JP2007238848A - Curable silicone composition and its production method and coating agent using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone composition capable of forming a cured coating film excellent in rigidity, cracking resistance, transparency, hardness, heat resistance, electric insulation and chemical resistance and to provide a method for producing the composition and a coating agent. <P>SOLUTION: A curable silicone composition having a weight average molecular weight of 500-100,000 in terms of standard polystyrene by the gel permeation chromatography comprises a polyorganosilsesquioxane containing a phenyl group, a straight chained, branched or cyclic C<SB>1-18</SB>aliphatic hydrocarbon group, a C<SB>1-3</SB>alkyl group and a hydrogen atom and a cyclic organosiloxane containing a straight chained, branched or cyclic C<SB>1-18</SB>aliphatic hydrocarbon group, a C<SB>1-3</SB>alkyl group and a hydrogen atom, wherein a cyclic organosiloxane of n of 3-8 is contained. The invention also relates to a method of producing the above composition and a coating agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a curable silicone composition, a method for producing the same, and a coating agent using the composition.

Polysilsesquioxane is a general term for silicones whose number of oxygen atoms is 1.5 with respect to the number of silicon atoms. It is excellent in transparency, heat resistance, electrical insulation and the like, and is widely used as an optical material application, semiconductor sealing, resist material, interlayer insulation film and the like. In particular, polyorganosilsesquioxane, which is known as an abbreviation for ladder silicone, has a skeleton structure similar to that of the silica, and is ideal for purposes such as hardness and heat resistance. It has a typical structure.

The polyorganosilsesquioxane having the ladder structure described above includes polymethylsilsesquioxane whose chain is a methyl group, polyphenylsilsesquioxane whose chain is a phenyl group, and a methyl group and a phenyl group in the chain. Polymethylphenylsilsesquioxanes having a group are generally known. Such a polyorganosilsesquioxane is dissolved in an organic solvent and used as a coating agent, and is coated on a substrate such as glass, silicon wafer, metal and plastic by a spray method, a dip method or a spine coating method, After volatilization of the solvent, when heated further, it is three-dimensionally cured by a condensation reaction involving dehydration or dealcoholization between silanol groups or alkoxy groups of polyorganosilsesquioxane, and has excellent heat resistance, electrical insulation properties, and chemical resistance Form a film.

For example, in the above-mentioned polymethylsilsesquioxane, methyltrichlorosilane is added in the presence of an amine in a ketone or ether solvent, and water is added dropwise at low temperature to hydrolyze to obtain a prepolymer, which is further condensed. It has been proposed that polymethylsilsesquioxane can be synthesized (Patent Document 1). In addition, an alkali metal carboxylate and a lower alcohol are dissolved in a mixed solution that forms two layers of water and an organic solvent, methyltrichlorosilane is dropped into the system, hydrolyzed, and further condensed to polymethylsilene. It has been proposed that sesquioxane can be synthesized (Patent Document 2).

In polyphenylsilsesquioxane, phenyltrichlorosilane is hydrolyzed to obtain a prepolymer or phenylsilanetriol, and water generated in the presence of a basic catalyst is azeotropically removed from the system in a toluene solvent. It has been proposed that polyphenylsilsesquioxane can be synthesized by condensation while being removed (Patent Document 3, Patent Document 4).

In addition, an alkali metal carboxylate and a lower aliphatic alcohol are dissolved in a mixed solution that forms two layers of water and an organic solvent, and phenyltrichlorosilane is dropped into the system to be hydrolyzed and further condensed to form an organic solvent. It has been proposed that a low molecular weight polyphenylsilsesquioxane having excellent compatibility with a solvent and a narrow molecular weight distribution can be synthesized (Patent Document 5).

Furthermore, in polymethylphenylsilsesquioxane, a prepolymer obtained by hydrolyzing methyltriethoxysilane and phenyltrimethoxysilane in the presence of an acidic catalyst, and a basic catalyst in a methyl isobutyl ketone solvent are also present. It has been proposed that an ultrahigh molecular weight polymethylphenylsilsesquioxane can be synthesized by reacting under the following conditions (Patent Document 6).

