JPS63226640A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin compsn. having superior transparency by blending a photosensitive adduct comprising a polyimide precursor having prescribed repeating units and an isocyanate compd. having a prescribed structure having at least one unsatd. double bond and a urethane bond in the molecule, a photopolymn. initiator and an org. solvent or by further adding a polymerizable unsatd. compd. CONSTITUTION:This photosensitive resin compsn. contains a photosensitive adduct comprising a polyimide precursor having repeating units represented by formula I and an isocyanate compd. represented by formula II and having at least one unsatd. double bond and a urethane bond in the molecule, a photopolymn. initiator and an org. solvent or further contains a polymerizable unsatd. compd. In the formula I, R1 is a quatervalent aliphat. or alicyclic group and R2 is a bivalent arom., aliphat. or alicyclic group or an organosiloxane group. In the formula II, R3 is a quatervalent org. group, R4 is a bivalent org. group, each of Y1-Y3 is H atom or a univalent org. group having an unsatd. double bond and at least one among Y1-Y3 is the univalent org. group.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a photosensitive resin composition, specifically, a coating film obtained that has excellent heat resistance, electrical and mechanical properties.

Photosensitive material with excellent solubility and light transmittance, capable of forming thick films, suitable as a forming material for insulating films and passivation films for solid-state devices in the semiconductor industry, and interlayer insulating materials for semiconductor integrated circuits, multilayer printed wiring boards, etc. The present invention relates to a synthetic resin composition.

(Prior art) In recent years, in the semiconductor industry, interlayer interlayer #1K organic materials have been used to take advantage of their properties, instead of conventional inorganic materials. materials are used. however,
Because pattern formation requires complicated processes, exposure,
There is a desire for a heat-resistant photosensitive material that can be used as an insulating material by leaving a pattern intact even after pattern formation.

Examples of these materials include photosensitive polyimide.

Heat-resistant photosensitive materials and the like using cyclized polybutadiene as a base polymer have been proposed, and photosensitive polyimides are attracting particular attention because of their excellent heat resistance and ease of removing impurities.

As a photosensitive polyimide, a system consisting of a polyimide precursor and a dichromate was first proposed (Japanese Patent Publication No. 49-1989).
Although this material has advantages such as practical photosensitivity and high film-forming ability, it has disadvantages such as poor storage stability and residual chromium ions in the polyimide.

It was not put into practical use. As another example, a photosensitive polyimide precursor has been proposed in which a photosensitive group is introduced into the polyimide precursor through an ester bond (Japanese Patent Publication No. 55-3020
No. 7), since a dehydrochloric acid reaction is involved when introducing a photosensitive group, chloride remains in the end, and its removal poses a problem.

In order to avoid such problems, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Unexamined Patent Publication No. 54-109
828) and a method of introducing a photosensitive group by reacting a functional group in a polyimide precursor with a functional group of a compound having a photosensitive group has also been developed (JP-A-56-24343, I!#). (Open F!fA60-100143).

However, these photosensitive polyimides.

An aromatic polyimide precursor is used as a base polymer from the viewpoint of its heat resistance. Such aromatic polyimide precursors have a fundamental problem in solubility and further have low light transmittance in the ultraviolet region, making it difficult to form a thick film. Because it is difficult to form a thick film, problems remain in flattening the circuit and lowering the dielectric constant when used as an insulating material.

Improvement is desired. For example, when an aromatic polyimide precursor and a compound having a photosensitive group are dissolved to form a photosensitive polyimide, most of the drawing solvent evaporates during the drying process to form a coating film from this solution, and the coating film after drying is ,
It is composed of an aromatic polyimide precursor and a compound having a photosensitive group. Compounds with such photosensitive groups are generally poor solvents for aromatic polyimide precursors, so the aromatic polyimide precursor becomes insolubilized and causes a whitening phenomenon in the coating film, which causes the good solubility to deteriorate. Due to this problem, it is difficult to subject it to the exposure process.

In addition, in most photosensitive resins including photosensitive polyimides, the light energy absorbed by the coexisting photopolymerization initiator acts as a trigger for the reaction9. Most of the current photopolymerization initiators have absorption wavelengths in the ultraviolet region.

