JPH0822124A - Photosensitive resin composition and its pattern forming method - Google Patents

Abstract

PURPOSE:To obtain a coating film having a certain residual solvent. content independently of heating conditions at the time of prebaking and to form a stable pattern by blending a specified polyamic ester with a high b.p. solvent and a low b.p. solvent. CONSTITUTION:This photosensitive resin compsn. contains a polyamic ester represented by formulae I-III, a solvent having 220-320 deg.C b.p. under 1atm and a solvent having 120-220 deg.C b.p. under 1atm as essential components. This compsn. is prepd. by blending the polyamic ester obtd. by introducing mono- or multifunctional photosensitive groups and lower alcohol into carboxyl groups in polyamic acid by covalent bonds with the high m.p. solvent, and the low b.p. solvent. In the formulae I-III, R1 is a tri- or tetravalent org. group, R2 is a divalent org. group, R3 is a group represented by formula IV R4 is a group represented by formula V, each of (l), (m) and (n) is 0 or 1, each of (x), (y) and (z) shows the percentage of the structural units, x>0, y<100, 0<z<80 and x+y+z=100. In the formulae IV, V, R5 is a di- to hexavalent org. group and R6 is H or CH3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having a high sensitivity and capable of obtaining a stable film irrespective of heating conditions for coating and drying on a substrate, and a pattern forming method thereof. .

[0002]

2. Description of the Related Art Conventionally, a polyimide having excellent heat resistance and excellent electrical insulation and mechanical strength has been used for a surface protective film, an interlayer insulating film, etc. of a semiconductor element. Recently, a technique for imparting photosensitivity to polyimide itself has been attracting attention in order to simplify the complicated process. For example, the following formula

[0003]

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There is known a polyimide precursor composition (for example, JP-B-55-41422) in which a photosensitive group is provided with an ester group having a structure shown by All of these are dissolved in a suitable organic solvent, applied in a varnish state, dried, and then irradiated with ultraviolet rays through a photomask,
A polyimide film is formed by developing and rinsing to obtain a desired pattern and further heat treatment. The use of polyimide with photosensitivity not only has the effect of simplifying the pattern creation process, but it is also safe because it does not require the use of highly toxic etching solutions, and it is also excellent in terms of pollution. Is expected to become an even more important technology in the future.

Polyimide precursors provided with such ester groups include N-methyl-2-pyrrolidone, α-butyrolactone, propylene glycol monomethyl ether acetate, dimethylacetamide, dimethylformamide,
It was dissolved in a polar solvent having a boiling point of less than 220 ° C., such as diethylene glycol dimethyl ether and cyclopentanone, to form a varnish. Therefore, after coating the substrate with a spinner or the like, the polar solvent is removed by heating with an oven, a heating plate or the like to obtain a film. However, in the case of such a conventional solvent, the amount of the residual solvent greatly varies depending on the heating conditions, and the pattern formability of the film is different, which has been a problem. Further, in order to improve work efficiency depending on heating conditions, there has been a demand for a photosensitive resin composition capable of obtaining a stable film at high temperature for a short time.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to add a monoborate or polyfunctional photosensitive group to a carboxyl group in a polyamic acid, a polyamic acid ester into which a lower alcohol is covalently introduced, and a high boiling point solvent. By blending a solvent having a low boiling point with a solvent having a low boiling point, a stable pattern can be obtained by obtaining a film having a substantially constant amount of residual solvent regardless of the heating conditions during prebaking.

[0006]

The present invention provides (A) a polyamic acid ester represented by the following formulas (1a), (1b) and (1c):

[0007]

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(B) The boiling point at 1 atm is 220 to 320 ° C.
Solvent and (C) the boiling point at 1 atm is 120 to 220 ° C.
Is a photosensitive resin composition containing the solvent as an essential component, and the photosensitive resin composition is further coated on a substrate,
It is a pattern forming method of irradiating light through a mask after removing the unirradiated portion with an organic solvent after drying for 1 to 5 minutes on a hot plate of 0 to 150 ° C. Formula (1a) used in the present invention,
The polyamic acid ester comprising the structural units represented by (1b) and (1c) exhibits high reactivity, and the cured product has good heat resistance, mechanical properties, and electrical properties.

