JP3363232B2 - Heat-resistant photosensitive resin composition and photosensitive dry film using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant photosensitive resin composition, particularly as a photo solder resist for printed wiring boards, which is excellent in heat resistance, chemical resistance, stability over time, etc. and has good adhesion to a substrate. The present invention relates to a heat-resistant photosensitive resin composition which is soluble in an alkaline aqueous solution and has little bleeding, and a photosensitive dry film using the same.

[0002]

2. Description of the Related Art Conventionally, in a printed wiring board manufacturing process, a pattern of a photo solder resist has been formed by a screen printing method. However, with the recent increase in the degree of integration in the electronic device field, even in the field of manufacturing printed wiring boards, there is a need for printed wiring boards with smaller line widths for both wiring patterns and insulating patterns, that is, highly integrated printed wiring boards. Has become. Further, there is an increasing demand for a photo solder resist excellent in heat resistance, chemical resistance, and stability over time.

However, in the conventional method of forming a resist pattern by screen printing, bleeding during printing,
Since phenomena such as bleeding or sagging occur, it has become impossible to cope with high integration.

Therefore, recently, a method of forming a resist pattern by a photolithography method has been developed in place of the conventional screen printing method. In this photolithography method, a liquid photosensitive resin composition is applied to a paper-glass, paper-phenol resin or glass-epoxy resin substrate on which a circuit is formed in advance, or a photosensitive film in a dry film form is thermocompression bonded. Then, active energy rays such as ultraviolet rays are selectively applied to this through a negative mask,
A required resist pattern is formed by developing.

The photosensitive resin composition used for this photo solder resist is required to have excellent heat resistance, chemical resistance, stability over time, good adhesion to a substrate and little bleeding. Further, from the viewpoints of recent environmental problems, protection of the human body from toxic substances, and the like, it is desirable that development can be carried out with an alkaline aqueous solution.

Therefore, in order to satisfy these conditions, for example, JP-A-2-23351 and JP-A-2-28651.
No. 2, JP-A-2-276812, and JP-A-5-27438.
As disclosed in Japanese Patent Application Laid-Open No. 5-32924 and the like, a photosensitive resin composition has been developed, but it is the current situation that a material reaching a practical range has not yet been obtained. .

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to develop a photo solder resist for printed wiring boards, which can be developed with an alkaline aqueous solution, and has heat resistance. , Excellent in chemical resistance, stability over time, etc., good adhesion to the substrate,
It is intended to provide a heat-resistant photosensitive resin composition and a photosensitive dry film using the same.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a binder polymer having an unsaturated double bond and having a specific range of acid value and molecular weight is used. A specific oxidation having an unsaturated double bond,
The present invention has been completed based on the finding that a heat-resistant photosensitive resin composition satisfying the above problems can be obtained by including an epoxy resin having an epoxy equivalent in the composition.

That is, the present invention provides (a) any of the following methods (a-1) and (a-2): (a-1) a carboxyl group-containing unsaturated monomer and ethylene
Form a copolymer with a system unsaturated double bond-containing monomer.
This is used as a raw material polymer, and carboxy in the raw material polymer
Reaction with an unsaturated monomer containing a glycidyl group,
Acryloyl group or methacryloyl group in the polymer
Method of addition, (a-2) glycidyl group-containing unsaturated monomer and ethylene
Forming a copolymer with an unsaturated double bond-containing monomer
As a raw material polymer, and a glycidyl group in the raw material polymer
By reacting a carboxyl group-containing unsaturated monomer with
Add acryloyl or methacryloyl group to polymer
And a weight average molecular weight of 5,000.
It is obtained by reacting (b) an epoxy resin with a carboxyl group-containing unsaturated monomer, a binder polymer having an acid value of 30 to 160 and an acid value of 30 to 160, and reacting an acid anhydride with the obtained reaction product. , Acid value 30 to 100, epoxy equivalent 1,000 to 9,000 (g / epoxy group 1 mol)
Which contains an unsaturated double bond-containing epoxy resin which is, (c) a photopolymerizable monomer, and (d) a photopolymerization initiator,
A heat-resistant photosensitive resin composition is provided.

The present invention also provides a photosensitive dry film comprising a support and a photosolder resist layer, a water-soluble resin layer, and a protective material layer laminated on the support, wherein the photosolder resist layer is the heat-resistant photosensitive resin composition. Is formed by using
A photosensitive dry film is provided.

The components of the heat-resistant photosensitive resin composition of the present invention and the photosensitive dry film using the same will be described in detail below.

The value of the epoxy equivalent used in the present invention represents the number of g of the resin contained per mol of the epoxy group.

First, the binder polymer as the component (a) contained in the heat-resistant photosensitive resin composition of the present invention has an acryloyl group or a methacryloyl group and has a weight average molecular weight of 5,000 to 80,000. , Acid number 30
~ 160.

The binder polymer is synthesized, for example, by using a raw material polymer obtained by copolymerizing at least one kind of a carboxyl group-containing unsaturated monomer and an ethylenically unsaturated double bond-containing monomer.

Examples of the unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate. , Monoethyl maleate, monopropyl maleate, sorbic acid and the like.

Examples of the ethylenically unsaturated double bond-containing monomer include 2-hydroxymethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethylene glycol monomethyl acrylate, ethylene glycol monomethyl methacrylate, ethylene glycol monoethyl acrylate, ethylene glycol monoethyl methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid dimethylaminoethyl ester, dimethyl methacrylate Aminoethyl ester, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl Acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate,
Benzyl methacrylate, carbitol acrylate, carbitol methacrylate, ε-caprolactone modified tetrafurfuryl acrylate, ε-caprolactone modified tetrafurfuryl methacrylate, diethylene glycol ethoxyl acrylate, isodecyl acrylate, isodecyl methacrylate, octyl acrylate, octyl methacrylate, lauryl Examples thereof include acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate and the like.