It is difficult to form a thick film using a nine-pace polymer using an aromatic polyimide precursor that has low light transmittance in this region. For this reason, with photosensitive polyimide using an aromatic polyimide precursor as a base polymer, the film thickness is limited due to the whitening phenomenon and poor light transmittance, making it extremely difficult to form a thick film pattern. In addition, in order to avoid such problems in solubility and light transmittance, a method has been developed in which a compound having a photosensitive group is mixed with an aliphatic polyimide precursor (Japanese Patent Laid-Open No. 131927/1983). However, such aliphatic polyimide precursors are susceptible to hydrolysis due to the presence of a large number of carboxyl groups adjacent to amide bonds.

A drawback is that the molecular weight of the aliphatic polyimide precursor decreases significantly due to hydrolysis when stored for a long period of time. i9. Method of mixing a compound having a photosensitive group into an adduct solution prepared by adding an epoxy compound having a polymerizable unsaturated bond to an aliphatic polyimide precursor C% 1986-68332
No. 3, No. 3, No. 3, No. 3, No. 3, No. 3, No. 1, No. 3, No. 3, No. 2, No. 1, No. 1, No. 2, No. 2, No. 2, No. 1, No. 3, No. 1, No. 1, No. 2, March 2006, and the polyimide precursor have also been developed, but there is a problem in that it is difficult to obtain an adduct due to the low reactivity between the epoxy group of the epoxy compound and the polyimide precursor.

(Problems to be Solved by the Invention) The present invention solves the problems of the prior art shown above, and provides a photosensitive resin with excellent solubility and light transmittance suitable for the above uses and capable of forming a thick film. A composition is provided.

(Means for eliminating problems) The present invention has one formula (1) (In the formula, & is a tetravalent aliphatic group or an alicyclic group.

The islands are divalent aromatic groups, aliphatic groups, alicyclic groups, or organosiloxane groups). So!D, R4 is a divalent organic group F), Yl
, Yx and Yl are groups selected from monovalent organic groups having a hydrogen atom and an unsaturated double bond 6'), Yl
s Photosensitivity with an isocyanate compound having at least one unsaturated double bond and urethane bond in the molecule represented by (at least one of Yl and Y3 is a monovalent organic group having an unsaturated double bond) Adducts, photoinitiators.

The present invention relates to a photosensitive resin composition containing an organic solvent and optionally a polymerizable unsaturated compound.

The polyimide precursor having a repeating unit represented by the above formula (1) in the present invention is a known compound, and can be easily obtained using an aliphatic or alicyclic tetracarbo/acid or its anhydride and a diamine compound as starting materials. can get.

Examples of aliphatic or alicyclic tetracarboxylic acids or their m-hydrates include butane, pentane, hexane, cyclopentane, bicyclohexene, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and methylcyclohexane. -, tetracarboxylic acid such as ethylene or its anhydride, λ3,5-)lycarboxycyclopentyl acetic acid or its anhydride, bicyclo(λs2)-
Octo-7en-2. a&6-tetracarboxylic acid or its anhydride, tetrahydrofuran-2,λ45-tetracarboxylic acid or its anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-
1,2-dicarboxylic acid or its anhydride, &&6-)dicarboxy-2-carboxymethylnorbonnan-2:5
, 5:8 or its anhydride 1 5'-thiobis(norbornane-2,3-dicarboxylic acid) or its anhydride, 5.5
'-Methylene dithiobis (norbonane-3-dicarboxylic acid) or anhydride of 5,5'-ethylene dithiobis (norbonane-3-dicarboxylic acid) or its anhydride.

5'-propylene dithiobis(norbonane-3-dicarbonate or its anhydride, 5'-sulfonylbis(
norbornane-2,3-dicarboxylic acid) or its anhydride; Anhydrous.

5'-propylene disulfonyl bis(norpinane-2)
, 3-dicarboxylic acid) or its anhydride.

Of course, the skeleton of these tetracarboxylic acids or their anhydrides may be substituted with a substituent such as an alkyl group. These tetracarboxylic acids or their anhydrides can be used alone or in combination of two or more.

