JPH1087834A - Polyorganosilsesquioxane, its production, and resin composition containing the same compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydroxylated polyorganosilsesquioxane having an excel lent storage stability, uniform and high reactivity, resistance to gelation during production and the capability of stable feeding and to provide a process for producing the same. SOLUTION: This invention provides a hydroxylated polyorganosilylsilsesquioxane wherein at least 75mol% of the terminal groups of the main chain are end capping groups, and the side chains are entirely composed of hydroxylated groups or substantially composed of hydroxylated groups and epoxidized groups, and the number-average molecular weight is 1,000-30,000. This compound is produced by reacting an epoxytrialkoxysilane with water to effect the hydrolysis and subsequent polycondensation and to effect the conversion into a diol by reacting the epoxy group with water and reacting the diol with a monofunctional silylating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hydroxyl-containing polyorganosilsesquioxane, a method for producing the same, and a resin composition containing the hydroxyl-containing polyorganosilsesquioxane. More particularly, the present invention relates to a hydroxyl-containing or epoxy-containing side chain-containing polyorganosilsesquioxane. The present invention relates to a polyorganosilsesquioxane having a reactive group such as a group (eg, glycidyl group), a method for producing the same, and a resin composition containing the hydroxyl-containing polyorganosilsesquioxane.

[0002]

BACKGROUND OF THE INVENTION Ladder-shaped polyorganosiloxanes represented by the general formula [-RSiO _3/ 2-: R is a side chain of an alkyl group, an aryl group, etc.] are commonly called "ladder silicones", It has been studied for a long time focusing on its simple structure and performance.

Nakahama et al. Reported that the side chain (R
Or R ′) as 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, and adding a vinyl group or a methacryloxypropyl group to the side chain together with a phenyl group. It reports that the ladder silicone was successfully synthesized (Pr
eprints Japan, 29, 73 (1980) Polymer).

Further, 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, Japanese Patent Application Laid-Open No. 50-111198, JP-A-3-20331).

Further, γ-methacryloxyalkyl trialkoxysilane (Japanese Patent Application Laid-Open No. 57-12 / 1990) is added to the terminal of the main chain of a ladder silicone containing a methyl group or a phenyl group in the side chain.
057) or γ-methacryloxyalkyldimethylchlorosilane (Japanese Patent Application Laid-Open No. 59-2132728) to form a photopolymerizable silicone compound used for a resist or the like; a methyl group and a γ-methacryloxy group are present in a side chain. Ladder silicone present at a ratio of 5/1 (number average molecular weight 450
No. 0), a ladder silicone containing a mercapto group obtained by reacting ω-dimercapto-modified dimethylpolysiloxane (Japanese Patent Laid-Open No. 5-125192); a linear chain containing at least one unsaturated group or mercapto group per molecule in the side chain And a graft-modified ladder silicone obtained by grafting a polysiloxane (JP-A-6-41307). JP-A-6-41307 discloses that the unsaturated group or the mercapto group is 12.5 to 1.5%. A synthesis example of a ladder silicone containing 20 mol% has been reported.

In Japanese Patent Application Laid-Open No. 6-41307, in addition to the unsaturated group and mercapto group, an alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted phenyl group is used as a side chain of the ladder silicone for grafting. Selected ones are preferred, and the examples illustrate ladder silicones with 75% by mole or more of methyl groups.

However, in this method, the reactivity of the methyltrialkoxysilane, which is a monomer, is significantly higher than that of other silane monomers.
It is produced with a probability of more than ten percent, and it is difficult to obtain a hydroxyl group-containing ladder silicone having uniformity and high reactivity.

On the other hand, Nakahama et al. Reported in the previous report that 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 and has a high gelling property. It was described that the synthesis was not possible.

The hydroxyl group-containing polyorganosilsesquioxane is described, for example, in Japanese Patent Application Laid-Open No. Hei 2-1077638, but there is no specific example, and the monomer for preparing the hydroxyl group-containing polyorganosilsesquioxane is not disclosed. When the synthesis of a hydroxyl group-containing polyorganosilsesquioxane equivalent to that described in this publication was attempted by a conventionally known method using a hydroxyl group-containing trialkoxysilane corresponding to the starting material, gelation occurred and the intended No hydroxyl-containing polyorganosilsesquioxane was obtained.

The present inventors have conducted intensive studies to obtain such polyorganosilsesquioxane having a hydroxyl group in the side chain. As a result, the present inventors have hydrolyzed an epoxy group-containing trialkoxysilane such as a glycidyl group. When a ladder structure is formed by polycondensation, a specific acidic catalyst is used to react an epoxy group of a side chain such as a glycidyl group with water, so that at least one molecule (in a side chain group)
The present inventors have found that a polyorganosilsesquioxane containing one or more hydroxyl groups can be obtained, and have completed the present invention.

[0011]

An object of the present invention is to solve the above-mentioned problems associated with the prior art, and to provide a polyorganosilsesquioxane having excellent storage stability, uniformity and high reactivity, and the hydroxyl group. It is an object of the present invention to provide a resin composition containing a polyorganosilsesquioxane.

An object of the present invention is to provide a method for producing a hydroxyl group-containing polyorganosilsesquioxane that can be stably supplied without gelling during production.

[0013]

SUMMARY OF THE INVENTION In the hydroxyl group-containing polyorganosilsesquioxane (functional group-containing polyorganosiloxane) according to the present invention, at least 75 mol% of the main chain terminal groups have an endcap group, preferably a tricap group. Any one or two or more groups selected from an alkylsilyl group, a triphenylsilyl group, a phenyldialkylsilyl group, and a diphenylalkyl group (provided that all or some of the hydrogen atoms in these groups are May be substituted with a halogen atom.), And whether all the side chain groups are hydroxyl group-containing groups or substantially consist of a hydroxyl group-containing group and an epoxy group-containing group. Is 10
It is characterized by being in the range of 00 to 30,000.

The method for producing a hydroxyl-containing polyorganosilsesquioxane according to the present invention comprises reacting an epoxy-containing trialkoxysilane with water to hydrolyze and condense the epoxy-containing trialkoxysilane. After reacting the epoxy group with water to form a diol,
It is characterized in that the above-mentioned hydroxyl-containing polyorganosilsesquioxane is obtained by reacting with a monofunctional silylating agent.

In the present invention, when the epoxy group-containing trialkoxysilane is hydrolyzed and polycondensed, an acid catalyst,
Preferably, the reaction is carried out in the presence of sulfuric acid. Further, sulfuric acid is used in an amount of 0.00005 to 0.
It is desirable to use it in an amount of 05 mol.

