JP3391896B2 - Heat resistant photosensitive resin composition - 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, and in particular, it has excellent long-term storage stability as a photo solder resist for printed wiring boards, and also has excellent solder heat resistance, chemical resistance, electrical insulation and the like. , A heat-resistant photosensitive resin composition developable with a dilute alkaline solution.

[0002]

2. Description of the Related Art A photo solder resist pattern used in a printed wiring board manufacturing process has conventionally been formed by a screen printing method. However, when printing, phenomena such as bleeding, bleeding, or sagging occur, so
It has not been possible to meet the demands in the field of highly integrated electronic devices in recent years, and recently, fine patterns have been formed by photolithography.

In the photolithography method, a liquid photosensitive resin composition is applied onto a substrate such as paper-glass, paper-phenol resin, glass-epoxy resin or the like on which a copper foil has been laminated in advance, or a photosensitive film in the form of a dry film. The desired film is formed by thermocompression-bonding a conductive film, selectively irradiating it with an active energy ray such as ultraviolet rays through a negative mask, and developing it.

The photosensitive resin composition used for the photo solder resist is required to have excellent heat resistance, chemical resistance, electrical insulation, long-term storage stability, etc., and to be able to be formed into a dry film. Further, from the viewpoints of recent environmental problems, protection of the human body from toxic substances, and the like, it is preferable that development can be performed with a dilute alkaline solution.

Therefore, in order to satisfy these conditions, for example, a reaction product obtained by reacting a novolac type epoxy resin with an unsaturated monocarboxylic acid and further reacting with a saturated or unsaturated polybasic acid anhydride A solder resist ink composed of a polymerization initiator, a diluent and an epoxy resin (Japanese Patent Laid-Open No. 61-243869) and a reaction product of a novolac type epoxy resin and an unsaturated monocarboxylic acid in the components of the solder resist ink are used. Solder resist ink obtained by adding an epoxy curing agent instead of a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group (JP-A-3-71137).
Have been developed, but all of them are difficult to store for a long period of time, and in the summer when the temperature is relatively high, they may be transformed into a gel and become unusable in a short period of time.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object of the present invention is to develop a dilute alkaline solution as a photo solder resist for printed wiring boards and to obtain a heat-resistant material. It is to provide a heat-resistant photosensitive resin composition which has excellent properties, chemical resistance, and electrical insulation properties, does not cause performance deterioration even when formed into a dry film, and is particularly excellent in long-term storage stability.

[0007]

[Means for Solving the Problems] As a result of intensive studies for solving the problems, the present inventors have epoxidized a hydroxyl group of a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group. By reacting with an unsaturated monocarboxylic acid, a compound obtained by further reacting this with a polybasic acid anhydride, and by combining an alicyclic epoxy resin, it was found that the above problems can be solved, The invention was completed.

That is, the present invention provides (a) general formula (I)

[0009]

[Chemical 8] (In the formula, R represents —H, —CH ₃ or —CH ₂ CH ₃ ; n represents an integer of 1 or more), and the glycidyloxy group of the epoxy resin is represented by the general formula (II). Group and group represented by general formula (III)

[0010]

[Chemical 9]

[0011]

[Chemical 10] {In the formula, R ₁ is

[0012]

[Chemical 11] (R ₅ represents an alkyl group having 1 to 3 carbon atoms); R
₂ is

[0013]

[Chemical 12] And a modified epoxy resin substituted with (b)
An ethylene-based monomer, (c) a photopolymerization initiator, and (d)
The present invention provides a heat-resistant photosensitive resin composition containing an alicyclic epoxy resin and, if necessary, further containing (e) an epoxy curing agent.

The heat-resistant photosensitive resin composition of the present invention will be described in detail below.

