JP2000199958A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive resin composition develable in an aqueous solution of alkali in a short time and high in transparency by incorporating a specified polymer and a photoacid-generator. SOLUTION: The photosensitive resin composition contains the polymer composed essentially of structural units represented by the formula and the photoacid generator, and a pattern can be formed by irradiation with light and the following development, and the polymer has carboxyl groups in an amount of 0.02-2.0 mmol per 1 g of the polymer. In the formula, R1 is a >=2C organic group having 3-8 valences; R2 is a >=2C organic group having 2-6 valences; R3 is an H atom or a 1-20C organic group and all of R3 are not an H atom at the same time; (n) is an integer of 3-100,000 (m) is 1 or 2; and (q) is an integer of 0-4 and p+q>0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applicable to an interlayer insulating film, a buffer coat film, an α-ray shielding film and the like of a semiconductor element and the like. The present invention relates to a photosensitive resin composition capable of forming a polymer.

[0002]

2. Description of the Related Art Hitherto, heat-resistant resins such as polyimide have been widely used as surface protective films and interlayer insulating films of semiconductor devices. When polyimide is used as a surface protective film, an interlayer insulating film, or the like, it is necessary to pattern the polyimide film for the purpose of forming through holes.
For example, a solution of a polyamic acid, which is a polyimide precursor, is applied to a substrate, converted to polyimide by heat treatment, and then a relief pattern of a positive photoresist is formed on the polyimide film, and hydrazine-based etching is performed using this as a mask. Pattern processing is performed by selectively etching the polyimide film with an agent. However, the above-described patterning of polyimide involves a complicated process because it involves steps such as application and stripping of a photoresist. Further, there is a problem that dimensional accuracy is reduced due to side etching. For these reasons, a photosensitive resin composition which is a heat-resistant resin or a precursor which can be converted into a heat-resistant resin by heat treatment or the like and which itself can be subjected to pattern processing has been studied.

[0003] Since the photosensitive resin composition has a pattern precision that can be adapted to the pattern formation of the passivation film,
First, a method of performing pattern processing and curing of the photosensitive resin composition on the passivation film before pattern formation, and then performing dry etching of the underlying passivation film using this pattern as a mask has been studied (collective opening). Law). According to this method, the process required for forming the pattern of the passivation film can be omitted, leading to cost reduction.

[0004] In using the photosensitive resin composition, it is usually applied to a substrate in a solution state, dried, and irradiated with actinic rays through a mask. Examples of the negative photosensitive resin composition in which an exposed portion remains after development include a polyamide acid obtained by adding a carbon-carbon double bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation ( Tokiko Sho 59
JP-A-52822), a product obtained by adding acrylamides to a polyamic acid (JP-A-3-170555),
A polyimide precursor containing a carbon-carbon double bond group, a specific oxime compound, and a sensitizer (Japanese Patent Application Laid-Open No. 61-118423) is known. However, when switching from the conventional non-photosensitive resin composition patterning process using a positive photoresist to a process using a negative photosensitive resin composition, changing the mask of the exposure apparatus and the development equipment There was a problem that needed to be changed. In addition, these negative photosensitive resin compositions use an organic solvent for development, but from the viewpoint of preventing environmental pollution and improving the working environment, a photosensitive material that can be developed with an aqueous developer instead of an organic developer is desired. Was rare. For these reasons, a positive photosensitive resin composition that can be alkali-developed has been studied.

[0005] Positive photosensitive resin compositions in which the exposed portions are dissolved by development with an aqueous alkali solution include o
A polyimide precursor having a nitrobenzyl group introduced through an ester bond (JP-A-60-37550), a mixture of a polyamic acid ester and an o-quinonediazide compound (JP-A-2-181149), and a phenolic hydroxyl group. Polyamide acid or polyamic acid ester having o-quinonediazide compound mixed therein (JP-A-3-115461), and polyimide having phenolic hydroxyl group mixed with o-quinonediazide compound (JP-A-3-177455). And a mixture of polyhydroxyamide and an o-quinonediazide compound (Japanese Patent Publication No. 1-46862).

However, the polyimide precursor having an o-nitrobenzyl group introduced through an ester bond has a problem in that the photosensitive wavelength is mainly 300 nm or less and the sensitivity is low. A mixture of a polyamic acid ester and an o-quinonediazide compound has a problem in that the sensitivity is low and the development time is long because the dissolution rate in an alkali developing solution is low. A mixture of a polyamic acid having a phenolic hydroxyl group and an o-quinonediazide compound,
There is a problem in that it can be applied only to a dilute developer because the solubility in an alkali developer is too large, and that it is difficult to process a fine pattern because an unexposed portion swells with the developer. A mixture of a polyamic acid or polyimide having a phenolic hydroxyl group and an o-quinonediazide compound improved the dissolution rate in an alkali developer, but had a problem in that it was difficult to control the dissolution rate. O- to polyhydroxyamide
The mixture containing a quinonediazide compound also improved the dissolution rate in an alkali developer, but had a problem in that the polymer composition had to be changed in order to further control the dissolution rate.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition which can be developed in an alkaline solution in a short time, has high transparency, and has high sensitivity.

[0008]

The present invention comprises (a) a polymer having a structural unit as a main component in which a bond between structural units is represented by the general formula (1) and (b) a photoacid generator. A positive photosensitive resin composition characterized by being capable of forming a pattern by light irradiation and subsequent development, wherein the total carboxyl groups contained in 1 g of the polymer are 0.02 mmol or more and 2.0 mmol or less. Things.

[0009]

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(R1 is a trivalent to octavalent organic group having at least 2 or more carbon atoms, R2 is a divalent to hexavalent organic group having at least 2 or more carbon atoms, R3 is hydrogen, or Represents an organic group having 1 to 20 carbon atoms, not all being hydrogen, n represents an integer of 3 to 100,000, m represents 1 or 2, p, q represents an integer of 0 to 4, and p + q > 0.)

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a polymer represented by the general formula (1) is heated or heated by a suitable catalyst.
It can be a polymer having an imide ring, an oxazole ring, or another cyclic structure. By having a ring structure,
Heat resistance and solvent resistance are dramatically improved. The polymer having the structural unit represented by the general formula (1) as a main component is:
It preferably has a hydroxyl group. In this case, due to the presence of the hydroxyl group, the solubility in an aqueous alkali solution becomes better than that of a polyamic acid having no hydroxyl group. In particular, among the hydroxyl groups, phenolic hydroxyl groups are preferable from the viewpoint of solubility in an aqueous alkaline solution.

In the general formula (1), the residue constituting R1 represents a structural component of an acid, and this acid component contains an aromatic ring and has 1 to 4 hydroxyl groups. Number 2-6
A trivalent to octavalent group of 0 is preferred. When R1 does not contain a hydroxyl group, the R2 component desirably contains 1 to 4 hydroxyl groups. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond. Examples of such a structure include those having the following structures, but the present invention is not limited thereto.