However, these known polyorganosilsesquioxanes are, for example, compatible with organic solvents or forming a uniform cured film, or the toughness, crack resistance, transparency, hardness, heat resistance of the obtained cured film. There has been some problem in any point such as property, electrical insulation, chemical resistance, etc., and the appearance of silicone having these balanced physical properties has been strongly demanded.

Japanese Patent Publication No. 1-443773 (Japanese Patent Laid-Open No. 58-13632) Japanese Patent No. 2977218 (Japanese Patent Laid-Open No. 3-227321) Japanese Patent Publication No. 3-60336 (Japanese Patent Laid-Open No. 59-108033) JP-A-8-143578 JP-A-5-39357 Japanese Patent No. 3272002 (Japanese Patent Laid-Open No. 5-125187)

As a result of diligent research and examination to solve the above problems, the present inventors have found that a specific silicone composition has excellent compatibility with an organic solvent and can form a uniform cured film. The resulting cured film should provide a balanced coating agent that improves the above-mentioned problems such as toughness, crack resistance, transparency, hardness, heat resistance, electrical insulation, chemical resistance, etc. Finally, the present invention has been completed.

That is, the present invention has a weight average molecular weight in terms of standard polystyrene as measured by gel permeation chromatography of 500 to 100,000, and the following general formula (1)

[Wherein, R ₁ is each independently a substituted or unsubstituted phenyl group, a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ₂ is each independently carbon. 1 to 3 alkyl groups and a hydrogen atom are shown, and m is an integer. And a polyorganosilsesquioxane represented by the general formula (2)

[Wherein, R ₃ is each independently a substituted or unsubstituted phenyl group, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ₄ is each independently carbon. A 1 to 3 alkyl group and a hydrogen atom, and n is 3 to 8. A curable silicone composition comprising a cyclic organosiloxane represented by formula (1).

Item 1 is characterized in that the weight average molecular weight in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane represented by the general formula (1) is 3,000 or more. The curable silicone composition described in (2).

Next, the present invention is characterized by containing 1 to 99% by weight of the cyclic organosiloxane represented by the general formula (2) with respect to the polyorganosilsesquioxane represented by the general formula (1). Item 3. A curable silicone composition according to Item 1 or 2 (Item 3).

Furthermore, this invention is characterized by containing 5-95 weight% of cyclic organosiloxane represented by General formula (2) with respect to the polyorganosilsesquioxane represented by General formula (1). Item 3. A curable silicone composition according to Item 1 or 2 (Item 4).

The present invention provides the polyorganosilsesquioxane represented by the general formula (1), wherein 10 mol% or more of R ₁ is a substituted or unsubstituted phenyl group. The curable silicone composition according to any one of (5).

Next, the present invention provides the cyclic organosiloxane represented by the general formula (2), wherein 12.5 mol% or more of R ₃ is a substituted or unsubstituted phenyl group. A curable silicone composition (Item 6).

Further, in the present invention, 25 mol% or more of R ₂ and R ₄ of the polyorganosilsesquioxane represented by the general formula (1) and the cyclic organosiloxane represented by the general formula (2) are hydrogen atoms. Item 7. The curable silicone composition according to any one of Items 1 to 6, which is characterized in that (Item 7).

Moreover, this invention mix | blends arbitrarily the polyorgano silsesquioxane represented by General formula (1), and the cyclic organosiloxane represented by General formula (2) of Claims 1 thru | or 7 characterized by the above-mentioned. It is a manufacturing method of the curable silicone composition in any one (item 8).

Furthermore, the present invention provides a first step in which an organotrialkoxylane is used as a raw material and the reaction is carried out in the presence of 0.01 to 1.49 moles of water with respect to the acidic or basic catalyst and the silane raw material. Item 8. The method for producing a curable silicone composition according to any one of Items 1 to 7, wherein the condensation is performed in a second step of reacting by adding 0.01 mole or more of water. Item 9).

Next, the present invention provides the method for producing a curable silicone composition according to Item 9, wherein the condensation reaction is further performed by heat treatment in the absence of a catalyst (Item 10).