The resin composition according to the present invention is characterized by containing the above-mentioned hydroxyl group-containing polyorganosilsesquioxane, an alcoholic hydroxyl group-containing acrylic resin, and a polyisocyanate.

The hydroxyl group-containing polyorganosilsesquioxane according to the present invention has excellent storage stability. According to the above method, such a hydroxyl group-containing polyorganosilsesquioxane can be produced without gelation.

In this specification, the amount (mol%) of the hydroxyl group-containing group and the epoxy group-containing group in the side chain group or the terminal capping group such as a trialkylsilyl group in the main chain is used. The amount (mol%) of the (end cap group) is represented by an average value unless otherwise specifically stated.

[0019]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the hydroxyl group-containing polyorganosilsesquioxane according to the present invention and a method for producing the same will be specifically described.

[Hydroxy group-containing polyorganosilsesquioki
Sun] In the hydroxyl group-containing polyorganosilsesquioxane according to the present invention, at least 75 mol% of the main chain terminal groups have an end cap group, preferably a trialkylsilyl group, a triphenylsilyl group, or a phenyl group. One or more groups (substituents) selected from a dialkylsilyl group and a diphenylalkylsilyl group, and all or some of the hydrogen atoms in these groups are substituted with halogen atoms. May be.

Moreover, in such a hydroxyl group-containing polyorganosilsesquioxane, the hydroxyl group-containing group accounts for 1 to 100 mol%, preferably 50 to 100 mol%, particularly preferably 75 to 100 mol%, of all side chain groups. Present in the amount of
The balance is substantially an epoxy group-containing group and has a number average molecular weight of 1,000 to 30,000 (30,000), preferably 1,000.
To 10,000 (10,000), particularly preferably 2000 to 50
00.

Although the above hydroxyl group-containing group accounts for less than 1 mol% of all side chain groups, there is no particular problem in terms of synthesis and stability of the oligomer, but such an amount is sufficient for curing isocyanate. There is a possibility that the effect cannot be exhibited.

If the hydroxyl group-containing polyorganosilsesquioxane has a number average molecular weight of less than 1,000, it tends to be difficult to form a ladder structure.
If it exceeds 00, the compatibility with general-purpose solvents tends to decrease.

Such a hydroxyl-containing polyorganosilsesquioxane has, for example, a structure represented by the following formula (A), wherein R ^m and R ⁿ are side-chain organic groups,
^{-O-R q, -O-R} r, -O-R s, -O-R t is the terminal group of the main chain, p is represents a repeating unit, a number of 2 to 90.

[0025]

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In the hydroxyl group-containing polyorganosilsesquioxane according to the present invention, (ii) the main chain terminal group (in the formula (A), R ^q , R ^r , R ^s , R ^t ) is replaced with the terminal blocking group. (End c
ap group), preferably any one or more groups (substituents) selected from trialkylsilyl, triphenylsilyl, phenyldialkylsilyl, and diphenylalkylsilyl groups, and All or a part of the hydrogen atoms in the group (substituent) may be substituted with a halogen atom.

The trialkylsilyl group has the formula: —SiR ¹⁰
R ¹¹ R ¹² (R ¹⁰ , R ¹¹ , and R ¹² each represent the same or different alkyl group, preferably a chain hydrocarbon group having 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.) , R
^10, the hydrogen atom of R ^11, in R ¹² is, in whole or in part Cl, Br, optionally substituted with a halogen atom such as I.

Specific examples of such a trialkylsilyl group include, for example, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, and an ethyldimethylsilyl group in which three chain hydrocarbon groups are bonded to an Si atom. ,
Diethylmethylsilyl group, propyldimethylsilyl group,
Dipropylmethylsilyl group, propyldiethylsilyl group, dipropylethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, etc .; triphenylsilyl group in which three aromatic hydrocarbon groups are bonded to Si atom;
Chloromethyldimethylsilyl group in which part of hydrogen atoms in a trialkylsilyl group is substituted with halogen atoms: -Si
(CH ₃ ) ₂ CH ₂ Cl; and the like.

The phenyldialkylsilyl group is represented by Si
A functional group in which one phenyl group is bonded to an atom and two chain hydrocarbon groups are bonded, such as a phenyldimethylsilyl group, a phenyldiethylsilyl group, a phenyldipropylsilyl group, a phenylethylmethylsilyl group, Examples include a phenylpropylmethylsilyl group and a phenylpropylethylsilyl group.

As the diphenylalkylsilyl group, S
A functional group in which two phenyl groups are bonded to an i atom and one chain hydrocarbon group is bonded, and examples thereof include a diphenylmethylsilyl group, a diphenylethylsilyl group, and a diphenylpropylsilyl group.

Further, a side chain group (R ^m , R ^{n in the} formula (A))
Are present in the hydroxyl group-containing polyorganosilsesquioxane in a plurality, and these side groups are substantially composed of either a hydroxyl group-containing group or an epoxy group-containing group,
The hydroxyl group-containing group is 1 to 100 in the side chain group (side chain organic group).
Mol%, preferably 50 to 100 mol%, more preferably 75 to 100 mol% (each of the epoxy group-containing groups is the remaining amount, and "substantially" means, in some cases, within several mol%. It is intended that other organic groups such as an alkyl group, an alkenyl group, and a phenyl group can exist). This hydroxyl group-containing group is 1 mol%
Although there is no particular problem in terms of the stability of the oligomer, etc. in terms of synthesis, there is a possibility that a sufficient effect cannot be exerted when the isocyanate is cured with such an amount.

As the hydroxyl group-containing group, diols, in particular,
α, β-diols, for example, the following formula (A)
Alternatively, the formula (b) is appropriate.

[0033]

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[0034]

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In the formula (A), A represents a cycloalkyl group having 5 to 8, preferably 6, carbon atoms, D represents a single bond or a divalent hydrocarbon group, and the divalent hydrocarbon group is Number 1
To 8, preferably 1 to 5, which is an alkylene group which may be linear or branched and may contain an oxygen atom (ether bond) and a sulfur atom (thioether bond). In the formula (b), n is an integer of 0 to 3, preferably 0, D represents a single bond or a divalent hydrocarbon group,
This divalent hydrocarbon group has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.
And an alkylene group which may be linear or branched and may contain an oxygen atom (ether bond) and a sulfur atom (thioether bond). As the hydroxyl group-containing group represented by the formula (A),
For example, β- (3,4-dihydroxycyclohexyl)
Ethyl group, β- (3,4-dihydroxycyclohexyl) propyl group, γ- (3,4-dihydroxycyclohexyl) propyl group, β- (3,4-dihydroxycycloheptyl) ethyl group, β- (3,4- Dihydroxycyclohexyl) butyl group, β- (3,4-dihydroxycyclohexyl) pentyl group and the like.
(3,4-dihydroxycyclohexyl) ethyl group, β
A-(3,4-dihydroxycyclohexyl) propyl group is preferred.

