JPH06175364A - Actinic sensitive polymer composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive polyimide compsn. which can be developed with an alkali aq. soln. without using an org. soln. for a developer by incorporating a specified polymer and a photo-amine producing agent. CONSTITUTION:This compsn. contains a polymer having a structural unit expressed by the formula and a photo-amine producing agent. In the formula, R<1> is a tervalent or quadrivalent org. group having at least two carbon atoms, R<2> is a bivalent org. group having at least two carbon atoms, R<3> is hydrogen atom or an alkali metal ion, and n is 1 or 2. R<1> is preferably a tervalent or quadrivalent group having 6-30 carbon number and containing aromatic rings or aromatic hetercycles, and for example, pyromellitic acid residual group. R<2> is preferably a bivalent group having 6-30 carbon number and containing aromatic rings or aromatic heterocycles, and for example, diaminodiphenyl ether residual group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive polyimide coating composition, and more particularly to a novel photosensitive polyimide composition.

[0002]

2. Description of the Related Art As a photosensitive polyimide composition, a polyamic acid, which can be dimerized or polymerized by actinic radiation, is used.
A composition containing a compound containing a carbon double bond and an amino group or a quaternized salt thereof (for example, JP-B-59-5282).
2) or a polyimide precursor composition obtained by introducing photosensitivity to a polyamic acid with an ester group (for example, USP39575).
12 specification, USP 4040831 specification) are known.

However, in such a conventional composition, as a developing solution, a polar solvent such as N-methyl-2-pyrrolidone and an organic solvent such as methanol, ethanol, toluene or xylene are usually used in combination. For this reason, the flash point of the developer is low, and it is necessary to take measures such as explosion proof.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel photosensitive polyimide composition which can be developed with an alkaline aqueous solution without using an organic solvent as a developing solution.

[0005]

The object of the present invention is as follows.
This is achieved by adopting the following configuration.

(1) An actinic radiation-sensitive polymer composition comprising a polymer having a structural unit represented by the following general formula [1] and a photoamine generator.

[0007]

[Chemical 4] (R ¹ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ² is a divalent organic group having at least 2 carbon atoms, R ³ is hydrogen or an alkali metal Represents an ion, and n is 1 or 2.)
(2) The actinic radiation-sensitive polymer composition according to claim 1, wherein the photoamine generator is a compound represented by the following general formula [2].

(R ⁴ —OCO—NH) _m —R ⁵ [2] [wherein at least one R ⁴ is at least one of the following general formula [3]:

[Chemical 5] (R ⁶ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. L is an integer of 1 to 3) or the following general formula [4],

[Chemical 6] (R ⁷ represents hydrogen or a nitro group. R ⁸ is hydrogen,
It represents a methyl group, an o-nitrophenyl group or an o, o-dinitrophenyl group. ), And other than that, represents an organic group having 1 or more and less than 20 carbon atoms. R
⁵ represents a monovalent to tetravalent organic group having 1 or more carbon atoms. m is 1
Is an integer of ~ 4. As the polymer having the structural unit represented by the general formula [1] in the present invention, a polymer having the structure represented by the above general formula and having an imide ring or other cyclic structure by heating or a suitable catalyst (hereinafter , "Polyimide-based polymer").

In the above general formula [1], R ¹ is at least 2
It is a trivalent or tetravalent organic group having one or more carbon atoms. From the heat resistance of the polyimide-based polymer, R ¹ preferably has a structure in which the bond with the carbonyl group of the polymer main chain is directly formed from the aromatic heterocycle. Therefore, R ¹ is preferably a trivalent or tetravalent group containing an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms.

Specific preferred examples of R ¹ include pyromellitic acid residue, 3,3 ', 4,4'-benzophenone tetracarboxylic acid residue, 3,3', 4,4'-biphenyltetracarboxylic acid residue. Acid residue, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid residue, 3,3', 4,4
Examples thereof include, but are not limited to, a'-diphenylsulfone tetracarboxylic acid residue, a butane tetracarboxylic acid residue, and a cyclopentane tetracarboxylic acid residue.

In the polymer of the present invention, R ¹ may be composed of one of these or a copolymer composed of two or more thereof.