[0013]

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Further, as the residue containing R1, a tetracarboxylic acid, tricarboxylic acid or dicarboxylic acid having no hydroxyl group can be used. Examples of these include:
Aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and diester compounds in which two carboxyl groups are converted to methyl groups or ethyl groups, butanetetra Aliphatic tetracarboxylic acids such as carboxylic acid and cyclopentanetetracarboxylic acid, diester compounds in which two carboxyl groups are converted to methyl or ethyl groups, and aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, and naphthalene tricarboxylic acid Can be mentioned.

In the general formula (1), the residue constituting R2 represents a structural component of diamine. Among them, preferred examples of R2 are those having an aromatic group and having 1 to 4 hydroxyl groups from the viewpoint of heat resistance of the obtained polymer. When R2 does not contain a hydroxyl group, it is desirable that the R1 component contains 1 to 4 hydroxyl groups. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond.

Specific examples include compounds such as bis (aminohydroxyphenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, diaminophenol and dihydroxybenzene, and those having the structures shown below. Can be

[0017]

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Further, a diamine containing no hydroxyl group can be used as the residue containing R2 in the general formula (1).
Such examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and aromatics thereof. Aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like, such as compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom, may be mentioned. These diamine compounds are used alone or in combination of two or more. They are,
It is preferable to use not more than 40 mol% of the diamine component. 40
If the copolymerization is at least mol%, the heat resistance of the obtained polymer will be reduced.

For the purpose of improving the adhesion to the substrate, a diamine compound having a siloxane structure can be used as long as the heat resistance is not reduced. Examples of the diamine compound having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane, bis (3-aminopropyl) tetraphenyldisiloxane, and bis (4
-Aminophenyl) tetramethyldisiloxane and the like are used.

R3 in the general formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. R3 has 20 carbon atoms
If it exceeds, it will not be dissolved in an alkaline aqueous solution. R3 is preferably an organic group from the viewpoint of the stability of the obtained photosensitive resin solution, but is preferably hydrogen from the viewpoint of the solubility of the aqueous alkali solution. That is, it is not preferable that R3 be all hydrogen or all organic groups. By controlling the amount of hydrogen and the organic group of R3, the dissolution rate in an alkaline aqueous solution changes, so that a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. From this fact, the carboxyl group in the polymer is 0.1 g / g of the polymer.
Preferably, it is contained in an amount of from 02 mmol to 2.0 mmol. More preferably 0.05 mmol or more and 1.5 m
mol or less. If it is less than 0.02 mmol, the solubility in the developing solution is too small, and if it is more than 2.0 mmol, the difference in dissolution rate between the exposed part and the unexposed part is difficult to be obtained. m represents 1 or 2, p and q are integers from 0 to 4, and p + q> 0. When p is 5 or more, the properties of the obtained heat-resistant resin film deteriorate.

It is also possible to control the amount of residual carboxyl groups by imidizing some of the carboxyl groups. As the imidation method, a known method may be used as long as the imidization can be performed. The imidation ratio at this time is preferably 1% or more and 50% or less. If the imidation ratio exceeds 50%, the absorption of the polymer by actinic radiation used for exposure increases, and the sensitivity decreases.

It is desirable that the polymer represented by the general formula (1) is as transparent as possible to actinic radiation to be exposed. Therefore, the absorbance of the polymer at 365 nm is preferably 0.1 or less per 1 μm. It is more preferably 0.08 or less. It is 365 when it exceeds 0.1
The sensitivity to exposure to nm actinic radiation is reduced.

The positive photosensitive resin composition of the present invention may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. There may be. In this case, it is preferable that the content of the structural unit represented by the general formula (1) is 90 mol% or more.
The type and amount of the structural unit used in the copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide-based polymer obtained by the final heat-treated film.

The polymer having a structural unit represented by the general formula (2) of the present invention as a main component is synthesized by a known method. For example, a method of reacting a tetracarboxylic dianhydride with a diamine compound at a low temperature (CE Sroog et al.,
Journal Polymer Science,
Part A-3, 1373 (1965)).

The polymer represented by the general formula (1) is obtained by esterifying a carboxyl group in the polymer represented by the general formula (2) with an acetal or ketal compound represented by the general formula (3) or (4). It can be obtained by a chemical treatment.

In the polymer represented by the general formula (1), the carboxyl group in the polymer represented by the general formula (2) is formed by a vinyl ether compound represented by the general formula (5) or a vinyl ether compound and an acid catalyst. It can be obtained by esterification.

In the general formula (3), R4 represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R5 represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, or an oxygen-containing group. R6 represents a monovalent organic group having 1 or more carbon atoms, and R7 represents a divalent organic group having 1 or more carbon atoms, and nitrogen-containing one of the general formulas (3) and (4). Shows either an organic group or an oxygen-containing organic group. Specifically, N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dibutyl acetal, N, N-dimethylformamide dibenzyl Acetal, N, N-dimethylformamide bis [2- (trimethylsilyl) ethyl] acetal, N, N-dimethylacetamide diethylacetal, trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthobutyrate, orthobutyric acid Triethyl, trimethyl orthobenzoate, triethyl orthobenzoate, 1,3-dimethylimidozolidinone dialkyl acetal, ethylene dialkyl acetal carbonate, propylene carbonate Dialkyl acetal, γ-butyrolactone dialkyl acetal, etc., preferably N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dibutyl Acetal, N, N-dimethylformamide dibenzyl acetal, N-methyl-2-pyrrolidone dimethyl acetal, N-methyl-2-pyrrolidone diethyl acetal, γ-butyrolactone dimethyl acetal, γ
-Butyrolactone diethyl acetal.

R8 in the general formula (5) represents a monovalent organic group having 1 or more carbon atoms. Specifically, methyl vinyl ether,
Ethyl vinyl ether, n-propyl vinyl ether,
Examples include, but are not limited to, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, and the like. Preferably, tert-butyl vinyl ether, cyclohexyl vinyl ether, and isopropyl vinyl ether are used.

Esterification treatment of the polymer represented by the general formula (2) with the compound represented by the general formula (3) or (4), or esterification treatment with the compound represented by the general formula (5) In this case, an imidization reaction also proceeds as a side reaction, but the ratio of the imidization reaction to the esterification reaction can be suppressed by selecting reaction conditions, that is, selecting a reaction solvent, a reaction temperature, and the like.

The reaction solvent for the esterification treatment of the polymer represented by the general formula (2) with the compound represented by the general formula (3) or (4) is N-methyl-2.
Aprotic polar solvents such as -pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethylimidozolidinone, hexamethylphosphoramide, γ-butyrolactone are preferred. , N-methyl-2-pyrrolidone,
N, N-dimethylformamide and N, N-dimethylacetamide are more preferred. The esterification reaction temperature is 0 ° C
To 150 ° C, preferably from 20 ° C to 10 ° C.
The temperature is 0 ° C, more preferably 30 ° C to 80 ° C.
If the reaction temperature is lower than 0 ° C., the time required for the reaction to be completed becomes long, which is not practical. When the reaction temperature is 15
When the temperature exceeds 0 ° C., the rate of the imidization reaction increases, and problems such as a decrease in the transparency of the polymer and generation of a gel component are likely to occur. In the esterification treatment with the compound represented by the general formula (3) or (4), trifluoroacetic acid, p-toluenesulfonic acid,
Acids such as methanesulfonic acid and bases such as triethylamine and pyridine can also be used in the range of 0.01 to 10 mol%.