Examples of the hydroxyl group-containing group represented by the formula (II) include, for example, β- (2,3-dihydroxypropyloxy) ethyl group, γ- (3,4-dihydroxypropyloxy) propyl group, γ- (3 , 4-dihydroxypropyloxy) butyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the like.
A-(2,3-dihydroxypropyloxy) ethyl group,
A γ- (3,4-dihydroxypropyloxy) propyl group is preferred. Particularly preferred is a γ- (3,4-dihydroxypropyloxy) propyl group.

The epoxy group-containing groups (oxygen-containing hydrocarbon ring-containing groups and oxirane group-containing groups) preferably include the following formulas (c) and (d).

[0038]

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In the formula (C), A represents a cycloalkyl group having 5 to 8, preferably 6, carbon atoms, D represents a single bond or a divalent hydrocarbon group, and the divalent hydrocarbon group is Number 1
To 8, preferably 1 to 5, which is an alkylene group which may be linear or branched and may contain an oxygen atom (ether bond) and a sulfur atom (thioether bond). Specific examples of such an alicyclic epoxy group-containing group include a β- (3,4-epoxycyclohexyl) ethyl group, a γ- (3,4-epoxycyclohexyl) propyl group, -(3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl)
Propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pentyl group, etc., and β- (3,4-dihydroxycyclohexyl) ethyl group, β- (3 And a 4-, 3-epoxycyclohexyl) ethyl group and a β- (3,4-epoxycyclohexyl) propyl group are preferred.

[0040]

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[In the formula (d), n is an integer of 0 to 3, preferably 0, and D represents a divalent hydrocarbon group.
The valent hydrocarbon group has 1 to 8, preferably 1 to 5 carbon atoms, may be linear or branched, and may contain an oxygen atom (ether bond) and a sulfur atom (thioether bond). It is an alkylene group. Examples of such a linear or branched aliphatic epoxy group-containing group include a β-glycidoxyethyl group,
Examples include a γ-glycidoxypropyl group, a γ-glycidoxybutyl group, a glycidyl group, a 3,4-epoxybutyl group, and a β-glycidoxyethyl group and a γ-glycidoxypropyl group are preferred. Particularly preferred is a γ-glycidoxypropyl group.

In the present invention, these hydroxyl group-containing groups and epoxy group-containing groups may be contained alone or in combination of two or more. As an organic group other than the epoxy group-containing group,
For example, a methyl group, an ethyl group, an n-propyl group, a phenyl group and the like can be contained within a few mol% of the side chain group.

[Production Method] Next, a method for producing such a hydroxyl group-containing polyorganosilsesquioxane will be described.

In the present invention, the following epoxy group-containing trialkoxysilane is reacted with water to hydrolyze and condense the epoxy group-containing trialkoxysilane, and the epoxy group is reacted with water to form a diol. After doing
It is preferable to react with a monofunctional silylating agent to produce the above-mentioned hydroxyl-containing polyorganosilsesquioxane.

Hereinafter, the reaction steps will be described in detail. <Epoxy group-containing trialkoxysilane> As the epoxy group-containing trialkoxysilane, the following (e-1),
Examples shown in (f-1) can be exemplified.

[0046]

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In the formula (E-1), A represents a cycloalkyl group having 5 to 8 carbon atoms, preferably 6 carbon atoms, D represents a single bond or a divalent hydrocarbon group, and the divalent hydrocarbon group Is an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, which may be linear or branched and may contain an oxygen atom (ether bond) and a sulfur atom (thioether bond). . R ³ , R ⁴ , and R ⁵ each independently represent a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and these hydrocarbon groups may be linear or branched. Good. R ³ , R ⁴ , and R ⁵ each independently have 1 to 8 carbon atoms.
It preferably represents 1 to 5 hydrocarbon groups, and these hydrocarbon groups may be linear or branched. Specific examples of the epoxy group-containing trialkoxysilane in which such an epoxy group is contained in an alicyclic hydrocarbon group include, for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-
(3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, β- (3,4-epoxycycloheptyl) ethyltrimethoxysilane, β- (3,4 -
Epoxycycloheptyl) ethyltriethoxysilane,
β- (3,4-epoxycyclohexyl) butyltrimethoxysilane, β- (3,4-epoxycyclohexyl) butyltriethoxysilane, β- (3,4-epoxycyclohexyl) pentyltrimethoxysilane, and the like. -(3,4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and β- (3,4-epoxycyclohexyl) propyltrimethoxysilane are preferably used.

[0048]

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[In the formula (F-1), n is an integer of 0 to 3,
It is preferably 0, and D represents a divalent hydrocarbon group, and the divalent hydrocarbon group has 1 to 8, preferably 1 to 5 carbon atoms, and may be linear or branched; An alkylene group which may contain an oxygen atom (ether bond) and a sulfur atom (thioether bond). R ³ , R ⁴ , R
⁵ is each independently 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.
And these hydrocarbon groups may be linear or branched. Specific examples of the epoxy group-containing trialkoxysilane in which the epoxy group (oxirane group) is bonded to a chain hydrocarbon group include, for example, β-glycidoxyethyltrimethoxysilane, β-glycide Xylethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, γ-glycidoxypentyltrimethoxysilane, γ-glycidoxypentyltriethoxysilane, glycidyltriethoxysilane, and the like. -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
β-glycidoxyethyltrimethoxysilane and β-glycidoxyethyltriethoxysilane are preferably used.

In the present invention, these epoxy group-containing trialkoxysilanes may be used alone or in combination of two or more. In the present invention, such an epoxy group-containing trialkoxysilane is reacted with water (hydrolysis / condensation polymerization, diolation). In this reaction, the total number of moles of the epoxy group-containing trialkoxysilane is Water is 1.0 to 8.0 times mol, preferably 1.5 to 8.0 times.
It is used in an amount of 8.0 moles, more preferably 3.0 to 6.0 moles.

Such a reaction is preferably carried out in the presence of the following acid catalyst, especially sulfuric acid. The acid catalyst is used in an amount of 0.0 mol per mol of epoxy group-containing trialkoxysilane.
0005-0.05 mole, preferably 0.005-
It is used in a molar amount of 0.05 times.

