JPS5913237A - Photoresist composition - Google Patents

Abstract

PURPOSE:To obtain a negative cyclized rubber type photoresist having superior adhesion to a substrate and high sensitivity, by using a cyclized conjugated diene type polymer having carboxylgroups. CONSTITUTION:An unsatd. monomer, such as acrylic or maleic acid is added to a homopolymer of conjugated diene monomer, such as isoprene, butadiene, or other pentadienes, or a copolymer of said diene and a monomer, such as styrene, ethylene, or acrylonirile. A cyclized rubber of a conjugated diene type polymer having 0.01-20mol of carboxylic groups or its precursor per 100mol of diene monomer is obtained by cyclizing said mixture. A photoresist compsn. is obtained by using said cyclized rubber and a photo-crosslinking agent, such as diazide compd., as main components, and mixing a sensitizing agent, and a storage stabilizer, when needed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber-based photoresist composition suitable for photolithography. More specifically, the present invention relates to a highly sensitive negative-working cyclized rubber-based photoresist composition that has excellent adhesion to a substrate by using a cyclized product of a conjugated diene-based polymer having a carboxyl group.

Semiconductor devices such as transistors, ICs, and LSIs that are manufactured using photolithography processing are becoming increasingly integrated circuits, that is, miniaturized, and are still considered one of the fields in which technology is undergoing the most dramatic technological disruption. Along with this, the required performance for each configuration for 4 minutes has become even more severe and high.

In general, the physical properties of this type of cyclized rubber are determined by its molecular structure, molecular weight distribution, cyclization rate, degree of cyclization, microstructure, etc., and it is well known that these factors have a large impact on the performance of photoresists. It is as follows. However, for example, in the case of a photoresist using cyclized polyisoprene rubber, the higher the molecular weight of the cyclized product, the higher the sensitivity as a photoresist, but conversely, if the molecular weight is too high, developability deteriorates and the resolution Among the many factors that affect resist suitability, certain factors are Even if only one material is changed in a strict manner, multiple physical properties are affected in a complex manner, and there is a tendency for some physical properties to be improved while others are accompanied by a decrease. For this reason, it is difficult to set the various factors unambiguously, and it is necessary to take into account the complex correlation between each factor and to define conditions within an appropriate range that takes into account the balance of various physical property values. . This makes this type of modification research complex and difficult.

Among the necessary performances of such photoresist compositions, one of the properties for which the importance and necessity of improvement (improvement) have always been emphasized is the adhesion of the resist to the substrate. Even in today's world of remarkable technological progress, these demands have not changed; in fact, with new technological innovations, improvements in adhesion combined with other physical properties are increasingly desired.

Improvement in adhesion has also been a problem in recently developed polybutadiene cyclized products.

The present inventors kept this point in mind and as a result of intensive studies, created a cyclized product of a conjugated diene polymer having a carboxyl group or a group that can be induced into a carboxyl group, and used the cyclized product in a photoresist. It is possible to significantly improve adhesion (adhesion), and by introducing a new sensory evaluation method that is different from conventional methods, it is possible to significantly change the balance of physical properties, improving sensitivity and resolution. The present invention has been completed by discovering a scale that can improve the above properties as well.

In other words, the present invention provides a photoresist composition containing a conjugated diene polymer cyclized product (a) and a photocrosslinking agent (b) as main components, in which the cyclized product is a carboxyl group or 0.01 to 2 per 100 diene monomer units of the conjugated diene polymer before cyclization of the derivatizing group
The present invention provides a high-resolution negative-working cyclized rubber-based photoresist composition that is characterized by being a cyclized rubber having 0 moles, has excellent adhesion, and has few pinholes.

Also used in the present invention is a carboxyl group. is a cyclized rubber having a group derived from the carboxyl group (where R
+ to 6 each represent a hydrogen atom, an alkyl group or an aryl group, which may be the same or different), or 1L7 1L9 Ra1-C-Raz (wherein , Ry~12 are each a hydrogen atom, a71/kl
or aryl group, which may be the same or different), or an unsaturated aliphatic hydrocarbon or unsaturated aromatic copolymerizable with a conjugated diene. Rings of polymers containing units based on hydrocarbons, nitrogen-containing aliphatic hydrocarbons, and units based on unsaturated single compacts such as @α,β-unsaturated carboxylic acids, their acid anhydrides, or their ester derivatives. rubber, such as (4) and/
or a polymer based on the unit of (R), or a polymer having 0 units is further formed on the polymer in the coexistence of an unsaturated monomer of the above υ, and the unit based on the plow is formed. Method (j) of obtaining a copolymer as a copolymerization component and then cyclizing the polymer based on the unit of (5) and/or (B), or the m polymer further having the unit of ((3)) Adding the unsaturated monomer of (g) to the polymer,
Method (2) of then cyclizing, or further cyclizing a polymer based on the intermediate position of (A) and/or (13) or a polymer having units of (Q), and then cyclizing the polymer having units of (Q); The cyclized product obtained by the method (1) above best meets the intended purpose of the present invention.