The esterification of the polymer represented by the general formula (2) with the compound represented by the general formula (3) or the general formula (4) is carried out by applying a solution obtained by dissolving the general formula (2) in an organic solvent. It is carried out by mixing and stirring the compounds represented by the formula (3) and the general formula (4). The solvent used in the synthesis of the polymer of the general formula (2) and the polymer are represented by the general formula (3)
And when the solvent used for the esterification treatment with the compound represented by the general formula (4) is the same, the compound represented by the general formula (3) or (4) is mixed and stirred into the solution after polymerization. By doing so, the processing can be performed.

When the polymer represented by the general formula (2) is esterified with the compound represented by the general formula (5) or the compound represented by the general formula (5) by an acid catalyst, a side reaction occurs. Although the cationic polymerization of vinyl ether also proceeds, the ratio of the cationic polymerization reaction to the esterification reaction can be suppressed by selecting vinyl ether and an acid catalyst, selecting reaction conditions, that is, selecting a reaction solvent and a reaction temperature. .

The polymer represented by the general formula (2) is selectively reacted with a compound represented by the general formula (5) or a compound represented by the general formula (5) by an esterification treatment with an acid catalyst. For the purpose of accelerating, an acid catalyst can be used in the range of 0.01 to 10 mol% based on the carboxyl group. Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and oxalic acid. Preferably, phosphoric acid or oxalic acid having a large pKa value is used. This is probably because an acid catalyst having a higher pKa value generates a counter anion having a higher nucleophilicity and suppresses the cationic polymerization reaction. In addition, amines such as triethylamine and pyridine can also be used as a reaction promoting catalyst.

The polymer represented by the general formula (2) is converted into a compound represented by the general formula (5) or a compound represented by the general formula (5) as a reaction solvent for esterification with an acid catalyst. N-methyl-2-pyrrolidone (NMP), N,
An aprotic polar solvent such as N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethylimidozolidinone, hexamethylphosphoramide, γ-butyrolactone is preferred, and N-methyl-2-pyrrolidone is preferred. , N, N-dimethylformamide and N, N-dimethylacetamide are more preferred. The reaction temperature ranges from -10 ° C to 80 ° C, preferably from 0 ° C to 40 ° C, more preferably from 10 ° C to 3 ° C.
0 ° C. If the reaction temperature is lower than −10 ° C., the time until the reaction is completed becomes long, which is not practical. On the other hand, when the reaction temperature exceeds 80 ° C., the ratio of the cationic polymerization reaction of vinyl ether becomes high, and problems such as a decrease in polymer transparency, generation of a gel component, and a decrease in physical properties of a cured film are likely to occur.

The esterification treatment of the polymer represented by the general formula (2) with the compound represented by the general formula (5) or the compound represented by the general formula (5) with an acid catalyst is carried out according to the general formula (2) This is carried out by mixing and stirring a compound represented by the general formula (5) and an acid catalyst in a solution in which is dissolved in an organic solvent. When the solvent used for synthesizing the polymer represented by the general formula (2) and the solvent used for esterifying the polymer are the same, the compound represented by the general formula (5) is added to the solution after polymerization. Alternatively, the treatment can be carried out by mixing and stirring the acid catalyst.

The photoacid generator used in the present invention includes diazonium salts, diazoquinonesulfonic acid amides, diazoquinonesulfonic acid esters, diazoquinonesulfonic acid salts, and the like.
Nitrobenzyl esters, onium salts, halides,
Compounds which are decomposed by light irradiation to generate an acid, such as halogenated isocyanate, halogenated triazine, bisarylsulfonyldiazomethane, disulfone and the like. In particular, an o-quinonediazide compound is desirable because it has an effect of suppressing the water solubility of an unexposed portion. Such compounds include 1,2-benzoquinone-2-azido-4-sulfonic acid ester or sulfonic acid amide, 1,2-naphthoquinone-2-diazido-5-sulfonic acid ester or sulfonic acid amide, -Naphthoquinone-2-diazide-4-sulfonic acid ester or sulfonic acid amide. These include, for example, 1,2-benzoquinone-2-azido-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and the like. By subjecting o-quinonediazidosulfonyl chlorides to a polyhydroxy compound or a polyamine compound in the presence of a dehydrochlorination catalyst.

Examples of the polyhydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-
Bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,
3,4,4'-tetrahydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, tris (4-hydroxyphenyl) methane, 1,1,1-
Tris (4-hydroxyphenyl) ethane, 1- [1-
(4-hydroxyphenyl) isopropyl] -4-
[1,1-bis (4-hydroxyphenyl) ethyl] benzene, methyl gallate, ethyl gallate and the like.

As the polyamine compound, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide and the like.

Examples of the polyhydroxypolyamine compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine.

The o-quinonediazide compound is preferably from 5 to 100 parts by weight, more preferably from 10 to 40 parts by weight, per 100 parts by weight of the polymer represented by the general formula (1).
It is blended in the range of parts by weight. If the amount is less than 5 parts by weight, sufficient sensitivity cannot be obtained, and if it exceeds 100 parts by weight, the heat resistance of the resin composition may be reduced.

In the positive photosensitive resin composition of the present invention, the polymer represented by the general formula (2) is represented by the general formula (3) and the general formula (4) or the general formula (5) and the acid catalyst. It is preferable to dissolve the polymer represented by the general formula (1) obtained by esterification with the compound to be obtained and the photoacid generator in a solvent, and use them in a solution state. Examples of the solvent include non-solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethylimidozolidinone, hexamethylphosphoramide, and γ-butyrolactone. Protic polar solvents are used alone or in combination of two or more.

If necessary, a surfactant may be used for the purpose of improving the coating property between the photosensitive precursor composition and the substrate.
Esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. Also, silicon dioxide, 2
Inorganic particles such as titanium oxide or powder of polyimide can also be added.

Further, in order to enhance the adhesiveness to an underlying substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent or the like is added to the varnish of the photosensitive resin composition in an amount of 0.5%.
To 10 parts by weight, or the base substrate can be pre-treated with such a chemical solution.

When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent and an aluminum chelating agent are added in an amount of 0.5 to 10% by weight based on the polymer in the varnish. Parts.

When treating the substrate, the above-mentioned coupling agent is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like. The solution in which 5 to 20 parts by weight are dissolved is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. In some cases, then 50 ° C to 300 ° C
The reaction between the substrate and the coupling agent proceeds by applying a temperature up to

Next, a method for forming a heat-resistant resin pattern using the photosensitive resin composition of the present invention will be described.

The photosensitive resin composition of the present invention is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Spin coating using a spinner as a coating method,
There are methods such as spray coating and roll coating.
The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like.
To 150 μm.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays or the like at a temperature of 50 ° C to 150 ° C for 1 minute to several hours.

Next, the film is exposed to actinic radiation through a mask having a desired pattern and exposed. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X rays.
In the present invention, the i-line (365n
m), h-line (405 nm) and g-line (436 nm) are preferably used.

The pattern of the heat-resistant resin is formed by removing the exposed portion using a developer after exposure. As a developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamine An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine is preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Even if alcohols such as isopropanol, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone are used alone or in combination of several kinds. Good. After development, it is rinsed with water. Here, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and acids such as carbon dioxide, hydrochloric acid and acetic acid to water.

