JP3446909B2 - Photoinitiator, photosensitive composition, photosensitive material and method for producing pattern - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photoinitiator, a photosensitive composition, a photosensitive material and a method for producing a pattern.

[0002]

2. Description of the Related Art A polyimide or its precursor, which itself has a photopatterning property, is called a photosensitive polyimide and is used for a surface protective film of a semiconductor. Several methods of imparting photosensitivity are known for photosensitive polyimide. The representative one is Japanese Patent Publication Sho 55-
And a polyamic acid ester with a hydroxy acrylate as proposed in Japanese Patent No. 41422,
JP-A-57-170929 and JP-A-54-145
It is known that a polyamic acid as proposed in Japanese Patent No. 794 is blended with a compound such as amino acrylate and a photosensitive group is introduced by a salt bond. In the former case, the photo-patterning property is relatively excellent, but it is difficult to increase the molecular weight, and the removal of the photosensitive group is likely to be incomplete. In the latter case, a high molecular weight is easily obtained and the photosensitive group is easily volatilized, so that the film characteristics are excellent, but the photopatterning property is not sufficient. In particular, in the case of a thick photosensitive polyimide having a film thickness of 5 μm or more after curing, the i-line stepper (36
There was a problem that good patterning properties could not be obtained when exposed with a 5 nm light), a g-line stepper (435 nm light was used), or a mirror projection type exposure machine using all wavelengths of a mercury lamp.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and is a photoinitiator for producing a photosensitive composition and a photosensitive material exhibiting excellent photosensitivity. The present invention provides a method for producing a photosensitive composition, a photosensitive material and a pattern using the same.

[0004]

The present invention is a 3-substituted coumarin compound represented by the following formula (I):

[Chemical 4] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms,
Amino group substituted with one alkyl group having 1 to 5 carbon atoms, Amino group substituted with two alkyl groups having 1 to 5 carbon atoms, Alkoxy group having 1 to 5 carbon atoms, Acyloxy group, Aryl group A halogen atom or a thioalkyl group having 1 to 5 carbon atoms, and R ₆ is a phenyl group, a biphenyl group, a naphthyl group, a thienyl group, a benzofuryl group, a furyl group, a pyridine group, a coumarinyl group, an amino group, or a carbon number of 1 to 5 An amino group substituted with an alkyl group, a cyano group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a haloalkyl group, a formyl group, an alkoxycarbonyl group having 1 to 5 carbon atoms, or Carbon number 1
To 5 acyloxy groups, and phenyl group, biphenyl group, naphthyl group, thienyl group, benzofuryl group, furyl group, pyridine group and coumarinyl group may be substituted with an acyl group having 1 to 5 carbon atoms), Titanocene compound represented by formula (II)

[Chemical 5] (In the formula, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R _13
14 , R ₁₅ and R ₁₆ are a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring such as 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, imidazolyl and pyrazolyl) and the following formulas: N-aryl-α-amino acid represented by III)

[Chemical 6] (In the formula, R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or an alkylsulfone group having 1 to 4 carbon atoms, At least one of R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ is a cyano group or an alkylsulfone group having 1 to 4 carbon atoms, and R ₂₂ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, cyclo An alkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group or aryl group having 1 to 12 carbon atoms, and R ₂₃ and R ₂₄ are hydrogen atoms or 1 carbon atoms To R 8 are alkyl groups of R ₁₇ , R ₁₈ , R ₁₉ , R
₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ may be the same).

The photosensitive composition and photosensitive material of the present invention described below may further contain other photoinitiators, if necessary. Other photoinitiators include, for example, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4'-bis (N, N-diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone , 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, 2- (O-ethoxycarbonyl) oxyimino-1,3-diphenyl-1,2,3-trione, 2
-(O-phenoxycarbonyl) oxyimino-1,3
-Diphenyl-1,2,3-trione, 2- {O-
(2'-Methoxy) ethoxycarbonyl} oxyimino-1,3-diphenyl-1,2,3-trione, 2-
(O-n-heptyloxycarbonyl) oxyimino-
1,3-diphenyl-1,2,3-trione, 2- (O
-Benzyloxycarbonyl) oxyimino-1,3-
Diphenyl-1,2,3-trione,

[Chemical 7] Etc. There is no particular limitation on the amount of these photoinitiators used.

The present invention also relates to a photosensitive composition containing an addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure and the above photoinitiator.