Examples of conjugated diene polymers based on units (A) and/or (B) include polymers or copolymers of conjugated dienes such as isoprene, butadiene, pentadiene or phenylbutadiene, and (4) and/or The conjugated diene polymers based on the units of (B) and (Q) include copolymers of the conjugated dienes and, for example, styrene, α-methylstyrene, ethylene, fluoropylene, isobutylene, or acrylonitrile.

Among these, polyisoprene particularly satisfies the intended purpose of the present invention, so examples of the unsaturated monomers preferably used include acrylic acid, methacrylic acid, methyl acrylate, Acrylic acid compounds such as ethyl acrylate, methyl methacrylate, and ethyl methacrylate; Maleic acid compounds such as maleic acid, maleic anhydride, maleic acid methyl ester, maleic acid dimethyl ester; A Taconic acid, fumaric acid, and crotonic acid. Or mesaconic acid etc. are mentioned. Among these, maleic acid compounds are most preferably used, and when they are added to a conjugated diene polymer system, they react with the conjugated diene polymer and form succinic acid residues or succinic anhydride residues. , a carboxyl group-containing conjugated diene polymer having a succinic acid derivative residue such as a succinic acid monoester residue or a succinic acid diester residue as a side chain is produced.

In a conjugated diene polymer having a carboxyl group or a group that can be induced into a carboxyl group, a carboxyl group or a group that can be induced into a carboxyl group is provided. If you don't get it, or if you get too much.

This makes it difficult not only to perform separation and purification steps during the production of the cyclized product, but also to set conditions during photoresist development.

Therefore, the amount thereof is 0.01 to 20 mol, preferably 0.01 to 20 mol, per diene monomer unit of the conjugated diene polymer.
1 to 10 mol is suitable. In addition, when the conjugated diene polymer is cyclized and then a carboxyl group or a carboxyl group is introduced into the carboxyl group, the amount thereof is the amount per 100 diene monomer units of the conjugated diene polymer before cyclization. The amount is the same as the amount of the conjugated diene polymer having a carboxyl group or a group derived from a carboxyl group.

The cyclization reaction of a conjugated diene polymer can be carried out using conventional Friedel-Craft catalysts such as sulfuric acid, para-toluenesulfonic acid, tripodized boron, aluminum chloride, although the reaction conditions may differ slightly depending on the presence or absence of carboxyl groups, etc. It can be carried out using tin tetrachloride, titanium tetrachloride, zinc chloride, ethylaluminum dichloride, trialkylaluminum/titanium tetrachloride, or alkyl albinium halide/halogenated hydrocarbon or halogenacetic acid.

In the present invention, if the number average molecular weight of the cyclized rubber is too small, the solubility of the photoresist during development will be high, resulting in poor film retention and poor film strength. - If the amount is too high, workability may deteriorate due to high viscosity and low solubility, and resolution may deteriorate. Therefore, its number average molecular weight is 10.000 to soo, ooo, preferably 50,000 to 5oOoo.

A range of is appropriate.

As the photocrosslinking agent used in the present invention, diazide compounds are preferably used. Examples include 4.4'-diazidebenzophenone, 4.4'-diazidechalcone, 4.
4-diazidiphenyl, p-phenylenebisamide,
2.6-bis-(4'-azidobenzal)-5-methylcyclohexanone and the like are used. If the amount used is too small, the effect of addition will be small, while if it is too large, the residual film rate after development will be low and defects may appear. Parts by weight are preferred.

The photoresist composition of the present invention mainly contains a cyclized rubber and a photocrosslinking agent, but it is also possible to add a sensitizer and a storage stabilizer. Further, additives for negative-type cyclized rubber photoresists such as light-absorbing materials for preventing halation can be blended. The sensitizers include benzophenone, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 2-methylanthraquinone,
Carbonyl compounds such as benzanthrone, violanthrone, and 9-anthraldehyde; aromatic hydrocarbons such as anthracene and chrysene; Compound, nitroaniline, 2-chloro-4-= lo 7 = 17
Nitrogen compounds such as cyclone, 2,6-cyclo-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene, and sulfur compounds such as diphenyl disulfide are mentioned.