After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 ° C. to 500 ° C. This heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

The heat-resistant resin film formed by the photosensitive resin composition according to the present invention can be used as a semiconductor passivation film,
It is used for applications such as protective films for semiconductor devices and interlayer insulating films for multilayer wiring for high-density mounting.

[0053]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Measurement method of characteristics Measurement of film thickness Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.
Was used and the measurement was performed at a refractive index of 1.64.

Measurement of Absorbance The polymer solution was applied to a glass substrate (manufactured by Matsunami Glass) having a size of 5 cm × 5 cm and a thickness of 1.2 mm so that the film thickness after pre-baking was about 10 μm, and a hot plate (Dainippon) at 120 ° C. for 3 minutes Prebaked with SCW-636 manufactured by Screen. The absorbance at 365 nm of this film was measured using UV-240 manufactured by Shimadzu Corporation, and the absorbance per 1 μm of film thickness was determined by dividing the film by the actual film thickness.

Measurement of imidation ratio The polymer solution was applied to a 4-inch silicon wafer so that the film thickness after pre-baking was about 7 μm, and was heated at 120 ° C. for 3 minutes on a hot plate (SCW-6 manufactured by Dainippon Screen).
36) Prebaked. First, background measurement was performed using a 4-inch silicon wafer on which the polymer solution was not applied as a reference. Subsequently, the infrared absorption spectra of the film before and after thermal curing were measured by using FT-7 manufactured by Horiba, Ltd.
20. Then, using an inert oven INH-21CD manufactured by Koyo Lindberg Co., 200 ° C.
After 30 minutes of heat treatment, the temperature was raised to 350 ° C. over 1 hour,
Heat treatment was performed at 350 ° C. for 1 hour to completely imidize. The infrared absorption spectrum of this sample was measured, and the imidization ratio was determined from the ratio of the peak (1380 cm ^-1 ) of the CN stretching vibration derived from the imide bond before and after the cure imidization treatment. That is, assuming that the peak value at 1380 cm ^-1 before the 350 ° C. treatment is A and the peak value at 1380 cm ⁻¹ of the sample after the 350 ° C. treatment is B, the imidation ratio I is I = A / B
× 100.

Measurement of Residual Carboxyl Group Concentration (Quantitative Determination of Carboxyl Group in Polymer) The polymer solution was dropped into pure water to precipitate the polymer.
It was dried under reduced pressure at 0 ° C. for 48 hours. 0.5 g of dry polymer
With 40 ml of N-methyl-2-pyrrolidone (NMP),
Dissolve in 10 ml of methanol and use Shibata Scientific Instrument Engineering F
The free carboxyl group in the polymer was titrated with a 1/10 normal methanol solution of tetrabutylammonium hydroxide using Model 702 to determine the content. Polymer 1
The carboxyl group per g can be obtained by calculating the molar amount of tetrabutylammonium hydroxide required for this neutralization, assuming that a 1/10 normal tetrabutylammonium hydroxide methanol solution required to reach the neutralization point in this titration is xml. , X / 10 mmol. Since this molar amount is equal to the amount of carboxyl groups per 0.5 g of polymer, the carboxyl groups per g of polymer can be obtained by dividing by 0.5, so that x / 10 / 0.5, that is, x / 5 (Mmol).

Measurement of Residual Sodium, Potassium and Iron Ions 2 g of a dried sample was weighed, and a solution diluted with 25 ml of NMP was measured using a Z8000 Zeerman atomic absorption spectrophotometer manufactured by Hitachi, Ltd. For calibration of the concentration, a standard concentration solution of each ion was used. When the content of these metal ions is 10 ppm or more, when used as a coating agent, there is a risk of corrosion, which is a problem.

Measurement of Concentration of Residual Chloride Ion 100 mg of the dried sample was weighed, dispersed in 20 ml of water, and subjected to ultrasonic wave for 2 hours using an ultrasonic cleaner (B20H manufactured by BRANAON) to extract chloride ions. This was measured with a chlorine ion electrode (8002 manufactured by Horiba, Ltd.) using an ion meter N-8M manufactured by Horiba, Ltd. Calibration of the chloride ion concentration used an aqueous solution of potassium chloride with a known concentration. If the chlorine ion content is 30 ppm or more, when used as a coating agent or the like, there is a risk of corrosion and a problem.

Resolution The prebaked film formed on the silicon wafer was exposed through a mask having various widths, and when developed, the resolution was defined as the minimum width in which the pattern of the exposed portion after development was completely dissolved. Therefore, the smaller the width,
It is possible to obtain a finer pattern and determine that the resolution is good.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) under a stream of dry nitrogen
18.3 g (0.05 mol) and 34.2 g (0.3 mol) of allyl glycidyl ether were dissolved in 100 g of gamma-butyrolactone (GBL) and cooled to -15 ° C. Here, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After dropping, 0 ° C
For 4 hours.

This solution was concentrated by a rotary evaporator and added to 1 liter of toluene to obtain an acid anhydride. This is shown below. The resulting material did not show a clear melting point up to 350 ° C.

[0062]

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Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (1) 18.3 g (0.05 mol) of BAHF was added to acetone 10
0ml, propylene oxide 17.4g (0.3mo
1) and cooled to -15 ° C. A solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at −15 ° C. for 4 hours, and then returned to room temperature. The solution was concentrated by a rotary evaporator, and the obtained solid was recrystallized from a solution of tetrahydrofuran and ethanol.

The solid collected by recrystallization was mixed with 100 parts of ethanol.
dissolved in 300 ml of tetrahydrofuran and 5 ml of
2 g of palladium-carbon was added and stirred vigorously.
Here, hydrogen was introduced by a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon did not deflate any more, and the reaction was terminated. After completion of the reaction, the mixture was filtered to remove the palladium compound as a catalyst, and concentrated by a rotary evaporator to obtain a diamine compound. This is shown below.
The obtained solid was used for the reaction as it was.

[0065]

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Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (2) 30.8 g of 2-amino-4-nitrophenol (0.2
mol) in 200 ml of acetone, propylene oxide 6
It was dissolved in 0 g (0.68 mol) and cooled to -15 ° C. Here, 22.4 g (0.11 g of isophthalic acid chloride)
mol) was dissolved dropwise in 200 ml of acetone. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

30 g of the dried precipitate and 5% palladium-
3 g of carbon were added to a 500 ml autoclave together with 400 ml of methyl cellosolve. This was pressurized with hydrogen so that the internal pressure became 8 kgf / cm 2, and the mixture was stirred at 80 ° C. for 2 hours. Then, when the temperature of the solution became 50 ° C. or less, the pressure was released, and the precipitate was removed by filtration. The filtrate was concentrated on a rotary evaporator and the resulting solid was collected. This was dried in a vacuum dryer at 50 ° C. for 20 hours.
The structure is shown below.

