JPH086250A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin compsn. excellent in photosensitivity and resolution, not requiring heating at a high temp. and especially suitable for use as the material of the insulating layer of a printed circuit board, the protective film and interlaminar insulating film of IC, LSI, etc., a liquid crystal orienting film, etc. CONSTITUTION:This photosensitive resin compsn. contains polyimide resin (A) soluble in an org. solvent and represented by the formula [where R<1> is a tetravalent residue of an acid component, R<2> is a divalent residue of a diamine component, (n) is an integer of >=1 and each of >=25mol% residues among the residues represented by R<1> and R<2> contains an arom. ring], a photodegradable proton generating agent (B) and a multifunctional potentially electrophilic agent (C) as essential components.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition capable of forming a relief pattern with high sensitivity by irradiation with light or radiation.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin has been known as a polymer material having excellent properties such as heat resistance and electrical properties, and is used as a surface protective film for semiconductors and an interlayer insulating film. These polyimide resin films must be microfabricated by using a photoetching process using a photoresist or the like, and therefore, studies have been made to impart photosensitivity to this resin. Since the polyimide resin with photosensitivity can simplify and rationalize the pattern forming process as compared with the polyimide resin without photosensitivity, it is not necessary to use a highly toxic etching solution.
It is also excellent in safety and pollution, and is expected to become even more important in the future.

As the photosensitive polyimide resin, for example, a photosensitive resin composition [R. E. Kerwin, et al. , Polymer Eng. &
Sci. , 11 (5), 426 pp (1971)] are known.
However, this system has the drawback that the electrical properties and reliability are reduced due to the presence of dichromate in the final polyimide resin film obtained, and that the polyamic acid gels during storage due to a dark reaction, and further, There was a drawback that hexavalent chromium was contained in the waste liquid discharged in the manufacturing process.

Further, Japanese Patent Publication No. 55-30207 and Japanese Patent Publication No. 55-4
1422 discloses a polyimide precursor composition having a structure represented by the following formula, in which a photosensitive group is introduced into an ester group.

[0005]

Embedded image (However, in the formula, n represents an integer of 1 or more.) The photosensitive polyimide resin of this system not only has a complicated manufacturing process of the resin itself but also involves dehydrochlorination reaction at the stage of introducing a photosensitive group. Therefore, there is a drawback that chlorine ions remain in the obtained polyimide resin film and the electrical characteristics and the reliability of an element using this resin are poor.

Further, Japanese Patent Publication No. 54-145794 discloses a polyamic acid having a structure represented by the following formula:

[0007]

[Chemical 3] (In the formula, R ^a represents a tetravalent organic group, R ^b represents a divalent organic group, and R ^c represents an ester group.) A carbon-carbon double bond dimerizable or polymerizable by actinic radiation, Also, a composition added with a compound containing an amino group or a quaternized salt thereof is shown. Although the photosensitive polyimide resin of such a system does not have a problem of impurity ions, it has a low sensitivity of several hundreds to several thousands mJ / cm ² for practical use, and has a viscosity change during storage and There was a defect such as precipitation of the added compound.

Further, all of the above-mentioned conventional photosensitive polyimide resins are those obtained by imparting photosensitivity to a polyamic acid which is a precursor of a polyimide resin, and finally 300 ° C. to convert the polyamic acid into a polyimide resin. It had to be heat-treated at the above high temperature, and could only be used on a substrate or element that could withstand this heat, and there was the drawback that the resulting pattern had large dimensional changes such as volumetric shrinkage due to heat. .

[0009]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned drawbacks and has a high sensitivity, a high resolution, a relief pattern can be formed by irradiation of light or radiation, and high heat can be applied. It is intended to provide a photosensitive polyimide resin composition that does not require heat treatment.

[0010]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned object, and as a result of examining various chemical structures of polymers, it was found that the composition described below can achieve the above-mentioned object. They have found and completed the present invention.

That is, the present invention provides (A) an organic solvent-soluble polyimide resin represented by the following general formula,

[0012]

[Chemical 4] (However, in the formula, R ¹ represents a tetravalent acid component residue, R ² represents a divalent diamine component residue, n represents an integer of 1 or more, and at least 25 mol of R ¹ and R ² % Or more of the residues include an aromatic ring) (B) A photodegradable proton generator and (C) a polyfunctional latent electrophilic agent as essential components.

The present invention will be described in detail below.

