JPH0770321A - Reactive polymethylsilsesquioxane - Google Patents

Abstract

PURPOSE:To stably produce a ladder silicone having methyl and cross-linking reactive groups on the side chains. CONSTITUTION:A reactive polymethylsilsesquioxane is produced by trimethylsilylating 30-95mol% of hydroxyl and alkoxy groups of polymethylsilsesquioxane in which 50-99mol% of the org. groups on the side chains are methyl, 1-40mol% are cross-linking reactive groups or org. groups having cross-linking reactive groups, and the rest are 2-6C alkyl, optionally substd. phenyl, hydroxyl, or 1-6C alkoxy groups and which has a number-average mol.wt. of 500-100,000.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyorganosiloxane having a polymethylsilsesquioxane structure having a methyl group and a reactive group in a side chain as a main structural unit, which is suitable as a polymer-modifying material. is there.

[0002]

2. Description of the Related Art The ladder structure is an ideal molecular structure for heat-resistant polymers, and attempts have been made for polyacenes, polyperinaphthalenes, BBB polymers, etc. for carbocyclic and heterocyclic polymers, and also for polyimides. It is known that the performance is improved by intentionally incorporating a ladder structure in the molecule. In these carbon-based polymers, the ladder structure reaction can be realized only under extremely severe conditions, but in polysiloxane, the condensation reaction is based on the equilibrium reaction and the condensation proceeds via the cyclic compound. For this reason, it can be synthesized under relatively mild conditions, and the history of research is old.

However, the main research subjects to date are biased toward phenyl type ladder silicones because of their side chains because the ladder silicones of this type are highly regular and easy to synthesize, and the products This is because the storage stability of is excellent. For example, Nakahama et al. Synthesize a ladder silicone having a phenyl group and a methacryloxypropyl group as a side chain and incorporate it into a polystyrene molecular structure. (Polymer Preprints, Japa
n vol.29, no.1 (1980))

Nakahama et al. Also describe in this report that those containing a methyl group and a reactive group in the side chain caused gelation and could not be synthesized. In general, the side chain of a methyl group ladder silicone is extremely reactive, and it is not only difficult to synthesize it while avoiding gelation, but even if it can be synthesized, it should be stored frozen.
It is generally well known that the material is not stable, for example, it is forced to be stored only as a dilute solution.

However, the inventors of the present invention have found that it is a ladder silicone having a side chain of a methyl group that can best express the characteristics of the ladder silicone such as hardness, heat resistance, weather resistance and light resistance. We came to deeply recognize it from the analysis result of.

[0006]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a stable reactive ladder silicone having a methyl group and a crosslinkable reactive group in its side chain. is there.

[0007]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have earnestly studied in order to stably produce a reactive ladder silicone having a methyl group and a crosslinkable reactive group in a side chain. Have been piled up. As a result, they have found that a ladder silicone obtained by trimethylsilylating a certain amount of a molecular structure, particularly a side chain and a terminal hydroxyl group and an alkoxy group, meets the initial purpose, and completed the present invention. That is, in the present invention, 50 to 99 mol% of all side chain organic groups are methyl groups, 1 to 40 mol% are crosslinkable reactive groups or organic groups having a crosslinkable reactive group as a substituent, and the balance is carbon. Number 2
~ 6 alkyl groups, substituted or unsubstituted phenyl groups,
In a polymethylsilsesquioxane having a number average molecular weight of 500 to 100,000, which is a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms and the terminal group is a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, the hydroxyl group and the alkoxy group Of 30
~ 95 mol% trimethylsilylated reactive polymethylsilsesquioxane.
In the present invention, the above-mentioned crosslinkable reactive group is a vinyl group, an alkenyl group, an epoxy group, an amino group, a mercapto group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amidooxime group, a sulfone group, a chlorosulfone group, an aldehyde group,
It relates to one or more reactive polymethylsilsesquioxanes selected from acetylacetonato groups.

The reactive polymethylsilsesquioxane of the present invention can be mainly represented by the following chemical structure.

[Chemical 1] In the formula, R ¹ and OR ² represent the above side chain organic group and terminal group, respectively, and n represents the degree of polymerization.