In addition, the diamine compound that reacts with the above-mentioned tetracarboxylic acid or its anhydride to give a polyimide precursor is 9
Examples include compounds represented by formula (3) % formula % (3) (where & is a divalent aromatic group, aliphatic group, alicyclic group, or organosiloxane group). A preferable turtle in the formula (3) is 1, for example.

older brother (n is O19 is an integer of 1) (wherein, Xl, Xs, Xs and X4 may be the same or different and are a hydrogen atom, a hydrocarbon compound or a monovalent group of a substituent thereof; Ashi, Z is one--CsHa
-, -〇, -8+, -C-.

CHs CFs -(CHs), -(m is an integer from 2 to 40).

? H″ -(c city)s C-(CHI)s -C 几 し　　　　　 h horse (In the formula, R5 and Rs are divalent organic groups, and are islands.

&, R4 and Ell (1 is a monovalent group of the same or different hydrocarbon compound or its substituted product, J, k
is 0 or an integer from 1 to 20).

Specific examples of the diamine compound represented by the above formula (3) include p-phenylene diamine, m-7 22 diamine, and 4,4'-diaminodiphenylmethane.

44'-Diaminodiphenylethane, benzidine.

4.4'-diaminodiphenyl sulfide, 4.4'-
Diaminodiphenylsulfone, 44'-diaminodiphenyl ether, 3,3'-diaminobenzopheno/.

44'-diaminobenzophenone, 1,5-diaminonaphthalene, 3a'-dimethyl-44'-diaminobiphenyl, 34'-diaminodiphenyl ether.

2.2-(p-aminophenyl)hexa70propane, &4'-diaminobenzanilide, m-xylylenediamine, p-xylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine .

Hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 44'
-dimethyl hebutamethylene diamine.

1.4-diaminocyclohexane, tetrahydrodicyclope/tadienylene diamine, hexahydro-47-methanoindanilene symethylene diamine.

Trisif E'[6,2,1,07]-landecylenedimethyldiamine.

(R is Hl or CHI in both formulas) (R' is H, CHs, C1 or Br in both formulas)
Examples include CHI C, CHs, CHs, and the like. These diamine compounds are
One type can be used alone or two or more types can be used in combination.

Aliphatic Te is usually reacted with an alicyclic tetracarboxylic acid or its anhydride and a diamine compound in an inert organic solvent.
It is usually carried out at a temperature of 0 to 100°C, preferably 5 to 60°C, and is obtained as a solution of the polyimide precursor in an organic solvent. The ratio of the aliphatic or alicyclic tetracarboxylic acid or its anhydride and the diamine compound is 0.8/1 to 1.
It is preferable to use it in a ratio of 2/1 (molar ratio), and 'F
Preferably, it is used in molar equivalents of IK.

As the organic solvent used in the above reaction, a polar solvent that completely dissolves the polyimide precursor to be produced is generally preferred.9 For example, N-methyl-2-pyrrolid/.

N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea,
Examples include hexamethylphosphoric acid triamide, r-butyrolactone, and the like. In addition to these polar solvents, common organic solvents such as chthons, esters, lactos, ethers, halogenated hydrocarbons, hydrocarbons 1, such as acetone, methyl ethyl ketone, methyl imbutyl ketone,
Cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl chelate, diethyl lonate, r-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene/IJ: I-dimethyl ether, tetrahydrofuran, dichloromethane, l,
2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene.

O-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene [can be used]. The polyimide precursor and Kume K to be completely dissolved are:
It is desirable to use these general organic solvents in combination with the above-mentioned polar solvents.

In the present invention, the above formula (2
) A photosensitive adduct is obtained by adding an incyanate compound having at least one unsaturated double bond and urethane bond in the molecule represented by K.

In the present invention, the reaction between the polyimide precursor and the isocyanate compound is carried out at a temperature of usually θ to 100°C in an organic solvent used in the synthesis of the polyimide precursor.

Preferably it is carried out at a temperature of 20 to 70°C. The proportion of the incyanate compound to the polyimide precursor is usually 0.1 to 0.08 g per equivalent of sil group in the carboxyl group in the polyimide precursor from the viewpoint of sensitivity of the composition and heat resistance of the coating film.
equivalent, preferably 0.4 to O,S equivalent.

Furthermore, the reaction between the incyanate compound and the polyimide precursor includes triethylamine, 1,4-diazobicyclo(2,
2,2) It freezes easily when amines such as octane, tin compounds such as dibutyltin dilaurate, and dibutyltin diacetate are used. These can usually be used in an amount of about 0.05 to 25% by weight based on the incyanate compound.