The organic solvent-soluble polyimide resin (A) used in the present invention is a polyamic acid obtained by polycondensation reaction of an acid component and a diamine component, which is further dehydrated and cyclized, and is soluble in an organic solvent. . As the acid component used here, as specific compounds, for example, pyromellitic acid, 1,2,3,4-benzenetetracarboxylic acid, 1,2,3,4-
Cyclobutane tetracarboxylic acid, 1,2,4,5-cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, 3,3 ′, 4,4′-bicyclohexyl tetracarboxylic acid, 2, 3,5-tricarboxycyclopentyl acetic acid, 3,
4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-
Succinic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid, 2,3,
3 ', 4'-benzophenone tetracarboxylic acid, 3,3', 4,
4'-biphenyl ether tetracarboxylic acid (4,4'-
(Oxydiphthalic acid), 2,3,3 ', 4'-biphenyl ether tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) Propane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 2,2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 2,3,3', 4'-diphenylsulfone tetracarboxylic acid, 2,3,6,7- Naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 3,4,9,10-tetracarboxyperylene, 2,
2-bis [4- (3,4-dicarboxyphenoxy) phenyl]
Examples thereof include anhydrides such as propane and 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane, or lower alkyl esters thereof. These may be used alone or as a mixture. it can.

Specific examples of the diamine component include, for example, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5. ′ -Tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-
Diaminodiphenylmethane, 3,3'-dimethyl-5,5'-
Diethyl-4,4'-diaminodiphenylmethane, 4,4'-
Methylenebis (cyclohexylamine), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3 '
-Dimethoxy-4,4'-diaminodiphenylmethane, 3,
3'-diethoxy-4,4'-diaminodiphenylmethane,
Bis (3-aminophenyl) ether, bis (4-aminophenyl) ether, 3,4'-diaminodiphenyl ether, 3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4, 4'-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl]
Ether, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenyl sulfone, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl-4,4'-diaminodiphenylpropane, 3, 3'-dimethoxy-4,4 '
-Diaminodiphenylpropane, 3,3'-diethoxy-
4,4'-diaminodiphenylpropane, 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 1,3-bis (4
-Aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-diethyl -4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 2,2'-diaminodiethyl sulfide , 2,4'-diaminodiphenyl sulfide, m-
Phenylenediamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,1-bis (4-aminophenyl) ethane, bis (3 -Aminophenyl) sulfone, bis (4-aminophenyl) sulfone, o-toluidine sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,
4'-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, Bis (4-aminophenyl)-
N-phenylamine, bis (4-aminophenyl) -N-
Methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diamino Naphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 9,9-bis (4- Aminophenyl) fluorene,
4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl,
3,3'-Dimethyl-4,4'-diaminobiphenyl, 3,4 '
-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4-
Aminophenoxy) biphenyl, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,
5-diaminotoluene, 1,3-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dichlorobenzene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4, 6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,
4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,4-bis (2-methoxy-4-aminopentyl) benzene, 1, 4-bis (1,1-
Dimethyl-5-aminopentyl) benzene, 1,4-bis (4-
Aminophenoxy) benzene, 3,5-diaminobenzoic acid,
2,5-diaminobenzoic acid, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 3,3′-diaminobenzophenone, 4,4′-diamino Benzophenone, 2,6-diaminopyridine, 3,5-diaminopyridine, 1,3-diaminoadamantane, 3,3′-diamino-1,1,1′-diadamantane, N- (3-aminophenyl) -4 -Aminobenzamide, 4,4'-diaminobenzanilide, 4-aminophenyl-3-aminobenzoate, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 4- (2-chloro-4-aminophenyl Phenoxy) phenyl] hexafluoropropane,
1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2 , 2-Trifluoroethane, 1,3-bis (3-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane, 1,4-
Examples thereof include bis (3-aminophenyl) but-1-en-3-yne, which may be used alone or in combination of two or more.

