JPS61278532A - Production of hydroxyphenyl-terminated ladder polysiloxane - Google Patents

Abstract

PURPOSE:To obtain a hydroxyphenyl-terminated ladder polysiloxane of good heat resistance, by polycondensing an intermediate obtained by cohydrolyzing phenyltrichlorosilane with a specified silane compound by using a chloroformate ester as a catalyst. CONSTITUTION:Phenyltrichlorosilane is cohydrolyzed with a compound of the formula (wherein X is H, methyl, ethyl, or phenyl and m is 0-4). The obtained intermediate is polycondensed by using a chloroformate ester as a catalyst to obtain a hydroxyphenyl-terminated ladder polysiloxane having photosensitive groups as side chains. Examples of the silane compounds of the formula include vinyltrichlorosilane and allyltrichlorosilane. In performing said polycondensation reaction, the catalyst is added to a solution obtained by dissolving said intermediate in an organic solvent and this solution is heated to about 130 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a process for producing a terminal '4+ nitroxyphenyl ladder polysiloxane having a photosensitive group in its side chain.

[Conventional Support i1 Photosensitive heat-resistant materials have been developed for use in electronic components or LSI interlayer insulating films, and among photosensitive heat-resistant materials, there are two trends in the development of polymeric materials. 1
One is aimed at improving the heat resistance of the conventional 7-otoresist, and the other is aimed at imparting photosensitivity to a heat-resistant polymer material. The former is cyclized polybutadiene (Japanese Journal of Applied Physics, 1980, Vol. 19, p. 460), and the latter is photosensitive polyimide resin (Eletronics, 1981, p. 3). etc.

[Problems to be solved by the invention] Conventional photopolymerizable compounds such as those described above have a chain-like molecular structure and therefore have poor heat resistance, and also have poor adhesion to the substrate, requiring surface treatment. There are problems such as.

The present invention has been made to solve such problems.

[Means for Solving the Problem 1] The present invention provides phenyltrichlorosilane and the general formula (■
): 1(I) CH= C) IenCH, ~SiCm (wherein, This invention relates to a method for producing a terminal hydroxyphenylrag-polysiloxane having a photosensitive group in a side chain by condensation polymerizing an intermediate obtained by cohydrolysis using a chloroformic acid ester as a catalyst.

[Example] According to the present invention, phenyltrichlorosilane and general formula (I): 1(I) CH= CH→CH, ~SiCm (wherein, X is a hydrogen atom, a methyl group, an ethyl group or a 7enyl group) , the shoulder indicates an integer from O to 4) is condensed and polymerized using chloroformic acid esters as a catalyst to form a terminal hydroxyl compound having a photosensitive group in the side chain. Phenyllag-polysiloxane can be replaced.

The silane compound represented by the general formula (1) is a compound having a photosensitive group represented by the general formula (■): 1(■) C)I=C)IyenC11, ~, but When the terminal hydroxyphenyl rag-polysiloxane to be produced is exposed to light, a hydrogen atom, a methyl group, an ethyl group or a 7-enyl group are preferable because they have excellent photopolymerizability, and from the viewpoint of heat resistance, the material is Preferably, it is an integer from 0 to 4.

Examples of the thick compound represented by the general formula (I) include vinyltrichlorosilane, allyl chlorosilane, 2-phenylvinyl) +7 chlorosilane, 3
Examples include, but are not limited to, -phenylallyltrichlorosilane.

The above co-hydrolysis reaction is carried out by preparing phenyltrichlorosilane and the compound represented by general formula (I), dissolving this in the same volume of organic solvent as the prepared solution, and then dropping it into a large amount of ion-exchanged water with stirring. This is done by washing the generated hydrochloric acid with ion-exchanged water. *Since the intermediate obtained above is a low molecular weight compound and there is no suitable precipitant, it can be obtained as a solid compound by distilling off the solvent and drying.

The dehydration condensation reaction is carried out as follows.

The cohydrolyzate obtained by hydrolysis is dissolved in an organic solvent to form a uniform layer.

The organic solvent includes, for example, keto'R,9 ethyl ether such as methyl isobutyl ketone, methyl ethyl ketone, and acetone; ethers such as isopropyl ether;
Examples include solvents that can dissolve hydrolyzable compounds such as aromatic hydrocarbons such as xylene, toluene, and benzene, but it is preferable to use one type or a mixture of two or more non-aqueous solvents.

