JP3331667B2 - Polymethylsilsesquioxane-based polymer and vinyl copolymer resin having polymethylsilsesquioxane structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymethylsilsesquioxane-based polymer and a vinyl copolymer resin having a polymethylsilsesquioxane structure, and more particularly, it can be produced without gelation, and The present invention relates to a polymethylsilsesquioxane having excellent storage stability and a polymethylsilsesquioxane having excellent durability and storage stability in which such a polymethylsilsesquioxane is bonded to a main chain and / or a side chain of a vinyl monomer. The present invention relates to a vinyl copolymer resin having a methylsilsesquioxane structure.

[0002]

2. Description of the Related Art Various methods for improving the characteristics of polymers by introducing a polysiloxane structure into the main chain or side chain of an organic polymer have been known. For example, JP-A-60-
No. 231720 discloses a method for producing a polysiloxane graft copolymer having a polysiloxane structure in a side chain by radical copolymerizing a siloxane-containing monomer with an ethylenically unsaturated monomer or a diene monomer. It is described that the polysiloxane graft copolymer thus obtained is excellent in surface properties such as water repellency, antifouling property, and releasability, and durability.

However, if the content of polysiloxane in the polymer is increased for the purpose of further improving its durability, the resulting polysiloxane graft copolymer has a hardness, since the polysiloxane itself has a soft property. It becomes low, easily scratched, and has low stain resistance.

Japanese Patent Application Laid-Open No. 62-275132 discloses a polymethylsilsesquioxane structure (ladder structure).
A functional group comprising a hydroxyl group or an alkoxy group
By copolymerizing a polysiloxane-based macromonomer having at least one polysiloxane and a vinyl monomer, the
A method for producing a vinyl polymer into which a siloxane side chain having at least one siloxane is introduced is disclosed. It is described that the vinyl polymer into which the siloxane side chain is introduced has excellent cross-linking properties, compatibility with other resins, and excellent properties such as weather resistance, light resistance, water resistance, and stain resistance. ing.

In the polysiloxane-containing resin obtained by this method, the polysiloxane in the resin has a ladder structure, and the crosslink density is increased by the above-mentioned functional groups, so that the polysiloxane content is high. It has excellent hardness.

[0006] However, it is desired that the durability and hardness of the vinyl polymer into which such a siloxane side chain is introduced are further improved.

It is to be noted that polymethylsilsesquioxane having a certain number or more of polysiloxane side chains as a methyl group, having few aromatic side chains, and having a hydroxyl group or an alkoxy group at a terminal or a side chain has a terminal or side chain. It has been reported that the functional groups such as a hydroxyl group and an alkoxy group in the chain have high reactivity and are very easy to gel (Seiichi Nakahama et al., Polymer
Preprints, Japan 29 (1) 73
(1980)).

For this reason, gelation or the like occurs of a polysiloxane containing a certain number or more of methyl groups in a side chain per molecule and containing a certain number or more of functional groups comprising a hydroxyl group or an alkoxy group in a terminal and / or a side chain. It is extremely difficult to synthesize such a polymer without such a method, and there is a problem that a polymer having such a polysiloxane introduced into a molecular structure lacks storage stability.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and can be produced without causing gelation and has excellent storage stability. It is intended to provide oxane, and such polymethylsilsesquioxane can be used as a polymer, in particular, as a main chain and / or a vinyl polymer.
Another object is to provide a polymer having a polymethylsilsesquioxane structure which is bonded to a side chain and has excellent durability and storage stability.

[0010]

The polymethylsilsesquioxane polymer according to the present invention has the following general formula:

Embedded image (In the formula, 50 to 99.9 mol% of R ¹ and R ² is a methyl group, 0.1 to 25 mol% is a vinyl group or an organic group having a vinyl group as a substituent, and the remainder is a carbon atom. An alkyl group of 2 or more, a substituted or unsubstituted phenyl group,
A hydroxyl group or an alkoxy group, R ³ , R ⁴ , R ⁵ ,
R ⁶ is a hydrogen atom or an alkyl group, and n indicates the degree of polymerization. ), So that the total number of hydroxyl groups and / or alkoxy groups contained in the polymethylsilsesquioxane is 2 or less per molecule of the polymethylsilsesquioxane. It is characterized by becoming.

