JPH11282155A - Photosensitive resin composition and production of solder resist using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. excellent in heat resistance, adhesion property and moisture resistance (PCT resistance) and to provide a producing method of a substrate having a solder resist excellent in workability and photosensitive characteristics. SOLUTION: This photosensitive resin compsn. contains (A) a polyimide or its precursor obtd. by the reaction of a tetracarboxylic acid dianhydride or its deriv. and a diamine compd., (B) a photopolymerizable unsatd. compd. having at least one ethylene-type unsatd. group at the molecular end, (C) a compd. having a dihydrobenzoxazine ring, and (D) a photopolymn. initiator which produces free radicals by irradiation of actinic rays. A soln. of the photosensitive resin compsn. above described is applied on a substrate, dried, exposed according to an image and developed by using an alkali aq. soln. as a developer containing 0.1 to 50 wt.% surfactant or org. solvent and 0.01 to 30 wt.% inorg. alkali compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition and a method for producing a substrate having a solder resist using the same.

[0002]

2. Description of the Related Art In recent years, in response to the miniaturization, weight reduction, multi-functionality, high reliability, and low price of electronic devices, printed wiring boards do not use component holes but use components and substrates on the surface of conductive patterns. A component mounting method for making an electrical connection with the device (this method is called a surface mounting method) is rapidly expanding. Conventionally, in the manufacture of printed wiring boards, photosensitive solder resist has been used for the purpose of limiting soldering positions and protecting wiring, but photosensitive solder resist used for printed wiring boards using a surface mounting method has been used. Is more heat resistant than before,
Where moisture resistance and adhesiveness are required, conventional solder resists mainly composed of epoxy resin have insufficient heat resistance, moisture resistance and adhesiveness, resulting in pressure
When the cooker test (hereinafter abbreviated as PCT) is performed, there is a problem that the resist is blistered or peeled off.

On the other hand, in the field of semiconductors, photosensitive polyimide resins having excellent heat resistance, moisture resistance and adhesion are used for protecting wiring. However, photosensitive polyimide is used in the form of a polyamic acid as a polyimide precursor at the time of image formation, and since a high-boiling nitrogen-containing polar solvent is used as a solvent, a cured film having the above excellent characteristics is obtained. Requires high temperature drying and curing, usually at 300 ° C. or higher. Therefore, there is a problem that it cannot be used for a printed wiring board from the viewpoint of heat resistance of a substrate or the like.

Accordingly, a photosensitive resin composition which can be cured at a low temperature by using a special monomer or a non-nitrogen-containing polar solvent as a polyimide precursor has been developed. However, this photosensitive resin composition is excellent in low-temperature curability, heat resistance, adhesion and the like, but is still insufficient in moisture resistance.

[0005]

SUMMARY OF THE INVENTION The first aspect of the present invention provides a photosensitive resin composition having excellent heat resistance, adhesion and moisture resistance (PCT resistance). The invention of claim 2 provides a photosensitive resin composition having more excellent moisture resistance (PCT resistance) in addition to the invention of claim 1. The third aspect of the present invention provides a photosensitive resin composition having excellent low-temperature curability, heat resistance, adhesion, and moisture resistance (PCT resistance). A fourth aspect of the present invention provides a photosensitive resin composition having excellent low-temperature curability in addition to the third aspect of the present invention. Claim 5
The invention described above provides, in addition to the invention described in claim 4, a photosensitive resin composition having more excellent moisture resistance (PCT resistance). The invention described in claim 6 provides a method for manufacturing a substrate having a solder resist excellent in workability and photosensitive characteristics. The invention according to claim 7 provides, in addition to the invention according to claim 6, a method for manufacturing a substrate having a solder resist excellent in various properties required for the solder resist, such as heat resistance, adhesion, moisture resistance, and electrical characteristics. Is what you do.

[0006]

The present invention provides (A) a polyimide or a precursor thereof obtained by reacting a tetracarboxylic dianhydride or a derivative thereof with a diamine compound;
(B) a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal, (C) a dihydrobenzoxazine ring-containing compound, and (D) a photopolymerization initiator that generates free radicals upon irradiation with active light. The present invention relates to a photosensitive resin composition contained therein.

The present invention also provides a polyimide precursor (A) or a derivative thereof in an amount of 20 to 95 parts by weight based on 100 parts by weight of the total of the components (A) and (B), The polymerizable unsaturated compound is 5-80 parts by weight based on 100 parts by weight of the total of the components (A) and (B), and the dihydrobenzoxazine ring-containing compound of the component (C) is the components (A) and (B). 0.05 to 100 parts by weight of the total amount of
40 parts by weight, the photopolymerization initiator of the component (D) is used in an amount of 0.01 to 2 with respect to 100 parts by weight of the total amount of the components (A) and (B).
The present invention relates to the photosensitive resin composition containing 0 parts by weight.

[0008] The present invention also relates to a photosensitive resin composition in which the component (A) further contains a non-nitrogen-containing solvent in these photosensitive resin compositions. The present invention relates to a photosensitive resin composition which is a lactone, an alicyclic ketone or an ether. The present invention also relates to a photosensitive resin composition obtained by reacting a compound having a corresponding phenolic hydroxyl group, formaldehyde and a primary amine in these photosensitive resin compositions with a dihydrobenzoxazine ring-containing compound.