The present invention also includes a photosensitive acid containing a polyamic acid, a compound having a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof, and the above-mentioned photoinitiator. The present invention relates to a material and a method for manufacturing a pattern using this photosensitive material.

Examples of the 3-substituted coumarin compound represented by the above formula (I) include 3-benzoylcoumarin and 3-
Benzoyl-7-methoxycoumarin, 3-benzoyl-
5,7-dimethoxycoumarin, 3- (4'cyanobenzoyl) -coumarin, 3- (4'cyanobenzoyl) -7
-Methoxycoumarin, 3- (4'-cyanobenzoyl)
-5,7-dimethoxycoumarin, 3-thienylcarbonylcoumarin, 7-methoxy-3-thienylcarbonylcoumarin, 5,7-dimethoxy-3-thienylcarbonylcoumarin, 7-N, N-diethylamino-3-thienylcarbonylcoumarin, 7-N, N-dimethylamino-3
-Thienylcarbonylcoumarin, 3- (4'-methoxybenzoyl) coumarin, 3- (4'-methoxybenzoyl) -7-methoxycoumarin, 3- (4'-methoxybenzoyl) -5,7-dimethoxycoumarin, 3, 3'-
Carbonyl bis (7-N, N-diethylaminocoumarin), 3,3'-carbonylbis (7-methoxycoumarin), 3,3'-carbonylbis (5,7-dimethoxycoumarin) and the like can be mentioned. You may use these in combination of 2 or more types.

An example of the titanocene compound represented by the above formula (II) is bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (pyrrol-1-yl) ethyl) phenyl. ] Titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (pyrrol-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6 -Difluoro-3- (2- (pyrrol-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium, Bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-dimethylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,2 - difluoro-3- (2,5
-Diethylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-diisopropylpyrrol-1-yl) phenyl] titanium, bis (cyclopenta) (Dienyl)
-Bis [2,6-difluoro-3- (2,5-bisdimethylaminopyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,2 5-dimethyl-3-methoxypyrrole-
1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-ethoxy Phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-isopropoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-n-propoxyphenyl ] Titanium etc. are mentioned. You may use these in combination of 2 or more types.

Examples of the N-aryl-α-amino acid represented by the above formula (III) include N- (p-methylsulfonylphenyl) -N-methylglycine and N- (p-methylsulfonylphenyl) -N. -Ethylglycine, N-
(P-Methylsulfonylphenyl) -Nn-propylglycine, N- (p-methylsulfonylphenyl) -N
-N-butylglycine, N- (p-cyanophenyl)-
Glycine, N- (p-cyanomethylsulfonylphenyl) -N-methylglycine, N- (p-cyanomethylsulfonylphenyl) -N-ethylglycine, N- (p-
Cyanomethylsulfonylphenyl) -Nn-propylglycine, N- (p-cyanomethylsulfonylphenyl) -Nn-butylglycine, N- (p-ethylsulfonylphenyl) -N-methylglycine, N- (p -Ethylsulfonylphenyl) -N-ethylglycine, N-
(P-Ethylsulfonylphenyl) -Nn-propylglycine, N- (p-ethylsulfonylphenyl) -N
-N-butylglycine, N- (p-2'-cyanoethylsulfonylphenyl) -N-methylglycine, N- (p
-2'-cyanoethylsulfonylphenyl) -N-ethylglycine, N- (p-2'-cyanoethylsulfonylphenyl) -NN-propylglycine, N- (p-
2′-Cyanoethylsulfonylphenyl) -Nn-butylglycine, N- (p-cyanophenyl) -N-methylglycine, N- (p-cyanophenyl) -N-ethylglycine, N- (p-cyanophenyl) ) -Nn-propylglycine, N- (p-cyanophenyl) -Nn-
Butylglycine, N- (pn-propylsulfonylphenyl) -N-methylglycine, N- (pn-butylsulfonylphenyl) -N-methylglycine , and the like . You may use these in combination of 2 or more types. The N-aryl-α-amino acid represented by the formula (III) is represented by R
_At least one of ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ is a cyano group or an alkylsulfonyl group having 1 to 4 carbon atoms . The N-aryl-α-amino acid can be obtained by, for example, performing an aromatic nucleophilic substitution reaction of a corresponding substituted halobenzene and a glycine compound.

The proportions of the 3-substituted coumarin compound, the titanocene compound and the N-aryl-α-amino acid used are not particularly limited, but usually, the N-aryl-α-amino acid and the titanocene compound are used as a 3-substituted coumarin compound. Used as more parts by weight than compound.

