JPH08339089A - Developer for photosentitive polyimide - Google Patents

Abstract

PURPOSE: To obtain a developer for photosensitive polyimide capable of giving a pattern excellent in various characteristics such as sensitivity, resolution and pattern shape. CONSTITUTION: In a developer for photosensitive polyimide contg. an aprotic polar solvent having a bipolar structure and a bad solvent to the photosensitive polyimide, N,N-dimethylacrylamide is used as the aprotic polar solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide developer, and more particularly to a photosensitive polyimide developer capable of giving a good pattern.

[0002]

2. Description of the Related Art In recent years, photosensitive polyimides whose solubility is changed by light irradiation have been developed. For example, a composition obtained by adding a photo-crosslinking agent to a polyamic acid (polyimide precursor), a precursor obtained by introducing an acryloyl group into a polyamic acid (Japanese Patent Publication No. 55-30207, Japanese Patent Publication No. 55-41).
422), a precursor in which an acryloyl group is introduced into a polyamic acid in the form of a salt (Japanese Patent Publication No. 59-52822), a precursor in which an o-nitrobenzyl ester group is introduced into a polyamic acid, and the like are proposed. Recently, a method of sensitizing not the polyimide precursor but the polyimide itself has been developed. Polyimide, because it is difficult to dissolve in a solvent, for example, to obtain a solvent-soluble polyimide by using an asymmetric diamine as the amine component in the synthesis of the polyimide, or from benzophenone tetracarboxylic anhydride and aromatic diamine, in the solvent It has been proposed to obtain a soluble, photosensitive polyimide.

To form a fine pattern using a photosensitive polyimide, a solution is applied onto a substrate to form a photosensitive film, a latent image is formed by light irradiation, and the latent image is developed with a developing solution. A general lithographic technique for forming an image can be adopted. When the polyimide precursor is used, the remaining exposed film of the film is heated to be polyimidized.

As a developing solution for the photosensitive polyimide, there are an alkaline developing system using an alkaline aqueous solution and an organic solvent system using a combination of a good solvent and a poor solvent. Among these, an organic solvent developing solution is used. Widely used.
Examples of good solvents for organic solvent-based developers include N, N-
Dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidine, N-acetyl-ε-caprolactam, γ-butyrolactone , Sulfolane, cyclopentanone, cyclohexanone, hexamethylphosphoric triamide, acetonitrile, tetrahydrofuran and other aprotic polar solvents (dipolar aprotic polar solvents) having a bipolar structure are used, while the poor solvent is ,
For example, water, alcohols, aromatic hydrocarbons, ketones, esters and the like are used. Among these, as the dipolar aprotic polar solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N
-Methyl-2-pyrrolidone and the like are widely used.

Conventionally, attempts have been made to improve sensitivity, resolution, pattern shape and the like by using a specific solvent in combination in an organic solvent type developing solution. For example, a developer in which a dipolar aprotic polar solvent, an aromatic hydrocarbon and water are combined (Japanese Patent Laid-Open No. 4-1330).
No. 62), when a pattern is formed using a photocrosslinkable polymer composition obtained by modifying a polyimide precursor with a compound having a photosensitive group, dimethyl sulfoxide of 1 to 30% by weight is used as a developing solution. Method using mixed solution containing in proportion (JP-A-6-51535), N-methyl-2-pyrrolidone, xylene, dimethylformamide, and water mixed solution (JP-A-5-241352)
Have been proposed.

In recent years, in microfabrication using photosensitive polyimide, higher levels of various characteristics such as sensitivity, resolution and pattern shape are required, and further improvement is required for the developing solution. Has been. However, it is the current situation that the conventional developing solution does not reach the advanced required level in the characteristics such as sensitivity, resolution and pattern shape, and development of a new developing solution is required.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a developing solution for a photosensitive polyimide capable of giving a pattern excellent in various characteristics such as sensitivity, resolution and pattern shape. As a result of intensive studies to solve the above-mentioned problems of the prior art, the inventors have found that in an organic solvent-based developer in which a good solvent and a poor solvent are combined, N, N is used as an aprotic polar solvent having a bipolar structure. -By using dimethylacrylamide, as compared with the case of using a conventional developer, the resolution is improved, the residual film rate is high, there is no development residue, and there is no wrinkling on the pattern surface, which is excellent. We found that the pattern shape can be obtained.

