JPS62235330A - Polysiloxane compound - Google Patents

Abstract

PURPOSE:A polysiloxane compound, containing phenyl groups substituted by sulfonic acid groups, having improved heat and cold resistance, electrical characteristic, etc., as well as good hydrophilicity. CONSTITUTION:A polysiloxane compound expressed by formula I (R1, R2 and R3 are H, alkyl or phenyl; l, m and n represent 0 or positive integers and either one of l and m represents 0) or formula II. Examples of producing the above- mentioned polysiloxane compound include a method for obtaining the compound by heating polyphenylsilsesquioxane and silver sulfate together, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a polysiloxane compound that has various properties such as heat resistance, cold resistance, and electrical properties, as well as excellent hydrophilicity. In general, polysiloxane compounds are known to exhibit superior heat resistance, cold resistance, and electrical customization properties compared to organic polymer compounds. Among these, those having a phenyl group in the molecule, such as polydiphenylsiloxane and polyphenylsilsesquioxane, are attracting attention as high-strength thin film materials because of their particularly high glass transition temperatures.

Therefore, in order to further improve various custom orders for the above-mentioned polysiloxane compounds, the inventors have developed polysiloxane compounds obtained by chloromethylating polysiloxane compounds such as the above-mentioned polydiphenylsiloxane and polyphenylsilsesquioxane. It was shown that chloromethylated compounds can be used as resist materials and high-performance membrane materials such as ion exchange membranes (Japanese Patent Application No. 58-66892, % Application No. 58-66893).
).

Totoro looks like this, lolomethylated compound I: If there is,
Since both the polysiloxane skeleton and the a-romethyl group are I: hydrophobic, there have been disadvantages such as difficulty in use in Application 1, which requires hydrophilicity.

(Objective) This invention was made in view of the above circumstances (2), and its object is to provide a polysiloxane compound which has not only heat resistance, cold resistance and air resistance properties, but also water resistance with round pores. What to provide: Yes.

(A rounding means to solve the problem) In order to achieve this purpose, the inventors conducted repeated studies and found that polysiloxane compound 6 having a phenyl group in the molecule: It was found that the material showed excellent round pore aqueous properties.

That is, the first invention of the present invention is based on the formula 8% (wherein R,, R2 and R3 each represent nine groups selected from the group consisting of a hydrogen atom, an alkyl group, and a phenyl group; tas& and n are respectively Oma and t.
represents a positive integer, and each of 71. of t and m. On the other hand,
It is characterized by being a borish OJP sun compound represented by

When a polysiloxane compound td represented by the above formula (T), such as polyphenylsilsesquioxane, is used as a double compound, and this is sulfonated, C is obtained.

Since this polysiloxane compound has two mono-reactive sulfonic acid groups in its molecule, by introducing sodium etc. into the sulfonic acid groups, it can be used as an ion-exchange resin or an ion-exchange compound. Application I for membranes, etc.: Can be used. Please note that this polysiloxane compound has high resistance to gas plasma (2) such as carbon tetrachloride, carbon tetrafluoride, and oxygen, and has a high decomposition temperature, so it may be used to protect resist materials, wafer chips, etc. Use of hhh materials, etc. 5: Suitable, Next (:, Method C: for producing such polysiloxane compounds will be explained. First, polyphenylsilsesquioxane is reacted with concentrated sulfuric acid using silver sulfate as a catalyst. Zazeru.

Here, the reaction temperature is determined depending on the sulfonation rate in the sulfonated product obtained, and is usually in the range of about 95 to 105°C. .

Further, the reaction time is determined depending on the reaction temperature of above C and the sulfonation rate in the obtained sulfonated product, and is in the range of about 30 minutes to 30 hours. The opening of the container in which the reaction is to be carried out is preferably completely sealed with a cork or the like to prevent moisture from entering the reactor before the reaction begins.