Then, a copolymer is formed by reacting at least one kind selected from the carboxyl group-containing unsaturated monomer and the ethylenic unsaturated double bond-containing monomer, and forming a copolymer. The raw material polymer.
These may be used alone or in combination of two or more kinds as appropriate.

The raw material polymer may be a block-polymerized product of the components selected from the above as oligomers.

As a suitable selection of the above-mentioned monomers, a combination of acrylic acid or methacrylic acid / methyl acrylate, methyl methacrylate, ethyl acrylate or ethyl methacrylate is preferable, and methacrylic acid / methyl acrylate, methyl methacrylate, ethyl acrylate is particularly preferable. Or ethyl methacrylate /
Examples thereof include 2-hydroxymethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

Next, the carboxyl group in the raw material polymer (copolymer) thus obtained is reacted with a glycidyl group-containing unsaturated monomer to give a side chain of the raw material polymer an acryloyl group or a methacryloyl group. Add. Examples of the glycidyl group-containing unsaturated monomer include glycidyl acrylate, glycidyl methacrylate, 2-methyl-2,3-epoxypropyl acrylate, 2-methyl-2,3-epoxypropyl methacrylate, 2-
Ethyl-2,3-epoxypropyl acrylate, 2-
Examples thereof include ethyl-2,3-epoxypropyl methacrylate and the like, and glycidyl methacrylate is preferably used from the viewpoints of handling safety and availability. In the reaction of the above-mentioned unsaturated monomer containing a glycidyl group with a carboxyl group, the glycidyl group is opened and a hydroxyl group is added.

Then, in order to adjust the acid value, the above-mentioned raw material polymer to which an acryloyl group or a methacryloyl group is added is subjected to the following reaction (i) or (ii),
A binder polymer as the component (a) of the present invention is synthesized. (I) A hydroxyl group added by ring opening of the glycidyl group of the above-mentioned raw material polymer is reacted with an acid anhydride to synthesize a binder polymer as the component (a) of the present invention. Examples of the acid anhydride include phthalic anhydride, dihydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride and the like.

Alternatively, (ii) as the ethylenically unsaturated double bond-containing monomer for forming the raw material polymer, a primary hydroxyl group-containing unsaturated monomer (for example, 2-hydroxymethyl acrylate, 2-hydroxy). When methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc.) is used, the primary hydroxyl group is reacted with an acid anhydride to synthesize the binder polymer as the component (a) of the present invention. To do.

Instead of using as a raw material polymer a copolymer (copolymer) obtained by copolymerizing at least one kind of the above-mentioned carboxyl group-containing unsaturated monomer and ethylenically unsaturated double bond-containing monomer. , Using a glycidyl group-containing unsaturated monomer in place of the carboxyl group-containing unsaturated monomer, first of all the glycidyl group-containing unsaturated monomer and the ethylenically unsaturated double bond-containing monomer A polymer may be formed and used as a raw material polymer, and a glycidyl group in the raw material polymer may be reacted with a carboxyl group-containing unsaturated monomer to add an acryloyl group or a methacryloyl group.

In the present invention, the binder polymer as the component (a) has a weight average molecular weight of 5,000.
To 80,000, preferably 7,000 to 40,
It is 000. This is because if the weight average molecular weight is less than 5,000, the coating properties at the time of coating are poor and the heat resistance is poor, while if the weight average molecular weight exceeds 80,000, the developing performance is reduced. The acid value is 30 to 160, preferably 50 to 120. This is because if the acid value is less than 30, it becomes difficult to develop with an alkaline aqueous solution, while if the acid value exceeds 160, the water resistance of the obtained photosolder resist decreases.

(B) of the heat-resistant photosensitive resin composition of the present invention
The unsaturated double bond-containing epoxy resin as a component is obtained by first reacting an epoxy group of the epoxy resin with a carboxyl group-containing unsaturated monomer and then reacting the obtained reaction product with an acid anhydride. , An acid value of 30 to 100,
The epoxy equivalent is 1,000 to 9,000 (g / epoxy group 1 mol).

Examples of the epoxy resin include the following. (I) Phenol novolac type epoxy resin, ortho-cresol novolac type epoxy resin, meta-cresol novolac type epoxy resin, para-cresol novolac type epoxy resin, ortho-cresol / meta-cresol novolac type epoxy resin, meta-cresol / para-cresol novolac type epoxy resin, Ortho-cresol / para-cresol novolac type epoxy resin, ortho-cresol / meta-cresol / para-cresol novolac type epoxy resin, halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin or phenol or cresol novolac type epoxy resin, (ii ) Bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Bisphenol type epoxy resin such as bisphenol S type epoxy resin, (iii) tris- (2,3-diepoxyethyl) isocyanurate, tris- (2,3-diepoxypropyl) isocyanurate, tris- (2,
Epoxidized triazine resins such as 3-diepoxybutyl) isocyanurate.

The above-mentioned (i) phenol or cresol novolac type epoxy resin is, for example, "Epicoat 15".
2 "(manufactured by Yuka Shell Co., Ltd.)," Epicote 154 "
(The same), "Araldite ECN1299" (manufactured by Ciba Geigy), "Araldite ECN1273"
(The same), "EOCN104" (manufactured by Nippon Kayaku Co., Ltd.),
"EOCN103" (same), "EOCN102"
(Same), "EOCN101" (Same), "BREN"
(The same), "DEN438" (manufactured by Dow Chemical Co., Ltd.),
"DEN431" (same), "YDPN-638" (manufactured by Tohto Kasei Co., Ltd.), "YDPN-601" (same) "YDP
-602 "(the same).