As the poor solvent, it is preferable to use at least one selected from the group consisting of water, alcohols, ketones, aromatic hydrocarbons, and esters.
Further, as the poor solvent, it is preferable to use water in combination with at least one organic solvent selected from the group consisting of alcohols, ketones, aromatic hydrocarbons, and esters. By the way, N, N-dimethylacrylamide is known as a reaction solvent for a polyimide precursor (JP-A-3-296758). However, N, N-
The use of dimethylacrylamide as a developing solution for photosensitive polyimide has not been proposed. As a matter of course, the peculiar effect of the developer containing N, N-dimethylacrylamide as an essential component has not been known. The present invention has been completed based on these findings.

[0009]

Thus, according to the present invention, an aprotic polar solvent having a bipolar structure and a developing solution for a photosensitive polyimide containing a poor solvent for the photosensitive polyimide are used. Provided is a developing solution for a photosensitive polyimide, characterized by using N, N-dimethylacrylamide as a protic polar solvent.

Further, according to the present invention, the following preferred embodiments are provided. (1) The content ratio of N, N-dimethylacrylamide is 6
The photosensitive polyimide developing solution, which is 0 to 95% by weight. (2) The content ratio of N, N-dimethylacrylamide is 7
0 to 90% by weight of the photosensitive polyimide developing solution. (3) The developer for photosensitive polyimide, wherein the poor solvent is at least one selected from the group consisting of water, alcohols, ketones, aromatic hydrocarbons, and esters. (4) The photosensitive polyimide developer, wherein the poor solvent is a combination of water and at least one organic solvent selected from the group consisting of alcohols, ketones, aromatic hydrocarbons, and esters. . (5) The developer for photosensitive polyimide, wherein the use ratio of water and the organic solvent is 1: 2 to 2: 1 (weight ratio). (6) 60 to 95% by weight of N, N-dimethylacrylamide, 2 to 25% by weight of water, and alcohols and ketones,
The developing solution for a photosensitive polyimide, containing 2 to 25% by weight of at least one organic solvent selected from the group consisting of aromatic hydrocarbons and esters. (7) N, N-dimethylacrylamide 70 to 90% by weight, water 5 to 20% by weight, and alcohols, ketones,
The photosensitive polyimide developing solution containing 5 to 20% by weight of at least one organic solvent selected from the group consisting of aromatic hydrocarbons and esters.

The present invention will be described in detail below. Photosensitive Polyimide The photosensitive polyimide that is the object of use of the developing solution of the present invention is one in which a photosensitive group is introduced into polyimide or a polyimide precursor, or a photosensitive compound having a photosensitive group is blended to improve sensitivity to light. It was given. As the photosensitive group, those that dimerize or polymerize with light to cause cross-linking between polymers, those that generate cross-linking between active polymers such as radicals or ions generated by light, or those active substances with polymers Examples thereof include those that react to change the solubility of the polymer. Specific examples of the photosensitive group include a carbon-carbon double bond, an azido group, a quinonediazide group and the like. Further, specific examples of the photosensitive compound include a dichromate, a bisazide compound, a naphthoquinonediazide compound, and a vinyl compound having an amino group.

Preferred specific examples of the photosensitive polyimide include (1) a polyamic acid compound (polyamic acid, polyamic acid ester, etc.) obtained by reacting a diamine compound with tetracarboxylic acid or an anhydride thereof, and Introducing a polymerizable acryloyl group,
(2) A polyamic acid compound having an actinic ray functional group introduced at its end, (3) a solution of a polyamic acid compound (polyimide varnish) mixed with an amino compound having a photosensitive group such as methacrylic acid, (4) ) A polyamic acid compound into which a dimerizable or polymerizable group by light is introduced by an ester bond, a polyimide varnish mixed with an N-methylolacrylamide compound, (5) a polyimide varnish mixed with an acrylic monomer. ,
(6) An ester bond is attached to the side chain of the polyamic acid compound,
Examples thereof include those in which a photosensitive group such as a vinyl group, an allyl group, an acryl group, a methacryl group, a cinnamyl group, and a maleimide group is introduced by a chemical bond such as an ether bond, an amide bond, and a urethane bond.