The organic solvent-soluble polyimide resin used in the present invention can be obtained by reacting the above-mentioned acid component with the above-mentioned diamine component, and is used in an amount of 25 mol% or more of at least one of the acid component and the diamine component. A component containing an aromatic ring is used. When the content of this component is less than 25 mol%, the reaction point of the polyfunctional latent electrophilic agent decreases, and the sensitivity is poor, which is not preferable. Polyamic acid which is a precursor of polyimide resin is 0.5 g / N-methyl-2-pyrrolidone.
As a 100 ml concentrated solution, the logarithmic viscosity at 30 ° C is
To 4.0, and more preferably 0.3 to 2.0. The polyamic acid is obtained by subjecting an acid component and a diamine component to an addition polymerization reaction in an organic solvent at a reaction temperature of 30 ° C. or lower, preferably 20 ° C. or lower for 3 to 12 hours. As the organic solvent in this polymerization reaction, for example, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N
-Diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide and the like,
These may be used alone or in combination of two or more. The polyamic acid obtained as described above is then dehydrated and cyclized to obtain a polyimide resin. A known method can be used for the dehydration cyclization, and for example, a chemical cyclization method using acetic anhydride and pyridine, a thermal cyclization method by refluxing toluene, xylene, or the like can be used. This polyimide resin solution contains acetic anhydride used for dehydration, pyridine, or toluene, xylene, etc., so the polyimide resin solution is poured into a poor solvent such as water or methanol, reprecipitated, and further dried. Polyimide resin powder is used. Dissolve this in the desired organic solvent,
A solution of an organic solvent-soluble polyimide resin used in the present invention. As the organic solvent used here, in addition to the solvent used for the synthesis of the polyamic acid described above, a general-purpose organic solvent can be used alone or in combination as long as it can dissolve the polyimide resin used. The concentration of the organic solvent solution of the organic solvent-soluble polyimide resin using these solvents is not particularly limited because it may be appropriately determined according to the purpose of use of the present invention, the method of use.
Used between 1 and 30%.

The photodegradable proton-generating agent (B) used in the present invention is an allyldiazonium salt (Ar N
₂ ⁺ X ⁻ ), diallyl iodonium salt (Ar ₂ I
⁺ X ⁻ ), triallyl sulfonium salt (Ar ₃ S ⁺ X
^- ), Aromatic sulfonic acid ester, etc., and these can be used alone or in combination of two or more kinds.
It is desirable that the photodecomposable proton generating agent is mixed in an amount of 1 to 50% by weight based on the solid content of the polyamic acid solution. It is preferably in the range of 5 to 20% by weight. If the content is less than 1% by weight, the acid generation rate will be slow and sufficient sensitivity cannot be obtained, and if it exceeds 50% by weight, the storage stability of the resin composition will be poor, such being undesirable.

As the polyfunctional latent electrophilic agent (C) used in the present invention, one molecule is a functional group capable of causing an electrophilic substitution reaction such as carbocation with an acid generated from the above-mentioned photodegradable proton generating agent. There is no particular limitation as long as it produces two or more of them, but it is preferable that the blocking acid is liberated when the carbocation is produced. Specific compounds include, for example, 1,4-bis (acetoxymethyl) benzene, 1,3,5-
Tri (acetoxymethyl) benzene, 3,4-bis (acetoxymethyl) furan, 1,4-bis (sulfoxymethyl)
Examples thereof include benzene, 1,3,5-tri (sulfoxymethyl) benzene and 3,4-bis (sulfoxymethyl) furan, which may be used alone or in combination of two or more. The proportion of the polyfunctional latent electrophilic agent is preferably 1 to 50% by weight based on the solid content of the polyamic acid solution described above. It is preferably in the range of 5 to 20% by weight. If the blending amount is less than 1% by weight, the cross-linking density between molecules becomes small, and sufficient sensitivity and resolution cannot be obtained.
If it exceeds 50% by weight, the storage stability of the resin composition and the physical properties of the polyimide film are deteriorated, which is not preferable.

The photosensitive resin composition of the present invention can be easily produced by blending the above-mentioned organic solvent-soluble polyimide resin solution, photodegradable proton generator and polyfunctional latent electrophilic agent. Further, although each of the above-mentioned components is an essential component, other additives can be blended within a range not deviating from the object of the present invention. The photosensitive resin composition thus obtained is used as an insulating material for printed circuit boards, ICs, and LSIs.
It is a suitable material for the interlayer insulating film, the surface protective film, the liquid crystal alignment film, and the like.