Of the hydroxyl group and the alkoxy group, 30 to 30
95 mol% is trimethylsilylated to give -OS
i (CH ₃ ) ₃ . The reactive polymethylsilsesquioxane of the present invention can be produced by trimethylsilylating the hydroxyl groups and alkoxy groups of the corresponding polymethylsilsesquioxane at a desired ratio.

That is, the trimethylylsilylation is carried out by using 50 to 99 mol% of all side chain organic groups as a methyl group, 1 to 40 mol% of a crosslinkable reactive group or an organic group having a crosslinkable reactive group as a substituent,
The number of the remainder being an alkyl group having 2 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and the terminal group being a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. Trimethylsilanol may be reacted with polymethylsilsesquioxane having an average molecular weight of 500 to 100,000 (hereinafter referred to as "raw material polysiloxane"), but it is effective to react hexamethyldisiloxane under weak acidity. is there. The reaction conditions in this case are that hexamethyldisiloxane is used in an excess amount less than the calculated amount, a small amount of ethanol or the like is used as a solvent, and the reaction temperature is 50-
The reaction time is 100 ° C. and the reaction time is 1 to 8 hours, but of course, these reaction conditions may vary depending on the type of the raw material polysiloxane, the degree of trimethylsilylation, the solvent, the type of the solution, and the like.

In the present invention, it is necessary that 30 to 95 mol% of the side chain and / or terminal hydroxyl groups and alkoxy groups are trimethylsilylated, and 30 mol%
Below, there are problems such as poor storage stability of the reactive polymethylsilsesquioxane. On the other hand, when it is 95 mol% or more, there arises a problem in the compatibility of the reactive polymethylsilsesquioxane with a general-purpose polymer. The raw material polysiloxane of the present invention can be produced by cohydrolyzing and condensing trialkoxysilane or trichlorosilane. When trialkoxysilane is used as the raw material, the side chains and terminal groups are hydroxyl groups and / or alkoxy groups, and when trichlorosilane is used as the raw material, the side chains and terminal groups are hydroxyl groups.

Examples of the methyltrialkoxysilane or methyltrichlorosilane used for producing the raw material polysiloxane of the present invention include the following. Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltrichlorosilane. In the reactive polymethylsilsesquioxane of the present invention, when the methyl group in all side chain organic groups is 50 mol% or less, this reactive polymethylsilsesquioxane is utilized by utilizing the reactivity of the crosslinkable reactive group. When incorporated into a polymer,
The hardness and weather resistance of this polymer are insufficient. Again 99
When it is more than mol%, the number of crosslinkable reactive groups becomes relatively small, and when the reactivity of the crosslinkable reactive groups is used to incorporate this reactive polymethylsilsesquioxane into a polymer, the durability of this polymer is adversely affected. May occur.

The crosslinkable reactive group used in the present invention may be a functional group having a reactivity capable of incorporating the reactive polymethylsilsesquioxane of the present invention into the main chain and / or side chain of the polymer. A vinyl group, an alkenyl group, an epoxy group, an amino group, a mercapto group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amidoxime group, a sulfone group, a chlorosulfone group, an aldehyde group, and an acetylacetonate group are suitable. . Examples of the trialkoxysilane or trichlorosilane having a crosslinkable reactive group used for producing the raw material polysiloxane of the present invention include the following. Vinyltriethoxysilane, vinyltrichlorosilane, allyltrimethoxysilane, allyltrichlorosilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrichlorosilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltrichlorosilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrichlorosilane, γ-hydroxypropyltrimethoxysilane.

Further, in the present invention, a polymethylsilsesquioxane having a crosslinkable reactive group precursor capable of forming a crosslinkable reactive group is first produced, and the crosslinkable reactive group precursor of this polymethylsilsesquioxane is produced. Can also be produced by converting the compound into a crosslinkable reactive group by a polymer reaction. In the reactive polymethylsilsesquioxane of the present invention,
When this reactive polymethylsilsesquioxane is incorporated into a polymer by utilizing the reactivity of the crosslinkable reactive group, the crosslinkable density becomes high when the crosslinkable reactive group is 40 mol% or more, and the hardness of the polymer increases, It is brittle and causes problems in terms of conformability to deformation and impact. When the content is 1% or less, the number of crosslinkable reactive groups becomes relatively small, and when the reactivity of the crosslinkable reactive groups is used to incorporate this reactive polymethylsilsesquioxane into a polymer, the durability of the polymer is improved. Adverse effects may occur.