The photosensitive polyimide may be blended with a photopolymerization initiator, a photosensitizer, a crosslinking aid, etc., if necessary. The photosensitive polyimide is usually used by uniformly dissolving each component in a sufficient amount of solvent.
Examples of such a photosensitive polyimide include Japanese Patent Publication No. 59-52822, Japanese Patent Laid-Open No. 61-127731, Japanese Patent Laid-Open No. 4-70661, and Japanese Patent Laid-Open No. 6-777.
No. 41 publication, the photosensitive resin composition, commercially available Asahi Kasei's "TL-500" and other "Pimel" series,
Examples include "Photo Nice" series such as "Photo Nice UR-5100" manufactured by Toray Industries, Inc. As the polyamic acid compound into which an actinic radiation functional group is introduced, those proposed in Japanese Patent Application Nos. 6-256222 and 6-247109 can be preferably used.

The polyamic acid compound and the preferable photosensitive polyimide will be described in more detail below. The polyamic acid compound can be synthesized by subjecting a diamine compound and a tetracarboxylic acid or an anhydride thereof to a polycondensation reaction in an organic polar solvent at 0 to 100 ° C. under anhydrous conditions. A compound having a photosensitive group is added to the solution of the polyamic acid compound (polyimide varnish) thus obtained, or a photosensitive group is introduced into the polyamic acid compound to produce a photosensitive polyimide.
When introducing an actinic radiation functional group into the end of the polyamic acid compound, during the synthesis of the polyamic acid compound, for example,
A method in which trimellitic acid derivatives and aminobenzenes are present is preferable.

<Diamine Compound> Examples of the diamine compound include 2,2′-di (p-aminophenyl)-
6,6'-bisbenzoxazole, 2,2'-di (p
-Aminophenyl) -5,5'-bisbenzoxazole, m-phenylenediamine, 1-isopropyl-2,
4-phenylenediamine, p-phenylenediamine,
4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'diaminodiphenylethane, 4,
4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide,
4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, benzidine, 4,4 ″ -diamino-p-terphenyl, 3, 3 ″ -diamino-p-terphenyl, bis (p
-Aminocyclohexyl) methene, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-
Methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene,
1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5
-Aromatic diamines such as diamine, p-xylene-2,5-diamine, m-xylylenediamine and p-xylylenediamine; 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino Heterocyclic diamines such as -1,3,4-oxadiazole; alicyclic diamines such as 1,4-diaminocyclohexane; piperazine, methylenediamine, ethylenediamine, propylenediamine, 2,2-dimethylpropylenediamine, tetra Methylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, heptamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4 −
Dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylnonamethylenediamine, decamethylenediamine, 1,10-diamino-1,10-
Dimethyldecane, 2,11-diaminododecane, 1,1
In addition to aliphatic diamines such as 2-diaminooctadecane, 2,12-diaminooctadecane and 2,17-diaminoeicosane, diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-diamino-4 , 4'-dicarboxylic benzidine and the like.

These diamines may be used alone or in combination of two or more.
Among these, 2,2'-di (p-aminophenyl)
-6,6'-bisbenzoxazole, and 2,2'-
Di (p-aminophenyl) -5,5'-bisbenzoxazole is particularly preferable because it gives a polymer having low thermal expansion and high heat resistance.

<Tetracarboxylic acid or its acid anhydride>
Examples of the tetracarboxylic acid or its acid anhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, benzene-
1,2,3,4-tetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride , Naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5
-Tetracarboxylic dianhydride, naphthalene-1,2,
5,8-tetracarboxylic dianhydride, naphthalene-1,
2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,
8-Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8- Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,
3,6,7-Tetrachloronaphthalene-1,4,5,8
-Tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 2,3 ", 4,4" -p
-Terphenyltetracarboxylic dianhydride, 2,2 ",
3,3 "-p-terphenyltetracarboxylic dianhydride, 2,3,3", 4 "-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) ) -Propane dianhydride, 2,2-bis (3,4
-Dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3 -Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,
3,8,9-tetracarboxylic dianhydride, perylene-
3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride,
Perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride , Phenanthrene-1, 2, 9,
Aromatic tetracarboxylic dianhydrides such as 10-tetracarboxylic dianhydride and hydrogenated products thereof; cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, Bicyclo [2,2
2] Oct-7-ene-2-exo, 3-exo, 5-
Exo, 6-exotetracarboxylic acid 2,3: 5,6-
Alicyclic acid anhydride such as dianhydride, bicyclo [2,2,1] heptane-2-exo, 3-exo, 5-exo, 6-exotetracarboxylic acid 2,3: 5,6-dianhydride Stuff;
Pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride And the like heterocyclic derivatives. These can be used alone or in combination of two or more. Among these, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and combinations thereof are
It is particularly preferable in order to realize good low thermal expansion, crack resistance, resolution and the like.

