JPH09134014A - Photosensitive resin composition and pattern forming method using that composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable development with a water-based solvent by incorporating a polymer having carboxyl groups and a photo-base producing agent which produces a base by irradiation of electromagnetic waves. SOLUTION: This photosensitive resin contains a carboxylic acid polymer having the mol.wt. between >=10000 and <=1000000 expressed by formula by >=20wt.% of the whole resin amt., and to the carboxyl groups in the carboxylic acid polymer, 0.0-2.0mol.equiv. secondary and/or tertiary amines, 0.01-0.5mol. equiv. photo-base producing agent which produces a base by irradiation of electromagnetic waves, and 0.1-2.0mol.equiv. base-base producing agent which produces a base by another base. In formula, R1 is 2-40C org. group, n is an integer 10 to 20000, and R2 is 1-20C org. group, hydrogen or halogen atom, thereby developing the obtd. resin can with a water-based solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel photosensitive resin composition and a pattern forming method using the same.

[0002]

2. Description of the Related Art Photosensitive resin compositions are widely used in the field of electrical and electronic industries as materials that can greatly simplify the wiring forming process. These photosensitive resin materials are classified into a positive type in which an exposed portion is mainly etched and a negative type in which an unexposed portion is mainly etched.
The negative photosensitive material is disadvantageous in performing fine processing with high resolution because swelling of the exposed portion by the developing solution occurs.
In some cases, a positive photosensitive heat-resistant material is required in the process, and a positive photosensitive heat-resistant material has been desired. Further, from the viewpoint of preventing environmental pollution and improving the working environment, a photosensitive resin composition that can be developed with an aqueous solvent is desired instead of the conventional photosensitive resin composition using a developing solution mainly containing a chlorine-based solvent or an organic solvent. It was rare.

In the semiconductor industry, inorganic materials such as silicon oxide are widely used as insulating films and passivation films for solid-state devices.

On the other hand, organic materials retain properties such as low stress, smoothness, and high purity as compared with inorganic materials. In recent years, a technique used as an insulating layer or a passivation layer has been developed. It has been put to practical use in some semiconductor devices.

When an organic material is used as the above-mentioned material, it is required to use a heat-resistant organic material because the material is required to have thermal stability because it undergoes working steps such as die bonding. Therefore, polyimides having excellent heat resistance have been widely studied.

For example, after coating a substrate with a polyimide precursor, polyamic acid, and performing heat treatment to convert it into polyimide, a photoresist relief pattern is formed on the polyimide film, and the polyimide is selected with a hydrazine-based etching agent. Etching is performed to transfer the relief pattern to polyimide.

However, the patterning of the polyimide in the above step includes steps such as photoresist coating and peeling, which makes the process very complicated. In addition, the transfer of the relief pattern through the resist causes a decrease in dimensional accuracy. Therefore, development of a heat-resistant material that can be finely processed by direct light has been desired in order to simplify the fine processing step and increase the precision.

As a material for the above purpose, various materials have been already disclosed for a negative type, but in some cases a positive type photosensitive heat resistant material is required in the process. As positive-type photosensitive heat-resistant materials, a photosensitive polyamic acid nitrobenzyl ester (Japanese Patent Publication No. 1-59571) and a photosensitive heat-resistant material composed of a polyamic acid and a dihydropyridine derivative (Japanese Patent Laid-Open No. 6-43648) are disclosed. Has been done. In order to obtain the above-mentioned positive photosensitive heat-resistant material, it is necessary to use an acid chloride as a monomer. Therefore, it was necessary to strictly control conditions such as reaction temperature and water removal during the synthesis. Further, the produced precursor also has a problem in terms of purity such as the need to remove chlorine ions, which adversely affects the film properties and also the developing properties are insufficient.

[0009]

For the purpose of solving the above problems, a positive agent developable with an aqueous solvent, which comprises a polymer having a carboxyl group and a photobase generator capable of generating a base upon irradiation with an electromagnetic wave. Type photosensitive materials are conceivable. However, in the positive type photosensitive heat resistant material described above,
The amount of irradiation for obtaining a pattern is relatively large, and coloring occurs due to a reaction caused by electromagnetic wave irradiation, so that absorption occurs on the film surface. Further, the difference in solubility between the exposed area and the unexposed area at the time of development was insufficient due to the difference in solubility between the polyamic acid and the polyamic acid salt. Therefore, the developable film thickness, resolution, and sensitivity are limited.

An object of the present invention is to provide a polarity change type photosensitive resin composition which can solve the above problems and can be developed with an aqueous solvent.

[0011]

In order to achieve the above object, the present invention uses the following technical means.

The first means is a carboxylic acid polymer represented by the chemical formula 1 and having a molecular weight of 10,000 or more and 1,000,000 or less.

[0013]

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(In the formula, R ₁ is an organic group having 2 to 40 carbon atoms,
n is a positive integer between 10 and 20,000, and R ₂ is any one of an organic group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom), and is 20% or more by weight with respect to the total amount of resin, Two
Of a photo-base generator which generates a base by irradiation of electromagnetic waves with 0.0 to 2.0 molar equivalents of a primary or / and a tertiary amine to the carboxyl group of the carboxylic acid polymer. 0.01 to the carboxyl group of the polymer
The photosensitive resin composition contains 0.5 molar equivalent and a base-base generator that generates a base by a base in an amount of 0.1 to 2.0 molar equivalents based on the carboxyl groups of the carboxylic acid polymer. .

The second means is to generate a base in the presence of a base,
The present invention relates to a photosensitive resin composition containing a base-base generator capable of causing a self-decomposition reaction by the base, and a polymer characterized in that the catalytic reaction of the base improves the solubility in an aqueous solvent.

The third means is to generate a base in the presence of a base,
A base-base generator capable of causing an autolysis reaction by the base, and a polarity change due to the catalytic reaction of the base (Chemical Formula 3)
A carboxylic acid ester polymer having a molecular weight of 10,000 or more and 1,000,000 or less represented by

[0017]

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(In the formula, R ₆ is an organic group having 2 to 40 carbon atoms,
n is a positive integer between 10 and 20,000, R ₇ includes an organic group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, and R ₈ includes an organic group having 1 to 30 carbon atoms). This is due to the characteristic photosensitive resin composition.

The fourth means is to generate a base by irradiating with an electromagnetic wave such that the carboxylic acid ester polymer represented by the above (Chemical Formula 3) and having a molecular weight of 10,000 or more and 1,000,000 or less is 20% or more by weight with respect to the total resin amount. The photobase generator is added to the carboxylic acid ester polymer in an amount of from 0.01 to
A photosensitive resin composition containing 0.5 molar equivalent and a base-base generator that generates a base by a base in an amount of 0.1 to 2.0 molar equivalents based on the ester groups of the carboxylic acid ester polymer. is there.

A fifth means is a hydroxyl-protected phenolic polymer represented by the chemical formula 7 and having a molecular weight of 10,000 or more and 1,000,000 or less.