Further, the present invention provides a method for applying a solution of any of these photosensitive resin compositions on a substrate and drying the solution.
Imagewise exposure, then add surfactant or organic solvent to 0.1
To 50% by weight and an inorganic alkaline compound in an amount of 0.01 to 3%.
Using an alkaline aqueous solution containing 0% by weight as a developer,
The present invention relates to a method for producing a substrate having a solder resist, which is characterized by performing development. The present invention also relates to a method for manufacturing a substrate having a solder resist, which includes a step of irradiating active light after development and a step of post-heating in this manufacturing method.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive resin composition of the present invention will be described in detail. In the photosensitive resin composition of the present invention, the polyimide as the component (A) or the tetracarboxylic dianhydride as a raw material of the precursor thereof may be, for example, a compound represented by the general formula (I)

Embedded image (Wherein R ¹ has 2 to 240 carbon atoms, preferably 4 carbon atoms)
To 60, particularly preferably a 4 to 30 tetravalent organic group, more specifically a residue of a tetracarboxylic dianhydride, preferably a group containing an aromatic group such as a benzene ring). The derivatives thereof include monoalkyl esters and dialkyl esters having an alkyl group having 1 to 4 carbon atoms.

The diamine compound used as a raw material for the polyimide (A) or its precursor is, for example, a compound represented by the following general formula (II):

Embedded image (Wherein R ² has ² to 240 carbon atoms, preferably 2
To 60, particularly preferably 2 to 30 divalent organic groups, more specifically, a residue of a diamine compound, preferably a group containing an aromatic group such as a benzene ring).

The tetracarboxylic dianhydride includes:
There is no particular limitation, for example, pyromellitic acid, 3,3 ′,
4,4'-benzophenonetetracarboxylic acid, 3,
3 ', 4,4'-biphenyltetracarboxylic acid, 2,
3 ', 3,4'-biphenyltetracarboxylic acid, 2,
3 ', 4,4'-biphenyltetracarboxylic acid, 3,
3 ', 4,4'-diphenylethertetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid,
2,3,6,7-naphthalenetetracarboxylic acid, 1,
4,5,8-naphthalenetetracarboxylic acid, 2,3
5,6, -pyridinetetracarboxylic acid, 3,4,9,1
0-perylenetetracarboxylic acid, 3,3 ', 4,4'-
Diphenylsulfonetetracarboxylic acid, m-terphenyl-3,3 ', 4,4'-tetracarboxylic acid, p-terphenyl-3,3', 4,4'-tetracarboxylic acid,
1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4 -Dicarboxyphenyl) propane, 2,2-bis [4 '-(2,3
-Or 3,4-dicarboxyphenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-
2,2-bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 2,3,6,7
-Anthracenetetracarboxylic acid, 1,2,7,8-phenanthrenetetracarboxylic acid, 4,4'-bis (2,
Dianhydride of aromatic tetracarboxylic acid such as 3-dicarboxyphenoxy) diphenylmethane; the following general formula (III)

Embedded image (Wherein, R ³ and R ⁴ represent a monovalent hydrocarbon group, and may be the same or different, and k is an integer of 1 or more). Examples thereof include dianhydrides of aliphatic tetracuronic acids such as butenetetracarboxylic acid and butanetetracarboxylic acid, and these are used alone or in combination of two or more.

The diamine compound is not particularly restricted but includes, for example, 2,2-bis- [4- (4-aminophenoxy) phenyl] propane and 2,2-bis- [3-
(4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis- [4
-(3-Aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy)] biphenyl, bis [1- (4-aminophenoxy)] Biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl]
Methane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy)] benzophenone, bis [4- (3- Aminophenoxy)] benzophenone, bis [4- (4-aminophenoxy)] benzanilide, bis [4- (3-aminophenoxy)] benzanilide, 9,9-bis [4- (4
-Aminophenoxy) phenyl] fluorene, 9,9-
Bis [4- (3-aminophenoxy) phenyl] fluorene, 4,4 '-(or 3,4'-, 3,3'-, 2,
4 '-, 2,2'-) diaminodiphenyl ether,
4,4'- (or 3,4'-, -3,3'-, 2,4 '
-, 2,2 '-) diaminodiphenylmethane, 4,4'
-(Or 3,4'-, 3,3'-, 2,4'-, 2,
2'-) diaminodiphenyl sulfone, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-)
Diaminodiphenyl sulfide, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone, 4,4'-methylene-bis- (2,6-
Diethylaniline), 4,4'-methylene-bis-
(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4 ′
-Benzophenone diamine, 1,1,1,3,3,3-
Hexafluoro-2,2-bis (4-aminophenyl)
Propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-
4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, benzidine, 2,6
-Diaminopyridine, 3,3'-dimethoxybenzidine, 1,4-bis (4-aminophenoxy) benzene,
1,3-bis (4-aminophenoxy) benzene, 4,
4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 3,5
Aromatic diamines such as diaminobenzoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,2-diaminocyclohexane, and a compound represented by the following general formula (I
V)

Embedded image (Wherein, R ⁵ and R ⁶ each represent a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different,
R ⁷ and R ⁸ each represent a monovalent hydrocarbon group, and may be the same or different, and m is an integer of 1 or more), 1,3-bis (aminomethyl) cyclohexane , Sun Techno Chemical Co., Ltd.
Jeffamine D-230, D-400, D-2
000, D-4000, ED-600, ED-900,
Examples thereof include aliphatic diamines such as polyoxyalkylenediamines such as ED-2001 and EDR-148. These are used alone or in combination of two or more.