In the above general formula [1], R ² is at least 2
It is a divalent organic group having one or more carbon atoms. Similar to R ¹ , in view of the heat resistance of the polyimide polymer, R ² preferably has a structure in which the carbonyl group of the polymer main chain is directly bonded from the aromatic heterocycle. Therefore, R ²
Is preferably a divalent group containing an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms.

Preferred specific examples of R ² include diaminodiphenyl ether residue, diaminodiphenyl sulfide residue, diaminodiphenylmethane residue, diaminodiphenyl sulfone residue, phenylenediamine residue, benzidine residue, bisaminophenoxypropane residue. Groups and the like, but are not limited thereto.

In the polymer of the present invention, R ² may be composed of one of these or a copolymer composed of two or more thereof.

Further, in order to improve the adhesiveness of the polyimide-based polymer, it is possible to copolymerize an aliphatic group having a siloxane bond as R ² within a range that does not lower the heat resistance. A preferred specific example is bis (3
-Aminopropyl) tetramethyldisiloxane and the like.

In the above general formula [1], R ³ represents hydrogen or an alkali metal ion, and n is 1 or 2.

The polymer in the present invention may be composed of only the structural unit represented by the general formula [1],
It may be a copolymer or blend with other structural units. At that time, the structural unit represented by the general formula [1] was 9
It is preferable to contain 0% or more. It is desirable to select the type and amount of the structural unit used for copolymerization or blending within a range that does not significantly impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

Specific examples of the polymer in the present invention include pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. 4'-diaminodiphenyl ether, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and 3,3' (or 4,4 ') -Diaminodiphenyl sulfone, pyromellitic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 3,3' (or 4,4
′) -Diaminodiphenyl sulfone, 3,3 ′, 4,4
'-Benzophenonetetracarboxylic acid dianhydride and 3,3
′ (Or 4,4 ′)-diaminodiphenyl sulfone,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′ (or 4,4 ′)-diaminodiphenyl sulfone, pyromellitic dianhydride and 4,4′-diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride and 4,4'- Diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and paraphenylenediamine, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, pyromellitic Acid dianhydride and 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride and paraphenylenediamine, pyromellitic dianhydride and 3 , 3 ', 4,4'-biphenyltetracarboxylic acid dianhydride and paraphenylenediamine, 3,3', 4,4'-diphenylether tetracarboxylic acid dianhydride and 4,4'-diaminodiphenylether, 3,3 ′, 4,4′-Diphenyl ether tetracarboxylic acid dianhydride and para-phenylenediamine, butanetetracarboxylic acid dianhydride and 1,3-bis (3-aminophenoxy) benzene, cyclopentanetetracarboxylic acid dianhydride and 4 , 4'-diaminodiphenylmethane,
Polyamic acid synthesized from pyromellitic dianhydride, 4,4′-diaminodiphenyl ether, bis (3-aminopropyl) tetramethyldisiloxane, etc. is preferably used.

The actinic radiation polymer composition of the present invention contains a photoamine generator as an essential component. The photoamine generator refers to a compound that generates an amine upon irradiation with light. When an amine is generated in the system by light irradiation, remarkable effects such as imidization progress and insolubilization due to a reaction between a carboxylic acid in the polymer and the amine to form a crosslink are obtained.

Suitable photoamine generators in the present invention include:
The compound represented by general formula [2] can be mentioned.

(R ⁴ —OCO—NH) _m —R ⁵ [2] In the above general formula [2], R ⁴ is a group capable of photoelimination reaction, and R ⁴ is at least one in the molecule. The above is the following general formula [3],

[Chemical 7] (R ⁶ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. L is an integer of 1 to 3) or the following general formula [4],

[Chemical 8] (R ⁷ represents hydrogen or a nitro group. R ⁸ is hydrogen,
It represents a methyl group, an o-nitrophenyl group or an o, o-dinitrophenyl group. ), And other than that, represents an organic group having 1 or more and less than 20 carbon atoms. Specific examples of the group represented by the general formula [3] include (α-methyl)
Methoxybenzyl group, (α-methyl) dimethoxybenzyl group, (α-methyl) trimethoxybenzyl group, (α,
Examples include α-dimethyl) methoxybenzyl group, (α, α-dimethyl) dimethoxybenzyl group, and (α, α-dimethyl) trimethoxybenzyl group.

