JPS62184028A - Polysiloxane compound - Google Patents

Abstract

PURPOSE:To obtain a benzene ring-containing polysiloxane which comprises specified three kinds of repeating units and is hydrophilic and from which various derivatives can be synthesized, by acylating a polyphenylsilsesquioxane or the like and reducing or oxidizing the product. CONSTITUTION:Polyphenylsilsesquioxane, diphenyldilanediol or the like is acylated with an acylating agent (e.g., acetyl chloride). The acylated polymer is recovered and purified, and the acylated polysiloxane is oxidized with an oxidizing agent such as a hypochlorite or reduced with a reducing agent such as LiAlH4. In this way, the purpose polysiloxane compound containing three kinds of repeating units represented by formulas I, II and III (wherein X is lower acyl, carboxyl or a group of formula IV and R is a lower alkyl) at a ratio of l:m:n (wherein l, m and n are 0 or positive integers and are not 0 at the same time).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to polysiloxane compounds that can be used as photosensitive resins, surface protective films, insulating films between multilayer wiring, electronic materials such as ion exchange resins, and functional films. It is something.

Conventional technology Compared to organic polymers, polysiloxane has excellent heat and cold resistance, and its electrical properties are stable over a wide temperature range, so it has many applications as functional film materials and electrical/electronic materials. It's coming. In particular, phenyl group-containing polysiloxane has a high glass transition temperature, so it is thought that strong and hard films can be obtained, and the range of its use is expected to expand significantly.

However, none of the conventional polysiloxanes has a suitable reactive group in the molecule, and almost no functional groups have been introduced to exhibit high functionality. The present inventors have previously shown that functional films such as resists and ion exchange films can be made by chloromethylating polysiloxanes containing benzene rings such as polydiphenylsiloxane and polyphenylsilsesquioxane ( (Japanese Patent Application No. 58-66892, No. 58-66893, etc.)

However, since the fluoromethyl group is hydrophobic and the polysiloxane skeleton itself is hydrophobic, these chloromethylated products have the disadvantage that they are difficult to use in cases where hydrophilicity is required. Hydrophilicity may be improved by introducing a hydrophilic group into the phenyl group, but even if a hydrophilic group is introduced, the raw materials are hydrophobic and the product is hydrophilic, so during synthesis, Due to the uniformity of the reaction system and the difficulty of separation, no polysiloxane with hydrophilic groups introduced has been obtained so far.

Problems to be Solved by the Invention As mentioned above, in order to improve the functionality of polysiloxane, which is expected to have a wide range of applications due to its various properties, and to further expand the field of application, it is necessary to develop appropriate reactions. It is thought that it is advantageous to introduce a group, and such an idea has not been made at all in the past, except for the above-mentioned patent application by the present inventors.

As an example of increasing the functionality of polysiloxane, it is generally considered to make hydrophobic polysiloxane hydrophilic.

This makes it possible to obtain a polysiloxane that is advantageous even in fields where hydrophilicity is required, making it possible to further expand its range of use. D. Its excellent heat resistance, cold resistance,
It becomes possible to advantageously apply stable electrical characteristics and the like.

Furthermore, by introducing such a substituent, D can be provided with yet another function, and can also serve as an intermediate for that purpose. However, in order to realize this, there are various difficulties as mentioned above, and the current situation is that it has not been realized so far.

Therefore, an object of the present invention is to solve the above-mentioned disadvantages that may be expected when making polysiloxane hydrophilic. That is, the object of the present invention is to provide a benzene ring-containing polysiloxane that is hydrophilic and allows the synthesis of a wide variety of derivatives.

Means for Solving the Problems The present inventors conducted various studies to obtain the above-mentioned polysiloxane having a parent wood group.
We found that further reduction and oxidation treatments were effective, and were able to obtain the target compound.

That is, to summarize the present invention, the first invention of the present invention is one in which a hydrophilic substituent is introduced into polyphenylsilsesquioxane D, and the following repeating units A, B and C: (in the formula X represents one selected from a lower acyl group and a carboxyl group, and may be the same or different. It represents an integer and is contained in a ratio of 1.m cannot be 0 at the same time).

On the other hand, the second invention of the present invention is one in which a hydrophilic substituent is introduced into polydiphenylsiloxane D, and the following repeating units D, E and F: (wherein X is a lower acyl group, a carboxyl group, 1':m':n'(1',m',n'
represents 0 or a positive integer, and l' and m' cannot be 0 at the same time).

These polysiloxanes of the present invention can be obtained, for example, by first acylating a raw material polysiloxane and then further reducing or oxidizing the resulting acylated product. First, acylation is performed by dissolving polyphenylsilsesquioxane, diphenylsilanediol, low molecular weight diphenylsiloxane, or diphenylsiloxane oligomer in an acylating agent such as acetyl chloride, acetic anhydride, or propionyl chloride, and then dissolving these in the presence of a 7-Riedel-Crafts type catalyst. This is done by reacting below.

