JPH09325479A - Manufacture of photosensitive composition, photosensitive material, relief pattern, and polyimide pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the photosensitive characteristic and storage stability by containing a specific catechol compound, a titanocene compound, and an addition polymerization compound having the specific boiling point at the normal pressure. SOLUTION: A catechol compound expressed by the formula I, a titanocene compound expressed by the formula II, and a addition polymerization compound having the boiling point of 100 deg.C or above at the normal pressure are contained. In the formulas, R<1> -R<4> represent hydrogen atom, alkyl group having 1-5 carbon atoms, phenyl group, nitro group, halogen atom, or heterocyclic ring, and R<5> -R<14> independently represent hydrogen atom, halogen atom, alkoxy group having 1-20 carbon atoms, or heterocyclic ring. 3-methyl catechol or 4-methyl catechol is used as the catechol compound, for example. Bis(cyclopentadienyl)-bis[2,6- difluoro-3-(2-(1H-pyrrole-1-yl)propyl)phenyl] titanium is used at the titanocene compound, for example.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photosensitive composition, a photosensitive material, a method for producing a relief pattern, and a method for producing a polyimide pattern.

[0002]

2. Description of the Related Art Polyimide or a precursor thereof which also has photopatterning properties by itself is called photosensitive polyimide, and is used for a surface protective film of a semiconductor or the like. Several photosensitive methods are known for photosensitive polyimide. A representative one is Japanese Examined Japanese Patent Publication No.55-4.
No. 1422, which is an ester of a polyamic acid with hydroxyacrylate, or a compound such as an amino acrylate which is mixed with a polyamic acid proposed in Japanese Patent Application Laid-Open No. 54-145794. It is known to introduce a photosensitive group through a salt bond. These materials have a drawback in that the sensitivity of the film formed by spin coating or the like is lower than that of a conventional ultraviolet curable paint or dry film resist because the polyamic acid itself is rigid. The sensitivity can be increased by adding an oxime ester compound, a phenylglycine compound, or the like to improve this. However, on the other hand, there is a drawback that the viscosity change of the varnish during storage and the photosensitive characteristics are deteriorated in the state of being dissolved in the polar solvent during storage. For this reason, there was a problem that it was not possible to achieve both high sensitivity in a film state and storage stability in a solution state during storage.

[0003]

SUMMARY OF THE INVENTION The first aspect of the present invention provides a photosensitive composition exhibiting excellent photosensitive characteristics and storage stability. The invention described in claim 2 provides the effects of the invention described in claim 1 and provides a photosensitive composition having more excellent storage stability. The invention according to claim 3 provides a photosensitive material exhibiting excellent photosensitive characteristics, storage stability and heat resistance. The invention described in claim 4 provides the effect of the invention described in claim 3 and provides a photosensitive material having more excellent storage stability. The invention described in claim 5 provides a photosensitive material exhibiting more excellent photosensitive characteristics in addition to the effects of the invention described in claim 3 or 4. The invention according to claim 6 provides a method for producing a relief pattern that gives a polyimide pattern exhibiting excellent heat resistance, adhesion and chemical resistance. The invention according to claim 7 provides a method for producing a polyimide pattern exhibiting excellent heat resistance, adhesion and chemical resistance.

[0004]

The present invention provides a compound represented by the following general formula (I):

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom and a carbon number of 1 to
5 represents an alkyl group, a phenyl group, a nitro group, a halogen atom or a heterocycle), and a catechol compound represented by the general formula (II)

[Chemical 6] (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring), and a titanocene compound represented by 10 at normal pressure.
The present invention relates to a photosensitive composition containing an addition-polymerizable compound having a boiling point of 0 ° C or higher. In addition, the present invention further provides
The present invention relates to the above-mentioned photosensitive composition containing a dye compound having absorption at 50 to 600 nm.

The present invention also provides the following general formula (I)

[Chemical 7] (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom and a carbon number of 1 to
5 represents an alkyl group, a phenyl group, a nitro group, a halogen atom or a heterocycle), and a catechol compound represented by the general formula (II)

Embedded image (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocycle), a titanocene compound represented by a polyamic acid, dimerized with actinic radiation or The present invention relates to a light-sensitive material containing a compound having a polymerizable carbon-carbon double bond and an amino group or a quaternized salt thereof. In addition, the present invention further provides 450-
The present invention relates to the above light-sensitive material containing a dye compound having an absorption at 600 nm.