In addition, the storage stabilizers include hydroquinone, hydroxyaromatic compounds such as methoxyphenol sP'-butylcatechol, benzoquinone, p-torquinone, P
-quinones such as xyloquinone, amines such as phenyl-α-naphthylamine%l1lI+-diphenylphenylenediamine, dilaurylthiodipropionate, 4.4
-thiobis(6-t-butyl-3-methylphenol)
, 2,2'-thiobis(4-methyl-6-t-butylphenol), 2-(3,5-di-t-butyl-4-hydroxyaniline), 4,6-bis(N-octylthio)
Examples include sulfur compounds such as -S-triazine.

The photoresist composition of the present invention has particularly excellent adhesion (adhesiveness) to the substrate, and the use of highly cyclized rubber to improve resolution, which was conventionally considered unsuitable due to decreased adhesion. It becomes possible to pursue improvements such as lowering the viscosity by increasing the molecular weight, increasing the degree of cyclization, and improving sensitivity by narrowing the molecular weight distribution. This provides excellent film properties such as strength, fewer pinholes, high resolution, and uniquely excellent adhesion. Here, the cyclization rate and the degree of cyclization mean what is usually said in Karasu Molecular Chemistry (for example, in the case of polyisoprene, C.M.,
See "R&D Report AN1: Synthesis and Application of Photosensitive Resins (Continued)" edited by C Company, p. 637 (1980, published by CM and C Company). ).

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 and Comparative Example 1 Polyisoprene 5 with a number average molecular weight of 151,000 obtained by polymerizing isoprene monomer with n-butyllithium at 60°C in toluene under a nitrogen atmosphere
% toluene solution was prepared, maleic anhydride was added to the solution, and the mixture was reacted in a pressurized reactor with stirring at 160° C. for 4 hours to obtain modified polyisoprene.

The modified polyisoprene had an infrared absorption spectrum. Next, the modified product was made into a 5% xylene solution, and reacted with stirring at 90° C. for 5 hours in the presence of a l)-toluenesulfonate catalyst to obtain a cyclized product. The number average molecular weight of this cyclized product is 1
31,000, and as a result of structural analysis using nuclear magnetic resonance spectroscopy, the degree of cyclization was 5.1, and the cyclization rate was 75.8.
%, and both were resolved and 2.6-bis(!-acidobenzal)cyclohexanone 0; 55p% 0.15 g of 2.2'-methylenebis(4-methyl-6-1-butylphenol) was A xylene solution of a photoresist composition was prepared using the following method. The solution was spin-coated onto a silicon wafer with a silicone oxide film using a spinner to a film thickness of 1.0μ, and heated at 85 to 95°C.
Prebaked for 30 minutes. Next, using a 200 W high-pressure mercury lamp, exposure was performed through a Resolution Test Chart chrome mask manufactured by Toppan Printing to print the image.

The film was then developed with a xylene developer, rinsed with n-butyl acetate, post-baked at 150°C for 30 minutes, and etched with a semiconductor etching agent (NH+, F/IIF water bath).

On the other hand, for comparison, a cyclized polyisoprene was prepared in the same manner as above except that maleic anhydride was added and reacted. The number average molecular weight, degree of cyclization, and cyclization rate of the cyclized product were 115,000, S, O, and 75.0, respectively. This cyclized product was used as a resist composition and subjected to baking, development, and etching treatments in the same manner as above.

When these two types of photoresists were compared, it was found that when a cyclized product of polyisoprene added with maleic anhydride was used, the adhesion of the film was poor despite the high degree and rate of cyclization. The developed image was clear and good, no peeling tendency was observed after the development process, and the etching resistance was also good. On the other hand, the cyclized product of unmodified polyisoprene had poor adhesion, which is thought to be due to its high degree of cyclization, resulting in poor image quality, particularly poor etching resistance.

Example 2 A cyclized product having a number average molecular weight of 173,000, a degree of cyclization of 2.9, and a cyclization rate of 69.2% was prepared in the same manner as in Example 1, except that the proportion of maleic anhydride added was changed. 31
Compound 10 f, 0.20 p of 2,6-bis(4-azidobenzal)cyclohexanone, 0.10 p of 2,2-methylenehis(4-methyl-6-t-butylphenol)
g was added to prepare a photoresist composition solution.

MIRl was coated with a spinner onto a silicone wafer on which aluminum had been deposited to a thickness of 1.0 μm.

After prebaking at 95°C for 30 minutes, as in Example 1,
Developed, zest baked at 150-160°C for 60 minutes,
Next, it was etched with phosphoric acid.

When the resulting resist film was visually inspected, it was found that the adhesion to the wafer was good, and the image condition after development and its etching resistance were both satisfactory.

Example 3 The polyisoprene used in Example 1f was dissolved in toluene,
P-) In the presence of a toluenesulfonic acid catalyst, the cyclization reaction was carried out at 80°C, and the number average molecular weight was 151.0.00. A cyclized product with a degree of cyclization of 2.81 and a cyclization rate of 73% was obtained. This cyclized product was made into a 4% Tornidi solution, maleic anhydride was added, and 16
The amount was 1.9 mol per 111-position 100 of isoprene monomers in the polyisoprene before being sealed under pressure at 0° C. for 5 hours.