If the reaction can be carried out in a solvent such as chloroform, carbon tetrachloride, trichloroethane, etc., the reaction time is 30 minutes to 30 minutes.
The reaction is completed in 0 hours, and the acylated polymer can be recovered by pouring the reaction solution into ice water containing hydrochloric acid.

The obtained polymer is purified by reprecipitation with a ketone-alcohol system.

Examples of Friedel-Kraf type catalysts include stannic chloride, aluminum chloride, ferric chloride, boron trifluoride,
Examples include zinc chloride, titanium tetrachloride, and other materials that are used as catalysts in general free-sol fluorine reactions.

Further, the polysiloxane of the present invention in which X in the above general formula is a carboxyl group can be obtained by, for example, oxidizing the acylated polysiloxane produced as described above by an appropriate method, that is, by following a conventional method for oxidizing a carbonyl group. It can be manufactured by This oxidation can be achieved by, for example, using hypochlorous acid as an oxidizing agent and refluxing in a suitable solvent.

The polysiloxane derivatives of the present invention, which are This can be carried out by refluxing in a solvent.

An obstacle to introducing hydrophilic groups into functional polysiloxanes and expanding their uses has been the difficulty in separating the raw materials and products due to the difference in their properties. However, especially in the case of polysiloxanes having benzene rings, these difficulties can almost be overcome by treatment according to the present invention. That is, it can be advantageously produced by first acylating, then reducing and oxidizing.

The benzene ring-containing polysiloxane of the present invention has a high glass transition temperature and can form a uniform film.

Furthermore, while the raw material polysiloxane is completely insoluble in polar solvents such as alcohol and water, the benzene ring-containing polysiloxane of the present invention is soluble not only in alcohol but also in alkaline water.

In addition, the obtained polymer has a benzene ring that is resistant to carbon tetrachloride and carbon tetrafluoride gas plasma, and has a siloxane structure that is highly resistant to oxygen gas plasma, so it is suitable for By adding a photosensitizer, it can be used as a two-layer resist.

Further, the benzene ring-containing polysiloxane of the present invention enables the synthesis of a wide variety of derivatives, and can be used as a highly functional membrane.

EXAMPLES Hereinafter, manufacturing examples of the present invention will be described in detail, but the present invention is not limited to these examples.

Production Example 1 Production of Niacetylated Polyphenylsilsesquioxane Capacity: 300 m with stirrer, thermometer, and dropping funnel installed
Add 15 g of anhydrous aluminum chloride and 50 ml of acetyl chloride to a flask and stir. Next, the molecular weight is 7,800
A solution of 5 g of polyphenylsilsesquioxane dissolved in 50 ml of acetyl chloride was gradually added dropwise. temperature to 25
Continue the reaction by keeping at ℃. Hydrogen chloride is generated as the reaction progresses. After continuing the reaction for 3 hours, the mixture was cooled and the contents were poured into ice water containing hydrochloric acid. Stir well to decompose the aluminum chloride, make sure the ice water is acidic, and filter out the precipitated polymer. Wash thoroughly with dilute hydrochloric acid and water, and finally dry in a vacuum dryer. The molecular weight of the obtained polymer was 7.900. 16 in the infrared absorption spectrum
Carbonyl group absorption was observed at 70 cm-', and methyl group absorption was observed at δ=2.4 in NMR, confirming acetylation. The acetylation rate at this time was found to be 60% from NMR.

Production Example 2 Production of Niacetylated Polydiphenylsiloxane Capacity: 300 m with stirrer, thermometer, and dropping funnel installed
1 flask with 25ml of stannic chloride and 50ml of acetic anhydride.
Add 1 and stir. Next, a solution of 6 g of diphenylsilanediol dissolved in 50 ml of acetic anhydride is gradually added dropwise. Acetylated polysiloxane was obtained in the same manner as in Production Example 1. The molecular weight of the obtained polymer is 15.000
In D, the acetylation rate was 42%.

Production Example 3: Production of carboxyl polyphenyl silsesquioxane 6 g of the acetylated polyphenyl silsesquioxane obtained in Production Example 1 was added to 10% of an aqueous solution of sodium hypochlorite.
0ml and reflux for 12 hours. When the resulting clear liquid is made acidic by adding hydrochloric acid, precipitation occurs. A yellowish white solid was obtained by filtration. In the infrared absorption spectrum, the absorption of the carbonyl group at 1670 cm-' disappears, while the absorption of the carboxyl group is seen at 1700 cm-',
Carboxylation was observed. Yield 70%.