The polyimide precursor according to the present invention is obtained by reacting the tetracarboxylic dianhydride with the diamine compound in an organic solvent. Is preferably in the range of 1.1 / 1.0 to 1.0 / 1.1 (molar ratio). If it exceeds this range, the molecular weight of the polyimide precursor does not grow, so that heat resistance and the like tend to decrease.

The solvent used in the reaction for producing the polyimide precursor of the present invention is preferably a non-nitrogen-containing polar solvent, and specific examples thereof include γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-caprolactone. Lactones such as heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl, Ethers such as dibutyl) ether and tetraethylene glycol (or diethyl, dipropyl, dibutyl) ether;
Carbonates such as ethylene carbonate and propylene carbonate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol dimethyl (or monomethyl) ether, triethylene glycol dimethyl (or monomethyl) Alcohols such as ether and tetraethylene glycol dimethyl (or monomethyl) ether; phenols such as phenol, cresol and xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate; toluene, xylene, diethylbenzene and cyclohexane Hydrocarbons such as trichloroethane, tetrachloroethane, mono It can be used halogenated hydrocarbons such as chlorobenzene and the like, can impart low-temperature curability a highly volatile γ- butyrolactone being most preferred.

The amount of the non-nitrogen-containing polar solvent used is preferably 1 to 10 times (weight ratio) the polyimide precursor to be produced. If it is less than 1 time, the viscosity at the time of synthesis tends to be too high and the synthesis tends to be difficult due to inability to stir. If it exceeds 10 times, the reaction rate tends to decrease.

The reaction between the tetracarboxylic dianhydride and the diamine compound is preferably carried out at 80 ° C. or lower.
It is particularly preferred to carry out at 0 ° C. This produces polyamic acid. The polyamic acid may be partially imidized, and these are collectively referred to as a polyimide resin precursor. Therefore, the reaction temperature may be raised to 250 ° C. The polyimide precursor is preferably soluble in the solvent of the composition for a liquid crystal alignment film. This precursor, when forming a layer of the liquid crystal alignment film-forming resin on the substrate, namely,
It is preferable that when the composition for a liquid crystal alignment film is applied and heated and dried, it is completely imidized to be a polyimide resin. The polyimide resin precursor can be imidized in advance if it is soluble in the solvent of the composition for a liquid crystal alignment film. For imidation, the above reaction is carried out at 120-
There are thermal imidization performed at 250 ° C. and chemical imidization performed in the presence of a dehydrating agent. As the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide and the like are preferable, and 1 to 1 mol of tetracarboxylic dianhydride is preferable.
It is preferable to use up to 8 mol. At this time, pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like can be used as a dehydration catalyst as required. The dehydration catalyst is preferably used in an amount of 1 to 8 mol per 1 mol of tetracarboxylic dianhydride.

The photopolymerizable unsaturated compound having at least one ethylenically unsaturated group as the component (B) is not particularly limited, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, Butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, pentenyl methacrylate, benzyl acrylate, benzyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, polyethylene glycol (meth) acrylate (ethylene Groups having a sum of 2 to 14), polypropylene glycol di (meth) acrylate (having a sum of 2 to 14 propylene groups), trimethylolpropane diacrylate, Limethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropaneethoxytriacrylate, trimethylolpropaneethoxytrimethacrylate, trimethylolpropanepropoxytriacrylate, trimethylolpropanepropoxytrimethacrylate, tetramethylolmethanetetra Acrylate, tetramethylolmethanetetramethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, Styrene, divinylbenzene, 4-
Vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylene Bisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, triacrylate of tris (β-hydroxyethyl) isocyanurate, the following general formula (V)

Embedded image (Wherein R ⁹ represents hydrogen or a methyl group, and q and r represent 1
Or a compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound, for example, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl. Esterified products of polyhydric carboxylic acids such as ether di (meth) acrylate, for example, phthalic anhydride and the like, and a compound having a hydroxyl group and an ethylenically unsaturated group, for example, β-hydroxyethyl (meth) acrylate, and tolylene diisocyanate Of urethane (meth) acrylate, diamine and isocyanate, such as a reaction product of trimethylhexane diisocyanate, cyclohexane dimethanol and 2-hydroxyethyl (meth) acrylate, and a reaction product of trimethylhexane diisocyanate, cyclohexane dimethanol and 2-hydroxyethyl (meth) acrylate. And the reaction product of a monoisocyanate compound having an ethylenically unsaturated double bond, a urea bond-containing compounds, and the like. These can be used alone or 2
More than one type can be used in combination.