<Introduction of Actinic Radical Functional Group> In the present invention, various photosensitive polyimides can be used.
A polyamic acid compound having an actinic radiation functional group introduced at its end is preferable. Therefore, at the time of synthesizing a polyamic acid compound, a trimellitic acid derivative such as trimellitic acid anhydride [tris (acryloyl) pentaerythritol] ester and trimellitic acid anhydride [tris (methacryloyl) pentaerythritol] ester (Japanese Patent Application No. -256222), or p-
An aminobenzenecarboxylic acid ester such as aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester (Japanese Patent Application No. 6-247109) can be present.

The polyamic acid having such an actinic radiation functional group is added to a diamine compound by adding a trimellitic acid derivative and tetracarboxylic acid or an acid anhydride thereof to a condensation reaction by a conventional method. To a mixture with an acid derivative, tetracarboxylic acid or an acid anhydride thereof is added, and a condensation reaction is carried out by a conventional method,
It can be synthesized by a method such as adding tetracarboxylic acid or its acid anhydride to a mixture of a diamine compound and an aminobenzenecarboxylic acid ester and conducting a condensation reaction by a conventional method.

<Photosensitive Aid> A typical example of a photosensitive auxiliary is a (meth) acrylic acid compound such as pentaerythritol triacrylate. Examples of the acrylic acid-based compound include acrylic acid, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carbitol 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, trimethylolpropane monoacrylate, allyl acrylate, 1,3-propylene glycol diacrylate Acrylate, 1 4- butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, 2,2-bis - (4-
Acryloxydiethoxyphenyl) propane, 2,2-
Bis- (4-acryloxypropyloxyphenyl) propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylic formal, tetramethylolmethane tetraacrylate, tris (2-hydroxy Ethyl) acrylic acid ester of isocyanuric acid,

[0021]

Embedded image (In the formula, b represents an integer of 1 to 30),

[0022]

Embedded image (In formula, c and d represent the integer used as c + d = 2-30.),

[0023]

Embedded image

[0024]

[Chemical 4] Etc. can be mentioned.

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, hydroxyethyl methacrylate, hydroxy Propyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, N, N-dimethylaminomethacrylate, N, N-diethylaminomethacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacryloxypropyltrimethoxysila , Allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, 2,2-bis- (4-methacryloxy) Diethoxyphenyl) propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethane tetramethacrylate, tris (2-hydroxyethyl)
Methacrylic acid ester of isocyanuric acid,

[0026]

Embedded image (In the formula, e represents an integer of 1 to 30),

[0027]

[Chemical 6] (In formula, f and g represent the integer which becomes f + g = 1-30.),

[0028]

[Chemical 7]

[0029]

Embedded image Etc. can be mentioned.

These compounds can be used alone or in combination of two or more. Of these, pentaerythritol triacrylate and the compound of Chemical formula 4 (b = 3) are particularly preferable.
Examples of commercially available products include 3EG-A (manufactured by Kyoei Chemical Co., Ltd.) and Viscoat 300 (manufactured by Osaka Organic Chemical Co., Ltd.). The photosensitizer is usually 10 to 40 parts by weight, preferably 15 to 10 parts by weight, based on 100 parts by weight of the polyamic acid compound.
It is desirable to use 35 parts by weight, more preferably 20 to 30 parts by weight.

<Solvent> As the solvent used for dissolving the photosensitive polyimide, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide and tetramethylurea are used. , Hexamethylphosphoric triamide, γ-butyrolactone, and other polar solvents. In addition to these polar solvents, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate,
Esters such as diethyl malonate; diethyl ether,
Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran; dichloromethane, 1,2-dichloroethane,
Halogenated hydrocarbons such as 1,4-dichlorobutane, trichloroethane, chlorobenzene and o-dichlorobenzene; hydrocarbons such as hexane, heptane, octane, benzene, toluene and xylene can also be used. These solvents may be used alone or in combination of two or more. Among these, N, N-dimethylacetamide and N-methyl-2-
Pyrrolidone and the like are particularly preferable. The amount of the solvent used is sufficient to uniformly dissolve each component.