The above reactants were then dissolved 1:1 in a large amount of ice water containing glacial acetic acid.
The precipitate is purified by reprecipitation in a mixture of acetone and water, and then dried to obtain the desired sulfonated polyphenylsilsesquioxane.

The sulfonated product (polysiloxane compound) thus obtained has a sulfonic acid group introduced into the molecule9,
For example, in alcoholic solvents such as 30 volume methanol solution, aqueous alkaline liquids such as 104 caustic soda aqueous solution and 54 tetramethylhydroxyammonium aqueous solution. Become.

9. The second invention of the present invention is, (in the formula, nl * R2 and R3 represent 9 groups selected from the group consisting of a hydrogen atom, an alkyl group, and a phenyl group, respectively; n represents 0 or a positive integer, and one of t and m is 0
It is characterized by being a polysiloxane compound represented by ).

Polysiloxane compound u represented by the above formula (1), example,
(For example, by using diphenylsilanediol, diphenylsiloxane, diphenylsiloxane oligomer, etc. as a precursor compound and sulfonating it. Like the polysiloxane compound, it has a reactive I: rich sulfonic acid group in its molecule, so by introducing a sulfonic acid group such as sodium, it can be used for applications such as ion exchange resins and ion exchange membranes. This polysiloxane compound may also contain carbon tetrachloride,
Because it has high resistance to gas plasmas such as carbon tetrafluoride and oxygen and has a high decomposition temperature, it is suitable for use in applications such as resist materials and protective film materials for quenched surfaces.

Next, an example of a method for producing such a polysiloxane compound will be explained. First, for example, put predetermined amounts of diphenylsilanediol and tetrachloroethane into the same container and stir and mix.
A predetermined amount of rusulfonic acid is added dropwise, and the mixture is further stirred at room temperature for a predetermined time. eK+=, This mixed solution -: Add glacial acetic acid until no hydrogen chloride gas is generated, then pour the mixed solution in the container into a large amount of water to obtain a precipitate. The product is purified by reprecipitation in a mixture of acetone and water, and then dried to obtain a chlorosulfonated product.

Next, the chlorosulfonated product is heated with fuming sulfuric acid at a high temperature for a predetermined period of time, and then a precipitate is obtained in a large amount of ice water containing glacial acetic acid. Next, this precipitate is reprecipitated in a mixture of acetone and water, selected, and dried to obtain a sulfonated product.

The sulfonated product (polysiloxane compound) thus obtained exhibits excellent hydrophilicity similar to that shown by the above-mentioned formula (1).

Production examples of the present invention and application examples thereof will be shown below.

(Surface Example 1) Polyphenylsilsesquioxane 10j' and sulfuric acid chain 0
．． 2.9 was added, and the mouth of the flask was completely sealed with a 1 Nicok stopper, being careful not to allow moisture to enter the flask. Next, the inside of the flask was heated to maintain a temperature of about 100° C. and reacted for 20 hours.

Next C1: Pour the reaction solution in the above flask into a large amount of ice water containing glacial acetic acid to obtain a precipitate. This precipitate is reprecipitated in a mixture of acetone and water, and then dried. A sulfonated polyphenylsilsesquioxane was obtained.

The sulfonated polyphenylsilsesquioxane obtained in this way is rich in wood-philic C, and has a molecular weight of 8500, and contains 1.2 sulfones per aromatic nucleus. An acid group was introduced. In addition, the above sulfonated products had high resistance to gaspants such as carbon tetrachloride, carbon tetrafluoride, and phosphorus. Furthermore, the above-mentioned sulfonated products can be used to synthesize sulfonic acids with high reactivity, an example of which will be shown in the application examples below.

(Mold making example 2) Add 6 diphenylsilane diol to a $13oo flask.
g and 20 liters of tetrachloroethane? Add chlorosulfonic acid 509 dropwise to this mixed solution and stir for an additional 4 hours at room temperature.
Next, add the mixed solution C diglacial acetic acid until the generation of hydrogen chloride gas stops, and then add the mixed solution in the flask to a large amount of C in water.
: Pouring to obtain a precipitate 9. This precipitate was reprecipitated in a mixture of acetone and water, and then dried to obtain a sulfonated product. After heating with sulfuric acid at 140 to 150°C for 2 hours, a precipitate was obtained by pouring into a large amount of ice water containing glacial acetic acid.
Next, this precipitate was reprecipitated in a mixed solution of acetone and water, and then dried to obtain a sulfonated product.