Specific examples of the group represented by the general formula [4] include o-nitrobenzyl group, (α-methyl) o-nitrobenzyl group, (α- (o-nitrophenyl)) o-nitrobenzyl group. Group, o, o-dinitrobenzyl group, (α-methyl) o, o-dinitrobenzyl group, (α- (o-nitrophenyl)) o, o-dinitrobenzyl group and the like.

Examples of R ⁵ include C 1 or more and 1 to 4 valent organic groups, preferably C 1 to C 20 alkyl groups, halogenated alkyl groups, phenyl groups, naphthyl groups, anthryl groups and benzyl. Group, methylene group, poly (methylene) group, phenylene group, methylphenylene group, methanediphenylene group, triphenylmethane group and the like. m is an integer of 1 to 4.

Specific examples of the compound represented by the general formula [2] include the following (a) to (d).

(A) Monofunctional compound [(α-methyl) methoxybenzyloxycarbonyl] cyclohexylamine, [(α-methyl) dimethoxybenzyloxycarbonyl] cyclohexylamine,
[(Α-Methyl) trimethoxybenzyloxycarbonyl] cyclohexylamine, [(α, α-dimethyl) methoxybenzyloxycarbonyl] cyclohexylamine, [(α, α-dimethyl) dimethoxybenzyloxycarbonyl] cyclohexylamine, [(α , Α-Dimethyl) trimethoxybenzyloxycarbonyl] cyclohexylamine, (o-nitrobenzyloxycarbonyl) cyclohexylamine, [(α-methyl) o-nitrobenzyloxycarbonyl] cyclohexylamine,
[(Α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] cyclohexylamine, (o, o-
Dinitrobenzyloxycarbonyl) cyclohexylamine, [(α-methyl) o, o-dinitrobenzyloxycarbonyl] cyclohexylamine, [(α- (o-
Nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] cyclohexylamine and the like.

[(Α-methyl) methoxybenzyloxycarbonyl] propylamine, [(α-methyl) dimethoxybenzyloxycarbonyl] propylamine,
[(Α-methyl) trimethoxybenzyloxycarbonyl] propylamine, [(α, α-dimethyl) methoxybenzyloxycarbonyl] propylamine, [(α,
α-Dimethyl) dimethoxybenzyloxycarbonyl]
Propylamine, [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] propylamine, (o-nitrobenzyloxycarbonyl) propylamine,
[(Α-methyl) o-nitrobenzyloxycarbonyl] propylamine, [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] propylamine, (o, o-dinitrobenzyloxycarbonyl) propylamine, [(Α-methyl) o, o-dinitrobenzyloxycarbonyl] propylamine, [(α
-(O-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] propylamine and the like.

[(Α-methyl) methoxybenzyloxycarbonyl] hexylamine, [(α-methyl) dimethoxybenzyloxycarbonyl] hexylamine,
[(Α-methyl) trimethoxybenzyloxycarbonyl] hexylamine, [(α, α-dimethyl) methoxybenzyloxycarbonyl] hexylamine, [(α,
α-Dimethyl) dimethoxybenzyloxycarbonyl]
Hexylamine, [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] hexylamine, (o-nitrobenzyloxycarbonyl) hexylamine,
[(Α-methyl) o-nitrobenzyloxycarbonyl] hexylamine, [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] hexylamine, (o, o-dinitrobenzyloxycarbonyl) hexylamine, [(Α-methyl) o, o-dinitrobenzyloxycarbonyl] hexylamine, [(α
-(O-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] hexylamine and the like.

[(Α-methyl) methoxybenzyloxycarbonyl] benzylamine, [(α-methyl) dimethoxybenzyloxycarbonyl] benzylamine,
[(Α-methyl) trimethoxybenzyloxycarbonyl] benzylamine, [(α, α-dimethyl) methoxybenzyloxycarbonyl] benzylamine, [(α,
α-Dimethyl) dimethoxybenzyloxycarbonyl]
Benzylamine, [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] benzylamine, (o-nitrobenzyloxycarbonyl) benzylamine,
[(Α-methyl) o-nitrobenzyloxycarbonyl] benzylamine, [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] benzylamine, (o, o-dinitrobenzyloxycarbonyl) benzylamine, [(Α-methyl) o, o-dinitrobenzyloxycarbonyl] benzylamine, [(α
-(O-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] benzylamine and the like.

