JPS61218604A - Reactive polymer and production thereof - Google Patents

Abstract

PURPOSE:A reactive polymer useful as a resist having high resolving power, etc., which is a reactive polymer containing a specific monomer unit, and causes extremely easily a crosslinking reaction by irradiation with ionizing radiation. CONSTITUTION:A hydrogen halide is brought into contact with a solution of a vinyl group-containing polymer obtained by copolymerizing divinylbenzene with a polymerizable vinyl group-containing monomer, to give a reactive polymer containing a monomer unit shown by the formula (X is halogen). Preferably the polymerization reaction is carried out usually at 5-100% monomer concentration and at a molar ratio of divinylbenzene to the whole monomer of 0.02-0.50.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a reactive polymer that undergoes a crosslinking reaction by irradiation with ultraviolet rays, X-rays, r-rays, electron beams, etc., and a method for producing the same.

[Conventional technology]

Many types of reactive polymers are used for the purpose of manufacturing semiconductor devices, printed wiring boards, etc. For example, many types of reactive polymers are used, such as acrylic acid, methacrylic acid, styrene, and phenol. coalescence is known.

[Problem that the invention seeks to solve]

Due to the increasing integration of semiconductor devices, reactive polymers with even higher sensitivity and higher resolution are desired.

[Means for solving problems]

The inventors of the present invention have conducted extensive studies on methods for solving the above problems, and have completed the present invention.

That is, the present invention is a reactive polymer containing a monomer unit represented by the general formula I (wherein, X is a halogen atom).

The present invention is also characterized in that hydrogen halide is brought into contact with a solution of a vinyl group-containing polymer obtained by copolymerizing divinylbenzene represented by the general formula (2) and a polymerizable vinyl group-containing monomer. This is a method for producing a reactive polymer containing a monomer unit represented by the general formula I (wherein, X is a halogen atom).

In the monomer unit represented by general formula I (wherein X is a halogen atom) in the polymer of the present invention, X is fluorine, chlorine, bromine, or iodine, and the total weight of the monomer unit is 0.
02 or more is preferable from the viewpoint of reactivity. Other monomer units of the polymer are not particularly limited, but are preferably monomers containing an aromatic ring, and specific examples include styrene, α-methylstyrene, and ring-substituted derivatives thereof. .

Examples of their ring-substituted derivatives include alkyl residues such as methyl, ethyl, propyl, and butyl, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, and halogen atoms such as fluorine, chlorine, bromine, and iodine, etc. Examples include those in which one to several hydrogen atoms are substituted in an aromatic ring such as -methylstyrene.

Although there is no particular restriction on the molecular weight of the polymer of the present invention,
From the viewpoint of reactivity, it is preferable that the intrinsic viscosity measured in a toluene solution at 30°C is 0.01 or more.

The manufacturing method of the present invention will be explained next.

As for divinylbenzene represented by the general formula ", which is used as one monomer in the present invention, it is possible to separate the isomers and use them. It is convenient to use with a mixture of

In the present invention, the polymerizable vinyl group-containing monomer may be any monomer as long as it is copolymerizable with divinylbenzene, and is not particularly limited, but preferably is an aromatic ring-containing monomer, such as styrene, α
-Methylstyrene and substituted products thereof are mentioned as preferred examples. Those substituents include styrene, α
- One to several hydrogen atoms in the aromatic ring of methylstyrene are alkyl groups such as methyl, ethyl, propyl, and butyl, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, and halogen atoms such as fluorine, chlorine, bromine, and iodine. A specific example is one in which .

Any polymerization method such as radical, cationic, or coordination polymerization can be used for the polymerization reaction. Among these methods, radical polymerization at a relatively low temperature using a catalyst that initiates radical polymerization at a relatively low temperature, such as an azobisnitrile compound or a redonx system that combines an amine and a peroxide, can cause metal residues to remain in the polymer. Mona (preferred method).

The polymerization reaction is usually carried out at a monomer concentration of 5 to 100q6 and a ratio of divinylbenzene to total monomers of 0.02 to 0.
．． This reaction is generally carried out at a molar ratio of 0.02 to 50% of the vinyl group-containing monomer unit based on the total monomers.
It is possible to obtain one containing 0.50 molar ratio.

