JPH11174676A - Resist composition for printed wiring board, and manufacture of printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the resist composition excellent in liquid stability, dilutable with water excellent in chemical resistance, heat resistance and galvanic corrosion resistance with heating after the development by including a polymerizable unsaturated group, a carboxyl group, a specified photo-polymerizable resin, photo-polymerization initiator and the oxazoline group-containing compound. SOLUTION: This composition contains a photo-polymerizable resin (A) containing a polymerizabule unsaturated group and a carboxyl group obtained by neutralizing a part or the whole of the carboxyl group with an amine compound; a photo-polymerization initiator, and the oxazoline group-containing compound. The resin (A) is obtained by neutralizing the polymerizable unsaturated resin formed by adding a compound having a polymerizable unsaturated group and a glycidyl group or the like in one molecule to a high acid number acrylic resin with the amine compound, and an equivalent of unsaturation of 100-5000. A well-known photo-polymerization initiator is used, and the blended variable at 0.1-10 wt.% in relation to the resin (A) is desirable. As an oxazoline group-containing compound, 2,2'-bis(2-oxazoline) or the like is used, and preferably blended at 0.3-2.0 of equivalent in relation to one equivalent of the carboxyl group of the resin (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resist composition for a printed wiring board and a method for manufacturing a printed wiring board using the same. The resist composition of the present invention can be used for a solder resist, an etching resist, a plating resist, an interlayer insulating material and the like.

[0002]

2. Description of the Related Art Conventionally, in the production of printed wiring boards, a method of forming a pattern by a photographic method has been widely used. Among these methods, the method using a dilute alkali developing type or water developing type photoresist has problems such as toxicity to the human body, environmental pollution and fire danger, compared with the method using an organic solvent developing type photoresist. It has the advantage of being small. Therefore, for example, a photoresist that can be developed with a diluted alkali using a resin having a carboxyl group has been proposed. For example, JP
Japanese Patent Application Laid-Open No. 1-243869 discloses an active energy ray-curable resin obtained by reacting a novolak type epoxy compound with an unsaturated monocarboxylic acid and adding an acid anhydride to a generated hydroxyl group, a photopolymerization initiator, a diluent, and an epoxy compound. A photocurable and thermosetting liquid resist ink composition comprising: Japanese Unexamined Patent Publication No. 6-324490 discloses an unsaturated group-containing poly obtained by reacting a polyvalent epoxy compound with an unsaturated monocarboxylic acid and a polyvalent hydroxyl group-containing monocarboxylic acid compound and adding an acid anhydride to the hydroxyl group. A resist ink composition comprising a carboxylic acid resin, a photopolymerization initiator, a diluent, and a curing component is disclosed. These compositions are:
Although the performance as a solder resist is satisfactory, the two-pack type is the mainstream, and the pot life after mixing is as short as several hours to one day. In addition, when performing electrostatic spray coating or curtain coating, it cannot be diluted with water. In addition, there is a problem that the method has to be diluted with a large amount of an organic solvent, and there are problems such as coating workability, environmental pollution and fire risk.

As a water-dilutable photo solder resist, JP-A-5-202330 discloses a photosensitive resin having an unsaturated group and a carboxyl group neutralized with an amine compound in one molecule, a photopolymerizable monomer, A photocurable and thermosetting solder resist ink composition comprising a photopolymerization initiator, an amino resin and a diluent is disclosed.
In this case, since an amino resin is used as an auxiliary cross-linking agent, there is a concern that a catalyst used in the production process may be mixed into the resist ink composition as ionic contaminants, adversely affecting the electrolytic corrosion.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to obtain a resist composition for a printed wiring board without the above-mentioned problems, and as a result, the carboxyl group was neutralized with an amine compound. By using a photopolymerizable resin and an oxazoline group-containing compound, it is excellent in one-pack stability and can be diluted with water, and can be developed with water or dilute alkaline water. After development, the carboxyl group and oxazoline group are heated. Reacted to obtain a crosslinked coating film, and found that this crosslinked coating film had excellent properties such as chemical resistance, heat resistance, and electrolytic corrosion resistance, and completed the present invention.