And this invention contains the curable silicone composition in any one of claim | item 1 thru | or 7, It is a coating agent composition characterized by the above-mentioned (item 11).

A feature of the present invention is that the cyclic organosiloxane represented by the general formula (2) acts as a highly cross-linking agent for the polyorganosilsesquioxane represented by the general formula (1), and the cured film obtained in particular. It is the point which gave the outstanding toughness and crack resistance, and found that the uniform cured film was obtained.

The curable silicone composition of the present invention is excellent in compatibility with an organic solvent and can form a uniform cured film, and the obtained cured film has particularly high toughness, crack resistance, transparency, Excellent performance as a coating agent, such as excellent hardness, heat resistance, electrical insulation and chemical resistance. The coating agent using the curable silicone composition of the present invention can be easily coated by a commonly used coating method such as a spray method, a dip method, or a spine coating method. For example, for a variety of uses as described below. It is preferably used or expected to be used.
1) Heat resistant paint (or heat resistant coating agent)
2) Protective film for semiconductor 3) Interlayer insulating film 4) Resist material 5) Adhesive 6) Other optical communication members such as optical waveguides and optical fibers

Hereinafter, the curable silicone composition of the present invention, the production method thereof, and the coating agent using the composition will be specifically described in detail.
The curable silicone composition of the present invention has a weight average molecular weight in terms of standard polystyrene by gel permeation chromatography of 500 to 100,000, and the following general formula (1)

[Wherein, R ₁ is each independently a substituted or unsubstituted phenyl group, a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ₂ is each independently carbon. 1 to 3 alkyl groups and a hydrogen atom are shown, and m is an integer. And a polyorganosilsesquioxane represented by the general formula (2)

[Wherein, R ₃ is each independently a substituted or unsubstituted phenyl group, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ₄ is each independently carbon. A 1 to 3 alkyl group and a hydrogen atom, and n is 3 to 8. It contains the cyclic organosiloxane represented by this.

The present invention is characterized in that the cyclic organosiloxane represented by the general formula (2) acts as a highly cross-linking agent for the polyorganosilsesquioxane represented by the general formula (1) and is obtained. It was found that a particularly hardened film can be obtained by providing particularly excellent toughness and crack resistance.

Further, the present invention is characterized in that the polyorganosilsesquioxane represented by the general formula (1) has a weight average molecular weight of 3,000 or more in terms of standard polystyrene by gel permeation chromatography. If a weight average molecular weight is 3,000 or less, when forming a cured film, the shrinkage stress of resin is high and the crack resistance made into the objective of this invention tends to fall. On the other hand, if the molecular weight is too high, there is a problem in compatibility with an organic solvent and formation of a uniform cured film. Accordingly, the weight average molecular weight of the polyorganosilsesquioxane represented by the general formula (1) is preferably 3,000 or more, particularly preferably in the range of 3,000 to 100,000, and 5,000 to 50,000. More preferably, it is the range.

Further, the cyclic organosiloxane represented by the general formula (2) is usually contained in an amount of 1 to 99% by weight with respect to the polyorganosilsesquioxane represented by the general formula (1). However, particularly preferably, the polyorganosilsesquioxane represented by the general formula (1) contains 5 to 95% by weight of the cyclic organosiloxane represented by the general formula (2), and more preferably, It is characterized by containing 10 to 90% by weight.

Furthermore, in the polyorganosilsesquioxane represented by the general formula (1), each R ₁ is independently a substituted or unsubstituted phenyl group, linear, branched or cyclic carbon number 1-18. An aliphatic hydrocarbon group is shown, and among them, 10 mol% or more, preferably 25 mol% or more is preferably a substituted or unsubstituted phenyl group. When the substituted or unsubstituted phenyl group is less than 10 mol%, the compatibility with the organic solvent targeted by the present invention tends to be reduced. The remaining group other than the substituted or unsubstituted phenyl group of R ₁ is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms. Group, ethyl group, n-propyl group, i-propyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, vinyl group, allyl group And cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, norbornyl group, norbornenyl group, adamantyl group and the like. Further, a part of hydrogens of these aliphatic hydrocarbon groups may be substituted with a hydroxyl group, an ester group, an alkyl halide, or the like, or may contain oxygen, sulfur, or nitrogen of a hetero atom.