When the amount of water used in the hydrolysis and condensation reaction is less than 1.0 mole, hydrolysis does not proceed sufficiently, and when the amount of water exceeds 8.0 mole, the condensation reaction rapidly occurs. And gelation is likely to occur.

When the amount of the acid is less than 0.00005 mol per mol of the epoxy group-containing trialkoxysilane,
Hydrolysis and condensation are extremely slow and inefficient. When the amount of the acid exceeds 0.05 mol, an irregular three-dimensional condensation reaction occurs, so that not only a desired highly ordered ladder structure cannot be obtained, but also gelation tends to occur.

As the acid, specifically, for example, hydrochloric acid,
Examples thereof include inorganic acids such as nitric acid and sulfuric acid, and organic acids such as formic acid, acetic acid and oxalic acid, and sulfuric acid is preferably used. Incidentally, an acid which reacts with a glycidyl group to form an ester, for example, hydrochloric acid,
Acetic acid reacts with glycidyl groups during the reaction,
Hydrolysis / condensation does not proceed with the above catalyst amount, and use in this reaction is not so preferable. Further, nitric acid is not preferable because a highly dangerous nitrate compound may be generated, and it is most preferable to use sulfuric acid in this reaction.

The reaction conditions are not particularly limited.
Generally, the reaction temperature is usually about 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 of 0 to 20 ° C for 0.5 to 1.
After performing for 0 hours, the temperature was continuously raised to 50 to 100 ° C.
Preferably, the reaction is performed at 60 to 75 ° C for 1 to 10 hours. Such a reaction is preferably performed in an inert gas, and examples of such an inert gas include a nitrogen gas and an argon gas.

The condensation reaction is stopped by neutralizing the reaction solution with an alkali.
It is removed by filtration or washing with water. In some cases, prior to desalination, it is necessary to sufficiently remove water,
At that time, a solvent having an azeotropic property with water, for example, butyl acetate, alcohol, toluene or the like may be added to carry out a distillation operation.

As the alkali, specifically, for example,
Examples include sodium hydroxide, potassium hydroxide, n-butylamine, triethylamine and the like. The above reaction (hydrolysis of epoxy group-containing trialkoxysilane
When the polycondensation reaction and the diol conversion of the epoxy group) are carried out, a hydroxyl-containing polyorganosilsesquioxane (a) having a main chain terminal unblocked is obtained. A hydroxyl group and / or an alkoxy group is present at the end of the main chain of the obtained hydroxyl-containing polyorganosilsesquioxane (a) which is not sealed at the main chain terminal.

In the present invention, the end-capping (silylation) reaction of the unsealed main chain terminal is carried out using a monofunctional silylating agent, whereby at least 7 main chain terminal ends are obtained.
It is desirable to substitute 5 mol% or more, preferably 80 to 100 mol%, with a terminal capping group (end cap group).
If the amount of substitution of the unblocked main chain terminal group to the endcap group (terminal capping group), that is, the amount of the terminal capping group is less than 75 mol%, the hydroxyl-containing polyorganosilsesquioxane (b) ( Example: Poor stability during storage of polyorganosilsesquioxane containing hydroxyl groups in all side chains,
Gelation is likely to occur, which may cause practical problems.

In order to carry out the terminal silylation reaction of the hydroxyl group-containing polyorganosilsesquioxane (a) whose main chain ends are not blocked, the hydroxyl group-containing polyorganosilsesquioxane whose main chain terminals are not blocked is used. The following silylating agent (end capping agent, end cap agent) may be added to the solution of a) and reacted. The term “end cap” as used herein refers to a highly reactive Si—OR directly bonded to a silicon atom of polyorganosilsesquioxane, an OR group of Si—OH, an OH group, or the like.
Substitution with i (CH ₃ ) ₃ or the like (R: alkyl group). By performing the end capping, the polysilsesquioxane polymerization reaction is slowed, and the storage stability is improved.

In such a reaction, the terminal blocking agent (eg, hexamethyldisiloxane) is used in an amount slightly larger than the calculated amount (eg, usually 1: 1 for one terminal silanol group).
(About 2 to 5 times).

Such a silylation (end capping) reaction is carried out, for example, in the same manner as the above-mentioned hydrolysis / condensation polymerization of epoxy group-containing trialkoxysilane, diolation, and the like.
In an inert gas such as nitrogen, usually 20 to 100 ° C, preferably 30 to 95 ° C, more preferably 50 to 90 ° C
For example, it is performed for about 1 to 8 hours. In order to stop such a reaction, for example, a methanol solution of potassium hydroxide is used.

As a solvent, for example, a small amount of ethanol, methanol, isopropyl alcohol, butyl acetate, ethyl acetate, MIBK, etc. [a hydroxyl group-containing polyorganosilsesquioxane (a) whose main chain ends are not sealed and a silylating agent 10 to 1000 parts by weight, preferably about 10 to 100 parts by weight, based on 100 parts by weight of the total. In a preferred embodiment of the present invention, an alcohol (preferably methanol, ethanol or a mixture thereof) by-produced when producing a hydroxyl-containing polyorganosilsesquioxane by hydrolyzing and condensation-polymerizing an epoxy-containing trialkoxysilane. Is preferably used as a solvent in the step of substituting a hydroxyl group and / or an alkoxy group at the end of the main chain with a main chain terminal capping group (endcap group).

It is effective to carry out such a reaction under acidic conditions of pH 1 to 6, preferably pH 3 to 5. In this case, examples of the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid, acetic acid, and oxalic acid.

The above reaction conditions can be appropriately set depending on the required degree of end capping (eg, trimethylsilylation) and the type of solvent. <Terminal blocking agent (silylating agent)> Terminal blocking agent (end c)
Examples of ap) include those that are not easily affected by an excessive amount of water during the hydrolysis, and those that become a silylating agent when the trialkylsilylating agent itself is hydrolyzed in an acidic atmosphere. .

As such a terminal blocking agent, the following formula
(i):

[0066]

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(In the formula (i), R ^a , R ^b and R ^{c each} have 1 carbon atom.
The above-mentioned unsubstituted or substituted hydrocarbon groups are shown, and these may be the same or different. A is
Shows a hydroxyl group or a hydrolyzable group. )) Are preferred.

The hydrolyzable group A in the formula (i) means a group that is hydrolyzed by an excess of water required for hydrolyzing and condensing the monomer. Specifically, for example, hydrogen, mercapto, halogen, hydroxy, vinyl, amino, glycidyl, carboxyl, unsubstituted or substituted hydrocarbon group-containing oxy groups (eg, aralkyloxy group, aryloxy Group), an amino group, a carbonyloxy group containing an unsubstituted or substituted hydrocarbon group, or the following formula (ii):

[0069]

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(In the formula (ii), R ^e , R ^f , and R ^g each represent an unsubstituted or substituted hydrocarbon group having 1 or more carbon atoms. These may be the same or different. Is also good.
B represents an ether oxygen or an amino group. And the like.