In order to promote the polymerization reaction, the concentration of the polyester intermediate is preferably 40% or more in the organic solvent.

The catalyst used in the condensation polymerization reaction is, for example, methyl chloroformate, ethyl chloroformate, which is soluble in an organic solvent.
Examples include chloroformate esters such as butyl chloroformate and isopropyl chloroformate.
It is used by mixing two or more species and adding them to a solution obtained by dissolving the intermediate.

In this case, the amount of the catalyst added is determined by the number of hydroxyl groups in the intermediate and the molecular weight of the desired photosensitive terminal hydroxyphenyl ladder polysiloxane. As the amount of catalyst added increases, the molecular weight increases, and a thick film is likely to be obtained when spin-coating onto a substrate using a spinner.
．． It is used by adding 5 parts by weight. The amount added is 0.0
If the amount is 1 part by weight at the end, the polymerizability will be poor, and if it exceeds 0.5 parts by weight, the side reaction will become the main reaction, which is not preferable.

The condensation polymerization reaction proceeds as shown by the reaction formula (■): The progress of the above reaction is confirmed by detecting HCl, CO2, or alcohol produced.

Generally, the time required for the reaction is shorter as the reaction temperature is higher, but in the above reaction, it may be about 5 hours at a reaction temperature of 130°C.

After the above reaction is completed, by pouring the concentrated reaction solution into a precipitant such as methanol or n-hexane,
A terminal hydroxyphenyl ladder polysiloxane having a photosensitive group in its side chain is obtained as a precipitate.

Unseparated hydrochloric acid can be easily removed from the obtained terminal hydroxyphenyl lag polysiloxane by drying it under reduced pressure with a rotary pump using an aspirator.

When the thus obtained terminal hydroxyphenyl ladder polysiloxane was analyzed by infrared spectroscopy, it was found that S! -CJs
The absorption peaks assigned to 1595c-1 and 1430
cz-', and absorption peaks at 1135c+++-' and 101045c', which are attributed to the antisymmetric stretching vibration of 5i-0-Si, which indicates that the polymer has a ladder structure.
The absorption peak attributed to 5i-OH, which contributes to the adhesion with the substrate, is at 3400 cz-', and the absorption peak attributed to the vinyl group, which indicates that the polymer is photosensitive, is at 12 f0 cJl''''. Each is observed.

These results confirm that the above polymer is a terminal hydroxyphenylrag-polysiloxane having a photosensitive group in the side chain.

Next, the method for producing the terminal hydroxyphenyl ladder polysiloxane of the present invention will be explained using Examples, but the present invention is not limited to these Examples.

Reference example 1 Phenyltrichlorosilane (C, HsSiCj!5) 1
05.8 g (0.50 mol) and 8.1 g (0.0 mol) of vinyltrichlorosilane (CH2=CH-3iC1,*)
A solution of 50 mol) dissolved in 200 ml of diethyl ether was attached to a stirrer and a thermometer, and the temperature was kept below 10°C while stirring into 1000xf of ion-exchanged water in a 21 4-bottle flask cooled in a water bath. Hydrolysis was carried out by gradually dropping the solution over a period of about 3 hours. Thereafter, the liquid temperature was returned to room temperature and stirred for an additional 30 minutes to complete the hydrolysis reaction.

The ether layer was separated from the resulting two-layered reaction solution and washed several times with ion-exchanged water until it became neutral.

Since the intermediate has a low molecular weight and there is no suitable precipitating agent, the solvent was distilled off under reduced pressure and the intermediate was recovered as a white powder.

When the white powder was analyzed by infrared spectroscopy, it was found that 34
The absorption peak of 5i-OH is found at
S i -0 as described in Volume C-1, 83
-The absorption peak attributed to the antisymmetric stretching vibration of Si is 11
35cm-' and 1045c, and C1. =CH-
An absorption peak was observed at 1270 cz-'.

From these results, it was confirmed that the white powder obtained was a terminal hydroxyphenyl rag-type siloxane having a vinyl group in the side chain.

The powder has a melting temperature of about 90°C and a molecular weight of about 150°C.
It was 0.