Then, a coating film was formed on the wafer 1 in the same manner as in Example 1,
Development and etching were performed. Adhesion, image clarity, and resistance to peeling of the coating film were examined and all were found to be good.

Example 4 Maleic anhydride addition and cyclization reactions were carried out under the same conditions as in Example 1, except that a masticated product of commercially available polyisoprene rubber (Cariflex manufactured by Shell Chemical Co., Ltd.) was used, and the amount of maleic anhydride was cyclized. It is 2.05 mol per 100 isoprene monomer units of the previous polyisoprene, and the degree of cyclization is 2.8.
A cyclized product with a cyclization rate of 74.9% was obtained.

Using this cyclized product, a photoresist composition was prepared by straining in the same manner as in Example 1, and its performance was subsequently investigated. It was found that the photoresist composition gave stable and clear images due to the adhesion improving effect. It was something.

Patent Applicant Rira Shi Co., Ltd. Agent Patent Attorney Proposed Procedural Amendment September 14, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1, Patent Application No. 704 No. 123-1981 2, Name of the Invention Photoresist composition (108) RiRa Raypus Kvm Tsuguo Okabayashi 4, agent Telephone Tokyo 03 (277) 318.25, Column 6 of "Detailed description of the invention" of the specification to be amended, Contents (1) "Usual free sol fluorine catalysts, such as sulfuric acid, p-toluenesulfonic acid, boron silicate" described on page 2, lines 14 to 16 of the specification,
(Hara)/reninsulfonic acid, conventional free-sol Tarafluorocatalysts, such as boron trifluoride.”

(2) The "5% toluene solution" described on page 13, line 12 of the same is corrected to "50% toluene solution."

(3) "When a cyclized product is used" on page 15, lines 1-10 of the same document is corrected to "when a hydrolyzed cyclized product is used."

(4) Correct 1 to ``When a cyclized product is used, although it is thought that this is because the cyclized product has a high degree of cyclization,'' stated in the same page 15, line 15 @ Maro.

(5) "A cyclized product with a number average molecular weight of 173,000, a degree of cyclization of 2.9, and a cyclization rate of 69.2%" described on page 15, line 20 to page 16, line 1 of 173.0.0
0, carboxyl group content (isograne monomer degree 10
0) 1.5 mol, degree of cyclization 2.9, cyclization rate 69.2
% of cyclized product” Procedural amendment to be corrected by Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1, Indication of the case Patent Application No. 123704/1982 2, Name of the invention Photoresist composition (108) Rira Co., Ltd. Representative Director Oka Hayashi J (Male 4, Agent: Tokyo Kogyo; 1, 03 (277+31825, Subject of amendment, Detailed Description of the Invention-1, Column 6, Contents of Amendment (1), Specification, Page 7 “or・” written in lines 3 to 8
... (omitted) "is a polymer based on the units of (A) and/or (B), or a polymer further having the units of (0) is cyclized, and then the above-mentioned (0) ) a method of adding an unsaturated intermediate (D) of
or cycloaddition to a polymer based on the units of (A) and/or (B) or a polymer further having the unit of (0) in the presence of the unsaturated intermediate of the above (D). method (mV) etc. Among these, the cyclized product obtained by the method (厘) or (ff) above best meets the intended purpose of the present invention. Correct it to -1.

Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office1, Indication of Case Patent Application No. 14, No. 1237 (14 No. 2, Title of Invention Photoresist Composition 3, Relationship with the Amendment Person Case) Patent Applicant 1621 Sakazu (108), Kurashiki City Rira Shi□ Representative Director Iya Ueno -4, Deputy
Hitokuragi City 'tN Tsu 7'f jI III 2045-1 Telephone Tokyo 03 (27713182) 5. Subject of amendment □ Full text of specification □ 6. Contents of amendment as shown in the attached sheet.

Full text corrected specification 1, title of the invention 2, claims (2) The cyclized rubber (a) of a conjugated diene polymer having a carboxyl group or a vine group derived from the carboxyl group is a conjugated diene polymer The cyclized product according to claim (1) is a cyclized product obtained by adding a maleic acid compound to and then cyclizing! How to proceed.

Helmet Cyclized rubber (A) costs 10,000 to 500. OO
A method for producing a composition according to claim (1), which is a cyclized product having a number average molecular weight of O.

(4) The method for producing a composition according to claim (1)□, wherein the photocrosslinking agent is a diazide compound.