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Synthesis Example 4 Synthesis of hydroxyl-containing diamine (3) 15.4 g of 2-amino-4-nitrophenol (0.1
mol) in acetone 80 ml, propylene oxide 30
g (0.34 mol) and cooled to -15 ° C. Here, 19.5 g of 3-nitrobenzoyl chloride
(0.105 mol) in 80 ml of acetone was slowly dropped. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

25 g of the dried solid and 2 g of 5% palladium-carbon were added to a 500 ml autoclave together with 300 ml of methyl cellosolve. Thereafter, a precipitate of the desired product was obtained in the same manner as in Synthesis Example 23. This was dried in a vacuum dryer at 50 ° C. for 20 hours. The structure is shown below.

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Synthesis Example 5 Synthesis of naphthoquinonediazide compound 20.2 g of 1,1,2-tri (3,5-dimethyl-4-hydroxyphenyl) propane (0.
05 mol) and 40.3 g (0.15 mol) of 5-naphthoquinonediazidosulfonyl chloride were dissolved in 400 g of 1,4-dioxane and heated to 40.degree. Here, 15.2 g (0.15 mol) of triethylamine mixed with 40 g of 1,4-dioxane was added at a temperature of 4 in the system.
The solution was dropped so as not to reach 5 ° C. or higher. 2 at 40 ° C after dropping
Stirred for hours. The by-product triethylamine hydrochloride was filtered, and the filtrate was poured into 3 liters of 1% hydrochloric acid. Thereafter, the deposited precipitate was collected by filtration. This precipitate was washed twice with 10 l of water and dried in a vacuum dryer at 50 ° C. for 20 hours.
A naphthoquinonediazide compound was obtained. The structure of the obtained compound is shown below.

[0073]

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Example 1 20.0 g (100 mmol) of 4,4'-diaminodiphenyl ether was placed in a 1-liter four-necked flask under a stream of dry nitrogen.
l) was dissolved in 350 g of NMP. Here, 71.4 g (100 mmol) of the acid anhydride synthesized in Synthesis Example 1 was added to GB
L was added together with 40 g, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Further, 23.8 g of N, N-dimethylformamide dimethyl acetal (200
mmol) and stirred at 50 ° C. for 5 hours to obtain a partially esterified polymer solution. The carboxyl group in 1 g of this polymer was 0.07 mmol, and the imidation ratio was 10%.
And the absorbance at 365 nm is 0.083 per μm.
Met.

To 100 g of the obtained solution, 3 mol of 1,2-naphthoquinone-2-diazide-5-flufonyl chloride was added to 1 mol of the quinonediazide compound 4NT-300 (1 mol of 2,3,4,4′-tetrahydroxybinzophenone).
Was added to obtain a solution of the photosensitive resin composition.

The above solution was applied onto a 6-inch silicon wafer so that the film thickness after pre-baking was 7 μm, and then a hot plate (SKW-6 manufactured by Dainippon Screen Co., Ltd.) was used.
36), a prebaking was performed at 120 ° C. for 3 minutes to obtain a photosensitive resin precursor film. Next, an exposure machine (Nikon i-line stepper NSR-1755-i7A)
And the reticle with the pattern cut is set to 50 mJ / cm ² from 100 mJ / cm ² to 800 mJ / cm ^2.
I-ray exposure was performed at intervals of / cm ² . After that, NMD-
3 (tetramethylammonium hydroxide 2.38%
Aqueous solution: manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 100 seconds, and further washed with water for 20 seconds to form a pattern.

As shown in Table 1, the film thickness of the unexposed portion after development was 5.6 μm (residual film ratio: 80%), and the reduction in film thickness by development was 1.4 μm. Further, the minimum light irradiation amount at the time of pattern formation was as small as 300 mJ / cm ² and the sensitivity was good. Further, when the cross section of the pattern was observed with an electron microscope, a 5 μm line and space were well resolved.

Example 2 Under a dry nitrogen stream, 24.2 g (40 mmol) of the diamine compound synthesized in Synthesis Example 2 was placed in a 1-liter four-necked flask with N
Dissolved in 100 g of MP and 11.8 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (40 mmol)
l) was added and the mixture was stirred at 80 ° C for 3 hours. N, N-
8.8 g of dimethylformamide diethyl acetal (6
0 mmol) and stirred at 80 ° C. for 2 hours to obtain a partially esterified polymer solution. The carboxyl group in 1 g of this polymer was 0.55 mmol, and the imidation ratio was 35
% And the absorbance at 365 nm is 0.06 / μm.
It was 6.

100 g of this polymer solution and 3.5 g of the quinonediazide compound 4NT-300 used in Example 1 were mixed to obtain a photosensitive resin composition solution.

The evaluation was performed in the same manner as in Example 1 except that the development time was changed to 50 seconds. The results are shown in Table 1. as a result,
The film thickness of the unexposed portion after development was 5.8 μm (residual film ratio 8
3%), and the film loss due to development was 1.2 μm. The light irradiation amount at the time of pattern formation is 250 mJ /
cm ² and high sensitivity. Further, when the cross section of the pattern was observed with an electron microscope, it was found that a 10 μm line was well resolved.

Example 3 In Example 1, the composition of the diamine was changed to 2,2-bis (3-
Amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 18.3 g (50 mmol) 4,
8.0 g of 4'-diaminodiphenyl ether (40 mm
ol) and 2.5 g (10 mmol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were used to polymerize the polymer in the same manner. The carboxyl group in 1 g of this polymer was 0.35 mmol, and the imidization ratio was 14
%, And the absorbance at 365 nm is 0.04 / μm.
It was 5. 30 g of this polymer was dissolved in 70 g of GBL, and the quinonediazide compound 4NT-3 used in Example 1 was dissolved.
6 was dissolved to obtain a solution of the photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. As a result, the film thickness of the unexposed portion after development was 6.
The film thickness was 0 μm (remaining film ratio: 86%), and the film loss due to development was 1.0 μm. Further, the light irradiation amount at the time of pattern formation was as high as 250 mJ / cm ² . Further, when the cross section of the pattern was observed with an electron microscope, it was found that the lines and spaces of 10 μm were well resolved.

Example 4 A polymer was polymerized in the same composition as in Example 1. afterwards,
22.4 g of potassium-t-butoxide (200 mmol)
l) and stirred for 2 hours, followed by ethyl iodide 34.3.
g (220 mmol) was added dropwise. Two hours later, the polymer solution was poured into pure water to precipitate and dry the polymer. The carboxyl group in 1 g of this polymer was 1.2 mmol, the imidation ratio was 20%, and the absorbance at 365 nm was 1 μm.
Per unit was 0.088. 30 g of this polymer is GB
L was dissolved in 70 g, and 6 g of the quinonediazide compound 4NT-300 used in Example 1 was dissolved to obtain a solution of the photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. As a result, the film thickness of the unexposed portion after development was 5.
The film thickness was 5 μm (residual film ratio: 79%), and the film loss due to development was 1.5 μm. The light irradiation amount at the time of pattern formation was 300 mJ / cm ² . Further, when the cross section of the pattern was observed with an electron microscope,
m lines and spaces were well resolved.

Example 5 N-methyl-2-pyrrolidone diethyl acetal 2 was used instead of N, N-dimethylformamide dimethyl acetal
Example 1 except that 9.45 g (200 mmol) was used.
The mixture was stirred at 50 ° C. for 5 hours with the same composition as described above to obtain a partially esterified polymer solution. The carboxyl group in 1 g of this polymer was 0.28 mmol, the imidation ratio was 8%, and the absorbance at 365 nm was 0.082 per 1 μm. Using this polymer, a photosensitive solution similar to that of Example 1 was prepared.