The above-mentioned bisphenol type epoxy resin (ii) is available, for example, as "Epicoat 1002" (produced by Yuka Shell Co., Ltd.).

The epoxidized triazine resin of the above (iii) is, for example, "TEPIC-G" (Nissan Chemical Co., Ltd.).
Made), "TEPIC-P" (the same), "TEPIC-L"
(The same), "TEPIC-S" (the same), "TEPIC-
H ”(the same) and the like.

In the present invention, the epoxy group of these epoxy resins is first reacted with a carboxyl group-containing unsaturated monomer to give the epoxy resin photopolymerizability. As the carboxyl group-containing unsaturated monomer, those exemplified as being usable in the process of synthesizing the binder polymer of the component (a) can be used. At this time, as esterification catalysts, diethylamine acetate, diethylamine hydrochloride, triethylamine, etc.
Grade and tertiary salts may be used. In the above reaction, the epoxy group is opened and the hydroxyl group is added.

Next, the acid value is adjusted by reacting an acid anhydride with the hydroxyl group obtained by ring-opening of the epoxy group of the thus obtained reaction product, and (b) of the present invention which can be developed in an alkaline aqueous solution. An unsaturated double bond-containing epoxy resin as a component is obtained. As the acid anhydride, the above-mentioned phthalic anhydride, dihydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydroxyphthalic anhydride, maleic anhydride,
Succinic anhydride or the like can be used. These may be used alone or in combination of two or more.

In the present invention, the unsaturated double bond-containing epoxy resin as the component (b) has an acid value of 30 to 100.
And preferably 40 to 80. If the acid value is less than 30, the alkali developability will be poor, while if the acid value is more than 100, the water resistance and moisture resistance will be poor and good electrical properties may not be obtained. Further, the epoxy equivalent is 1,000 to 9,000 (g / epoxy group 1 mol), and preferably 3,000 to 85,000. When the epoxy equivalent is less than 1,000, the alkali developability is deteriorated, and a residue may be generated in the unexposed portion of the obtained pattern. On the other hand, when the epoxy equivalent is more than 9,000, the crosslinking efficiency is lowered and the heat resistance is deteriorated. This is because the resistance and chemical resistance may deteriorate.

By heating the component (b) after forming a pattern, the epoxy group is subjected to ring-opening polymerization to increase the crosslink density and further improve the heat resistance.

The unsaturated double bond-containing epoxy resin as the component (b) is preferably contained in the composition in an amount of 10 to 500 parts by weight based on 100 parts by weight of the binder polymer as the component (a). This is because if it is less than 10 parts by weight, photo-curing failure or development failure may occur, while if it exceeds 500 parts by weight, the stability over time may deteriorate.

Next, the photopolymerizable monomer as the component (c) of the heat-resistant photosensitive resin composition of the present invention is contained in the composition in order to increase the crosslinking efficiency and heat resistance. .
Examples of the photopolymerizable monomer include acrylic acid, which is a monomer that can be used in the synthesis of the component (a),
Methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, sorbic acid,
2-hydroxymethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethylene glycol monomethyl acrylate, ethylene glycol monomethyl methacrylate,
Ethylene glycol monoethyl acrylate, ethylene glycol monoethyl methacrylate, glycerol acrylate, glycerol methacrylate, dipentaerythritol monohydroxy methacrylate, dipentaerythritol monohydroxy acrylate, acrylic acid dimethylaminoethyl ester, methacrylic acid dimethylaminoethyl ester, tetrahydrofurfuryl acrylate , Tetrahydrofurfuryl methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,
Isobutyl acrylate, isobutyl methacrylate,
2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, carbitol acrylate, carbitol methacrylate, ε-caprolactone modified tetrafurfuryl acrylate, ε-caprolactone modified tetrafurfuryl methacrylate, diethylene glycol ethoxyl acrylate, isodecyl Acrylate, isodecyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and other polyfunctional monomers such as , Ethylene glycol diacrylate , Ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate , Trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate,
Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol Diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxy diacrylate, ε-
Caprolactone-modified dipentaerythritol monoacrylate, ε-caprolactone-modified dipentaerythritol monomethacrylate, ε-caprolactone-modified dipentaerythritol diacrylate, ε-caprolactone-modified dipentaerythritol dimethacrylate, ε-caprolactone-modified dipentaerythritol triacrylate, ε- Caprolactone-modified dipentaerythritol trimethacrylate, ε-caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, allyl acrylate, allyl methacrylate,
Decaethylene glycol diacrylate, decaethylene glycol dimethacrylate, pentadecaethylene glycol diacrylate, pentadecaethylene glycol dimethacrylate, pentacontahector ethylene glycol diacrylate, pentacontahector ethylene glycol dimethacrylate, phthalic acid diethylene glycol diacrylate, phthalic acid Diethylene glycol dimethacrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 2-propenoic acid [2- [1,1-
Dimethyl-2-[(1-oxo-2-propenyl) oxy] ethyl] -5-ethyl-1,3-dioxan-5-
Il] methyl ester and the like can be used. These may be used alone or in combination of two or more.

Further, a monomer having a hydroxyl group in the molecule, such as diethylene glycol monoacrylate, trimethylolpropane dimethacrylate, and pentaerythritol trimethacrylate, is used as maleic anhydride, phthalic anhydride, tetrahydroxyphthalic anhydride, and hexahydroxyphthalic anhydride. Those esterified with a polybasic acid anhydride such as an acid can also be preferably used.