[0021]

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(In the formula, R ₁₆ is an organic group having 2 to 40 carbon atoms,
n is a positive integer between 10 and 20,000, R ₁₇ is an organic group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, and R ₁₈ is an organic group having 1 to 30 carbon atoms by weight. 20% or more with respect to the total amount of resin, a photobase generator that generates a base upon irradiation with electromagnetic waves, 0.01 to 0.5 molar equivalents to the hydroxyl groups of the hydroxyl group-protected phenol polymer, and a base with a base. This is because the photosensitive resin composition contains a base-base generator that generates 0.1 to 2.0 molar equivalents based on the ester groups of the carboxylic acid ester polymer.

A sixth means is to use a polymer containing a carboxyl group, a secondary or / and a tertiary amine, and

[0024]

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(In the formula, R ₂₂ is an organic group having 1 to 10 carbon atoms,
It is either a hydrogen atom or a halogen atom. p is 0-4
Is an integer. R ₂₃ is hydrogen or an organic group having 1 to 10 carbon atoms, R ₂₄ and R ₂₅ are a hydrogen atom or an organic group having 1 to 12 carbon atoms, and a photobase generator and a base-base generator are included. This is due to the photosensitive resin composition.

As a seventh means, a polymer containing an alkoxycarbonyl group, a secondary or / and a tertiary amine, a photobase generator represented by the chemical formula 11 and a base-base generator are used. It is due to the photosensitive resin composition containing.

The eighth means is a polymer containing a protected hydroxyl group, a secondary or / and a tertiary amine, and
It is based on a photosensitive resin composition containing a photobase generator represented by 1) and a base-base generator.

The ninth means is a polymer containing a carboxyl group, a secondary or / and tertiary amine, a photobase generator, and

[0029]

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(In the formula, R ₂₆ is an organic group having 1 to 20 carbon atoms,
Any of the halogen atoms, R ₂₇ is any one of an organic group having 1 to 20 carbon atoms, hydrogen and a halogen atom. Also, R ₂₈ ,
R ₂₉ is hydrogen or an organic group having 1 to 12 carbon atoms, and R ₃₀ and R ₃₁ are hydrogen or an organic group having 1 to 20 carbon atoms;
This is due to the photosensitive resin composition containing a base generator.
A tenth means is a photosensitive composition containing a polymer containing an alkoxycarbonyl group, a secondary or / and a tertiary amine, a photobase generator, and a base-base generator represented by the chemical formula (12). This is due to the resin composition.

The eleventh means is a polymer having a protected hydroxyl group, a secondary or / and tertiary amine, a photobase generator, and a base-base generator represented by the above (formula 12). It is based on the photosensitive resin composition containing.

The twelfth means comprises a polymer containing a carboxyl group, a secondary or / and tertiary amine, a photobase generator and a base-base generator, and can be patterned by electromagnetic wave irradiation. This is due to the photosensitive resin composition.

A thirteenth means is a photosensitive resin composition characterized by containing a polymer containing an alkoxycarbonyl group, a photobase generator and a base-base generator and capable of forming a pattern by electromagnetic wave irradiation. It is a thing.

A fourteenth means comprises a protected hydroxyl group-containing polymer, a photobase generator, and a base-base generator,
The photosensitive resin composition is characterized in that a pattern can be formed by electromagnetic wave irradiation.

A fifteenth means is to use a carboxylic acid polymer represented by the above-mentioned (Chemical formula 1) having a molecular weight of 10,000 or more and 1,000,000 or less in an amount of 20% or more by weight based on the total amount of the resin, secondary or / and
And a tertiary amine in an amount of 0.0 to 1.0 molar equivalent with respect to a carboxyl group of the carboxylic acid polymer, and a photobase generator in an amount of 0.01 to 0.01 with respect to a carboxyl group of the carboxylic acid polymer. 0.5 mol equivalent and a base-base generator are added in an amount of 0.1 to 2.2 with respect to the carboxyl group of the carboxylic acid polymer.
It is based on a pattern forming method including a step of applying a photosensitive resin composition containing 0 molar equivalent on a substrate and drying, a step of irradiating an electromagnetic wave through a light-shielding mask, and a step of developing.

A sixteenth means is to generate a base by irradiating an electromagnetic wave with a carboxylic acid ester polymer represented by the above (Chemical formula 3) having a molecular weight of 10,000 or more and 1,000,000 or less and 20% or more based on the total amount of resin. A photobase generator was added to the ester group of the carboxylic acid ester polymer in an amount of 0.0
A photosensitive resin composition containing 1 to 0.5 molar equivalents and a base-base generator which generates a base by a base in an amount of 0.1 to 2.0 molar equivalents based on the ester groups of the carboxylic acid ester polymer. The pattern forming method includes a step of coating and drying on a substrate, a step of irradiating an electromagnetic wave through a light shielding mask, and a step of developing.

A seventeenth means is that the hydroxyl group-protected phenolic polymer having a molecular weight of 10,000 or more and 1,000,000 or less represented by the chemical formula (7) is 20% or more by weight based on the total amount of the resin.
A photobase generator that generates a base upon irradiation with electromagnetic waves is added to the hydroxyl group of the hydroxyl group-protected phenol polymer in an amount of 0.0
A photosensitive resin composition containing 1 to 0.5 molar equivalents and a base-base generator which generates a base by a base in an amount of 0.1 to 2.0 molar equivalents based on the ester groups of the carboxylic acid ester polymer. The pattern forming method includes a step of coating and drying on a substrate, a step of irradiating an electromagnetic wave through a light shielding mask, and a step of developing.

In the present invention, examples of means for generating a base include electromagnetic wave irradiation, electron beam irradiation, and amine solution spraying.

The present invention has been achieved by utilizing the fact that the solubility of a molecule having a carboxyl group in the structure of (Chemical Formula 1) is greatly changed by the presence of a base. Therefore, any compound having a carboxyl group in its structure can be applied. However, the carboxyl groups are limited to those that do not cause a decarboxylation reaction in the step before development. As for the molecular weight of a molecule having a carboxyl group, when solubility in a developing solution and mechanical characteristics of a relief pattern are taken into consideration, 1
The upper limit of the molecular weight is preferably 0000 or more, but the upper limit of the molecular weight is not particularly limited, but when considering the solubility in a solvent, the ease of handling a sensitizer varnish, and the solubility in a developer,
It is desirable to be 1000000 or less.

As a repeating unit which gives a polymer structure having a carboxyl group by chain polymerization, Polymer Data Handbook, Basic Edition (Polymer Society of Japan, Baifukan, 198)
6) Examples include polyacrylic acid and alkyl polyacrylate derivatives shown in Table 9.1, maleic acid and its derivatives shown in Table 14.1, fluoroalkyl maleate and vinyl acetate. Specific examples include acrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid,
Examples include 3-propylacrylic acid, 3-isopropylacrylic acid, α-acetoxyacrylic acid, α-trifluoromethylacrylic acid, methacrylic acid, maleic acid, methylmaleic acid, fluoromaleic acid, fluoroalkyl maleate and vinyl acetate. To be The present invention can be applied as it is to polymers of the monomers listed here and polymers containing the monomers listed here as a copolymerization component. Further, even in the case of a polymer that does not contain a carboxyl group as a monomer during polymerization, the present invention can be applied by introducing a carboxyl group by chemical modification.