The amounts of the polyimide precursor and the photopolymerizable unsaturated compound having at least one ethylenically unsaturated group are determined based on the amount of the polyimide precursor (A) and the amount of the ethylenically unsaturated group (B). Assuming that the total amount of the photopolymerizable unsaturated compound having at least one is 100 parts by weight, 95 to 20 parts by weight of the polyimide precursor and 5 to 80 parts by weight of the photopolymerizable unsaturated compound having at least one ethylenically unsaturated group are preferable. . If the amount of the polyimide precursor is too large, the photosensitivity tends to be inferior, and if the amount of the polyimide precursor is too small, the heat resistance and mechanical properties of the cured film tend to be inferior.

The dihydrobenzoxazine ring-containing compound as the component (C) of the present invention is synthesized by adding a mixture of a compound having a phenolic hydroxyl group and a primary amine to formaldehyde heated to 70 ° C. or higher. ~ 110
C., preferably at 90 to 100.degree. C. for 20 to 120 minutes, followed by drying under reduced pressure at a temperature of 120.degree. C. or less. It is preferable that all the phenolic hydroxyl groups of the compound having a phenolic hydroxyl group react with the primary amine and formaldehyde to form a dihydrobenzoxazine ring.

The compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include bisphenol compounds such as bisphenol A, bisphenol F, bisphenol E, and biphenol, trisphenol compounds, tetraphenol compounds, and phenol resins. Examples of the phenolic resin include a phenolic compound such as phenol or xylenol, t-butylphenol, a monohydric phenol compound such as alkylphenol such as octylphenol, resorcinol, and a novolak resin obtained by reacting a phenol compound such as a polyhydric phenol compound such as bisphenol A with formaldehyde. Resole resin,
There are phenol-modified xylene resin, melamine phenol resin, polybutadiene-modified phenol resin and the like. The primary amine is not particularly limited, and examples thereof include methylamine, cyclohexylamine, aniline, and substituted aniline. Formaldehyde may be used in the form of formalin or polyparaformaldehyde.

The amount of the dihydrobenzoxazine ring-containing compound used depends on the solid content of the polyimide precursor as the component (A) and the amount of the photopolymerizable unsaturated compound having at least one ethylenically unsaturated group as the component (B). The total amount is 0.1 to 40 parts by weight based on 100 parts by weight. This usage amount is 0.
If it is less than 1 part by weight, the moisture resistance tends to be inferior, and if it exceeds 40 parts by weight, the storage stability of the photosensitive resin composition tends to be inferior. In addition, the photosensitive resin composition of the present invention may contain a photopolymerization initiator, if necessary.

As the photopolymerization initiator as the component (D),
There is no particular limitation, for example, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-diethylthioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2
Morpholino-1-propanone, benzyldiphenyl disulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate,
2,6-bis (p-diethylaminobenzal) -4-methyl-4-azacyclohexanone, N-ethyl-N-
(P-chlorophenyl) glycine, 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, 3,3
-Carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6-difluoro-3- (pyr-1-yl) phenyl] titanium,
3,3'-dimethoxy-4,4'-diazadobiphenyl, 3,5-bis (4-diethylaminobenzylidene)
-1-methyl-4-azacyclohexanone, 4-methyl-7-diethylaminocoumarin, 4,6-dimethyl-7
-Ethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, benzyldimethylketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethyl 4-diethylaminobenzoate , 1,3-diphenylpropanetrione-2
-(O-ethoxycarbonyl) oxime, N- (4-cyanophenyl) glycine, 1,7-bis (9-acridinyl) heptane and the like. These can be used alone or in combination of two or more.

The use amount of the photopolymerization initiator is preferably 0.01 to 30% by weight, more preferably 0.05 to 10% by weight, based on the resin content of the polyimide precursor. If the amount is less than 0.01% by weight, the light sensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention can contain an azide compound, if necessary.

As the azide compound, for example,

Embedded image

Embedded image And the like. These can be used alone or in combination of two or more.

The amount of the azide compound used is preferably 0.01 to 30% by weight based on the resin content of the polyimide precursor. If this amount is less than 0.01% by weight,
Photosensitivity tends to be inferior, and when it exceeds 30% by weight, mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage. As the radical polymerization inhibitor or the radical polymerization inhibitor, for example,
Hydroquinone, hydroquinone monomethyl ether, benzoquinone, diphenyl-p-benzoquinone, pyrogallol, phenothiazine, catechol, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-
1-naphthylamine, N-phenyl-2-naphthylamine, cuperon, phenothiazine, 2,5-toluquinone,
Examples include tannic acid, parabenzylaminophenol, nitrosamines and the like. These can be used alone or in combination of two or more. The amount of the radical polymerization inhibitor or the radical polymerization inhibitor used is preferably 0.01 to 30% by weight based on the resin content of the polyimide precursor. If the amount is less than 0.01% by weight, the storage stability tends to be inferior, and if it exceeds 30% by weight, the photosensitivity and the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention may contain a blocked polyisocyanate compound or a bismaleimide compound in order to improve the curability.