(B) Bifunctional compound bis [(α-methyl) methoxybenzyloxycarbonyl] hexamethylenediamine, bis [(α-methyl)
Dimethoxyhexamethylenedioxycarbonyl] hexamethylenediamine, bis [(α-methyl) trimethoxyhexamethylenedioxycarbonyl] hexamethylenediamine, bis [(α, α-dimethyl) methoxybenzyloxycarbonyl] hexamethylenediamine, bis [ (Α, α-Dimethyl) dimethoxybenzyloxycarbonyl] hexamethylenediamine, bis [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] hexamethylenediamine, bis (o-nitrobenzyloxycarbonyl) hexamethylenediamine, bis [ (Α-Methyl) o-nitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] hexamethylenediamine, bis (o, o- Nitrobenzyloxycarbonyl) hexamethylenediamine, bis [(alpha-
Methyl) o, o-dinitrobenzyloxycarbonyl]
Hexamethylenediamine, bis [(α- (o-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] hexamethylenediamine and the like.

Bis [(α-methyl) methoxybenzyloxycarbonyl] phenylenediamine, bis [(α-
Methyl) dimethoxyhexamethylenedioxycarbonyl] phenylenediamine, bis [(α-methyl) trimethoxyhexamethylenedioxycarbonyl] phenylenediamine, bis [(α, α-dimethyl) methoxybenzyloxycarbonyl] phenylenediamine, bis [( α, α-dimethyl) dimethoxybenzyloxycarbonyl] phenylenediamine, bis [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] phenylenediamine, bis (o-nitrobenzyloxycarbonyl) phenylenediamine, bis [(α-methyl) ) O-nitrobenzyloxycarbonyl] phenylenediamine,
Bis [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] phenylenediamine, bis (o, o-dinitrobenzyloxycarbonyl) phenylenediamine, bis [(α-methyl) o, o-dinitrobenzyloxy Carbonyl] phenylenediamine, bis [(α- (o-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] phenylenediamine and the like.

Bis [(α-methyl) methoxybenzyloxycarbonyl] methylphenylenediamine, bis [(α-methyl) dimethoxyhexamethylenedioxycarbonyl] methylphenylenediamine, bis [(α-methyl) trimethoxyhexamethylenedioxy Carbonyl] methylphenylenediamine, bis [(α, α-dimethyl) methoxybenzyloxycarbonyl] methylphenylenediamine, bis [(α, α-dimethyl) dimethoxybenzyloxycarbonyl] methylphenylenediamine, bis [(α, α-dimethyl) ) Trimethoxybenzyloxycarbonyl] methylphenylenediamine, bis (o-nitrobenzyloxycarbonyl) methylphenylenediamine, bis [(α-methyl) o-nitrobenzyloxycarbonyl] methylphen Diamine, bis [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] methylphenylenediamine, bis (o, o-dinitrobenzyloxycarbonyl) methylphenylenediamine, bis [(α-methyl) o, o-dinitrobenzyloxycarbonyl] methylphenylenediamine, bis [(α- (o-nitrophenyl)) o, o
-Dinitrobenzyloxycarbonyl] methylphenylenediamine and the like.

Bis [(α-methyl) methoxybenzyloxycarbonyl] methanediphenylenediamine, bis [(α-methyl) dimethoxyhexamethylenedioxycarbonyl] methanediphenylenediamine, bis [(α-
Methyl) trimethoxyhexamethylenedioxycarbonyl] methanediphenylenediamine, bis [(α, α-dimethyl) methoxybenzyloxycarbonyl] methanediphenylenediamine, bis [(α, α-dimethyl) dimethoxybenzyloxycarbonyl] methanedi Phenylenediamine, bis [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] methanediphenylenediamine, bis (o-nitrobenzyloxycarbonyl) methanediphenylenediamine, bis [(α-methyl) o-nitrobenzyloxycarbonyl ] Methandiphenylenediamine, Bis [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] Methandiphenylenediamine, Bis (o, o-dinitrobenzyloxycarbonyl) methanediphenylene Diamine, bis [(α-methyl) o, o-dinitrobenzyloxycarbonyl] methanediphenylenediamine, bis [(α- (o-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] methanediphenylenediamine and the like.