In the formulas (1a), (1b) and (1c), R
₁ is introduced from a compound having a trivalent or tetravalent organic group, and usually an aromatic tetracarboxylic acid or its derivative and an aromatic tricarboxylic acid or its derivative are mainly used. For example, trimellitic anhydride, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-
Benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4 5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1 , 2, 3, 5, 6,
7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,
5,6,7, -hexahydronaphthalene-2,3,6
7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
2,7-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1 , 4,5,8-tetrachloronaphthalene-2,
3,6,7-tetracarboxylic dianhydride, 3,3 ′,
4,4'-diphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic Acid dianhydride, 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,3,3 ",
4 ″ -p-terphenyltetracarboxylic dianhydride,
2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) Ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (2,2
3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic Acid dianhydride, perylene-3,4,9,10-
Tetracarboxylic dianhydride, perylene-4,5,10,
11-tetracarboxylic dianhydride, perylene-5,6
11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2 , 9,10-Tetracarboxylic acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, pyrrolidine-2 , 3, 4, 5
-Tetracarboxylic dianhydride, thiophene-2,3
Examples thereof include, but are not limited to, 4,5-tetracarboxylic dianhydride and 4,4′-hexafluoroisopropylidene diphthalic dianhydride. Further, in use, one kind or a mixture of two or more kinds may be used.

In the formulas (1a), (1b) and (1c), R
₂ is a divalent organic group, and an aromatic diamine and / or its derivative is usually used for its introduction. For example, m-phenylene-diamine, 1-isopropyl-2,4-phenylene-diamine, p-phenylene-diamine, 4,4'-
Diamino-diphenylpropane, 3,3'-diamino-
Diphenylpropane, 4,4'-diamino-diphenylethane, 3,3'-diamino-diphenylethane, 4,
4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 4,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,
3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4'-diamino −
Biphenyl, 3,3'-dimethoxy-benzidine, 4,
4 ″ -diamino-p-terphenyl, 3,3 ″ -diamino-p-terphenyl, bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p -Β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-amino-pentyl) benzene, p-bis (1,1-dimethyl-)
5-amino-pentyl) benzene, 1,5-diamino-
Naphthalene, 2,6-diamino-naphthalene, 2,4-
Bis (β-amino-t-butyl) toluene, 2,4-diamino-toluene, m-xylene-2,5-diamine,
p-xylene-2,5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2,5-diamino-1,3,4- Oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,
2-dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine, hexamethylene-diamine, 2,5-dimethyl-hexamethylene-diamine, 3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2, 5-dimethyl-heptamethylene-diamine, 3-methyl-heptamethylene-diamine, 4,4-dimethyl-heptamethylene-diamine,
Octamethylene-diamine, nonamethylene-diamine,
5-methyl-nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10-diamino-1,10-dimethyl-decane, 2,11-diamino-dodecane, 1,12-diamino- Octadecane, 2,12-diamino-octadecane, 2,17-diamino-icosane, diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-diamino-4,4'-dicarboxylic benzidine, 2,5-diamino-p-xylene, 1,
3-bis (3-aminophenoxyno) benzene, 1,3
Examples thereof include, but are not limited to, bis (3-aminopropyl) tetramethyldisiloxane. In use, one kind or a mixture of two or more kinds may be used.

In the formulas (1a), (1b) and (1c), R
₃ is a photosensitive group having 1 to 5 acrylic (methacrylic) groups, R ₄ is a photosensitive group having 1 to 5 acrylic (methacrylic) groups, or a methyl group or an ethyl group.
When the acryl (methacryl) group in R ₃ and R ₄ is 0, a crosslinked structure cannot be obtained, which is not preferable. Further, 6 or more acryl (methacryl) groups are not preferable because not only they are industrially difficult to produce but also the compatibility is lowered because the molecular weight becomes large. Examples of the compound for introducing R ₃ and R ₄ include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, Glycerol diacrylate, glycerol dimethacrylate, glycerol acrylate methacrylate, trimethylolpropane diacrylate, 1,3-diacryloylethyl-5-hydroxyethyl isocyanurate, 1,3-dimethacrylate-5
-Hydroxyethyl isocyanurate, ethylene glycol-modified pentaerythritol triacrylate, propylene glycol-modified pentaerythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, glycidyl Examples thereof include, but are not limited to, acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polyethylene glycol-modified methacrylate, polyethylene glycol-modified acrylate, polypropylene glycol-modified methacrylate and the like. In using these, one kind or a mixture of two or more kinds may be used. The methyl group or ethyl group of R ₄ is usually derived from methanol, ethanol or the like.