The modified epoxy resin as the component (a) is
For example, the glycidyloxy group of the epoxy resin represented by the general formula (I) is reacted with an unsaturated monocarboxylic acid to replace the glycidyloxy group with the group represented by the general formula (II), and the polybasic acid By reacting an anhydride, the compound of the general formula (I
It can be obtained, for example, by further substituting the group substituted with I) with the general formula (III), but is not limited thereto. Here, "substituting with a group represented by the general formula (II) and a group represented by the general formula (III)" means, for example, when the above reaction is taken as an example, substitution at a mid-stage in the reaction process, It is meant to include all permutations.

The epoxy resin represented by the above general formula (I) can be prepared by a known method (Japanese Patent Application Laid-Open No. 57-141419).
Etc.), for example, phenols such as phenol, o-cresol, m-cresol, p-cresol, and 2-ethylphenol, and an aromatic aldehyde having a phenolic hydroxyl group (eg, hydroxybenzaldehyde, salicylaldehyde). , Etc.) with epichlorohydrin. As the unsaturated monocarboxylic acid, acrylic acid,
Examples thereof include methacrylic acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate and the like.

Photopolymerizability is imparted to the epoxy resin by the reaction of the glycidyloxy group of the epoxy resin and the unsaturated monocarboxylic acid. At this time, secondary and tertiary salts such as diethylamine acetate, diethylamine hydrochloride and triethylamine may be used as the esterification catalyst. In this reaction, it is preferable to react the unsaturated monocarboxylic acid in an amount of 0.7 to 1.1 mol, more preferably 0.9 to 1.1 mol with respect to 1 mol of the glycidyloxy group of the epoxy resin. . If it is less than 0.7 mol, the residual glycidyloxy group is excessively large and the storage stability becomes poor. on the other hand,
If it exceeds 1.1 mol, unsaturated groups derived from unsaturated monocarboxylic acid will increase in the resin, impairing the resist performance as a photo solder resist. In this reaction, the glycidyloxy group is opened and a hydroxyl group is added.

Next, a polybasic acid anhydride is reacted with the hydroxyl group by the above-mentioned glycidyloxy ring-opening of the reaction product thus obtained to adjust the acid value, and the component (a) which can be developed in a dilute alkaline solution. To obtain a modified epoxy resin.
As the polybasic acid anhydride, phthalic anhydride, dihydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride and the like can be used. These may be used alone or in combination of two or more. In this reaction,
0.2 to 1 mol of polybasic acid anhydride per 1 mol of glycidyloxy group of the epoxy resin represented by the general formula (I),
More preferably, the reaction is carried out under the reaction condition of 0.3 to 0.8 mol. If it is less than 0.2 mol, it becomes difficult to develop with a dilute alkali solution, while if it exceeds 1 mol, it is overdeveloped in a dilute alkali solution and the undercut becomes large.

Thus, the glycidyloxy group of the epoxy resin represented by the general formula (I) is changed to the above general formula (II).
A modified epoxy resin as the component (a) substituted with the group represented by and the group represented by the general formula (III) is obtained. Here, 70% or more of the glycidyloxy group is preferably substituted, which can be advantageously obtained by carrying out the reaction under each of the suitable reaction conditions described above.

The modified epoxy resin as the component (a) is 5 to 90 parts by weight, more preferably 10 to 100 parts by weight of the total of 100 parts by weight of the component (a) and the components (b) and (d) described below. It is mixed in a ratio of 80 parts by weight.

The ethylene-based monomer as the component (b) is contained in the composition in order to increase the cross-linking efficiency and heat resistance. As such an ethylene-based monomer,
For example, 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, 2 -Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol Acrylate, glycerol methacrylate, dipentaerythritol trihydroxymethacrylate , Dipentaerythritol trihydroxy 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 Acme Related, ε-
Caprolactone-modified tetrafurfuryl methacrylate,
Monofunctional monomers such as diethylene glycol ethoxy acrylate, isodecyl acrylate, isodecyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate and glycidyl methacrylate, 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 Recall dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,
1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxy diacrylate, 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- It may be used polyfunctional monomers such as Tan diol dimethacrylate. These may be used alone or in combination of two or more.