The structure of (formula 1) is (formula 2)

[0042]

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In the case of the above, the effect of the present invention is exerted more.

For example, when polyamic acid which is a polycondensation type polymer is applied to the present invention, heat resistance and chemical resistance are obtained by forming a relief image and then heating or chemically imidizing it to convert it into polyimide. Since a relief image having excellent properties can be obtained, it exhibits excellent performance as a protective film for an LSI, an insulating film for a wiring board, and the like. The polyamic acid used in the present invention is obtained by reacting a diamine or diisocyanate with a tetracarboxylic acid or its derivative. As the tetracarboxylic acid derivative, an acid anhydride,
There are acid chlorides. The use of an acid anhydride is preferable in terms of reactivity and by-products. Examples of the diamine and acid anhydride derivative used in the present invention include those described in JP-A No. 61-181829.

The present invention has been achieved by utilizing the fact that the solubility of a molecule having a carboxyl group in the structure of (Chemical Formula 1) in water is greatly improved by the presence of a base. Therefore, as the amine used in the present invention, it is necessary that the polymer does not exhibit water solubility even when it reacts with a carboxyl group in the polymer to form a salt.
Specific compounds include most tertiary alkylamines or bulky secondary amines such as diisopropylamine and diphenylamine. It was also found that a good relief pattern was obtained when the amount added was 0.6 to 1.0 molar equivalent with respect to the carboxyl groups in the polymer.

Irradiation with electromagnetic waves or a base generated by a base reacts with a carboxyl group in the polymer to change the solubility of the polymer. That is, the base and the carboxyl group react to form a salt, the solubility in water is improved,
Solubility in organic solvents decreases. As a result, a positive image can be obtained when a highly polar water solvent is used as a developing solution, and a negative image can be obtained when an organic solvent is used as a developing solution. Since the bond between the carboxyl group and the generated base is weak, it can be easily desorbed in the imidization process to provide a relief pattern having strength and excellent flatness. Since the relief pattern is based on salt formation, the amounts of the carboxyl group and the base generator in the resin composition are important. As a result of investigating the blending amount of these, it was found that a good relief pattern was obtained when the content of the polymer containing a carboxyl group was 20% by weight or more based on all the resin components.

In the present invention, the solubility of (Chemical Formula 3) is greatly changed by the decomposition of the alkoxycarbonyl group in the structure in the presence of a base into a carboxyl group. Therefore, any base-decomposable ester having a carboxyl group in its structure can be applied. The molecular weight of the polymer having a carboxyl group is 100 in consideration of solubility in a developing solution and mechanical characteristics of a relief pattern.
The upper limit of the molecular weight is not particularly limited, but is preferably 1000 or more when considering the solubility in a solvent, the ease of handling a photosensitive varnish, and the solubility in a developing solution.
It is desirable to be 000 or less.

As a repeating unit which gives a polymer structure having a carboxyl group by chain polymerization, the Polymer Data Handbook, Basic Edition (Polymer Society of Japan, Baifukan, 198)
6) Examples include polyacrylic acid and alkyl polyacrylate derivatives shown in Table 9.1, maleic acid and its derivatives shown in Table 14.1, fluoroalkyl maleate and vinyl acetate. Specific examples include acrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid,
Examples include 3-propylacrylic acid, 3-isopropylacrylic acid, α-acetoxyacrylic acid, α-trifluoromethylacrylic acid, methacrylic acid, maleic acid, methylmaleic acid, fluoromaleic acid, fluoroalkyl maleate and vinyl acetate. To be The present invention can be applied as it is to a polymer of a base-decomposable ester of the monomers listed here and a polymer having the monomer as a copolymerization component. Further, even in the case of a polymer which does not contain a carboxyl group as a monomer at the time of polymerization, the present invention can be applied by introducing an alkoxycarboxyl group by chemical modification.

The structure of (formula 3) is (formula 4)

[0050]

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In the case of the above, the effect of the present invention is exerted more. For example, when a polyamic acid ester, which is a polycondensation type polymer, is applied to the present invention, after forming a relief image, it is heated or chemically imidized to be converted into a polyimide to improve heat resistance and chemical resistance. Since an excellent relief image can be obtained, it exhibits excellent performance as a protective film for an LSI, an insulating film for a wiring board, and the like.

In the present invention,

[0053]

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The reaction mechanism of the decomposition of the alkoxycarbonyl group of the carboxylic acid ester polymer represented by is that the hydrogen on the carbon at the β-position of the carboxyl group is abstracted by the base to generate a carbanion. Therefore,
In the structural formula, the group represented by R ₁₄ is preferably an electron-withdrawing group or an aromatic group which stabilizes the carbanion. R ₁₂ ~ R
_The group represented by ₁₅ is preferably an organic group having 12 or less carbon atoms from the viewpoint of film slippage during the relief pattern formation.
More preferably, an organic group having 1 to 3 carbon atoms is preferable. In addition, the protective group used in the present invention may be used regardless of the above structure as long as it decomposes in the presence of a base to generate a carboxyl group and a hydroxyl group. Specific protecting groups for carboxylic acid include 2-cyano-1-methylethyl group, 2,2-dicyano-1-methylethyl group, 9-fluorenylmethyl group,
2-methylsulfonylethyl group, 2-acetyl-1-
Examples thereof include a methylethyl group, a 2-benzoyl-1-methylethyl group, and a 2-cyano-2-ethoxycarbonyl-2-methylethyl group. The polyamic acid ester used in the present invention is obtained by a reaction of a diamine or diisocyanate with a tetracarboxylic acid diester, or a reaction of a polyamic acid with a chloroformic acid ester or p-nitrophenoxyformate ester.

In the present invention, the solubility of the chemical formula (7) is greatly changed by the decomposition of the alkoxycarbonyloxy group in the structure into a hydroxyl group in the presence of a base. Therefore, any base-decomposable alkoxycarbonyloxy compound having a hydroxyl group in its structure can be applied. The molecular weight of the molecule having a hydroxyl group is preferably 10,000 or more in consideration of the solubility in the developer and the mechanical characteristics of the relief pattern. The upper limit of the molecular weight is not particularly limited, but the solubility in a solvent, Considering the ease of handling the photosensitive varnish and the solubility in the developer, it is preferably 1000000 or less.

Polymers having a hydroxyl group include polysaccharides,
Phenol resins and the like can be mentioned. Specific examples include cellulose, amylose, chitin, novolac, resol and the like. As the repeating unit that gives a polymer structure having a hydroxyl group by chain polymerization, hydroxyl groups in styrene and its derivatives described in Table 5.1, Polymer Data Handbook, Basic Edition (edited by The Polymer Society of Japan, Baifukan, 1986),
Examples thereof include those having a hydroxyalkyl group.
Specific examples include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2,4-dihydroxystyrene, 2,5-dihydroxystyrene, p.
-Vinylbenzyl alcohol, vinyl alcohol and the like can be mentioned. The present invention can be applied as it is to a polymer of a base-decomposable alkoxycarbonyloxy compound of the monomers listed here and a polymer having the monomer as a copolymerization component. Further, even in the case of a polymer which does not contain an alkoxycarbonyloxy group as a monomer at the time of polymerization, the present invention can be applied by introducing a base-decomposable alkoxycarbonyloxy group by chemical modification.

