hydrochloric acid, sulfuric acid, acetic acid, formic acid and the like.

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 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 0.5 to 1.
It is desirable that the reaction is carried out at 0 to 100 ° C., preferably at 60 to 75 ° C. for 1 to 10 hours after performing for 0 hours.

The polycondensation reaction is stopped by neutralizing the reaction solution with an alkali, and salts formed at that time are removed by filtration or washing with water. In some cases, prior to desalination, it is necessary to completely remove water.In this case, a solvent having an azeotropic property with water, for example, butyl acetate, alcohol, toluene, or the like is added, and a distillation operation is performed. You may. Examples of the alkali used in the present invention include sodium hydroxide, potassium hydroxide, n-butylamine, triethylamine and the like.

The hydroxyl group and / or alkoxy group at the terminal of the main chain in the polyorganosilsesquioxane containing all side chain mercapto groups obtained as described above is subjected to a silylation reaction with a monofunctional silylating agent. , At least 75% or more of the main chain terminal groups are substituted with endcap groups on average.

If the substitution of the end of the main chain with the end cap group is less than 75% on average, the storage stability of the hydroxyl group-containing polyorganosilsesquioxane during storage is poor, and gelation tends to occur. Also, when reacting with all side chain mercapto group-containing polyorganosilsesquioxane and a hydroxyl group-containing unsaturated compound, the gelation easily occurs, and the storage stability of the obtained hydroxyl groups-containing polyorganosilsesquioxane also becomes poor, Practical disadvantages arise.

The terminal silylation of the polyorganosilsesquioxane containing all side chain mercapto groups of the raw material is performed by adding a silylating agent to a solution of the polyorganosilsesquioxane containing all side chains of the raw material mercapto groups. Can be. The silylating agent may be one containing no halosilane and being less susceptible to excess water required for hydrolysis, or one itself hydrolyzed in an acidic atmosphere to become a silylating agent.

As the silylating agent, the following compounds can be exemplified. Trimethylsilanol, hexamethyldisiloxane, acetyltriphenylsilane, ethoxytriphenylsilane, triphenylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, hexaethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethyl Ethoxysilane and the like.

In a preferred embodiment of the present invention, trimethylsilylation can be carried out by reacting trimethylsilanol with the starting material containing all side chain mercapto group-containing polyorganosilsesquioxane. It is also effective to react raw polyorganosilsesquioxane containing all side chain mercapto groups under acidic conditions with hexamethyldisiloxane as a silylating agent. In this case, the reaction conditions are as follows: hexamethyldisiloxane is used in a slight excess from the calculated amount, and a small amount of ethanol or the like is used as a solvent, the reaction temperature is 50 to 100 ° C., and the reaction time is 1 to 8 hours. These reaction conditions can vary depending on the degree of trimethylsilylation, the type of solvent, and the like.

In a preferred embodiment of the present invention, an alcohol (preferably methanol) is produced by hydrolyzing a mercapto group-containing trialkoxysilane and producing a polyorganosilsesquioxane containing all side chain mercapto groups as a raw material for condensation polymerization. , Ethanol or a mixture thereof) is used as a solvent in the step of substituting a hydroxyl group and / or an alkoxy group at the terminal of the main chain with an endcap group.

As the hydroxyl group-containing unsaturated compound (a) to be reacted with all the side chain mercapto group-containing polyorganosilsesquioxanes, the following compounds can be exemplified. That is, examples thereof include alcoholic hydroxyl group-containing vinyl compounds such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate. Hydroxyethyl acrylate is preferred.

As the (meth) acrylate compound (b) to be reacted with the polyorganosilsesquioxane containing all side chain mercapto groups, the following compounds can be exemplified. That is, methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isodecyl acrylate, isodecyl methacrylate, n-lauryl acrylate, (Meth) acrylate compounds such as n-lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, n-stearyl acrylate, n-stearyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, and isobornyl methacrylate And methyl (meth) acrylate is preferred, and a single compound or two or more compounds may be used.

The first hydroxyl group-containing polyorganosilsesquioxane of the present invention is obtained by reacting the above-mentioned all-side-chain mercapto group-containing polyorganosilsesquioxane with a hydroxyl group-containing unsaturated compound in the presence of a radical initiator. It can be manufactured by doing. The second hydroxyl group-containing polyorganosilsesquioxane has a molar ratio of the total side chain mercapto group-containing polyorganosilsesquioxane to the hydroxyl group-containing unsaturated compound (a) and (meth) acrylate (b) ( It can be produced by reacting a) / (b) = 99/1 to 1/99 with a mixture in the presence of a radical initiator.