R ₅ is a divalent to hexavalent organic group obtained by removing a hydroxyl group and an acryloyloxy group or a methacryloyloxy group from the compound for introducing R ₃ or R ₄ described above, and among these, preferred is It is a divalent or trivalent aliphatic group. Formulas (1a), (1b) and (1) used in the present invention
polyamic acid ester comprising a structural unit represented by c), the structural units (1 R ₃ is introduced into the carboxyl group
the proportion of a) is x, the R ₃ a part of the carboxyl groups, the proportion of remaining in the introduction of R ₄ structural units (1b) is y, the carboxyl group is substituted by R ₄ structural units (1c) The ratio is z, and three types of structural units are mixed. 0 <x, y <100, 0 <z <80,
In addition, x + y + z = 100 is satisfied, and x, y, and z represent the mole percentage of each structural unit. When R ₄ is a methyl group or an ethyl group, when z is 80 or more, the amount of the photosensitive group is small, the sensitivity is low and the practicality is low. The polyamic acid ester in the present invention is usually synthesized as follows. First, a compound having an alcohol group for introducing the polyfunctional photosensitive groups R ₃ and R ₄ is dissolved in a solvent, and excess acid anhydride or its derivative is reacted with this. After that, the remaining carboxyl group and acid anhydride group can be reacted with diamine to synthesize.

The present invention relates to formulas (1a), (1b) and (1
The polyamic acid ester shown in c) is mixed with a solvent having a boiling point of 220 to 320 ° C. at 1 atm and a boiling point of 120 at 1 atm.
Dissolve into a varnish using a solvent at ~ 220 ° C. Solvents with a boiling point of 220-320 ° C at 1 atm are almost volatilized when such a varnish solution is coated on a substrate and lightly dried on a heating plate etc., so that the amount of residual solvent is almost constant regardless of heating conditions. Used to obtain a film having If the boiling point at 1 atm is less than 220 ° C., it will be volatilized during drying of a hot platen or the like, which is not preferable. When the solvent temperature exceeds 320 ° C., the residual solvent amount can be kept constant, but the solvent remains after the final curing, which is not preferable. A more preferable boiling point is 240 to 300 ° C. Boiling point at 1 atm is 22
As a solvent at 0 to 320 ° C., tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, ethylene glycol monobutyl ether, ethylene carbonate, propylene carbonate, butylene carbonate, sulfolane, 3-methylsulfolane, hexamethylphosphoric triamide, 1,3-dimethyl -2-
Examples thereof include, but are not limited to, imidazolidinone, triethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, and propylene glycol monophenyl ether. Among these, sulfolane and tetraethylene glycol dimethyl ether are preferable. When used, it may be one kind or a mixture of two or more kinds.

The amount of the solvent having a boiling point of 220 to 320 ° C. at 1 atmospheric pressure is 0.2 to 100 parts by weight of the polyamic acid ester represented by the formulas (1a), (1b) and (1c).
20 parts by weight is preferred. More preferably, 0.5-10
Parts by weight. If the addition amount is less than 0.2 parts by weight, the addition amount is too small to show the effect clearly. If it exceeds 20 parts by weight, a certain amount of solvent is volatilized, so that high temperature and long time are required, and the photosensitive resin reacts, which is not preferable. A solvent having a boiling point of 120 to 220 ° C. at 1 atm coats the varnish solution on a substrate and volatilizes easily and does not foam when lightly dried on a hot platen or the like to form a non-adhesive film. Used for easy acquisition. When the boiling point at 1 atm is less than 120 ° C., it is not preferable because it is likely to volatilize during coating and foam during drying. For solvents above 220 ° C,
Volatility is slow and not preferable. More preferably 140-
It is 210 ° C.

As the solvent having a boiling point of 120 to 220 ° C. at 1 atm, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, Dimethyl sulfoxide, 3-methoxybutanol, 3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethyl cellosolve, butyl cellosolve, ethyl carbitol, diethyl carbonate, cyclohexanone, Examples include methylcyclohexanone, diisobutyl ketone, cyclopentanone, butyl acetate, and nitrobenzene. These include but are not limited. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monomethyl ether acetate are preferable. Also, one kind or a mixture of two or more kinds may be used. Further, the boiling point at 1 atm is 120 to 220.
The solvent at 0 ° C. preferably dissolves the polyamic acid ester represented by the formulas (1a), (1b) and (1c), but is not necessarily limited thereto. The addition amount of polyamic acid ester (1a), (1b) and (1c) is 100.
50 to 300 parts by weight is preferable with respect to parts by weight. If it is less than 50 parts by weight, the solution viscosity in the varnish is too high, which is not preferable. If it exceeds 300 parts by weight, the solution viscosity of the varnish is too low, which is not preferable. In the present invention, a sensitizer may be added to improve lithographic properties such as sensitivity and resolution. As a sensitizer