Furthermore, the melamine acrylate obtained by reacting 1 mol of hexamethoxymethylmelamine with 1 mol or more of hydroxyalkyl acrylate or hydroxyalkyl methacrylate is adjusted to 1 to 6 acrylates by adjusting the reaction molar ratio. Can
These can be appropriately selected and used as needed. Such melamine acrylate is obtained by reacting melamine with hexamethylolmelamine to form hexamethoxymelamine, and then reacting it with hydroxyalkyl acrylate or hydroxyalkyl methacrylate such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate. You can This melamine acrylate is further crosslinked and cured by heating when a methoxy group remains in the melamine acrylate molecule even after photopolymerization by ultraviolet irradiation, so that the heat resistance can be further improved.

The photopolymerizable monomer as the component (c) is preferably contained in the composition in an amount of 10 to 100 parts by weight based on 100 parts by weight of the binder polymer as the component (a). If the blending ratio is less than 10 parts by weight, photo-curing failure will occur, and it will be difficult to obtain sufficient heat resistance and chemical resistance. On the other hand, if it exceeds 100 parts by weight, the tack on the surface of the composition after drying will be strong, This is because workability is not good.

(D) of the heat-resistant photosensitive resin composition of the present invention
As the photopolymerization initiator as a component, any conventionally known one can be used. Specifically, benzophenone, 4, 4 '
Benzophenone derivatives such as bis (dimethylamino) benzophenone and 3,3-dimethyl-4-methoxy-benzophenone; anthraquinone derivatives such as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tert-butylanthraquinone; benzoin, benzoin methyl ether , Benzoin ethyl ether,
Benzoin alkyl ether derivatives such as benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, acetophenone derivatives such as 2,2-diethoxyacetophenone; 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, diisopropylthioxanthone, etc. Thioxanthone derivatives; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-
2-methylpropiophenone, 4'-isopropyl-2
-Acetophenone derivatives such as 2-hydroxy-2-methylpropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone; Michler's ketone, benzyl, 2,4,6- (trihalomethyl) ) Triazine, 2- (o-chlorophenyl) -4,
5-diphenylimidazolyl dimer, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane,
1,5-bis (9-acridinyl) pentane, 1,3-
Bis (9-acridinyl) propane, dimethylbenzyl ketal, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenyl sulfone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. However, the present invention is not limited to these. One of these,
Alternatively, two or more kinds can be used in combination.

The photopolymerization initiator may be contained in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the heat-resistant photosensitive resin composition (as solid content excluding the solvent).

In the present invention, in addition to the above-mentioned essential constituents, other constituents can be added if necessary.

An epoxy curing agent can be given as an example of such a component. As the epoxy curing agent, generally known amine-based curing agents, acid anhydride-based curing agents, phenol resins, melamine resins, cationic epoxy curing agents and the like can be used, but in the present invention, there is little influence on the sensitivity. Particularly, it is preferable to use an amine type epoxy curing agent and a cationic type epoxy curing agent. As such an epoxy curing agent, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole,
2 phenyl 4,5-dihydroxymethyl imidazole,
2-Methylimidazole isocyanuric acid adduct (2MZ-OK manufactured by Shikoku Chemicals Co., Ltd.), 1- (4,5-
Diamino-2-triazinyl) -2- (2-methyl-1)
-Imidazolyl) ethane (manufactured by Shikoku Chemicals Co., Ltd .: 2M
Z-AZINE) and other imidazole compounds, benzylmethylamine, dimethylaminomethylphenol, and other 3 compounds
Amino complex compounds such as primary amine, boron trifluoride monoethylamine, boron trifluoride triethanolamine, etc., and cationic epoxy curing agent (CG-261 manufactured by Ciba-Geigy Co., Ltd.) that produces a Lewis acid upon irradiation with ultraviolet rays. Is effective. These may be used alone or in combination of two or more.

The amount of these epoxy curing agents used is
1 to 20 with respect to the epoxy resin as the component (b)
%, Preferably 2 to 10% by weight. If the amount of the epoxy curing agent used is less than 1% by weight, heat curing may take a long time and the effect as an epoxy curing agent may not be exhibited, while if it is more than 20% by weight, the stability will be poor. Sometimes.

In addition to these, tackiness improvers can be mentioned. This is a solid at room temperature, preferably an alkali-soluble compound that polymerizes or crosslinks by light or heat,
For example, it is possible to use a copolymer having a carboxyl group and an N-alkoxyacrylamide group, or a compound obtained by reacting hydroxyethyl methacrylate with a copolymer of styrene and maleic anhydride.

Further, silicone-based or fluorine-based defoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether for preventing gelation and improving storage stability, phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, etc. A colorant may be added, and silica having a particle size of about 0.001 to 10 μm, talc, barium sulfate, calcium carbonate,
Clay, hydrous silicic acid, aluminum hydroxide, aluminum oxide, antimony trioxide, magnesium carbonate, aluminum silicate, magnesium silicate, aerosil, etc. can be added as a filler.

Further, in the present invention, a solvent may be used in order to adjust the viscosity and improve the coating property.
Examples of the solvent used in the heat-resistant photosensitive resin composition of the present invention include hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, benzyl alcohol, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol. ,
Propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl Acetate, 2-
Ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3
-Methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, propyl acetate, Butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, methyl propionate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl butyrate,
In addition to ethyl butyrate, propyl butyrate, etc., "Swazol" (manufactured by Maruzen Petrochemical Co., Ltd.), "Solvesso"
Examples include petroleum-based solvents available under the product names such as (Tonen Petrochemical Co., Ltd.). Among these, especially ethylene glycol monoethyl ether, ethyl lactate,
3-methoxybutyl acetate, propyl acetate,
Butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, methyl propionate, ethyl propionate and the like are preferably used.