(C) Trifunctional Compound Tris [(α-methyl) methoxybenzyloxycarbonyl] triphenylmethanetriamine, Tris [(α-
Methyl) dimethoxyhexamethylenedioxycarbonyl] triphenylmethanetriamine, tris [(α-methyl) trimethoxyhexamethylenedioxycarbonyl] triphenylmethanetriamine, tris [(α, α
-Dimethyl) methoxybenzyloxycarbonyl] triphenylmethanetriamine, tris [(α, α-dimethyl) dimethoxybenzyloxycarbonyl] triphenylmethanetriamine, tris [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] triphenylmethane Triamine, tris (o-nitrobenzyloxycarbonyl) triphenylmethanetriamine, tris [(α-methyl) o-nitrobenzyloxycarbonyl] triphenylmethanetriamine, tris [(α-
(O-Nitrophenyl)) o-nitrobenzyloxycarbonyl] triphenylmethanetriamine, tris (o, o-dinitrobenzyloxycarbonyl) triphenylmethanetriamine, tris [(α-methyl) o,
o-dinitrobenzyloxycarbonyl] triphenylmethanetriamine, tris [(α- (o-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] triphenylmethanetriamine and the like.

(D) Tetrafunctional compound tetra [(α-methyl) methoxybenzyloxycarbonyl] hexamethylenetetraamine, tetra [(α-methyl) dimethoxyhexamethylenedioxycarbonyl]
Hexamethylenetetramine, tetra [(α-methyl)
Trimethoxyhexamethylenedioxycarbonyl] hexamethylenetetraamine, tetra [(α, α-dimethyl) methoxybenzyloxycarbonyl] hexamethylenetetraamine, tetra [(α, α-dimethyl) dimethoxybenzyloxycarbonyl] hexamethylenetetraamine , Tetra [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] hexamethylenetetraamine, tetra (o-nitrobenzyloxycarbonyl) hexamethylenetetraamine, tetra [(α-methyl) o
-Nitrobenzyloxycarbonyl] hexamethylenetetramine, tetra [(α- (o-nitrophenyl))
o-nitrobenzyloxycarbonyl] hexamethylenetetraamine, tetra (o, o-dinitrobenzyloxycarbonyl) hexamethylenetetraamine, tetra [(α-methyl) o, o-dinitrobenzyloxycarbonyl] hexamethylenetetraamine, tetra [(Α-
(O-nitrophenyl)) o, o-dinitrobenzyloxycarbonyl] hexamethylenetetramine and the like.

Among the above, particularly preferable are:
Bis [(α, α-dimethyl) methoxybenzyloxycarbonyl] hexamethylenediamine, bis [(α, α-
Dimethyl) dimethoxybenzyloxycarbonyl] hexamethylenediamine, bis [(α, α-dimethyl) trimethoxybenzyloxycarbonyl] hexamethylenediamine, bis (o-nitrobenzyloxycarbonyl)
Hexamethylenediamine, bis [(α-methyl) o-nitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α- (o-nitrophenyl)) o-nitrobenzyloxycarbonyl] hexamethylenediamine,
Bis (o, o-dinitrobenzyloxycarbonyl) hexamethylenediamine, bis [(α-methyl) o, o-
Dinitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α- (o-nitrophenyl)) o, o
-Dinitrobenzyloxycarbonyl] hexamethylenediamine and the like.

The photoamine generator represented by the general formula [2] can be usually synthesized by a condensation reaction between a benzyl alcohol derivative and an isocyanate compound.

Other than the above, ammonia complexes of transition metals such as cobalt are also known as photoamine generators, but they are not preferred because of problems such as metal components remaining.

The photoamine generator is 1 to 2 relative to the polymer.
It is preferable to add it in an amount of 00% by weight, preferably 3 to 100% by weight. If it is out of this range, the image cannot be formed,
Care should be taken as the mechanical properties of the membrane may be degraded.

If desired, a sensitizer may be added to the composition of the present invention. Examples of the sensitizer suitable for the present invention include aromatic amines such as N-phenyldiethanolamine, N-phenylglycine and Michler-ketone, and aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, 3,3 '. -Carbonylbis (diethylaminocoumarin), etc., which are generally used for photocurable resins, and others which are used as a charge transfer agent for electrophotography may be preferably used.

The sensitizer is 0.1 to 5% by weight based on the polymer.
It is preferable to add in the range of. If it is out of this range, the photosensitivity may be lowered, or the mechanical properties of the polymer may be lowered, so that caution is required. These sensitizers can be used alone or in admixture of two or more.