This inocyanate compound is synthesized using a hydroxy compound having at least one unsaturated double bond and a diinocyanate compound as starting materials. Hydroxy compounds having at least one unsaturated double bond include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethane diacrylate, trimethycoolethane dimethacrylate.

Pentaerythritol triacrylate, pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate.

2-hydroxy-3-phenoxypropyl 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, dicrysecol triallyl ether, cuctyl alcohol,
Vinylphenol, cinnamyl alcohol.

Allylphenol, 0-cinnamylphenol OR α--OC-C-CHt ■ R (n is an integer from 1 to 30) (几 is H or CHs) -C&-CH-CHs H (R is H or CHs) (R is Hl or CHs) etc. These hydroxy compounds are.

One type can be used alone or two or more types can be used in combination. In addition, examples of the diisocyanate compound which reacts with this hydroxy compound to give an isocyanate compound having an unsaturated double bond and a urethane bond in the molecule include 44'-diphenylmethane diisocyanate, dianisidine incyanate, tridene diisocyanate, hexamethylene diisocyanate, 2.4-) lylene diisocyanate, 2.6-) lylene diisocyanate.

metaxylylene diisocyanate, 1.5-naphthalene diisocyanate, transvinylene diisocyanate, 2I2,4-)limethylhexamethylene diinocyanate, 2.44-)limethylhexamethylene diinocyanate, 3-inocyanatomethyl -3,5,5-)limethyl-cyclohexyl isocyanate CO 2 and the like. Furthermore, these diincyanate compounds can be used singly or in combination of two or more.

The reaction between a hydroxy compound having at least one unsaturated double bond in the molecule and a diisocyanate compound is carried out without a solvent or in an inert organic solvent at usually 0 to 100°C.
, preferably at a temperature of 20 to 70°C. Hydroxy compounds and diisocyanate compounds having at least one unsaturated double bond in the molecule have a ratio of 0.
It is preferable to use them in a ratio of 8/1 to 1.2/1 (molar ratio), particularly preferably in equimolar amounts. Furthermore, the reaction between a hydroxy compound having at least one unsaturated double bond in one molecule and a diincyanate compound can be performed using triethylamine, 1,4-diazobicyclo[lambda]
2] This is facilitated by using an amine such as octane or a tin compound such as dibutyltin dilaurate or dibutyltin diacetate.

These range from about 0.05 to the diisocyanate compound.
It can usually be used within a range of 25% by weight.

In the present invention 8A, there are various polymerizable unsaturated compounds that can be used as needed, but acrylic acid compounds, methacrylic acid compounds, etc. are practical. Specific acrylic acid compounds include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate-tobenzyl acrylate, carpitol acrylate, methoxyethyl acrylate, Ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butylene glycol monoacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol monoacrylate , trimethiculpropane monoacrylate, allyl acrylate, 1.3-propylene glycol diacrylate, L4-butylene glycol diacrylate, 1.6-hexane glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, S2 -bis-(4-
Acryloxyjethoxyphenyl)furopane, 2.2-
Bis-(4-acryloxypropylxyphenyl)furopane.

Trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacryl formal.

Tetramethylolmethanetetraacrylate, Tris(
Acrylic acid ester of 2-hydroxyethyl) isocyanuric acid.

(n is an integer of 1 to 30) (n, m is an integer of n-) - m is an integer of 2 to 30) HsBr, etc., and examples of methacrylic acid compounds include methacrylic acid, methyl methacrylate , ethyl methacrylate, propyl methacrylate, inglovir methacrylate, butyl methacrylate, inbutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate.

Ethoxyethyl methacrylate, butoxyethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, N,N-dimethylamino methacrylate, N,N-diethylamino methacrylate.

Glycidyl methacrylate, tetrahydromifurfuryl methacrylate, methacryloxypropyltrimethoxysilane, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1.3-butylene glycol dimethacrylate, 1.6-hexane glycol dimethacrylate, neo Pentyl glycol dimethacrylate, 2,2-bis-(4-methacryloxyjethoxyphenyl)propane.

Trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethanetetramethacrylate, methacrylic acid ester of tris(2-hydroxyethyl)in cyanuric acid.

(n is an integer of 1 to 30) Hs (n, m is an integer of n-) - m is an integer of 1 to 30) Cl Br 0 Br Br etc., butyl crotonate, glycerin monoclonate, vinyl butyrate, vinyl trimethyl acetate, vinyl caproate.

Vinyl chloroacetate, vinyl lactate, vinyl benzoate, divinyl succinate, divinyl 7-talate,
Methacrylamide, N-methylmethacrylamide, N-
Ethyl methacrylamide, N-aryl methacrylamide, N-hydroxyethyl-N-methyl methacrylamide, acrylamide, N-t-butylacrylamide,
N-methylolacrylamide, N-imbutoxymethylacrylamide, N-butoxymethylacrylamide, diaseptone acrylamide, hexyl vinyl ether, ethylhexyl vinyl ether.

Vinyl tolyl ether, polyvinyl ether of polyhydric alcohol, styrene derivatives such as styrene divinylbenzene with substituents such as alkyl groups, alkoxy groups, norogen, carboxyl groups, and allyl groups at the ortho and hhala positions, allyloxyethanol, Diallyl ester of dicarboxylic acid.

N-vinyloxazolidone, N-vinylimidazole,
Examples include N-vinylpyrrolidone and N-vinylcarbazole. These may be used alone or as a mixture.

As the photopolymerization initiator, various compounds that are generally used as photopolymerization initiators for ultraviolet curable paints can be used. For example, Michler's ketone, benzoin, 2-methylbenzoin, be/zoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-1-butylanthraquinone, l,2-benzo-9,10-anthraquinone, anthraquinone , methylanthraquinone, 4,4'-bis(
diethylamino)benzophenone, acenaphthene.

Benzophenone, thioxanthone, L5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone,
1-Hydroxycyclohexylphenylketone, 2-methyl-[4-(methylthio)phenyl]-2-mol 7 olino 1-propane, diacetyl, benzyl, benzyl dimethyl ketal.

Benzyl diethyl ketal, diphenyl disulfide,
Anthracene and the like can be mentioned. The amount of these photopolymerization initiators used is usually 0 per 100 parts by weight of the photosensitive adduct or 109 parts by weight of the photosensitive adduct and the polymerizable unsaturated compound, from the viewpoint of the sensitivity of the two compositions and the heat resistance of the coating film. .01～
The amount is 30 parts by weight, preferably α1 to 10 parts by weight. A small amount of amines, which are known sensitizing aids, can also be used in combination with these photopolymerization initiators. In order to improve the thermal stability of the maso composition, it is preferable to coexist with a known thermal polymerization inhibitor.

Specific examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, phenothiazine, floranil, 7-tylamine,
β-naphthol, 2.6-di-t-butyl-p-cresol, h+)dine, nitrobenzene, p-)luidine, methylene blue, 2゜2'-methylenebis(4-methyl-6-t-butylphenol), 2 .2'-methylenebis(4-ethyl-6-t-butylphenol), etc., and the amount used is usually 100 parts by weight of the photosensitive adduct or 100 parts by weight of the photosensitive adduct and the polymerizable unsaturated compound. The amount is preferably 0.001 to 10 parts by weight.

The photosensitive resin composition FJAK of the present invention contains an organic solvent, but the organic solvent used in the above reaction may be used, or the organic solvent used in the 2 reactions may be used in addition to those described above. You may change it to an organic solvent.

The amount of the organic solvent used is 10 to 95% by weight of the photosensitive resin composition, preferably 30 to 80% by weight from the viewpoint of the viscosity of the composition.

The photosensitive resin composition of the present invention contains the above-mentioned components, but there are no particular restrictions on the order, mixing method, etc. of these components.