3. Detailed Description of the Invention The present invention relates to a method for producing a rubber-based photoresist composition suitable for photolithography. More specifically, by using a cyclized product of a conjugated diene polymer having a carboxyl group, a highly sensitive negative-working cyclized rubber-based photoresist composition with excellent adhesion to the substrate can be produced in high yield and yield. Relating to a method of manufacturing.

Semiconductor devices such as transistors, ICs, and LSIs that are manufactured using photolithography processing are becoming increasingly integrated circuits, that is, miniaturized, and are still considered to be one of the fields in which technology is undergoing the most dramatic technological disruption. Along with this, the required performance for each configuration for 4 minutes has become even more severe and high.

Generally, the physical properties of this type of cyclized rubber are determined by its molecular weight, molecular weight distribution, cyclization rate, degree of cyclization, microstructure, etc., and it is well known that these factors have a large impact on the performance of photoresists. That's right. however,
For example, in the case of a photoresist using cyclized polyisoprene rubber, the higher the molecular weight of the cyclized product, the higher the sensitivity of the photoresist, but conversely, if the molecular weight is too high, the photoresist properties will deteriorate and the resolution will decrease. The higher the cyclization rate, the higher the resolution and the better the edge sharpness, but the adhesion to the substrate decreases. Among the many factors that affect resist suitability, it is important to consider only certain factors. Even if changes are made in a thorough manner, multiple physical properties are always influenced in a complex manner, and while some physical properties improve, others tend to deteriorate. Therefore, it is difficult to unambiguously set the various factors, and it is necessary to take into account the complex correlation between each factor and to define conditions within an appropriate range that takes into account the balance of various physical property values. stomach. This makes this type of modification research complex and difficult.

Among the necessary performances of such a photoresist composition, the importance and necessity of improvement (improvement) have always been emphasized, especially the adhesion of the resist to the substrate. Even in today's world of remarkable technological progress, these demands have not changed, and in fact, with new technological innovations, it is increasingly desired to improve adhesion in conjunction with other physical properties.

Improvement in adhesion has also been a problem in recently developed polybutadiene cyclized products.

As a method to solve such problems, a method using a photoresist composition consisting of a maleated rubber or an epoxidized cyclized rubber and a diazide photocrosslinking agent (% opening/closing 50
However, the maleated cyclized rubber is a product in which maleic anhydride or maleic acid derivatives such as maleic acid, maleic acid ester, and maleic acid amide are added to the cyclized rubber. The method for producing cyclized rubber requires high temperatures or a radical-generating catalyst during maleation, which causes side reactions, especially reactions that produce a large amount of gel2, and requires a lot of effort in the purification process. Not only does it require a soluble portion, but it also broadens the molecular weight distribution of the soluble portion. Therefore, when used in photoresist compositions, it improves adhesion to the substrate, but it is necessary to remove by-products. [Quality control regarding products and products with complicated operations; i M! If L<, problems such as performance deterioration due to resolution reduction are likely to occur.

It is well known that the most important issue required in micropattern forming technology for semiconductor device manufacturing is the pursuit of high sensitivity and high resolution, as well as ensuring high yield through stable product quality control. Therefore, with regard to semiconductor device manufacturing technology, a certain level of performance can be ensured with high yield and yield, and high performance such as the inherent adhesion of -C can be exerted.

The present inventors kept this point in mind and as a result of intensive studies, they developed a complete cyclized rubber of a conjugated diene polymer containing a carboxyl group or a group derived from a carboxyl group, and used the cyclized rubber as a photoresist. By using this method, it is possible to achieve high yields and yields, and to significantly improve adhesion (adhesion).In addition, by introducing a method different from the conventional method of introducing a new functional group, physical properties can be improved. We have completed the present invention by discovering that it is now possible to change the balance significantly, and that sensitivity, resolution, etc. can also be improved.

That is, in producing a photoresist composition containing a cyclized rubber and a photocrosslinking agent as main components, the present invention uses diene monomer unit 1 of a diene polymer as the cyclized rubber.
High yield, characterized by using a cyclized rubber of a conjugated diene polymer having 0.01 to 20 moles of carboxyl group or a group derivable to the carboxyl group per 0.00;
The present invention provides a method for producing a high-yield, high-resolution negative-working cyclized rubber-based photoresist composition that has excellent adhesion and few pinholes.