In the present invention, the solvent component is used in a mixing ratio of 50 to 900 parts by weight based on 100 parts by weight of the heat-resistant photosensitive resin solid content.

The heat-resistant photosensitive resin composition according to the present invention comprises
For example, after being prepared as follows, it is used as a photo solder resist for printed wiring boards.

That is, if necessary, a predetermined amount of a filler, a polymerization inhibitor, a defoaming agent or the like is added to the above components (a) to (e), and this is well dissolved and dispersed in a three-roll mill, a ball mill, a sand mill or the like. Then, the mixture is kneaded to obtain the heat-resistant photosensitive resin composition according to the present invention.

The heat-resistant photosensitive resin composition thus prepared is applied onto a substrate (for example, glass fiber + epoxy resin laminate). The coating is preferably performed with a roll coater, reverse coater, spinner, curtain flow coater, or the like. After coating, the coating is left to stand at room temperature for several hours to several days, or placed in a warm air heater or infrared heater for several tens of minutes to several hours to remove the solvent, and the coating film thickness is adjusted to about 1 to 250 μm.

Next, exposure is performed through a negative mask having a predetermined pattern. The amount of ultraviolet energy applied to the heat-resistant photosensitive resin composition of the present invention varies slightly depending on the composition, but is preferably about 50 to 2,000 mJ / cm ² .

After exposure, development is carried out by a spray gun, a dipping method or the like. As a developing solution, monoethanolamine,
Organic-based ones such as diethanolamine and triethanolamine, and alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts are preferably used. After the exposure, the unexposed portion of the coating film is dissolved and removed to obtain a printed wiring board on which a desired resist pattern is formed.

The obtained resist pattern is 100 to 20
By leaving it in the range of 0 ° C. for several tens of minutes to several hours, the epoxy group is subjected to ring-opening polymerization to improve the crosslinking density of the crosslinking agent.

In addition to this, the heat-resistant photosensitive resin composition can be used as a resist for a photosensitive dry film, thereby providing the photosensitive dry film according to the present invention.

That is, as shown in FIG. 1, the photosensitive dry film 10 comprises a support 1, a water-soluble resin layer 2, a photo solder resist layer (photosensitive resin composition layer) 3, and a protective material layer 4. It has a structure in which layers are sequentially stacked.

The support 1 supports the photo solder resist layer 3 and needs to have appropriate flexibility. Generally, a polyethylene terephthalate (PET) film having a thickness of 10 to 200 μm is used, but besides this, a synthetic resin film of polyethylene, polypropylene, polycarbonate, polyvinyl chloride or the like is also suitably used.

The water-soluble resin layer 2 is for preventing the oxygen desensitizing action of the heat-resistant photosensitive resin composition forming the photo solder resist layer 3 and for preventing the adhesion of the mask pattern during exposure. It must be water-soluble so that it can be removed by liquid. Since the heat-resistant photosensitive resin composition used in the present invention can be developed with an alkaline aqueous solution,
The water-soluble resin layer 2 is soluble in an alkaline aqueous solution. Preferable examples of such a material include a 2 to 20 wt% aqueous solution of 70 to 90% partially saponified polyvinyl alcohol resin. In order to improve the releasability from the support 1, 100 parts by weight of the above material is further added with one or more oxyalkylene compounds selected from ethylene glycol, propylene glycol, or a condensation product or derivative thereof. It is also preferable to add 0.001 to 10 parts by weight.

The water-soluble resin layer 2 used is an aqueous solution of 2 to 20% by weight, and a dry film thickness of 1 to 1 is obtained by a bar coater, a roll coater, a curtain flow coater or the like.
It is obtained by coating so as to have a thickness of 0 μm. If the film thickness is less than 1 μm, adhesion may occur, while 10 μm
If it exceeds, the resolution tends to deteriorate. When preparing the aqueous solution, consider the viscosity of the solution, defoaming, etc.
For example, methanol, ethylene glycol monomethyl ether, acetone or the like may be added and used.

As the photo solder resist layer 3, the heat-resistant photosensitive resin composition according to the present invention described above is used, and a dry film thickness of 10 to 1,000 μm is obtained by using an applicator, a bar coater, a roll coater, a curtain flow coater or the like.
It was applied so that

The protective material layer 4 is made of the photosensitive dry film 10.
This is for stably protecting the photo solder resist layer 3 when not in use, and is peeled off when the dry film is used. Therefore, it is necessary that the dry film is not easily peeled off when it is not used, and has an appropriate releasability that can be easily peeled off when it is used. As a material satisfying such a condition, a PET film, a polypropylene film, a polyethylene film or the like having a film thickness of 10 to 200 μm, which is coated with silicone, particularly baked, is preferably used.

In the photosensitive dry film 10 according to the present invention having such a structure, the resist pattern 8 is formed as shown in FIG. 2, for example. That is, first, the protective material layer 4 is peeled from the photo solder resist layer 3 and the exposed side of the photo solder resist layer 3 is thermocompression-bonded to the substrate 5 for a printed wiring board, and the photosensitive dry film 10 is laminated on the substrate 5. (FIG. 2 (a)). The substrate 5 is made of, for example, a glass-epoxy resin plate laminated with copper, a paper-phenol resin plate laminated with copper, or the like.

Next, the support 1 is peeled off, and the negative mask 6 having a predetermined pattern is placed on the exposed water-soluble resin layer 2,
Ultraviolet 7 is irradiated to perform exposure (FIG. 2B). After the exposure, development is performed to dissolve and remove the unexposed portions of the water-soluble resin layer 2 and the photo solder resist layer 3 to obtain a printed wiring board on which a desired resist pattern 8 is formed (FIG. 2 (c)).

