JPS61211355A - Reactive resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which causes a crosslinking reaction when irradiated with ultraviolet light, X-rays or r-rays to thereby make it insoluble in solvents, by blending an isopropenyl group-contg. polymer with a halogenated hydrocarbon. CONSTITUTION:An isopropenyl group-contg. polymer (A) having an intrinsic viscosity of 0.05 or above (in toluene soln. at 30 deg.C) and a ratio of the isopropenylbenzene unit of the formula to the monomer unit in the polymer of 0.02 or above, obtd. by reacting diisopropenylbenzene with other polymerizable monomer (e.g. styrene) is blended with a halogenated hydrocarbon (e.g. tetrachloroethane) to obtain the titled compsn. The compsn. is very sensitive to ultraviolet rays, X-rays, r-ray and electron beams and reacts when irradiated with them, it is useful as a reactive compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a reactive resin composition that undergoes a crosslinking reaction and becomes insolubilized by irradiation with ultraviolet rays, X-rays, γ-rays, etc.

[Conventional technology]

Reactive resin compositions are used for applications such as resists, and resin compositions made of acrylic acid-based polymers, methacrylic acid-based polymers, phenol-based polymers, styrene-based polymers, etc. Widely used (used in semiconductor device manufacturing, etc.)

[Problem that the invention seeks to solve]

° Improvements such as higher sensitivity and higher resolution are desired for reactive resin compositions such as higher integration of semiconductor devices.

[Means to solve the problem]

The present inventors have diligently studied the above-mentioned problems, particularly the increase in sensitivity, and have discovered that the reactivity of a resin composition consisting of a specific polymer and a specific compound is extremely high, and have completed the present invention.

This is a reactive resin composition comprising an isopropenyl group-containing polymer in which the ratio of the monomer units expressed by the following to the monomer units in the total polymer is 0.02 or more and a halogenated hydrocarbon.

Monomer units other than those represented by the general formula of the impropenyl group-containing polymer constituting the resin composition of the present invention include:
Although not particularly limited, aromatic monomer units such as styrene, α-methylstyrene derivatives, etc. are preferred, such as methylstyrene, chlorostyrene, methoxystyrene,
Examples include ring-substituted styrene derivatives such as cyanostyrene and α-' methylstyrene derivatives in which the α-position thereof is substituted with a methyl group.

Further, the molecular weight of the impropenyl group-containing polymer is 0.05 or more, preferably 0.1 to 2 as the intrinsic viscosity measured in a toluene solution at 30°C, in view of the film forming properties and reactivity of the composition. .0.

Any halogenated hydrocarbon constituting the reactive resin composition of the present invention can be used, but from the viewpoint of ease of handling, those with a relatively high boiling point are preferred and used. Specifically, tetrachloroethane,
hexachloroethane, ) IJ / lorpropane, α-
Chlorotoluene, α, α-dichlorotoluene, α, α,
Chlorinated hydrocarbon compounds such as α-trichlorotoluene,
Brominated hydrocarbon compounds such as carbon tetrabromide, ethane tetrabromide, hexabromoethane, tribromopropane, α-bromotoluene, α,α-cyfuromtoluene, α,α,α-tribromotoluene, iodination Examples include iodinated hydrocarbon compounds such as ethylene, ethylidene iodide, short ethylene, short propane, benzene iodide, and benzene diiodide.

As a method for producing the impropenyl group-containing polymer constituting the composition of the present invention, diisopropenylbenzene and other polymerizable monomers, such as the above-mentioned styrene and α→
Obtained by copolymerizing a derivative of methylstyrene so that the number of diisopropenylbenzene units is 0.02 or more; for example, an impropenyl group-containing polymer is obtained by radical copolymerization, anionic copolymerization, or cationic copolymerization. be able to. For example, a copolymer of diisopropenylbenzene and styrene with a diisopropenylbenzene content (ratio of impropenyl group-containing monomer units) of up to about 0.4 can be produced by radical polymerization; The copolymerization of isopropenylbenzene and α-methylstyrene is
Polymerization can be carried out using an anionic polymerization initiator such as butyllithium up to a content of diisopropenylbenzene of about 0.3.