The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. As a result, the film thickness of the unexposed portion after development was 5.
The film thickness was 5 μm (residual film ratio: 79%), and the film loss due to development was 1.5 μm. The light irradiation amount at the time of pattern formation was 300 mJ / cm ² . Further, when the cross section of the pattern was observed by an electron microscope,
Lines and spaces were well resolved.

Example 6 Hydroxyl group-containing diamine compound (2) synthesized in Synthesis Example 3 in a 1-liter four-necked flask under a stream of dry nitrogen.
6 g (36 mmol), 0.99 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (4 mmol
l) was dissolved in 100 g of NMP and 3,3 ', 4,4'
-Diphenyl ether tetracarboxylic dianhydride12.
4 g (40 mmol) was added and the mixture was stirred at 80 ° C. for 3 hours. Further, 9.5 g (80 mmol) of N, N-dimethylformamide dimethyl acetal was added, and the mixture was stirred at 50 ° C. for 2 hours. Thereafter, 5 g of acetic acid was added to decompose the remaining acetal compound to obtain a partially esterified polymer solution. The polymer solution was poured into 5 l of water, and the polymer precipitate was collected by filtration. The polymer was dried in a vacuum dryer at 80 ° C. for 20 hours. The carboxyl group in 1 g of this polymer was 0.12 mmol, the imidation ratio was 12%, and the absorbance at 365 nm was 0.066 per μm.

100 g of this polymer solution and 2 g of the naphthoquinonediazide compound synthesized in Synthesis Example 5 were mixed to obtain a solution of a photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1 except that the developing time was changed to 70 seconds. The results are shown in Table 1. as a result,
The film thickness of the unexposed portion after development was 5.5 μm (residual film ratio 7
9%), and the film loss due to development was 1.5 μm. The light irradiation amount at the time of pattern formation is 250 mJ /
cm ² . Further, when the cross section of the pattern was observed with an electron microscope, it was found that a 10 μm line was well resolved.

Example 7 In a dry nitrogen stream, a hydroxyl group-containing diamine compound (3) (8.7) synthesized in Synthesis Example 4 was placed in a 1-liter four-necked flask at a rate of 8.7.
5 g (36 mmol), 0.99 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (4 mmol
l) was dissolved in 100 g of NMP and 3,3 ', 4,4'
-12.9 g of benzophenonetetracarboxylic dianhydride
(40 mmol) and stirred at 50 ° C. for 3 hours. Further, 10.7 g (90 mmol) of N, N-dimethylformamide dimethyl acetal was added, and the mixture was stirred at 50 ° C. for 2 hours to obtain a partially esterified polymer solution. The carboxyl group in 1 g of this polymer was 0.08 mmol, the imidation ratio was 11%, and the absorbance at 365 nm was 1 μm.
0.066 per unit.

100 g of this polymer solution and 3.5 g of the quinonediazide compound 4NT-300 used in Example 1 were mixed to obtain a solution of a photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1 except that the developing time was 90 seconds. The results are shown in Table 1. as a result,
The film thickness of the unexposed portion after development was 5.8 μm (residual film ratio 8
3%), and the film loss due to development was 1.2 μm. The light irradiation amount at the time of pattern formation is 450 mJ /
cm ² . Further, when the cross section of the pattern was observed with an electron microscope, it was found that a 10 μm line was well resolved.

Comparative Example 1 A photosensitive resin precursor solution was obtained in the same manner as in Example 1 except that N, N-dimethylformamide dimethyl acetal was not added. The carboxyl group of 1 g of this polymer was 2.3 mmol, the imidation ratio was 7%, and
The absorbance in nm was 0.083 per μm. The evaluation was performed in the same manner as in Example 1, but all the films were dissolved.

Comparative Example 2 50 g of pyromellitic dianhydride and 300 ml of ethanol
Was placed in a 500 ml flask, 0.2 ml of pyridine was added, and the mixture was stirred at 30 ° C. for 10 hours under a nitrogen atmosphere. Excess ethanol was distilled off under reduced pressure, and the residue was dried in vacuum to obtain pyromellitic acid diethyl ester.

The obtained pyromellitic acid diethyl ester (31.4 g, 100 mmol), thionyl chloride (100 m)
was placed in a flask, stirred at room temperature for 1 hour, and then refluxed for 3 hours. Excess thionyl chloride was removed with an aspirator to obtain chloride.

The obtained chloride was treated with gamma-butyrolactone 6
36.62 g of BAHF dissolved in 0 g and kept at 0 ° C.
(100 mmol) and 50 ml of pyridine in NMP200
The solution was added dropwise to the solution dissolved in ml. After continuing stirring at 0 ° C. for 3 hours, the mixture was further stirred at 30 ° C. for 3 hours. After filtering the insoluble matter, the filtrate was poured into 5 liters of water to precipitate a polymer. The carboxyl group of 1 g of this polymer is 0 mm
The imidation ratio was 4%, and the absorbance at 365 nm was 0.072 per 1 μm.

The residual chlorine ion concentration of this polymer was as large as 100 ppm. The residual sodium, potassium and iron ions were all at 10 ppm or less.

The obtained polyamic acid diethyl ester 2
0 g was dissolved in 60 g of NMP, and 5 g of the quinonediazide compound 4NT-300 used in Example 1 was dissolved to obtain a solution of the photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1. However, even if the film was immersed in a developing solution for 5 minutes or more, the exposed portion was not completely dissolved.
The film thickness of the portion exposed to 0 mJ / cm ² was 5.1 μm, and the film thickness of the unexposed portion remained at 7 μm.

Comparative Example 3 A solution of a photosensitive resin precursor was obtained in the same manner as in Example 1 except that the polymerization and the esterification reaction were carried out at 180 ° C. The carboxyl group of 1 g of this polymer is 0.01 m
The imidation ratio was 65%, and the absorbance at 365 nm was 0.153 per 1 μm. Evaluation is Example 1
The same was done. As a result, the film thickness of the unexposed portion after development was 5.5 μm, and the film loss due to development was 1.5 μm.
J / cm ² or more was required.

Example 8 20.0 g (100 mmol) of 4,4'-diaminodiphenyl ether was placed in a 1-liter four-necked flask under a stream of dry nitrogen.
l) was dissolved in 350 g of GBL. Here, 71.4 g (100 mmol) of the acid anhydride synthesized in Synthesis Example 1 was added to GB
L was added together with 40 g, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Furthermore, after cooling to 20 ° C., 24.0 g of tert-butyl vinyl ether was used.
(240 mmol) and stirred at 20 ° C. for 24 hours,
A partially esterified polymer solution was obtained. The carboxyl group in 1 g of this polymer was 0.18 mmol, the imidation ratio was 20%, and the absorbance at 365 nm was 0.084 per 1 μm.