Examples of the radical initiator include benzoyl peroxide, methyl ethyl ketone peroxide, azobisisobutylnitrile, cumene hydroperoxide, t-butylhydroperoxide, azobisisobutyronitrile, and the like. Not something. Such a reaction is preferably performed in an organic solvent, and examples of the organic solvent include methanol, ethanol, 2-propanol, ethyl acetate, butyl acetate, and 4-
Methyl-2-pentanone and the like. The amount of the radical initiator to be added is 0.0001 to 0 with respect to the hydroxyl group-containing unsaturated compound to be reacted with all the side chain mercapto group-containing polyorganosilsesquioxane or the mixture of the hydroxyl group-containing unsaturated compound and the (meth) acrylate. .5 moles,
Preferably it is 0.01 to 0.1 times mol.

In the production method of the present invention, the polyorganosilsesquioxane containing all side chain mercapto groups and the unsaturated compound containing a hydroxyl group, or the unsaturated compound containing a hydroxyl group (a)
The reaction with the mixture of (a) and (meth) acrylic acid ester (b) is carried out by dissolving the polyorganosilsesquioxane containing all side-chain mercapto groups in an organic solvent and reacting with a hydroxyl-containing unsaturated compound or a hydroxyl-containing unsaturated compound. (A)
It is preferable to add a mixture of (a) / (b) = 99/1 to 1/99 and a radical initiator, which are composed of (meth) acrylic acid ester (b), and the radical initiator little by little.
The reaction conditions in this case are a reaction temperature of 50 to 100 ° C. and a reaction time of 1 to 8 hours. These reaction conditions are based on the type of the raw material hydroxyl group-containing unsaturated compound, the type of the reaction solvent, and the type of the radical initiator. It can change depending on the situation.

The first and second hydroxyl-containing polyorganosilsesquioxanes of the present invention are stable because they have an end cap group of at least 75% at the terminal of the main chain, and are stable because they have hydroxyl groups on the side chains. It has good reactivity with other compounds and is useful as a coating agent.

[0045]

As described above, the first hydroxyl group-containing polyorganosilsesquioxane of the present invention has at least 75% of an end cap group at the terminal of the main chain and a compound containing a hydroxyl group in the side chain is added. It is stable, does not cause gelation, has high reactivity, and can be reacted with other compounds.

The second hydroxyl group-containing polyorganosilsesquioxane of the present invention has an end cap group of 75% or more at the terminal of the main chain, and is obtained by adding an unsaturated compound containing a hydroxyl group and a compound not containing a hydroxyl group. Because it is excellent in stability, it can be reacted with other compounds with high reactivity, and the content of hydroxyl group can be adjusted,
Compatibility with other resins and solvents can be improved.

The method for producing a hydroxyl group-containing polyorganosilsesquioxane of the present invention comprises: a polyorganosilsesquioxane having all side chain mercapto groups and a hydroxyl group-containing unsaturated compound;
Alternatively, since the hydroxyl group-containing unsaturated compound and the (meth) acrylate are reacted, the first and second hydroxyl group-containing polyorganosilsesquioxanes as described above can be efficiently produced.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS 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. Number average molecular weight; GPC method Adhesion: Cross-cut method according to JIS K5400 (100 squares)

Production Example 1 A polyorganosilsesquioxane containing all side chain mercapto groups was produced as follows. Under a nitrogen stream, 196.34 g (1,000 mmol) of γ-mercaptopropyltrimethoxysilane was added to a 500 ml flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, and 54.
06 g (3,000 mmol) were charged and the mixture was cooled to 5 ° C. 10.13 g of a 3.6% hydrochloric acid aqueous solution (10 mm
ol) was added dropwise to the mixture over 30 minutes, after which the mixture was
C. for 60 minutes. The temperature of the reaction vessel was adjusted with a water bath to keep the reaction temperature of the mixture at 70 ° C. The hydrolysis-condensation reaction was performed for 3 hours under a nitrogen stream, and then 65 g (400 mmol) of hexamethyldisiloxane was added, and the silylation reaction was performed for 3 hours. The obtained reaction solution was cooled to 40 ° C. The reaction solution was neutralized with aqueous potassium hydroxide solution, and the mixture was kept at room temperature overnight. The lower layer of the solution separated into two layers was collected, butyl acetate was added, and the mixture was 200 mmHg, 4
Distill at 0 ° C. to remove 240 g of solvent. After adding 200 g of butyl acetate to the obtained solution, the mixture was stirred for 1 hour. Filtration through a 0.8 micron filter gave 900 g of a colorless and transparent solution. The number average molecular weight of the polyorganosilsesquioxane containing all side chain mercapto groups is 1,200,
The total number of hydroxyl groups and alkoxy groups in the main chain terminal groups determined from the peaks of ¹ H, ¹³ C and ²⁹ Si-NMR was 21% of the main chain terminal groups. Further, it was excellent in storage stability and did not gel even after the lapse of time.