Specific examples of such a terminal blocking agent include the following compounds. That is, trimethylsilanol, methoxytrimethylsilane, methoxytriethylsilane, triethylethoxysilane, 2-chloroethoxytrimethylsilane, chloromethyldimethylethoxysilane, ethoxytrimethylsilane, 2-propynyloxytrimethylsilane, dimethylethoxyethynylsilane, 1-chloromethyl -2-chloroethoxytrimethylsilane, allyloxytrimethylsilane, ethoxydimethylvinylsilane, isopropeneoxytrimethylsilane, 3-chloropropyltrimethylsilane, allyloxydimethylvinylsilane, 1-chloromethylethoxydimethylvinylsilane, tert-
Butoxytrimethylsilane, 1-methylpropyloxytrimethylsilane, isobutoxytrimethylsilane, butoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, furfuryloxytrimethylsilane,
Trimethylpentyloxysilane, isopentyloxytrimethylsilane, 2,4-dichlorophenyloxytrimethylsilane, chloromethyldimethylphenoxysilane, 2-chlorophenoxytrimethylsilane, 4-nitrophenoxytrimethylsilane, hydroxyphenoxytrimethylsilane, dimethylfurfuryloxyvinylsilane , 2-hydroxyphenoxytrimethylsilane, 1
-Chlorohexenyloxytrimethylsilane, cyclohexyloxytrimethylsilane, hexyloxytrimethylsilane, butyl-2-hydroxyethylthiomethyldimethylsilane, dimethylethynyl-2,4,5-trichlorophenoxysilane, 2,4-dichlorophenoxyethynyldimethylsilane , Trimethylsilylbenzoate, benzyloxychloromethyldimethylsilane, 3-
Aminophenoxydimethylvinylsilane, dimethylethoxy-3-glycidoxypropylsilane, dimethyl-2
-[(2-ethoxyethoxy) ethoxy] vinylsilane, methoxytripropylsilane, dimethyl-3-methyl-4-chlorophenoxyvinylsilane, dimethyl-2
-Methyl-4-chlorophenoxyvinylsilane, chloromethyldimethyl-2-phenylethoxysilane, benzyldimethylethoxysilane, dimethyl-2-piperidinoethoxyvinylsilane, 2-ethylhexyloxytrimethylsilane, octyltrimethylsilane, triethylsilylbenzoate, benzylidene -3-ethoxydimethylsilylpropylamine, diphenylethoxymethylsilane, dodecyloxytrimethylsilane, diphenylethoxyvinylsilane, acetyltriphenylsilane,
Ethoxytriphenylsilane, triphenylsilanol, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, pentamethyldisiloxane, 1,3-diethynyl-1,1,
3,3-tetramethyldisiloxane, N, O-Bis
(Trimethylsilyl) trifluoroacetamide, 1,
3-divinyl 1,1,3,3-tetramethyldisiloxane, Bis (trimethylsilyl) uracil, Bis (trimethylsilyl) tyrosine, 1,3-Bis (acetoxymethyl) tetramethyldisiloxane, 1- (N, N-
Dimethylthiocarbamoylthiomethyl) -1,1,3,
3-tetramethyl-3-vinyldisiloxane, 1,3-
Bis (3-chloropropyl) tetramethyldisiloxane, 1,3-Bis (3-mercaptopropyl) tetramethyldisiloxane, 1,3-Bis (3-hydroxypropyl) -1,1,3,3-tetramethyl Disiloxane, 1,3-Bis (3-aminopropyl) tetramethyldisiloxane, 1,3-Bis (2-aminoethylaminomethyl) -1,1,3,3-tetramethyldisiloxane, 3-methylpi Peridinomethylpentamethyldisiloxane, 4-methylpiperidinomethylpentamethyldisiloxane, hexaethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane, 1-
(2-methylpiperidinomethyl) -1,1,3,3-tetramethyl-3-vinyldisiloxane, 1- (3-methylpiperidinomethyl) -1,1,3,3-tetramethyl- 3-vinyldisiloxane, pentamethyl-3-piperidinopropyldisiloxane, 1,3-Bis (3-acetoxypropyl) tetramethyldisiloxane, 1,3-
Bis [3- (N-methylcarbamoyloxypropyl) tetramethyldisiloxane, 3- (4-methylpiperidinopropyl) pentamethyldisiloxane, 3- (2
-Methylpiperidinopropyl) pentamethyldisiloxane, 1,3-diphenyl-1,1,3,3-tetramethyldisiloxane, 1,3-Bis (dioxyanylethyl) -1,1,3,3 -Tetramethyldisiloxane,
1,3-Bis (3-glycidoxypropyl) -1,
1,3,3-tetramethyldisiloxane, hexapropyldisiloxane, 1,3-dimethyl-1,1,3,3-
Tetraphenyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinylsiloxane, allyldimethylsilane, diethylmethylsilane, triethylsilane,
Butyldimethylsilane, dimethylphenylsilane, methylphenylvinylsilane, tripropylsilane, diphenylmethylsilane, triphenylsilane, 1-piperidinomethyl-1,1,3,3-tetramethyl-3-vinyldisiloxane, 1,3-divinyl -1,1,3,3-tetramethyldisilazane, pentamethylpiperidinomethyldisiloxane, 4-trimethylsiloxyphenyltrimethylsilane, hexamethyldisiloxane, 3- (3-methylpiperidinopropyl) pentamethyldi Siloxane,
Trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, diethylmethylchlorosilane, ethyldimethylchlorosilane, butyldimethylchlorosilane, t-butyldimethylchlorosilane, butyldiethylchlorosilane, t-butyldiethylchlorosilane, triphenylchlorosilane, diphenylmethylchlorosilane, phenyldimethylchlorosilane, etc. .

These terminal blocking agents can be used alone or in combination of two or more. Among such terminal blocking agents, trimethylsilanol, hexamethyldisiloxane, chloromethyldimethylethoxysilane, acetyltriphenylsilane, ethoxytriphenylsilane, triphenylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, hexa Ethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane are preferred, and hexaethyldisiloxane, hexamethyldisiloxane, trimethylsilanol, and triethylsilanol are more preferably used.