<Photopolymerization Initiator> As the photopolymerization initiator,
For example, Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone,
1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis- (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene,
2,2-dimethoxy-2-phenylacetophenone, 1
-Hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulfide, anthracene, phenanthrenequinone, riboflavintetra Butyrate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis (p-diethylaminobenzylidene) -4-methyl-4-azacyclohexanone, 6-bis (p-dimethylaminobenzylidene).
-Cyclopentanone, 2,6-bis (p-diethylaminobenzylidene) -4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compound, biscoumarin compound, N-phenylglycine, N-phenyldiethanolamine, 3,3 ', 4,4'-tetra (t-
Butyl peroxy carbonyl) benzophenone etc. can be mentioned. The photopolymerization initiator is usually used in a proportion of 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polyamic acid compound.

<Other Additives> The photosensitive polyimide may further contain various additives such as an adhesion aid, a leveling agent and a polymerization inhibitor, if necessary.

Method of Using Photosensitive Polyimide A photosensitive polyimide composition containing a photosensitive polyimide, a solvent and, if necessary, various additives, is first prepared by using an appropriate support such as a silicon wafer, a ceramic or an aluminum substrate. Apply to. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after prebaking at a relatively low temperature to dry the coating film,
The desired pattern shape is irradiated with actinic rays (actinic rays).
As the actinic rays, X rays, electron rays, ultraviolet rays, visible rays and the like can be used. Next, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. In the present invention, a mixed solution containing N, N-dimethylacrylamide is used as the developing solution. As a developing method, various methods such as spraying, paddle, dipping, and ultrasonic wave can be adopted. The relief pattern formed by development is rinsed. Examples of the rinse liquid include methanol, ethanol, isopropyl alcohol, butyl acetate and the like. Next, heat treatment is performed to form an imide ring, and the polyamic acid compound is polyimidized to obtain a final pattern having high heat resistance.

Developer In the present invention, a mixture with a poor solvent containing N, N-dimethylacrylamide as an essential component is used as a developer for photosensitive polyimide. N, N-dimethylacrylamide acts as a good solvent for the photosensitive polyimide. As long as the objects and effects of the present invention are not impaired,
Other solvent conventionally used as a good solvent can be added, and the amount thereof is usually 10% by weight or less, preferably 5% by weight or less, based on N, N-dimethylacrylamide.

N, N-dimethylacrylamide is N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, which has been conventionally used as a dipolar aprotic polar solvent in a photosensitive polyimide developer. Compared with γ-butyrolactone and the like, the affinity for the exposed area is weak and swelling is unlikely to occur. As a result, it is possible to obtain high resolution without wrinkling on the pattern surface. The use ratio of N, N-dimethylacrylamide is usually 60 to 95% by weight, preferably 70 to 90% by weight, based on the whole developing solution. If this proportion exceeds 95% by weight, the affinity of the developing solution for the exposed area becomes too strong and swelling tends to occur.
If it does not satisfy the above condition, residual development is likely to occur, which is not preferable in any case.

As the poor solvent for the photosensitive polyimide, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol,
Alcohols such as isobutanol; acetone, methyl ethyl ketone, acetophenone, cyclohexane, methyl vinyl ketone and other ketones; toluene, xylene,
Aromatic hydrocarbons such as ethylbenzene and isopropylbenzene; esters such as methylcellosolve, ethylcellosolve and isopropylcellosolve,
Alcohols, aromatic hydrocarbons and ketones are preferable, and alcohols and aromatic hydrocarbons are more preferable. These are used alone or in combination of two or more.

The poor solvent is usually 5 to 5 based on the total amount of the developing solution.
It is used in a proportion of 40% by weight, preferably 10 to 30% by weight. It is preferable to use two or more kinds of poor solvents in combination, and it is more preferable to use water and an organic solvent (alcohols, ketones, aromatic hydrocarbons, esters, etc.) in combination. The ratio of water to the organic solvent used is usually 1: 2 to 2: 1 (weight ratio). If the amount ratio of water to the organic solvent exceeds 2 times (weight basis), the exposed surface is likely to be roughened after development, and if less than 0.5 times, cracks are likely to occur during development. Either case is not preferable. Further, the developer of the present invention may contain an antioxidant, a polymerization inhibitor or the like usually used in this field in order to prevent deterioration of the developer.