Next, using the photosensitive resin composition of the present invention,
An example of forming a relief pattern will be described. First, an organic solvent-soluble polyimide resin solution, a photodegradable proton generator, and a polyfunctional latent electrophilic agent are blended to prepare a photosensitive resin composition. This composition is applied onto a substrate by a conventional method such as spin coating or printing and dried to remove the organic solvent.
Next, the obtained coating film is exposed to a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, etc. through a negative type photomask. After exposure, development is performed by spraying a developing solution to remove the unexposed portion or immersing the substrate in the developing solution. This developing solution is preferably an organic solvent capable of dissolving and removing the unexposed area in the coating film within an appropriate time, and for example, N, N-dimethylsulfoxide,
N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, etc., alone or mixed, and further these A poor solvent such as methanol, ethanol, isopropanol, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, and acetic acid isoamyl ester can be mixed with a good solvent to adjust the solubility before use. After development, a relief pattern can be formed by washing the substrate with an appropriate rinse solution. As the rinse liquid used here, methanol, ethanol, isopropanol, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, acetic acid isoamyl ester or the like can be used alone or in combination. The substrate on which the relief pattern is obtained is 50 to 250 ° C., preferably 150 ° C.
It heat-processes at -200 degreeC for 60-90 minutes, and the organic solvent in a polyimide resin is dried. In this way, a relief pattern having heat resistance, insulation, etc. can be obtained.

[0021]

[Function] The photosensitive resin composition of the present invention is obtained by subjecting a benzene ring in a polyimide resin main chain to an electrophilic substitution reaction with a cross-linking agent capable of generating two or more carbocations in one molecule, to obtain a polyimide resin molecule. By cross-linking each other, a difference in solubility between the exposed portion and the unexposed portion with respect to the developing solution appears, whereby a relief pattern having high sensitivity and high resolution can be formed. Furthermore, since a relief pattern can be obtained in the state of polyamic acid, and then heat conversion can be performed to form a polyimide film,
There is an advantage that a high-density pattern can be obtained.

[0022]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 Dry nitrogen was passed through a flask equipped with a stirrer, a condenser and a nitrogen inlet tube to replace the inside of the flask, and then 3,3 ', 5,5'
-Tetramethyl-4,4'-diaminodiphenylmethane 25.6
4 g and 231.4 g of N-methyl-2-pyrrolidone were added and dissolved. To this solution, 32.22 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added as a powder in several divided portions while paying attention to heat generation. While suppressing the heat generated by the reaction in an ice bath, stirring was continued for 8 hours to prepare a polyamic acid solution. A part of this polyamic acid solution was put into a mixed solvent of water and methanol and reprecipitated to obtain a polyamic acid powder. This powder is N-methyl-2-
Dissolve pyrrolidone to a concentration of 0.5 g / 100 ml,
The logarithmic viscosity at ℃ was 1.18dl / g.
20.58 g of acetic anhydride and 1 of pyridine were added to this polyamic acid solution.
5.82 g was added and the mixture was stirred for 10 hours for imidization. The reaction solution was poured into a large amount of a mixed solution of water and methanol to reprecipitate the polyimide resin, which was further vacuum dried for 12 hours to obtain a polyimide resin powder. Solid content of this resin powder
It was dissolved in cyclohexanone to 10% to obtain a polyimide resin solution.

100 g of this polyimide resin solution was mixed with triphenylsulfonium trifluoromethanesulfonate.
1.0g and 1,4-bis (acetoxymethyl) benzene 1.5g
Was dissolved and pressure-filtered with a 1.0 μm filter to produce a photosensitive resin composition.

This composition was spin-coated on a silicon wafer with a spinner and then dried on a hot plate at 80 ° C. for 5 minutes to obtain a coating film having a thickness of 3 μm. A mask having a relief pattern was brought into close contact with this coating film and exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. The exposure dose at this time was 8 mJ / cm ² . After exposure, it was developed with a mixed solvent of cyclohexanone and isopropanol to obtain a relief pattern. This development resolved lines with a pattern width of 4 μm. This pattern
The residual organic solvent was dried by heating at 200 ° C for 1 hour to obtain a heat-resistant relief pattern. In this pattern, even if heat treatment was further performed at 200 ° C. for 1 hour, the pattern was not blurred and the heating loss was not caused.