The present invention further relates to the above-mentioned photosensitive material containing a bisazide compound. Also, the present invention
It relates to a method for producing a relief pattern, which comprises irradiating a pattern of an actinic ray on a coating film of the photosensitive composition or the photosensitive material and developing and removing an unirradiated portion. Further, the present invention relates to a method for producing a polyimide pattern, wherein the relief pattern obtained by the method for producing a relief pattern is heated.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive composition of the present invention has the following general formula (I):

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom and a carbon number of 1 to
5 represents an alkyl group, a phenyl group, a nitro group, a halogen atom or a heterocycle), and a catechol compound represented by the general formula (II)

Embedded image (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring), and a titanocene compound represented by 10 at normal pressure.
An addition-polymerizable compound having a boiling point of 0 ° C. or higher is contained as an essential component.

Examples of the catechol compound represented by the formula (I) in the present invention include catechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3-fluorocatechol, 4-t-butylcatechol, 3,3,3 ', 3'-tetramethyl-1,1'
-Spirobisindene 5,5 ', 6,6'-tetrol, 3,4-dihydroxyphenyl glycol, 3,5
-Diisopropylcatechol, 3,5-di-t-butylcatechol, tetrachlorocatechol, tetrabromocatechol and the like can be mentioned. These may be used alone or in combination of two or more. The amount of these catechol compounds used is not particularly limited, but is usually 0.01 to 1 part by weight with respect to 100 parts by weight of the solid content excluding the catechol compound in the photosensitive resin composition of the present invention.

Examples of the titanocene compound represented by the general formula (II) in the present invention include bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2-
(1H-Pyrrol-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-
Difluoro-3- (2- (1H-pyrrol-1-yl)
Methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyrrole-1)
-Yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-dimethylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3
-(2,5-Diethylpyrrol-1-yl) phenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3- (2,5-diisopropylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-
Bisdimethylaminopyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-
Difluoro-3- (2,5-dimethyl-3-methoxypyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methoxyphenyl] titanium, bis (cyclo Pentadienyl)
-Bis [2,6-difluoro-3-isopropoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-n-propoxyphenyl]
Examples thereof include titanium. These are used alone or in combination of two or more. The amount of the titanocene compound used is not particularly limited, but is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content excluding the titanocene compound in the photosensitive resin composition of the present invention. .

Examples of the addition-polymerizable compound having a boiling point of 100 ° C. or higher at atmospheric pressure in the present invention include compounds obtained by condensing a polyhydric alcohol and an α, β-unsaturated carboxylic acid (ethylene glycol diacrylate). ,
Triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, 1,2-propylene glycol diacrylate,
Di (1,2-propylene glycol) diacrylate,
Tri (1,2-propylene glycol) diacrylate, tetra (1,2-propylene glycol) diacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate,
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, methacrylate corresponding thereto), styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone , 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-
Examples include 2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide and the like, and these are used alone or in combination of two or more.

The photosensitive composition of the present invention may contain 4 parts by weight of the photosensitive composition.
A dye compound having absorption in 50 to 600 nm may be contained, and as such a dye compound, 450 to 600 nm is included.
There is no particular limitation as long as it has absorption, for example,
Phenolphthalene, phenol red, neal red, pyrogallol red, pyrogallol violet,
Disperse Red 1, Disperse Red 13, Disperse Red 19, Disperse Orange 1, Disperse Orange 3, Disperse Orange 13, Disperse Orange 25, Disperse Blue 3, Disperse Blue 14, Eosin B, Lodamin B, Quinalizarin, 5- (4-dimethylaminobenzylidene) rhodanine, aurin tricarboxyside, aluminone, alizarin, pararosaniline, emodin, thionine, methylene violet and the like. These are used alone or in combination of two or more. The amount of these dye compounds used is not particularly limited, but usually, in the photosensitive composition of the present invention, solid component 1 excluding the dye compounds is used.
It is 0.1 to 5 parts by weight with respect to 00 parts by weight.

The photosensitive composition of the present invention may optionally contain 1
It may contain one or more high molecular weight organic polymers. By adding a high molecular weight organic polymer in the photosensitive composition,
Properties such as adhesion to a substrate, chemical resistance, and film properties can be improved. From the viewpoint of photocurability, the amount of the high molecular weight organic polymer is preferably 0.1 to 70 parts by weight based on 100 parts by weight of the total amount of the high molecular weight organic polymer and the addition polymerizable compound. Weight average molecular weight of high molecular weight organic polymer (measured by gel permeation chromatography,
Value converted to standard polystyrene. The same applies hereinafter) is 10,0
00 to 700,000 is preferable.

Examples of high molecular weight organic polymers include copolyesters (polyhydric alcohols (diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol, etc.) and polyhydric carboxylic acids (terephthalic acid, isophthalic acid). ,
Copolyesters manufactured from sebacic acid, adipic acid, etc.), vinyl polymers (methacrylic acid, acrylic acid, methacrylic acid or acrylic acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, 2-acrylate)
A homopolymer or a copolymer such as hydroxyethyl acrylate, phenyl acrylate, benzyl acrylate, 2-dimethylaminoethyl acrylate, 2-ethylhexyl acrylate, methacrylate and the like corresponding thereto), polyformaldehyde, polyurethane, polycarbonate, polyamide, cellulose ester (methyl cellulose) , Ethyl cellulose, etc.), polyamic acid and the like.

As the polyamic acid, known ones can be used without particular limitation, and examples thereof include those obtained by addition-polymerizing a tetracarboxylic dianhydride and a diamine compound.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3',
4,4'-biphenyltetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, m
-Terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, p-terphenyl-3,3 ", 4,4"-
Tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,
3,3,3-hexafluoro-2,2'-bis [4-
(2,3-Dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2'-bis [4- (3,4-dicarboxyphenoxy) phenyl ] Propane dianhydride can be mentioned. These tetracarboxylic dianhydrides are used alone or in combination of two or more.

Examples of the diamine compound include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 3,3'-dimethylbenzidine, 3 and the like. , 3'-dimethoxybenzidine, 4,4 '
(Or 3,4'-, 3,3'-, 2,4 '-)-diaminodiphenylmethane, 4,4' (or 3,4'-, 3,
3'-, 2,4 '-)-diaminodiphenyl ether,
4,4 '(or 3,4'-, 3,3'-, 2,4'-)
Diaminodiphenylsulfone, 4,4 '(or 3,
4 '-, 3,3'-, 2,4 '-)-diaminodiphenyl sulfide, 4,4'-benzophenone diamine,
3,3'-benzophenonediamine, 4,4'-di (4
-Aminophenoxy) phenylsulfone, 4,4'-
Bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,1,1,3
3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3-dimethyl-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-di (3-aminophenoxy) phenylsulfone, 3,3'-diaminodiphenylsulfone,
Aromatic diamines such as 2,2'-bis (4-aminophenyl) propane, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, 2,7-diaminobenzofuran; 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 2,
5-diamino-1,3,4-thiadiazole, 2,4-
Heterocyclic diamines such as diamino-6-phenyl-s-triazine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine, the following general formula (III)

Embedded image (In the formula, R ¹⁵ , R ¹⁶ , R ^17, and R ¹⁸ each independently represent an alkyl group having 1 to 6 carbon atoms, and m and n are each independently an integer of 1 to 10). Aliphatic diamines such as the represented diaminopolysiloxanes may be mentioned. These diamine compounds are used alone or in combination of two or more.

The photosensitive composition of the present invention may optionally contain a sensitizer. Examples of such a sensitizer include 7-N, N-diethylaminocoumarin and 3,3′-
Carbonylbis (7-N, N-diethylamino) coumarin, 3,3'-carbonylbis (7-N, N-dimethoxy) coumarin, 3-thienylcarbonyl-7-N, N-
Diethylaminocoumarin, 3-benzoylcoumarin, 3
-Benzoyl-7-N, N-methoxycoumarin, 3-
(4'-methoxybenzoyl) coumarin, 3,3'-carbonylbis-5,7- (dimethoxy) coumarin, benzalacetophenone, 4'-N, N-dimethylaminobenzalacetophenone, 4'-acetaminobenzal −
4-methoxy acetophenone etc. are mentioned. These are used alone or in combination of two or more.
The amount of these sensitizers used is not particularly limited, but is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content excluding the sensitizer in the photosensitive composition of the present invention. .

The photosensitive composition of the present invention may optionally contain a photoinitiator. Examples of such a photoinitiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4′-bis (pN, N-). Diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2
-Phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone,
Benzyl, diphenyl disulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, N-phenyldiethanolamine,
2- (o-ethoxycarbonyl) oxyimino-1,3
-Diphenylpropanedione, 1-phenyl-2- (o
-Ethoxycarbonyl) oxyiminopropan-1-one, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, N- (p-cyanophenyl) glycine, N- (p-methylsulfonyl) Phenyl) glycine and the like. These can be used alone or
Used in combination with more than one type. The amount of these photoinitiators used is not particularly limited, but is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content excluding the photoinitiator in the photosensitive composition of the present invention. .

The photosensitive composition of the present invention may contain an organic solvent, if necessary. As such an organic solvent,
For example, acetone, methyl ethyl ketone, diethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol monomethyl ether, xylene, tetrahydrofuran, dioxane, N, N-dimethylacetamide,
N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide,
Ethylene carbonate, propylene carbonate, sulfolane, etc. are used. These organic solvents are used alone or in combination of two or more. The amount of such an organic solvent used is not particularly limited, but from the viewpoint of coatability and the like, an amount such that the solid content of the photosensitive composition is 5 to 95% by weight is preferable, and 10 to 50% by weight. More preferably, the amount will be%.

The photosensitive composition of the present invention may contain other additives such as plasticizers and adhesion promoters.

The light-sensitive material of the present invention has the following general formula (I).

[Chemical 12] (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom and a carbon number of 1 to
5 represents an alkyl group, a phenyl group, a nitro group, a halogen atom or a heterocycle), and a catechol compound represented by the general formula (II)

Embedded image (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocycle), a titanocene compound represented by a polyamic acid, dimerized with actinic radiation or A compound having a polymerizable carbon-carbon double bond and an amino group or a quaternized salt thereof is contained as an essential component.

As the polyamic acid in the light-sensitive material of the present invention, the above-mentioned polyamic acid can be used.

In the light-sensitive material of the present invention, the compound represented by the general formula (I)
The use amount of the catechol compound represented by is preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the polyamic acid. If it is less than 0.01 parts by weight, the stability improving effect tends to be small, and if it exceeds 1.0 parts by weight, the photocurability tends to be low. In the light-sensitive material of the present invention, the amount of the titanocene compound represented by the general formula (II) used is
It is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of polyamic acid. If it is less than 0.1 part by weight, the photocurability tends to be low, and if it exceeds 10 parts by weight, the heat resistance tends to be poor.

Examples of the compound containing a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof contained in the light-sensitive material include the following compounds.

[0025]

Embedded image

From the viewpoint of photocurability, heat resistance, etc., the amount of this compound used is preferably an amount that is equimolar to the carboxyl group of the polyamic acid. This amount is usually 30 to 120 parts by weight based on 100 parts by weight of the polyamic acid.

The light-sensitive material of the present invention may optionally contain the above-mentioned dye compound having absorption at 450 to 600 nm. This usage amount is stable and easy to handle.
The amount is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of polyamic acid.

The light-sensitive material of the present invention may optionally contain a bisazide compound. Examples of such a bisazide compound include the following compounds.

Embedded image

Embedded image

When a bisazide compound is used, its amount is 100% in terms of heat resistance and photocurability.
It is preferably 0.01 to 10 parts by weight with respect to parts by weight.

The light-sensitive material of the present invention may contain a photoinitiator, if necessary. Such photoinitiators include those described above. When the photoinitiator is used, the amount thereof is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polyamic acid from the viewpoints of heat resistance, photocurability and the like.

The light-sensitive material of the present invention may contain a sensitizer if necessary. Such sensitizers include those described above. When a sensitizer is used, its amount is 100% in terms of heat resistance, photocurability and the like.
It is preferably 0.1 to 10 parts by weight with respect to parts by weight.

The light-sensitive material of the present invention may contain an organic solvent, if necessary. As the organic solvent, those mentioned above can be mentioned. When an organic solvent is used, its amount is not particularly limited, but from the viewpoint of coatability and the like, it is preferably an amount such that the solid content of the photosensitive material is 5 to 95% by weight. More preferably, the amount is about 50% by weight.

The light-sensitive material of the present invention may contain additives such as a plasticizer and an adhesion promoter.

The photosensitive composition and the photosensitive material of the present invention are coated on a substrate such as a silicon wafer, a metal substrate, a glass substrate, a ceramic substrate, etc. by a dipping method, a spray method, a screen printing method, a spin coating method, etc. When an organic solvent is included, most of the organic solvent is heated and dried to form a non-tacky coating film. The coating film is irradiated with actinic rays in a pattern. The actinic rays to be irradiated include ultraviolet rays, far ultraviolet rays, visible light, electron beams, and X-rays. After the irradiation, a desired relief pattern is obtained by dissolving and removing the unirradiated portion with an appropriate developer.

The developer is not particularly limited, but examples thereof include flame-retardant solvents such as 1,1,1-trichloroethane, alkaline aqueous solutions such as sodium carbonate aqueous solution, N, N-dimethylformamide, N, N-dimethylacetamide. , N
A mixed solvent of a good solvent such as -methyl-2-pyrrolidone and a poor solvent such as lower alcohol, water and aromatic hydrocarbon is used. After development, rinsing may be performed with a poor solvent or the like, if necessary, and the relief pattern can be stabilized by drying at about 100 ° C. By heating the relief pattern thus obtained (usually at 80 to 400 ° C. for 5 to 300 minutes), imide ring closure can be performed to obtain a polyimide pattern. By using the relief pattern or the polyimide pattern as a mask, the passivation film formed using an inorganic material such as SiO or SiN can be processed by dry etching or the like.

[0036]

The present invention will be described below with reference to examples. Examples 1 to 4 and Comparative Example 1 10 g of N-methyl-2-pyrrolidone solution of polyamic acid obtained by reacting 4,4'-diaminodiphenyl ether and pyromellitic dianhydride in equimolar amounts by a conventional method.
(Solid content 20% by weight), 2-dimethylaminoethyl methacrylate 1.8 g, bis (cyclopentadienyl)-
By blending 0.1 g of bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium, 0.02 g of 4,4′-bisazido-3,3′-biphenyl, a catechol compound and a coloring compound. After producing the light-sensitive material, it was taken out into a glass sample bottle and left at room temperature in a yellow room for storage stability test. Table 1 shows the viscosities of the light-sensitive materials immediately after compounding and after 7 days from standing.

Further, these photosensitive materials were spin-coated on a silicone wafer, and were then coated on a hot plate at 100 ° C. for 20 minutes.
It was heated for 0 seconds and the organic solvent was dried to obtain a photosensitive coating film.
The film thickness after drying was 23 microns. Pattern exposure was performed on the coating film via a photomask with a mirror projection exposure machine using an ultra-high pressure mercury lamp as a light source. After this N-
Immersion development was performed with a mixed solution of methyl-2-pyrrolidone and methyl alcohol (volume ratio: 4/1), followed by rinsing with isopropanol. The pattern shape after development was observed, and the exposure amount at which the residual film ratio (value obtained by dividing the film thickness by the initial film thickness) was 90% is shown in Table 1 as the sensitivity. In addition, the minimum mask size of the pattern opened at that time is taken as the resolution in Table 1.
It was shown to. For the photosensitive materials of Example 1 and Comparative Example 1, Tables 2 and 3 show the resolution when the standing time from coating to exposure and from exposure to development were changed, respectively.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

Further, with respect to the wafer obtained in Example 1, this was subjected to 200 ° C. for 15 minutes at 200 ° C. under a nitrogen atmosphere for 200 minutes.
The final cured film was heated at 20 ° C. for 20 minutes and at 350 ° C. for 60 minutes. A good patterned polyimide pattern having a final cured film thickness of 10 μm was obtained. This polyimide pattern showed excellent heat resistance, adhesion and chemical resistance.

[0042]

The photosensitive composition according to the first aspect exhibits excellent photosensitive characteristics and storage stability. The light-sensitive material according to claim 2 exhibits excellent light-sensitive properties, storage stability and heat resistance.
The light-sensitive material according to the third aspect exhibits the effect of the invention according to the second aspect and exhibits more excellent light-sensitive properties. The method for manufacturing a relief pattern according to claim 4 gives a polyimide pattern exhibiting excellent heat resistance, adhesion and chemical resistance. Claim 5
The production method of the described polyimide pattern has excellent heat resistance,
Shows adhesion and chemical resistance.

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Claims (7)

[Claims] 1. A compound represented by the following general formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom and a carbon number of 1 to
5 represents an alkyl group, a phenyl group, a nitro group, a halogen atom or a heterocycle), a catechol compound represented by the general formula (II): (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring), and a titanocene compound represented by 10 at normal pressure.
A photosensitive composition containing an addition-polymerizable compound having a boiling point of 0 ° C. or higher. 2. The photosensitive composition according to claim 1, further comprising a dye compound having an absorption at 450 to 600 nm. 3. The following general formula (I): (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom and a carbon number of 1 to
5 represents an alkyl group, a phenyl group, a nitro group, a halogen atom or a heterocycle), a catechol compound represented by the general formula (II): (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocycle), a titanocene compound represented by a polyamic acid, dimerized with actinic radiation or A light-sensitive material comprising a compound having a polymerizable carbon-carbon double bond and an amino group or a quaternized salt thereof. 4. The light-sensitive material according to claim 3, further comprising a dye compound having an absorption at 450 to 600 nm. 5. The light-sensitive material according to claim 3, further comprising a bisazide compound. 6. A photosensitive composition according to claim 1 or 2 or a coating film of the photosensitive material according to claim 3, 4 or 5 is irradiated with actinic rays in a pattern to remove the unirradiated portion by development. A method of manufacturing a relief pattern. 7. A method for producing a polyimide pattern, which comprises heating the relief pattern obtained by the method according to claim 6.