Further, as a method for obtaining a polymer having a high diisopropenylbenzene content, an example is known, for example, from JP-A-59-207905.

The composition of the present invention is obtained by mixing the impropenyl group-containing superpolymer and a halogenated hydrocarbon, and dissolving both in a relatively low boiling point medium to obtain a relatively uniform composition. It is also possible to adopt a method in which the low boiling point medium is then removed by evaporation. Or in some cases,
A reactive resin composition solution dissolved in a medium can also be used for desired purposes.

The composition of the present invention causes a crosslinking reaction when irradiated with ultraviolet rays, X-rays, γ-rays, or electron beams and becomes insoluble in solvents, so that it can be used, for example, in resists.

〔Effect of the invention〕

The composition of the present invention reacts with extremely high sensitivity to irradiation with ultraviolet rays, X-rays, γ-rays, electron beams, etc., and therefore is extremely useful as a reactive composition and has industrial value.

〔Example〕

Hereinafter, the present invention will be further explained with reference to Examples.

Example 1 In a 200-mm round bottom flask, 80- toluene, 56-styrene, and diimpropenylbenzene (94 wt% m-diisopropenylbenzene, the remainder was impromyl-α-
Methystyrene) 24- and 0.49 g of azobisisobutyronitrile were added, polymerized at 70°C for 8 hours, toluene-insoluble matter was filtered off, and poured into methanol (No. 11) to precipitate the polymer. The yield was 18.47, and the intrinsic viscosity of the 30°C toluene solution was 0.34. The ratio of impropenyl group-containing units measured by proton NMR was 0.28.

50 kg of carbon tetrabromide per 1 g of the copolymer thus obtained
was dissolved and mixed in 10-ml chloroform, coated on a glass plate to a thickness of about 20 μm, dried, and then coated on a 1 m
A slit-shaped aluminum plate was placed at intervals of m, and light was irradiated from a position of 20 crrL using a 300 W high-pressure mercury lamp. When treated with chloroform after 1 hour, the irradiated area did not dissolve at all.

Comparative Example 1 The amount of diisopropenylbenzene was 8-8, and the amount of styrene was 8-8.
In the same manner as in Example 1 except that 01t was used, 26.52 of a polymer having 0.01 impropenyl group-containing units was obtained. The intrinsic viscosity number was 0.48.

This polymer was mixed with carbon tetrabromide and subjected to a light irradiation test in the same manner as in Example 1, but it dissolved in chloroform even after 5 hours of light irradiation.

Example 2 In the same manner as in Example 1 except that 70 m of styrene, 10-diisopropenylbenzene, and 0.3 g of azobisisobutyronitrile were used, 0.1 impropenyl group-containing unit was prepared.
3. A polymer 19.67 having an intrinsic viscosity number of 0.61 was obtained.

When this polymer was mixed with carbon tetrabromide in the same manner as in Example 1 and subjected to a light irradiation test, the irradiated portion became insoluble in chloroform.

Example 3 The same procedure as Example 1 was carried out except that hexabromoethane was used in place of carbon tetrabromide. The irradiated portion became insoluble in chloroform.

Example 4 Toluene 30-1 α-methylstyrene 27-, diisopropenylbenzene 3d and diglyme 1- were placed in a 200-mm round bottom flask, and butyllithium (10
After adding 1.2- (wt% hexane solution) and polymerizing at -5°C for 2 hours, the mixture was deactivated with methanol (1-), filtered, and poured into methanol (11) to precipitate the polymer.

When this polymer was mixed with carbon tetrabromide and subjected to a light irradiation test in the same manner as in Example 1, the light irradiated portion was insolubilized.

Claims (1)

[Claims] 1. Containing isopropenyl group in which the ratio of the monomer units represented by the general formula ▲There are numerical formulas, chemical formulas, tables, etc.▼ to the monomer units in the total weight is 0.02 or more A reactive resin composition consisting of a polymer and a halogenated hydrocarbon.