[0016]

[Chemical 4]

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[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

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[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

Examples thereof include, but are not limited to: As the photopolymerization initiator in the present invention, the following compounds used for general UV curable resins can be used. That is,

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

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Examples thereof include, but are not limited to: When used, one kind or a mixture of two or more kinds may be used. The above-mentioned sensitizer also functions as a photopolymerization initiator. The addition amount of the sensitizer or the photopolymerization initiator is 0.1 with respect to 100 parts by weight of the polyamic acid ester.
-20 parts by weight is preferred. If it is less than 0.1 part by weight, the amount of addition is too small and it is difficult to obtain the effect of improving the sensitivity. If the amount exceeds 20 parts by weight, the strength of the cured film decreases, which is not preferable.

In the present invention, a storability improver may be added for the purpose of improving the storability. As the storage stability improver, 1-phenyl-5-mercapto-1H-tetrazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, pentaerythritol tetrakis- (thioglycolate), thioglycolic acid , Ammonium thioglycolate, butyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, trimethylolpropane tris- (thioglycolate), ethylene glycol dithioglycolate, β-mercaptopropionic acid, β-mercaptopropionic acid Octyl, trimethylolpropane tris- (β-thiopropionate), pentaerythritol tetrakis- (β-thiopropionate), 1,4-butanediol dithiopropionate , Thiosalicylic acid, furfuryl mercaptan,
Benzyl mercaptan, α-mercaptopropionic acid,
p-hydroxythiophenol, p-methylthiophenol, thiophenol, p-methylphenol, 2,6
Examples thereof include, but are not limited to, -t-butylphenol and catechol. Further, in the present invention, a photopolymerizable monomer having a carbon-carbon double bond can be added for the purpose of further improving the sensitivity. For example, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, N-methylol acrylamide,
It is possible to use N, N-dimethylacrylamide and acrylates thereof, or those obtained by changing acrylamide to methacrylate or methacrylamide. An adhesion aid such as a silane coupling agent, an inhibitor, a leveling agent and various fillers may be added to the photosensitive resin composition according to the present invention.

In the method for producing a relief pattern using the photosensitive resin composition of the present invention, the composition is first applied to an appropriate support such as a silicon wafer, ceramics, aluminum substrate or the like. The coating method is spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Then 60-180 ℃
Dry the coating at moderate temperature. As a drying method, there are an oven, an infrared furnace, a heating plate, and the like, but the heating plate is preferable from the viewpoint of efficiency and easy temperature control. When drying with this hot plate,
It is preferable to dry at 100 to 150 ° C. for 1 to 5 minutes.
If the temperature is lower than 100 ° C. or lower than 1 minute, the drying is insufficient, which is not preferable. If the temperature exceeds 150 ° C and exceeds 5 minutes,
It is not preferable because the drying becomes excessive. More preferred is
110 to 140 ° C. and 2 to 4 minutes.

Next, a desired pattern shape is irradiated with actinic rays. As the actinic rays, X-rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are particularly preferable. Next, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. An organic solvent is preferable as the developing solution. As the organic solvent, N-methyl-2
-Aprotic polar solvents such as -pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide and dimethylsulfoxide are more preferable, and iso-propyl alcohol, xylene, propylene glycol methyl ether acetate and diethylene glycol are used to adjust the solubility of these. You may add dimethyl ether, butyl acetate, etc. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. As the rinse liquid, toluene, xylene, ethanol, methanol, iso-propyl alcohol, butyl acetate, water or the like can be used. Subsequently, heat treatment is performed to form an imide ring, and a final relief pattern having high heat resistance is obtained. The photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, a liquid crystal alignment film, and the like.