<Uses> The hydroxyl group-containing polyorganosilsesquioxane (b) as described above can be used alone as it is as an adhesive, a heat-resistant coating material, a printing plate-making material, a printed wiring material, a lettering resist material, or the like. It may be used for applications.

Alternatively, this hydroxyl group-containing polyorganosilsesquioxane (b), for example, an alcoholic hydroxyl group-containing acrylic resin, and polyisocyanate or melamine are blended to form a resin composition for use in adhesives, paints and the like. May be used. Such a resin composition can be used for adhesion to a metal such as aluminum, glass, an acrylic resin, an ABS resin, polycarbonate, and the like, and is particularly excellent in adhesion to aluminum. When such a resin composition is used as the metal adhesive, such a resin composition contains 0.01 to 20 parts by weight of a hydroxyl group-containing polyorganosilsesquioxane (b), preferably Is 0.1
The alcoholic hydroxyl group-containing acrylic resin is used in an amount of 10 to 90 parts by weight, preferably 30 to 60 parts by weight, and the polyisocyanate or melamine is used in an amount of 10 to 9 parts by weight.
Solvents (viscosity modifiers) such as toluene, xylene, butyl acetate, and propylene glycol methyl ether acetate, which are optionally contained in an amount of 0 parts by weight, preferably 30 to 60 parts by weight, are 10 to 90 parts by weight, preferably 30
Up to 60 parts by weight may be included. However, the total of all components in the resin composition is 100 parts by weight.

Examples of the alcoholic hydroxyl group-containing acrylic resin include, for example, a hydroxyl value of 20 to 200 (KOH mg /
g) Acrylic polyols, polyether polyols, polyester polyols and the like of the order.

Examples of the polyisocyanate include hexamethylene diisocyanate polyisocyanate,
Examples include isophorone diisocyanate-based polyisocyanate.

Although such a resin composition depends on its use, for example, when used as a paint,
In addition to the above components, color pigments, plasticizers, pigment dispersants, thickeners, insecticides / bactericides, fillers (bulking agents), rust inhibitors, matting agents, antifouling agents (poisonous substances), metals Optional components such as powder may be included.

[0078]

As described above, the hydroxyl group-containing polyorganosilsesquioxane according to the present invention has uniform and high reactivity, has excellent storage stability, and hardly gels during production. .

The resin composition of the present invention comprising a hydroxyl-containing polyorganosilsesquioxane, an acrylic copolymer resin having an alcoholic hydroxyl group, and a polyisocyanate compound has excellent adhesion to metals, particularly aluminum. ing.

[0080]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

The physical properties in the examples and comparative examples were measured according to the following methods. [Adhesion] Evaluated by a grid method (100 squares) according to JIS K5400.

[Nuclear Magnetic Resonance Spectrum Analysis] Bruke
¹ H-NMR, ¹³ C-NM using AMX-400 manufactured by R
R, ²⁹ Si-NMR analysis was performed.

[Infrared Absorption Spectrum Analysis] Using a VALOR-III type Fourier transform infrared spectrophotometer manufactured by JASCO Corporation, an infrared absorption spectrum was measured by transmittance measurement.

[Number average molecular weight] The number average molecular weight was measured using gel permeation chromatography (GPC). In the measurement, “CR-3A” manufactured by Shimadzu Corporation was used, and “Showdex KF-8” manufactured by Showa Denko KK was used for the column.
01, KF-802, KF-803, KF-804 "were used in series, and polystyrene was used as a standard substance.

[0085]

Example 1 γ-glycidoxypropyltrimethoxysilane was placed in a 500 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube under a nitrogen stream.
36.34 g (1000 mmol), water 54.06 g
(3000 mmol), and the mixture in the flask was cooled to 5 ° C.

Next, an aqueous solution of sulfuric acid having a concentration of 10.0% was used.
After 9 g (5 mmol) was added dropwise to the mixture over 30 minutes, the mixture was kept at 10 ° C. for 60 minutes. Then, the temperature of the reaction vessel was adjusted with a water bath to raise the reaction temperature of the mixture to 7.
It was kept at 0 ° C. The hydrolysis-condensation reaction was performed for 3 hours under a nitrogen stream, and then 65 g of hexamethyldisiloxane (400 m
mol) was added to carry out the silylation reaction for 3 hours.

The obtained reaction solution was cooled to 40 ° C. Next, the reaction solution was neutralized with an aqueous potassium hydroxide solution, and the reaction solution (mixture) was kept at room temperature (25 ° C.) overnight.

As a result, the reaction solution was separated into two layers. Next, 150 g of butyl acetate was added to the lower layer of the two layers.
Was added and the mixture was distilled at 200 mmHg, 40 ° C. to remove 200 g of solvent.

After adding 200 g of butyl acetate to the obtained solution, the mixture was stirred for 1 hour. Next, the average pore diameter is set to 0.
The solution was filtered through an 8 micron filter to give a clear and colorless solution (9
00g).

The number average molecular weight of this compound (solution) measured by GPC was 3,600. ¹ H-N of this compound
As a result of the MR measurement, no glycidyl group of the raw material was observed, and the result of the IR measurement revealed that a hydroxyl group was generated. From these facts, it is considered that a glycidyl group and water reacted to generate a hydroxyl group.

Further, the hydroxyl group formed here was replaced with heavy water, and the disappeared hydroxyl group was quantified by ¹ H-NMR measurement. As a result, the equivalent amount of the glycidyl group charged to the diol formed by the reaction with water was measured. It was confirmed that the hydroxyl group had disappeared, and it was confirmed that most of the side chain (95 mol% or more) of the polyorganosilsesquioxane synthesized here was converted to a diol.

Further, when confirmed by ¹ H-NMR, an average of 75 mol% or more (specifically, 82%) of the main chain terminal groups of the synthesized polyorganosilsesquioxane was trialkylsilylated. Was.

[0093]

Comparative Example 1 A hydroxyl group-containing polyorganosilsesquioxane was produced in the same manner as in Example 1, except that the amount of water during the hydrolytic condensation was changed as follows.

Under a nitrogen stream, γ-glycidoxypropyltrimethoxysilane 2 was placed in a 500 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube.
36.34 g (1000 mmol), 18.02 g of water
(1000 mmol) and the mixture was cooled to 5 ° C. 4.9 g of a 10.0% hydrochloric acid aqueous solution (5 mm
l) was added dropwise to the mixture over 30 minutes, after which the mixture was
C. for 60 minutes.