The photosensitive resin composition of the present invention is applied to a substrate such as a copper-clad laminate or silicone laminate by an appropriate means and dried. In this case, the photosensitive adduct, which is the backbone of the photosensitive resin composition of the present invention, has very good solubility and light transmittance, is uniform even in the presence of the 9-polymerizable unsaturated compound, and has excellent transparency. Gives a coating. When actinic light is irradiated from a mask with a desired pattern drawn on this coating film, polymerization occurs in the irradiated areas due to K, and the solubility is greatly reduced compared to the non-irradiated areas. In some cases, irradiation with ionizing radiation such as electron beams or radiation can also provide a similar effect. Thus, a desired thick resin pattern can be obtained by developing and removing the non-irradiated areas using an appropriate organic solvent or alkaline aqueous solution as a developer. As the organic solvent, the above-mentioned synthetic solvent for the polyimide precursor is used. Further, when using such an organic solvent, water may be added to the organic solvent when development residues are generated. The amount of water used is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the organic solvent.

Suitable bases for use in alkaline aqueous solutions include hydroxides of alkali metals and quaternary ammonium.

Carbonates, bicarbonates, silicates, phosphates, pyrophosphates, acetates, amines, etc. are used. Specific examples of these include lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonium hydroxide.

Trimethylpendylammonium hydroxide.

Tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate.

Examples include sodium silicate, sodium phosphate, sodium birophosphate, sodium acetate, monoethanolamine, jetanolamine, triethanolamine, and the like. The amount used is usually 0.00 parts by weight per 100 parts by weight of water.
01 to 30 parts by weight, preferably o, oos to 5 parts by weight.

In addition, if such an alkaline aqueous solution causes development residue, an organic solvent may be added to the alkaline aqueous solution. As the organic solvent, the polar solvent used during the synthesis of the polyimide precursor mentioned above is general KtFFt.
L. In addition to this polar solvent, the above-mentioned general organic solvents can also be used. The amount of organic solvent used is usually 0.1 to 100 parts by weight per 100 parts by weight of the alkaline aqueous solution.
Parts by weight, preferably 5 to 50 parts by weight.

The obtained thick resin pattern can be converted into an interlayer insulating film for semiconductors, multilayer printed wiring boards, etc., which has excellent heat resistance by subsequent baking, that is, by post-curing. The resin composition.

It is very useful mainly in the field of microfabrication as mentioned above.

(Effects of the Invention) The photosensitive resin composition of the present invention is a photosensitive resin composition that is excellent in solubility and light transmittance, and is suitable for the above-mentioned uses capable of forming a thick film.

(Examples) Next, the present invention will be explained with reference to two examples, but the present invention is not limited to these examples.

The isocyanate compounds (1) and (II) used in Examples and having at least one unsaturated double bond and urethane bond in the molecule were prepared as follows.

(1) 2 equipped with a thermometer, nitrogen gas inlet and stirring device
00ml! 17.49 (0.1 mol) of 44-tolylene diisocyanate, 100 ml of dried methyl ethyl ketone, and 21.1 g of dibutyltin dilaurate were added to a four-bottle flask, and the mixture was stirred at room temperature under a stream of dry nitrogen gas. Next, 11.69 (0.1 mol) of 2-hydroxyethyl acrylate was added.

After stirring this solution at room temperature for 8 hours, methyl ethyl ketone was removed to obtain incyanate compound (1).

In the H-NMR spectrum of the product, 435p1)m
The signal of 0CR-rich CHsO- and &7~6.4p
A signal of pm KCH=CHs was seen.

(2) 2 equipped with a thermometer, nitrogen gas inlet and stirring device
In a 00 ml four-bottle flask, 2229 (0.1 mol) of 3-isocyanatomethyl-3,5,5-)limethyl-cyclohexyl isocyanate, 100 ml of dried methyl ethyl ketone, and 2! IIg was added, and the mixture was stirred at room temperature under dry nitrogen gas flow. Next, add 2-hydroxypropyl acrylate to 11
．． Add 3 g (0.1 mol).

After stirring this solution at room temperature for 8 hours, methyl ethyl keto/ was removed to obtain isocyanate compound (II).

"H-NMR of the product, 1, vector, 4.28p
I) mK-OCH-CH*0-tD signal and 5.
A -CH-CH signal was observed at 7 to a4 ppm.