The structure of (Chemical formula 7) is (Chemical formula 8)

[0058]

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In case of the above, the effect of the present invention is more exerted. For example, when an alkoxycarbonyloxy protected body of a polybenzoxazole precursor, which is a polycondensation type polymer, is applied to the present invention, after forming a relief image, it is heated or chemically oxazole-ized to give polybenzoxyxene. By converting to zazole, a relief image having excellent heat resistance and chemical resistance can be obtained, and thus it exhibits excellent performance as a protective film of LSI, an insulating film of a wiring board, and the like.

In the present invention,

[0061]

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The reaction mechanism of the decomposition of the alkoxycarbonyloxylated hydroxyl group of the hydroxyl group-protected phenolic polymer represented by is that the hydrogen on the β-position carbon of the carbonyloxyl group is abstracted by a base to generate a carbanion. Is. Therefore, in the structural formula, the group represented by R ₁₄ is preferably an electron-withdrawing group or an aromatic group which stabilizes the carbanion. The groups represented by R _{12 to} R ₁₅ are preferably organic groups having 12 or less carbon atoms from the viewpoint of film slippage during the relief pattern formation. More preferably, an organic group having 1 to 3 carbon atoms is preferable. In addition, the protective group used in the present invention may be used regardless of the above structure as long as it decomposes in the presence of a base to generate a carboxyl group and a hydroxyl group. Specific protective groups for the hydroxyl group include 2-cyano-1-methylethoxycarbonyloxyl group, 2,2-dicyano-1-methylethoxycarbonyloxyl group, 9-fluorenylmethoxycarbonyloxyl group, 2 -Methylsulfonylethoxycarbonyloxyl group, 2-acetyl-1-methylethoxycarbonyloxyl group, 2-benzoyl-1-methylethoxycarbonyloxyl group, 2-cyano-2-ethoxycarbonyl-2-methylethoxycarbonyl group Examples thereof include a xyl group. The alkoxycarbonyloxy protected form of the polybenzoxazole precursor used in the present invention can be obtained by reacting a dicarboxylic acid or dicarboxylic acid chloride with a diaminodialkoxycarbonoxy compound, or a polybenzoxazole precursor and a chloroformate. Or p-
Obtained by reaction of nitrophenoxyformate.

The irradiation of electromagnetic waves or the base generated by the base acts as a catalyst for the decomposition reaction of the protective group in the polymer and changes the solubility of the polymer. That is, since a highly polar hydroxyl group and a carboxyl group are generated, the solubility in an aqueous solvent is improved and the solubility in an organic solvent is lowered. As a result, a positive image can be obtained when a highly polar water solvent is used as a developing solution, and a negative image can be obtained when an organic solvent is used as a developing solution. Since the bond between the carboxyl group and the generated base is weak, it can be easily desorbed in the imidization process to provide a relief pattern having strength and excellent flatness. Since the relief pattern is based on the formation of highly polar carboxyl group and hydroxyl group, the amount of the carboxyl group and hydroxyl group and the base generator in the resin composition is important. As a result of examining the blending amount of these, it was found that a good relief pattern can be obtained when the polymer containing a carboxyl group and a hydroxyl group is 20% by weight or more based on all the resin components.

Examples of the photobase generator used in the present invention include compounds such as tosylamine and carbamate.
Specific compounds include cyclohexyl paratoluene sulfonylamine, N- [1- (3,5-dimethoxyphenyl) -1-methylethoxycarbonyl] cyclohexylamine, N-[(2,6-dinitrophenyl) methoxycarbonyl] cyclohexyl. Amine, N- [1-
(2,6-dinitrophenyl) ethoxycarbonyl] cyclohexylamine, N- [bis (2,6-dinitrophenyl) methoxycarbonyl] cyclohexylamine,
N- [bis (2-nitrophenyl) methoxycarbonyl] octadecylamine, N-[(2-nitrophenyl) methoxycarbonyl] octadecylamine, N-
[1- (2-Nitrophenyl) ethoxycarbonyl] octadecylamine, N-[(2-nitrophenyl) methoxycarbonyl] piperidine, N, N'-bis [(2-
Nitrophenyl) methoxycarbonyl] -1,6-diaminohexane, N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] octadecylamine, N- [1- (4-methyl-2-nitrophenyl) ) Ethoxycarbonyl] octadecylamine, N- [1-
(6-methyl-2-nitrophenyl) ethoxycarbonyl] octadecylamine and the like. For the synthesis method and structure of these, see J. Am. Chem. Soc. 1991,
113, 4303-4313, Fahey, J. et al. T. and Frech
et, JM J. (1991) Proc. SPIE, 1466, 6
7, Frechet, J. M. J., Stanciulescu, M., Lizawa,
T., and Willson, C. G., (1989) Proc. ACS Div. Po
lym. Mater. Sci. Eng., 60, 170. Graziano, K .;
A., Thompson, S. D., and Winkle, M. R. (1990)
Proc. SPIE, 1466, 75. , Etc.,
Researchers in this field can easily synthesize the required photobase generator. All of these compounds are decomposed by light irradiation to generate a base. Of these, the photobase generator represented by the chemical formula (11) has high generation efficiency and excellent characteristics when used in the present invention. More preferably, an organic group having 5 to 10 carbon atoms is preferable. In addition, the photobase generator used in the present invention can be used regardless of the above structure as long as it can generate a water-soluble aliphatic amine by irradiation with electromagnetic waves. Considering the solubility in the developer and the film slip of the relief pattern, the addition amount of the photobase generator is
The amount is preferably 0.01 to 0.5 molar equivalent with respect to the carboxyl group of the carboxylic acid polymer or the alkoxycarbonyloxyl group of the hydroxyl group-protected phenol polymer. More preferably, it is 0.05 to 0.2 molar equivalent.

In the present invention, the base-base generator represented by the chemical formula 11 has absorption in the visible and ultraviolet regions. Therefore, electromagnetic waves having a wavelength of 250 to 600 nm are desirable. Considering the absorption of the resin compound and the extinction coefficient of (Formula 11), the wavelength of the electromagnetic wave is 300 to 450 nm.
Is more desirable.

The present invention can be easily achieved by mixing a carboxylic acid polymer, a carboxylic acid ester polymer, or a hydroxyl group-protected phenolic polymer synthesized by the above method with a photobase generator. In the present invention, a combination use with a triplet sensitizer, an adhesion improver comprising various amine compounds,
It goes without saying that it can be used in combination with a surfactant or the like.