Next, the temperature of the reaction vessel was adjusted with a water bath, the reaction temperature of the mixture was maintained at 70 ° C., and the hydrolysis / condensation reaction was carried out for 3 hours under a nitrogen stream, followed by 65 g (400 mmol) of hexamethyldisiloxane. Was added and a silylation reaction was carried out at the same temperature (70 ° C.) under a nitrogen stream 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 (25) ° C. overnight. Then butyl acetate 150
g was added and the mixture was distilled at 200 mm Hg, 40 ° C. to remove 200 g of solvent. 200 in the resulting solution
After adding g of butyl acetate, the mixture was stirred for 1 hour. The solution was filtered through a filter having an average pore diameter of 0.8 micron to obtain a colorless and transparent solution (900 g).

The number average molecular weight of the obtained compound measured by GPC was 2,000. ¹ H-NM of this compound
From the R measurement, many unreacted glycidyl groups were confirmed, and this compound had poor stability and gelled after 3 days.

[0098]

Comparative Example 2 A hydroxyl group-containing polyorganosilsesquioxane was produced in the same manner as in Example 1, except that the amount of the acid during the hydrolytic condensation was changed as follows.

Under a nitrogen stream, γ-mercaptopropyltrimethoxysilane 23 was placed in a 500 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube.
6.34 g (1000 mmol), water 54.06 g (3
000 mmol) and the mixture was cooled to 5 ° C. 0.01 g of a 10.0% hydrochloric acid aqueous solution (0.01 mm
ol) was added dropwise over 30 minutes to the mixture,
It was kept at 0 ° C. for 60 minutes.

Next, the temperature of the reaction vessel was adjusted with a water bath, the reaction temperature of the mixture was maintained at 70 ° C., and the hydrolysis / condensation reaction was carried out under a nitrogen stream for 3 hours, and then 65 g (400 mmol) of hexamethyldisiloxane was obtained. Was added and a silylation reaction was carried out at the same temperature (70 ° C.) under a nitrogen stream 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. 150 g of butyl acetate was added to the obtained reaction mixture, and the mixture was distilled at 200 mmHg and 40 ° C.,
240 g of solvent were removed.

After adding 200 g of butyl acetate to the obtained solution, the mixture was stirred for 1 hour. The solution was filtered through a filter having an average pore diameter of 0.8 micron to obtain a colorless and transparent solution (900 g).

The number average molecular weight of the obtained compound was 600 as measured by GPC. ¹ H-NM of this compound
When R and ²⁹ Si-NMR were measured, the hydrolysis-condensation reaction of the raw material monomer did not proceed sufficiently, many unreacted monomers and low molecular oligomers were observed, and the desired ladder structure was hardly constructed. Was.

[0103]

Comparative Example 3 A hydroxyl group-containing polyorganosilsesquioxane was produced in the same manner as in Example 1, except that the type of acid used during the hydrolytic condensation was changed as follows.

Under a nitrogen stream, γ-mercaptopropyltrimethoxysilane 23 was introduced into a 500 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube.
6.34 g (1000 mmol), water 54.06 g (3
000 mmol), and the charged mixture is cooled to 5 ° C.
Cooled down. 10.13 g of 3.6% hydrochloric acid aqueous solution
(10 mmol) was added dropwise to the mixture over 30 minutes and the resulting mixture was kept at 10 ° C. for 60 minutes.

Next, the temperature of the reaction vessel was adjusted with a water bath, the reaction temperature of the mixture was maintained at 70 ° C., and the hydrolysis / condensation reaction was carried out for 3 hours under a nitrogen stream, and then 65 g (400 mmol) of hexamethyldisiloxane was obtained. Was added and a silylation reaction was carried out at the same temperature (70 ° C.) under a nitrogen stream for 3 hours. The obtained reaction solution was cooled to 40 ° C. The reaction solution was neutralized with an aqueous solution of potassium hydroxide, and the resulting mixture was kept at room temperature overnight.

Next, 150 g of butyl acetate was added to the mixture.
Was added, and the resulting mixture was subjected to 200 mmHg, 40 ° 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.
The solution was filtered through a filter having an average pore diameter of 0.8 micron to obtain a colorless and transparent solution (900 g).

The number average molecular weight of the obtained compound was 600 as measured by GPC. In this compound, hydrochloric acid as a catalyst reacts with a glycidyl group and hydrolysis and condensation hardly proceed, and as a result of ¹ H-NMR measurement,
The addition reaction of water to the glycidyl group hardly proceeded, and no hydroxyl group was generated.

[0108]

Example 2 Using the resin prepared in Example 1, a composition was prepared by uniformly mixing and blending the following components. This composition was applied on an aluminum steel plate (JIS A1050P) so that the obtained dry film thickness was 20 μm, and then left at room temperature for 7 days to prepare a substrate. The grid adhesion of this substrate was evaluated, and was 100/100.

(Hydroxyl-containing polyorganosilsesquioxane) obtained in Example 1 0.5 parts by weight A801 59.0 parts by weight (Acrylic polyol manufactured by Dai Nippon Ink Co., Ltd.) Hydroxyl value 100 KOHmg / g) Sumidur N-3500 ··· 10.0 parts by weight (Hexamethylene diisocyanate polyisocyanate manufactured by Sumitomo Bayer Urethane Co.) Propylene glycol methyl ether acetate ··· 30.5 parts by weight

[0110]

Example 3 Using the resin prepared in Example 1, a composition was prepared by uniformly mixing and blending the following components. This composition was applied on an aluminum steel plate (JIS A1050P) so that the obtained dry film thickness was 20 μm, and then left at room temperature for 7 days to prepare a substrate. The grid adhesion of this substrate was evaluated, and was 100/100.

[0111] (Hydroxyl-containing polyorganosilsesquioxane) obtained in Example 1... 0.05 part by weight A801... 59.0 parts by weight Sumidur N-3500. 0 parts by weight Propylene glycol methyl ether acetate ... 30.95 parts by weight

[0112]

Comparative Example 4 A composition was prepared by uniformly mixing the following components. The obtained composition was coated on an aluminum sheet (JIS A10).
After coating on 50P) so that the dry film thickness was 20 μm, the substrate was left at room temperature for 7 days to prepare a substrate. When the grid adhesion of this base material was evaluated, it was 0/100.

A801 ··· 59.0 parts by weight Sumidur N-3500 ··· 10.0 parts by weight Propylene glycol methyl ether acetate ··· 31.0 parts by weight In the above applied examples and comparative examples, Table 1 also shows the results of measuring the physical properties of the coating film (cross-cut adhesion test).