Examples of the blocked polyisocyanate compound include tolylene diisocyanate, diphenyl methane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenyl sulfone diisocyanate, triphenyl methane diisocyanate, hexamethylene diisocyanate, and 3-isocyanatomethyl-isocyanate.
3,5,5-trimethylcyclohexyl isocyanate, 3-isocyanatoethyl-3,5,5-trimethylcyclohexyl isocyanate, 3-isocyanatoethyl-3,5,5-triethylcyclohexyl isocyanate, diphenylpropane diisocyanate, phenylene diisocyanate, cyclohexyl Polyisocyanates such as silylene diisocyanate, 3,3'-diisocyanate dipropyl ether, triphenylmethane triisocyanate, diphenyl ether-4,4'-diisocyanate, and phenols such as phenol and xylenol, oximes, imides, and mercaptans , Alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite,
Those blocked with boric acid or the like can be mentioned. These are used alone or in combination of two or more. As commercially available products, for example, Desmodur BL3175, AP Stable, AP-
12 stable, CT stable, BL1100, BL
1190, BL1265, AP-2170 stable,
BL4165, TPLS-2759, Desmo Cup 1
1, 12, Cleran UT, UI, U12, TPKL5
-2668, TPLS-2727, Desmosam 21
70, 2265, WD 2502 manufactured by Hitachi Chemical Co., Ltd.
Etc. can be used. These can be used alone or in combination of two or more.

As a method of adding the blocked polyisocyanate compound, the block polyisocyanate compound to be added can be dissolved in the same solvent as the solvent contained in the photosensitive resin composition in advance and then added. It can also be added to objects. The blocked polyisocyanate compound has a total amount of component (A) and component (B) of 1
The amount is preferably from 0.1 to 50 parts by weight, particularly preferably from 0.5 to 40 parts by weight, based on 00 parts by weight. If the amount of the blocked polyisocyanate compound is too small, the curability will be insufficiently improved, and if it is too large, the viscosity stability of the composition tends to be poor.

As the bismaleimide compound, for example,
4,4'- (or 3,4'-, -3,3'-, 2,4 '
-, 2,2'-) diaminodiphenyl ether), 4,
4 '-(or 3,4'-, -3,3'-, 2,4'-,
2,2 '-) diaminodiphenylmethane, 4,4'-
(Or 3,4'-, -3,3'-, 2,4'-, 2,
2 '-) diaminodiphenyl sulfone, 4,4'- (or 3,4'-, -3,3'-, 2,4'-, 2,2'
-) Diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidinesulfone, 4,4'-methylene-bis- (2,6
-Diethylaniline), 4,4'-methylene-bis-
(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4 ′
-Benzophenonediamine, bis [4- (4'-aminophenoxy) phenyl] sulfone, 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, bis [4- (3'-aminophenoxy) phenyl] sulfone, 2,2-bis (4-aminophenyl)
Bismaleimidated aromatic diamines such as propane and 3,5-diaminobenzoic acid can be used. These can be used alone or in combination of two or more.

The bismaleimide compound can be added by dissolving the bismaleimide compound in the same solvent as the solvent contained in the photosensitive resin composition in advance and then adding the bismaleimide compound directly to the photosensitive resin composition. It can also be added. The bismaleimide compound is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
It is preferably 0 parts by weight, particularly preferably 0.5 to 40 parts by weight. If the amount of the bismaleimide compound is too small, the curability is likely to be insufficiently improved. If the amount is too large, the viscosity stability of the composition tends to be poor.

When a bismaleimide compound is added, an organic peroxide can be added as a polymerization initiator in order to improve the curability. As organic peroxides,
For example, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylicyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-3,3,5-trimethylhexanoate,
t-butyl peroxyisopropyl carbonate, 2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-
(Butylperoxy) hexane, t-butylperoxy (2-ethylhexanoate), di-t-butylhydroperoxide, t-butylperoctoate, benzoyl peroxide, and the like can be used. These can be used alone or in combination of two or more. The organic oxide is a bismaleimide compound 100
It is preferably 0.001 to 10 parts by weight based on parts by weight. If the amount of the organic oxide is too small, the curability is likely to be insufficiently improved. If the amount is too large, the viscosity stability of the composition tends to be poor.

The photosensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer, a metal substrate, a ceramic substrate, or a copper-clad laminate by a coating method, a dipping method, a spray method, a screen printing method, or a spin coating method. By heating and drying most of the solvent, a coating film having no tackiness can be obtained. After irradiating the coating film with actinic rays or actinic rays through a mask on which a desired pattern is drawn, the unirradiated portion is dissolved and removed with an appropriate developer to produce a solder resist.

As the actinic ray or actinic ray for irradiating the photosensitive resin composition of the present invention, for example, a contact / proximity exposure machine using a super-high pressure mercury lamp, a mirror projection exposure machine, an i-line stepper, a g-line stepper And other ultraviolet rays, visible rays, X-rays, and electron beams.

The surfactant or the organic solvent used in the developer may be a well-mixed one with water to form a uniform developer, or a surfactant which is hardly mixed with water and becomes a non-uniform developer. . Examples of such a surfactant or organic solvent include butyl carbitol, N, N-dimethylacetamide, N, N-dimethylformamide, methyl cellosolve, ethyl cellosolve, 3-methyl-3-methoxybutyl acetate, heptanoic acid Diethanolamide, polyoxyethylene-p-cumylphenyl ether and the like can be used.
Cumyl phenyl ether is preferred. The surfactant or the organic solvent is preferably contained in the developer in an amount of 0.1 to 50% by weight.