Example 2 Dry nitrogen was passed through a flask equipped with a stirrer, a condenser and a nitrogen introducing tube to replace the inside of the flask, and then 25.92 g of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane And 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 18.31 g and N-methyl-2-pyrrolidone 264.16 g were added and dissolved. To this solution, 21.81 g of pyromellitic dianhydride was added as a powder in several divided portions while paying attention to heat generation. While suppressing the heat generated by the reaction in an ice bath, stirring was continued for 10 hours to prepare a polyamic acid solution. A part of this polyamic acid solution was put into a mixed solvent of water and methanol and reprecipitated to obtain a polyamic acid powder. This powder was dissolved in N-methyl-2-pyrrolidone at a concentration of 0.5 g / 100 ml and the logarithmic viscosity at 30 ° C. was measured to be 0.84 dl / g. 20.58 g of acetic anhydride and 15.82 g of pyridine were added to this polyamic acid solution, and the mixture was stirred for 12 hours for imidization.
The reaction solution was poured into a large amount of a mixed solution of water and methanol to reprecipitate the polyimide resin, which was further vacuum dried for 12 hours to obtain a polyimide resin powder. Dissolve this resin powder in γ-butyl lactone so that the solid content becomes 10%,
A polyimide resin solution was obtained.

To 100 g of this polyimide resin solution, 1.5 g of diphenyliodonium trifluoromethanesulfonate
And 1,4-bis (acetoxymethyl) benzene (1.2 g) were dissolved and pressure-filtered with a 1.0 μm filter to produce a photosensitive resin composition.

This composition was spin coated on a silicon wafer with a spinner and then dried on a hot plate at 80 ° C. for 5 minutes to obtain a coating film having a thickness of 3 μm. A mask having a relief pattern was brought into close contact with this coating film and exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. The exposure dose at this time was 5 mJ / cm ² .
After exposure, it was developed with a mixed solvent of γ-butyl lactone and acetic acid isoamyl ester to obtain a relief pattern. This development resolved a line with a width of 3.5 μm. This pattern 2
Heat treatment at 00 ℃ for 1 hour to dry the residual organic solvent,
A heat resistant relay pattern was obtained. When this pattern was further heat-treated at 200 ° C for 1 hour, there was no blurring of the pattern or heating loss.

Example 3 Dry nitrogen was passed through a flask equipped with a stirrer, a cooler, a Dean-Stark separator and a nitrogen introducing tube to replace the inside of the flask, and then 10.01 g of 4,4'-diaminodiphenyl ether was added.
And 2,2'-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane 18.31 g and N-methyl-2-pyrrolidone 237.4 g were added and dissolved. To this solution, 31.02 g of 4,4'-oxydiphthalic dianhydride was added as a powder in several divided portions while paying attention to heat generation. While suppressing the heat generated by the reaction in an ice bath, stirring was continued for 12 hours to prepare a polyamic acid solution. A part of this polyamic acid solution was put into a mixed solution of water and methanol and reprecipitated to obtain a polyamic acid powder. This powder was dissolved in N-methyl-2-pyrrolidone to a concentration of 0.5 g / 100 ml and the logarithmic viscosity at 30 ° C. was measured to be 0.82 dl / g. 40.0 g of toluene was added to this polyamic acid solution, and the mixture was refluxed at 200 ° C. for 3 hours for imidization. Water generated by imidization was continuously taken out of the system by a Dean-Stark water separator. This reaction solution is poured into a large amount of water and methanol mixed solution to reprecipitate the polyimide resin,
Further, this was vacuum dried for 12 hours to obtain a polyimide resin powder. This resin powder was dissolved in cyclohexanone so that the solid content was 10% to obtain a polyimide resin solution.

IRGAC was added to 100 g of this polyimide resin solution.
URE261 (Ciba Geigy, trade name) 1.5 g and 1,
0.85 g of 3,5-tri (acetoxymethyl) benzene was dissolved and pressure-filtered with a 1.0 μm filter to produce a photosensitive resin composition.

This composition was spin coated on a silicon wafer with a spinner and then dried on a hot plate at 80 ° C. for 5 minutes to obtain a coating film having a thickness of 3 μm. A mask having a relief pattern was brought into close contact with this coating film and exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. The exposure dose at this time was 6 mJ / cm ² .
After exposure, it was developed with a mixed solution of cyclohexanone and isopropyl alcohol to obtain a relief pattern. This development resolved lines with a pattern width of 2.5 μm. This pattern was heated and pressed at 200 ° C. for 1 hour to dry the residual organic solvent to obtain a heat-resistant relief pattern. When this pattern was further heat-treated at 200 ° C for 1 hour, there was no blurring of the pattern or heating loss.