Example 1 9500 with thermometer, nitrogen gas inlet and stirring device
5-(λ5-dioxotetrahydro7lyl)-3-methyl-3-cyclohexene-1 in a four-necked flask of mj'
, 2-dicarboxylic anhydride (manufactured by Dainippon Ink & Chemicals Co., Ltd.) 52.849 (0.2 mol) and 250 ml of N,N-dimethylacetamide were added, and the mixture was stirred at room temperature under dry nitrogen gas flow. Next, 40.059 (0.2 mol) of 44'-diaminodiphenyl ether (manufactured by Mitsui Toatsu Ihigaku Co., Ltd.) was added and the solution was stirred at room temperature for 8 hours to obtain a viscous polyimide precursor. Furthermore, 29.0 g (0.1 mol) of the isocyanate compound obtained in (1) was added at room temperature under light shielding.
The mixture was added and stirred for 24 hours. Carbon dioxide was evolved during the reaction. Add 92-9 g of tetraethylene glycol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) to this solution, add 5.4 g of benzophenone and 0.69 g of 4,4'-bis(diethylamino)benzophenone under light shielding, stir and mix, and filter. A photosensitive resin composition was obtained by filtration.

This composition was applied to a copper-clad laminate (MCL-manufactured by Hitachi Chemical Co., Ltd.).
E-61) with a bar coater to a dry thickness of 50 μm
300 m
A clear resin pattern was obtained by irradiating ultraviolet rays at 250 °C for 1 hour, developing with N-methylpyrrolidone, and rinsing with ethyl alcohol. After Bost Cure,
When thermogravimetric analysis was performed, a 10% weight loss in temperature 4
It had good heat resistance of 18°C.

Example 2 In the same manner as in Example 1, 1.2.3.4-butanetetracarboxylic dianhydride was added to the flask using Seitoatsu Fine Co., Ltd. 1) 39
．． 4. Proceed as in Example 1, adding 63s (0.2 mol) and 2 s Oml of N,N-dimethylacetamide.
4'-diaminodiphenyl ether 40.059 (0,
2 mol) was added to obtain a viscous bolyimide precursor.

Further, in the same manner as in Example 1, incyanate compound (1)j9.09 (0.1 mol) obtained in (1) was added at room temperature,
Stirred for 24 hours. Carbon dioxide was evolved during the reaction. Add this solution to FA-731A (Tris (manufactured by Hitachi Chemical Co., Ltd.)).
2-acryloylethyl)in cyanurate) at 79.
3G, add 4.2 g of benzyl dimethyl ketal (manufactured by Ciba Geigy) under light shielding, stir and mix, and filter through a filter to obtain a photosensitive resin composition. This composition was applied in the same manner as in Example 1 to obtain a transparent coating film with a thickness of 50 μm. After this coating, irradiation was carried out at 300 mJ/ai" and rinsing was performed in the same manner as in Example 1, and a clear resin pattern was obtained.

When this resin pattern coating film was subjected to thermogravimetric analysis using the method described in Example 11C, the 10 inch weight loss temperature was 42.
It had good heat resistance of 4°C.

Example 3 In the same manner as in Example 1, 5-(sludioxotetrahydrofuryl)-3-methyl-3-cyclohexene-
1,2-dicarboxylic anhydride 51849 (0.2 mol)
and 250 ml of N,N-dimethylacetamide were added, and in the same manner as in Example 1, a viscous polyimide precursor was obtained using 40.05 (0,29) of 4,4'-diaminodiphenyl ether. Furthermore, 36.59 (0.1 mol) of incyanate compound (II) obtained in (2) was added at room temperature, and the mixture was stirred for 24 hours. Carbon dioxide was evolved during the reaction.

This solution KFA-731A (tris(2-acryloylethyl)in cyanurate manufactured by Hitachi Chemical Co., Ltd.) was added at 91%
89 plus 5.4 g of benzophenone under light exclusion and 4.
4'-bis(diethylamino)benzophenone 0.6g
After stirring and mixing, filter the mixture using a filter to obtain a photosensitive resin composition.

This composition was applied in the same manner as in Example 1, and a transparent 50%
A coating film with a thickness of μm was obtained. When this coating film was irradiated with 300 mJ/an'' and developed and rinsed in the same manner as in Example 1, a clear resin pattern was obtained.

When thermogravimetric analysis was performed on this resin pattern coating film using the method described in Example 1, it was found that the weight decreased by 10% at 422°C on the hot car.
It had good heat resistance.