The melamine acrylate obtained by reacting 1 mol of hexamethoxymethyl melamine with 1 mol or more of hydroxyalkyl acrylate or hydroxyalkyl methacrylate may be adjusted to 1 to 6 acrylates by adjusting the reaction molar ratio. It is possible to appropriately select and use these. Such a melamine acrylate, after converting from melamine to hexamethylolmelamine to hexamethoxymelamine,
It can be obtained by reacting with hydroxyalkyl acrylate or hydroxyalkyl methacrylate such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate. This melamine acrylate is further crosslinked and cured by heating when the methylol group remains in the melamine acrylate molecule even after photopolymerization by ultraviolet irradiation, so that the heat resistance can be further improved.

The ethylene-based monomer as the component (b) is 5 to 90 parts by weight, more preferably 10 parts by weight based on 100 parts by weight of the total of the component (a), the component (b) and the component (d) described later. It is compounded in a ratio of -80 parts by weight.

Any conventionally known photopolymerization initiator may be used as the component (c). Specifically, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 3,3′-dimethyl-4-methoxy-benzophenone and other benzophenone derivatives; anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, te
Anthraquinone derivatives such as rt-butylanthraquinone; Benzoin alkyl ether derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether; acetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxyacetophenone, 2-hydroxy-
2-methylpropiophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone and other acetophenone derivatives; 2-
Thioxanthone derivatives such as chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, diisopropylthioxanthone; 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, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenyl Sulfone, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like can be used. Among these,
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one is preferably used because undercutting of a pattern hardly occurs during exposure and development.

The photopolymerization initiator as the component (c) is
The component (a), the component (b), and the component (d) described below are added in an amount of 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight in total.

Examples of the alicyclic epoxy resin as the component (d) include those represented by the general formula (IV)

[0027]

[Chemical 13] (In the formula, R represents —H or an alkyl group having a straight chain or a side chain having 1 to 5 carbon atoms; n represents an integer of 1 to 30), or a general formula (V).

[0028]

[Chemical 14] (In the formula, R represents —H or an alkyl group having 1 to 5 carbon atoms and having a straight chain or a side chain; n represents an integer of 1 to 30), or A compound obtained by polymerizing at least one selected from the monomers having the structural formula of 29 with the monofunctional monomer represented by the component (b) may also be used.

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

[0035]

[Chemical 21]

[0036]

[Chemical formula 22]

[0037]

[Chemical formula 23]

[0038]

[Chemical formula 24]

[0039]

[Chemical 25]

[0040]

[Chemical formula 26]

[0041]

[Chemical 27]

[0042]

[Chemical 28]

[0043]

[Chemical 29] (In the above Chemical Formulas 15 to 29, R ₁ represents —H or —CH ₃ ; R ₂ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms; R ₃ represents 1 to 10 carbon atoms. Represents a divalent hydrocarbon group; m represents an integer of 1 to 10) In the above Chemical Formulas 15 to 29, R ₂ is, for example, a methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene group. Examples thereof include linear or branched alkylene groups and the like. R ₃ is, for example, methylene, ethylene,
Propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene,

[0044]

[Chemical 30] Etc. can be mentioned.

As the alicyclic epoxy resin as the component (d), the alicyclic epoxy resin represented by the general formula (IV) or (V) among the above is the glass after the photocuring of the composition of the present invention. It is preferably used because it has a high transition point and is excellent in heat resistance, transparency and electric characteristics.

In the present invention, by combining the above-mentioned component (a) and this component (d), the polymerization initiation reaction can be started only after irradiation with ultraviolet rays, so that a fine pattern is formed at the time of resist pattern formation. Therefore, even if pre-drying before development is carried out for a sufficient time, it does not become gelled and excellent long-term storage stability is obtained.