The preferred developer composition of the present invention is N, N
-Dimethylacrylamide 60-95% by weight, water 2
.About.25 wt%, and the organic solvent (poor solvent) is 2 to 25 wt%. The more preferable composition of the developing solution of the present invention is N,
N-dimethylacrylamide is 70 to 90% by weight, water is 5 to 20% by weight, and the organic solvent (poor solvent) is 5 to 20% by weight. The developing solution of the present invention is particularly high with respect to a commercially available ion-crosslinking type photosensitive polyimide manufactured by Toray Co., Ltd., or a polyamic acid compound type photosensitive polyimide end-modified with an actinic functional group. The effect can be obtained.

[0040]

EXAMPLES The present invention will be described in more detail below with reference to Reference Examples, Synthesis Examples and Examples. In addition, part and% in each example
Is weight basis unless otherwise specified.

[Synthesis Example 1] p-Aminobenzoic acid [tris (methacryloyl) penta]
Synthesis of erythritol] ester (1) Pentaerythritol trimethacrylate (13.1 g), triethylamine (4.1 g) and methylene chloride (35 ml) were added to a reactor, and p-nitrobenzoyl chloride (6.7 g) was added while stirring under ice cooling. Then, 25 ml of methylene chloride was added dropwise, and the mixture was reacted under ice cooling for 2 hours and then at room temperature for 2 hours. After completion of the reaction, chloroform and water were added to the reaction solution, and then hydrochloric acid was added to separate the chloroform layer. The pale yellow oily substance obtained by distilling off chloroform under reduced pressure was purified by column chromatography to give 15.1 g of p-nitrobenzoic acid [tris (methacryloyl) pentaerythritol] ester (yield 85.
8%). (2) In the reactor, p-nitrobenzoic acid [tris (methacryloyl) pentaerythritol] ester 15.1
g, stannous chloride 35.1 g, and tetrahydrofuran 150 ml were added, and hydrogen chloride gas was introduced under ice cooling and stirring. After reacting for 1 hour under ice-cooling and then for 1 hour at room temperature, water and sodium carbonate were added to the reaction solution to make it weakly alkaline. Next, the mixture was extracted with chloroform, the chloroform was distilled off under reduced pressure, and the residue was purified by column chromatography to give 13.8 g of p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester (yield 92.3). %) Was obtained.

[Synthesis Example 2] 2,2'-di (p-aminophenyl) -6,6 was added to a photosensitive polyimide synthesis reactor.
110.5 g of 6'-bisbenzoxazole (0.26
4 mol), and 10.1 g (0.022 m) of p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester obtained in Synthesis Example 1 as an amine for terminal modification.
Ol), 552 g of dimethylacetamide, and 552 g of N-methyl-2-pyrrolidone to prepare a uniform solution, which was then stirred under ice-cooling under stirring to obtain 3,3 ′, acid anhydride.
4,4'-benzophenone tetracarboxylic acid anhydride 8
8.6 g (0.276 mol) was added as a powder in small portions. Then, the mixture was reacted under ice cooling for 3 hours and then at room temperature for 20 hours to synthesize a polyamic acid.

[Examples 1 to 4, Comparative Examples 1 to 4] Synthesis Example 2
625.0 parts by weight of the polyamic acid (solid content 1
00 parts by weight), 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (hereinafter, referred to as B
2 parts by weight of TTB: λmax = 340 nm, manufactured by NOF CORPORATION, 2 parts by weight of N-phenylglycine, and 28 parts by weight of 3EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) as a photosensitizer were added and dissolved at room temperature. In this way, the photosensitive polyimide composition prepared was coated on a silicon wafer with a spinner,
Dry for about 30 minutes at 80 ° C with a dryer to a thickness of about 10μ
m coating film was obtained. The thickness of the coating film is the surface shape measuring device P-
It was measured with 10 (manufactured by Tencor Co., Ltd.). Exposure equipment PLA-
Line & Space (L / L) on 501F (Canon)
S) Set a resolution evaluation mask (made by Toppan Printing Co., Ltd.),
Soft contact mode exposure 250 mJ or 350
It was exposed with mJ. Then, spray development was performed with any one of the developing solutions 1 to 4 having the following composition to obtain a pattern.