Further, the chain measurement R ₃ of the cyclic organosiloxane represented by the general formula (2) is independently a substituted or unsubstituted phenyl group, linear, branched, or cyclic C 1-18 aliphatic. Of these, 12.5 mol% or more, preferably 25% or more of these are preferably substituted or unsubstituted phenyl groups. When the substituted or unsubstituted phenyl group is less than 12.5 mol%, the compatibility with the organic solvent targeted by the present invention tends to be reduced. Further, the remaining group other than the substituted or unsubstituted phenyl group of R ₃ is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms. Group, ethyl group, n-propyl group, i-propyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, vinyl group, allyl group And cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, norbornyl group, norbornenyl group, adamantyl group and the like. Further, a part of hydrogens of these aliphatic hydrocarbon groups may be substituted with a hydroxyl group, an ester group, an alkyl halide, or the like, or may contain oxygen, sulfur, or nitrogen of a hetero atom.

Furthermore, 25% or more, preferably 50% or more of R ₂ and R ₄ of the polyorganosilsesquioxane represented by the general formula (1) and the cyclic organosiloxane represented by the general formula (2) are hydrogen atoms. Preferably there is. If it is 25% or less, an alkoxy group remains in the resulting cured film, and the toughness, hardness, and heat resistance aimed at by the present invention tend to decrease.

In the curable silicone composition of the present invention, an individually synthesized polyorganosilsesquioxane represented by the general formula (1) and a cyclic organosiloxane represented by the general formula (2) are arbitrarily blended. In general, those synthesized by known methods can be used.

Furthermore, the curable silicone composition of the present invention can be condensed by dropping organotrichlorosilane into a system that forms two layers of a water-insoluble organic solvent and water, or a homogeneous layer system of a solvent that is miscible with water and water. The curable silicone composition of the present invention having an arbitrary composition can be taken out.

The curable silicone composition of the present invention can also be prepared by adding water and an acidic or basic catalyst required for the reaction to the organoalkoxysilane, and condensing them in a solvent-free or solvent. The curable silicone composition of the present invention having a composition can be taken out.

Furthermore, the curable silicone composition of the present invention is a polymer represented by the general formula (1) having a weight average molecular weight in terms of standard polystyrene of 3,000 or less by gel permeation chromatography synthesized by a known method. A silicone composition containing an organosilsesquioxane and a cyclic organosiloxane represented by the general formula (2); and a polyorganosilsesquioxane represented by the general formula (1) having a weight average molecular weight of 3,000 or more; Can be prepared by arbitrarily blending.

Further, the curable silicone composition of the present invention can be easily taken out from the reaction mass in one pot by reacting under specific conditions using organotrialkoxylane as a raw material. . This one-pot manufacturing method is a first step in which the reaction is carried out in the presence of 0.01 to 1.49 times mole of water with respect to an acidic or basic catalyst and organotrialkoxysilane, and further 0.01 times mole or more. It is characterized by taking out the curable silicone composition by so-called two-stage condensation in the second step of performing the reaction by adding water.

Here, the purpose of the first step is, in particular, in a reaction in an organic solvent that is not miscible with water or in the absence of a solvent, as the reaction proceeds, the alcohol concentration in the system increases and the state in the system changes from the dispersed state. The purpose is to suppress the sudden change of the reaction and the rise of the temperature in the system. In the presence of water in excess of the theoretical amount, an abrupt reaction occurs, the production rate of cyclic organosiloxane is reduced, and there are also problems in terms of work safety. Therefore, 0.01 to 1.49 times mol, preferably 0.1 to 1.0 times mol, more preferably 0.1 to 0.5 times mol of water relative to the organotrialkoxylane. It was found that it is preferable to carry out the condensation in the second step by adding one more necessary water after the one reaction is carried out and the reaction partially proceeds.