As the alkali component used in the developer, sodium carbonate, sodium hydroxide, sodium tetraborate and the like can be used in the range of 0.01 to 30% by weight.

The temperature of the developing solution used for development is
It is controlled by the developability of the photosensitive layer. Further, other surfactants, antifoaming agents and the like may be mixed in the developer.

After development, it is preferable to rinse with water or a poor solvent, if necessary, and to dry the pattern at a temperature of room temperature or higher and about 100 ° C. or lower to stabilize the pattern.
Further, after the development, ultraviolet irradiation by a high-pressure mercury lamp or heating may be performed for the purpose of improving wet heat resistance, solder heat resistance, chemical resistance, and the like. It is preferable that the amount of ultraviolet irradiation at the time of ultraviolet irradiation is 0.2 to 10 J / cm ^2, and the temperature at the time of irradiation is 60 to 150 ° C. The heating temperature is preferably from 150 to 250 ° C., and the heating time is preferably from 15 to 120 minutes. Either of the ultraviolet irradiation and the heating may be performed first, but it is more preferable that the ultraviolet irradiation is performed first and the heating is performed thereafter.

By heating this relief pattern, a patterned high heat-resistant polyimide can be formed. The heating temperature at this time is 80 to 45
The temperature is preferably set to 0 ° C, more preferably from 80 ° C to 250 ° C. When the heating temperature is less than 80 ° C. and 4
If it exceeds 50 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease. The heating time at this time is
It is preferable to set it to 0.05 to 10 hours. If the heating time is less than 0.05 hours or more than 10 hours, the mechanical properties and thermal properties of the polyimide film tend to decrease.
Thus, the photosensitive resin composition of the present invention can be used for various protective films, insulating films, and the like.

[0042]

Since the photosensitive resin composition of the present invention contains a compound containing a dihydrobenzoxazine ring, the photocured product thereof also contains a compound containing a dihydrobenzoxazine ring. When the compound is heated, the dihydrobenzoxazine ring is cleaved, and a hydroxyl group and an amino group are formed to become a hindered phenol compound, which functions as an antioxidant. Thereby, when the above-mentioned photocured material comes into contact with metallic copper (for example, copper in a wiring portion of a circuit board, etc.), oxidation of copper ions dissolved by heating or the like is prevented, and an interface between the photocured product and copper is prevented. The generation of copper oxide is suppressed, and the adhesion is maintained.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. Synthesis Example 1 (Synthesis of Polyimide Precursor Solution) 100 equipped with a stirrer, thermometer, nitrogen inlet tube and cooling water
In a ml flask, 2,2'-bis (4
-(4-Aminophenoxy) phenyl) propane 8.2
11 g (0.02 mol) and γ-butyrolactone
After charging 739 g, 6.702 g (0.0208 mol) of 4,4'-benzophenonetetracarboxylic dianhydride was added little by little. After the addition, the reaction was continued at 45 ° C. for about 5 hours, and then cooled to room temperature to obtain a polyimide precursor solution (PI-1) having a nonvolatile content of 25% by weight. The weight average molecular weight of the obtained polyimide precursor solution was 84,000. The weight average molecular weight was determined by gel permeation chromatography (GPC, apparatus manufactured by Hitachi, Ltd.) in terms of standard polystyrene. The dried polyimide precursor was subjected to an infrared absorption spectrum (manufactured by JEOL Ltd., JIR-1) by the KBr method.
00-inch) was measured, both, the C = O absorption of the amide group near 1600 cm ^-1, around 3300 cm ^-1 N-
H absorption was confirmed.

Synthesis Example 2 (Synthesis of Photopolymerizable Unsaturated Compound) 210 g (1.00 mol) of trimethylhexamethylene diisocyanate was placed in a 1-liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel and cooling tube. And 137.3 g of toluene, and then heated to 70 ° C.
Cyclohexane dimethanol 72
g (0.50 mol) and 130 g (1.00 mol) of 2-hydroxyethyl methacrylate were added dropwise little by little.
After the dropwise addition, the reaction was continued at 70 ° C. for about 5 hours, and then cooled to room temperature to obtain a photopolymerizable unsaturated compound (M-1).

Synthesis Example 3 (Synthesis of Compound Containing Dihydrobenzoxazine Ring) <Synthesis of Phenol Novolak Resin> Phenol 190
g, formalin (37% aqueous solution) 100 g and oxalic acid 0.4 g were charged into a 5-liter flask and reacted at a reflux temperature for about 6 hours. 6.66 × 10 ³ P inside
After reducing the pressure to below a, unreacted phenol and condensed water were removed. The obtained resin has a softening point of 84 ° C (ring and ball method),
The ratio was 3 to polynuclear / binuclear: 82/18 (peak area ratio by GPC).