As the addition-polymerizable compound contained in the photosensitive composition of the present invention, one having a boiling point of 100 ° C. or higher at normal pressure is used. If the boiling point is lower than 100 ° C. under normal pressure, the addition-polymerizable compound is volatilized and volatilized undesirably when the solvent contained in the system is removed by drying or irradiated with an actinic ray. Further, the addition-polymerizable compound is preferably soluble in a commonly used organic solvent in order to form a uniform composition with the photoinitiator and the like.

Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl. Ether, xylene, tetrahydrofuran, dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-
Pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethylene carbonate, propylene carbonate,
Sulfolane or the like is used.

As the addition-polymerizable compound having a boiling point of 100 ° C. or higher under normal pressure, polyhydric alcohol and α, β-
A compound obtained by condensation with an unsaturated carboxylic acid, for example, ethylene glycol di (meth) acrylate (meaning diacrylate or dimethacrylate, the same applies hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, di (1,2-
Propylene glycol) di (meth) acrylate, tri (1,2-propylene glycol) di (meth) acrylate, tetra (1,2-propylene glycol) di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, 1,4-
Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine , N
-Vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2
-Hydroxypropane, methylenebisacrylamide,
Examples thereof include N, N-dimethylacrylamide and N-methylolacrylamide, and these may be used in combination of two or more kinds. N- (p-cyanophenyl) -glycine, 7-N, N-diethylamino-3-thienylcarbonylcoumarin, bis (cyclopentadienyl) -bis [2,6-difluoro-3-pyrrol-1-yl) phenyl ] A combination of titanium, 3-dimethylaminopropyl methacrylate and polyamic acid is preferred.

From the viewpoint of photosensitivity and film strength, the photoinitiator is 0.01 to 30% by weight, preferably 0.05 to 10% by weight, based on the addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure. It is used at an addition amount of%.

The photosensitive composition of the present invention may optionally contain one or more high molecular weight organic polymers. The high molecular weight organic polymer has a molecular weight of 10,000 to 70.
Those having 10,000 are preferred. For example, the following is used.

(A) Copolyester polyhydric alcohol such as diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol and the like and polyvalent carboxylic acid such as terephthalic acid, isophthalic acid, sebacic acid, adipic acid and the like. Copolyester manufactured from

(B) Vinyl Polymer Methacrylic acid, acrylic acid, methacrylic acid or alkyl ester of acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Phenyl (meth) acrylate, benzyl (meth)
Homopolymers or copolymers of vinyl monomers such as acrylate, 2-dimethylaminoethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate

(C) Polyformaldehyde (D) Polyurethane (E) Polycarbonate (F) Polyamide (G) Polyamic acid

Polyamic acid can be obtained by addition polymerization using the following tetracarboxylic dianhydride and diamine compound. As the tetracarboxylic dianhydride,
For example, 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, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-di) Carboxyphenyl) 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. Examples of the diamine compound include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 3,3′-dimethylbenzidine, 3,3 ′. -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'
-)-Diaminodiphenyl sulfone, 4,4 '(or 3,4'-, 3,3'-, 2,4'-)-diaminodiphenyl sulfide, 4,4'-benzophenone diamine, 3,3'-benzophenone Diamine, 4,4'-di (4-aminophenoxy) phenyl sulfone, 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) phenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,
Aromatic diamines such as 2'-bis (4-aminophenyl) propane, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-S-triazine,
2,7-diaminodibenzofuran, 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 2,5
-Diamino-1,3,4-thiadiazole, 2,4-diamino-6-phenyl-s-triazine and other heterocyclic diamines, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine Examples thereof include aliphatic diamines such as diaminopolysiloxane shown below.

[Chemical 8] (N and m are integers of 1 to 10, and n and m may be the same)

The above tetracarboxylic dianhydride and diamine compound may be used alone or in combination of two or more kinds.

(H) Cellulose ester, for example, methyl cellulose, ethyl cellulose

By adding a high molecular weight organic polymer to the photosensitive composition, properties such as adhesion to a substrate, chemical resistance and film property can be improved. From the viewpoint of photocurability, this high molecular weight organic polymer has a content of 20 to 20 based on the total weight of the high molecular weight organic polymer and the addition-polymerizable compound.
It is preferably in the range of 80% by weight. Even when using a high molecular weight organic polymer, the amount of the photoinitiator used is 0.01 to 30% by weight, preferably 0.05 to 30% by weight based on the addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure. The range is 10% by weight.