The vinyl copolymer resin having a polymethylsilsesquioxane structure according to the present invention is characterized in that the above-mentioned polymethylsilsesquioxane-based polymer and a vinyl monomer are copolymerized.

In the present invention, it is preferable that a part of the vinyl monomer has a crosslinkable reactive group.

According to the present invention, there is provided polymethylsilsesquioxane which can be produced without gelation and which has excellent storage stability. According to the present invention, such a polymethylsilsesquioxane is bonded to a main chain and / or a side chain of a vinyl polymer, and has a polymethylsilsesquioxane structure excellent in durability and storage stability. A polymer is provided.

Hereinafter, the polymethylsilsesquioxane-based polymer and the vinyl polymer having a polymethylsilsesquioxane structure according to the present invention will be specifically described.

In the polymethylsilsesquioxane polymer according to the present invention, a specific polymethylsilsesquioxane is obtained by adding a hydroxyl group and / or an alkoxy group contained in the polymethylsilsesquioxane in total. The polymethylsilsesquioxane is trimethylsilylated so that the number of polymethylsilsesquioxane is 2 or less per molecule.

In the general formula, R is a side chain group.
¹ , 50 to 99.9 mol% of R ² , preferably 60 to 9
5 mol% is a methyl group, and 0.1 to 25 mol%, preferably 5 to 20 mol% is a vinyl group or an organic group having a vinyl group as a substituent. When the methyl group in the side chain is less than 50 mol%, when the polymethylsilsesquioxane is incorporated into the vinyl copolymer resin, the hardness and weather resistance of the vinyl copolymer resin become insufficient. On the other hand, if it exceeds 99.9 mol%, the amount of vinyl groups or organic groups having a vinyl group as a substituent decreases, and the vinyl copolymerization reaction becomes insufficient.
This has an adverse effect on durability and the like. If the vinyl group or the organic group having a vinyl group as a substituent is more than 25 mol%, gelation tends to occur in the production of the vinyl copolymer resin. In addition, even if it can be produced, the hardness is high, but it is brittle and follows the deformation and impact. A problem arises in terms of gender.

In R ¹ and R ² , a methyl group, a vinyl group or an alkyl group having 2 or more carbon atoms or a substituted or unsubstituted phenyl group among the remaining groups other than the organic group having a vinyl group as a substituent is a hardness. Since the durability is inferior to that of the methyl group, it is desirable to reduce the durability as much as possible.

The side groups R ¹ and R ² and / or the terminal groups OR ³ , OR ⁴ and OR ^{5 of the} polymethylsilsesquioxane having a vinyl group or an organic group having a vinyl group as a substituent used in the present invention. , hydroxyl and / or alkoxy groups of oR ⁶ may optionally be trimethylsilylated, sum the polymethylsilsesquioxane structure per the free hydroxyl group and an alkoxy group, it is necessary not to exceed 2.

When the total of free hydroxyl groups and alkoxy groups is 2 or more per polymethylsilsesquioxane structure, the polymethylsilsesquioxane structure is extremely easily gelled at the time of production, and is not only difficult to handle but also difficult to handle. When incorporated into the molecular structure of vinyl copolymer resin,
The resin itself also lacks storage stability, causing practical inconvenience.

In the trimethylsilylation, the polymethylsilsesquioxane may be reacted with trimethylsilanol, but it is efficient to react hexamethyldisiloxane under weak acidity. Further, it is convenient and preferable from the viewpoint of the reaction operation to carry out a reaction of tritrimethylsilylation before copolymerizing the polymethylsilsesquioxane with a vinyl monomer.

In the present invention, the total amount of the hydroxyl group and the alkoxy group on the side chain and the terminal of the polymethylsilsesquioxane containing a vinyl group or an organic group having a vinyl group as a substituent is determined as follows. Can be.

First, by adding hexamethyldisiloxane under weak acidity and heating to about 50 ° C., it is confirmed by NMR analysis that the hydroxyl group and the alkoxy group completely react. Therefore, an excess amount of hexamethyldisiloxane is added. To measure the residual amount after the reaction, and calculate the consumed amount. This residue is analyzed by gel permeation chromatography (GP
It can be quantified using C). The absolute molecular weight of the polymethylsilsesquioxane is measured by means such as vapor pressure measurement. From the above two data, the total amount of hydroxyl groups and alkoxy groups per molecule of hexamethyldisiloxane is calculated. As a practical measure, the total amount of the polymethylsilsesquioxane side chain and the hydroxyl group at the terminal and the alkoxy group before the silylation is determined in advance, and the total amount of the silyl is adjusted so as to have a predetermined silylation degree. It is desirable to carry out a chemical reaction.