The alicyclic epoxy resin as the component (d) is preferably 5 to 80 parts by weight in 100 parts by weight of the total of the components (a) and (b) and the component (d).
It is blended in a proportion of 0 to 75 parts by weight. If the amount is less than 5 parts by weight, the crosslinked structure is not sufficiently obtained and the heat resistance is deteriorated.
If it exceeds 0 parts by weight, the developing speed will be poor.

In the present invention, the above components (a) to (d) include
Furthermore, (e) an epoxy curing agent can be suitably added, which can further improve the thermosetting property of the component (d). Examples of the epoxy curing agent include dicyandiamide and its derivatives (eg, phenylpiguanide); organic acid hydrazides (eg, adipic acid hydrazide); urea, melamine and their derivatives (eg, diallylmelamine); imidazole compounds (For example, 2-ethyl-4-methylimidazole, 1-
Cyanoethyl-2-ethyl-4-methylimidazole,
2,4-diamino-6- (2'-methylimidazole-
1) -Ethyl-S-triazine, 2,4-diamino-6
-(2'-Methylimidazolyl-1) -ethyl-S-triazine / isocyanuric acid adduct, 2-methylimidazole, 1-phenyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. ); Triazine compounds (for example, 2,4-diamino-6-vinyl-S-triazine / isocyanuric acid adduct, 2-vinyl-4,6-diamino-S-triazine,
2-methoxyethyl-4,6-diamino-S-triazine and the like); urea compounds (for example, 3- (3,4-dichlorophenyl) -1,1′-dimethylurea, 1,1′-isophorone-bis (3-) Methyl-3-hydroxyethylurea), 1,1′-tolylene-bis (3,3-dimethylurea), etc .; aromatic amine compounds (eg 4,4′-
Diamino-diphenylmethane etc.); Aliphatic amine compounds (eg diethylenetriamine etc.); Polyphenol compounds (eg polyvinylphenol, phenol novolac etc.); Organic acid phosphine compounds (eg tributylphosphine, triphenylphosphine etc.) and cationic photopolymerization catalysts (For example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylselenium hexafluorophosphate, triphenylselenium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, 2,4- Cyclopentadiene-1-yl ((1-methylethyl) -benzene) -Fe- Kisa hexafluorophosphate (manufactured by Ciba-Geigy Corporation; Irgacure 261). And the like can be given These may be used in combination of two or more kinds may be used in combination.

When these epoxy curing agents are added, the total amount of the above components (a), (b) and (d) is 100.
0.01 to 20 parts by weight, preferably 0.
It can be contained in a mixing ratio of 1 to 10 parts by weight.

Further, in the present invention, other components can be added if necessary. Such ingredients include:
First, a tackiness improver can be mentioned. This is preferably a compound that is solid at room temperature and is soluble in alkali and polymerizes or crosslinks by light or heat. For example, a copolymer of a compound having a carboxyl group and an N-alkoxyacrylamide group, or a copolymer of styrene and maleic anhydride. It is possible to use a compound obtained by reacting a substance with hydroxyethyl methacrylate.

Further, silicone-based or fluorine-based antifoaming 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 diameter of about 0.001 to 10 μm, talc, barium sulfate, calcium carbonate, clay, hydrous silicic acid, aluminum hydroxide, aluminum oxide, antimony trioxide, magnesium carbonate, silicic acid. Aluminum, magnesium silicate, aerosil, etc. can be added as a filler.

Furthermore, a solvent can be used to adjust the viscosity and improve the coating property. The solvent that can be used in the present invention, 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 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 pro In addition to pionate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl butyrate, ethyl butyrate, propyl butyrate, etc., "Swazol" (Maruzen Petrochemical Co., Ltd.) ),
Examples thereof include petroleum-based solvents available under the product names such as “Solvesso” (manufactured by Tonen Petrochemical Co., Ltd.), but are not limited thereto. 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. It is preferably used. These solvent components are used in an amount of 10 to 900 parts by weight based on 100 parts by weight of the photosensitive resin composition.