In the polyorganosilsesquioxane containing all side chain mercapto groups obtained above, R ¹ and R ² in the above formula [1] are γ-mercaptopropyl groups, OR ^{3 to} O ^3.
It was confirmed that 18% of R ⁶ was a ladder silicone having a methoxy group, 82% being a trimethylsilyloxy group, and m being 3.6.

Example 1 A polyorganosilsesquioxane containing all side chain mercapto groups and an unsaturated compound containing a hydroxyl group were reacted as follows. 10.00 g (8.3 mmol) of a polyorganosilsesquioxane containing all side-chain mercapto groups produced in Production Example 1 under a nitrogen stream in a 100 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube. ), 33.91 g of ethanol was charged, and the temperature of the reaction vessel was adjusted with a water bath to maintain the reaction temperature of the mixture at 70 ° C. Next, 7.40 g of hydroxyethyl acrylate (56.86 mmo)
l), 0.53 g (2.29 mmol) of dimethyl 2,2'-azobis (2-methylpropionate) and 7.93 g of ethanol were mixed, and this solution was added dropwise to the reaction system over 60 minutes. The addition reaction was performed for 3 hours, and the obtained reaction solution was cooled to 40 ° C. Mixture at 200mmHg, 40 ℃
, And 40 g of the solvent was removed.
g was obtained.

The number average molecular weight of the obtained hydroxyl group-containing polyorganosilsesquioxane was 3,200. The mercapto group reacted quantitatively with hydroxyethyl acrylate. According to ¹ H-NMR, the unreacted mercapto group was less than 1% of all side chains.

The above-mentioned hydroxyl-containing polyorganosilsesquioxane is represented by the following formula [7].

Embedded image (Wherein OR ^{19 to} OR ²² are 18% methoxy group, 82%
Is a trimethylsilyloxy group, R ²³ is a group represented by the following formula [8], and m is 3.6. )

[0054]

Embedded image Of the hydroxyl group-containing polyorganosilsesquioxane ¹
The results of 1 H-NMR and IR analysis are shown in Table 6.

Example 2 A polyorganosilsesquioxane containing all side chain mercapto groups and a mixture of a hydroxyl group-containing unsaturated compound (a) and a (meth) acrylate (b) were reacted as follows. . 10.00 g (8.3 mmol) of a polyorganosilsesquioxane containing all side-chain mercapto groups produced in Production Example 1 under a nitrogen stream in a 100 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube.
l), 32.32 g of ethanol was charged, the temperature of the reaction vessel was adjusted with a water bath, and the reaction temperature of the mixture was maintained at 70 ° C. Next, 2.22 g of hydroxyethyl acrylate (1
7.06 mmol), 3.99 g of methyl methacrylate (3
9.85 mmol), 0.53 g (2.29 mmol) of dimethyl 2,2'-azobis (2-methylpropionate) and 6.74 g of ethanol were mixed, and this solution was added dropwise to the reaction system over 60 minutes. . The addition reaction was performed for 3 hours, and the obtained reaction solution was cooled to 40 ° C. 200mmH mixture
g, distilled at 40 ° C. to remove 40 g of the solvent to obtain 16.5 g of a colorless and transparent solution.

The number average molecular weight of the hydroxyl-containing polyorganosilsesquioxane was 3,000. The mercapto group reacted quantitatively with hydroxyethyl acrylate and methyl methacrylate, and according to ¹ H-NMR, unreacted mercapto group was less than 1% of all side chains.

The hydroxyl group-containing polyorganosilsesquioxane has the following formula:

It is shown by [9].

Embedded image (Wherein OR ^{19 to} OR ²² are 18% methoxy group, 82%
Is a trimethylsilyloxy group, R ²⁴ and R ²⁵ are groups represented by the above formula [8], and groups represented by the following formula [10],
m is 3.6. However, the ratio of the group represented by the formula [8] to the group represented by the formula [10] is 30.6: 69.4. )

[0058]

Embedded image Table 6 shows the results of ¹ H-NMR and IR analysis.

Example 3 A reaction was conducted in the same manner as in Example 2 except that the molar ratio of hydroxyethyl acrylate and methyl methacrylate was changed to 5/5. The number average molecular weight of the obtained hydroxyl-containing polyorganosilsesquioxane was 3,200. The mercapto group reacted quantitatively with hydroxyethyl acrylate and methyl methacrylate. According to ¹ H-NMR, the unreacted mercapto group was less than 1% of all side chains. Of the hydroxyl group-containing polyorganosilsesquioxane
Table 6 shows the results of ¹ H-NMR and IR analysis.