To 100 g of the obtained solution, 5.5 g of the quinonediazide compound 4NT-300 used in Example 1 was added to obtain a solution of a photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1. As shown in Table 1, the film thickness of the unexposed portion after development was 5.6 μm.
m (residual film ratio: 80%), and the film loss by development is 1.4.
μm. Further, the minimum light irradiation amount at the time of pattern formation was as small as 350 mJ / cm ^2, and the sensitivity was good.
Further, when the cross section of the pattern was observed with an electron microscope, it was found that the lines and spaces of 10 μm were well resolved.

Example 9 24.2 g (40 mmol) of the diamine compound (1) synthesized in Synthesis Example 2 was placed in a 1-liter four-necked flask under a stream of dry nitrogen.
l) was dissolved in 100 g of NMP and 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride 11.8 g (4
0 mmol) and stirred at 80 ° C. for 3 hours. Further, 9.2 g of cyclohexyl vinyl ether (72 mmo
l) was added and the mixture was stirred at 20 ° C. for 24 hours to obtain a partially esterified polymer solution. The carboxyl group of 1 g of this polymer was 0.4 mmol, the imidation ratio was 36%,
The absorbance at 365 nm was 0.065 per μm. In addition, the remaining sodium, potassium,
The iron ion concentration was a good value of 10 ppm or less. Also, the residual chlorine concentration was a good value of 10 ppm or less.

100 g of this polymer solution and 3.5 g of the quinonediazide compound 4NT-300 used in Example 1 were mixed to obtain a solution of a photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1 except that the development time was changed to 50 seconds. As a result, the film thickness of the unexposed portion after the development was 5.7 μm (remaining film ratio: 81%), and the film loss due to the development was 1.3 μm. The light irradiation amount at the time of pattern formation was 400 mJ / cm ² . Further, when the cross section of the pattern was observed with an electron microscope, it was found that a 10 μm line was well resolved.

Example 10 In Example 8, the composition of the diamine was changed to 18.3 g of BAHF.
(50 mmol), 8.0 g (40 mmol) of 4,4'-diaminodiphenyl ether, 2.5 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1
The polymer was polymerized in the same manner except that the amount was 0 mmol). The carboxyl group of 1 g of this polymer is 0.21 mm
The imidation ratio was 20%, and the absorbance at 365 nm was 0.056 per 1 μm. This polymer 30
g was dissolved in 70 g of GBL, and 6 g of the quinonediazide compound 4NT-300 used in Example 1 was dissolved to obtain a solution of the photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1. As a result, the film thickness of the unexposed portion after development was 6.0 μm (remaining film ratio: 86%), and the film loss due to development was 1.0 μm.
The light irradiation amount for forming the pattern is 350 mJ.
/ Cm ² . Further, when the cross section of the pattern was observed with an electron microscope, it was found that the lines and spaces of 10 μm were well resolved.

Example 11 A polymer was polymerized in the same composition as in Example 8. afterwards,
After cooling to 20 ° C., 24.0 g (240 mmol) of tert-butyl vinyl ether was added, and
2 g (5.52 mmol) were added dropwise. After stirring at 20 ° C. for 24 hours, the polymer solution was put into pure water to precipitate and dry the polymer. The carboxyl group of 1 g of this polymer was 0.08 mmol, the imidation ratio was 10%,
The absorbance at 5 nm was 0.042 per μm. 30 g of this polymer was dissolved in 70 g of GBL, and 6 g of the quinonediazide compound 4NT-300 used in Example 1 was dissolved to obtain a solution of a photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1. As a result, the film thickness of the unexposed portion after the development was 6.4 μm (remaining film ratio: 91%), and the film loss due to the development was 0.6 μm.
The light irradiation amount for pattern formation is 250 mJ.
/ Cm ² and high sensitivity. Further, when the cross section of the pattern was observed with an electron microscope, a 5 μm line and space were well resolved.

Example 12 A polymer was polymerized in the same composition as in Example 8. afterwards,
20.9 g of isopropyl vinyl ether (240 mm
ol) and 0.72 g (5.52 mmol) of phosphoric acid
Was added dropwise. The mixture was stirred at 25 ° C. for 20 hours to obtain a partially esterified polymer solution. 1 g of this polymer had a carboxyl group of 0.12 mmol, an imidization ratio of 12%, and an absorbance at 365 nm of 0.083 per μm. 30 g of this polymer was dissolved in 70 g of GBL, and 6 g of the quinonediazide compound 4NT-300 used in Example 1 was dissolved to obtain a solution of a photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1. As a result, the film thickness of the unexposed portion after the development was 5.7 μm (remaining film ratio: 81%), and the film loss due to the development was 1.3 μm.
The light irradiation amount for forming the pattern is 300 mJ.
/ Cm ² . Further, when the cross section of the pattern was observed with an electron microscope, a 5 μm line and space were well resolved.

Example 13 Hydroxyl group-containing diamine (2) synthesized in Synthesis Example 3
18.9g (0.05mol), BAHF 16.5g
(0.045 mol), 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.00
5 mol) was dissolved in 250 g of NMP and brought to 30 ° C. To this, 31.0 g (0.1 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride was added together with 50 g of NMP, and the mixture was added at 30 ° C. for 1 hour,
Stirred at 0 ° C. for 2 hours. Thereafter, the solution temperature is maintained at 50 ° C., and N, N′-dimethylformamide dimethyl acetal 2 is added.
A solution obtained by diluting 3.8 g (0.2 mol) with 80 g of NMP was added, and stirring was continued at 50 ° C. for 2 hours. Then, the temperature of the solution was raised to 30 ° C., and 60 g (1 mol) of acetic acid was added to NMP.
The mixture was added together with 80 g, and stirred at 30 ° C. for 1 hour to decompose excess acetal compound. After completion of the reaction, the polymer solution was poured into 10 l of water to obtain a polymer precipitate. This was collected by filtration and dried in a ventilation oven at 80 ° C. for 24 hours. The residual sodium, potassium and iron ion concentrations of this polymer were as good as 10 ppm or less. Also, the residual chlorine concentration was a good value of 10 ppm or less.

The carboxyl group in 1 g of this polymer was 0.43 mmol, the imidation ratio was 11%, and
The absorbance in nm was 0.075 / μm. 10 g of this polymer was dissolved in 70 g of NMP, and 2 g of a photosensitizer (MG-300 manufactured by Toyo Gosei) obtained by reacting 3 mol of 5-naphthoquinonediazidesulfonic acid chloride with 1 mol of methyl gallate was dissolved to obtain a solution of a photosensitive resin composition. Was.

Evaluation was performed in the same manner as in Example 1 except that the developing time was changed to 70 seconds. The results are shown in Table 1. as a result,
The film thickness of the unexposed portion after development was 5.8 μm (residual film ratio 8
3%), and the film loss due to development was 1.2 μm. Further, the light irradiation amount at the time of pattern formation is 350 mJ /
cm ² . Further, when the cross section of the pattern was observed with an electron microscope, it was found that the lines and spaces of 10 μm were well resolved.