The heat-resistant photosensitive resin composition according to the present invention comprises
For example, after being prepared as follows, it is used as a liquid photosolder resist for a printed wiring board. (1) The above components (a) to (d), if necessary, (e)
Predetermined amounts of the components, filler, defoaming agent, etc. are added, and this is well dissolved, dispersed, and kneaded by a three-roll mill, a ball mill, a sand mill and the like. (2) The heat-resistant photosensitive resin composition thus prepared is applied onto a substrate (glass fiber + epoxy resin laminate, etc.) on which copper foil is laminated. The application is preferably performed by screen printing, a roll coater, a reverse coater, a spinner, a curtain flow coater, an applicator or the like.
After coating, the coating film 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. (3) Exposure treatment Next, exposure is performed through a negative mask having a predetermined pattern. The amount of UV energy applied to the heat-resistant photosensitive resin composition of the present invention is slightly different depending on the composition.
It is preferably about 000 mJ / cm ² . (4) Development processing After exposure, development is performed by a spray gun, a dipping method or the like.
As the developing solution, organic ones such as monoethanolamine, diethanolamine and triethanolamine and alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salt are preferably used. After the exposure, the unexposed portion of the coating film is dissolved and removed to obtain a resist pattern. (5) Post-exposure heat treatment By leaving the obtained resist pattern at 100 to 200 ° C for several tens of minutes to several hours, the glycidyloxy group is subjected to ring-opening polymerization to improve the crosslinking density of the crosslinking agent.

In this way, the printed wiring board on which the desired fine resist pattern is formed can be obtained.

When the heat-resistant photosensitive resin composition of the present invention is used as a photosensitive dry film, the heat-resistant photosensitive resin composition prepared in the above (1) is placed on a plastic film support such as polyethylene or polyethylene terephthalate. Then, using a bar coater, a roll coater, a reverse coater, an electrostatic coating machine, a spinner, an applicator or the like, the film thickness after drying is 1 to 200 μm, preferably 10 to 100 μm.
To form a photosensitive layer by coating and drying to a thickness of μm, a plastic film such as polyethylene or polyethylene terephthalate with a thickness of 20μ is used for long-term storage.
As a protective layer of about m, it is laminated on the photosensitive layer and wound in a roll to form a dry film. In order to improve the adhesion to the negative mask during exposure, the support may be matted or a mat layer may be provided between the support and the photosensitive layer.

When this photosensitive dry film is used, first, the protective layer (plastic film) is peeled off from the dry film, the photosensitive layer is laminated on the substrate and laminated, and then the support is peeled off from the photosensitive layer. (3)
A photo solder resist pattern can be obtained by following the steps (5) to (5).

Examples of the present invention will be described below, but the present invention is not limited thereto.

[0058]

Example A heat-resistant photosensitive resin composition was prepared according to the composition shown in Tables 1 and 2 below.

[0059]

[Table 1]

[0060]