<Introduction of Dihydrobenzoxazine Ring> 170 g of phenol novolak resin synthesized as described above
(Corresponding to 1.6 moles of hydroxyl groups) to 140 g of aniline (1.6
Mol.) And stirred at 80 ° C for 5 hours to prepare a uniform mixed solution. Separately, 259 g of formalin was charged into a 500 ml flask, heated to 90 ° C., and the mixed solution of phenol novolak and aniline prepared above was added little by little over 30 minutes. After completion of addition, 3
5. Keep at reflux temperature for 0 minutes, then at 100 ° C. for 2 hours
The condensation water was removed by reducing the pressure to 66 × 10 ³ Pa or less, and a compound (R-1) in which a dihydrobenzoxazine ring was introduced into all of the reactive hydroxyl groups was synthesized. Excess aniline and formalin are removed during drying and the end of the compound is 3
34 g. This indicates that 1.4 moles of the hydroxyl groups of the phenol novolak resin reacted and were cyclized with dihydrobenzoxazine.

Synthesis Example 4 (Synthesis of Dihydrobenzoxazine Ring-Containing Compound) Bisphenol F20 was placed in a 1-liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel and cooling tube.
0 g and 230 g of methyl ethyl ketone were charged and dissolved.
143 g of formalin was added and stirred. Next, the solution was heated to 60 ° C., and 82 g of aniline was added dropwise in small portions over 45 minutes. After completion of the dropwise addition, the reaction was continued under reflux for 7 hours. Thereafter, the mixture was concentrated at 100 ° C. for 1 hour at a reduced pressure of 6.66 × 10 ³ Pa or less to obtain 300 g of a compound (R-2) into which a desired dihydrobenzoxazine ring was introduced.

Examples 1 to 7, Comparative Example 1 The polyimide precursor solution (PI-1) obtained in Synthesis Examples 1 to 4 was placed in a flask equipped with a stirrer, cooling tube and thermometer.
Photopolymerizable unsaturated compound (M-1), dihydrobenzoxazine ring-containing compounds (R-1, R-2), benzyldimethyl ketal as a photoinitiator (I-
651) and Victoria Pure Blue (dye) were blended in the weight ratio shown in Table 1, stirred and mixed, filtered through a filter, and mixed with a uniform photosensitive resin composition solution (PPI-1 to PPI-1).
-7) was obtained.

[0049]

[Table 1]

A copper-clad laminate of 18 μm copper foil (Hitachi Chemical Industries, Ltd.)
MCL E-679) manufactured by Sumitomo 3M Limited was polished with Scotch Bright, washed with water, and dried at 80 ° C. for 15 minutes. The photosensitive resin composition solution (PPI-1 to PPI-4) was uniformly applied to the test substrate using an applicator. Then, using a hot plate, 9
Heating was performed at 0 ° C. for 480 seconds to form a coating film of about 20 μm.

The test substrate on which the layer of the photosensitive resin composition thus obtained was formed was evaluated for developability, storage stability, solder heat resistance and PCT resistance by the following methods. The evaluation results are shown in Tables 2 and 3. (1) Developability The test substrate on which the layer of the photosensitive resin composition obtained above was formed was subjected to 45 ° C. using an alkaline aqueous solution containing 5% by weight of heptanoic acid diethanolamide and 0.5% by weight of sodium carbonate. For 60 seconds. The developability was evaluated by visual observation of the resin remaining after being magnified 30 times.
The evaluation criteria are as follows. ：: good developability (no resin left on substrate surface) ×: poor developability (residual resin left on substrate surface) (2) Storage stability Obtained above The photosensitive resin composition is heated at room temperature (23 ° C.) to 1
After storing for a week, a test substrate was prepared in the same manner as in (1), and the developability was evaluated. The evaluation criteria are as follows. ：: Good storage stability (no resin left on the substrate surface) ×: Poor storage stability (a little resin left on the substrate surface)

(3) Solder heat resistance The above-mentioned copper-clad laminate having a copper thickness of 18 μm (Hitachi Chemical Industries, Ltd.)
MCL E-679) was polished with Scotch Bright manufactured by Sumitomo 3M Limited, washed with water, and dried at 80 ° C. for 15 minutes. The photosensitive resin compositions (PPI-1 to PPI-4) were uniformly applied to the test substrate using an applicator. Then, the mixture was heated at 90 ° C. for 480 seconds using a hot plate to form a coating film of about 20 μm. Next, a negative mask was brought into close contact with the photosensitive resin composition layer, and exposed with an exposure amount of 500 mJ / cm ² using an HMW-680 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Next, after the negative mask was peeled off, polyoxyethylene-p-
Cumyl phenyl ether 2% by weight, sodium carbonate
Using an aqueous alkali solution containing 0.5% by weight,
Spray developed at 60 ° C for 60 seconds. After development, 10
Then, the film was heated and dried again for 3 minutes and irradiated with ultraviolet rays at a dose of ³ J / cm ² using an ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd., and then further heated in a dryer at 200 ° C. for 60 minutes (in an air atmosphere). A rosin-based flux A-226 (manufactured by Tamura Kaken) is applied to the surface of the test substrate thus obtained,
Was immersed in a solder bath for 180 seconds, and then immersed in trichlene at 25 ° C. for 20 seconds to remove the flux. After performing such an operation, the appearance of the photosensitive resin composition layer was evaluated. The evaluation criteria are as follows. ：: good solder heat resistance (no cracks or floating in the photosensitive resin composition layer, no peeling) ×: poor solder heat resistance (cracks or floating in the photosensitive resin composition layer, What causes peeling)

