JPH0228208A - Radiation-sensitive copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer, capable of being soluble and insoluble in solvents according to wavelengths of radiation to be irradiated and suitable as resist materials for transferring picture images by reacting specific two kinds of compounds and an amine compound. CONSTITUTION:The objective copolymer, obtained by reacting a compound expressed by formula I [R<1> and R<2> are halogen, alkyl or aryl) [e.g., di(nitrophenyl) 2,4-dimethylcyclobutane-1,3-dicarboxylate] with a compound expressed by formula II (R<3> is bifunctional organic group; R<4> and R<5> are H, halogen or cyano; y and z are 0-3) [e.g., di(nitrophenyl) phenylene diacrylate] and an amine compound (e.g., 1,3-dipiperidylpropane) and having structural units expressed by formulas III and IV and 0.1-4dl/g reduced viscosity (0.5g/dl in concentrated sulfuric acid at 30 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] y and Z are the aforementioned radiation-sensitive copolymers, and in particular, radiation-sensitive copolymers suitable as resist materials for transferring image images and their production. Regarding the method.

[Prior Art] Currently, radiation-sensitive resins are widely used for various purposes. There are two types of radiation-sensitive resins: negative-type resins in which the irradiated part becomes insoluble in the solvent, and positive-type resins in which the irradiated part becomes soluble in the solvent. Polymer resins are used differently depending on their purpose. These radiation-sensitive resins include, for example, IC5LSI
In microfabrication of printed circuit board circuits, etc., it is used as a resist material to form a resist pattern onto which an image is transferred.

[Problems to be solved by the invention] However, when conventional radiation-sensitive resins are used as resist materials, unnecessary resist patterns are generated when transferring images. It was not possible to selectively modify the resist pattern.

The present invention solves the above problems, and when irradiated with radiation, a crosslinking reaction or a decomposition reaction occurs by selecting the wavelength, making it solvent soluble or solvent insoluble. For example, it can be used as a resist material. The object of the present invention is to provide a radiation-sensitive copolymer that allows unnecessary resist patterns to be corrected later when used.

[Means for Solving the Problems] That is, the present invention provides a structure having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (n) and having a reduced viscosity of 0. 1-4 licks/g (0.5g/dj2.
1JJ2 at 30°C) and a method for producing the same.

(In the formula, R1 and R2 may be the same or different and represent a halogen atom, an alkyl group, or an aryl group.)
R' 0+1 1 -Cc=cH+CH=CH+R, 3+CH=CH+-
CH=C-C-(II) (wherein, R3 represents a divalent organic group, R4 and R5 may be the same or different, represent a hydrogen atom, a halogen atom or a cyano group, and y and 2
is a number from 0 to 3) The radiation-sensitive copolymer of the present invention (hereinafter simply referred to as "copolymer")
) has the structural units represented by the general formulas (I) and (n) in a molar ratio of usually 1:9 to 9:1, preferably 2:8 to 8:2.

R1 and R2 in the general formula (I) include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom; a phenyl group , a xylyl group, a tolyl group, a nitrophenyl group, a cyanophenyl group, a methoxyphenyl group, and other aryl groups having 6 to 20 carbon atoms, and R1 and R2 may be the same or different.

Among these R1 and R2, phenyl group, methoxyphenyl group, nitrophenyl group, cyanophenyl group, etc. are preferable.

y and 2 in the general formula (I) are preferably 0.

In addition, examples of the organic group represented by R3 in the general formula (II) include alkylene groups having 1 to 6 carbon atoms such as methylene group, ethylene group, propylene group, and tetramethylene group, phenylene group, xylylene group, tolylene group, Examples include arylene groups having 6 to 20 carbon atoms such as nitrophenylene group, cyanophenylene group, and naphthylene group, with phenylene group, xylylene group, and tolylene group being preferred.

Furthermore, as the halogen atoms that are R4 and R5,
Examples include fluorine atom, chlorine atom, bromine atom, and iodine atom.

The copolymer of the present invention has the general formulas (I) and (II)
The structures represented by are usually bonded via a structure represented by the following general formula (V).

