JPH06329795A - Production of partially imidized photosensitive poly(amic acid) ester - Google Patents

Abstract

PURPOSE:To obtain the desired ester useful as a photosensitive resin having high sensitivity and reduced shrinkage by subjecting a partially imidized poly(amic acid) obtained by a given method and specific alcohols to an ester-forming addition reaction. CONSTITUTION:A tetracarboxylic dianhydride and/or a tetracarboxylic acid derivative (e.g. 3,3',4,4'-benzophenonetetracarboxylic dianhydride) is reacted with a diamine (derivative) (e.g. 4,4'-diaminodiphenyl ether) at 50-120 deg.C to conduct amide-forming polyaddition and ring-closure imidization with dehydration. The partially imidized poly(amic acid) thus obtained is reacted with alcohols in the presence of a carbodiimide derivative (e.g. N,N-dicyclohexylcarbodiimide) by an ester-forming addition reaction, the alcohols comprising an alcohol (a) represented by the formula wherein R1 is a di- to hexavalent organic group; R2 is H or CH3; and p is 1-5 and one or more alcohols (b) selected from CH3OH, C2H5OH, and C3H7OH, the molar amount (x) of the alcohol (a) and that (y) of the alcohol (b) satisfying the relation 0.2<[x/(x+y)]<1.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photosensitive resin having high sensitivity and low shrinkage.

[0002]

2. Description of the Related Art Conventionally, surface protection films, interlayer insulation films, etc. of semiconductor elements have excellent heat resistance and excellent electrical insulation properties.
Polyimide having mechanical strength and the like is used, but a technique of imparting photosensitivity to polyimide itself has been recently attracting attention in order to simplify a complicated process of forming a polyimide pattern. For example, the following formula

[0003]

[Chemical 2]

There is known a polyimide precursor composition (for example, Japanese Examined Patent Publication (Kokoku) No. 55-41422) in which a photosensitive group is provided with an ester group having a structure as shown in FIG. 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 a photosensitized polyimide not only has the effect of simplifying the pattern creation process, but it is also safe and excellent in pollution because it does not require the use of highly toxic etching solutions. It is expected that it will become an even more important technology in the future.

However, as a method for introducing an ester group, first, an acid dianhydride is reacted with an alcohol-containing photosensitive group, and then a chlorine-containing compound such as an acid chloride is used as a condensing agent to copolymerize with a diamine (Japanese Patent Publication No. 55-41422), and a method using a carbodiimide as a condensing agent as a method not using a chlorine-containing compound (JP-A-60-22).
No. 8537) and the like are known. However, in either method, carboxylic acid and diamine must be polycondensed under mild conditions such that carbon-carbon double bond does not react, it is difficult to obtain a high molecular weight product, and further, molecular weight and photosensitive group substitution between synthesis lots are difficult to obtain. There was a large variation in the introduction rate. Therefore, the photosensitive resin composition obtained from this resin has only low sensitivity and low cured film mechanical properties. Further, as a method of solving these various problems, a method of previously synthesizing a high-molecular-weight polyamic acid and introducing an ester bond via an isoimide (JP-A-4-204452) is also known. On the other hand, in the case of non-photosensitive polyamic acid, a method of quantitatively imidizing a part of the carboxyl group to control storage stability and processing workability (Japanese Patent Application No. 4-3).
38991). However, in the conventional method for producing a photosensitive polyamic acid ester compound via a polyamic acid, since the purpose is to make the ester substitution rate 100%, a highly sensitive photosensitive resin can be obtained but the shrinkage upon curing does not occur. Is large and stress is liable to be generated, so that there is a problem that cracks easily occur in the pattern corners and the like.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a photosensitive resin having high sensitivity and having a small shrinkage upon curing.

[0007]

According to the present invention, a tetracarboxylic dianhydride and / or a tetracarboxylic acid derivative is reacted with a diamine and / or a diamine derivative at 50 to 120 ° C. to carry out an amidation polyaddition reaction. A partially imidized photosensitive polyamic acid ester obtained by subjecting a partially imidized polyamic acid obtained by dehydration ring-closure imidization reaction and an alcohol compound represented by the following formula (1) to an ester addition reaction in the presence of carbodiimides: It is a manufacturing method.

