JPS5896654A - Photosensitive silicon resin composition - Google Patents

Abstract

PURPOSE:To obtain novel titled composition with high heat resistance after photochemical reaction, useful for printing plate making, resists for forming the circuits of electronic parts, etc., comprising a (terminal hydroxy) polyladder siloxane and an aromatic (sulfonyl)azide compound. CONSTITUTION:The objective composition comprising (A) a polyladder siloxane of formulaI[R1 and R2 are each monovalent (substituted) hydrocarbon; n is a positive integer]and/or a terminal hydroxypolyladder siloxane of formula II[R3 and R4 are monovalent (substituted) hydrocarbon; m is an integer]and (B) an aromatic azide compound (e.g. of formula III, or IV) and/or an aromatic sulfonylazide compound (e.g. of formula V, or VI). For the application, the above composition is usually dissolved in a solvent such as bonzene, acetone, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive silicone resin composition.

The method for producing photosensitive silicone resins is l) a method in which a polysilane having a hydroxyl group is reacted with an alkoxysilane having a methacrylic group (Japanese Unexamined Patent Publication No. 49-39200
Publication No.).

2) A method of addition-reacting a compound such as allyl methacrylate to a polysiloxane having a water-like structure (Unexamined Japanese Patent Publication No. 52
36719), various other methods are known for introducing photosensitive groups into polysiloxanes. However, in the method of introducing photosensitive groups into these polysiloxanes.

The manufacturing method thereof is very complicated, and the photosensitive resin composition obtained using this method has a drawback of poor heat resistance after photoreaction.

In view of these drawbacks, the present inventors aimed to obtain a silicone resin composition that can be easily produced without using the above-mentioned photosensitive resin, has excellent heat resistance after photoreaction, and has good and poor photoresist properties. Nine results were obtained after repeated consideration.

The photosensitive silicone resin composition of the present invention has been achieved.

The present invention is.

(4) General formula (where R1 and Rs are -valent hydrocarbon groups or monovalent substituted hydrocarbon groups, and they may be the same or different (, n is a positive integer). The polyladder siloxanes and/or shown have the general formula (where ns, R4 is a -valent hydrocarbon group, and R4 is a monovalent substituted hydrocarbon group, and these may be the same or 4 different). The present invention relates to a photosensitive silicone resin composition containing a terminal hydroxypolyladder siloxane represented by (em is an integer), an aromatic azide compound (I3), and an aromatic sulfonyl azide compound (I3).

　　.

The photosensitive silicone resin composition of the present invention is as follows.

This can be easily done by mixing the above-mentioned polyladder siloxane and/or terminal hydroxy polyladder siloxane as the base resin with an aromatic azide compound and/or aromatic sulfonyl azide compound as a photosensitive compound in the presence of an appropriate solvent. can be obtained. Furthermore, the photosensitive silicone resin composition of the present invention has excellent heat resistance after rounding and photoreaction using polygonal ladder siloxane or terminal hydro-Φ grained ladder siloxane as the base resin.

Hereinafter, one aspect of the present invention will be explained in detail.

The polyladder siloxane used in the photosensitive silicone resin composition of the present invention is disclosed in Japanese Patent Publication No. 40-15989, U.
, 8. P, 3017386, etc., and its production method is 1, for example, by hydrolyzing trichlorosilane represented by the general formula R8jC/s (where R is a monovalent hydrocarbon group) to obtain a neutral mer. It is obtained by polymerization using an alkaline catalyst such as caustic potash.

The terminal human j-xyboryladasi-p xane is JP-A-F! 853
-88099, etc., and is already a known and good compound. In the above formula showing the above-mentioned polyladder siloxane or terminal hydroxy polyladder siloxane in the present invention, R1, L, and R4 are monovalent hydrocarbon groups or monovalent substituted hydrocarbon groups, and Tob is the same. For example, methyl group, ethyl group.

There are aromatic hydrocarbon groups such as alkyl groups such as propyl groups, phenyl groups, substituted phenyl groups, and substituted products of these groups. is preferred.

In the above formula, n and m are positive integers, which are usually larger than 50.

91 The aromatic azide compound and the aromatic sulfonyl azide compound, which are the photosensitive compounds used in the photosensitive silicone resin composition of the present invention, produce an active species nitrene when irradiated with light, and this active species undergoes dimerization and duplication. addition to the bond,
It is known to cause hydrogen abstraction reactions. Therefore, these photosensitive compounds added to polyladder siloxane or terminal hydroxy polyladder siloxane cause a difference in solubility in the current solution between the previously irradiated area and the unirradiated area through the above reaction. Examples of the aromatic azide compound used in the present invention include monoazide compounds such as the following.

Bisazide compounds such as (9) Examples of aromatic sulfonyl azide compounds include bissulfonyl azide compounds such as monosulfonyl azide compounds (1) and the like.