Example 4 39.63 (0.2 mol) of 1.2.3.4-butanetetracarboxylic dianhydride and 250 ml of N,N-dimethylacetamide were added to a flask in the same manner as in Example 1. A viscous polyimide precursor was obtained in the same manner as above using 40.059 (0.2 mol) of 4,4'-diaminodiphenyl ether. Furthermore, in the same manner as in Example 3, 15.5 G of incyanate compound (If) was added at room temperature and stirred for 24 hours.

To this solution was added 79.69 g of A-BPE-10 (s2-bis(4-acryloquine pentaethoxyphenyl) propane manufactured by Shin-Nakamura Chemical Co., Ltd.) and 5.4 g of benzophenone was added under light shielding.
g and 44'-bis(diethylamino)benzopheno 7
After adding 0.6g and stirring and mixing.

A photosensitive resin composition was obtained by filtration with a filter.

This composition was applied in the same manner as in Example 9'll, and a transparent coating film with a thickness of 50 μm was obtained. When this coating film was irradiated with 300 mJ/♂, developed and rinsed in the same manner as in Example 1, a clear resin pattern was obtained.

When thermogravimetric analysis was performed on this resin pattern coating film using the method described in Example 1, it was found that the weight decreased by 10% at 416°C on the hot car.
It had good heat resistance.

Implementation PU5 In the same manner as in Example 1, 5-(ZS-dioquinetetrahydrofuryl)-3-methyl-3-cyclohexene-
111 g of 1,2-dicarbonate, 5zs9 (0.2 mol) of hydrate, and 250 ml of N,N-dimethylacetamide were added, and the mixture was stirred at room temperature under dry nitrogen gas flow. Next, 49.6 g (o, z mol) of silicone diamine (LP-103, manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structural formula was added, and the solution was stirred at room temperature for 8 hours to form a viscous solution. A polyimide precursor was obtained. Furthermore, 29.0 g (o, i mol) of the incyanate compound obtained in (1) was added at room temperature while shielding from light, and the mixture was stirred for 24 hours. Carbon dioxide was evolved during the reaction. Add to this solution FA-731AC Tris (2-7 Chryloyl Ethyl) Isocyanuride (manufactured by Hitachi Chemical) 79.
3 g was added thereto, and benzyl dimethyl ketal (manufactured by Ciba Geigy) 429 was added under light shielding, stirred and mixed, and filtered through a filter to obtain a photosensitive resin composition. This composition was applied in the same manner as in Example 1, and dried by heating at 80°C for 30 minutes, resulting in a transparent coating film with a thickness of 50 μm. This coated film surface was pattern-masked and irradiated with ultraviolet rays at 300 mJ/am'', developed and rinsed in the same manner as in Example 1, and a clear resin pattern was obtained.

When thermogravimetric analysis was performed on this resin pattern coating film using the method described in Example 1, it was found that the weight decreased by 10% on the hot car.
It had good heat resistance at ℃.

Examples 6 to 14 The photosensitive resin composition obtained in Example M1 was applied to a steel-clad laminate (
Apply VCI to a dry thickness of 50 μm using a bar coater on MCL-E-61 (manufactured by Hitachi Chemical Co., Ltd.)! ! engineered,
After drying at 80°C for 30 minutes, the coating surface was irradiated with pattern mask L and 300 mJ/li of ultraviolet rays.
When developed with an alkaline aqueous solution shown in Table IK below and rinsed with water, a clear resin pattern was obtained.

Margin below

Claims (1)

[Claims] 1. Formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1 is a tetravalent aliphatic group or alicyclic group,
R_2 is a divalent aromatic group, aliphatic group, alicyclic group, or organosiloxane group) Polyimide precursor having a repeating unit represented by formula (2) ▲ Numerical formula, chemical formula, table, etc. ▼ ( 2) (wherein R_3 is a tetravalent organic group, R_4 is a divalent organic group, Y_1, Y_2 and Y_3 are selected from monovalent organic groups having a hydrogen atom and an unsaturated double bond) and at least one of Y_1, Y_2 and Y_3 is a monovalent organic group having an unsaturated double bond) and has at least one unsaturated double bond and urethane bond in the molecule. A photosensitive resin composition comprising a photosensitive adduct with an isocyanate compound, a photopolymerization initiator, an organic solvent, and optionally a polymerizable unsaturated compound.