[0008]

[Chemical 3]

[0009]

As the tetracarboxylic dianhydride or tetracarboxylic acid derivative used in the present invention, aromatic tetracarboxylic dianhydride or its derivative is mainly used. For example, 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 acid 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 Anhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p
-Terphenyltetracarboxylic 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 (2,3 -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 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 dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene Examples thereof include, but are not limited to, -2,3,4,5-tetracarboxylic dianhydride and derivatives thereof. Further, in use, one kind or a mixture of two or more kinds may be used.

As the diamine and diamine derivative used in the present invention, aromatic diamine or its derivative is mainly used. 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-benzyl) 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, hexa. Methylene-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-
Examples include, but are not limited to, eicosane, 2,6-diamino-4-carboxylic benzene, 3,3′-diamino-4,4′-dicarboxylic benzidine, and derivatives thereof. Furthermore, equation (2)
It is also possible to use a diaminosiloxane represented by

[0011]

[Chemical 4]

(In the formula, R ₉ and R _{10 are} divalent carbon atoms 1 to 5
Of the aliphatic groups or aromatic groups having 6 or more carbon atoms, which may be the same as or different from each other. R ₁₁ and R _{12 are} monovalent aliphatic groups or aromatic groups, which may be the same or different. (n: an integer of 1 to 100) In addition, one kind or a mixture of two or more kinds may be used.

In the present invention, it is preferable that the reaction of the tetracarboxylic acid dianhydride and / or its derivative with the diamine and / or its derivative is carried out in an equimolar amount as much as possible because the polymerization degree becomes large. Either one is 10 mol%
If it exceeds, the degree of polymerization is remarkably lowered, and a low molecular weight product having poor film-forming properties is obtained, which is not preferable. Usually, acid component is 1
It is preferable to use a large amount of 6 mol% to improve the film characteristics.

The degree of polymerization of the polyamic acid in the present invention is not particularly limited, but those having a degree of polymerization of 5 to 10,000 are usually used, and more preferably about 20 to 1000. If the degree of polymerization is less than 5, heat resistance, mechanical strength, elongation and the like when converted into polyimide after curing is unfavorable. If it exceeds 10,000, not only the viscosity increases and handling becomes difficult, but also it is necessary to reduce the resin content concentration of the solution in order to obtain a constant viscosity, and the solution concentration at the time of pattern formation decreases. This is not preferable because the property is significantly reduced, the thickness of the stepped substrate such as a semiconductor is reduced at the stepped corners, and the coating film is likely to crack at the stepped portion. The end of the polyamic acid in the present invention is not particularly limited, but an acid anhydride-terminated type, the use of a terminal terminator such as phthalic anhydride, and further a structure in which the acid anhydride is terminated with an alcohol compound having an acryl group or a methacryl group Are preferred. The presence of an amino group at the terminal is not preferable because the amino group reacts with the carboxyl group of the polyamic acid activated by the carbodiimide to easily cause gelation. A structure in which the terminal acid anhydride is terminated by an alcohol compound having an acryl group or a methacryl group, that is, a polyamic acid represented by the following formula (3) in which the actinic radiation-sensitive group P ′ is at the terminal is more preferable.

[0015]

[Chemical 5]

An example of the method for synthesizing the polyamic acid used in the present invention is as follows. When synthesizing a polyamic acid having a degree of polymerization m of about 1000, tetracarboxylic acid dianhydride 1000 is used.
Alcohol compound 2 having mol and actinic radiation reactive group P '
Mol can be obtained by first reacting in an inert aprotic polar solvent and then reacting 1000 mol of diamine.

The solvent of the reaction system in the present invention is an organic polar solvent having a dipole moment whose functional group does not react with tetracarboxylic dianhydride and its derivative, diamine and its derivative. Is inert to the system,
And besides being a solvent for the product, the organic polar solvent must be a solvent for at least one of the reaction components, preferably both. Typical solvents of this type are N, N-dimethylformamide, N, N
-Dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoramide, N-methyl-2-pyrrolidone,
Pyridine, dimethyl sulfone, tetramethyl sulfone,
There is dimethyltetramethylene sulfone and the like, and these solvents are used alone or in combination. In addition to these, as those used in combination as a solvent, non-solvents such as benzene, benzonitrile, dioxane, butyrolactone, xylene, toluene, cyclohexanone, a dispersion medium of the raw material,
A reaction regulator, or a solvent volatilization regulator from the product,
Used as a film smoothing agent.

The reaction is generally preferably carried out under anhydrous conditions. This is because the tetracarboxylic dianhydride and its derivative may be ring-opened and deactivated by water to stop the reaction. Therefore, it is necessary to remove both the water content in the raw material and the water content in the solvent. The heating reaction temperature is preferably 50 to 120 ° C, more preferably 60 to 90 ° C.
Is appropriate. If the temperature is lower than 50 ° C, the imidization progresses very slowly, which is not preferable. Further, if it exceeds 120 ° C, hydrolysis takes precedence over ring closure and the molecular weight remarkably decreases, which is not preferable. The imidization ratio after the heating reaction is not limited, but is preferably 5 to 50%. If the imidization ratio is less than 5%, the resulting polyamic acid ester is unfavorably large in shrinkage during curing. If the imidization ratio exceeds 50%, the viscosity is increased or gelation occurs during the reaction, which is not preferable. Various methods for measuring the imidization ratio are known. There are nuclear magnetic resonance spectroscopy (NMR method), Fourier transform infrared spectroscopy (FT-IR method), a method of directly quantifying water accompanying imide ring closure, and a method of indirectly calculating from neutralization titration value of carboxylic acid. .

The alcohol compound having an acryl group or a methacryl group used in the present invention is bonded to a polyamide side chain by an ester bond, and the acryl group or methacryl group is further photocrosslinked to give a negative photosensitive resin. It becomes the raw material of resin. In the alcohol compound having an acryl or methacryl group, the number of acryl groups or methacryl groups (p in the formula (1)) is preferably 1 to 5. 0
However, since it does not contain an acrylic group or a methacrylic group, the photocrosslinking reaction does not proceed, which is not preferable. On the other hand, when it is 6 or more, not only is it industrially difficult to produce, but also the reaction is difficult to proceed, which is not preferable.

Examples of the alcohol compound having an acryl group or a methacryl group 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 acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polyethylene glycol modified methacrylate,
Examples thereof include, but are not limited to, polyethylene glycol-modified acrylate, polypropylene glycol-modified acrylate, and polypropylene glycol-modified methacrylate. When using these, even one type is 2
It may be a mixture of more than one kind.

Methanol, ethanol and propyl alcohol used in the present invention undergo an esterification reaction with a carboxyl group of a partially imidized polyamic acid similarly to an alcohol compound having an acrylic group or a methacrylic group,
They are derived into methyl ester, ethyl ester and propyl ester, respectively. These are introduced for the purpose of reducing shrinkage during curing and improving the solubility of the obtained polyamic acid ester. An alcohol compound having 4 or more carbon atoms is not preferable because not only the reactivity decreases but also the curing shrinkage reducing effect is small. These two alcohol compounds are

[0022]

[Chemical 6]

0.2 <[x] / ([x] +
[Y]) <1.0 is preferable. More preferably 0.4
~ 0.8. If it is less than 0.2, the sensitivity during processing is low, which is not preferable. When it is 1.0, the shrinkage upon curing becomes large, which is not preferable. The carbodiimides used in the present invention are used as a dehydrating agent in the esterification reaction of the carboxyl group of polyamic acid with an alcohol compound having an acrylic group or a methacrylic group and an alcohol group of methanol, ethanol or propyl alcohol. As a method of accelerating the esterification reaction, a method of passing through an acid chloride, a method of reacting with an acid or an alkali as a catalyst, and a method of reacting trifluoroacetic anhydride or the like as a dehydrating agent are known. The method (2) is also unavoidable because a large amount of ionic impurities is mixed in the reaction system. Examples of the carbodiimides include, but are not limited to, N, N-dicyclohexylcarbodiimide, N, N-diisopropylcarbodiimide and the like.

The esterification reaction in the present invention is carried out at 70 ° C.
Hereafter, it is more preferable to carry out in the range of 0 to 50 ° C. If the temperature exceeds 70 ° C., the acrylics or methacrylics are likely to undergo thermal polymerization, and the storage stability of the resulting ester-substituted polyamic acid also decreases, which is not preferable. Further, the order of addition is not particularly limited, but after adding the carbodiimides to the polyamic acid and then adding the alcohol compound, the carbodiimides are dissolved and suspended in the polyamic acid and then reacted. Alternatively, dissolving and suspending carbodiimides in an alcohol compound and adding and reacting polyamic acid here does not go through an unstable isoimide structure, or is converted into a stable esterified product in an extremely short time, and side reactions occur. It is difficult to occur and is preferable.

The photosensitive resin obtained by the present invention can be used only by filtering off the carbodiimide condensing agent residue with a filter paper or the like. However, for the purpose of further purifying the product, and for the purpose of changing the dissolving solvent, added dropwise to water or a poor solvent such as methanol or ethyl alcohol,
It is also possible to precipitate the product, filter it out, dry it, and dissolve it again in an aprotic polar solvent or the like for use. As the solvent used for the dissolution, an amide compound having a carbon-carbon double bond and the like can be used in addition to the aprotic polar solvent. Examples of the amide compound having a carbon-carbon double bond include N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide. , N-acryloylpiperidine, N-acryloylmorpholine, N, N-
Examples thereof include dimethylmethacrylamide, N, N-diethylmethacrylamide, and N, N-dimethylaminoethylmethacrylamide, but are not limited thereto.

Further, when the photosensitive resin obtained in the present invention is used, it is preferable to add a photopolymerization initiator for the purpose of improving the sensitivity.

As the photopolymerization initiator in the present invention, the following compounds used for general UV curing resins can be used. Michler's ketone, benzyl, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyldimethylketal, 2-n-butoxyethyl-4. -Dimethylaminobenzoate, 2-chlorothioxanthone,
2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-dimethylaminoethylbenzoate, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3'-dimethyl-
4-methoxybenzophenone, 2,4-dimethylthioxanthone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-
Methyl-1-phenyl-propan-1-one, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one isopropylthioxanthone, methylbenzoylformate, 2-methyl-1- [4
(Methylthio) phenyl] -2-morpholinopropanone-1, N-phenylglycine, 1-phenyl-1 ', 2
-Propanedion-2- (O-ethoxycarbonyl) oxime, tetra (t-butylperoxycarbonyl) benzophenone and the like can be mentioned, but the present invention is not limited thereto. In addition, these may be one kind or a mixture of two or more kinds.

In the present invention, a photopolymerizable monomer having a carbon-carbon double bond may be added for the purpose of further improving the sensitivity. Specific examples thereof include 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, N, N-
Dimethyl acrylamide and acrylates of these and those obtained by changing acrylamide to methacrylate or methacrylamide can be used.

To the negative photosensitive resin composition according to the present invention, an adhesion aid, an inhibitor, a leveling agent and other various fillers may be added.

In the method of using the negative photosensitive resin composition according to the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic or an aluminum substrate.
The coating method is spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after prebaking at a low temperature of 60 to 100 ° C. to dry the coating film, 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 preferable.

Next, the non-irradiated portion is dissolved and removed with a developing solution to obtain a negative relief pattern. As the developing solution, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, or the like is used alone or mixed with methanol, isopropyl alcohol, water, xylene, or the like. 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, methanol, xylene, ethanol, isopropyl alcohol, butyl acetate, water or the like is used. Next, heat treatment is performed to form an imide ring, and a final 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 for a multilayer circuit, a cover coat for a flexible copper clad plate, a solder resist film, a liquid crystal alignment film and the like.

[0033]

The present invention will be described in detail with reference to the following examples. Example 1 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 322.2 g (1.0 mol), 4,4'-diaminodiphenyl ether 190.2 g (0.95 mol)
Was suspended in N-methyl-2-pyrrolidone and reacted at 80 ° C. for 3 hours. When the imidation ratio of the obtained polyamic acid was measured by using H-NMR, it was 24%. Next, in the reaction system, glycerol dimethacrylate 228.3
g (1.0 mol) Methanol 32.0 g (1.0 mol)
Was added and stirred for 30 minutes, then N, N dissolved in N-methyl-2-pyrrolidone while maintaining the reaction system at 10 ° C. or lower.
-Dicyclohexylcarbodiimide 412.6 g (2.
(0 mol) was added dropwise over about 20 minutes, and then at 5 ° C at 5 ° C.
The reaction was carried out over time. After filtering off dicyclohexylurea,
It was reprecipitated in a 1: 1 mixed solution of methanol and water and further dried under reduced pressure to obtain a yellowish white polyamic acid ester. Furthermore,
To 100 g of the obtained resin, 0.01 g of methyl ether hydroquinone as a polymerization inhibitor, 4 g of N-phenylglycine as a photopolymerization initiator, and 4 g of trimethylolpropane triacrylate as an acrylic monomer were added,
It was dissolved in N-methyl-2-pyrrolidone at room temperature to obtain a resin composition. The obtained resin composition is applied onto a silicon wafer with a spinner and dried at 80 ° C. for 1 hour by a dryer,
A film having a thickness of about 8 μm was obtained. Mask for resolution measurement manufactured by Toppan Printing on this film (Topographic test chart No. 1)
UV rays of ² J / cm ² and then 50% by weight of N-methyl-2-pyrrolidone and 50% by weight of xylene.
When developed with the developing solution of No. 3, a good pattern without breakage was obtained. Furthermore, in a clean oven, 150 ℃
It was cured for 30 minutes at 350 ° C. for 30 minutes. No collapse was observed in the pattern after curing.

Example 2 The reaction of polyamic acid in Example 1 was carried out at 80 ° C. for 3 hours to 6 hours.
It was changed to 0 ° C for 7 hours. The imidation ratio of the obtained polyamic acid was 21%. Furthermore, a polyamic acid ester was obtained in the same manner as in Example 1, and the same formulation and the same evaluation were performed. The pattern after development was a good pattern with no collapse, and the good pattern was maintained even after curing. Example 3 The reaction of polyamic acid in Example 1 was carried out at 80 ° C. for 3 hours to 1
The temperature was changed to 00 ° C. for 2 hours, and the test was performed. The imidation ratio of the obtained polyamic acid was 29%. Furthermore, a polyamic acid ester was obtained in the same manner as in Example 1, and the same formulation and the same evaluation were performed. The pattern after development was a good pattern with no collapse, and the good pattern was maintained even after curing. Example 4 In Example 1, the glycerol dimethacrylate was changed to 130.1 g (1.0 mol) of 2-hydroxyethyl methacrylate, a polyamic acid ester was obtained in the same manner, and the same formulation and the same evaluation were performed. The pattern after development was a good pattern with no collapse, and the good pattern was maintained even after curing.

Example 5 In Example 1, methanol was added to 46.1 g (1.
0 mol) to obtain a polyamic acid ester in the same manner,
Similar formulations and similar evaluations were performed. The pattern after development was a good pattern with no collapse, and the good pattern was maintained even after curing. Example 6 In Example 1, the amount of glycerol dimethacrylate was 13
Reduced to 6.9 g (0.6 mol), methanol 44.8 g
(1.4 mol) to obtain the same polyamic acid ester, and the same composition and the same evaluation were carried out. The pattern after development is a good pattern without collapse,
Even after the curing, the good pattern was maintained without collapse. Example 7 In Example 1, the amount of glycerol dimethacrylate was 31
Increased to 9.6 g (1.4 mol), 19.2 g of methanol
(0.6 mol), the polyamic acid ester was obtained in the same manner, and the same formulation and the same evaluation were carried out. The pattern after development was a good pattern with no collapse, and the good pattern was maintained even after curing. Example 8 N, N-dicyclohexylcarbodiimide 4 in a flask
12.6 g (2.0 mol) and glycerol dimethacrylate 228.3 g (1.0 mol), methanol 32.
0 g (1.0 mol) was dissolved in N-methyl-2-pyrrolidone, and the polyamic acid obtained in Example 1 was added dropwise over 1 hour while maintaining the reaction system at 10 ° C or lower. After dropping, the mixture was further reacted at 40 ° C. for 5 hours. Furthermore, a polyamic acid ester was obtained in the same manner as in Example 1, and the same formulation and the same evaluation were performed. The pattern after development was a good pattern with no collapse. In addition, a good pattern that did not collapse was retained even after curing.

Comparative Example 1 The reaction of polyamic acid in Example 1 was carried out at 80 ° C. for 3 hours to 2 hours.
The procedure was changed to 5 ° C. for 20 hours. The imidation ratio of the obtained polyamic acid was 0%. Furthermore, a polyamic acid ester was obtained in the same manner as in Example 1, and the same formulation and the same evaluation were performed. As the pattern after development, a good pattern without collapse was obtained. However, since the shrinkage was large after curing, cracks were generated from the pattern corners. Comparative Example 2 The reaction of polyamic acid in Example 1 was carried out at 80 ° C. for 3 hours to 1
The temperature was changed to 50 ° C. for 1 hour. Gelation occurred during the reaction, and the next reaction could not be performed. Comparative Example 3 In Example 1, the amount of methanol was changed to 228.2 g (1.0 mol) of glycerol dimethacrylate, and the total amount of glycerol dimethacrylate was changed to 2 mol. An evaluation was carried out. As the pattern after development, a good pattern without collapse was obtained. However, after curing, cracks were generated from the pattern corners.

[0037]

Industrial Applicability According to the present invention, a photosensitive resin having a high sensitivity and a small shrinkage upon curing can be synthesized with good reproducibility and is industrially useful.

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[Procedure amendment]

[Submission date] June 15, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

However, as a method for introducing an ester group, first, an acid dianhydride is reacted with an alcohol-containing photosensitive group, and then a chlorine-containing compound such as an acid chloride is used as a condensing agent to copolymerize with a diamine (Japanese Patent Publication No. 55-41422), and a method using a carbodiimide as a condensing agent as a method not using a chlorine-containing compound (JP-A-60-22).
No. 8537) and the like are known. However, in either method, carboxylic acid and diamine must be polycondensed under mild conditions such that carbon-carbon double bond does not react, it is difficult to obtain a high molecular weight product, and further, molecular weight and photosensitive group substitution between synthesis lots are difficult to obtain. There was a large variation in the introduction rate. Therefore, the photosensitive resin composition obtained from this resin has only low sensitivity and low cured film mechanical properties. Further, as a method for solving these various problems, a method of first synthesizing a high molecular weight polyamic acid and introducing an ester bond via an isoimide (Japanese Patent Laid-Open No. 254547/1986).
Japanese Patent Laid-Open No. 4-204452). On the other hand, in a non-photosensitive polyamic acid, a method of quantitatively imidizing a part of a carboxyl group to control storage stability and processing workability (Japanese Patent Application No. 4-338991).
Etc. However, in the conventional method for producing a photosensitive polyamic acid ester compound via a polyamic acid, since the purpose is to make the ester substitution rate 100%, a highly sensitive photosensitive resin can be obtained but the shrinkage upon curing does not occur. Is large and stress is liable to be generated, so that there is a problem that cracks easily occur in the pattern corners and the like.

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Claims (1)

[Claims] 1. A tetracarboxylic dianhydride and / or a tetracarboxylic acid derivative is reacted with a diamine and / or a diamine derivative at 50 to 120 ° C. to carry out an amidation polyaddition reaction and a dehydration ring-closure imidization reaction, A method for producing a partially imidized photosensitive polyamic acid ester, which comprises subjecting the obtained partially imidized polyamic acid and an alcohol compound represented by the following formula (1) to an ester addition reaction in the presence of carbodiimides. [Chemical 1]