In the present invention, the base-generating mechanism of the base-base generator represented by the chemical formula (12) is that the hydrogen on the β-position carbon of the carbamoyl group is abstracted by the base to generate a carbanion. is there. Therefore, in the structural formula, the group represented by R ₂₆ is preferably an electron-withdrawing group or an aromatic group which stabilizes the carbanion. The groups represented by R _{27 to} R ₂₉ are preferably organic groups having 12 or less carbon atoms from the viewpoint of film slippage during the relief pattern formation. More preferably, an organic group having 1 to 3 carbon atoms is preferable. The base-base generator used in the present invention may be any one that can generate a water-soluble aliphatic amine in the presence of a base, regardless of the above structure. In the structural formula, R ₃₀ and R ₃₁ are preferably amines having 12 or less carbon atoms in order to obtain water solubility by salt formation. More preferably, an organic group having 1 to 3 carbon atoms is preferable. Specific compounds include 2-cyano-1-methylethyl-N-isopropylcarbamate, 2,2-dicyano-1-methylethyl-N-isopropylcarbamate, 9-fluorenylmethyl-N-isopropylcarbamate, 2- Methylsulfonylethyl-N-isopropylcarbamate, 2-acetyl-1-methylethyl-N-isopropylcarbamate, 2-benzoyl-1
-Methylethyl-N-isopropylcarbamate, 2-
Cyano-2-ethoxycarbonyl-2-methylethyl-
N-isopropyl carbamate etc. are mentioned. These are the reaction (J. Org. Chem. 199) of the corresponding alcohol and isocyanate in the presence of a catalytic amount of methyllithium.
0,55,5919-5922, Cameron, J .; F. and Freche
t, J. M. J. (1990)) or by reacting the corresponding alcohol with carbamil chloride. The amount of the base-base generator added is preferably 0.1 to 2.0 molar equivalents with respect to the carboxyl groups of the carboxylic acid polymer, in consideration of the solubility in the developing solution and the film slip of the relief pattern. It is more preferably 0.5 to 1.0 molar equivalent.

Among the base-base generators used in the present invention, the base-base generator capable of undergoing an autolysis reaction by the base generated by the decomposition reaction newly generates a base serving as the catalyst. As the reaction progresses, the catalyst concentration increases and the reaction is promoted (self-promoting effect). From the viewpoint of the catalyst, the basic substance (catalyst) is generated by the decomposition reaction of the photobase generator by irradiation with electromagnetic waves, and increases in a self-amplifying manner by the decomposition reaction of the base-base generator. Therefore, the reaction does not stop in the middle of the reaction, which is essentially different from the chemical amplification reactions known so far, and it is a "self-amplification reaction".
Can be defined as Therefore, unlike the chemical amplification reaction which can be applied only to the catalytic reaction, it can be applied to the non-catalytic reaction such as the acid-base reaction of the present invention. Further, in a reaction in a solid such as a light-sensitive material, in a chemical amplification reaction, there is a limit to the deactivation of the catalyst in the course of the reaction and the diffusion distance of the catalyst, so that the reaction may not proceed or may not be completed. There were many. However, in the self-amplification reaction, the catalyst concentration increases with the progress of the reaction, so that the catalyst is not deactivated, and since one catalyst generated by electromagnetic waves does not need to diffuse in a wide range, the reaction is prompt, Moreover, it progresses quantitatively. Furthermore,
When the self-amplification reaction is combined with the catalytic reaction, a substance that causes the catalytic reaction is catalytically generated, which results in a double chemical amplification reaction, and the target reaction is achieved with a smaller irradiation dose.

Since a larger amount of base is generated by the base generated by the irradiation of electromagnetic waves, the exposed portion changes to basic by self-amplification. Therefore, a large amount of base can be generated in the system by a small amount of irradiation with a small amount of photobase generator. In a polymer containing a carboxyl group, it reacts with a large amount of generated base to form a carboxylate. Since the polymer containing the carboxylate salt behaves as an electrolyte, the solubility in water is increased, and water development between the unexposed area and the unexposed area becomes possible. On the other hand, in a carboxylic acid ester polymer and a hydroxyl group-protected phenolic polymer, irradiation with electromagnetic waves or a small amount of base generated by a base causes catalytic decomposition of a camboxyl group and a hydroxyl group-protecting group, resulting in a highly polar carbonyl group, Since the hydroxyl group is generated, the solubility in the aqueous solvent is improved only in the exposed portion.

[0070]

BEST MODE FOR CARRYING OUT THE INVENTION

(Example 1) 1-Hydroxy-1-methyl-2-butanone 20.4 g (200 mmol) of tetrahydrofuran (T
HF) solution (100 ml) at room temperature under nitrogen flow with stirring, 1.4 N methyllithium ether solution 13.6 m
1 (19.0 mmol) is added dropwise. After stirring at room temperature for 5 hours,
A solution of 17.1 g (203 mmol) 2-propylisocyanate in THF (30 ml) is slowly added dropwise. After heating under reflux for 10 hours, the mixture is left to stand until it reaches room temperature. After the solvent is distilled off, chloroform is added, washed with water and brine, dried over magnesium sulfate, and the solvent is distilled off. By recrystallization from a hexane solution, 2-acetyl-1-methylethyl-
15.0 g (40%) of N-isopropyl carbamate was obtained.

Oxydiphthalic acid dianhydride (ODPA) and an equivalent amount of diaminodiphenyl ether (DDE) were reacted in N-methyl-2-pyrrolidone (NMP) to obtain a polyamic acid solution having a solid content of 12% by weight. To this polyamic acid solution, 2.0 equivalents of triethylamine, 0.05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine, and 2.0 equivalents of ODPA were added. Equivalent of 1,1-dimethyl-2
-Phenylethyl-N-isopropyl carbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. By further heat-treating at 300 ° C. for 1 hour, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained. (Example 2) By the method of Example 1, 1-hydroxy-1-
1,1-dimethyl-2 instead of methyl-2-butanone
1-Dimethyl-2-cyanoethyl-N-isopropylcarbamate was synthesized by using -cyanoethanol (37%).

ODPA was added to the polyamic acid solution of Example 1.
To 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine;
0 equivalents of 1,1-dimethyl-2-cyanoethyl-N-
Isopropyl carbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating and dried at 80 ° C. to give a film thickness of 5 to 20 μm.
A film of Light from a high-pressure mercury lamp is passed through a light-shielding mask with a 365 nm bandpass filter to 100 mJ /
cm ^{2 was} irradiated. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. 1 at 300 ° C
By heat treatment for a time, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

Example 3 In the method of Example 1, 2-methylsulfonylethyl-N-isopropylcarbamate was prepared by using 2-methylsulfonylethanol instead of 1-hydroxy-1-methyl-2-butanone. Synthesized (29%).

ODPA was added to the polyamic acid solution of Example 1.
To 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine;
0 equivalent of 2-methylsulfonylethyl-N-isopropylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. By further heat-treating at 300 ° C for 1 hour, the thermal decomposition temperature is 450 ° C or higher.
It was possible to obtain a relief pattern having a tensile strength of kg / mm ² or more.

Example 4 The procedure of Example 1 was repeated except that 9-fluorenylmethanol was used in place of 1-hydroxy-1-methyl-2-butanone to obtain 9-fluorenylmethyl-N-isopropyl. Carbamate was synthesized (56%).

ODPA was added to the polyamic acid solution of Example 1.
To 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine;
0 equivalent of 9-fluorenylmethyl-N-isopropylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm.
Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. Further heat treatment at 300 ℃ for 1 hour, 15kg /
A relief pattern having a tensile strength of mm ² or more could be obtained.