Example 14 Hydroxyl group-containing diamine (3) synthesized in Synthesis Example 4
12.2 g (0.05 mol), BAHF 16.5 g
(0.045 mol), 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.00
5 mol) was dissolved in 180 g of NMP and brought to 30 ° C. To this, 31.0 g (0.1 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride was added together with 50 g of NMP, and the mixture was added at 30 ° C. for 1 hour,
Stirred at 0 ° C. for 2 hours. Thereafter, the solution temperature was maintained at 50 ° C., and 23.8 g of dimethylformamide dimethyl acetal was obtained.
(0.2 mol) diluted with 80 g of NMP was added, and stirring was continued at 50 ° C. for 2 hours. Thereafter, the temperature of the solution was lowered to 30 ° C., and 24 g (0.4 mol) of acetic acid was added to N
MP was added together with 30 g, and the mixture was stirred at 30 ° C. for 1 hour to decompose excess acetal compound. After completion of the reaction, the polymer solution was poured into 10 l of water to obtain a polymer precipitate. This was collected by filtration and dried in a ventilation oven at 80 ° C. for 24 hours. The residual sodium, potassium and iron ion concentrations of this polymer were as good as 10 ppm or less. Also,
The residual chlorine concentration was also a good value of 10 ppm or less.

The carboxyl group in 1 g of this polymer was 0.44 mmol, the imidation ratio was 11%, and
The absorbance in nm was 0.055 per μm. 30 g of this polymer was dissolved in 70 g of NMP, and 6 g of MG-300 used in Example 13 was dissolved to obtain a solution of the photosensitive resin composition.

The evaluation was performed in the same manner as in Example 1 except that the developing time was changed to 60 seconds. The results are shown in Table 1. as a result,
The film thickness of the unexposed portion after development was 6.0 μm (residual film ratio 8
6%), and the film loss due to development was 1.0 μm. Further, the light irradiation amount at the time of pattern formation is 350 mJ /
cm ² . Further, when the cross section of the pattern was observed with an electron microscope, it was found that the lines and spaces of 10 μm were well resolved.

Examples 15 to 17 Hydroxyl group-containing diamine (1) synthesized in Synthesis Example 2
57.4 g (0.095 mol), 1,3-bis (3-
1.24 g of aminopropyl) tetramethyldisiloxane
(0.05 mol) dissolved in 180 g of NMP,
° C. Here, 31.0 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride (0.1 mol
l) was added together with 30 g of NMP, and the mixture was stirred at 30 ° C for 1 hour, and then at 50 ° C for 2 hours. Thereafter, the solution temperature is set to 50 ° C.
Example 15: 20.2 g (0.17 mol) of N, N'-dimethylformamide dimethyl acetal
Example 16: 22.6 g (0.19 mol), Example 1
7: A predetermined amount of 25.0 g (0.21 mol) was added to NMP.
Added with 100 g. Thereafter, stirring was continued at 50 ° C. for 2 hours. Thereafter, the temperature of the solution was set to 30 ° C., and 24 g of acetic acid was added.
(0.4 mol) was added, and the mixture was stirred at 30 ° C. for 1 hour to decompose excess acetal compound. After completion of the reaction, the polymer solution was poured into 10 l of water to obtain a polymer precipitate. This was collected by filtration and dried in a ventilation oven at 80 ° C. for 24 hours. The residual sodium, potassium and iron ion concentrations of all the polymers were good values of 10 ppm or less. Also, the residual chlorine concentration was a good value of 10 ppm or less.

In Example 15, the carboxyl group in 1 g of the polymer was 0.6 mmol, and the imidation ratio was 9%, 365 n
m is 0.044 per 1 μm, and in Example 16, the carboxyl group in 1 g of the polymer is 0.47 mmol,
The imidation ratio was 9%, the absorbance at 365 nm was 0.044 per 1 μm, and in Example 17, the carboxyl group in 1 g of the polymer was 0.41 mmol, the imidation ratio was 11%, 36
The absorbance at 5 nm was 0.045 per μm. 30 g of each of these polymers was charged with 35 g of GBL,
In 35 g, 6 g of the naphthoquinonediazide compound synthesized in Synthesis Example 5 was dissolved to obtain solutions of the respective photosensitive resin compositions.

The evaluation was performed with a development time of 50 seconds (Example 15).
The operation was performed in the same manner as in Example 1 except that 70 seconds (Example 16) and 90 seconds (Example 17) were used. The results are shown in Table 1. Further, when the cross section of the pattern was observed with an electron microscope, the line and space of 5 μm were well resolved in each case.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

According to the present invention, it is possible to obtain a photosensitive resin composition which enables alkali development in a short time, has high transparency, and has high sensitivity.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) (72) Inventor Ryoji Okuda 1-1-1 Sonoyama, Otsu-shi, Shiga Pref.

Claims (9)

[Claims] 1. A polymer comprising (a) a polymer having a structural unit as a main component represented by the general formula (1), and (b) a photoacid generator. A pattern can be formed by subsequent development, and the total carboxyl groups contained in 1 g of the polymer are 0.02 mm
ol or more and 2.0 mmol or less. Embedded image (R1 is a trivalent to octavalent organic group having at least 2 or more carbon atoms, R2 is a divalent to hexavalent organic group having at least 2 or more carbon atoms, R3 is hydrogen or a carbon atom having 1 or more carbon atoms. Represents an organic group from 1 to 20 and is not all hydrogen; n is an integer from 3 to 100000;
Represents 1 or 2, p and q each represent an integer from 0 to 4, and p + q> 0. ) 2. The positive photosensitive resin composition according to claim 1, wherein said photoacid generator is a quinonediazide compound. 3. The polymer represented by the general formula (1), wherein a part of the carboxyl groups is imidized, and the imidation ratio (imidation ratio) is 1% or more and 50% or less. The positive photosensitive resin composition according to claim 1 or 2, wherein 4. The polymer of the formula (1)
The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the absorbance at 65 nm is 0.1 or less per 1 µm of film thickness. 5. The method according to claim 1, wherein a polymer having a structural unit represented by the general formula (2) as a main component is esterified with a compound represented by the general formula (3) and / or (4). The positive photosensitive resin composition according to any one of claims 1 to 4, wherein Embedded image (R1 is a trivalent to octavalent organic group having at least 2 or more carbon atoms, R2 is a divalent to hexavalent organic group having at least 2 or more carbon atoms, and n is 3 to 1.
An integer up to 00000, m is 1 or 2, p, q
Is an integer from 0 to 4 and p + q> 0. ) Embedded image (R4 represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R5 represents any one of a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group; R
6 represents a monovalent organic group having 1 or more carbon atoms, and R7 represents any one of a divalent cyclic organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group. ) 6. General formula (3) and / or general formula (4)
6. The positive photosensitive resin composition according to claim 5, wherein the compound represented by the formula is N, N-dimethylformamide dialkyl acetal. 7. The positive type according to claim 1, wherein a polymer having a structural unit represented by the general formula (2) as a main component is esterified with a compound represented by the general formula (5). Photosensitive resin composition. Embedded image (R8 represents a monovalent organic group having 1 or more carbon atoms.) 8. The positive photosensitive resin composition according to claim 5, wherein the compound represented by the general formula (5) is cyclohexyl vinyl ether. 9. A polymer having a structural unit represented by the general formula (2) as a main component is represented by the general formulas (3), (4) and (5):
The positive photosensitive resin composition according to claim 7, wherein the composition is subjected to an esterification treatment with a compound represented by the formula and an acid catalyst.