The sulfonated product thus obtained was highly hydrophilic, with a molecular weight of 10,800 and a sulfonation rate of 854. Also,
This sulfonate has high resistance to gas plasmas such as carbon tetrachloride, carbon tetrafluoride and oxygen.

(Application Example 1) The sulfonated polyphenylsilsesquioxane obtained in Production Example 1 was dissolved in 2-ethoxyethyl acetate, and 20 weight portions of the above sulfonated product were added to diazonaphthoquinone. The obtained resist solution was applied to a silicon wafer with a Cfi cloth to a thickness of approximately 0.3 μm.
The silicon wafer was prebaked at approximately 100°C for 20 minutes in a nitrogen gas stream.Then, the resist film surface 1 of the silicon wafer was irradiated with light using a photo aligner, and then aqueous solution of tetramethylhydroxyanmonium was applied. I developed it inside. At this time, the irradiation amount at which the thickness of the resist film becomes 0 due to the irradiation of the photoaligner is 85 mJ.
/cm2, and had higher sensitivity than conventional photoresists.

(9) When a pattern was transferred to the resist film of the silicon wafer shown above through a quartz mask, 0.5 μm lines/spaces were easily formed.

Furthermore, when reactive ion etching was performed on the resist film of the silicon wafer described above in a hydrogen gas, the etching rate was 4 nm/min, indicating that it has high resistance. .

(r5 Example 2) The 9-polysiloxane compound obtained in Example 2 was used as a resist film on a silicon wafer and irradiated with light. 120
whJ/cvpz2 and 0.4 μm'
The y-in/space can be easily resolved, and the etching rate for reactive ion etching in streetcar gas is 5.
nm/win.

From these results, it was found that this polysiloxane compound exhibits resist properties that are sufficient for practical use.

(Application Example 3) After sufficiently drying the sulfonated polyphenylsilsesquioxane obtained in Production Example 1, it was boiled in an INW soda aqueous solution for 1 hour to clear the sulfone crystals in the sulfonated product. It was used as a base.

Next, after washing with water, air dry.

The cation exchange capacity of the polymer obtained in this way is 3.5~L Omaq/li, and this polymer can be used as an ion exchange tA resin or an ion exchange membrane.

(Application Example 4) Polymer C obtained in Production Example 1.2: When the decomposition temperature was measured using thermal 11fn analysis (TGA), the polymer of Production Example 1 had a temperature of 295°C, and In the case of the polymer of Production Example 2, the temperature was 305°C.

From this result, it can be seen that the polymers obtained in Production Example 1゜2 are all ? : 6. It is found that it is feverish. 9.
It has also been found that these polymers can also be used as a protective film for the wafer chip surface, which requires heat resistance.

(Effects of the Invention) As explained above, since the polysiloxane compound of the present invention has a sulfonic acid group in the molecule, it has high water resistance.

Furthermore, since this polysiloxane compound has a highly reactive sulfonic acid group in one molecule, it can serve as a starting material for derivatives exhibiting high functionality.

Applicant: Nippon Telegraph and Telephone Corporation □

Claims (2)

[Claims] (1) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1, R_2 and R_3 each represent a group selected from the group consisting of a hydrogen atom, an alkyl group, and a phenyl group. m and n each represent 0 or a positive integer, and either l or m represents 0.) A polysiloxane compound represented by: (2) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1, R_2 and R_3 each represent a group selected from the group consisting of a hydrogen atom, an alkyl group, and a phenyl group. m and n each represent 0 or a positive integer, and either l or m represents 0.) A polysiloxane compound represented by: