JPH02157845A - Photosensitive resin composition and photosensitive element using the same - Google Patents

Abstract

PURPOSE:To provide high photosensitivity as a thick film and to improve heat resistance by incorporating a photosensitive addition product of a specific polyimide precursor and isocyanate compd. and a specific compd. or a photoinitiator contg. amino acid as well as an org. solvent into the above compsn. CONSTITUTION:The photosensitive resin comps. is prepd. by incorporating the photosensitive addition product of the polyimide precursor having the repeating unit of the general formula I and the isocyanate compd. expressed by the general formula II or III and the aminobenzylidene carbonyl compd. of the general formula VI, the photoinitiator contg. the N-aryl-alpha-amino acid of the general formula V, as well as the org. solvent which completely dissolves the precursor such as N-methyl-2-pyrrolidone into this compsn. This compsn. is laminated on a base to form the photosensitive element. The thick film having the high photosensitivity and the excellent heat resistance is obtd. even in the case of utilizing this compsn. as the thick film.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin composition with excellent heat resistance that can have high photosensitivity even when used as a thick film, and a photosensitive resin composition using the same. Concerning photosensitive elements.

(Prior Art) Conventionally, heat-resistant polymers such as polyimide have excellent heat resistance, electrical and mechanical properties, and are therefore used as forming materials for solid-state devices such as insulating films and passivation films in the semiconductor industry. It is also used as a resist material for forming semiconductor integrated circuits, and is also widely used in the field of printed wiring boards as a resist material for forming circuit patterns on substrates, or as an interlayer insulating material.

In recent years, in the semiconductor industry, organic materials with excellent heat resistance, such as polyimide resin, have been used mainly as interlayer insulation materials, taking advantage of their properties, instead of inorganic materials. There is.

By the way, pattern formation for semiconductor integrated circuits and printed circuit boards is a complicated process that involves forming a film of resist material on the surface of the base material, exposing certain areas to light, removing unnecessary areas by etching, etc., and cleaning the surface of the base material. Since pattern formation is performed through a wide variety of processes, it is desired to develop a heat-resistant photosensitive material that can be used as an insulating material, with the resist material in the necessary areas remaining intact even after pattern formation through exposure and development. ing.

Therefore, heat-resistant photosensitive materials using base polymers such as photosensitive polyimide and cyclized polybutadiene have been proposed as these materials. In particular, photosensitive polyimide is
It is attracting particular attention because of its excellent heat resistance and the ease with which impurities can be removed.

As such photosensitive polyimide, for example,
9-17374, a system consisting of a polyimide precursor and a dichromate was first proposed, but while this material has advantages such as practical photosensitivity and high film-forming ability, It lacks storage stability and has drawbacks such as residual chromium ions in the polyimide.
It was not put into practical use.

As another example, Japanese Patent Publication No. 55-30207 proposes a photosensitive polyimide precursor in which a photosensitive group is introduced into a polyimide precursor through an ester bond, but this material has low photosensitivity and cannot be put to practical use. is insufficient.

On the other hand, JP-A-57-168942 proposes a photosensitive composition whose main component is a mixture of polyamic acid and an amine having a photoactive functional group.

However, this photosensitive composition has the problem that as the film thickness increases, the photosensitivity decreases and the image swells during development.

Furthermore, a photosensitive composition is proposed in JP-A-59-84936, in which a long-wavelength sensitizer is blended into a composition mainly composed of polyamic acid having a double bond in its side chain. However, similar to the above, this thick film had low photosensitivity and was insufficient for practical use.

(Problems to be Solved by the Invention) The present invention has been made in view of the problems of the prior art as described above. (Means for Solving the Problems) The present invention provides (1) a polyimide precursor having a repeating unit represented by general formula (I);

(In the formula, R1 represents a tetravalent aromatic group, R2 represents a divalent organic group) An isocyanate compound represented by the general formula (II) or an isocyanate compound represented by the general formula (III) (in the formula, R3, R4 and R5 each independently represent a hydrogen atom or a methyl group, R6, R, represents a divalent hydrocarbon group, R8 represents a tetravalent organic group, Y, , Y2 and Y3 each independently represent hydrogen. At least one group selected from the group consisting of an atom and a monovalent organic group having an ethylenically unsaturated group, and at least one of Y, Y2 and Y3 is a monovalent organic group having an ethylenically unsaturated group. (2) an aminobenzylidenecarbonyl compound represented by the general formula (IV) (which is an aryl group, an aroyl group, an acyl group, or a nitrogen atom substituted with a hydrogen atom) and a general formula N-aryl-α-amino acid represented by (V).

(IV) (wherein Rs, R10, R1+ and RI2 are each independently an alkyl group, R13 and R54 are each independently a hydrogen atom, cyano group, alkoxycarbonyl group, alkyl group or aryl group, R15, R1
6, R17+ R18+ R'9. R20, R21
and R22 are each independently a hydrogen atom, a chlorine atom, a bromine atom, or an alkyl group.

an aryl group or an alkoxy group, X is an oxygen atom,
Sulfur atom or alkyl group, aralkyl group.

(In the formula, R23, R24, R25, R26 and R27
each independently represents a hydrogen atom, a cyano group, an alkyl group, or a halogen atom; R2B represents a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aminoalkyl group, or an aryl group;
29 and R3° are each independently a hydrogen atom or an alkyl group) and (3) a photosensitive resin composition comprising an organic solvent.

The polyimide precursor having a repeating unit represented by the above general formula (I) in the present invention can be obtained by a known method using an aromatic tetracarboxylic dianhydride and the following amine compound as starting materials.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3. 3', 4゜4'-
Benzophenone tetracarboxylic dianhydride, 3, 3'
, 4.4'-biphenyltetracarboxylic dianhydride, 1. 2. 5. 6-naphthalenetetracarboxylic dianhydride, 2. 3.6. 7-naphthalenetetracarboxylic dianhydride, 2. 3. 5. 6-pyridinetetracarboxylic dianhydride, 1.4.5゜8-naphthalenetetracarboxylic dianhydride, 3゜4, starvation 10-perylenetetracarboxylic dianhydride, 4,4'-sulfonylsiphthalic acid dianhydride, m-terphenyl-3,3″, 4
．． Examples include 4'-tetracarboxylic dianhydride and p-terphenyl-3,3,4,4'-tetracarboxylic dianhydride.

Of course, the benzene ring of these aromatic tetracarboxylic dianhydrides may be substituted with a substituent such as an alkyl group.

In addition to these aromatic tetracarboxylic dianhydrides, aliphatic (
A cycloaliphatic) tetracarboxylic dianhydride may also be used.

By reacting with the above tetracarboxylic dianhydride, the general formula (I
) Examples of the amine compound that provides a polyimide precursor having a repeating unit represented by: 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone,
4.4'-diaminodiphenylsulfide, benzidine, metaphenylenediamine, para-phenylenediamine, 1.5-naphthalenediamine, 2,6-naphthalenediamine, 2,2-bis(4-aminophenoxyphenyl)propane, bis( Aromatic diamines such as 4-aminophenoxyphenyl) sulfone and 2,2-di(P-aminophenyl)hexafluoropropane are mentioned.

In addition, a diaminoamide compound represented by general formula (VI) can also be used.

(However, Ar is an aromatic group, Y is SO2 or CO, and one amino group and Y-NH2 are located at the ortho position to each other.) Examples of the compound represented by the general formula (VI') include: 4.4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-
4-sulfonamide, 3.4'-diaminodiphenyl ether-3'-sulfonamide, 3.3'-diaminodiphenyl ether-4-sulfonamide, 4,4'-
Diaminodiphenylmethane-3-sulfonamide, 3.
4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-diaminodiphenylmethane-3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfone Amide, 3゜4'-diaminodiphenylsulfone-4-sulfonamide, 3.4'
-Diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4゜4'-diaminodiphenylsulfide-3-sulfonamide, 3,4'-diaminodiphenylsulfide-4- Sulfonamide, 3.3'
-Diaminodiphenyl sulfide-4-sulfonamide, 3,4' -Diaminodiphenyl sulfide-
3'-sulfonamide, 1,4-diaminobenzene-2
-sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3゜4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether-3'-carbonamide, 3
, 3'-diaminodiphenyl ether-4-carbonamide, 4゜4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane-3'-carbonamide amide, 3,3'diaminodiphenylmethane-4-carbonamide, 4,4'-
Diaminodiphenylsulfone-3-carbonamide, 3
．． 4'-diaminodiphenylsulfone-4-carbonamide, 3.4'-diaminodiphenylsulfone-3
'-Carbonamide, 3.3'-diaminodiphenylsulfone-4-carbonamide, 4.4'-diaminodiphenylsulfide-3-carbonamide, 3.4
' -diaminodiphenyl sulfide-4-carbonamide, 3. 3'-diaminodiphenyl sulfide-4-carbonamide, 3,4'-diaminodiphenyl sulfide-3'-sulfonamide, 1.4-
Examples include diaminobenzene-2-carbonamide.

Further, a diaminodiamide compound represented by the general formula (■) can also be used.

(In the formula, Ar is an aromatic group, Y is S02 or CO, and one amino group and one Y-NH2 group are positioned in the ortho position to each other as a pair.) Examples of this compound include 4. 4'-Diaminodiphenyl ether-3,3'-sulfonamide, 3.4
'-Diaminodiphenyl ether-4,5'-carbonamide, 3.3'-diaminodiphenyl ether-4,4'-sulfonamide, 4.4'-diaminodiphenylmethane-3,3'-carbonamide, 3.4
'-diaminodiphenylmethane-4,5'-sulfonamide and the like.

These amine compounds can be used alone or in combination of two or more.

In addition, when using an aliphatic (cycloaliphatic) tetracarboxylic dianhydride, a diaminoamide compound represented by the general formula (VI), and a diaminoamide compound represented by the general formula (■), the polyimide precursor is It can contain a repeating unit different from the repeating unit represented by general formula (I).

Therefore, the reaction between the aromatic tetracarboxylic dianhydride and the amine compound is usually carried out in an inert organic solvent at a temperature of 0 to 100°C, preferably 5 to 60°C, and the polyimide precursor is It can be obtained as a solution of the body in an organic solvent.

These tetracarboxylic dianhydrides and amine compounds are
The former/latter ratio is 0.8/1 to 1. It is preferable to use them in a ratio of 2/1 (molar ratio), and more preferably in equimolar amounts.

Furthermore, as the organic solvent used in the above reaction, a polar solvent that completely dissolves the polyimide precursor to be produced is generally preferred, such as N-methyl-2-pyrrolidone, N,N-
Dimethylacetamide, N.

N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-
Examples include butyrolactone.

In addition to these polar solvents, - inboard organic solvents such as ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, Ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane,
1.4-dichlorobutane, trichloroethane, glorbenzene, 0-dichlorobenzene, hexane, heptane,
Octane, benzene, toluene, xylene, etc. can also be used.

The photosensitive resin composition of the present invention can contain an organic solvent as described above. In such a case, the amount of organic solvent used is preferably 40 to 95% by weight, more preferably 60 to 85% by weight of the photosensitive resin composition.

In the present invention, the above general formula (II) is added to the polyimide precursor having a repeating unit represented by the general formula (I).
A photosensitive adduct can be obtained by adding an isocyanate compound represented by (III) or an isocyanate compound represented by (III).

The reaction between the polyimide precursor and the isocyanate compound in the present invention is carried out in the organic solvent used for the synthesis of the polyimide precursor, usually at 0 to 100°C, preferably at 20 to 70°C.
It can be carried out at a temperature of °C.

The ratio of the isocyanate compound to the polyimide precursor containing repeating units represented by the general formula (I) is determined based on 1 equivalent of carboxyl group in the polyimide precursor from the viewpoint of sensitivity of the photosensitive resin composition and heat resistance of the coating film. It is usually preferable to react in an amount of 0.01 to 0.8 equivalents.

It is more preferable to react in an amount of 0.1 to 0.5 equivalents.

Furthermore, the reaction between the isocyanate compound and the polyimide precursor can be carried out using catalytic agents such as amines such as triethylamine and 1,4-diazobicyclo[2,2,2]octane, and tin compounds such as dibutyltin dilaurate and dibutyltin diacetate. It becomes easier when used.

The above-mentioned catalytically used compounds can be used generally in an amount of 0.01 to 5% by weight based on the isocyanate compound.

Examples of the isocyanate compound represented by general formula (II) include isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, isocyanatopentyl acrylate, isocyanatohexyl acrylate, isocyanatooctyl acrylate, and isocyanatodecyl acrylate. , isocyanate octadecyl acrylate,
Isocyanate ethyl methacrylate, isocyanate propyl methacrylate, isocyanate butyl methacrylate, isocyanate pentyl methacrylate, isocyanate hexyl methacrylate, isocyanate octyl methacrylate, isocyanate decyl methacrylate, isocyanate octadecyl methacrylate, isocyanate ethyl crotonate, Examples include isocyanatopropyl crotonate and isocyanatohexyl crotonate. Isocyanate ethyl methacrylate can be obtained as a commercial product, for example, from Dow Chemical Co., Ltd. or Showa Ropeia Co., Ltd.

Further, the isocyanate compound represented by the general formula (m) is synthesized using a hydroxy compound having at least one ethylenically unsaturated group and a diisocyanate compound as starting materials.

Examples of the hydroxy compound having at least one ethylenically unsaturated group include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, pentaerythri! -rutriacrylate, pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoquinepropyl acrylate, 2-hydroxy-3 - phenoxypropyl methacrylate, allyl alcohol, glycerin diallyl ether, trimethylolpropane diallyl ether, trimethylolethane diallyl ether, pentaerythritol diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, dicrycerol triallyl ether, crotyl alcohol, Vinylphenol, cinnamyl alcohol, allylphenol, 0-cinnamylphenol, CH,-(CL)n-C-0-CH+ -C-CL
OHOCH+ -0-C-C-CH+ R (n is an integer from 1 to 30, R represents H or CH8)
.

RO (n is an integer from 2 to 30, R represents H or CH3)
.

RO (n is an integer from 3 to 30, R represents H or CH3)
.

(R represents H or CH3).

Examples of the compound include 4,4'-diphenylmethane diisocyanate, dianisidine isocyanate, tridene diisocyanate, hexamethylene diisocyanate, 24-tolylene diisocyanate, 2,6-tolylene diisocyanate, and metaxylene diisocyanate. Diisocyanate, 1,5-naphthalene diisocyanate, transvinylene diisocyanate, 2. 2.4-trimethylhexamethylene diisonanate, 2,4.4-trimethylhexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexyl isocyanate, (R is H or CH3 ), etc. can be mentioned.

These hydroxy compounds can be used alone or in combination of two or more.

Also, by reacting with this hydroxy compound, 0 CN in the molecule
(■CH2ago NGO H3 CHl etc. are mentioned.

Furthermore, these diisocyanate compounds can be used alone or in combination of two or more.

The reaction between a hydroxy compound having at least one ethylenically unsaturated group in the molecule and a diisocyanate compound is usually carried out without a solvent or in an inert organic solvent at a reaction time of 0 to 10
It is carried out at a temperature of 0°C, preferably 20 to 70°C, and the ratio of former/latter is 0.8/1 to 1. It is preferable to use a ratio of 2/1 (molar ratio), and it is particularly preferable to use equimolar amounts.

・Furthermore, the reaction between a hydroxy compound having at least one ethylenically unsaturated group in the molecule and a diisocyanate compound can be performed using an amine such as triethylamine, 14-diazobicyclo[2,2,2]octane, or dibutyltin dilaurate, Alternatively, it becomes easy to use a tin compound such as dibutyltin diacetate as a catalyst.

The above-mentioned catalytically used compound can be used in an amount of 0.01 to 5% by weight based on the diisocyanate compound.

Further, the isocyanate compound represented by the general formula (Ir) and the isocyanate compound represented by the general formula (III) can be used alone or in combination of two or more types.

In the present invention, an aminobenzylidenecarbonyl compound represented by the general formula (IV) is used in the photoinitiator system, and this aminobenzylidenecarbonyl compound is
For example, Qrganic reaction (Qrganic)
It can be easily synthesized by appropriately selecting conditions for aldol-type condensation of a cyclohexanone derivative and p-aminobenzaldehyde according to the method described in detail in Volume 16 of Reaction).

The aminobenzylidenecarbonyl compound represented by general formula (IV) is, for example, 2,6-bis(p-N, N-dimethylaminobenzylidene)-4-oxocyclohexanone, 2,6-bis(p-N).

N-diethylaminobenzylidene)-4-oxocyclohexanone, 2,6-bis(p-N,N-dimethylaminobenzylidene)-4-thiacyclohexanone, 2.6
-Bis(p-N,N-diethylaminobenzylidene)-
4-Thiacyclohexanone, 2,6-bis(p-N,N
-dimethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 2,6-bis(p-N, N-
diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 2,6-bis(p-N, N-dimethylaminobenzylidene)-4-ethyl-4-azacyclohexanone, 2,6-bis(p-N.

N-diethylaminobenzylidene)-4-ethyl-4-
Azacyclohexanone, 2,6-bis(4-N,N-diethylamino-2'-methoxybenzylidene)-4-
Oxocyclohexanone, 2゜6-bis(4'-N,N
-diethylamino-2'-methylbenzylidene)-4-
Oxocyclohexanone, 2,6-bis(4'-N,N
-diethylamino-2'-methoxybenzylidene)-4
-thiacyclohexanone, 2,6-bis(4' -N
.

N-diethylamino-2'-methylbenzylidene)-4
-thiacyclohexanone, 2,6-bis(4N,N-diethylamino-2'-methoxybenzylidene)-4-
Methyl-4-azacyclohexanone, 2,6-bis(4
'-N,N-diethylamino-2'-methylbenzylidene)-4-methyl-4-azacyclohexanone, 2
,6-bis(4'-N,N-diethylamino-2'-
methoxybenzylidene)-4-azacyclohexanone,
2.6-bis(4'-NN-diethylamino-2'-methylbenzylidene)-4-ethyl-4azacyclohexanone, etc., but from the viewpoint of sensitivity, in general formula (IV), X has 1 to 12 carbon atoms. Alkyl group or carbon number 1-12
Preferred are compounds in which the nitrogen atom is substituted with an aralkyl group.

The above aminobenzylidene carbonyl compounds may be used alone or in combination of two or more.

In the present invention, an N-aryl-α-amino acid represented by the general formula (V) is used in the photoinitiator system. can be easily synthesized by appropriately selecting.

Examples of the compound represented by the general formula (V) include N
-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N -(n-
propyl)-N-phenylglycine, N-(n-butyl)-N-phenylglycine, N-(2-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine , N-(
n-propyl)-N-phenylalanine, N-(n-butyl)-N-phenylalanine, N-methyl N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N-(p-tolyl)glycine , N-ethyl-N
-(p-tolyl)glycine, N-(n-propyl)-N
-(p-tolyl)chrysin, N -(n-butyl)-N
-(p-tolyl)glycine, N-methyl-N-(p-chlorophenyl)glycine, N-ethyl-N-(p-chlorophenyl)glycine, N-(n-propyl)-N-(
p-chlorophenyl)glycine, N-methyl-N-(p
-bromophenyl)glycine, N-ethyl-N-(p-
bromophenyl)glycine, N-(n-butyl)-N-
(p-bromophenyl)glycine, N, N-diphenylglycine, N-methyl-N=(p-iodophenyl)
Examples include glycine, but from the viewpoint of sensitivity and storage stability, those having a phenyl group substituted with a halogen or cyano group are preferred.

The N-aryl-α-amino acids represented by the above general formula (V) may be used alone or in combination of two or more.

From the viewpoint of the sensitivity of the photosensitive resin composition and the heat resistance of the coating film, the amount of these photoinitiator systems to be used is determined based on 100 parts by weight of the photosensitive resin composition excluding the photoinitiator and organic solvent. , it is preferable to use 0.01 to 30 parts by weight, and 0.01 to 30 parts by weight.
．． It is more preferable to use 1 to 10 parts by weight.

Furthermore, in order to improve the thermal stability of the photosensitive resin composition, a known thermal polymerization inhibitor can be present.

Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, phenothiazine, floranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, p-1 luidine,
Methylenepur, 2,2'-methylenebis(4-methyl-
6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), etc., and the amount used is determined from the photosensitive resin composition by polymerization inhibitor, organic solvent, and photoinitiator. It is preferable to use 0.001 to 10 parts by weight per 100 parts by weight of the components excluding.

In the present invention, a polymerizable unsaturated compound may be used as necessary. Although there are various types of such polymerizable unsaturated compounds, acrylic acid-based compounds or methacrylic acid-based compounds are practical.

Examples of acrylic acid compounds include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carpitol acrylate). Methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate-1.
, hydroxyethyl acrylate, hydroxypropyl acrylate, butylene glycol monoacrylate,
N, N-dimethylaminoethyl acrylate, N,
N-diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate,
Pentaerythritol monoacrylate, trimethylolpropane monoacrylate, allyl acrylate, 1
．． 3-propylene glycol diacrylate, 1.4-
Butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, 2.2-bis-(4-acryloxyjethoxyphenyl)propane, 2.2-bis=( 4-Acryloxypropylxyphenyl)propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacryl formal, tetramethylolmethanetetraacrylate, tris(2-hydroxyethyl)isocyanurate Acrylic ester of acid (n represents an integer from 1 to 30).

÷CH2Cl120→-C-CIl-C112(n,
m represents an integer selected such that n+m is 2 to 30).

LBr I can list many things.

Examples of methacrylic acid compounds include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate,
H3 Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, N, N-dimethylamino methacrylate, N, N-diethylamino methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacryloxypropyltrimethoxysilane, allyl methacrylate, Trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane gelicol dimethacrylate, neopentyl glycol dimethacrylate, 2,2-bis-(4-methacryloxyjethoxyphenyl) ) propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethanetetramethacrylate, methacrylic acid ester of tris(2-hydroxyethyl)isocyanuric acid, (n is 1 to 30
).

1←CH+ CHr O→--=CC-C-cH+CH+ (n, m represent integers selected such that n+m is 1 to 30).

CHIB+ (, I, 3r OCH+ etc. can be mentioned.

In addition, butyl crotonate, glycerin monoclonate,
Vinyl butyrate, vinyl trimethyl acetate, vinyl caproate, vinyl chloroacetate, vinyl lactate, vinyl benzoate, divinyl succinate, divinyl phthalate, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-arylmethacryl Amide, N-hydroxyethyl-N-methylmethacrylamide, acrylamide, N-t-butylacrylamide, N-methylolacrylamide, N-
Isobutoxymethylacrylamide, N-butoxymethylacrylamide, diaseptone acrylamide, hexyl vinyl ether, ethylhexyl vinyl ether, vinyl tolyl ether, polyvinyl ether of polyhydric alcohol, alkyl groups and alkoxy groups in the ortho and para positions.

Styrene derivatives having substituents such as halogen, carboxyl group, allyl group, divinylbenzene, allyloxyethanol, diallyl ester of dicarboxylic acid, N-vinyloxazolidone, N-vinylimidazole, N-vinylpyrrolidone, N-vinylcarbazole, etc. Compounds can also be used.

These compounds may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention contains an organic solvent, but
The organic solvent used in the above reaction may be used as this organic solvent, or the organic solvent used in the reaction may be replaced with another organic solvent described above.

The amount of organic solvent used is preferably 40 to 95% by weight of the photosensitive resin composition from the viewpoint of viscosity, and more preferably 60 to 85% by weight. .

Further, although the photosensitive resin composition of the present invention contains the above-mentioned components, there are no particular restrictions on the order and method of mixing them, and the photosensitive resin composition of the present invention can be prepared by a dipping method, a spray method, a screen printing method, a spinner coating method, etc. It is applied to base materials such as copper-clad laminates and silicon wafers and dried to form a coating film.

Alternatively, a photosensitive element with a sandwich structure is prepared in advance by coating and drying a photosensitive resin composition on a flexible substrate 1, such as a polyester film, and then providing a cover sheet of polyethylene or the like thereon. It is also possible to peel off the polyethylene cover sheet of the photosensitive element to form a coating on the substrate to be coated. A cover sheet does not necessarily have to be used.

By irradiating this coating film with actinic rays from a mask with a desired pattern drawn thereon, polymerization occurs in the irradiated areas, and the solubility of the irradiated areas in a developing solution is significantly lower than that of the non-irradiated areas.

As the actinic light, ultraviolet light is usually used, but in some cases, ionizing radiation such as electron beams or radiation can also be used to give the same effect to the coating film.

When the coating film treated as described above is treated with an appropriate developer, the non-irradiated areas that maintain high solubility are developed and removed, and the solubility is reduced by irradiation with actinic rays. The irradiated area remains, and a desired resin pattern can be obtained.

The developer is preferably one that can completely dissolve and remove the non-irradiated area within an appropriate time, such as N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N- Examples include polar solvents such as dimethylacetamide, dimethylsulfoxide, hexamethylene phosphoric triamide, and γ-butyrolactone.

Alternatively, alcohols such as methanol, ethanol, isopropanol, aromatic hydrocarbon compounds such as toluene and xylene, acetone, methyl ethyl ketone,
A mixture of general organic solvents such as ketones such as methyl isobutyl ketone, esters such as ethyl acetate and methyl propionate, and ethyl such as tetrahydrofuran and dioxane may be used.

In addition, if such an organic solvent causes residual development, a basic compound or an aqueous solution of a basic compound may be further added and used.

Examples of basic compounds include alkali metals.

Quaternary ammonium hydroxide, carbonate monobicarbonate.

Silicates, phosphates, pyrophosphates, acetates, amines, etc. are used.

Specific examples of these include lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium silicate, phosphorus. sodium acid, sodium pyrophosphate, sodium acetate,
Examples include monoethanolamine, jetanolamine, triethanolamine, and the like.

When preparing an aqueous solution of a basic compound, the amount of the basic compound used is 0.0001 to 100 parts by weight of water.
30 parts by weight is preferable, and 0.05 to 5 parts by weight is more preferable.

The resulting thick film resin pattern is then heated at 80-450°.
The photosensitive resin composition of the present invention can be converted into an interlayer insulating film for semiconductors, multilayer printed wiring boards, etc. having excellent heat resistance by baking or post-curing C and further exposure to actinic rays if necessary. The material is also very useful primarily in the field of microfabrication as mentioned above.

(Example) Next, the present invention will be explained using Examples 1 to 12 and Comparative Examples 1 to 8, but the present invention is not limited to these.

Synthesis Example (1) The isocyanate compound represented by the general formula (m) having at least one unsaturated double bond and urethane bond in the molecule used in the example was prepared as follows.

200 equipped with a thermometer, nitrogen gas inlet and stirring device
In a secondary 4-bottle flask, 17.4 g (0.1 mol) of 2.41-lylene diisocyanate and 100 T of dried methyl ethyl ketone! 2 mg of & and dibutyltin dilaurate were added, and the mixture was stirred at room temperature for 4 hours under dry nitrogen gas flow.

Next, add 2-hydroxyethyl acrylate to 11. 6
After adding g (0.1 mol) and stirring the solution at room temperature for 8 hours, methyl ethyl ketone was removed to obtain an isocyanate compound (A).

The 'H-NMR spectrum of the product shows 4.35 p
10CH2CH,,0- signal at pm and 5°7~
A signal of -CH=CH2 was observed at 6.4 ppm.

Furthermore, in the IR spectrum of the product, absorption due to stretching vibration of the carbonyl of the amide group was observed at 1650c, confirming the production of the desired compound.

Synthesis Example (2) Among the aminobenzylidenecarbonyl compounds represented by the general formula (rV) shown in Table 1, 2,6-bis(p-N,
N-diethylaminobenzylidene)-4-methyl-4-
Azacyclohexanone (K-1) was synthesized by the following method.

Other compounds were synthesized and used in the same manner.

That is, in the synthesis of K-1, N-methyl-4-
Piperidone 2g (17.7mmol) and p-N,N
-diethylaminobenzaldehyde 6°26g (35
, 4 mmol) into a 100 va eggplant-shaped flask, add 50 tungsten methanol in which 0.5 g of sodium hydroxide has been dissolved, and heat with a reflux condenser while stirring with a magnetic stirrer. Refluxed. After cooling,
The precipitated orange crystals were separated and thoroughly washed with methanol.

It was purified by recrystallization from benzene/chloroform solvent.

Tables 3 and 4 show the Hl-NMR data of the aminobenzylidenecarbonyl compound thus synthesized (using deuterated chloroform as the solvent and tetramethylsilane as the internal standard) and the UV-visible absorption characteristics in methanol, respectively. Shown below.

Synthesis example (3) A photosensitive inride solution was prepared as follows.

(A) - A polyimide precursor having a repeating unit represented by formula (I) was prepared as follows.

50 with thermometer, nitrogen gas inlet and stirring device
0 wdl in 4 loaf flasks, 3. 64.44 g (0.2 mol) of 3', 4'-4'-benzophenone tetracarboxylic dianhydride (manufactured by Aldrich) and 250 vtQ of N, N-dimethylacetamide were added,
The mixture was stirred at room temperature under a stream of dry nitrogen gas.

(b) Next, 40.05 g (0.2 mol) of 4,4-diaminodiphenyl ether (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added to this solution, and the mixture was stirred at room temperature for 3 hours to form a viscous polyimide precursor solution. Obtained.

Furthermore, the isocyanate compound (A) 29. obtained in Synthesis Example (1) was added to the polyimide precursor solution at room temperature under light shielding.
0 g (0.1 mol) was added and stirred for 8 hours.

During the reaction, carbon dioxide was evolved.

The resulting photosensitive adduct solution is named rPI-IJ (non-volatile content 34.8%).

Synthesis example (4) A photosensitive inride solution was prepared as follows.

3. In the same manner as in Synthesis Example 3. 3', 4.4'benzophenonetetracarboxylic dianhydride 64°44g (
0,2 mol) and N,N-dimethylacetamide 2
50 mm was added, and the mixture was stirred for 1 hour at room temperature under dry nitrogen gas flow.

Next, 40.05 g (0.2 mol) of 4,4-diaminodiphenyl ether was added to this solution, and the mixture was stirred at room temperature for 3 hours to obtain a viscous polyimide precursor solution.

Furthermore, 15.5 g (0.1 mol) of isocyanatoethyl methacrylate-1 (trade name: IEM manufactured by Dow Chemical Company) was added to the above polyimide precursor solution at room temperature under light shielding.
Stir for hours.

This photosensitive adduct solution was mixed with rPI-24 (non-volatile content: 32.
4%).

Examples 1 to 8 100 g of photosensitive adduct solutions of PI-1 and PI-2 were dropped onto each photoinitiator and heavy bar shown in Table 1, and spin-coded at a rotation speed of 1500 rpm for 30 seconds.

The obtained coating film was dried at 80° C. for 10 minutes, and the film thickness of the coating film was determined to be 411.

Next, using a line-and-space photomass with a coating film of 80 μm, it was exposed for 70 seconds to an ultra-high pressure mercury lamp (8 mw/cJ).

Then 1 volume of N,N-dimethylacetamide.

After development was carried out with a mixture of 4 volumes of ethyl alcohol and 4 volumes of 1% aqueous tetramethylammonium hydroxide solution, the film was rinsed with water and dried by air spray.

The cured state of the pattern was determined by the remaining film rate of the coating film after development (thickness of the coating film after development÷thickness of the coating film before development)×100.

Further, the coating film was heat-treated at 350° C. for 1 hour in a nitrogen atmosphere to produce a film, and its thermal decomposition onset temperature was investigated.

The results obtained are shown in Table 1.

Comparative Examples 1 to 5 100 g of photosensitive adduct solutions of PI-1 and PI-2 were dropped onto each photoinitiator and heavy bar shown in Table 2, and spin coded at a rotation speed of 150 rpm for 30 seconds.

The resulting coating film was dried at 80°C for 10 minutes, and the thickness of the coating film was measured.

The properties of this coating film were examined in the same manner as in Examples 1-8.

The results obtained are shown in Table 2.

Table 4 Ultraviolet-visible absorption properties (in MeOH) (Effects of the invention) The photosensitive resin composition of the present invention and the photosensitive element using the same are particularly suitable for use as thick films.

Claims (1)

[Claims] 1. (1) Polyimide precursor having a repeating unit represented by general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a tetravalent aromatic group, R_2 represents a divalent organic group) Isocyanate compound represented by general formula (II) or isocyanate compound represented by general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ Mathematical formulas, chemical formulas , tables, etc.▼(III) (In the formula, R_3, R_4 and R_5 each independently represent a hydrogen atom or a methyl group, and R_6, R_7 are 2
valent hydrocarbon group, R_8 represents a tetravalent organic group, Y_
1, Y_2 and Y_3 are each independently at least one group selected from the group consisting of monovalent organic groups having a hydrogen atom and an ethylenically unsaturated group, and Y_1, Y
At least one of _2 and Y_3 is a monovalent organic group having an ethylenically unsaturated group), (2) an aminobenzylidene carbonyl compound represented by the general formula (IV) ▲ mathematical formula, chemical formula , tables, etc.▼(IV) (In the formula, R_9, R_1_0, R_1_1, and R_
1_2 are each independently an alkyl group, R_1_3
and R_1_4 are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group, an alkyl group, or an aryl group, R_1_5, R_1_6, R_1_7, R_
1_8, R_1_9, R_2_0, R_2_1 and R
_2_2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group, an aryl group, or an alkoxy group, and X is an oxygen atom, a sulfur atom, or an alkyl group, an aralkyl group, an aryl group, an aroyl group, an acyl group, or a hydrogen atom ) and N-aryl-α-amino acids represented by the general formula (V), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_2_3, R_2_4, R_2_5, R_2
_6 and R_2_7 are each independently a hydrogen atom, a cyano group, an alkyl group, or a halogen atom, and R_2_
8 is a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aminoalkyl group or an aryl group, R_2_9 and R_3_0 are each independently a hydrogen atom or an alkyl group); 3) A photosensitive resin composition containing an organic solvent. 2. A photosensitive element obtained by laminating the photosensitive resin composition according to claim 1 on a substrate.