An adhesion aid may be appropriately used in order to improve the adhesiveness between the coating of the composition of the present invention or the polyimide coating after heat treatment and the support.

As the adhesion aid, oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organosilicon compounds such as methacryloxypropyltrimethoxysilane, aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate and aluminum tris (acetylacetonate), or titanium bis (acetylacenate)
Titanium chelate compounds and the like are preferably used.

As other additives, a copolymerization monomer or an adhesion improver with a substrate may be contained within a range in which sensitivity and heat resistance are not significantly lowered.

An example of the method for producing the composition of the present invention will be described. First, a diamine compound and an acid dianhydride are reacted in a solvent to obtain a polymer having a structural unit represented by the general formula [1] as a main component. Next, the composition is obtained by dissolving and compounding the photo amine generator and other additives as required in this solution. As the above-mentioned polymer, a solid polyamic acid polymer or a polymer separated and purified from a solution after the reaction may be redissolved and used.

As the solvent used in the above production method, a polar solvent is preferably used from the viewpoint of polymer solubility, and an aprotic polar solvent is particularly preferable. As the aprotic polar solvent, N-methyl-2-pyrrolidone, N, N-
Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorotriamide, γ-butyrolactone and the like are preferably used.

Next, the method of using the composition of the present invention will be described. The composition of the present invention can be patterned by a known fine processing technique using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Examples of the material of the support include metal, glass, semiconductor, metal oxide insulator, silicon nitride and the like.

As a coating method, spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating and the like can be used. The coating film thickness can be adjusted depending on the coating means, the solid content concentration of the composition, and the viscosity, but it is usually coated in the range of 1 to 30 μm.

Next, the composition of the present invention formed into a coating film on the support is irradiated with actinic rays in a desired pattern. Examples of actinic rays include X-rays, electron rays, ultraviolet rays, and visible rays, but ultraviolet rays and visible rays of short wavelengths, that is, 200 to 500 nm in the wavelength range are preferable.

After exposure, baking treatment is carried out to carry out imidization reaction and crosslinking reaction. This temperature is 60-160
The range of ° C is preferred. If the amount is out of this range, the reaction may not proceed or the entire region may not be dissolved, so be careful.

Then, the unirradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. A suitable developer can be selected according to the structure of the polymer,
Ammonia, an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of diethanolamine, or the like can be preferably used. In addition, N-methyl-2-pyrrolidone and N-acetyl-2, which are solvents for the composition, are used.
-Pyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide and the like are also preferably used alone or as a mixture of a composition such as methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene and xylene with a non-solvent. can do.

The development can be carried out by a method of spraying the above-mentioned developing solution on the coating film surface, immersing in the developing solution, or applying ultrasonic waves while immersing.

Next, it is desirable to wash the relief pattern formed by development with a rinse liquid. As the rinse liquid, water is preferably used when the development is performed with an alkaline aqueous solution. When developing with an organic solvent,
Methanol, ethanol, isopropyl alcohol, butyl acetate and the like, which have good miscibility with the developing solution, are preferably used.

The relief pattern polymer obtained by the above treatment is a precursor of a heat-resistant polyimide polymer, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. As the heat treatment temperature,
It is preferably carried out at 135 to 400 ° C. The heat treatment is usually
The temperature is raised stepwise or continuously.

The actinic radiation-sensitive polymer composition of the present invention is used for a semiconductor passivation film, a buffer coat film for a passivation film, an interlayer insulating film for a multilayer integrated circuit, an interlayer insulating film or a surface protective film for a hybrid integrated circuit, and a printed circuit. It is used to form the soldering protective film, the liquid crystal alignment film, the interlayer insulating film of the mounting substrate, and the like. Further, it can be applied to metal adhesion and dry etching process as a highly heat resistant photoresist. It can be applied to other known uses of polyimide.

[0056]

【Example】

<Synthesis of photoamine generator> Synthesis of (o-nitrobenzyloxycarbonyl) cyclohexylamine 15.3 g of o-nitrobenzyl alcohol was dissolved in 50 ml of tetrahydrofuran. Cyclohexyl isocyanate was added dropwise thereto with (dibutyl) (dilauryl) tin as a catalyst, and the reaction was carried out at 30 ° C. for 2 hours. The reaction product was poured into water and recovered to obtain (o-nitrobenzyloxycarbonyl) cyclohexylamine. This is designated as a photoamine generator (1).