These photosensitive compounds can be used alone or in combination of two or more.

The photosensitive silicone resin composition of the present invention is usually used in a state in which polyladder siloxane and/or terminal hydroxy polyladder siloxane and a photosensitive compound are dissolved in a suitable organic solvent.

The solvent used in this case is preferably one that dissolves both the polyladder siloxane, the terminal hydroxy polyladder siloxane, and the photosensitive compound.9 For example, benzene, toluene.

Aromatic hydrocarbons such as xylene, ketone solvents such as acetone, methyl ethyl ketone, etc. are used. These may be used alone or in combination.

It is possible to use various sensitizers in combination with the photosensitive silicone resin composition of the present invention.

Sensitizers aim to improve photosensitivity by expanding the sensitive wavelength range of photosensitive compounds 9 and efficiently imparting light energy to photosensitive compounds. In the present invention, 9 for example, benzoin or its derivatives, Benzin ethers such as benzoin methyl ether, benzyl and its derivatives.

Aryldiazonium salts, anthraquinone and its derivatives, acetophenone or its derivatives, sulfur compounds such as diphenyl disulfide, benzophenone or its derivatives, etc. can be used, and these may be used singly or as a mixture of two or more thereof.

As for the composition of the photosensitive silicone resin composition in the present invention, the photosensitive compound is preferably 1 to 50 parts by weight, more preferably It is used in a range of 5 to 30 parts by weight. If there is too much photosensitive compound, the photosensitive compound may precipitate during storage.

The heat resistance after photoreaction decreases, and if the amount of the photosensitive compound is too small, the ability to form a shibata pattern, in which the difference in solubility in a developing solution between the light irradiated area and the unexposed area is small, tends to decrease after the photoreaction.

The photosensitive silicone resin composition of the present invention is as follows.

Make the above-mentioned organic solvent solution with the above-mentioned composition.

After coating the base material by an appropriate method and drying the solvent, irradiation with light is performed, followed by the above-mentioned nine organic solvents.

A pattern can be formed using a suitable developer such as a dilute alkaline solution.

Hereinafter, one aspect of the present invention will be explained in detail.

Example 1 Using phenyltrichlorosilane
9 polyphenyl ladder siloxane (weight average molecular weight 200,000) lO? produced according to Reference Example 1 and Examples of Publication No. 89. , 3,3'-diazide diphenyl sulfone
? was added and dissolved in benzene 100PK to prepare a photosensitive silicone resin composition. Composition of 5011X5
Coated to a film thickness of 1 μm on a glass plate of
Dry the benzene for 0 minutes and transfer the Xe −
Light irradiation was performed using an Hg lamp at 50 aiN/3.

After that, I washed it with toluene for 2 minutes and placed a good pattern.

No change was observed in this pattern even after heating at 400° C. for 60 minutes.

Example 2 JP-A-53-8809 using methyltrichlorosilane
It was produced according to Examples 1 and 3 of Publication No. 9, and a terminal-terminated hydroxypolymethyl 2-dersiloxane (weight average molecular weight 20,000) lO? paraazidobenzoic acid 2-(dimethylamino)
Ethyl 3? Add.

Toluene 150? A photosensitive silicone resin composition was prepared. This composition was subjected to the same treatment as in Example 1, irradiated with light, and then developed with a dilute alkaline solution to obtain a pattern that was easy to draw. No change was observed in this pattern even after heating at 300° C. for 60 minutes.

Example 3 The same excellent results as in Example 1 were obtained with the polyphenyl 2-darsiloxane 1O composition of Example 1.

According to the invention, polyladder siloxane and/or terminal hydroxyboriradarsi 011? A photosensitive silicone resin composition can be easily produced by simply mixing sun and a photosensitive compound. First, the photosensitive silicone resin composition of the present invention has excellent heat resistance after photoreaction and can withstand heat treatment at 300° C. to 400° C. or higher after pattern formation. Accordingly, the photosensitive silicone resin composition of the present invention can be used not only for printing plate making, but also as a resist for circuit formation of electronic components, a soldering adhesive film for printed circuits, a semiconductor pad page coating, and a multilayer integrated circuit. 1 can also be used as an interlayer insulating film, an alignment film for liquid crystal, a resist for dry etching, etc.

Claims (1)

[Claims] 1. (A) General formula (where e R1e & is a -valent hydrocarbon group and is a monovalent substituted hydrocarbon group, and these may be the same or different. , n is a positive integer) and/or a general formula (where R4 and R4 are -valent hydrocarbon groups or To#), These may be the same or different (where m is an integer) and (B) a photosensitive compound containing an aromatic azide compound and/or an aromatic sulfonyl azide compound. Silicone resin composition.