The present invention will be specifically described with reference to the following examples. Example 1 65.5 g (0.30 mol) of pyromellitic dianhydride and 225.5 g (0.70 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride were mixed with 2- Hydroxy-1,3-dimethacryloxypropane 456 g
After reacting with (2.00 mol) to esterify the carboxyl group, 4,4'-diaminodiphenyl ether 1
70.2 g (0.85 mol) was reacted with dicyclohexylcarbodiimide as a condensing agent to obtain a polyamic acid ester copolymer. After filtering off dicyclohexylurea,
It was reprecipitated with ethanol, the solid matter was filtered, and dried under reduced pressure. 100 parts by weight of this polyamic acid ester, 6 parts by weight of N-phenylglycine, 1-phenyl-5-mercapto-1
1 part by weight of H-tetrazole, 1 part by weight of 2- (p-dimethylaminostyryl) benzoxazole, 10 parts by weight of tetraethylene glycol diacrylate and 5 parts by weight of sulfolane
It was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone and 200 parts by weight of N-methyl-2-pyrrolidone to obtain a photosensitive resin composition. The resulting solution is
It was coated on an inch silicon wafer with a fully automatic coater (DSPIN-636 manufactured by Dainippon Screen Co., Ltd.) and dried at 110 ° C. for 3 minutes with a heating plate. Separately, a coating film was formed at 120 ° C. for 3 minutes and 130 ° C. for 3 minutes.
The obtained coating film was overlaid with a resolution measuring mask (Topographic test chart No. 1) manufactured by Toppan Printing Co., Ltd., and 500 mJ / c.
When it was developed with a developer containing 50% by weight of N-methyl-2-pyrrolidone and 50% by weight of iso-propyl alcohol, it was irradiated with ultraviolet rays of m ² and was excellent in that it did not collapse even when dried at any temperature. The pattern was obtained.

Example 2 Example 2 was repeated except that the amount of 2-hydroxy-1,3-dimethacryloxypropane in Example 1 was reduced to 228 g (1.00 mol) and 32 g (1.00 mol) of methanol was added. Reaction was carried out in the same manner as in Example 1 to obtain a photosensitive resin composition, which was evaluated in the same manner as in Example 1. A good pattern with no collapse was obtained even when dried at any temperature. Example 3 The 2-hydroxy-1,3-dimethacryloxypropane in Example 1 was replaced with 2-hydroxyethyl methacrylate 24.
Reaction was carried out in the same manner as in Example 1 except that the amount was changed to 0 g (2.00 mol) to obtain a photosensitive resin composition.
Was evaluated in the same way as A good pattern with no collapse was obtained even when dried at any temperature. Example 4 To the photosensitive resin composition obtained in Example 1, 3 parts by weight of trimethoxysilylpropyl methacrylate was added,
The obtained photosensitive resin composition was evaluated in the same manner as in Example 1. A good pattern with no collapse was obtained even when dried at any temperature. Example 5 A photosensitive resin composition was obtained in the same manner as in Example 1 except that the sulfolane in Example 1 was changed to tetraethylene glycol dimethyl ether, and evaluated in the same manner as in Example 1. A good pattern with no collapse was obtained even when dried at any temperature.

Example 6 A photosensitive resin composition was obtained in the same manner as in Example 1 except that N-methyl-2-pyrrolidone in Example 1 was changed to γ-butyrolactone. evaluated. A good pattern with no collapse was obtained even when dried at any temperature. Example 7 A photosensitive resin composition was obtained in the same manner as in Example 1 except that 100 parts by weight of 200 parts by weight of N-methyl-2-pyrrolidone in Example 1 was changed to propylene glycol methyl ether acetate. Evaluation was performed in the same manner as in Example 1. A good pattern with no collapse was obtained even when dried at any temperature. Example 8 A photosensitive resin composition was obtained in the same manner as in Example 1 except that the addition amount of sulfolane in Example 1 was changed to 1 part by weight.
Evaluation was performed in the same manner as in Example 1. A good pattern with no collapse was obtained even when dried at any temperature. Example 9 A photosensitive resin composition was obtained in the same manner as in Example 1 except that the addition amount of sulfolane in Example 1 was changed to 10 parts by weight, and evaluated in the same manner as in Example 1. A good pattern with no collapse was obtained even when dried at any temperature. Example 10 The photosensitive resin composition of Example 1 was mixed with a hot plate at 120 ° C. for 2 hours.
Minutes and 4 minutes, the reaction was performed in the same manner as in Example 1 to obtain a photosensitive resin, which was evaluated in the same manner as in Example 1.
A good pattern with no collapse was obtained at any drying time.