Synthesis of bis (o-nitrobenzyloxycarbonyl) hexamethylenediamine 15.3 g of o-nitrobenzyl alcohol was dissolved in 50 ml of tetrahydrofuran. Hexamethylene diisocyanate was added dropwise thereto with methyllithium as a catalyst, and the reaction was carried out at 30 ° C. for 2 hours. The reaction product was poured into water and recovered to obtain bis (o-nitrobenzyloxycarbonyl) hexamethylenediamine. This is designated as a photoamine generator (2).

Synthesis of bis [(α-methyl) p-methoxybenzyloxycarbonyl] methylenephenylenediamine (α-methyl) p-methoxybenzyl alcohol 15.
3 g was dissolved in 50 ml of tetrahydrofuran. Methylenebis (phenylisocyanate) was added dropwise with (dibutyl) (dilauryl) tin as a catalyst at 30 ° C.
Was reacted for 2 hours. The reaction product was poured into water and recovered to obtain bis [(α-methyl) p-methoxybenzyloxycarbonyl] methylenephenylenediamine. This is designated as a photoamine generator (3).

<Synthesis of Polyimide Stock Solution>4,4'-diaminodiphenyl ether 100.1 g
Was dissolved in 670 g of N-methyl-2-pyrrolidone at room temperature, and 157.5 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid was added to 10 g of N-methyl-2-pyrrolidone 10.
It was added together with 3 g and vigorously stirred. At this time, the liquid temperature rapidly rises to 50 ° C., but then becomes a steady state. React as it is at 30 ° C for 1 hour, and further 60
The liquid temperature was raised to ° C and the reaction was carried out for 4 hours to obtain a polyamic acid solution (A).

100.1 g of 4,4'-diaminodiphenyl ether was dissolved in 670 g of N-methyl-2-pyrrolidone at room temperature, and 108.2 g of pyromellitic dianhydride was added together with 80 g of N-methyl-2-pyrrolidone, followed by vigorous stirring. Was done. At this time, the liquid temperature rapidly rises to 50 ° C.
However, the steady state is reached after that. 30 ℃ as it is
The reaction was carried out for 1 hour, and the liquid temperature was further raised to 60 ° C. for 4 hours to obtain a polyamic acid solution (B).

124.3 g of 3,3'-diaminodiphenyl sulfone was dissolved in 600 g of N-methyl-2-pyrrolidone at room temperature, and 146.5 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid was added to N-. Methyl-2-pyrrolidone was added together with 100 g, and the mixture was vigorously stirred. At this time, the liquid temperature rapidly rises to 50 ° C., but then becomes a steady state. The reaction was continued for 1 hour at 30 ° C., the liquid temperature was further raised to 60 ° C., and the reaction was performed for 4 hours to obtain a polyamic acid solution (C).

205.1 g of bis (4-aminophenoxy) diphenylpropane was dissolved in 670 g of N-methyl-2-pyrrolidone at room temperature, and 157.5 g of 3,3 ', 4,4'-benzophenonetetracarboxylic acid was added to N. -Methyl-2-pyrrolidone (103 g) was added, and the mixture was vigorously stirred. At this time, the liquid temperature rapidly rises to 50 ° C., but then becomes a steady state. The reaction was continued at 30 ° C. for 1 hour, the liquid temperature was further raised to 60 ° C., and the reaction was performed for 4 hours to obtain a polyamic acid solution (D).

Example 1 5 g of photo amine generator (1) and polyamic acid solution (A) 1
00g was mixed. This solution was spin-coated on a 4-inch silicon wafer. Then, using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.),
Heat treatment was performed at 120 ° C. for 3 minutes. The film thickness at this time was 5 μm.

After the heat treatment, exposure was carried out at 600 mJ / cm ² (measured value at 365 nm) using a contact aligner (PLA-501 manufactured by Canon Inc.) with a gray scale as a mask.

Next, an alkaline developing solution (N
It was developed by immersing it for 30 seconds using MD-3).

At an exposure dose of 240 mJ / cm ² or more,
The statue remains. The film thickness at an exposure dose of 600 mJ / cm ² was 4.5 μm.