Reference Examples 2 to 6 Intermediates were produced in the same manner as in Reference Example 1 using the amounts shown in Table 1. The obtained intermediate was confirmed by infrared spectroscopy to be a terminal hydroxyphenyl rag-type siloxane having a photosensitive group in the side chain.

All of the obtained intermediates melted at about 90°C and had a molecular weight of about 1500.

Example 1 A reflux condenser, a stirrer, and a thermometer were attached to the flask, and the intermediate 10 obtained in Reference Example 1 was placed in the flask. Add 30 tl of c9 thin, dissolve and add ethyl chloroformate 0.1. was added, and the homogeneous layer was reacted at about 130° C. for 3 hours.

After the reaction was completed, the solution was cooled and poured into 10 times the volume of methanol to obtain a white precipitate. The obtained white precipitate was dried under reduced pressure using an aspirator and a rotary pump.
When the yield was measured, it was about 9 g.

Next, when the obtained white powder was analyzed by infrared analysis, an absorption peak of 5i-Off was found at 3400c Taki-1, and an absorption peak attributable to the antisymmetric stretching vibration of 5i-0-Si was found at 1135cg-' and 1045cz-', and C
The absorption peak based on H, = C) l- is 1270 cm
−' was observed. Compared to the white powder obtained in the reference example, the relative intensity of the absorption peak at 3400cx"" decreased,
The necks of the two absorption peaks at 1135cm-' and 1045cm-' became deeper, but no change was observed in the absorption peak at 12f0cjI-'.

From these results, it was confirmed that the obtained white powder was a terminal hydroxyphenylrag-polysiloxane having a vinyl group in the side chain.

The molecular weight of the polymer was measured to be about 25,000, and it did not melt when heated, and thermogravimetric measurement (in a nitrogen atmosphere, temperature increase rate of 10°C/min) showed a significant weight loss at 458°C.

The viscosity of the polymer dissolved in toluene (15% by weight) is about 5eP, and the solution is spun at about 2 rotations using a spinner.
When coated on a glass substrate at 000 rpm, it was approximately 2μ
Taki's thin film has been changed.

Examples 2 to 12 Silicone compounds of the present invention were produced according to the method of Example 1 using the amounts shown in Table @2. The obtained silicone compound was analyzed by infrared spectroscopy and was found to be a terminal hydroxyphenylragubo+1 siloxane having a photosensitive group in the side chain. Molecular weight of the obtained silicone compound, 15% solution in toluene The viscosity, thermogravimetry, and thickness of the spin-coated film on the glass substrate were measured according to the method of Example 1. The results are shown in Table 2.

Comparative Example 1 A photosensitive heat-resistant material in which photosensitivity was imparted to polyimide, which is a heat-resistant polymer material, was produced as follows.

100 tl four lowers equipped with a thermometer, stirrer, nitrogen inlet pipe, and calcium chloride pipe? 2 g (0.01 mol) of 4,4'-di7mi7nophenyl ether and 15 g of dried N-methyl-2-pyrrolidone (hereinafter referred to as Nl4P) were thoroughly mixed in a Scoop. 3.3', 4 to the resulting solution
．． 4'-benzophenone tetracarboxylic dianhydride 3
．． 22° (0.61 mol) was added and stirred at 25°C for 4 hours to obtain polyamic acid.

Add 3.1 g (0.02 mol) of 2-(aziridinyl)ethyl methacrylate to the above polyamic acid solution,
A photosensitive heat-resistant material was produced by reacting at 0°C for 4 hours.

When this photosensitive heat-resistant material was subjected to thermogravimetric measurement in the same manner as in Example 1 (in a nitrogen atmosphere, at a heating rate of 10°C/min), a weight loss was observed at 400°C.

Further, the viscosity of a 15% by weight NMP solution of the polymer is about 10
This solution was spun at 20 rpm using a spinner at 00 cP.
When coated on a glass substrate at 0.00 rpm, approximately It has a soothing effect.

Claims (1)

[Claims] (1) Phenyltrichlorosilane and general formula (I)
:▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) Co-hydrolysis of a compound represented by A method for producing a terminal hydroxyphenyl ladder polysiloxane having a photosensitive group in the side chain by condensation polymerizing the intermediate obtained by using a chloroformic acid ester as a catalyst.