(Example 5) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and an equivalent amount of diaminodiphenyl ether (DDE) were added to N-methyl-2.
-The reaction was carried out in pyrrolidone to obtain a polyamic acid solution having a solid content of 12% by weight. In this polyamic acid solution, OD
2.0 equivalents of triethylamine to PA, 0.05
An equivalent amount of N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine and 2.
0 equivalent of 9-fluorenylmethyl-N-isopropylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm.
Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. Further heat treatment at 300 ℃ for 1 hour, 15kg /
A relief pattern having a tensile strength of mm ² or more could be obtained.

Example 6 1,2,4,5-Cyclopentanetetracarboxylic dianhydride (CPDA) and an equivalent amount of diaminodiphenyl ether (DDE) were added to N-methyl-2.
-The reaction was carried out in pyrrolidone to obtain a polyamic acid solution having a solid content of 12% by weight. CP is added to this polyamic acid solution.
2.0 equivalents of triethylamine to DA, 0.05
An equivalent amount of N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine and 2.
0 equivalent of 9-fluorenylmethyl-N-isopropylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm.
Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 C for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. Further heat treatment at 300 ℃ for 1 hour, 15kg /
A relief pattern having a tensile strength of mm ² or more could be obtained.

Example 7 Oxydiphthalic acid dianhydride (ODPA) and an equivalent amount of phenylenediamine (PDA) were mixed with N 2.
-Methyl-2-pyrrolidone was reacted in a solid content of 1
A 2% by weight polyamic acid solution was obtained. To this polyamic acid solution, 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-
2-nitrophenyl) ethoxycarbonyl] isopropylamine and 2.0 equivalents of 9-fluorenylmethyl-N-
Isopropyl carbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating and dried at 80 ° C. to give a film thickness of 5 to 20 μm.
A film of Light from a high-pressure mercury lamp is passed through a light-shielding mask with a 365 nm bandpass filter to 100 mJ /
cm ^{2 was} irradiated. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. 1 at 300 ° C
By heat treatment for a time, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

Example 8 Oxydiphthalic acid dianhydride (ODPA) and an equivalent amount of p-xylylenediamine (XYDA) were mixed with N 2.
-Methyl-2-pyrrolidone was reacted in a solid content of 1
A 2% by weight polyamic acid solution was obtained. To this polyamic acid solution, 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-
2-nitrophenyl) ethoxycarbonyl] isopropylamine and 2.0 equivalents of 9-fluorenylmethyl-N-
Isopropyl carbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating and dried at 80 ° C. to give a film thickness of 5 to 20 μm.
A film of Light from a high-pressure mercury lamp is passed through a light-shielding mask with a 365 nm bandpass filter to 100 mJ /
cm ^{2 was} irradiated. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. 1 at 300 ° C
By heat treatment for a time, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

Example 9 In the polyamic acid solution of Example 1, 2.0 equivalents of diisopropylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-
2-nitrophenyl) ethoxycarbonyl] isopropylamine and 2.0 equivalents of 9-fluorenylmethyl-N-
Isopropyl carbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating and dried at 80 ° C. to give a film thickness of 5 to 20 μm.
A film of Light from a high-pressure mercury lamp is passed through a light-shielding mask with a 365 nm bandpass filter to 100 mJ /
cm ^{2 was} irradiated. After heating at 100 ° C. for 3 minutes and developing in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. 1 at 300 ° C
By heat treatment for a time, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

Example 10 The same experiment as in Example 1 was carried out by changing the developing solution to NMP, and as a result, a relief pattern could be obtained with almost no contact with the exposed dew part.
By further heat-treating at 300 ° C. for 1 hour, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

Example 11 4.36 g (20 mmol) of pyromellitic dianhydride and 6 ml of triethylamine (4
3 mmol, 4- (N, N-dimethylamino) pyridine 0.49 g (4 mmol) tetrahydrofuran (THF)
To 10 ml of the solution, 5.2 ml (50 mmol) of 1,1-dimethyl-2-cyanoethanol was added dropwise at room temperature, the mixture was stirred for 3 hours, 100 ml of THF was added, and crystals were obtained by filtration.
Add 100 ml of THF and 1N-HCl (30 ml x 3)
After washing with 30 ml × 4 brine and drying with magnesium sulfate, the solvent is distilled off. Recrystallization from a hexane solution gave 2.55 g (31%) of the corresponding p-pyromellitic acid dialkyl ester (pPMDE).

The obtained pPMDE (8.33 g, 20 mM)
l) and diaminodiphenyl ether (DDE) 4.00 g
(20 mmol) in the presence of N, N-dicyclohexylcarbodiimide (DCC) 8.25 g (40 mmol).
-Stirred in dimethylacetamide for 4 hours. After filtration,
The polyamic acid ester solid was obtained by dropping the filtrate into 3 l of ethanol. Polyamic acid ester having a solid content of 12% by weight, N-methyl-2-pyrrolidone (NM
P) solution was prepared and 0.1 equivalent of N- to DDE
[1- (2-Nitrophenyl) ethoxycarbonyl] octadecylamine and 0.5 equivalent of 1,1-dimethyl-
2-Cyanoethyl-N-octadecylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C. for 3 minutes and developing in NMD3 for 30 seconds, a relief pattern could be obtained with almost no contact with the unexposed rear part. By further heat-treating at 300 ° C. for 1 hour, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

(Embodiment 12) Using the method of Embodiment 11,
The corresponding polyamic acid ester solid was obtained by using 9-fluorenylmethanol instead of 1-dimethyl-2-cyanoethanol. Solid content 12% by weight
A solution of the polyamic acid ester of N-methyl-2-pyrrolidone (NMP) was prepared by adding 0.1 equivalent of N- [1- (2-nitrophenyl) ethoxycarbonyl] octadecylamine to DDE and 0.5 An equivalent amount of 1,1-dimethyl-2-cyanoethyl-N-octadecylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating,
It was dried at 0 ° C. to obtain a film having a film thickness of 5 to 20 μm. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. 100 ℃
After heating for 3 minutes in NMD3 and developing for 30 seconds in NMD3, a relief pattern could be obtained with almost no contact with the unexposed rear part. Further heat treatment at 300 ℃ for 1 hour, 15kg /
A relief pattern having a tensile strength of mm ² or more could be obtained.

Example 13 To a solution of 12 g (100 mmol) of polyhydroxystyrene (PHS) (Mw = 30,000) and 14 ml (110 mmol) of triethylamine in 10 ml of THF was added 9-fluorenylmethyl chloroformate 25. 9g (100mmol) THF solution (100m
l) was added dropwise, and after stirring for 10 minutes, 500 ml of THF was added, triethylamine hydrochloride was removed by filtration, and the filtrate was added dropwise to 5 l of methanol to give poly- (9-fluorenylmethoxycarbonyloxystyrene) (FmocPST).
21.5 g (63%) of a solid was obtained. Solid content of 20% by weight
A diglyme solution of FmocPST was prepared and the DDE was adjusted to 0.
1 equivalent of bis (1- (2-nitrophenyl) ethoxycarbonyl) hexanediamine and 0.5 equivalent of 1,1
-Dimethyl-2-cyanoethyl-N-octadecylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. 1
After heating at 00 ° C. for 3 minutes and developing in NMD3 for 30 seconds, a relief pattern could be obtained with almost no contact with the unexposed rear part. By further heat-treating at 300 ° C for 1 hour, the thermal decomposition temperature is 450 ° C or higher.
A relief pattern having a tensile strength of 5 kg / mm ² or more could be obtained.