The amount of energy of the ultraviolet rays to be irradiated, the developing solution (alkaline aqueous solution), the developing method and the like are the same as in the case of coating the above-mentioned liquid heat-resistant photosensitive resin composition on the substrate. be able to.

[0064]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to this. A. Synthesis of Binder Polymer Synthetic Example 1 80 parts by weight of methyl methacrylate 50 parts by weight of acrylic acid 80 parts by weight of benzyl methacrylate 240 parts by weight of ethylene glycol monomethyl ether acetate 240 parts by weight of the above-mentioned compounding ingredients at a temperature of 75 ° C. with 2 parts by weight of azobisisobutyronitrile as a catalyst. Polymerization reaction is carried out for a period of time, and then 45 parts by weight of glycidyl methacrylate in which 2 parts by weight of methylhydroquinone are dissolved is added as a thermal polymerization inhibitor, and the mixture is further reacted for 2 hours to obtain a binder polymer having a weight average molecular weight of 40,000 and an acid value of 84. (A-1) was obtained. Synthetic Example 2 Methyl methacrylate 80 parts by weight Acrylic acid 50 parts by weight Benzyl methacrylate 80 parts by weight Ethylene glycol monomethyl ether acetate 240 parts by weight Polymerization reaction of the above compounded components at 75 ° C. for 3 hours with 3 parts by weight of azobisisobutyronitrile as a catalyst. After that, 35 parts by weight of glycidyl methacrylate in which 2 parts by weight of methylhydroquinone are dissolved is added as a thermal polymerization inhibitor, and the mixture is further reacted for 2 hours to give a binder polymer (A- 2 having a weight average molecular weight of 8,000 and an acid value of 105). ) Got. Synthesis Example 3 Methyl methacrylate 80 parts by weight Acrylic acid 50 parts by weight Benzyl methacrylate 80 parts by weight Ethylene glycol monomethyl ether acetate 240 parts by weight The above compounding ingredients are polymerized at 75 ° C. for 10 hours using 1.5 parts by weight of azobisisobutyronitrile as a catalyst. After the reaction, 35 parts by weight of glycidyl methacrylate in which 2 parts by weight of methylhydroquinone was dissolved was added as a thermal polymerization inhibitor, and the mixture was further reacted for 2 hours to give a weight average molecular weight of 70,0.
A binder polymer (A- 3 ) having an acid value of 00 and an acid value of 103 was obtained. Comparative Synthesis Example 1 Methyl methacrylate 65 parts by weight Styrene 15 parts by weight Methacrylic acid 20 parts by weight Ethylene glycol monomethyl ether acetate 100 parts by weight Using the above-mentioned compounding ingredients, azobisisobutyronitrile 1.
Polymerization reaction was carried out at 75 ° C. for 10 hours with 5 parts by weight as a catalyst, and then 45 parts by weight of glycidyl methacrylate in which 2 parts by weight of methylhydroquinone was dissolved was added as a thermal polymerization inhibitor, and the reaction was further continued for 2 hours to give a weight average molecular weight. 7
Binder polymer (A-
7) was obtained. It contains no ethylenically unsaturated double bonds. Comparative Synthetic Example 2 Methyl methacrylate 80 parts by weight Acrylic acid 50 parts by weight Benzyl methacrylate 80 parts by weight Ethylene glycol monomethyl ether acetate 240 parts by weight Using the above-mentioned components, 4 parts by weight of azobisisobutyronitrile as a catalyst for 2 hours at 75 ° C. A polymerization reaction was performed, and then 35 parts by weight of glycidyl methacrylate in which 2 parts by weight of methylhydroquinone was dissolved was added as a thermal polymerization inhibitor, and the mixture was further reacted for 2 hours to give a weight average molecular weight of 4,50.
A binder polymer (A-8) having an acid value of 0 and an acid value of 104 was obtained. Comparative Synthesis Example 3 Methyl methacrylate 80 parts by weight Acrylic acid 50 parts by weight Benzyl methacrylate 80 parts by weight Ethylene glycol monomethyl ether acetate 240 parts by weight Using the above-mentioned compounded components, 1 part by weight of azobisisobutyronitrile as a catalyst was used at 75 ° C. for 16 hours. A polymerization reaction was carried out, and then 35 parts by weight of glycidyl methacrylate in which 2 parts by weight of methylhydroquinone was dissolved was added as a thermal polymerization inhibitor, and the mixture was further reacted for 2 hours to give a weight average molecular weight of 90,0.