Examples of such polymethylsilsesquioxane include trialkoxysilane and / or trichlorosilane having a vinyl group or an organic group having a vinyl group as a substituent, methyltrialkoxysilane and / or methyltrihalolosilane. Can be obtained by hydrolysis and co-condensation.

In the present invention, examples of the trialkoxysilane and / or trichlorosilane having a vinyl group or an organic group having a vinyl group as a substituent include the following. Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrichlorosilane, γ- Acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane. The following can be exemplified as methyltrialkoxysilane, methyltrihalolosilane and the like. Methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, trichlorosilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane.

The polymethylsilsesquioxane polymer thus obtained has a number average molecular weight of 500 to 10
000, preferably 1,000 to 10,000.
0. Next, a vinyl copolymer resin having a polymethylsilsesquioxane structure will be described.

In the vinyl polymer having a polymethylsilsesquioxane structure according to the present invention, the above-mentioned polymethylsilsesquioxane-based polymer is bonded to the vinyl polymer by a vinyl group in the polymer. . Such a vinyl polymer is excellent in durability and the like, and is excellent in storage stability.

In order to bond the above-mentioned polymethylsilsesquioxane-based polymer to the main chain and / or side chain of the vinyl polymer, it is necessary to form the vinyl polymer with the polymethylsilsesquioxane-based polymer. May be copolymerized with a vinyl monomer. Examples of the vinyl monomer copolymerized with polymethylsilsesquioxane in the present invention include the following. Of course, the present invention is not limited to these exemplified monomers at all.

Methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate,
Esters of acrylic acid or methacrylic acid such as lauryl methacrylate, stearyl acrylate, stearyl methacrylate and a monohydric alcohol having 1 to 22 carbon atoms;
Other vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, acrylonitrile, vinyl acetate, and vinyl chloride.

The above-mentioned copolymerization reaction is preferably carried out by a commonly used method, for example, in the presence of a polymerization initiator such as an organic peroxide or a polymerization catalyst. As a specific example, when formed by radical polymerization of a vinyl monomer, a polymerization initiator such as benzoyl peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, cumene hydroperoxide, or t-butyl hydroperoxide is used. It goes without saying that it is not limited to these. Such a reaction
The reaction is preferably performed in an organic solvent, and examples of such an organic solvent include xylene, toluene, butyl acetate, and methyl isobutyl ketone.

The vinyl copolymer thus obtained has a number average molecular weight of 1,000 to 100,000, preferably 3,000 to 30,000.

Further, as described below, in a composition containing the vinyl copolymer resin of the present invention,
Further, as a vinyl copolymer resin suitable for three-dimensional curing according to the purpose and application, a vinyl monomer having a crosslinkable reactive group as a part of the vinyl monomer and the polymethylsilsesquioxane-based polymer of the present invention. A vinyl copolymer resin having a polymethylsilsesquioxane structure characterized by being copolymerized is exemplified. Such a resin can be obtained, for example, by applying the above-described copolymerization reaction to a vinyl monomer having a crosslinkable reactive group.

Examples of the vinyl monomer having a crosslinkable reactive group used as a part of the vinyl monomer in the present invention include the following. Alcoholic hydroxyl-containing vinyl monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; vinyl monomers containing carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride; acrylic acid Epoxy group-containing vinyl monomers such as glycidyl and glycidyl methacrylate; amide group-containing vinyl monomers such as acrylamide, methacrylamide, N-methylolamide, and N-methylol methacrylamide; dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, and tert-methacrylate Amine-based vinyl monomers such as butylaminoethyl; sulfonic acid groups such as vinylsulfonic acid and vinylsulfonyl chloride, and vinylmonomers containing chlorosulfonic acid groups Chromatography; other mercapto group, an amidoxime group, an aldehyde group, an acetyl acetonate group-containing vinyl monomers.