The photosensitive composition according to the present invention may also contain coloring substances such as dyes and pigments, if necessary. Examples of coloring substances include fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria pure blue, malachite green, night green B,
Examples include spirone proof.

The photosensitive composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage. For such a thing p
-Methoxyphenol, p-benzoquinone, hydroquinone, pyrogallol, naphthylamine, phenothiazine, aryl phosphite, nitrosamine and the like.

The photosensitive composition according to the present invention may contain other additives known to be used in photosensitive resin compositions, for example, plasticizers, adhesion promoters and other additives.

The light-sensitive material of the present invention comprises a carbon-carbon double bond and an amino group which are dimerizable or polymerizable by actinic radiation in the above polyamic acid and the above-mentioned addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure. Alternatively, it contains a compound having a quaternized salt thereof and a photoinitiator. The use ratio of these is the same as in the case of the photosensitive composition. As the polyamic acid, it is preferable to use a compound having carbon, a carbon double bond, and an amino group or a quaternized salt thereof that are dimerizable or polymerizable by actinic radiation in an amount that is equimolar to the carboxyl group of the polyamic acid. .

The photosensitive material of the present invention is coated on a substrate, dried, exposed and developed to form a pattern. The light-sensitive material of the present invention is applied on a substrate such as a silicon wafer, a metal substrate, a glass substrate, a ceramic substrate by a dipping method, a spray method, a screen printing method, a spin coating method, etc., and most of the solvent is dried by heating. By doing so, a coating film having no tackiness can be obtained. This coating film is exposed to actinic rays or actinic rays through a mask on which a desired pattern is drawn.
Examples of the actinic ray or actinic ray to be applied include ultraviolet rays, far ultraviolet rays, visible light, electron rays, and X-rays. After irradiation, the non-irradiated portion is dissolved and removed with an appropriate developing solution to obtain a desired pattern. As a developing solution, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-
A good solvent such as 2-pyrrolidone or a mixed solvent thereof with a lower solvent such as lower alcohol, water or aromatic hydrocarbon is used. After development, if necessary, rinse with a poor solvent or the like and dry at about 100 ° C. to stabilize the pattern.

The light-sensitive material may contain a bisazide compound, and examples of the bisazide compound include

[Chemical 9]

[Chemical 10] Etc. The bisazide compound is preferably used in the range of 0.01 to 10% by weight with respect to the polyamide.

Examples of compounds having 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.

[Chemical 11]

[0031]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 3 , Comparative Examples 1 to 3, Reference Examples 1 to 3 Synthesis of N- (4-cyanophenyl) -glycine 4-cyanoaniline (100 g, 847.4 mmol) was added to 5
Place in a 3-neck flask of 00 ml, add 300 ml of water further, set a water cooling tube, a mechanical stirrer and a dropping funnel, heat at an oil temperature of 100 ° C., and while stirring well, an aqueous solution of monochloroacetic acid (104 g, 1116 mmol). (150 ml of water) was added dropwise over about 30 minutes, and 2.
The mixture was heated under reflux for 5 hours. After cooling, about 100 ml of ethyl acetate
In addition, the insoluble matter was dissolved and the organic layer was separated with a separating funnel. The remaining water layer and this organic layer weigh 100 ml 5
The aqueous layers extracted with aqueous NaOH solution are combined to give 1/10 N H.
Cl was acid-deposited, the resulting precipitate was separated by filtration, and further washed with water several times for washing. After heating and drying in an oven at 60 ° C. for 3 hours, it was dried overnight in a vacuum desiccator. The resulting pale beige powder showed no melting point and decomposed at 233.1 ° C. The yield was 38.8 g (26%).

Synthesis of N- (4-cyanophenyl) -N-methylglycine 4-fluorobenzonitrile (10.44 g, 86.2)
6 mmol), N-methylglycine (8.45 g, 94.8)
9 mmol) and potassium carbonate (14.28 g, 103.
48 mmol) to a 500 ml eggplant-shaped flask, and further 2
Add 00 ml of dimethylsulfoxide as a solvent, attach a water cooling tube and stir with a magnetic stirrer 1
Heat in an oil bath at 00 ° C. for 9 hours. After allowing to cool, it was dissolved in 1 liter of water, acidified with 1 / 10N HCl, and the precipitate was filtered off. After thoroughly washing with water, it was further washed with hexane / benzene (volume ratio 4/1). The yield of the dried product was 14.21 g (74.79 mmol, 86.7%), and the melting point was 64.5 ° C.