In the reactive polymethylsilsesquioxane of the present invention, the reactivity of the crosslinkable reactive group is utilized to incorporate the reactive polyorganosiloxane into the main chain and / or side chain of the polymer molecular structure. When there is only one type of crosslinkable reactive group, a part thereof may react, or the whole may be used for the reaction. In addition, when a part of the crosslinkable reactive group remains, a step of three-dimensionally curing the resin of the present invention or the composition using the same can be adopted depending on the purpose and use. Similarly, in polymethylsilsesquioxane having a crosslinkable reactive group containing two or more kinds of crosslinkable reactive groups, as to incorporation into the main chain and / or side chain of the molecular structure of the polymer, one of these Crosslinkable reactive groups are used, and other crosslinkable reactive groups can also be used in the process of three-dimensional curing of compositions using this polymer.

In the reactive polyorganosilsesquioxane of the present invention, among all side chains, carbon atoms other than methyl group, crosslinkable reactive group or organic group having a crosslinkable reactive group as a substituent, hydroxyl group and alkoxy group It is an alkyl group having a number of 2 to 6 or a substituted or unsubstituted phenyl group, and these are not preferable in terms of hardness, durability, etc. Therefore, it is desirable to keep the amount as small as possible (10 mol% or less). The raw material polysiloxane of the present invention comprises 1.5 to 8 times the molar amount of water and 5 × 10 6 with respect to the total number of moles of the raw material trialkoxysilane or trichlorosilane corresponding to the target composition.
After hydrolyzing and condensing in the coexistence of ^{-6 to} 5 × 10 ^-1 molar amount of acid, neutralization with alkali if necessary, and further 5 × 10
It can be produced by adding ^{-6 to} 5 x 10 ^-1 molar amount of alkali to promote high molecular weight by condensation, and then removing coexisting water and salt.

The amount of water used for hydrolysis and condensation is 1.5
If it is less than twice the molar amount, the hydrolysis does not proceed sufficiently, and if the amount of water used exceeds 8 times the molar amount, the condensation reaction occurs rapidly and gelation tends to occur. The amount of acid or alkali used for hydrolysis and condensation is 5 × 10 ^{−6 with} respect to the total number of moles of the trialkoxysilane or trichlorosilane as the raw material.
~ 5 x 10 ^-1 molar amount. If the amount of acid or alkali used is less than 5 × 10 ^-6 mol, hydrolysis and condensation will be extremely slow, which is not efficient. The amount of acid or alkali used is 5
If the amount exceeds × 10 ^-1 mol, an irregular three-dimensional condensation reaction occurs, and not only the ladder structure with high regularity, which is the object of the present invention, cannot be obtained, but also gelation occurs.

Examples of the acid used in the present invention include hydrochloric acid, sulfuric acid, acetic acid, formic acid and the like. As the alkali, n-butylamine, triethylamine,
Examples include p-dimethylaminoethanol, sodium hydroxide, potassium hydroxide, ethylenediamine, diethylamine and the like. In the present invention, the number average molecular weight is 500 to 3000.
In order to produce the raw material polysiloxane of, it is preferable to use only an acid as a catalyst in hydrolysis and condensation,
Further, in order to produce a raw material polysiloxane having a number average molecular weight of more than 3000, first, a low molecular weight polymer is produced by using an acid as a catalyst in hydrolysis and condensation, and then an alkali is added as a catalyst to obtain a high molecular weight polymer. It is preferable to manufacture by converting into.

The reaction temperature is usually 20 to 100 ° C., and the reaction time is 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 20 to 60 ° C for 0.5 to 1 hour, and then the temperature is raised to 60 to 100 ° C. , Preferably 70-90
It is advisable to carry out the reaction at ℃ for 1 to 23 hours. The condensation reaction is stopped by neutralizing the reaction solution, and the salt generated at that time is removed by filtration or washing with water. In some cases, it is necessary to completely remove water prior to desalting, and a distillation operation may be performed by adding a high boiling point alcohol, toluene or the like.