Example 2 5 g of photoamine generator (2) and polyamic acid solution (B) 1
00g was mixed. This solution was spin-coated on a 4-inch silicon wafer. Then, using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.),
Heat treatment was performed at 120 ° C. for 3 minutes. The film thickness at this time was 5 μm.

After the heat treatment, 600 mJ / cm ² (measured value at 365 nm) was exposed using a contact aligner (PLA-501 manufactured by Canon Inc.) with a gray scale as a mask. After completion of the exposure, baking treatment was performed at 120 ° C. for 1 minute.

Next, an alkali developing solution (Tokyo Ohka N
It was developed by immersing it for 30 seconds using MD-3).

At an exposure dose of 240 mJ / cm ² or more,
The statue remains. The film thickness at an exposure dose of 600 mJ / cm ² was 4.3 μm.

Example 3 5 g of photoamine generator (3) and polyamic acid solution (C) 1
00g was mixed. This solution was spin-coated on a 4-inch silicon wafer. Then, using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.),
Heat treatment was performed at 120 ° C. for 3 minutes. The film thickness at this time was 5 μm.

After the heat treatment, exposure was carried out at 600 mJ / cm ² (measured value at 365 nm) using a contact aligner (PLA-501 manufactured by Canon Inc.) with a gray scale as a mask. After completion of the exposure, baking treatment was performed at 120 ° C. for 1 minute.

Next, an alkaline developing solution (Tokyo Ohka N
It was developed by immersing it for 30 seconds using MD-3).

At an exposure dose of 360 mJ / cm ² or more,
The statue remains. The film thickness at an exposure dose of 600 mJ / cm ² was 3.7 μm.

Example 4 5 g of photo amine generator (1) and polyamic acid solution (D) 1
00g was mixed. This solution was spin-coated on a 4-inch silicon wafer. Then, using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.),
Heat treatment was performed at 120 ° C. for 3 minutes. The film thickness at this time was 5 μm.

After the heat treatment, exposure was carried out at 600 mJ / cm ² (measured value at 365 nm) using a contact aligner (PLA-501 manufactured by Canon Inc.) with a gray scale as a mask. After completion of the exposure, baking treatment was performed at 120 ° C. for 1 minute.

Next, an alkaline developing solution (N
It was developed by immersing it for 30 seconds using MD-3).

At an exposure dose of 150 mJ / cm ² or more,
The statue remains. The film thickness at an exposure dose of 600 mJ / cm ² was 4.7 μm.

Comparative Example 2 g of triethylamine and 100 polyamic acid solution (A)
g were mixed. This solution was spin-coated on a 4-inch silicon wafer. Then, using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), 120
Heat treatment was performed at 3 ° C. for 3 minutes. The film thickness at this time is 5
was μm.

After the heat treatment, exposure was performed at 600 mJ / cm ² (measured value at 365 nm) using a contact aligner (PLA-501 manufactured by Canon Inc.) with a gray scale as a mask.

Next, an alkaline developing solution (Tokyo Ohka N
It was developed by immersing it in MD-3) for 30 seconds.
It did not dissolve at all.

[0082]

According to the present invention, it is possible to obtain a novel photosensitive polyimide composition which can be developed with an alkaline aqueous solution without using an organic solvent as a developing solution.

Claims (2)

[Claims] 1. An actinic radiation-sensitive polymer composition comprising a polymer having a structural unit represented by the following general formula [1] and a photoamine generator. [Chemical 1] (R ¹ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ² is a divalent organic group having at least 2 carbon atoms, R ³ is hydrogen or an alkali metal Represents an ion, and n is 1 or 2.) 2. The actinic radiation-sensitive polymer composition according to claim 1, wherein the photoamine generator is a compound represented by the following general formula [2]. (R ⁴ —OCO—NH) _m —R ⁵ [2] [wherein at least one R ⁴ in the molecule has the following general formula [3]: (R ⁶ represents hydrogen or an alkyl group having 1 or more and less than 10 carbon atoms. L is an integer of 1 to 3) or the following general formula [4], (R ⁷ represents hydrogen or a nitro group. R ⁸ is hydrogen,
It represents a methyl group, an o-nitrophenyl group or an o, o-dinitrophenyl group. ), And other than that, represents an organic group having 1 or more and less than 20 carbon atoms. R
⁵ represents a monovalent to tetravalent organic group having 1 or more carbon atoms. m is 1
Is an integer of ~ 4. ]