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) and the photoinitiator shown in Table 2 were mixed and stirred to prepare a light-sensitive material. After filtering with a filter, it was spin-coated on a silicon wafer. Then, it was heated on a hot plate at 100 ° C. for 200 seconds to dry the solvent to obtain a photosensitive coating film. The film thickness after drying was 20 microns. Pattern exposure was performed on the coating film through a photomask with a mirror projection exposure machine using an ultra-high pressure mercury lamp as a light source. The exposure amount at this time was 500 mJ / cm ² . After that, immersion development was performed with a mixed solution of N-methyl-2-pyrrolidone and methyl alcohol (volume ratio: 4/1). Further rinsed with isopropanol. The pattern shape after development was measured and observed, and the obtained residual film rate (value obtained by dividing the film thickness by the initial film thickness) and the minimum opening through hole diameter (opening diameter) are shown in Table 1. For the wafer of Example 1 , this was placed in a nitrogen atmosphere at 100 ° C. for 15 minutes at 200 ° C.
And heated at 350 ° C. for 60 minutes to obtain a final cured film.
A good polyimide pattern with a final cured film thickness of 10 microns was obtained. As shown in the examples, the photosensitive composition of the present invention has excellent photosensitivity as compared with the composition of the comparative example.

[Table 1] Examples 4 to 6 and Comparative Examples 4 to 6 and Reference Examples 4 to 6 Photosensitive materials obtained by adding a bisazide compound to the same composition as in Examples 1 to 3 and Comparative Examples 1 to 3 and Reference Examples 1 to 3. The results of the same test are shown in Table 2 together with the composition. As shown in the examples, the residual film ratio after development was improved by further adding the bisazide compound.

[Table 2]

[0034]

INDUSTRIAL APPLICABILITY The photoinitiator according to the present invention makes it possible to obtain a photosensitive composition and a photosensitive material exhibiting excellent photosensitivity, and a good pattern can be produced from this photosensitive material.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI G03F 7/027 514 G03F 7/027 514 7/038 504 7/038 504 H01L 21/027 H01L 21/312 B 21/312 21 / 30 502R 561 (56) Reference JP-A-3-223759 (JP, A) JP-A-5-158237 (JP, A) JP-A-5-19475 (JP, A) JP-A-6-67425 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42 H01L 21/027

Claims (5)

(57) [Claims] 1. A 3-substituted coumarin compound represented by the following formula (I): (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms,
Amino group substituted with one alkyl group having 1 to 5 carbon atoms, Amino group substituted with two alkyl groups having 1 to 5 carbon atoms, Alkoxy group having 1 to 5 carbon atoms, Acyloxy group, Aryl group A halogen atom or a thioalkyl group having 1 to 5 carbon atoms, and R ₆ is a phenyl group, a biphenyl group, a naphthyl group, a thienyl group, a benzofuryl group, a furyl group, a pyridine group, a coumarinyl group, an amino group, or a carbon number of 1 to 5 An amino group substituted with an alkyl group, a cyano group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a haloalkyl group, a formyl group, an alkoxycarbonyl group having 1 to 5 carbon atoms, or Carbon number 1
To 5 acyloxy groups, the phenyl group, biphenyl group, naphthyl group, thienyl group, benzofuryl group, furyl group, pyridine group and coumarinyl group having 1 to 5 carbon atoms.
Which may be substituted with an acyl group), and a titanocene compound represented by the following formula (II): (In the formula, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R _13
14 , R ₁₅ and R ₁₆ are a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocycle) and an N-aryl-α-amino acid represented by the following formula (III): (In the formula, R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or an alkylsulfone group having 1 to 4 carbon atoms, At least one of them is a cyano group or has 1 carbon atom
To R 4 are alkylsulfone groups , R ₂₂ is a hydrogen atom,
An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group or aryl group having 1 to 12 carbon atoms, and R ₂₃ And R ₂₄
Is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄
May be the same). 2. A photosensitive composition comprising an addition-polymerizable compound having a boiling point of 100 ° C. or higher at atmospheric pressure and the photoinitiator according to claim 1. 3. A photosensitive material containing a polyamic acid, a compound having a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof, and the photoinitiator according to claim 1. . 4. The photosensitive material according to claim 3 , further containing a bisazide compound. 5. A method for producing a pattern, which comprises applying the photosensitive material according to claim 3 or 4 onto a substrate, drying, exposing and developing.