[Table 2] The compounds having the trade names in Tables 1 and 2 are as follows. KAYARAD TCR-1025: Reaction product of trisphenol type epoxy acrylate and dibasic acid anhydride (acid value 103mgKOH / g) (Nippon Kayaku Co., Ltd.) * Note 1) KAYARAD CCR-1028: Cresol novolac type epoxy Reaction product of acrylate and di-salt-based acid anhydride (acid value 106mgKOH / g) (Nippon Kayaku Co., Ltd.) * Note 1) KAYARAD PCR-1005: Phenol novolac type epoxy acrylate and di-salt-based acid anhydride Reaction product with (acid value 103mgKOH / g) (Nippon Kayaku Co., Ltd.) * Note 1) SP-4010: Phenol novolac type epoxy acrylate (Showa Polymer Co., Ltd.) * Note 2) KAYARAD R -931: 2-hydroxyethyl acrylate adduct of styrene-maleic acid resin (acid value 188 mgKOH / g) (manufactured by Nippon Kayaku Co., Ltd.) * Note 1) Methyl methacrylate / acrylic acid copolymer (average molecular weight about 60,000) ) Tylene / Methyl methacrylate / Acrylic acid / Butyl acrylate copolymer (Average molecular weight about 40,000) Phenoxyethyl acrylate EHPE-3150: Alicyclic epoxy resin (manufactured by Daicel Chemical Industries, Ltd.) CYRACURE UVR-6100: Alicyclic epoxy resin (UCC Co., Ltd.) CYRACURE UVR-6110: Alicyclic epoxy resin (UCC Co., Ltd.) EPICRON N-695: Cresol novolac type epoxy resin (Dainippon Ink and Chemicals, Inc. ) EPPN-201: Phenol novolac type epoxy resin (Nippon Kayaku Co., Ltd.) EPIKOTE 1001: Bisphenol A type epoxy resin (Yukaka Shell Co., Ltd.) TEPIC SP: Tris (2,3-epoxypropyl) Isocyanurate (Nissan Chemical Co., Ltd.) KAYARAD DPHA: Dipentaerythritol Polyacrylate (Nippon Kayaku Co., Ltd.) NK ESTER TMPT: Trimethylolpropane Remethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) TONE 0301: Polyol resin (manufactured by UCC Co., Ltd.) DPM: Dipropylene glycol monomethyl ether (manufactured by Dow Chemical Co., Ltd.) Diethylene glycol monoethyl ether acetate: Solvent SWASOL 1500: Solvent naphtha (manufactured by Maruzen Petrochemical Co., Ltd.) IRGACURE 369: Photopolymerization initiator (manufactured by Ciba Geigy) IRGACURE 907: Photopolymerization initiator (manufactured by Ciba Geigy) KAYACURE DETX: Photopolymerization initiator (manufactured by Ciba Geigy) Nippon Kayaku Co., Ltd. KAYACURE EPA: Photopolymerization initiator (Nippon Kayaku Co., Ltd.) CYRACURE UVI-6974: Photocationic polymerization catalyst (U. C. C. CYRACURE UVI-6990: Cationic photopolymerization catalyst (manufactured by UCC Co., Ltd.) Dicyandiamide: Epoxy curing agent melamine: Epoxy curing agent KS-66: Defoaming agent (Shin-Etsu Chemical Co., Ltd.) Phthalocyanine green: Coloring pigment Talc: Body pigment barium sulfate: Body pigment * Note 1) "KAYARAD TCR-1025", "KAYARAD CCR-1028", "KAYARAD PCR-10 05" and "KAYARAD R-931" are respectively 24.5 parts by weight of diethylene glycol monoethyl ether acetate and 100 parts by weight of "SWASOL 1500" in 100 parts by weight of the product. Contains 5 parts by weight. ** Note 2) "SP-4010" contains 30 parts by weight of diethylene glycol monoethyl ether acetate in 100 parts by weight of the product. Coating Treatment For Examples 1 to 5 and Comparative Examples 1 to 6, the compounding ingredients were 3
After kneading with this roll mill, by screen printing method,
The copper through-hole printed wiring board was applied over the entire surface so that the film thickness after drying was 15 to 25 μm, and the coating film was pre-dried (80 ° C., 30 minutes, or 80 ° C., 60 minutes).
The back side was similarly printed and pre-dried.

In Example 6 and Comparative Example 7, the ingredients were kneaded in a three-roll mill and then the thickness was 0.025 mm.
On a support (polyethylene terephthalate film) of No. 2 by a bar coater so that the film thickness after drying becomes 40 μm, and the coating film is pre-dried (80 ° C., 30 minutes, or 8
(0 ° C., 60 minutes) to form a photosensitive layer, and further laminate a 0.016 mm-thick polyethylene film thereon,
A photosensitive dry film was prepared. Next, the protective layer was peeled off, the photosensitive layer was thermocompression-bonded onto the copper through-hole printed wiring board using a laminator, and then the support was peeled off.

The thus obtained product was evaluated for "dryness to the touch" as described below.
~ 4.