The cyclized rubber of a conjugated diene polymer having a carboxyl group and a group derivable to the carboxyl group used in the present invention is as follows: (Here, 1t1 to 6 each represent a hydrogen atom, an alkyl group or an aryl group. , which may be the same or different), or a unit based on a conjugated diene represented by Rn -C-R+2 (wherein R7-12 each represents a hydrogen atom, an alkyl group or an aryl group) , they may be the same or different), or unsaturated aliphatic hydrocarbons that can be copolymerized with zero conjugated dienes. It is a cyclized rubber of a polymer containing units based on nitrogen aliphatic hydrocarbons and intermediate units based on unsaturated monomers such as 0 α, β to unsaturated carboxylic acids, their acid anhydrides or their ester derivatives. , for example (Al and/
Alternatively, polymerization of a polymer based on the unit of ('B) or a polymer further having 0 units in the polymer is carried out in the coexistence of the unsaturated monomer of 0, and the units based on 0 are shared. A method of obtaining a copolymer as a polymerization component and then cyclizing it (+), a polymer based on units of (A) and/or (B), or a polymer having units of (Q) , method (II) of adding the unsaturated monomer of 0] and then cyclizing, or (8) and/or 03
> or a polymer based on the unit of
A method in which a polymer having units of
and/or...) or a polymer further having 0 units to the polymer, and then adding the 0 unsaturated monomer (M is also considered, but in this case Because the addition reaction of 0 to the cyclized product requires high temperatures or a radical-generating catalyst, side reactions occur and the yield is poor.In other words, a polymorphous gel is produced as a by-product during the addition reaction. Not only does the purification process require a great deal of effort, but the molecular weight distribution of the soluble portion from which the gel is removed greatly expands, and when used in a photoresist composition, resolution IB is likely to decrease. In addition, because the number average molecular weight is greatly reduced, the molecular weight of the raw diene polymer must be set considerably high in order to obtain the final product with the desired molecular weight. and workability deteriorates.

On the other hand, since the method (I) does not include an addition reaction step, the above-mentioned disadvantages do not occur. In addition, in method (■), when adding 0 to a conjugated diene polymer consisting of (5) and (C), high temperature or a radical generating catalyst is still required. However, unlike the case of adding ◎ to the cyclized product of a conjugated diene polymer, the influence of side reactions is small, and a conjugated diene polymer having a carboxyl group or a vine group derived from a carboxyl group can be produced in high yield. can do.

This difference is that when an addition reaction is carried out on a conjugated diene-based polymer, an addition reaction of unsaturated monomers occurs selectively, whereas in the case of a cyclized product of a conjugated diene-based polymer, an addition reaction occurs selectively. This is thought to be due to the fact that side reactions such as molecular cleavage and crosslinking occur accompanying the reaction.

Therefore, in the present invention, (I) or It)
It is preferable to use a cyclized product obtained by the method described above. In particular, the cyclized product obtained by the method (■) best meets the intended purpose of the present invention.

(Examples of conjugated diene polymers based on N and/or (b) units include polymers or copolymers of conjugated dienes such as isoprene, butadiene, pentadiene or jrt phenylbutadiene, and (5) and The conjugated diene polymer based on the units of / and 0 includes copolymers of the conjugated diene and, for example, styrene, α-methylstyrene, ethylene, propylene, isobutylene, or acrylonitrile. Among these, polyisoprene is particularly preferably used because it satisfies the intended purpose of the present invention.

Examples of unsaturated monomers for σ) include acrylic acid compounds such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, maleic acid, maleic anhydride, and maleic acid. Examples include maleic acid compounds such as methyl ester and dimethyl maleate, itaconoic acid, fumaric acid, crotonic acid, and mesaconic acid. Among these, maleic acid compounds are most preferably used, and when they are added to a conjugated diene polymer system, they react with the conjugated diene polymer and form succinic acid residues or succinic anhydride. A carboxyl group-containing conjugated diene polymer having a succinic acid derivative residue such as a succinic acid monoester residue or a succinic acid diester residue as a side chain is produced.

In a conjugated diene polymer having a carboxyl group or a group derivable into a carboxyl group, if the density of the 0-based group providing the carboxyl group or a group derivable into a carboxyl group is too small, a sufficient adhesion improving effect may not be obtained. If the amount is too high, it becomes difficult not only to perform the separation and purification process during the production of the cyclized product, but also to set the conditions during the development of the photoresist.

Therefore, the amount thereof is 0.01 to 20 mol, preferably 0.01 to 20 mol, per diene monomer unit of the conjugated diene polymer.
1 to 10 mol is suitable. In addition, when cyclizing a conjugated diene polymer and then introducing a carboxyl group or a group derivable into a carboxyl group, the amount thereof is the amount per 100 diene monomer units of the conjugated diene polymer before cyclization. This is the same amount as the amount of the conjugated diene polymer having a carboxyl group or a vine group derived from the carboxyl group. Aluminum chloride, tin tetrachloride, titanium tetrachloride, zinc chloride, ethylaluminum dichloride, trialkylaluminum/
Titanium tetrachloride can also be produced.