The number average molecular weight of the thus obtained copolymer with a vinyl monomer having a crosslinkable reactive group as a part of the vinyl monomer is from 1,000 to 100,000, preferably from 3,000 to 30. 2,000 is desirable. In addition, it is preferable to condense a polymethylsilsesquioxane-based polymer obtained by preliminarily trimethylsilylating polymethylsilsesquioxane with a vinyl monomer.However, polymethylsilsesquioxane that is not trimethylsilylated is converted to a vinyl monomer. After the condensation, the hydroxyl group and / or the alkoxy group in the polymethylsilsesquioxane bonded to the vinyl polymer may be trimethylsilylated.

The resin having a polymethylsilsesquioxane structure of the present invention can be used alone as a resin having excellent hardness, durability, etc., but includes a curing agent, an extender, a thickener, a coloring pigment, and an ultraviolet ray. It can also be used as a so-called resin composition to which an absorbent, an antioxidant, an antifoaming agent and the like are added.

When using the resin or the resin composition as described above, various solvents or reactive diluents can be used in combination in order to improve workability.
Solvents include alcohols such as propanol and butanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as cellosolve acetate and methyl cellosolve, esters such as ethyl acetate and butyl acetate, and aromatics such as toluene and xylene. Group hydrocarbons and the like. Of course, these solvents may be used as a mixture of two or more.

In the vinyl copolymer resin having a polymethylsilsesquioxane structure of the present invention or a composition using the same, when a part of the crosslinkable reactive group remains, the resin of the present invention or the resin of the present invention is used. Further, a step of three-dimensionally curing the composition using the composition according to the purpose and application can be adopted. Similarly, in the case of polymethylsilsesquioxane having a crosslinkable reactive group containing two or more kinds of crosslinkable reactive groups, as for the incorporation into the main chain and / or side chain of the molecular structure of the resin, one of these A crosslinkable reactive group is used, and other crosslinkable reactive groups can be used in the step of three-dimensional curing of the resin of the present invention or a composition using the same.

The vinyl copolymer resin having a polymethylsilsesquioxane structure of the present invention or a composition using the same can be used as a raw material for molding materials and sheets.
It is particularly useful as a coating for surfaces of articles, vehicles, buildings, etc., and as a base resin for paints. At this time, in order to three-dimensionally cure the resin composition, an appropriate curing method and curing conditions may be selected according to the types of the crosslinkable reactive group and the curing agent.

For example, when the crosslinkable reactive group is an alcoholic hydroxyl group, and when the curing agent is a diisocyanate, two-part room temperature or heat curing can be selected. When the curing agent is a melamine resin, the composition can be heated and cured. Becomes

[0039]

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. In addition, each physical property value in an Example and a comparative example was measured according to the following method.

(Surface hardness) It was measured according to JIS K5401 using a pencil scratch tester for paint. (Weather resistance) A carbon arc sunshine weather meter test was performed according to the provisions of JIS B7753. After 2,000 hours, the surface of the test specimen was observed and compared with that before the test to evaluate.

The polymethylsilsesquioxane having a vinyl group used in Examples and Comparative Examples was synthesized as follows.

(Synthesis of methacryl-reactive polymethylsilsesquioxane) In a 2-liter flask equipped with a thermometer, a stirrer and a reflux condenser, 50 g (0.2 mol) of γ-methacryloxylpropyltrimethoxysilane, methyl Charge 445 g (2.5 mol) of triethoxysilane, 20 g (0.1 mol) of phenyltrimethoxysilane, 200 g of acetone, 0.002 mol of hydrochloric acid, and 54 g (3 mol) of water, raise the temperature in the flask to 60 ° C., and stir. For 3 hours. Then, after raising the temperature to 70 ° C. and reacting for 1 hour,
After dropwise addition of 0.004 mol of KOH and further reaction for 2 hours, the mixture was neutralized, washed with water and toluene, and then the solvent, water and the like were removed using a rotary evaporator.
A viscous liquid having a viscosity of 1450 cps at 25 ° C. was quantitatively obtained.

The GPC curve was a single peak, and no residual peak derived from the monomer was observed.
Therefore, the monomer was considered to be completely co-condensed, and the molar ratio of the methyl group, γ-methacryloxypropyl group, and phenyl group in the side chain was 25: 2: 1 due to the molar ratio of the raw materials.

This is also the molecular weight determined by vapor pressure measurement.
(Mn) was 3,200, and the total amount of hydroxyl groups and alkoxy groups on the side chains and at the terminals was 5.4 per molecule, as calculated from this and measurement data obtained by silylation. Thus, silylation was carried out as follows so that the total amount of free side chains and terminal hydroxyl groups and alkoxy groups was 1.3.