Example 14 The procedure of Example 13 was repeated except that 9-fluorenylmethyl chloroformate was replaced with 4-nitrophenyl 1,1-dimethyl-2-cyanoethyl formate to give poly (1,2 1-Dimethyl-2-cyanoethoxycarbonyloxystyrene) (CocPST) solid 21.5
g (63%) was obtained. CocPST with a solid content of 20% by weight
Was prepared, and 0.1 equivalent of bis (1- (2-nitrophenyl) ethoxycarbonyl) hexanediamine and 0.5 equivalent of 1,1-dimethyl-2-cyanoethyl-N-based on DDE were prepared. Octadecyl carbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating,
It was dried at ℃ and a film having a film thickness of 5 to 20 µ was obtained. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C. for 3 minutes and developing in NMD3 for 30 seconds, a relief pattern could be obtained with almost no contact with the unexposed rear part. Further heat treatment at 300 ℃ for 1 hour, 15kg /
A relief pattern having a tensile strength of mm ² or more could be obtained.

(Example 15) 3,3'-dihydroxy-
4,4'-Diaminobiphenyl (HAB) and an equivalent amount of isophthalsan chloride (IPC) were stirred in DMAc for 4 hours, filtered, and the filtrate was added dropwise to 3 l of methanol to give the corresponding polybenzoxazole precursor. Got

By using the polybenzoxazole precursor instead of PHS in the method of Example 3, a poly (9-fluorenylmethoxycarbonyloxybenzoxazole precursor) (FmocPBO) solid was obtained. Got Solid content 10
A solution of wt% FmocPBO in NMP was prepared, and 0.1 equivalent of bis (1- (2-nitrophenyl) ethoxycarbonyl) hexanediamine to HAB and 0.5 equivalent of 1,1-dimethyl-2- Cyanoethyl-N-octadecylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C for 3 minutes, 30 in NMD3
After second development, a relief pattern could be obtained with almost no contact with the unexposed rear part. 300 ° C
By heat-treating for 1 hour, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

Example 16 The procedure of Example 15 was repeated except that 9-fluorenylmethyl chloroformate was replaced by 4-nitrophenyl 1,1-dimethyl-2-cyanoethyl formate to give poly (1,2 1-dimethyl-2-cyanoethoxycarbonyloxybenzoxazole precursor) (C
ocPBO) solid was obtained. An NMP solution of CocPBO having a solid content of 10% by weight was prepared, and 0.1 equivalent of bis (1- (2-nitrophenyl) ethoxycarbonyl) hexanediamine and 0.5 equivalent of 1,1-based on HAB were prepared. Dimethyl-2
-Cyanoethyl-N-octadecylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied on a glass substrate by a spin coating method and dried at 80 ° C. to obtain a film having a film thickness of 5 to 20 μm. Light from a high-pressure mercury lamp was irradiated with 100 mJ / cm ² through a light-shielding mask using a 365 nm bandpass filter. After heating at 100 ° C. for 3 minutes and developing in NMD3 for 30 seconds, a relief pattern could be obtained with almost no contact with the unexposed rear part. By further heat-treating at 300 ° C. for 1 hour, a relief pattern having a thermal decomposition temperature of 450 ° C. or more and a tensile strength of 15 kg / mm ² or more could be obtained.

[0091]

EFFECTS OF THE INVENTION According to the present invention, a positive photosensitive resin composition which can be developed with an aqueous solvent can be realized, and a film having a high sensitivity and a high film thickness relief pattern can be produced without problems of environmental pollution and working environment. I was able to get it.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08L 101/06 C08L 101/06 101/08 KAY 101/08 KAY G03F 7/004 503 G03F 7/004 503 7 / 038 504 7/038 504 (72) Inventor Yoshiaki Okabe 7-1-1 Omika-cho, Hitachi-shi, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Mina Ishida 7-1-1 Omika-cho, Hitachi-shi, Ibaraki No. 1 Hitachi Ltd., Hitachi Research Laboratory (72) Inventor Toshinori Hirano 7-1-1 Omika-cho, Hitachi City, Ibaraki Prefecture Hitachi Ltd. Hitachi Research Laboratory

Claims (24)