The number average molecular weight of the reactive polymethylsilsesquioxane in the present invention is 600 to 100,000, preferably
When the number average molecular weight is 1,000 or 10,000 and the number average molecular weight is 600 or less, properties such as hardness and stain resistance, which are features of ladder silicone, are insufficient. On the other hand, when the number average molecular weight is 100,000 or more, handling is difficult due to high viscosity, and storage stability is poor, and gelation may occur. The number average molecular weight of the reactive polymethylsilsesquioxane of the present invention is determined by gel permeation chromatography (GP
Using C), polystyrene can be used as a standard substance and can be easily measured. The present inventors have confirmed that the molecular weight measured by this GPC shows extremely good agreement with the number average molecular weight measured by methods such as vapor pressure measurement and osmotic pressure measurement.

The reactive polymethylsilsesquioxane having the polymethylsilsesquioxane structure of the present invention as a main structural unit and having a crosslinkable reactive group in its side chain is an alcohol such as ethanol, isopropanol or butanol, tetrahydrofuran or diethyl. Ethers such as ethers, ether alcohols such as ethylene glycol monoethyl ether and ethylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate,
It is soluble in organic solvents such as aromatic hydrocarbons such as toluene and xylene.

[0022]

EXAMPLES The present invention will be specifically described below by showing 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. (Infrared absorption spectrum) IR-435 manufactured by Shimadzu Corporation was used to examine the infrared absorption spectrum by measuring the transmittance. (NMR analysis) The proton was analyzed using AMX-400 manufactured by Bruker. (GPC) Shimadzu CR-3A is used, and Showa Denko K.K.Showdex KF-801, KF-802, KF-803, KF- is used for the column.
804 was used in series to quantify reactive polymethylsilsesquioxane and hexamethyldisiloxane. The molecular weight was calculated by polystyrene conversion.

Example 1 (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) was added. ), Methyltriethoxysilane 4
45 g (2.5 mol), phenyltrimethoxysilane 20 g (0.1
Mol), acetone 200 g, hydrochloric acid 0.002 mol, and water 54 g (3 mol) were charged, the temperature in the flask was raised to 60 ° C., and the mixture was maintained for 5 hours while stirring. Then, after raising the temperature to 70 ° C and reacting for 1 hour, 0.004 mol of KOH was added dropwise, and after reacting for another 4 hours, it was neutralized, washed with water and toluene, and then the solvent was removed using a rotary evaporator. , Water, etc. were removed and the precipitated salt was filtered off.
A viscous liquid of s was obtained quantitatively.

The GPC curve of this product 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 side-chain methyl group, γ-methacryloxypropyl group, and phenyl group was 25: 2: 1 due to the raw material molar ratio. Next, according to the procedure described below, 70% of the side chain and terminal hydroxyl groups and alkoxy groups of the above raw material polysiloxane are trimethylsilylated with hexamethyldisiloxane to synthesize methacryl-reactive polymethylsilsesquioxane. did. This is designated as Polymer A. The number average molecular weight (GPC measurement) of this polymer A is 6,100. It was also confirmed that Polymer A showed no change even after 4 weeks at 50 ° C. and was extremely excellent in storage stability.

(Quantification of Side Chain and Terminal Hydroxyl Group and Alkoxy Group and Trimethylsilylation) First, a method of quantifying the side chain and terminal hydroxyl group and alkoxy group of the raw material polysiloxane will be described. It was confirmed by infrared absorption spectrum and NMR analysis that the hydroxyl group and the alkoxy group were completely reacted when hexamethyldisiloxane (trimethylsilylating agent) was added to the raw polysiloxane solution under weak acidity and heated to about 50 ° C. It That is, as shown in the infrared absorption spectrum in FIG. 1, no absorption by the hydroxyl group is observed after trimethylsilylation. Further, as shown in FIG. 2, after the trimethylsilylation, the peaks due to the methoxy and ethoxy protons are extremely small, and are almost absent. Then, in order to quantify the hydroxyl group and the alkoxy group, in principle, an excess amount of hexamethyldisiloxane is added and reacted, the residual amount after the reaction is measured, and the consumption amount is calculated. This residual amount can be quantified using gel permeation chromatography (GPC) as shown in FIG. Actually, data of several points are taken, and the amount of hexamethyldisiloxane at which the residual amount becomes zero is determined by extrapolation to quantify the hydroxyl group and the alkoxy group.