In the present invention, if the number average molecular weight of the cyclized rubber is too small, the solubility of the photoresist during development will be poor, the film retention will be poor, and the film strength will also be poor. On the other hand, if too much is used, workability deteriorates, resolution decreases, etc. due to high viscosity and low solubility. Therefore, its number average molecular weight is 1 (1,0110-J500.00
0, preferably in the range of 50.0110 to 300.000.

As the photocrosslinking agent used in the present invention, diazide compounds are preferably used. Examples include 4,4-diazidebenzophenone, 4,4-diazidechalcone, 4,4-
diazidiphenyl, p-phenylenebisazide, 2.
6-bis-(4-7didopenzal)-3-methylcyclohexanone and the like are used. The risk of using it is that if it is used too little, the effect of adding it will be small, while if it is too much, the residual film rate after development will be low and defects may appear.
It is preferably in the range of 0.1 to 10 parts by weight per 00 parts by weight.

The photoresist composition of the present invention mainly contains a cyclized rubber and a photocrosslinking agent, but it is also possible to add a sensitizer and an RF stabilizer. Additionally, additives for negative-type cyclized rubber photoresists, such as light-absorbing materials for preventing halation, may be added. The sensitizers include carbonyl compounds such as benzophenone, anthraquinone% 1.2-naphthoquinone, 1.4-naphthoquinone, 2-methylanthraquinone, benzanthrone, violanthrone, and 9-anthraaldehyde, anthracene,
Aromatic hydrocarbons such as chrysene, nitro compounds such as nitrobenzene, p-dinitrobenzene, p-nitrobiphenyl, 2-nitrofluorene, 5-nidronaphthene,
Nitroaniline, 2-chloro-4-, =-) CI 7
Niline, 2.6-Cycloro4 Nitroaniline, 5-
Examples include nitrogen compounds such as nitro-2-aminotoluene and tetracyanoethylene, and sulfur compounds such as diphenyl disulfide.

The storage stabilizer is hydroxyl.

Hydroxyaromatic compounds such as methoxyphenol and p-t-butylcatechol, quinones such as benzoquinone, p-torquinone, and p-xyloquinone, amines such as phenyl-α-naphthylamine, p, Lauryl thiodipropionate, 4.4
-thiobis(6-t-dab-3-methylphenol), 2,4-thiobis(4-methyl-6-t-butylphenol), 2-(3,g-di-t-butyl-4-hydroxyphenol) aniline), 4,6-bis(N-octylthio)
Examples include sulfur compounds such as -S-triazine.

The photoresist composition of the present invention has particularly excellent adhesion (adhesiveness) to the substrate, and the pathology of cyclized rubber for resolution direction 1', which has conventionally been considered unsuitable due to decreased adhesion. It is possible to pursue lower viscosity by increasing the conversion rate and pathological degree, and improvement of sensitivity by narrowing the molecular weight distribution. As a result, it is possible to provide a unique and excellent adhesion that has excellent coating properties such as strong IB, has few pinholes, and has high resolution. Note that cyclization rate and cyclization degree here mean what is usually said in polymer chemistry (for example, in the case of polyisoprene,
See ``R&D Review'' A 11 [Synthesis and Application of Photosensitive Resins (Continued)'', p. 337, published by CM and C Publishing Co., Ltd. in 1980. ).

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 and Comparative Example 1 Number-average molecules [5 of 151,000 polyisoprene] obtained by polymerizing isoprene monomer with n-butyllithium at 60°C in toluene under a nitrogen atmosphere
A titoluene solution was prepared, maleic anhydride was added to the solution, and the mixture was reacted at 160° C. for 4 hours with stirring in a pressurized reactor to obtain modified polyisoprene.

The modified polyisoprene was evaluated by infrared absorption spectrum and was found to be a modified product with 1.1 mol of maleic anhydride added per 100 isoprene monomer units. next,
The modified product was made into a 50% xylene solution, and reacted with stirring at 90° C. for 5 hours in the presence of a p-toluenesulfonic acid catalyst to obtain a cyclized product.

The number average molecular weight of this cyclized product is 131.000, and as a result of structural analysis using nuclear magnetic resonance spectroscopy, the degree of cyclization is 3°1, and the cyclization rate is 75.8°, both of which are favorable results for resolution. It was an expensive thing to give.

Hydrolyzed product 15 of the cyclized product obtained in this way, O
2,6-bis(eacidobenzal)cyclohexanone 0.35F as a photocrosslinking agent and a storage stabilizer were added to f.
A xylene solution of a photoresist composition was prepared using 0.15 f of 2-methylenebis(4-methyl-6-t-butylphenol). Using a spinner, apply the solution onto a silicon wafer coated with a silicone oxide film to a film thickness of 1.
It was spin-coated so that the angle of the film was θμ, and prebaked at 85 to 95°C for 30 minutes. Next, using a 200W high pressure mercury lamp,
The image was printed by exposure through a Resolution Test Chart chrome mask manufactured by Toppan Printing. Next, it was developed with a xylene-based developer, rinsed with n-butyl acetate, and post-baked at 150°C for 30 minutes.
Etching treatment was performed using F/HF aqueous solution).