A binder polymer (A-9) having an acid value of 00 and an acid value of 105 was obtained, but when cooled to room temperature, the resin gelled and became unsuitable for use. Comparative Synthesis Example 4 Methyl methacrylate 40 parts by weight Acrylic acid 51 parts by weight 2-Hydroxyethyl methacrylate 11 parts by weight Propylene glycol monomethyl ether acetate 240 parts by weight Using the above-mentioned compounding ingredients, 2 parts by weight of azobisisobutyronitrile as a catalyst at 75 ° C. Polymerization was carried out for 4 hours, and then 26 parts by weight of acrylic acid in which 2 parts by weight of methylhydroquinone was dissolved was added as a thermal polymerization inhibitor, and further 12 parts by weight of tetrahydrophthalic anhydride was added and reacted to give a weight average molecular weight of 23 A binder polymer (A-10) having an acid value of 26 and an acid value of 26 was obtained. Comparative Synthetic Example 5 Methyl methacrylate 20 parts by weight Acrylic acid 28 parts by weight 2-Hydroxyethyl methacrylate 91 parts by weight Propylene glycol monomethyl ether acetate 240 parts by weight Using the above-mentioned compounding components, 2 parts by weight of azobisisobutyronitrile as a catalyst was used at 75 ° C. Polymerization reaction was carried out for 4 hours, then 14 parts by weight of acrylic acid in which 2 parts by weight of methylhydroquinone was dissolved was added as a thermal polymerization inhibitor, and further 106 parts by weight of tetrahydrophthalic anhydride was added and reacted to give a weight average molecular weight of 25 A binder polymer (A-11) having an acid value of 7,000 and an acid value of 173 was obtained. B. Synthesis of Unsaturated Double Bond-Containing Epoxy Resin Synthesis Example 1 Cresol novolac type epoxy resin (Ciba-Geigy Co., Ltd .: “Araldite ECN1273”) 115 parts by weight was dissolved in butylene glycol monomethyl ether acetate 150 parts by weight, and then dissolved. After adding 32 parts by weight of acrylic acid and 0.8 parts by weight of benzyldimethylamine and continuing the reaction at 100 to 120 ° C. for 8 hours, 32 parts by weight of tetrahydrophthalic anhydride was added and reacted at 100 ° C. for 8 hours to give an acid value of 69. An epoxy double bond-containing epoxy resin (B-1) having an epoxy equivalent of 3,090 was obtained. Synthesis example 2 Phenol novolac type epoxy resin (Tohto Kasei Co., Ltd.)
Manufactured: “YDPN-602”) 110 parts by weight are dissolved in 150 parts by weight of propylene glycol monomethyl ether acetate with heating, and then 34 parts by weight of acrylic acid,
Add benzyldimethylamine 0.8 parts by weight to 100-1
After continuing the reaction at 20 ° C. for 8 hours, 35 parts by weight of tetrahydrophthalic anhydride was added and reacted at 100 ° C. for 8 hours to obtain an unsaturated double bond-containing epoxy resin having an acid value of 73 and an epoxy equivalent of 5,930 (B- 2) was obtained. Synthetic Example 3 The same procedure as in Synthetic Example 1 was repeated except that the amount of acrylic acid was changed to 28 parts by weight and the amount of tetrahydrophthalic anhydride was changed to 27 parts by weight. 58, the epoxy equivalent of 1,450 and the unsaturated double bond containing epoxy resin (B-3) were obtained. Synthetic Example 4 Reaction was performed in the same manner as in Synthetic Example 1 except that the amount of acrylic acid was changed to 36 parts by weight in Synthetic Example 1, and the acid value was 7
8 and the epoxy equivalent were 8,000, and the unsaturated double bond containing epoxy resin (B-4) was obtained. Comparative Synthesis Example 1 Cresol novolac type epoxy resin (Toto Kasei Co., Ltd.)
(YDCN-701)) (100 parts by weight) was dissolved in 150 parts by weight of propylene glycol monomethyl ether acetate while heating, and then 22 parts by weight of tetrahydrophthalic anhydride was added to 23 parts by weight of acrylic acid to obtain 100 parts by weight.
Reaction for 8 hours at ℃, acid value 50, epoxy equivalent 910
To obtain an epoxy resin (B-5). Comparative Synthesis Example 2 Cresol novolac type epoxy resin (Toto Kasei Co., Ltd.)
(YDCN-701)) (100 parts by weight) was dissolved in 150 parts by weight of propylene glycol monomethyl ether acetate while heating, and then 12 parts by weight of tetrahydrophthalic anhydride was added to 28 parts by weight of acrylic acid to obtain 100 parts by weight.
Reaction for 8 hours at ℃, acid value 24, epoxy equivalent 1,8
60 epoxy resin (B-6) was obtained. Example A heat-resistant photosensitive resin composition according to the present invention was prepared according to the composition shown in Table 1 below.