General formula (V) can be mentioned.

The copolymer of the present invention includes, for example, a compound represented by the following general formula (III) (hereinafter referred to as "compound sea urchin"), a compound represented by the following general formula (IV) (hereinafter referred to as "compound ■"), and an amine. It is obtained by reacting the compound as a monomer.

(In the formula, R1 and R2 are the same as in the general formula (I).) Approximately 5 = C 000-@+N0t (IV)
The above compound I includes "2,4-dimethylcyclobutane-1,3-dicarboxylic acid ditrophenyl) ester, 3,4-dimethylcyclobutane-1,2-dicarboxylic acid ditrophenyl) ester," phenyl) ester, 2,4-dichlorocyclobutane-1,3 dicarboxylic acid ditrophenyl) ester, 3,4-dichlorocyclobutane-1,2-dicarboxylic acid ditrophenyl) ester, 2,4-diphenylcyclobutane- 1,3-dicarboxylic acid di(nitrophenyl) ester, 3,4-diphenylcyclobutane-1
, 2-dicarboxylic acid ditrophenyl) ester, 2,
4-di(methoxyphenyl)cyclobutane-1,3-dicarboxylic acid ditrophenyl) ester, 3,4-di(
methoxyphenyl)cyclobutane-1,2-dicarboxylic acid ditrophenyl) ester, 2,4-ditrophenyl)cyclobutane-1,3-dicarboxylic acid ditrophenyl) ester, 3゜4-ditrophenyl) )cyclobutane-1,2-dicarboxylic acid ditrophenyl) ester, 2,4-di(cyanophenyl)cyclobutane-1
゜3-dicarboxylic acid di(nitrophenyl) ester, 3
．． Examples include 4-di(cyanophenyl)cyclobutane-1゜2-dicarboxylic acid ditrophenyl) ester, and among these, 2゜4-diphenylcyclobutane-1,3-dicarboxylic acid ditrophenyl) ester. ) ester, 3,4-diphenylcyclobutane-1,2-dicarboxylic acid ditrophenyl) ester, 2,4-di(
methoxyphenyl)cyclobutane-1,3-dicarboxylic acid ditrophenyl) ester, 3,4-di(methoxyphenyl)cyclobutane-1,2-dicarboxylic acid ditrophenyl) ester, 2゜4-ditrophenyl) )cyclobutane-1,3 dicarboxylic acid ditrophenyl) ester, 3,4-ditrophenyl)cyclobutane-1
゜2-dicarboxylic acid ditrophenyl) ester, 2.
Preferred examples include 4-di(cyanophenyl)cyclobutane-1°3-dicarboxylic acid ditrophenyl) ester and 3,4-di(cyanophenyl)cyclobutane-1°2-dicarboxylic acid ditrophenyl) ester.

Among the above, for example, 2,4-diphenylcyclobutane-
1,3-dicarboxylic acid ditrophenyl) ester is
It can be obtained by reacting 2 moles of nitrophenol with 1 mole of truxylic acid chloride, and 3
．． 4-Diphenylcyclobutane-1,2-dicarboxylic acid ditrophenyl) ester can be obtained by subjecting nitrophenyl cinnamate, which is a reaction product of cinnamic acid chloride and nitrophenol, to a solid-phase photodimerization reaction. .