Here, specific examples of the organotrialkoxysilane used include, for example, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, t-butyltrimethoxysilane, pentyltrimethyl. Methoxysilane, neopentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, Cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, benzyltrimethoxysilane, phenethyltrimethoxysilane, norbornyltrimethoxysilane, norbornenyl Trimethoxysilane, adamantyltrimethylammonium silane and the like of these silane is exemplified.

Specific examples of the solvent used in the reaction include aromatic hydrocarbons [eg, benzene, toluene, xylene, etc.], halogenated hydrocarbons [eg, methylene chloride, chloroform, etc.], ethers [eg, tetrahydrofuran, diethyl ether, Ethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, 1,4-dioxane, etc.], ketones [eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.], esters [eg, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, etc. ], Alcohols [eg, methanol, ethanol, isopropyl alcohol, butyl alcohol, etc.], aliphatic hydrocarbons [eg, hexane, heptane, cyclohexane, etc.], nitrogen-containing [eg, N-methyl- - pyrrolidone, N, N-dimethylformamide, etc.], water, etc. are exemplified, and these solvents may be used singly or in combination.

Specific examples of the catalyst for promoting the condensation reaction include acidic catalysts such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, alkyl sulfuric acid, alkylbenzene sulfonic acid, polyoxyethylene alkyl ether sulfuric acid, and the like. In the catalyst, alkali metal hydroxides [eg, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, etc.], amines [eg, triethylamine, diethylamine, n-butylamine, p-dimethylaminoethanol, triethanolamine] Etc.], quaternary ammonium salts [eg, ammonia, tetramethylammonium hydroxide, tetramethylammonium fluoride, tetra n-butylammonium fluoride, benzyltrimethylammonium fluoride, etc.], fluorides [eg, fluoride Lithium, sodium fluoride, potassium fluoride, cesium fluoride, calcium fluoride, etc.] are exemplified monkey.

The amount of the catalyst used is not particularly limited, but it is preferably used in the range of 0.0001 to 20% by weight with respect to the organoalkoxysilane, and the reaction temperature is in the range of −5 to 200 ° C. It is preferred to do so. In addition, the amount of catalyst and the reaction temperature are suitably selected so that the reaction time can be in the range of 1 to 50 hours in terms of economy.

In addition, as a means for increasing the molecular weight of the curable silicone composition obtained by the above-described method, heat treatment is performed in the absence of a catalyst to further perform a condensation reaction. When the reaction is carried out in the presence of an acid or basic catalyst, the cyclic organosiloxane reacts and disappears by being incorporated into the polyorganosilsesquioxane, and it is difficult to control the molecular weight. Therefore, there is a problem in the compatibility with the organic solvent targeted by the present invention and the formation of a uniform cured film. The temperature of the heat treatment is not particularly limited as long as it is a temperature at which the terminal group reacts, but it is preferably performed in the range of 50 to 250 ° C. In addition, the reaction temperature which can be in the range of 1 to 50 hours in terms of economy is preferably selected.

The above curable silicone composition of the present invention is excellent in compatibility with an organic solvent and can form a uniform cured film. The obtained cured film is particularly tough, crack-resistant, and transparent. Excellent performance as a coating agent, such as excellent properties, hardness, heat resistance, electrical insulation, and chemical resistance. As a result, 1) heat-resistant paint (or heat-resistant coating agent), 2) semiconductor protective film, 3) interlayer insulating film, 4) resist material, 5) adhesive, and 6) other optical communication members such as optical waveguides and optical fibers. Etc. are expected to be applied.

Moreover, the coating agent using the curable silicone composition of the present invention can be easily coated by a commonly used application method such as a spray method, a dip method or a spine coating method, and as a balanced coating agent. It is obvious that various additives such as fillers, curing accelerators, ultraviolet absorbers, dyes, pigments, extender pigments, reinforcing materials, and silane coupling agents are used in actual use. Further, it can be used in combination with a thermoplastic resin such as polyethylene, polystyrene, polyethylene terephthalate (PET), or a thermosetting or photocurable resin such as an epoxy resin or an acrylic resin.

EXAMPLES Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited to the following Example.