An aliquot of the above viscous liquid was taken, and a predetermined amount of hexamethyldisiloxane and a small amount of hydrochloric acid were added thereto.
The mixture was reacted at a temperature of 4 ° C. and a pH of 4 for 2 hours. After neutralization, the same purification operation as described above was performed to obtain a polymethylsilsesquioxane polymer having a vinyl group used in the present invention. This is designated as polymer A.

For comparison, only the degree of silylation using hexamethyldisiloxane in the synthesis of polymer A was changed so that the total of free side chains and terminal hydroxyl groups and alkoxy groups was 3.5. A polymer B was obtained in the same manner as in the polymer A except that the above procedure was repeated.

For comparison, the molar ratio of methyl group, γ-methacryloxypropyl group and phenyl group was 12 by the same operation and formulation as in Polymer A except that the molar ratio of the starting alkoxysilane in Polymer A synthesis was changed. :
A polymethylsilsesquioxane having a ratio of 2:14 was obtained. This had a viscosity of 1400 cps at 25 ° C. and a molecular weight of 2500 by vapor pressure measurement. The total amount of the side chain and terminal hydroxyl groups and alkoxy groups is 5.7 per molecule, and the total amount of the free side chain and terminal hydroxyl groups and alkoxy groups becomes 1.3 by silylation. Was prepared. This is designated as polymer C.

For comparison, the molar ratio of methyl group, γ-methacryloxypropyl group, and phenyl group was changed to 16 by the same operation and formulation as in Polymer A, except that the reaction molar ratio of the starting alkoxysilane in Polymer A synthesis was changed. : 1
A polymethylsilsesquioxane having a ratio of 0: 2 was obtained. This had a viscosity of 1700 cps at 25 ° C. and a molecular weight of 3,800 as measured by vapor pressure. The total amount of the side chain and terminal hydroxyl groups and alkoxy groups is 5.5 per molecule, and the total amount of free side chain and terminal hydroxyl groups and alkoxy groups is 1.3 by silylation. Was prepared. This is designated as polymer D.

(Synthesis of vinyl-reactive polymethylsilsesquioxane) A thermometer, a stirrer, and a reflux condenser were installed.
In a 2 liter flask, add vinyltrimethoxysilane 6
5 g (0.4 mol), 392 g of methyltriethoxysilane
(2.2 mol), acetone 200 g, hydrochloric acid 0.002 mol,
54 g (3 mol) of water were charged and the temperature in the flask was raised to 60 ° C.
And kept for 3 hours with stirring. Then 70
After raising the temperature to 0 ° C and reacting for 1 hour, 0.004 mol of KOH was added dropwise, and the reaction was further performed for 2 hours, neutralized, washed with water and toluene, and then the solvent was removed using a rotary evaporator. After removing water and the like, the viscosity at 25 ° C. becomes 105
A viscous liquid of 0 cps was quantitatively obtained.

The GPC curve was a single peak, and no residual peak derived from the monomer was observed.
Therefore, the monomer was considered to be completely co-condensed, and the molar ratio of the methyl group and vinyl group in the side chain was 22: 4 due to the molar ratio of the raw materials.

This is also the molecular weight determined by vapor pressure measurement.
(Mn) was 2500, and the total amount of hydroxyl groups and alkoxy groups on the side chains and at the ends was 5.5 per molecule when calculated from this and measurement data obtained by silylation. Therefore, silylation was carried out as follows so that the total amount of free side chains and terminal hydroxyl groups and alkoxy groups was 0.9.

An aliquot of the above viscous liquid was taken, and a predetermined amount of hexamethyldisiloxane and a small amount of hydrochloric acid were added thereto.
The mixture was reacted at a temperature of 4 ° C. and a pH of 4 for 2 hours. After neutralization, the same purification operation as described above was performed to obtain a polymethylsilsesquioxane polymer having a vinyl group used in the present invention. This is designated as polymer E.

Example 1 The following composition was placed in a 2 liter flask equipped with a thermometer, a stirrer, and a reflux condenser, and reacted at 85 ° C. for 5 hours under reflux in a nitrogen stream. Reaction rate by permeation chromatography (GPC)
97%.