The compound (2) includes phenylene diacrylic acid ditrophenyl) ester, methylene diacrylic acid ditrophenyl) ester, xylylene diacrylic acid ditrophenyl) ester, tolylene diacrylic acid ditrophenyl) ester, Nitrophenyl diacrylic acid ditrophenyl) ester, naphthylene diacrylic acid ditrophenyl) ester, ditrophenyl) phenylene di(α-cyanoacrylate), di(nitrophenyl) methylene di(α-cyanoacrylate), xylylene di(α-cyanoacrylate), ditrophenyl) tolylene di(α-cyanoacrylate), nitrophenyl)
α-cyanoacrylate), ditrophenyl) phenylene di(α-fluoroacrylate), ditrophenyl) phenylene di(α-taloloacrylate), ditrophenyl) tolylene di(α-bromoacrylate), ditrophenyl) trophenyl) naphthylene di(α-iodoacrylate), ditrophenyl) phenylene di(α-cyanobutadiene carboxylate), ditrophenyl) ethylene di(α-cyanobutadiene carboxylate), ditrophenyl) tolylene di (α-cyanobutadiene carboxylate), ditrophenyl) xylylene di(
α-cyanobutadienecarboxylate), ditrophenyl)cyanophenylenedi(α-cyanobutadienecarboxylate), ditrophenyl)naphthylenedi(
α-cyanobutadienecarboxylate), ditrophenyl) tolylenedi(α-chlorobutadienecarboxylate), ditrophenyl)naphthylenedi(α-bromobutadienecarboxylate), ditrophenyl)
Phenylene di(α-iodobutadiene carboxylate), ditrophenyl)ethylene di(α-fluorobutadiene carboxylate), etc., preferably phenylene diacrylic acid ditrophenyl) ester, tolylene diacrylic acid ditrophenyl), etc. phenyl) ester, xylylene diacrylic acid ditrophenyl) ester, ditrophenyl) phenylene di(α-cyanoacrylate), ditrophenyl) tolylene di(α-cyanoacrylate)
, ditrophenyl) nitrophenylene di(α-cyanoacrylate-I-), ditrophenyl) phenylene di(
α-fluoroacrylate), ditrophenyl) phenylene di(α-cyanobutadiene carboxylate), ditrophenyl) tolylene di(α-cyanobutadiene carboxylate), ditrophenyl) cyanophenylene di(α-cyanobutadiene carboxylate), ditrophenyl) butadiene carboxylate), ditrophenyl) ethylene di(α-fluorobutadiene carboxylate), and the like.

In addition, amines and compounds include 1,3-dipiperidylpropane, 1,3-dipyrrolidylpropane, xylylenediamine, imidazolidine, piperazine, 1,4-naphthalenediamine, 2,4-pyridinediamine, 1,3 - primary and secondary diamine compounds such as propanediamine, oquindianiline, hexamethylenediamine, 1,4-cyclohexanediamine, preferably 1,3-dipiperidylpropane, 1,3-divirolidylpropane,
Examples include piperazine, imidazolidine, xylylene diamine, hexamethylene diamine, and the like.

The reaction of the compound (1), compound (2) and amine compound is as follows:
For example, at a molar ratio of 1:0.5 to 2:1 to 3, in a radiation-blocked environment, usually 0 to 60°C, preferably 15 to 3°C.
It is carried out at 0°C for 5 to 200 hours. At this time, 10 to 50 parts by weight of a polar solvent such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, tetrahydrofuran, methylene chloride, and chloroform are added to 101 parts by weight of the total fl of the monomers. It is preferable to add some degree. After the reaction, the reaction product is a mixture of alkaline compounds such as sodium carbonate, sodium bicarbonate, potassium carbonate, etc.
The copolymer is precipitated by adding it to a 10% by weight aqueous solution and stirring for 12 to 36 hours, and the copolymer is recovered by washing the separated copolymer with water and drying it.

Here, the compound (1), the compound (2), and the amine compound may be reacted simultaneously, or the compound (1) and the compound (2) may be reacted with the amine compound sequentially. When compound (1), compound (2) and amine compound are reacted simultaneously, structural units represented by formulas (I) and (If) are randomly present in the resulting copolymer, and compound I and compound (2) are sequentially reacted with amine. When reacted with a compound, the resulting copolymer contains a block that connects the structural unit represented by the general formula (I) with G and a block that connects the structural unit represented by the general formula (II).

When forming a resist using the copolymer of the present invention, the copolymer is usually used in a form dissolved in a solvent such as the above-mentioned polar solvent. Although the concentration of the copolymer in this case cannot be absolutely defined, it is determined depending on the thickness of the coated film, and is generally set at 5 to 30% by market weight.

Further, when a resist is constituted by the copolymer of the present invention, a stabilizer (antiaging agent), a sensitizer made of an amine compound, etc. can be added as necessary.