Synthesis example 1
30 L of water and 150.0 g of toluene were charged into a 1 L jacketed flask equipped with a thermometer, a stirrer, a reflux condenser, and a discharge cock, and the system temperature was adjusted to 25 ° C. Next, a mixed solution of 150.0 g (0.71 mol) of phenyltrichlorosilane and 150.0 g of toluene was dropped over 2 hours, and the mixture was kept at the same temperature for 0.1 hour. Thereafter, liquid separation is performed to remove the aqueous layer, and separation and washing are performed with water until the reaction mass becomes neutral. Toluene is recovered from the obtained toluene layer under reduced pressure to obtain polyphenylsilsesquioxane 93 as white powder. 0.0 g was obtained.

When the molecular weight of the obtained polyphenylsilsesquioxane was determined by gel permeation chromatography, the weight average molecular weight in terms of polystyrene was 3,800. The content of cyclic phenylsiloxanes was less than 1% by weight.

Synthesis example 2
30 L of phenyltriethoxysilane (1.25 mol) was charged into a 1 L jacketed flask equipped with a thermometer, a stirrer, a reflux condenser, and a discharge cock, and the system temperature was adjusted to 25 ° C. Subsequently, hydrochloric acid water consisting of 0.23 g (0.006 mol) of hydrochloric acid and 67.5 g (3.75 mol) of water was dropped, and the mixture was kept at 25 ° C. for 8 hours. In the middle, the reaction mass changed from a dispersed state to a uniform layer, and a rapid exotherm was observed up to 48 ° C. Thereafter, 300 g of toluene was added and dissolved, followed by separation and washing with water until the reaction mass became neutral, and the obtained toluene layer was allowed to stand at 5 ° C. or less for 48 hours. Thereafter, the precipitated white crystals were separated by filtration, suspended and purified with toluene, and dried to obtain 13.2 g of white crystals.

When the molecular weight of the obtained white crystals was determined by gel permeation chromatography, the weight average molecular weight was 550 in terms of polystyrene, and GPC spectrum (FIG. 1), IR spectrum (FIG. 2), and ¹ H-NMR spectrum. The analysis of (FIG. 3) etc. confirmed that the white crystals were cyclic tetramer 1,3,5,7-tetraphenylcyclotetrasiloxane-1,3,5,7-tetraol. It was.

Synthesis example 3
30 L of phenyltriethoxysilane (1.25 mol) was charged into a 1 L jacketed flask equipped with a thermometer, a stirrer, a reflux condenser, and a discharge cock, and the system temperature was adjusted to 25 ° C. Subsequently, hydrochloric acid water consisting of 0.23 g (0.006 mol) of hydrochloric acid and 67.5 g (3.74 mol) of water was dropped, and the mixture was kept at 25 ° C. for 8 hours. In the middle, the reaction mass changed from a dispersed state to a uniform layer, and a rapid exotherm was observed up to 48 ° C. Thereafter, 300 g of toluene was added and dissolved, and the mixture was washed with water until the reaction mass became neutral. Toluene was recovered from the obtained toluene layer under reduced pressure to obtain 152.5 g of a white powdery silicone composition. .

When the molecular weight of the obtained silicone composition was determined by gel permeation chromatography, the weight average molecular weight was 920 in terms of polystyrene. Also, cyclic phenylsiloxanes? The content of was 23.0% by weight.

Comparative Synthesis Example 1
In a 1 L jacketed flask equipped with a thermometer, stirring device, reflux condenser, and discharge cock, 481.4 g (2.7 mol) of methyltrimethoxysilane, 59.5 g (0.3 mol) of phenyltriethoxysilane, 0 hydrochloric acid .015 g (0.0004 mol) and 108.1 g (6.00 mol) of water were charged and reacted at 50 ° C. for 0.5 hour. Furthermore, this was heated up to 70 degreeC, and after reacting for 2 hours, water and alcohol were collect | recovered under reduced pressure. Thereafter, 1,500 g of methyl isobutyl ketone (MIBK) was added and dissolved, and 0.83 g (0.0082 mol) of triethylamine was added. This was further heated to 80 ° C., reacted for 3 hours, and then cooled. The reaction mass was separated and washed with water until the reaction mass became neutral, and MIBK was recovered under reduced pressure from the obtained MIBK layer to obtain 247.2 g of white powder of polymethylphenylsilsesquioxane.