<Developer 1> N, N-dimethylacrylamide 80 parts by weight Isopropyl alcohol 12 parts by weight Water 8 parts by weight <Developer 2> N, N-dimethylacrylamide 75 parts by weight Isopropyl alcohol 17 parts by weight Water 8 parts by weight < Developer 3> N, N-dimethylacetamide 75 parts by weight Isopropyl alcohol 17 parts by weight Water 8 parts by weight <Developer 4> N-methyl-2-pyrrolidone 75 parts by weight Isopropyl alcohol 17 parts by weight Water 8 parts by weight The above developer 1 Among the above-mentioned 4 to 4, the developing solutions 1 and 2 correspond to the examples of the present invention. After development, the pattern was observed with an optical microscope, the film thickness after development was measured, and the residual film rate was calculated. The results are shown in Table 1.

[0045]

[Table 1] (Footnote) (* 1) After exposure, the substrate was left in a clean bench for 3 days and then developed, and the obtained pattern was observed with an optical microscope.

From the results shown in Table 1, it can be seen that when the developers 1 and 2 of the present invention are used, a good pattern can be obtained with high sensitivity and high residual film ratio even with a small exposure amount. That is, when the developers 1 and 2 of the present invention are used, it is possible to form a pattern having a good resolution and a wrinkle or a development residue even at a low exposure amount.
Further, the performance does not change at all even after being left for 3 days after the exposure, but when using the developing solutions 3 and 4 having other formulations, the performance changes such as wrinkles and development residues.

[Examples 5 to 8 and Comparative Examples 5 to 8] As a photosensitive polyimide composition, Toray's trade name Photo Nice
UR-5100 is coated on a silicon wafer with a spinner and dried by a dryer at 80 ° C. for 30 minutes to give a thickness of about 1
A coating of 0 μm was obtained. The thickness of the coating film was measured with a surface profile measuring device P-10 (manufactured by Tencor Co., Ltd.). Exposure equipment PL
A line-and-space (L / S) resolution evaluation mask (manufactured by Toppan Printing Co., Ltd.) was set on A-501F (manufactured by Canon Inc.), and exposure was performed at a soft contact mode exposure amount of 250 mJ or 350 mJ. Then, the developer 1 of the above composition
Spray development was carried out with any one of 4 to obtain a pattern. Table 2 shows the results.

[0048]

[Table 2] (Footnote) (* 1) After exposure, the substrate was left in a clean bench for 3 days and then developed, and the obtained pattern was observed with an optical microscope.

As can be seen from Table 2, Developer 1 of the present invention
It can be seen that the use of Nos. 2 and 2 has good resolution at a low exposure amount and enables pattern formation without wrinkles or development residues. Further, the performance does not change at all even after being left for 3 days after the exposure, but in the developers 3 and 4 having other formulations, the performance changes such as wrinkles and development residuals.

[0050]

According to the present invention, there is provided a photosensitive polyimide developer capable of giving a pattern excellent in various characteristics such as sensitivity, resolution and pattern shape. In the present invention, a conventional developer is used by using N, N-dimethylacrylamide as an aprotic polar solvent having a bipolar structure in an organic solvent-based developer in which a good solvent and a poor solvent are combined. As compared with the case, the resolution is improved, the residual film ratio is high, there is no development residue, and an excellent pattern shape can be obtained without wrinkling on the pattern surface.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Satoshi Tasaki Satoshi Tazaki 1-2-1, Yokou, Kawasaki-ku, Kanagawa Prefecture Zeon Corporation (72) Inventor Kei Sakamoto 1-2-2 Yokou, Kawasaki-ku, Kanagawa Prefecture No. 1 in Zeon Corporation (72) Inventor Yasuhiro Yoneda 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited (72) Inventor, Takashi Yokouchi 1015 Kamitadanaka, Nakahara-ku, Kawasaki City, Kanagawa Within Fujitsu Limited (72) Inventor Masahide Yamamoto 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited (72) Inventor Yoshikatsu Ishizuki, 1015, Kamikodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited

Claims (1)

[Claims] 1. A developer for photosensitive polyimide containing an aprotic polar solvent having a bipolar structure and a poor solvent for the photosensitive polyimide, wherein N, N-dimethylacrylamide is used as the aprotic polar solvent having a bipolar structure. A developing solution for a photosensitive polyimide, which is used.