Based on the above data, it is possible to obtain the reactive polymethylsilsesquioxane of the present invention by reacting hexamethyldisiloxane necessary to achieve the set degree of trimethylsilylation under weak acidity. it can.
Hexamethyldisiloxane 7. Half of the methacryl-reactive polymethylsilsesquioxane synthesized under the above conditions was taken and dissolved in ethanol to give an 80% solution.
5 g and 0.001 mol of hydrochloric acid were added and reacted at 70 ° C. for 3 hours to trimethylsilylate 70% of the terminal hydroxyl groups and alkoxy groups.

Comparative Example 1 For comparison, a methyl group, γ-, was prepared by the same operation and formulation as in the polymer of Example 1 except that the reaction molar ratio of the starting alkoxysilane in the synthesis of the polymer of Example 1 was changed.
The molar ratio of methacryloxypropyl group to phenyl group is 12:
A methacryl-reactive polyorganosiloxa, such as 2:14, was obtained. This product has a viscosity of 2400 cps at 25 ℃.
And the number average molecular weight by vapor pressure measurement was 5,500. Further, by the same operation and formulation as in Example 1, 70% of the side chain and terminal hydroxyl groups and alkoxy groups were trimethylsilylated with hexamethyldisiloxane. This is designated as Polymer B. The number average molecular weight (GPC measurement) of this polymer B was 5,500.

Comparative Example 2 For comparison, a polymer C was obtained by the same operation and formulation as in Example 1 except that the trimethylsilylation degree in the polymer synthesis of Example 1 was 20%. This polymer C is
When stored at 50 ° C, it gelated after 2 weeks, and it was confirmed that there was a storage stability problem.

Comparative Example 3 For comparison, a polymer D was obtained by the same operation and formulation as in Example 1 except that the trimethylsilylation degree in the polymer synthesis of Example 1 was 100%. This polymer D is
No change was observed even after 4 weeks at 50 ° C, and the storage stability was extremely excellent, but there was a problem in compatibility with polyfunctional acrylates such as trimethylolpropane triacrylate described in Example 3. There was found.

Comparative Example 3'Polymer E was obtained by the same operation and formulation as in Example 1 except that the amount of KOH used in Example 1 was 0.012 mol. The viscosity of this polymer at 25 ° C is 320,000 cps.
In addition to being extremely difficult to handle, solubility in a solvent such as butyl acetate and toluene described in Example 3 is difficult, and it takes a long time to dissolve. Furthermore, the target 5
It was impossible to form a thin film having a thickness of about 0 μ.

Example 2 (Synthesis of mercapto-reactive polymethylsilsesquioxane) In a 2 liter flask equipped with a thermometer, a stirrer and a reflux condenser, 39 g (0.2 mol) of γ-mercaptopropyltrimethoxysilane, Methyltriethoxysilane 392g
(2.2 mol), phenyltrimethoxysilane 20 g (0.1 mol), acetone 200 g, hydrochloric acid 0.002 mol, water 54 g (3 mol)
Was charged, the temperature in the flask was raised to 60 ° C., and the temperature was maintained for 3 hours while stirring. Then, after heating to 70 ° C and reacting for 3 hours, 0.004 mol of KOH was added dropwise, and after reacting for another 3 hours, it was neutralized, washed with water and toluene, and then the solvent was removed using a rotary evaporator. After removing water, etc., a viscous liquid with a viscosity of 5100 cps at 25 ° C was quantitatively obtained. The GPC curve of this product 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 side-chain methyl group, γ-mercaptopropyl group, and phenyl group was 22: 2: 1 due to the raw material molar ratio.

This product also has a molecular weight measured by vapor pressure measurement.
(Mn) was 10800, and when calculated from this and the measurement data obtained by silylation, the total amount of side chain and terminal hydroxyl groups and alkoxy groups was 7.3 per molecule. By the same operation and formulation as in Example 1, 85% of the side chain and terminal hydroxyl groups and alkoxy groups were trimethylsilylated with hexamethyldisiloxane. This is designated as Polymer E. It was also confirmed that Polymer E did not show any change even after 4 weeks at 50 ° C. and was extremely excellent in storage stability.