[0065]

[Table 1] The compounds having the trade names in Table 1 are as follows. KAYARAD DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) KAYARAD TMPT: trimethylolpropane trimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) Irgacure 907: 2-methyl- [4- (methylthio) phenyl -2- Morpholino] -1-propane (manufactured by Ciba Geigy) Kayacure DTEX: diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) Kayacure DMBI: isoamyl ester of paramethylaminobenzoic acid (manufactured by Nippon Kayaku Co., Ltd.) Aerosil # 200: Finely powdered silica (manufactured by Nippon Aerosil Co., Ltd.) Dowanol PM: Propylene glycol monomethyl ether (manufactured by Dow Chemical Co., Ltd.) coating treatment 3 for each of Examples 1, 2 and 3 and Comparative Examples 2, 5 and 6.
After kneading with this roll mill, printing was carried out by a screen printing method and dried at 80 ° C. for 20 minutes . Ratio Comparative Examples 3 and 4
In regard to the above, after kneading with a three-roll mill, it was applied on a glass-epoxy resin substrate by a spray printing method and dried at 80 ° C. for 20 minutes.

In Example 4 and Comparative Example 1, after kneading with a three-roll mill, a support (P
ET film), a 10% aqueous solution of polyvinyl alcohol is applied to a dry film thickness of 0.2 μm and dried to form a water-soluble resin layer, and a heat-resistant photosensitive resin layer is further dried to a film thickness of 50 μm. Apply with the applicator 8
Dry for 20 minutes at 0 ° C, and then add 0.1 mm P
A photosensitive dry film was prepared using the EY film as a protective material layer. Next, the protective material layer was peeled off, thermocompression-bonded onto the substrate using a laminator, and then the support was peeled off. Exposure-Development Treatment Next, a negative mask was brought into contact with the coated surface to obtain 400 mJ / c.
Exposure with a light amount of m ² (150 for Example 4 and Comparative Example 1)
mJ / cm ² ), and then the unexposed portion is removed by spray development for 50 seconds with a 1 wt% sodium carbonate aqueous solution,
It was heat-cured at 50 ° C. for 60 minutes. Evaluation With respect to the heat-resistant photosensitive resin composition, stability with time and alkali resistance are used as evaluation items, and on the other hand, a photosensitive thermosetting film (photosolder resist layer) obtained by heat curing as described above.
The adhesiveness, solder heat resistance, and solvent resistance were used as evaluation items, and the following tests and evaluations were carried out. The results of each of these tests are shown in Table 2 below.

[0067]

[Table 2] The test method and evaluation method of each test are as follows. [Adhesiveness] The coating film (photosensitive thermosetting film) was cross-cut into a grid pattern in accordance with the test method of JIS D 0202 to 100
Make a square and then perform a peeling test using cellophane tape, and check the peeled state of the square with a magnifying glass.
According to IS D 0202, the number of 100 squares was examined and evaluated.

○: No peeling-off 100 pieces × ... No peeling-off 99 pieces or less [Solder heat resistance] After applying flux, immersing the test piece in a solder bath at 260 ° C for 10 seconds 5 After repeating times,
The state of the coating film was observed.

◯: No change in appearance was observed even after 5 times immersion. X: Stripping occurred on a part of the coating film after 2 to 5 times immersion. Note) The flux used was Sanei Chemical Co., Ltd. Made JS-6
It is 4P. [Solvent resistance] Immerse the test piece in methylene chloride for 30 minutes,
The state of the coating film was observed.

○: No change in appearance was observed ×: Swelling of the coating film [Alkali resistance] A test piece was immersed in a 10% aqueous sodium hydroxide solution at 25 ° C for 60 minutes to observe the change in the appearance of the coating film. did. At the same time, the adhesion after immersion in alkali was also examined by the same method as the above-mentioned adhesion test / evaluation method.

○: No change in appearance was observed ×: The coating film swelled and was partially peeled [Stability over time] The photosensitive resin composition was heated in an oven at 40 ° C for 30 days. After the aging test, the state of the composition and the state after development were examined.

◯: No gelation occurred in the photosensitive resin composition, and development was possible without problems ×: No gelation of the photosensitive resin occurred, but development was not possible [Developability] The photosensitive film after development processing was observed.

◯: No residue, etc. were observed, and a pattern faithful to the negative mask was obtained. Δ: Development time required 75 seconds. × ... Development was carried out for 100 seconds. [Water resistance] A part of the residue was observed. The patterned substrate was immersed in boiling water for 30 minutes, and then the shape of the pattern was observed.

○: No change was observed on the photosensitive film △: Swelling was observed in a part of the pattern ×: Swelling was observed in the entire pattern and some patterns were joined to each other As is clear from Table 2, which is no longer suitable for use, the heat-resistant photosensitive resin composition of the present invention has excellent storage stability as a one-component photosensitive resin composition, and has excellent heat resistance, chemical resistance, and It was found that the composition had good adhesion.

[0075]

As described in detail above, according to the present invention, particularly as a photo solder resist for printed wiring boards, heat resistance, chemical resistance, stability over time, etc. are excellent, and adhesion to a substrate is good, and Provided are a heat-resistant photosensitive resin composition having less bleeding and soluble in an alkaline aqueous solution, and a photosensitive dry film using the same.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of a photosensitive dry film of the present invention.

FIG. 2 is an explanatory diagram showing resist pattern formation using the photosensitive dry film of FIG.

[Explanation of symbols]

1 support 2 Water-soluble resin layer 3 Heat-resistant photosensitive resin layer (photo solder resist layer) 4 Protective material layer 5 substrates 6 Negative mask 7 UV 8 Photo solder resist pattern 10 Photosensitive dry film

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-173330 (JP, A) JP-A-5-53319 (JP, A) JP-A-59-165048 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03F 7/004 512 G03F 7/027 G03F 7/038 H05K 3/28

Claims (2)

(57) [Claims] 1. (a) The following (a-1) and (a-2)
Deferred method: (a-1) Carboxyl group-containing unsaturated monomer and ethylene
Form a copolymer with a system unsaturated double bond-containing monomer.
This is used as a raw material polymer, and carboxy in the raw material polymer
Reaction with an unsaturated monomer containing a glycidyl group,
Acryloyl group or methacryloyl group in the polymer
Method of addition, (a-2) glycidyl group-containing unsaturated monomer and ethylene
Forming a copolymer with an unsaturated double bond-containing monomer
As a raw material polymer, and a glycidyl group in the raw material polymer
By reacting a carboxyl group-containing unsaturated monomer with
Add acryloyl or methacryloyl group to polymer
The acryloyl group or methacryloyl group added by the method of adding , and having a weight average molecular weight of 5,000 to 80,000.
0, a binder polymer having an acid value of 30 to 160,
(B) An acid value of 30 to 100 and an epoxy equivalent of 1.00 obtained by reacting an epoxy resin with a carboxyl group-containing unsaturated monomer and reacting the obtained reaction product with an acid anhydride.
An unsaturated double bond-containing epoxy resin of 0 to 9,000 (g / epoxy group 1 mole), (c) a photopolymerizable monomer, and (d) a photopolymerization initiator, Heat-resistant photosensitive resin composition. 2. A heat-resistant photosensitive resin composition according to claim 1, which is a photosensitive dry film obtained by laminating a photosolder resist layer, a water-soluble resin layer, and a protective material layer on a support. A photosensitive dry film formed by using a material.