Example 4 Dry nitrogen was passed through a flask equipped with a stirrer, a condenser and a nitrogen introducing tube to replace the inside of the flask, and then, 19.83 g of 4,4'-diaminodiphenylmethane and 169.0 g of N-methyl-2-pyrrolidone were added. In addition, it dissolved. To this solution, 22.42 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride was added as a powder in several divided portions while paying attention to heat generation. Continue to stir while suppressing the heat generated by the reaction in the ice bath 12
The mixture was stirred for a time to prepare a polyamic acid solution. A part of this polyamic acid solution was put into a mixed solvent of water and methanol and reprecipitated to obtain a polyamic acid powder. This powder was dissolved in N-methyl-2-pyrrolidone at a concentration of 0.5 g / 100 ml and the logarithmic viscosity at 30 ° C. was measured.
It was 5 dl / g. Acetic anhydride was added to this polyamic acid solution.
20.58 g and 15.82 g of pyridine were added and the mixture was stirred for 12 hours for imidization. The reaction solution was poured into a large amount of a mixed solution of water and methanol to reprecipitate the polyimide resin, which was further vacuum dried for 12 hours to obtain a polyimide resin powder. This resin powder was dissolved in γ-butyl lactone so that the solid content was 10% to obtain a polyimide resin solution.

100 g of this polyimide resin solution was mixed with triphenylsulfonium trifluoromethanesulfonate.
0.9g and 1,3,5-tri (acetoxymethyl) benzene 0.7g
Was dissolved and pressure-filtered with a 1.0 μm filter to produce a photosensitive resin composition.

This composition was spin coated on a silicon wafer with a spinner and then dried on a hot plate at 80 ° C. for 5 minutes to obtain a coating film having a thickness of 3 μm. A mask having a relief pattern was brought into close contact with this coating film and exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. The exposure dose at this time was 6 mJ / cm ² .
After exposure, it was developed with a mixed solvent of γ-butyl lactone and methanol to obtain a relief pattern. This development resolved lines with a pattern width of 5 μm. This pattern is 200 ℃
After heating for 1 hour, the residual organic solvent was dried to obtain a heat-resistant relief pattern. This pattern is 2 more
Even if the heat treatment was carried out at 00 ° C for 1 hour, there was no blurring of the pattern or heating loss.

Comparative Example After dry nitrogen was passed through a flask equipped with a stirrer, a condenser and a nitrogen inlet tube, the inside of the flask was replaced with 20.02 g of 4,4'-diaminodiphenyl ether and 376.5 g of N-methyl-2-pyrrolidone. Dissolved. To this solution, 21.81 g of pyromellitic dianhydride was added as a powder in several divided portions while paying attention to heat generation. While suppressing the heat generated by the reaction in an ice bath, stirring was continued for 8 hours to prepare a polyamic acid solution. A part of this polyamic acid solution was put into a mixed solution of water and methanol and reprecipitated to obtain a polyamic acid powder. This powder was dissolved in N-methyl-2-pyrrolidone at a concentration of 0.5 g / 100 ml and the logarithmic viscosity at 30 ° C. was measured to be 1.32 dl / g.

2- (N, N) was added to 100 g of this polyamic acid solution.
-Dimethylamino) ethyl methacrylate 8.23 g and IRGACURE 907 (manufactured by Ciba-Geigy Co., Ltd., trade name) as a radical generator were mixed and dissolved, and pressure filtration was performed with a 1.0 μm filter to produce a photosensitive resin composition.

This composition was spin-coated on a silicon wafer with a spinner and then dried on a hot plate at 80 ° C. for 5 minutes to obtain a coating film having a thickness of 3 μm. A mask having a relief pattern was brought into close contact with this coating film and exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. The exposure amount at this time was 1200 mJ / cm ² . After exposure, it was developed with a mixed solvent of N-methyl-2-pyrrolidone and methanol to obtain a relief pattern. This development only resolved lines with a pattern width of 100 μm.

[0038]

As is apparent from the above description, the photosensitive resin composition of the present invention is excellent in photosensitivity and resolution and does not require heating at high temperature, and is particularly suitable for printing. It is suitable as an insulating layer for wiring boards, a protective film for ICs, LSIs, etc., an interlayer insulating film, an alignment film for liquid crystals, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication H01L 21/312 B H05K 3/06 H 3/28 D

Claims (1)

[Claims] 1. An organic solvent-soluble polyimide resin represented by the following general formula (A): (However, in the formula, R ¹ represents a tetravalent acid component residue, R ² represents a divalent diamine component residue, n represents an integer of 1 or more, and at least 25 mol of R ¹ and R ² % Or more of residues include an aromatic ring) (B) a photodegradable proton generator and (C) a polyfunctional latent electrophilic agent as essential components.