[0114]

[Table 1]

[0115]

Example 4 (Using Triphenylsilyl Group-Containing Compound for Silylation of Terminal) A γ-glycol was placed in a 50 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube under a nitrogen stream. Sidoxypropyltrimethoxysilane 23
6.34 g (1000 mmol), water 54.06 g (3
000 mmol), and the charged mixture is cooled to 5 ° C.
Cooled down.

Then, 4.9 g (5 mmol) of a sulfuric acid aqueous solution having a concentration of 10.0% by weight was dropped into the mixture over 30 minutes, and the resulting mixture was kept at 10 ° C. for 60 minutes.
Next, the temperature of the reaction vessel was adjusted with a water bath, the reaction temperature of the mixture was maintained at 70 ° C., and the hydrolysis / condensation reaction was carried out under a nitrogen stream for 3 hours.
3.92 g (400 mmol) was added, and the silylation reaction was performed at the same temperature (70 ° C.) under a nitrogen stream for 3 hours. The obtained reaction solution was cooled to 40 ° C. The reaction solution was neutralized with an aqueous solution of potassium hydroxide, and the resulting reaction solution (mixture) was left overnight at room temperature (25 ° C.).

Next, the lower layer of the liquid separated into two layers was collected. 150 g of butyl acetate was added to the collected material from the lower layer, and the obtained mixture was distilled at 200 mmHg and 40 ° C. to remove 200 g of the solvent. 200 in the resulting solution
After adding g of butyl acetate, the mixture was stirred for 1 hour.

Next, the mixture was filtered through a filter having an average pore diameter of 0.8 micron to obtain a colorless and transparent solution (1000 g). When the molecular weight was measured by GPC, the number average molecular weight of the obtained compound (solution) was 4,000.

As a result of ¹ H-NMR measurement of this compound, no glycidyl group as a raw material was observed, and a result of IR measurement revealed that a hydroxyl group was formed. From these facts, it is considered that a glycidyl group and water reacted to generate a hydroxyl group.

Further, the hydroxyl group generated here was replaced with heavy water, and the disappeared hydroxyl group was quantified by ¹ H-NMR measurement. As a result, the equivalent amount of the glycidyl group charged to the diol formed by the reaction with water was measured. It was confirmed that the hydroxyl group had disappeared, and it was confirmed that most of the side chain (95 mol% or more) of the polyorganosilsesquioxane synthesized here was converted to a diol.

Further, it was confirmed by ¹ H-NMR that an average of 75 mol% or more of the main chain terminal groups of the synthesized polyorganosilsesquioxane was trialkylsilylated.

[0122]

Example 5 246.4 g (1000 mmol) of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in a 50 ml flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube under a nitrogen stream. , And 54.06 g (3000 mmol) of water, and the charged mixture was cooled to 5 ° C.

Next, 4.9 g (5 mmol) of an aqueous solution of sulfuric acid having a concentration of 10.0% by weight was dropped into the mixture over 30 minutes, and the resulting mixture was kept at 10 ° C. for 60 minutes.
Then, the temperature of the reaction vessel was adjusted with a water bath, the reaction temperature of the mixture was maintained at 70 ° C., and the hydrolysis and condensation reaction was carried out for 3 hours under a nitrogen stream, followed by 65 g of hexamethyldisiloxane.
(400 mmol) and add the same temperature (70 ° C)
The silylation reaction was performed for 3 hours under a nitrogen stream. The obtained reaction solution was cooled to 40 ° C. The reaction solution was neutralized with an aqueous solution of potassium hydroxide, and the resulting reaction solution (mixture) was left overnight at room temperature (25 ° C.).

Then, the lower layer of the liquid separated into two layers was collected. 150 g of butyl acetate was added to the collected material from the lower layer, and the obtained mixture was distilled at 200 mmHg and 40 ° C. to remove 200 g of the solvent. 200 in the resulting solution
After adding g of butyl acetate, the mixture was stirred for 1 hour.

Next, the solution was filtered through a filter having an average pore diameter of 0.8 micron to obtain a colorless and transparent solution (900 g). When the molecular weight was measured by GPC, the number average molecular weight of the obtained compound (solution) was 3,700.

As a result of ¹ H-NMR measurement of this compound, no glycidyl group as a raw material was observed, and from a result of IR measurement, it was found that a hydroxyl group was formed. From these facts, it is considered that a glycidyl group and water reacted to generate a hydroxyl group.

Further, the hydroxyl group generated here was replaced with heavy water, and the disappeared hydroxyl group was quantified by ¹ H-NMR measurement. As a result, the equivalent amount of the glycidyl group charged to the diol formed by the reaction with water was measured. It was confirmed that the hydroxyl group had disappeared, and it was confirmed that most of the side chain (95 mol% or more) of the polyorganosilsesquioxane synthesized here was converted to a diol.

Further, as confirmed by ¹ H-NMR, an average of 75 mol% or more of the main chain terminal groups of the synthesized polyorganosilsesquioxane was trialkylsilylated.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 83/06 LRY C08L 83/06 LRY // C09D 175/04 PHP C09D 175/04 PHP (72) Inventor Yoichi Nanba Chiba 1-1-1 Onodai, Midori-ku, Chiba-shi, Japan Showa Denko KK

Claims (5)

[Claims] (1) at least 75 mol% of the main chain terminal groups are terminal blocking groups, and all of the side chain groups are hydroxyl group-containing groups or substantially all of the hydroxyl group-containing groups and the epoxy group-containing groups; A hydroxyl group-containing polyorganosilsesquioxane having a number average molecular weight of 1,000 to 30,000. 2. The method according to claim 1, wherein the terminal capping group is any one or two or more selected from trialkylsilyl, triphenylsilyl, phenyldialkylsilyl, and diphenylalkyl groups. The hydroxyl group-containing polyorganosilsesquioxane according to claim 1, wherein all or a part of the hydrogen atoms in the group (a) may be substituted with a halogen atom. 3. An epoxy group-containing trialkoxysilane is reacted with water to hydrolyze and polycondensate the epoxy group-containing trialkoxysilane, and the epoxy group is reacted with water to form a diol. The method for producing a hydroxyl-containing polyorganosilsesquioxane according to claim 1, wherein the method is reacted with a functional silylating agent. 4. The method according to claim 1, wherein sulfuric acid is used as an acid catalyst in an amount of 0.00005 to 0.05 mol per 1 mol of the silane when the epoxy group-containing trialkoxysilane is hydrolyzed and polycondensed. The method for producing a hydroxyl-containing polyorganosilsesquioxane according to claim 3. 5. A resin composition comprising the hydroxyl group-containing polyorganosilsesquioxane according to claim 1 or 2, an alcoholic hydroxyl group-containing acrylic resin, and a polyisocyanate.