When the molecular weight of the obtained polymethylphenylsilsesquioxane was determined by gel permeation chromatography, the weight average molecular weight in terms of polystyrene was 500,000 or more. Moreover, the content rate of cyclic organosiloxane was less than 1 weight%.

Examples 1-4
The polyphenylsilsesquioxane obtained in Synthesis Example 1 or the silicone composition obtained in Synthesis Example 3 and the cyclic phenylsiloxane obtained in Synthesis Example 2 are mixed in the ratio shown in Table 1 to obtain a curable silicone composition. Got. In addition, the numerical value in Table 1 represents weight%.

Example 5
30 L of phenyltriethoxysilane (1.25 mol) was charged into a 1 L jacketed flask equipped with a thermometer, a stirrer, a reflux condenser, and a discharge cock, and the system temperature was adjusted to 25 ° C. Next, hydrochloric acid water consisting of 0.22 g (0.006 mol) of hydrochloric acid and 67.46 g (3.74 mol) of water was prepared and dropped in two stages. First, 20% of the whole was dropped and kept at 25 ° C., and after the reaction mass changed from a dispersed state to a uniform layer (heat generation up to 29 ° C.), the remaining 80% was dropped and further 8 at the same temperature. Reacted for hours. Thereafter, 300 g of toluene was added and dissolved, and the mixture was washed with water until the reaction mass became neutral. Toluene was recovered from the obtained toluene layer under reduced pressure. This was further heated to 200 ° C., reacted for 1.5 hours, then cooled and pulverized to obtain 153.5 g of a white powdery silicone composition.

When the molecular weight of the obtained silicone composition was determined by gel permeation chromatography, the weight average molecular weight in terms of polystyrene was 4,400. The content of cyclic phenylsiloxanes was 15.2% by weight. Moreover, when the molar ratio of the silanol group and the ethoxy group was determined from the integrated intensity of ¹ H-NMR, it was 58:42.

Example 6
A 1 L jacketed flask equipped with a thermometer, a stirrer, a reflux condenser, and a discharge cock was charged with 160.5 g (0.900 mol) of methyltriethoxysilane and 72.1 g (0.300 mol) of phenyltriethoxysilane, The system temperature was adjusted to 5 ° C. Subsequently, hydrochloric acid water consisting of 0.22 g (0.006 mol) of hydrochloric acid and 64.9 g (3.60 mol) of water was prepared and dropped in two stages. First, 20% of the whole was dropped and kept at 5 ° C., and after the reaction mass changed from a dispersed state to a uniform layer (heat generation up to 8 ° C.), the remaining 80% was dropped and further 8 at the same temperature. Reacted for hours. Thereafter, 300 g of methyl isobutyl ketone (MIBK) was added and dissolved, and the mixture was washed with water until the reaction mass became neutral. MIBK was recovered from the obtained MIBK layer under reduced pressure, and further heated to 200 ° C. After reacting for 1.5 hours, the mixture was cooled and pulverized to obtain 97.1 g of a white powdery silicone composition.

When the molecular weight of the obtained silicone composition was determined by gel permeation chromatography, the weight average molecular weight was 15,600 in terms of polystyrene. The content of cyclic phenylsiloxanes was 11.8% by weight. Moreover, it was 72:38 when the molar ratio of a silanol group and an ethoxy group was calculated | required from the integrated intensity of < ¹ > H-NMR.

Using the curable silicone compositions obtained in Example 7 (compatibility with organic solvent and film forming property) and Comparative Examples 1 to 6, compatibility with organic solvent by the following method, The film forming property was evaluated. Further, as comparative examples, polymethylphenylsilsesquioxane obtained in Comparative Synthesis Example 1, polyphenylsilsesquioxane obtained in Synthesis Example 1, and cyclic tetramer obtained in Synthesis Example 2 , 3,5,7-Tetraphenylcyclotetrasiloxane-1,3,5,7-tetraol The results of the evaluation are also shown.