Examples of the stabilizer include hydroxy aromatic compounds such as hydroquinone, methoxyphenol, p-t-butylcatechol, and 2,2'-methylenebis(6-t-butyl-4ethylphenol); benzoquinone, p-1-ruquinone, Quinones such as p-xyquinone; phenyl-α
-Amines such as naphthylamine, p,p-diphenylphenyl diamine; dilaurylthiodipropionate, 4,4-thiobis(6-t-butyl-3methylphenol), 2,2'-thiobis(4methyl-6 -t
-butylphenol), 2-(3°5-di-t-butyl-4-hydroxyanilino)4,6-bis(N-octylthio)-δ-triazine, and the like. The amount of these added is usually about 0.5 to 5% by weight.

The copolymer of the present invention is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, and visible light, and is used in the production of ICs, LSIs, liquid crystal substrates, printing plates, television shadow masks, etc. that require particularly high resolution. It is especially suitable as a resist.

When the copolymer of the present invention is irradiated with radiation, a crosslinking reaction or a decomposition reaction occurs depending on the wavelength. Therefore, by selecting a solvent, the copolymer after irradiation can be made soluble in a solvent or solvent. It can also be made insoluble. For example, the wavelength is 3000 m or more 1-1 preferably 300 m or more
When irradiated with ultraviolet light of about 370 nm, the ultraviolet irradiated part becomes insoluble in the polar solvent, and when irradiated with ultraviolet light with a wavelength of less than 300 nm, preferably about 190 to 27 Or+m, the ultraviolet irradiated part becomes ethylene glycol, diethylene glycol, etc. It is soluble in alcohols and esters such as isoamyl acetate.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

In the examples, all parts and percentages are based on weight unless otherwise specified.

Example 1 (1) After dissolving 56.2 g of p-nitrophenol in 600 ml of tetrahydrofuran, 18.6 g of pyridine was dissolved.
g was added. Next, while maintaining the system temperature at 0 to 5°C,
67.2 g of cinnamic acid chloride was added to 2 g of tetrahydrofuran.
Solution 11k dissolved in 0ml was slowly added dropwise to the mixture. After reacting for 2 hours, the reaction mixture was poured into 8N water, and the resulting precipitate was separated and dried. Furthermore, 60 g of this dried precipitate was dispersed in a mixed solution of 1°000 ml of water and 250 ml of methanol, and irradiated with light for 10 hours.
diphenylcyclobutane-1,2-dicarboxylic acid di(p
(nitrophenyl) ester (hereinafter referred to as "β-BNPT") was synthesized. The obtained β-BNPT was purified by recrystallization with methyl ethyl ketone.

(2) Terephthalaldehyde 96.7g, malonic acid 17
A few drops of piperidine were added to a mixture of 4.1 g and 257.9 g of pyridine, and the mixture was stirred at 50°C for 2 hours and then at 100°C for 3 hours. Thereafter, the reaction mixture was allowed to cool to room temperature, poured into water at 5° C., and the deposited precipitate was separated and dried.

Furthermore, 115.4 g of thionyl chloride and 11 drops of dimethylformamide were added to 176.6 g of this dried precipitate, and the mixture was refluxed for 3 hours to react. Residual thionyl chloride was removed by vacuum distillation to obtain a product. Next, 102.6 g of p-nitrophenol was dissolved in 1,000 ml of tetrahydrofuran, and then 40.7 g of pyridine was added, and while the temperature inside the system was maintained at 0 to 5 g, 184.7 g of the above product was obtained.
A solution prepared by dissolving G in 60 ml of tetrahydrofuran was gradually added dropwise. After 2 hours of reaction, the reaction mixture was poured into water 152, and the precipitated p-phenylene diacrylic acid di(p-nitrophenyl) ester (hereinafter referred to as rP-NPDAJ) was separated and purified by recrystallization with dimethylformamide. .

(β-BNPT obtained in 31(1) 0.6731
g.