[Claims] 1. A carboxylic acid polymer represented by (Chemical formula 1) and having a molecular weight of 10,000 or more and 1,000,000 or less. (In the formula, R ₁ is an organic group having 2 to 40 carbon atoms, n is a positive integer between 10 and 20,000, and R ₂ is an organic group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom. 20% or more by weight based on the total amount of resin, secondary, and / or tertiary amine, and 0.0 to 2.0 molar equivalents to the carboxyl group of the carboxylic acid polymer, The photo-base generator that generates a base upon irradiation with electromagnetic waves is 0.01 to 0.5 molar equivalent to the carboxyl group of the carboxylic acid polymer, and the base-base generator that generates a base by a base is the above-mentioned. 0.1-based on the carboxyl group of the carboxylic acid polymer
A photosensitive resin composition comprising 2.0 molar equivalents. 2. The above (formula 1) is (formula 2) (In the formula, R ₃ is an organic group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom. R ₄ is an organic group having 2 to 20 carbon atoms, and R ₄ is an organic group having 4 to 20 carbon atoms. The photosensitive resin composition according to claim 1, wherein 3. A base-base generator that generates a base in the presence of a base and undergoes a self-decomposition reaction by the base, and a polymer characterized by having a catalytic reaction of the base to improve the solubility in an aqueous solvent. A photosensitive resin composition comprising: 4. A base-base generator which generates a base in the presence of a base and undergoes a self-decomposition reaction with the base, and a molecular weight of 100 represented by the formula (Chemical Formula 3) whose polarity is changed by the catalytic reaction of the base.
Carboxylic acid ester polymer of 00 or more and 1000000 or less (In the formula, R ₆ is an organic group having 2 to 40 carbon atoms, n is a positive integer between 10 and 20000, and R ₇ is an organic group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, R ₈ is an organic group having 1 to 30 carbon atoms), which is a photosensitive resin composition. 5. A carboxylic acid ester polymer represented by (Chemical Formula 3) having a molecular weight of 10,000 or more and 1,000,000 or less. (In the formula, R ₆ is an organic group having 2 to 40 carbon atoms, n is a positive integer between 10 and 20000, and R ₇ is an organic group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, R ₈ is an organic group having 1 to 30 carbon atoms) is 20% or more by weight with respect to the total amount of resin, and a photobase generator that generates a base upon irradiation with electromagnetic waves is used as an ester of the carboxylic acid ester polymer. 0.01 to 0.5 molar equivalents to the groups and a base-base generator that generates a base by a base are included in 0.1 to 2.0 molar equivalents to the ester groups of the carboxylic acid ester polymer. A photosensitive resin composition comprising: 6. The above (formula 3) is (formula 4) (In the formula, R ₉ is an organic group having 4 to 20 carbon atoms, R ₁₀ is any one of an organic group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom. R ₁₁ is an organic group having 2 to 20 carbon atoms. ) Is a photosensitive resin composition according to claim 5. 7. The above (Chemical formula 3) is (Chemical formula 5) (In the formula, R ₁₂ and R ₁₃ are an organic group having 1 to 12 carbon atoms, hydrogen,
It is one of the halogen atoms. Also, R ₁₄ has 1 to 1 carbon atoms.
20 organic groups or halogen atoms, and R ₁₅ is any of organic groups having 1 to 20 carbon atoms, hydrogen, and halogen atoms). 6. The photosensitive resin composition according to claim 5, wherein Stuff. 8. The photosensitive resin composition according to claim 5, wherein the chemical formula 3 is chemical formula 6. Embedded image 9. A hydroxyl-protected phenolic polymer represented by (Chemical formula 7) and having a molecular weight of 10,000 or more and 1,000,000 or less. (In the formula, R ₁₆ is an organic group having 2 to 40 carbon atoms, n is a positive integer between 10 and 20,000, and R ₁₇ is any one of an organic group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom, R ₁₈ is
Organic group having 1 to 30 carbon atoms) by weight based on the total amount of resin 2
0% or more, a photobase generator that generates a base upon irradiation with electromagnetic waves, 0.01 to 0.5 molar equivalents to the hydroxyl group of the hydroxyl group-protected phenol polymer, and a base-base that generates a base by a base A photosensitive resin composition comprising a generator in an amount of 0.1 to 2.0 molar equivalents based on the ester groups of the carboxylic acid ester polymer. 10. The above (Chemical formula 7) is (Chemical formula 8) (In the formula, R ₁₉ is an organic group having 4 to ₂₀ carbon atoms, R ₂₀ is an organic group having 1 to ₂₀ carbon atoms, a hydrogen atom or a halogen atom. R ₂₁ is an organic group having 2 to 20 carbon atoms. ] The photosensitive resin composition of Claim 9 characterized by these. 11. The photosensitive resin composition according to claim 8, wherein the chemical formula 7 is chemical formula 9. Embedded image 12. The photosensitive resin composition according to claim 8, wherein the chemical formula 7 is chemical formula 10. Embedded image 13. A polymer containing a carboxyl group and a secondary polymer,
Or / and a photosensitive resin composition containing a tertiary amine, a photobase generator, and a base-base generator, and capable of forming a pattern by electromagnetic wave irradiation. 14. A photosensitive resin composition comprising a polymer containing an alkoxycarbonyl group, a photobase generator, and a base-base generator and capable of forming a pattern by electromagnetic wave irradiation. 15. A photosensitive resin composition comprising a protected hydroxyl group-containing polymer, a photobase generator, and a base-base generator and capable of forming a pattern by electromagnetic wave irradiation. 16. A photobase generator is represented by the formula: (In the formula, R ₂₂ is any of an organic group having 1 to 10 carbon atoms, a hydrogen atom and a halogen atom. P is an integer of 0 to 4. R ₂₃ is hydrogen or has 1 to 10 carbon atoms. Organic groups,
R ₂₄ and R ₂₅ are each a hydrogen atom or an organic group having 1 to 12 carbon atoms). 16. The photosensitive resin composition according to claim 1, wherein 17. A base-base generator is represented by the formula: (Wherein, R ₂₆ is an organic group having 1 to 20 carbon atoms, or a halogen atom, R ₂₇ is either an organic group having 1 to 20 carbon atoms, hydrogen, halogen atoms. Also, R _28, R ₂₉ is hydrogen or an organic group having 1 to 12 carbon atoms, and R ₃₀ and R ₃₁ are hydrogen or an organic group having 1 to 20 carbon atoms). The photosensitive resin composition of. 18. A molecular weight of 10,000 represented by the chemical formula 1.
Carboxylic acid polymer of not less than 1,000,000 and not more than (In the formula, R ₁ is an organic group having 2 to 40 carbon atoms, n is a positive integer between 10 and 20000, and R ₂ is an organic group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom) Is 20% or more by weight with respect to the total amount of resin, and is a secondary, or / and 3
A secondary amine is used in an amount of 0.0 to 2.0 molar equivalents with respect to the carboxyl group of the carboxylic acid polymer, and a photobase generator that generates a base upon irradiation with electromagnetic waves is added to the carboxyl group of the carboxylic acid polymer. 0.01-0.5 molar equivalent and a base-base generator that generates a base with a base in a 0.1-2.0 molar equivalent with respect to the carboxyl group of the carboxylic acid polymer. A pattern forming method comprising: a step of applying an object on a substrate and drying, a step of irradiating an electromagnetic wave through a light-shielding mask, and a step of developing. 19. A molecular weight of 10,000 represented by the chemical formula 3.
The following carboxylic acid ester polymers of 1,000,000 or less are 20% or more by weight based on the total amount of resin, a photobase generator that generates a base upon irradiation with electromagnetic waves is added in an amount of 0.01 to 2.0 molar equivalents to the ester group of the carboxylic acid ester polymer, and A base-base generator that generates a base,
A step of applying a photosensitive resin composition containing 0.1 to 2.0 molar equivalents to the ester group of the carboxylic acid ester polymer on a substrate and drying, a step of irradiating an electromagnetic wave through a light-shielding mask, a development A method of forming a pattern, comprising: 20. A molecular weight of 10,000 represented by the chemical formula 7.
Not less than 1,000,000 and not more than 10000 hydroxyl protected phenolic polymers 20% or more by weight with respect to the total amount of resin, a photobase generator that generates a base upon irradiation with electromagnetic waves, 0.01 to 2.0 molar equivalents to the hydroxyl groups of the hydroxyl group-protected phenol polymer, and a base. A base-base generator that generates a base by
The hydroxyl group of the hydroxyl group-protected phenolic polymer is 0.
A method for forming a pattern, which comprises the steps of coating a substrate with a photosensitive resin composition containing 1 to 2.0 molar equivalents and drying it, irradiating electromagnetic waves through a light-shielding mask, and developing. 21. A photobase generator is represented by the formula: The pattern forming method according to any one of claims 18 to 20, wherein 22. The base-base generator is represented by the formula: 24. The pattern forming method according to claim 18, further comprising a base-base generator represented by: 23. The photobase generator is an α-ketocarboxylic acid ammonium salt, a phenylglyoxylic acid ammonium salt,
At least 1 sort (s) of 4-methylphenyl sulfonamide and N-cyclohexyl-4-methylphenyl sulfonamide is used, The photosensitive resin composition in any one of Claims 1-15 characterized by the above-mentioned. 24. The photobase generator is an α-ketocarboxylic acid ammonium salt, a phenylglyoxy acid ammonium salt,
21. The pattern forming method according to claim 18, wherein at least one of 4-methylphenyl sulfonamide and N-cyclohexyl-4-methylphenyl sulfonamide is used.