Polymer A 250 parts by weight Methyl methacrylate 180 parts by weight Butyl methacrylate 110 parts by weight 2-ethylhexyl acrylate 90 parts by weight Hydroxyethyl methacrylate 150 parts by weight 20 parts by weight methacrylic acid 20 parts by weight t-butyl dodecanethiol 20 parts by weight Azobis Isobutyronitrile 10 parts by weight Ethyl acetate 800 parts by weight

Thus, Polymer F having a number average molecular weight of 21,000 and a weight average molecular weight of 98,000 was obtained. Next, the following components were uniformly mixed, and a water glass-based multi-layer pattern spraying material was applied on a slate plate.
After coating to a thickness of μ, leave at room temperature overnight,
Heat curing was performed for a time.

Polymer F 48 parts by weight Polyfunctional aliphatic isocyanate 17 parts by weight (Sumitomo Bayer Co., Ltd. Sumidur N) dibutyltin dilaurate 0.3 parts by weight butyl acetate 20 parts by weight Xylene 15 parts by weight

Table 1 shows the thickness, surface pencil hardness, and weather resistance of the cured film. Comparative Example 1

The polymer A in Example 1 was replaced with the polymer B
An attempt was made to obtain a polymer by the same operation and formulation as in Example 1 except that the components were used, but gelation occurred 1 hour after the start of the reaction.

Comparative Example 2 A cured film was obtained by the same operation and formulation as in Example 1 except that polymer A in Example 1 was changed to Polymer C. The performance of this is shown in Table 1.

Comparative Example 3 An attempt was made to obtain a polymer by the same operation and formulation as in Example 1 except that the polymer A in Example 1 was changed to the polymer D component. The experiment was stopped.

Example 2 The following components were uniformly mixed, and 60
After coating to a thickness of μ, heat curing was performed at 70 ° C. for 1 hour and 150 ° C. for 1 hour.

Polymer E 45 parts by weight Styrene 55 parts by weight butyl acetate 30 parts by weight 2% methyl ethyl ketone peroxide 0.8 parts by weight

Table 1 shows the thickness, surface pencil hardness, and weather resistance of the cured film.

[0064]

[Table 1]

[0065]

Industrial Applicability The polymethylsilsesquioxane-based polymer of the present invention can be produced without causing gelation, and produces a vinyl copolymer having a polymethylsilsesquioxane structure having excellent storage stability. And a prepolymer for Further, when the vinyl copolymer resin of the present invention is three-dimensionally cured, a resin having high hardness and excellent weather resistance can be produced.

Continuing from the front page Examiner Yoko Nakajima (56) References JP-A-6-279586 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/38 C08F 299/08

Claims (3)

(57) [Claims] [Claim 1] The following general formula: (In the formula, 50 to 99.9 mol% of R ¹ and R ² is a methyl group, and 0.1 to 25 mol% is γ-acryloxypropyl
And the rest is an alkyl group having 2 or more carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group or an alkoxy group, and R ³ , R ⁴ , R ⁵ , R ⁶ Represents a hydrogen atom or an alkyl group, and n represents a degree of polymerization. ) And the number average molecular weight
Polymethylsilsesquioxane having a molecular weight of 500 to 100,000, when the total number of hydroxyl groups and / or alkoxy groups contained in the polymethylsilsesquioxane is 2 or less per molecule of the polymethylsilsesquioxane. A polymethylsilsesquioxane-based polymer characterized by being trimethylsilylated. 2. The following general formula: (In the formula, 50 to 99.9 mol% of R ¹ and R ² is a methyl group, and 0.1 to 25 mol% is γ-acryloxypropyl
And the rest is an alkyl group having 2 or more carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group or an alkoxy group, and R ³ , R ⁴ , R ⁵ , R ⁶ Is a hydrogen atom or an alkyl group, and n indicates the degree of polymerization. ) And the number average molecular weight
Polymethylsilsesquioxane having a molecular weight of 500 to 100,000, when the total number of hydroxyl groups and / or alkoxy groups contained in the polymethylsilsesquioxane is 2 or less per molecule of the polymethylsilsesquioxane. A vinyl copolymer resin having a polymethylsilsesquioxane structure, characterized in that a polymethylsilsesquioxane-based polymer and a vinyl monomer are copolymerized, characterized by being trimethylsilylated. . 3. The vinyl copolymer resin having a polymethylsilsesquioxane structure according to claim 2, wherein a part of the vinyl monomer has a crosslinkable reactive group.