Example 4 A reaction was carried out in the same manner as in Example 2 except that the molar ratio of hydroxyethyl acrylate and methyl methacrylate was changed to 7/3. The number average molecular weight of the obtained hydroxyl-containing polyorganosilsesquioxane was 3,200. The mercapto group reacted quantitatively with hydroxyethyl acrylate and methyl methacrylate. According to ¹ H-NMR, the unreacted mercapto group was less than 1% of all side chains. Of the hydroxyl group-containing polyorganosilsesquioxane
Table 6 shows the results of ¹ H-NMR and IR analysis.

Application Example 1 A composition was prepared by uniformly mixing the components having the mixing ratios shown in Table 1 below with the hydroxyl group-containing polyorganosilsesquioxane resin obtained in the above Examples. This composition was applied on a surface of a 1.0 mm-thick aluminum steel plate (JIS A1050P) so as to have a dry film thickness of 20 μm, and then left at room temperature for 3 days to prepare a base material. The adhesion was evaluated.

[0062]

[Table 1]

Application Example 2 A composition was prepared by uniformly mixing the components having the mixing ratios shown in Table 2 below with the hydroxyl-containing polyorganosilsesquioxane obtained in Example 2 above. This composition was coated on a 1.0 mm thick aluminum steel sheet (JIS A1050P) with a dry film thickness of 2
After coating so as to have a thickness of 0 μm, the substrate was allowed to stand at room temperature for 3 days to prepare a substrate, and the substrate was evaluated for cross-cut adhesion.

[0064]

[Table 2]

Application Example 3 A composition was prepared by uniformly mixing and mixing the components having the mixing ratios shown in Table 3 below with the hydroxyl-containing polyorganosilsesquioxane obtained in Example 3 above. This composition was coated on a 1.0 mm thick aluminum steel sheet (JIS A1050P) with a dry film thickness of 2
After coating so as to have a thickness of 0 μm, the substrate was allowed to stand at room temperature for 3 days to prepare a substrate, and the substrate was evaluated for cross-cut adhesion.

[0066]

[Table 3]

Application Example 4 A composition was prepared by uniformly mixing the components having the mixing ratios shown in Table 4 below with the hydroxyl group-containing polyorganosilsesquioxane obtained in Example 4 above. This composition was coated on a 1.0 mm thick aluminum steel sheet (JIS A1050P) with a dry film thickness of 2
After coating so as to have a thickness of 0 μm, the substrate was allowed to stand at room temperature for 3 days to prepare a substrate, and the substrate was evaluated for cross-cut adhesion.

[0068]

[Table 4]

Table 5 shows the results of measuring the physical properties of the coating films in Application Examples 1 to 4.

[Table 5]

[0070]

[Table 6]

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masami Matsuoka 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba Prefecture Within the Research Institute of Showa Denko KK (72) Inventor Yuji Ito 1-chome, Onodai, Midori-ku, Chiba-shi, Chiba No. 1 in Showa Denko KK

Claims (6)

[Claims] 1. A side chain mercapto group in which the main chain terminal group is substituted by an end cap group by 75% or more, all side chains are organic groups containing a mercapto group, and the number average molecular weight is 500 to 10,000. A hydroxyl-containing polyorganosilsesquioxane comprising an addition reaction product of a hydroxyl-containing polyorganosilsesquioxane and a hydroxyl-containing unsaturated compound. 2. A side chain mercapto group in which the main chain terminal group is substituted by an end cap group in an amount of 75% or more, all side chains are organic groups containing a mercapto group, and the number average molecular weight is 500 to 10,000. A hydroxyl group-containing polyorganosilsesquioxane comprising an addition reaction product of a hydroxyl-containing polyorganosilsesquioxane, a hydroxyl-containing unsaturated compound and a (meth) acrylate. 3. The hydroxyl-containing polyorganosilsesquioxane according to claim 1, wherein the hydroxyl-containing unsaturated compound is a hydroxyalkyl (meth) acrylate. 4. The hydroxyl group according to claim 2, wherein the (meth) acrylate compound is at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. Containing polyorganosilsesquioxane. 5. A side chain mercapto group in which the main chain terminal group is substituted by an end cap group by 75% or more, all side chains are organic groups containing a mercapto group, and the number average molecular weight is 500 to 10,000. A method for producing a hydroxyl-containing polyorganosilsesquioxane, which comprises reacting a hydroxyl-containing unsaturated compound with a hydroxyl-containing polyorganosilsesquioxane in the presence of a radical initiator. 6. A side chain mercapto group in which the main chain terminal group is substituted by an end cap group in an amount of 75% or more, all side chains are mercapto group-containing organic groups, and the number average molecular weight is 500 to 10,000. Molar ratio (a) / (b) consisting of a hydroxyl-containing unsaturated compound (a) and a (meth) acrylate (b) in a polyorganosilsesquioxane-containing polyorganosilsesquioxane
= 99/1 to 1/99 in the presence of a radical initiator. A process for producing a hydroxyl group-containing polyorganosilsesquioxane.