Film- forming properties compatible with organic solvents 30% by weight in propylene glycol monomethyl ether acetate (PGMEA), butyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone (Anon), butanol The solubility was evaluated. In the evaluation, “◯” indicates that the sample was completely dissolved, “Δ” indicates that haze and a small amount of insoluble matter were observed, and “x” indicates that insoluble matter was clearly observed.

A propylene glycol monomethyl ether acetate (PGMEA) solution having a film forming property of 15% by weight was prepared, spin-coated on a silicon wafer, fired at 400 ° C. to form a film, and the coating property and crack limit were evaluated. In the applicability evaluation, “◯” indicates that there is no problem in work and a uniform cured film is obtained, and a cured film is obtained, but “△” indicates that unevenness can be confirmed, and a cured film is obtained. Those that could not be indicated as "x".

The above curable silicone composition of the present invention is excellent in compatibility with an organic solvent and can form a uniform cured film. The obtained cured film is particularly tough, crack-resistant, and transparent. It exhibits excellent performance as a coating agent, such as excellent properties, hardness, heat resistance, electrical insulation, chemical resistance, etc., and has high industrial applicability.

4 is a GPC spectrum of cyclic phenylsiloxane of Synthesis Example 2. 3 is an IR spectrum of cyclic phenylsiloxane of Synthesis Example 2. 2 is a ¹ H-NMR spectrum of a cyclic phenylsiloxane of Synthesis Example 2.

Claims (11)

The weight average molecular weight in terms of standard polystyrene by gel permeation chromatography is 500 to 100,000, and the following general formula (1)
[Wherein, R ₁ is each independently a substituted or unsubstituted phenyl group, a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ₂ is each independently carbon. 1 to 3 alkyl groups and a hydrogen atom are shown, and m is an integer. And a polyorganosilsesquioxane represented by the general formula (2)
[Wherein, R ₃ is each independently a substituted or unsubstituted phenyl group, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ₄ is each independently carbon. A 1 to 3 alkyl group and a hydrogen atom, and n is 3 to 8. ] The curable silicone composition characterized by including the cyclic organosiloxane represented by this. The curable silicone according to claim 1, wherein the polyorganosilsesquioxane represented by the general formula (1) has a weight average molecular weight of 3,000 or more in terms of standard polystyrene by gel permeation chromatography. Composition. The polyorganosilsesquioxane represented by the general formula (1) contains 1 to 99% by weight of the cyclic organosiloxane represented by the general formula (2). The curable silicone composition described. The polyorganosilsesquioxane represented by the general formula (1) contains 5 to 95% by weight of the cyclic organosiloxane represented by the general formula (2). The curable silicone composition described. The polyorganosilsesquioxane represented by the general formula (1) is characterized in that 10 mol% or more of R ₁ is a substituted or unsubstituted phenyl group. Curable silicone composition. In cyclic organosiloxane represented by the general formula (2), the curable silicone composition according to any one of claims 1 to 5 to 12.5 mol% of R ₃ is substituted or unsubstituted phenyl group. 25% or more of R ₂ and R ₄ of the polyorganosilsesquioxane represented by the general formula (1) and the cyclic organosiloxane represented by the general formula (2) are hydrogen atoms. Item 7. The curable silicone composition according to any one of Items 1 to 6. The polyorganosilsesquioxane represented by the general formula (1) and the cyclic organosiloxane represented by the general formula (2) are optionally blended. A method for producing a curable silicone composition. The first step in which organotrialkoxylane is used as a raw material and the reaction is carried out in the presence of 0.01 to 1.49 times mole of water with respect to the acidic or basic catalyst and the silane raw material, and further 0.01 times mole The method for producing a curable silicone composition according to any one of claims 1 to 7, wherein condensation is performed in the second step of performing the reaction by adding the above water. The method for producing a curable silicone composition according to claim 9, wherein the condensation reaction is further performed by performing a heat treatment in the absence of a catalyst. A coating agent comprising the curable silicone composition according to claim 1.