0.5755 g of P-NPDA obtained in (2) and 0.5259 g of 1,3-dipiperidylpropane were placed in an Erlenmeyer flask, and after adding 5 ml of dimethylacetamide, the flask was tightly stoppered and reacted at room temperature for 19 hours. After completion of the reaction; the reaction mixture was added dropwise to 100 ml of a 5% aqueous sodium carbonate solution, and the precipitate was separated and dried to form a product having the following structure with a reduced viscosity of 0. A copolymer (hereinafter referred to as "copolymer A") of 94 g/J (0.5 g/cm!, in concentrated sulfuric acid, 30° C.) was obtained. In this copolymer A, structural units represented by general formula (I) and general formula (II) were randomly present. Incidentally, as a result of elemental analysis of copolymer A, carbon content was 77.48%, hydrogen content was 8.19%, and nitrogen content was 6.69%. The infrared absorption spectrum of copolymer A is shown in FIG.

Copolymer A Example 2 (1) 135.86 g of α-truxylic acid was added with 128 g of thionyl chloride. After adding 50 g and dimethylformamide 1a and stirring for 3 hours, the remaining thionyl chloride was removed by distillation under reduced pressure to obtain a product. Next, after dissolving 61.3 g of p-nitrophenol in 600 ml of tetrahydrofuran, 20.3 g of pyridine was added, and the temperature inside the system was lowered from 0 to 0.
A solution of 145.20 g of the above product dissolved in 20 ml of tetrahydrofuran was slowly added dropwise while maintaining the temperature at 5°C. After 2 hours of reaction, the reaction mixture was poured into water 82, and the resulting precipitate was separated and dried to give di(p-nitrophenyl 2,4-diphenylcyclobutane-1,2-dicarboxylate).
An ester (hereinafter referred to as [α-BNPTJ]) was synthesized. The obtained α-BNPT was purified by recrystallization with methyl ethyl ketone.

(2) Isophthalaldehyde 96.7g, malonic acid 17
A few drops of piperidine were added to a mixture of 4.1 g and 257.9 g of pyridine, and the mixture was stirred at 50°C for 2 hours and then at 100°C for 3 hours. Thereafter, the reaction mixture was allowed to cool to room temperature, and 51% of water was added. The precipitate was separated and dried. Furthermore, 115.4 g of thionyl chloride and 1 ti of dimethylformamide were added to 176.6 g of this dried precipitate, and the mixture was refluxed for 3 hours to react. Residual thionyl chloride was removed by vacuum distillation to obtain a product. Next, after dissolving 102.6 g of m-nitrophenol in 1,000 ml of tetrahydrofuran, 40.7 g of pyridine was added, and while maintaining the system temperature at 0 to 5° C., two series of products 184.
A solution of 7 g dissolved in 60 ml of tetrahydrofuran was gradually added dropwise. After 2 hours of reaction, the reaction mixture was mixed with 15 f of water.
! , m-phinidine diacrylate di(
m-nitrophenyl) ester (hereinafter referred to as 1m-NPDAJ)
) was separated and purified by recrystallization with dimethylformamide.

(α-BNPT obtained with (31(li) 0.6731
g.

0.5755 g of m-NPDA obtained in (2) and 0.5259 g of 1,3-dipiperidylpropane were placed in an Erlenmeyer flask, and after adding 5 ml of dimethylacetamide, the flask was tightly stoppered and reacted at room temperature for 19 hours. After completion of the reaction, the reaction mixture was added dropwise to 100 ml of 5% aqueous sodium carbonate solution, and the precipitate was separated and dried to give a reduced viscosity of 0.6 g/df., (0.5 g/df!) with the following structure, in concentrated sulfuric acid. , 30°C) (hereinafter referred to as "copolymer B")
I got it. In this copolymer B, structural units represented by general formula (I) and general formula (n) were randomly present. The results of elemental analysis of copolymer B were similar to those of copolymer A. The infrared absorption spectrum of copolymer B was
As shown in the figure.

Copolymer B Example 3 (1) 63.8 g of cyanoacetic acid and 104.3 g of p-nitrophenol were dissolved in 350 ml of ethyl acetate.

Next, while maintaining the system temperature at 0 to 5°C, dicyclohexylcarbodiimide 154. sr to ethyl acetate 350ml
was added dropwise to the mixture, and the mixture was stirred at the same temperature for 1 hour and then at room temperature for 1 hour to react.