The vinyl groups of the polymer thus obtained are extremely reactive, so they can be dissolved in a solvent such as a halogenated hydrocarbon and mixed with a hydrogen halide such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide at room temperature. By contacting, hydrogen halide is easily added, and a polymer containing a monomer unit represented by the general formula (1) (in the formula, or a halogen atom) is obtained.

This addition reaction of hydrogen halide causes the intrinsic viscosity of the polymer to change slightly, but not significantly. Therefore, when producing the above-mentioned vinyl group-containing polymer, By controlling the reaction temperature and the like, it is possible to obtain a force f polymer having a desired value, preferably about 0.01 to 2.0 from the viewpoint of handling.

〔Effect of the invention〕

The polymer of the present invention can be used for resists and the like because it very easily causes a crosslinking reaction when irradiated with ultraviolet rays, X-rays, γ-rays, or electron beams.

〔Example〕

The present invention will be further explained below with reference to Examples.

Example 1 500 mJ round bottom flask = +, torque x:y 3001
nt, styrene 72M, divinylbenzene (a mixture of 120m and p, 55% divinylbenzene, 45% ethylvinylbenzene), 16 ml, and 2.51 ml of asohisin butyronitrile were mixed together and heated at 60°C for 3 hours. After polymerization and filtration at room temperature, the filtrate was poured into methanol to precipitate and separate the polymer. When dry weighed, it was 22.
A polymer of 6.9 was obtained. The vinyl group-containing monomer unit accounts for 0.09 of the monomer units in the total polymer (proton N
By MR. ), the intrinsic viscosity measured in a toluene solution at 30°C was 0.28.

5 g of this copolymer was dissolved in 100 ml of chloroform, 2 g of hydrogen chloride gas was introduced at room temperature for 10 minutes, and the reaction was further continued for 1 hour. Thereafter, nitrogen was introduced to remove unreacted hydrogen chloride gas and chloroform. When the infrared absorption spectrum of this reaction product was measured, it was 16! +Ocm
The absorption of vinyl groups has disappeared, and elemental analysis shows that 258 wt% chlorine, 089.68 wt% H,
It was confirmed that hydrogen chloride was added to almost all the vinyl groups.

False the resulting polymer in chloroform! death,
Create a coating film with a thickness of 2μm on a glass plate, and apply 2wl on the coating film.
An aluminum grid was placed at intervals of &, and irradiated with light for 3 hours from a distance of 10 cm using a 300 W high pressure mercury lamp (300H manufactured by Toshiba). The irradiated area did not dissolve in chloroform.

Example 2 Divinylbenzene 20ml. The same procedure was used as in Example 1 except that 607 nl of styrene was used, and the elemental analysis value was 3.82 chlorine.
W ellipse, carbon 88.55wt%, hydrogen 7.58wt%; 2. The intrinsic viscosity having a monomer unit expressed as about -H is 0.34
A polymer was obtained. This polymer was made insoluble in chloroform by irradiation with light in the same manner as in Example 1.

Example 3 In a 200ml round bottom flask, α-methylstyrene 10
0+++l, divinylbenzene (same as Example 1) Bm
1, add 0.8 g of azobisisobutyronitrile, 60
Polymerization was carried out at .degree. C. for 6 hours, and the resulting solution was filtered at room temperature and poured into methanol to precipitate and separate the polymer.

After dry weighing, 3.8 g of polymer was obtained.

The vinyl group-containing monomer unit was 0.16 in the total polymer (based on proton NMR), and the intrinsic viscosity of the 30° C. toluene solution was 0.38.

This copolymer 11 was dissolved in 10 grams of chloroform, and 2
g of hydrogen bromide was introduced and the reaction was carried out for 2 hours.

Hereinafter, a reaction product was obtained in the same manner as in Example 1. A polymer was obtained containing about 16 units with elemental analysis values of 9.62 wt bromine, 82.18 wt carbon, and 7.78 wt hydrogen. When light irradiation was performed in the same manner as in Example 1, the light irradiated portion became insoluble in chloroform.

Claims (1)

[Claims] 1. A reactive polymer containing a monomer unit represented by the general formula I ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (wherein, X is a halogen atom) . 2.General formula II ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) A solution of a vinyl group-containing polymer obtained by copolymerizing divinylbenzene and a polymerizable vinyl group-containing monomer is added with a halogen. General formula characterized by contacting hydrogen hydride
I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, X is a halogen atom.) A method for producing a reactive polymer containing a monomer unit represented by the following.