Production Example 4: Production of carpoxyl polydiphenylsiloxane 6 g of acetylated polydiphenylsiloxane obtained in Production Example 2 was added to 100% of an aqueous solution of 10% sodium hypochlorite.
m1 and reflux for 12 hours. Thereafter, the carboxyl group was removed in the same manner as in Production Example 3. Yield 65%.

The carboxy fluorides obtained in Production Examples 3 and 4 were soluble in alkaline aqueous solutions, methanol, and ethanol (D), and insoluble in other organic solvents.

Production Example 5 Reduction of Niacylated Polyphenyl Silsesquioxane 5 g of the acetylated polyphenyl silsesquioxane obtained in Production Example 1 was dissolved in 100 ml of tetrahydrofuran, 3 g of LiAlH4 was added thereto, and the mixture was refluxed for 3 hours.

After the reaction was completed, the mixture was poured into ice water containing 5% hydrochloric acid to obtain a yellowish white solid. Yield 55%.

In the infrared absorption spectrum of the product, 16
The carbonyl absorption at 70 cm-' disappears, and 3100-3
Absorption due to OH groups was observed near 400c+n-', confirming that reduction had occurred.

Production Example 6: Reduction of acetylated polydiphenylsiloxane Acetylated polydiphenylsiloxane 5 obtained in Production Example 2
Dissolve g in 100 ml of tetrahydrofuran and add 3
g (DLiAI H) was added and refluxed. After the reaction was completed, it was poured into ice water containing 5% hydrochloric acid to obtain a yellowish white solid. Yield 66%.

The polymers obtained in Production Examples 5 and 6 were soluble in alkaline aqueous solutions and alcohols such as methanol.

Production Example 7: Propionylation was carried out by the same production method as in Production Example 1, using propionyl chloride instead of acetyl chloride. The molecular weight of the obtained polymer was 8500 (D), and the propionylation rate was found to be 43% from NMR.

Next, an application example will be described, but the invention is not limited to this example.

Application Example 1 The acylated polyphenylsilsesquioxane obtained in Production Example 1 was dissolved in 2-ethoxyethyl acetate, and naphthodiazoquinone was added thereto in an amount of 20% of the polymer. This was applied to a silicon wafer to a thickness of approximately 0.3 μm, and
Prebaking was carried out at ℃ for 20 minutes in a nitrogen stream.

After pre-beta, light irradiation was performed using a photo aligner. After irradiation, the wafer was placed in 5% tetramethylammonium hydroxide and developed. At this time, the irradiation dose at which the film thickness became 0 was 80 mJ/cnf, which was higher in sensitivity than conventional photoresists. Furthermore, when patterns were transferred through a quartz mask, 0.5 μm lines/spaces could be easily resolved. In addition, when reactive ion etching of 02 was carried out, the etching rate was 4nrn/min.
It was found to have high resistance.

Application Examples 2 to 6 The polymers obtained in Production Examples 2 to 6 were irradiated with light, developed, and then dry etched in the same manner as in Application Example 1. Table 1
It was found that the resist properties shown in Figure 1 were obtained and that the resist properties were sufficiently usable for practical use.

Table 1 Resist property application example 7.8 After thoroughly drying the carboxylated product obtained in Production example 3.4, it was boiled for 1 hour in an IN sodium hydroxide aqueous solution to completely convert the carboxylic acid groups into sodium carboxylate. After making some changes, it was found that this product was fully usable as an ion exchange resin and ion exchange membrane.

The cation exchange capacity of each is shown in Table 2 below.

Table 2 Cation Capacity Application Example 9 Each of the polymers obtained in Production Examples 1 to 6 was measured by TGA (thermogravimetric analysis) to examine the decomposition temperature. Table 3 shows the decomposition temperatures.

Each showed high decomposition temperature D and high heat resistance.

They actually coated wafers and chips with these polymers and formed a film by drying them. This film could be used as a protective film with high heat resistance.

As described in detail, by using the polysiloxane of the present invention, a uniform film with excellent D, heat resistance, and weather resistance can be obtained. Furthermore, the polymer of the present invention has the advantage that it is hydrophilic and can be synthesized into a wide variety of derivatives, allowing it to be used in a variety of applications.

Claims (2)

[Claims] (1) The following repeating units A, B, and C: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (A) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ ( C) (wherein, X is a lower acyl group, a carboxyl group, ▲numerical formula,
There are chemical formulas, tables, etc. ▼ (however, R is a lower alkyl group), which may be the same or different) is expressed as l:m:n (however, l , m, and n are 0 or a positive integer, and l and m are never 0 at the same time). (2) The following repeating units D, E, and F: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (D) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (E) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ ( F) (In the formula, X is a lower acyl group, a carboxyl group, -CH-
represents one selected from R (where R is a lower alkyl group, and may be the same or different) as l':m':n' (however, l', m' and n' represent 0 or a positive integer, and l' and m' are never 0 at the same time).