Example 11 65.5 g (0.30 mol) of pyromellitic dianhydride and 225.5 g (0.70 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were added as 2 parts. -Hydroxy-1,3-dimethacryloxypropane 228.3 g
(1.0 mol), 32.0 g of methanol (1.0 mol)
Is suspended in N-methyl-2-pyrrolidone, and pyridine 16
6.1 g (2.1 mol) was added and reacted at 25 ° C. for 10 hours. Next, after 270.2 g (2.0 mol) of 1-hydroxy-1,2,3-benzotriazole was added and completely dissolved in 1 hour, N was maintained while maintaining the reaction system at 10 ° C or lower.
412.6 g (2.0 mol) of dicyclohexylcarbodiimide dissolved in 400 g of -methyl-2-pyrrolidone was added dropwise over about 20 minutes. Then, the reaction was carried out at 25 ° C. for 3 hours. Then diaminodiphenyl ether 180.
2 g (0.9 mol) was added and the reaction was carried out at 25 ° C. for 5 hours. After dicyclohexylurea was filtered off, the reaction mixture was reprecipitated in methanol, the solid was collected by filtration, washed with methanol, and dried under reduced pressure for 48 hours. This polyamic acid ester was blended in the same manner as in Example 1 to obtain a photosensitive resin composition, which was evaluated in the same manner as in Example 1. A good pattern with no collapse was obtained even when dried at any temperature.

Comparative Example 1 A photosensitive resin composition was obtained in the same manner as in Example 1 except that N-methyl-2-pyrrolidone was used instead of sulfolane in Example 1, and evaluated in the same manner as in Example 1. , 110 ° C
And a good pattern was obtained at 120 ° C, but 1
At 30 ° C., the pattern was peeled off from the lower part of the corner. Comparative Example 2 A photosensitive resin composition was obtained and evaluated in the same manner as in Example 1 except that N-methyl-2-pyrrolidone in Example 1 was changed to sulfolane. Although it did not dry at any temperature, when it was dried at 150 ° C. for 5 minutes and evaluated, the unexposed area did not dissolve even after development. Comparative Example 3 A photosensitive resin composition was obtained and evaluated in the same manner as in Example 1 except that the addition amount of sulfolane in Example 1 was changed to 0.1 part by weight. A good pattern was obtained at 110 ° C. and 120 ° C., but at 130 ° C., peeling of the pattern from the lower part of the corner was recognized.

Comparative Example 4 A photosensitive resin composition was obtained in the same manner as in Example 1 except that the addition amount of sulfolane in Example 1 was changed to 30 parts by weight, and the same evaluation was performed. A good pattern was obtained at 130 ° C., but at 110 ° C. and 120 ° C., the exposed part swelled and the pattern collapsed. Comparative Example 5 The photosensitive resin composition of Example 1 was dried on a heating plate at 80 ° C. and 170 ° C. for 3 minutes each. At 80 ° C., the drying was insufficient and exposure was not possible. Further, at 170 ° C., the unexposed area was not dissolved at all. Comparative Example 6 The photosensitive resin composition of Example 1 was dried at 120 ° C. for 30 seconds and 10 minutes. At 30 seconds, the drying was insufficient and exposure was not possible. Further, after drying for 10 minutes, only the cracks were formed in the unexposed portion and the portions were not dissolved and no delicate pattern was obtained.

[0038]

EFFECTS OF THE INVENTION By blending a solvent having a high boiling point and a solvent having a low boiling point, it is possible to stabilize a film with high sensitivity and a substantially constant residual solvent amount regardless of the heating conditions during prebaking after coating on a substrate. Obtained.

Claims (5)

[Claims] 1. (A) a polyamic acid ester represented by the following formulas (1a), (1b) and (1c): A photosensitive resin composition comprising (B) a solvent having a boiling point of 220 to 320 ° C. at 1 atm and (C) a solvent having a boiling point of 120 to 220 ° C. at 1 atm as essential components. 2. A solvent having a boiling point of 220 to 320 ° C. at 1 atm of 0.2 to 20 parts by weight with respect to 100 parts by weight of the polyamic acid ester represented by the formulas (1a), (1b) and (1c). The photosensitive resin composition according to claim 1. 3. The photosensitive resin composition according to claim 1, wherein the solvent having a boiling point of 220 to 320 ° C. at 1 atmosphere is sulfolane and / or tetraethylene glycol dimethyl ether. 4. The solvent having a boiling point of 120 to 220 ° C. at 1 atm is at least one selected from N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monomethyl ether acetate. Item 2
Alternatively, the photosensitive resin composition according to claim 3. 5. The photosensitive resin composition according to claim 1 is coated on a substrate and heated on a hot plate at 100 to 150 ° C.
After drying for 5 minutes, light is irradiated through a mask, and a non-light-irradiated portion is removed with an organic solvent.