Exposure-Development Treatment Next, a negative mask having a predetermined pattern was brought into contact with the surface of the coating film, and 600 mJ / cm ^{2 was} applied on the Mylar film using a double-side simultaneous exposure device for ultra-high pressure mercury lamp (manufactured by Hitec Co., Ltd .; HTE 102S). Exposure with the light amount of 1.0 wt%
The unirradiated portion of the coating film was developed with the above sodium carbonate aqueous solution at a spray pressure of 2.0 kg / cm ² and a liquid temperature of 30 ° C. for a predetermined time until the unexposed portion was completely removed. The obtained product was evaluated for [developing property], [undercut] and [exposure sensitivity] as described below. The results are shown in Table 3 ~
4 shows.

Post-exposure heat treatment Then, heat curing is carried out at 150 ° C. for 60 minutes with a hot air dryer,
Regarding the test piece having the obtained thermosetting film (photo solder resist pattern), as described below, [coating hardness], [solder heat resistance], [electroless gold plating resistance], [alkali resistance] and [insulation resistance] An evaluation was made. The results are shown in Table 3 ~
4 shows.

Test method and evaluation method [Finger dryness] After being left to cool for 10 minutes, the dryness of the coating film was measured by JIS.
It was determined according to K 5400.

⊚: No tack was observed at all ○: Slight tack was observed ×: Remarkably tack was observed [Developability] Development time of unexposed area (break point; unexposed area was completely removed) The time until removal) was measured. The samples of Comparative Examples 1 to 6 which had been pre-dried at 80 ° C. for 60 minutes were developed for 100 seconds, but gelled during the development and could not be developed. [Undercut] The undercut was judged by observing a cross-sectional photograph of the edge portion of the coating film after development.

○: Less undercut △: Undercut is noticeable ×: Undercut is noticeable [Exposure sensitivity] Stouffer Gray Scales (Stouffer Graphic
A negative film made of Arts and having 21 steps with an optical density of 0.15) is adhered to the coating film obtained by predrying the both sides, and 600 mJ / cm ² using a 5 kW ultra-high pressure mercury lamp.
The amount of light (on mylar film) was applied. This coating film was developed under the above conditions, and the number of steps remaining on the copper foil was examined. [Coating film hardness] The hardness of the coating film was measured and evaluated according to JIS K 5400. [Solder Heat Resistance] According to the test method of JIS C 6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds 5 times or 4 times as described below, and the change in appearance was evaluated. (Post-flux resistance) Immersion was performed 5 times for 10 seconds to evaluate the change in appearance.

○: No change in appearance ×: Floating, peeling, solder slipping of coating film Note) Post flux used: JIS-64P (manufactured by Sanei Chemical Co., Ltd.) (flux resistance for levelers) 10 seconds immersion Do 4 times,
The change in appearance was evaluated.

○: No change in appearance ×: Floating, peeling, solder slipping of the coating film Note) Flux for leveler used: W-2304 (manufactured by Mec Co., Ltd.) [Electroless gold plating resistance] No nickel on the test piece Electrolytic plating (in Top-Nicolon N-47 at 90 ° C. for 20 minutes) was performed, and then using “Muden Gold” manufactured by Okuno Chemical Industries Co., Ltd., plating was performed at a liquid temperature of 90 ° C. for 10 minutes. After depositing 1 μm thick gold plating, the appearance change of the coating film was visually observed. For the adhesiveness, a peeling test was performed on the solder resist pattern portion with cellophane tape to determine the peeled state of the resist.

◯: No change in appearance and no peeling of the coating film ×: [Alkali resistance] test piece showing floating coating film was immersed in 10 vol /% sodium hydroxide aqueous solution at 25 ° C. for 15 minutes, The state of the coating film was evaluated in the same manner as in the electrolytic gold plating resistance test.