On the other hand, for comparison, polyisoprene rings and compounds were prepared in the same manner as above except that maleic anhydride was added and reacted. The number average molecular weight, degree of cyclization, and rate of cyclization of the cyclized product are each 115. (100.

They were 3.0 and 75.0. This cyclized product was used as a resist composition and subjected to baking, development, and etching treatments in the same manner as above.

A comparison of these two types of photoresists revealed that when a hydrolyzate of a cyclized product of maleic anhydride addition-modified polyisoprene was used, the adhesion of the film was poor despite the high degree and rate of cyclization. The developed image was clear and good, no peeling tendency was observed after the development process, and the etching resistance was also good. On the other hand, when a cyclized product of unmodified polyisoprene was used, adhesion was poor, resulting in poor image quality, particularly poor etchability.

Example 2 The same method as in Example 1 was carried out except that the addition ratio of maleic anhydride was changed, and the number average molecule ff1H]73.0(1
A cyclized product having a carboxyl group content of 1.5 mol (per 100 m-positions of isoprene monomer), a degree of cyclization of 2.9, and a cyclization rate of 69.2% was prepared. 2,6-bis(4
-azidobenzal) cyclohexanone 0.20? , 2.
0.10 f of 2-methylenebis(4-methyl-6-t-butylphenol) was added to prepare a photoresist composition solution. The solution was applied using a spinner onto aluminum-deposited silicone urethane to a thickness of 10 μm. After baking at 95 DEG C. for 30 minutes, it was developed in the same manner as in Example 1, post-baked at 15+1 to 160 DEG C. for 30 minutes, and then etched with phosphoric acid.

When the obtained resist film was examined, it was found that the adhesion to the wafer was good, and the condition of the image after development and its etching resistance were both satisfactory.

Example 3 Maleic anhydride addition and cyclization reactions were carried out under the same conditions as in Example 1, except that a masticated product of commercially available polyisoprene rubber (Califlex manufactured by Shell Chemical ■) was used, and the amount of maleic anhydride was cyclized. It is 2.05 mol per 100 isoprene monomer units of the previous polyisoprene, and the degree of cyclization is 2.8.
A cyclized product with a cyclization rate of 74.9% was obtained.

A photoresist composition was prepared using this cyclized product in the same manner as in Example 1, and its performance was investigated. It was found that the photoresist composition stably provides clear images due to its adhesion improving effect. Ta.

Example 4 Polymerized in the same manner as in Example 1 and with a number average molecular weight of 15
A 50%) toluene solution of 1,000 polyisoprene was prepared7, maleic anhydride was added and dissolved in the solution, and then tin tetrachloride was added and reacted at 80°C for 8.5 hours with stirring. A modified cyclized product was obtained. The modified cyclized product has 0.4 mole of maleic anhydride added per isoprene monomer unit 00 before reaction, and has a degree of cyclization of 4.5 and a degree of cyclization of 6.
It had a cyclization rate of 5.7%. Generally, in the case of the addition reaction of maleic anhydride to cyclized polyisoprene at high temperatures, a large amount of gel tends to be produced as a by-product, but in the above case, there was little gel by-product and the reaction was carried out smoothly. Using the hydrolyzed product of the modified cyclized product thus obtained, photoresist compositions were prepared in the same manner as in Example 1.
When we investigated the performance of Ml, we found that the previous Ml...
``The autoresist composition exhibited good adhesion and gave stable and clear images.Patent applicant: Rira Co., Ltd. Agent: Patent attorney Ken Fuyo

Claims (1)

Scope of Claims: (1) Cyclized rubber (a) of a conjugated diene polymer having 0.01 to 20 moles of carboxyl group per 100 diene monomer units or a group that can induce said carboxyl group□#5
and a photo-crosslinking agent (b) as main components. (2) Cyclized rubber of a conjugated diene polymer having a carboxyl group or a group that can be induced into the carboxyl group (a)
is a cyclized product obtained by adding a maleic acid compound to a conjugated diene polymer and then cyclizing the composition O according to claim (1). (3) A carboxyl group or the carboxyl group. The composition according to claim 1, wherein the group that can be derived from a cyclized rubber is a group that is introduced into the cyclized rubber by using an acrylic acid compound or a maleic acid compound. (4) Cyclized rubber (a) is 10,000 to 500,000
The composition according to claim (1), which is a cyclized product having a number average molecular weight of 0. (5) The composition according to claim (1), wherein the photocrosslinking agent (b) is a diazide compound.