(4) PCT Resistance The above-mentioned copper-clad laminate having a copper thickness of 18 μm (Hitachi Chemical Industry Co., Ltd.)
MCL E-679) was polished with Scotch Bright manufactured by Sumitomo 3M Limited, washed with water, and dried at 80 ° C. for 15 minutes. The photosensitive resin composition solution (PPI-1 to PPI-9) was uniformly applied to the test substrate using an applicator. Then, using a hot plate, 90 ° C
For 480 seconds to form a coating film of about 20 μm. Next, exposure was performed at an exposure of 500 mJ / cm ² using an HMW-680 type exposure machine manufactured by Oak Manufacturing Co., Ltd., and then re-irradiated at an amount of ³ J / cm ² using an ultraviolet irradiation apparatus manufactured by Toshiba Electric Materials Co., Ltd. Then, it was further heated in a dryer at a predetermined temperature for 60 minutes (in an air atmosphere). The test substrate thus obtained was subjected to a test at 121 ° C. and 2.0 ° C. using a PCT tester manufactured by Hirayama Seisakusho.
PCT treatment was performed for up to 300 hours under the condition of 13 × 10 ⁵ Pa, and the PCT resistance was evaluated by the following method. PCT resistance
The adhesiveness was evaluated by a cross-cut test after the PCT treatment for a predetermined time. In addition, the cross cut test is 1 mm with a cutter knife.
Scratch in the shape of a grid so that 100 squares are formed, and peel off this with cellophane tape in accordance with JIS standard (JIS K5400). It is a way to represent.

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

The photosensitive resin composition according to the first aspect is excellent in heat resistance, adhesion and moisture resistance (PCT resistance), and is suitable for various protective films, insulating films and the like, especially for solder resists.
The photosensitive resin composition according to the second aspect has the effects described in the first aspect, and is further excellent in moisture resistance. The photosensitive resin composition according to the third aspect is excellent in low-temperature curability, heat resistance, adhesion, and moisture resistance (PCT resistance). The photosensitive resin composition according to the fourth aspect has the effects described in the third aspect, and is further excellent in low-temperature curability. The photosensitive resin composition according to the fifth aspect has the effects described in the third aspect, and is further excellent in moisture resistance (PCT resistance). The method for producing a solder resist according to claim 6,
Excellent workability and photosensitive characteristics. The method for producing a solder resist according to the seventh aspect has the effects described in the sixth aspect, and is further excellent in various properties required for the solder resist, such as heat resistance, adhesion, moisture resistance (PCT resistance), and electrical properties. .

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/004 501 G03F 7/004 501 7/30 7/30 H05K 3/28 H05K 3/28 D (72) Inventor Nishizawa ▲ Hiro ▼ 4-3-1, Higashi-cho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Ibaraki Research Laboratories (72) Inventor Teruki Aizawa 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Industry Co., Ltd. Shimodate Plant (72) Inventor Shunichi Numata 1500 Ogawa, Shimodate, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd.

Claims (7)

[Claims] 1. A polyimide or a precursor thereof obtained by reacting (A) a tetracarboxylic dianhydride or a derivative thereof with a diamine compound, and (B) a photopolymerization having at least one ethylenically unsaturated group at a terminal. Unsaturated compounds,
A photosensitive resin composition comprising (C) a dihydrobenzoxazine ring-containing compound and (D) a photopolymerization initiator that generates free radicals upon irradiation with actinic light. 2. The polyimide of the component (A) or its precursor is 20 to 95 parts by weight based on 100 parts by weight of the total of the components (A) and (B), and the photopolymerizable unsaturated compound of the component (B) 5 to 80 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B), and the dihydrobenzoxazine ring-containing compound of the component (C) as 100 parts by weight in total of the components (A) and (B) The photopolymerization initiator of the component (D) is used in an amount of 0.05 to 40 parts by weight based on the total amount of the component (A) and the component (B).
The photosensitive resin composition according to claim 1, which is contained in an amount of 0.01 to 20 parts by weight based on 00 parts by weight. 3. The method according to claim 1, further comprising a non-nitrogen-containing solvent.
Or the photosensitive resin composition according to 2. 4. The photosensitive resin composition according to claim 3, wherein the non-nitrogen-containing solvent is a lactone, an alicyclic ketone or an ether. 5. The dihydrobenzoxazine ring-containing compound as the component (C) is obtained by reacting a corresponding compound having a phenolic hydroxyl group, formaldehyde and a primary amine. The photosensitive resin composition as described in the above. 6. A solution of the photosensitive resin composition according to claim 1, which is applied on a substrate, dried, exposed imagewise, and then added with a surfactant or an organic solvent in an amount of 0.1%. -50% by weight and 0.01-30% by weight of inorganic alkaline compound
A method for producing a substrate having a solder resist, wherein development is performed using an alkaline aqueous solution contained in the developer. 7. The method for producing a substrate having a solder resist according to claim 6, which comprises a step of irradiating active light after development and a step of post-heating.