Example 3 The following components were uniformly mixed, and a water glass meter multi-layer pattern spraying material was applied on a slate plate and then baked on a base substrate.
After coating so as to have a thickness of 50 μ, it was cured by heating at 90 ° C. for 1 hour. Polymer A 40 parts by weight Dipentaerythritol tetraacrylate 15 parts by weight 1,6-hexanediol diacrylate 20 parts by weight Butyl acetate 15 parts by weight Toluene 5 parts by weight 2% Methyl ethyl ketone peroxide 0.5 parts by weight The thickness of the cured film of this cured film Table 1 shows the surface pencil hardness, and weather resistance data. The evaluation was performed as follows.

(Surface hardness) It was measured according to JIS K5401 using a pencil scratch tester for paints. (Weather resistance) A carbon arc sunshine weather meter test was performed according to JIS B7753. The surface of the test body after 2000 hours was observed and evaluated by comparing and observing the surface before the test.

Comparative Example 4 A cured film was obtained by the same operation and formulation as in Example 1, except that the polymer A component in Example 3 was replaced with the polymer B component. The performance of this product is shown in Table 1.

[0036]

[Table 1]

[0037]

INDUSTRIAL APPLICABILITY According to the present invention, it becomes possible to stably produce a ladder silicone having a methyl group and a crosslinkable reactive group in its side chain, and this reactive polymethylsilsesquioxane Utilizing the reactivity of the crosslinkable reactive group of the chain, incorporating it into various general-purpose polymers to improve its performance,
It can be used to impart a new performance which has not been known in the past. Even in ladder silicone,
Since it has a polymethylsilsesquioxane structure, which is expected to have particularly inorganic properties, as a main structural unit, it is useful as a material capable of expanding the range of polymer modification possibilities.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum before and after trimethylsilylation in Example 1.

FIG. 2 NM after trimethylsilylation in Example 1
It is the spectrum which analyzed R.

FIG. 3 is a diagram showing separation and quantification of a silylating agent using GPC in Example 1.

[Procedure amendment]

[Submission date] May 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

Comparative Example 1 For comparison, a methyl group, γ-, was prepared by the same operation and formulation as in the polymer of Example 1 except that the reaction molar ratio of the starting alkoxysilane in the synthesis of the polymer of Example 1 was changed.
The molar ratio of methacryloxypropyl group to phenyl group is 12:
A methacryl-reactive polyorganosiloxane such as 2:14 was obtained. This product has a viscosity of 2400 cp at 25 ℃
s and the number average molecular weight by vapor pressure measurement was 5,500. Further, by the same operation and formulation as in Example 1, 70% of the side chain and terminal hydroxyl groups and alkoxy groups were trimethylsilylated with hexamethyldisiloxane. This is designated as Polymer B. The number average molecular weight (GPC measurement) of this polymer B was 5,500.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

Example 3 The following components were uniformly mixed, a water glass-based multi-layer pattern spraying material was applied on a slate plate, and the baked base substrate was baked.
After coating so as to have a thickness of 50 μ, it was cured by heating at 90 ° C. for 1 hour. Polymer A 40 parts by weight Dipentaerythritol tetraacrylate 15 parts by weight 1,6-hexanediol diacrylate 20 parts by weight Butyl acetate 15 parts by weight Toluene 5 parts by weight 2% Methyl ethyl ketone peroxide 0.5 parts by weight The thickness of the cured film of this cured film Table 1 shows the surface pencil hardness, and weather resistance data. The evaluation was performed as follows.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuji Ito 5-1 Okawa-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Sho

Claims (2)

[Claims] 1. Out of all side chain organic groups, 50 to 99 mol% is a methyl group, 1 to 40 mol% is a crosslinkable reactive group or an organic group having a crosslinkable reactive group as a substituent, and the balance is A number average molecular weight of an alkyl group having 2 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and a terminal group being a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. Reactive polymethylsilsesquioxane, characterized in that, in 500 to 100,000 polymethylsilsesquioxane, 30 to 95 mol% of its hydroxyl groups and alkoxy groups are trimethylsilylated. 2. The crosslinkable reactive group is a vinyl group, an alkenyl group, an epoxy group, an amino group, a mercapto group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amidooxime group, a sulfone group, a chlorosulfone group, an aldehyde group, and acetyl. The reactive polymethylsilsesquioxane according to claim 1, which is one kind or two or more kinds selected from an acetonate group.