After the reaction, the precipitate was separated from each other, and the crystals generated by concentrating the P solution were dissolved in a mixed solvent of benzene and n-hexane (4
:1).

(2) Add 15.0 g of terephthalaldehyde to 22 ml of water, and then add 0.85 ml of a 1.74% aqueous solution of potassium hydroxide.
added. After this solution was purged with nitrogen for 1 hour, a solution of 18.8 ml of acetaldehyde dissolved in 150 ml of water was added dropwise under a nitrogen stream. After the dropwise addition was completed, stirring was continued for 1 hour under a nitrogen stream, and the precipitated crystals were separated and washed with water.

[3] 18.6 g of the crystals obtained in (2) were dissolved in 500 ml of acetonitrile, and 41.2 g of the crystals obtained in (1) were further dissolved. Next, 2 ml of piperidine was added, and after reacting at room temperature for 24 hours, it was poured into 22 water, and the precipitated di(p-nitrophenyl) p-phenylenedi(α-cyanobutadienecarboxylate) (hereinafter referred to as "p-NPD")
(abbreviated as CB)) was purified by recrystallization with nitrobenzene.

4) 0.210 g of dicyclohexylcarbodiimide and β-BNPT obtained in Example 1 (1) 0°37
After dissolving 7 g in 2 ml of dimethylacetamide and reacting for 24 hours, the p-NPDCB obtained in (3)
．． 169 g was added and the reaction was further continued for 96 hours. After the reaction is complete, add 50ml of 5% sodium carbonate aqueous solution to the reaction solution.
The resulting precipitate was separated and dried to obtain a reduced viscosity of 0°40dR/g (0.5g/df) having the following structure.
! , in concentrated sulfuric acid at 30°C) (hereinafter referred to as "Copolymer C") was obtained. The infrared absorption spectrum of Copolymer C is shown in FIG.

Copolymer C Example 4 (1) 10.0 g of terephthalaldehyde was dissolved in 300 ml of acetonitrile, and 30.0 g of the crystals obtained in Example 3 (1) were dissolved. 9g: was dissolved. Then piperidine 1
．． After adding 5 ml and reacting at room temperature for 24 hours, it was poured into 2e of water and the precipitated di(p-nitrophenyl)p-phenylenedi(α-cyanoacrylate) (hereinafter referred to as "p-NPD") was added.
CJ) was sent to each household and purified by recrystallization with nitrobenzene.

(2) Dicyclohexylcarbodiimide 0.210
g and β-BNPT O obtained in Example 1 (1).

Dissolve 377g in 2ml of dimethylacetamide,
After reacting for an hour, p-NPDC0, obtained in (1),
153 g was added and the reaction was further continued for 96 hours. After the reaction is complete, the reaction solution is added dropwise to 50 ml of a 5% aqueous sodium carbonate solution, and the resulting precipitate is separated and dried to give a reduced viscosity of 0. 15 rinses/g (0.5dI2/g
, in concentrated sulfuric acid at 30°C) (hereinafter referred to as "copolymer DJ")
) was obtained. Figure 4 shows the infrared absorption spectrum of the copolymer.

Copolymer Test Example 1 A 30% methylene chloride solution of copolymer A was applied onto a quartz plate and dried to obtain a film of copolymer A having a thickness of 1 μm. This film of copolymer A was exposed to 254 nm of a 500 W ultra-high pressure mercury lamp.
and 365 nm wavelengths were irradiated separately from a distance of 20 cm, and changes in the ultraviolet absorption spectrum of Polymer A were measured. The results are shown in Figure 5.

In Figure 5, (a) shows the results after irradiation with ultraviolet rays with a wavelength of 365 nm+ for 60 minutes, (b) shows the results without irradiation with ultraviolet rays, and (C) to (f) each show the results after irradiating with ultraviolet rays with a wavelength of 365 nm for 60 minutes. , shows the change in spectral absorption when irradiated with ultraviolet rays with a wavelength of 245 nm for 2 minutes, 5 minutes, 10 minutes, and 20 minutes. From Figure 5, 365
It can be seen that when irradiated with na+ ultraviolet rays, the absorption near 330 nIi decreases due to crosslinking, whereas when irradiated with 254 nm ultraviolet rays, a new absorption appears near 27 OnIi as copolymer A decomposes.