◯: There is no change in appearance and there is almost no film loss of the coating film. X: The film loss is severe and the film is not suitable for use. [Insulation resistance] Using a test piece, IPC-SM-840B
Insulation resistance after 7 days of moisture absorption and electrolytic corrosion was measured according to the test method (IPC class III) of.

[0072]

[Table 3]

[0073]

[Table 4] As is clear from Tables 3 and 4, the heat-resistant photosensitive resin composition of the present invention was subjected to preliminary drying at 80% in the evaluation of developability.
Gelation does not occur even at 60 ° C. for 60 minutes, and the developability (long-term storability) is extremely excellent as compared with Comparative Examples.
Further, it can be seen that it is excellent in any other characteristics such as heat resistance and chemical resistance.

[0074]

As described above in detail, according to the present invention, a heat resistance feeling which can be developed with a dilute alkaline solution is excellent as a photo solder resist for a printed wiring board and has excellent long-term storage stability, heat resistance, chemical resistance and the like. A light-sensitive resin composition is provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03F 7/031 G03F 7/031 7/032 501 501/03/03 501 H05K 3/06 H05K 3/06 H 3/28 3/28 D (56) References JP-A-6-93221 (JP, A) JP-A-6-166843 (JP, A) JP-A-6-107831 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) G03F 7/038 503 G03F 7/027 515 G03F 7/031 G03F 7/032 501 C08G 59/20 C08G 59/40 C08L 63/00 H05K 3/06 H05K 3/28

Claims (8)

(57) [Claims] 1. (a) General formula (I): (In the formula, R represents —H, —CH ₃ or —CH ₂ CH ₃ ; n represents an integer of 1 or more), and the glycidyloxy group of the epoxy resin is represented by the general formula (II). A group and a group represented by the general formula (III): [Chemical 3] {In the formula, R ₁ is (R ₅ represents an alkyl group having 1 to 3 carbon atoms); R
₂ is [Chemical 5] And a modified epoxy resin substituted with (b)
An ethylene-based monomer, (c) a photopolymerization initiator, and (d)
An alicyclic epoxy resin is contained, The heat-resistant photosensitive resin composition characterized by the above-mentioned. 2. The heat-resistant photosensitive resin composition according to claim 1, further comprising (e) an epoxy curing agent. 3. In the (a) modified epoxy resin, 70% or more of the glycidyloxy groups of the epoxy resin represented by the general formula (I) are the group represented by the general formula (II) and the general formula (III). 3. The heat-resistant photosensitive resin composition according to claim 1, wherein the heat-resistant photosensitive resin composition is substituted with a group represented by 4. The (a) modified epoxy resin is obtained by reacting an epoxy resin represented by the general formula (I) with an unsaturated monocarboxylic acid, and the resulting reaction product is added with 1 mol of a glycidyloxy group of the epoxy resin. The heat-resistant photosensitive resin composition according to any one of claims 1 to 3, which is produced by reacting 0.2 to 1 mol of a polybasic acid anhydride. 5. The method according to claim 1, wherein the photopolymerization initiator (c) is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one. The heat-resistant photosensitive resin composition according to any one of 1. 6. A total of 100 parts by weight of the (a) modified epoxy resin, (b) ethylene-based monomer and (d) alicyclic epoxy resin, and (d) alicyclic epoxy resin in an amount of 5 to 8
The heat-resistant photosensitive resin composition according to claim 1, wherein the heat-resistant photosensitive resin composition is contained in an amount of 0 part by weight. 7. The alicyclic epoxy resin (d) has the general formula (IV): (In the formula, R represents —H or an alkyl group having a straight chain or a side chain having 1 to 5 carbon atoms; n represents an integer of 1 to 30). The heat-resistant photosensitive resin composition according to any one of 1 to 6. 8. The alicyclic epoxy resin (d) has the general formula (V): (In the formula, R represents —H or an alkyl group having a straight chain or a side chain having 1 to 5 carbon atoms; n represents an integer of 1 to 30). The heat-resistant photosensitive resin composition according to any one of 1 to 6.