Further, 125 g of the copolymer A 2 O was dissolved in 25 ml of concentrated sulfuric acid, and the solution was replaced with nitrogen for 30 minutes.The viscosity was then measured by irradiating the solution with ultraviolet rays having a wavelength of 254 nIl from an ultra-high pressure mercury lamp from a distance of 20 cm. As a result, it was confirmed that the viscosity decreased with the irradiation time and that copolymer A was decomposed by the 254 nm ultraviolet rays.

Test Example 2 A 20% methylene chloride solution of copolymer C was applied onto a quartz plate and dried to obtain a film of copolymer A having a thickness of 1 μm. This Copolymer C film was heated to 254 nm using a 500 W ultra-high pressure mercury lamp.
Ultraviolet rays with wavelengths of m and 365 nm were irradiated separately from a distance of 20 cm, and changes in the ultraviolet absorption spectrum of Polymer C were measured.

The results are shown in Figure 6.

In Figure 6, (a) is a sample that was irradiated with ultraviolet rays with a wavelength of 365r+a+ for 180 minutes, (b) is a sample that was not irradiated with ultraviolet rays, and (C) to (f) are each with a wavelength of 365 nm.
The figure shows changes in spectral absorption after irradiation with ultraviolet rays with a wavelength of 254 nm for 180 minutes, followed by irradiation with ultraviolet rays with a wavelength of 254 nm for 5 minutes, 10 minutes, 30 minutes, and 60 minutes. From Figure 6, irradiation with 365 nm ultraviolet rays causes cross-linking, resulting in 380 nm
While the absorption near n's increases, when irradiated with 254 nm ultraviolet light, copolymer C decomposes and the absorption near 280 n's increases.
It can be seen that new absorption appears near o+.

Test Example 3 Changes in the ultraviolet absorption spectrum were measured in the same manner as Test Example 2 except that Copolymer C was used instead of Copolymer C. The results are shown in FIG.

In addition, in FIG. 7, (a) to (f) respectively show those irradiated with ultraviolet rays in the same manner as in Test Example 2. From Figure 7, irradiation with 365 nm ultraviolet rays causes crosslinking, resulting in 320 nm
While the absorption near r+m increases, when irradiated with 254 nm ultraviolet rays, the copolymer decomposes and 290 no.
It can be seen that new absorption appears near +.

[Effects of the Invention] The radiation-sensitive copolymer of the present invention can be made solvent-soluble or solvent-insoluble depending on the wavelength of the irradiated radiation. This makes it possible to correct unnecessary resist patterns that occur when the resist pattern is transferred.

[Brief explanation of the drawing]

Figures 1 to 4 show the infrared absorption spectra of the copolymers produced in Examples 1 to 4 of the present invention, and Figures 5 to 7 show the wavelength and amount of ultraviolet absorption in Test Examples 1 to 3. FIG. Patent applicant: Japan Synthetic Rubber Co., Ltd. Ultraviolet absorption amount Ultraviolet absorption amount

Claims (2)

[Claims] (1) Having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), the reduced viscosity is 0.1 to 4 dl/g (0.5 g/dl, in concentrated sulfuric acid, 3
0°C) radiation-sensitive copolymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 may be the same or different and represent a halogen atom, an alkyl group, or an aryl group) ▲Mathematical formulas, chemical formulas, tables, etc. ▼(II) (In the formula, R^3 represents a divalent organic group, and R^4 and R
^5 may be the same or different and represent a hydrogen atom, a halogen atom, or a cyano group, and y and z are numbers from 0 to 3) (2) A method for producing a radiation-sensitive copolymer, which comprises reacting a compound represented by the following general formula (III), a compound represented by the following general formula (IV), and an amine compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^1 and R^2 are the same as the general formula (I) above) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula , R^3, R^4, R^5, y and z are the same as in the above general formula (II))