[0005] Thus, according to the present invention, (a) a photopolymerizable resin containing a polymerizable unsaturated group and a carboxyl group, wherein a part or all of the carboxyl group is neutralized with an amine compound; A resist composition for a printed wiring board comprising a photopolymerization initiator and (c) an oxazoline group-containing compound, and a method for manufacturing a printed wiring board using the same are provided.

Hereinafter, the present invention will be described in more detail.

The photopolymerizable resin used in the resist composition for a printed wiring board of the present invention includes the following (1) to
A resin selected from the group (6) is neutralized with an amine compound.

(1) A polymerizable unsaturated resin obtained by adding a compound having a polymerizable unsaturated group and a glycidyl group or an alicyclic epoxy group in one molecule to a high acid value acrylic resin;
Examples of the polymerizable unsaturated resin include glycidyl (meth) acrylate, a high acid value acrylic resin obtained by copolymerizing acrylic acid, methacrylic acid, and the like with another copolymerizable monomer.
Examples thereof include compounds obtained by adding a compound having a polymerizable unsaturated group and a glycidyl group to one molecule, such as 3,4-epoxycyclohexylmethyl (meth) acrylate.

(2) A resin obtained by adding a compound having a polymerizable unsaturated group and a carboxyl group in one molecule to an acrylic resin having a glycidyl group, and then adding a dibasic anhydride to the resulting hydroxyl group; Examples of the polymerizable unsaturated resin include an acrylic resin obtained by copolymerizing glycidyl (meth) acrylate and other copolymerizable monomers with (meth)
After adding a compound having a polymerizable unsaturated group and a carboxyl group in one molecule such as acrylic acid, the resulting hydroxyl group is treated with a dihydric anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and succinic anhydride. A resin obtained by half-esterifying a basic acid can be used.

(3) A resin obtained by adding a compound having a polymerizable unsaturated group and a carboxyl group in one molecule to an epoxy resin and then adding a dibasic anhydride to the resulting hydroxyl group; As the resin, bisphenol A
(Or F) type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin, alicyclic epoxy group-containing resin, etc. have a polymerizable unsaturated group and a carboxyl group in one molecule such as (meth) acrylic acid After addition of the compound, a resin obtained by half-esterifying a dibasic anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and succinic anhydride to the generated hydroxyl group can be used.

(4) a polymerizable unsaturated resin obtained by adding a compound having a polymerizable unsaturated group and a glycidyl group or an alicyclic epoxy group in one molecule to a high acid value polyester;
As the polymerizable unsaturated resin, maleic anhydride, fumaric acid, dibasic acid having a polymerizable unsaturated group such as itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, Adipic acid,
Polybasic acids such as trimellitic acid and ethylene glycol,
Glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and other glycidyl group-containing non-glycidyl groups are added to high acid value polyesters obtained by condensation with polyhydric alcohols such as propylene glycol, neopentyl glycol, and trimethylolpropane. A resin to which a saturated compound is added can be given.

(5) A resin obtained by adding or condensing a compound having a polymerizable unsaturated group and a hydroxyl group in one molecule to a part of the acid of an acid-containing polyimide; Acid or carboxylic anhydride or carboxyl group of an acid-containing polyimide obtained by the reaction of a tetracarboxylic anhydride such as benzophenone tetracarboxylic anhydride with a diamine such as 4,4'-diaminodiphenylmethane, hexamethylenediamine or diaminobenzoic acid. Examples of the resin include a resin obtained by adding or condensing a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate.

(6) A resin obtained by adding a compound having a polymerizable unsaturated group and a hydroxyl group in one molecule to an isocyanate group of a polyurethane having an acid and an isocyanate group; dimethylol is a polymerizable unsaturated resin. Polyurethane having an acid and an isocyanate group added by a hydroxyl group and an isocyanate group to a compound having a hydroxyl group and an acid such as propionic acid and dimethylolbutanoic acid and an isocyanate compound such as tolylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. Examples of the resin include a resin obtained by adding a hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate or 2-hydroxypropyl acrylate to an isocyanate group.

The unsaturated equivalents of the resins (1) to (6) are 100 to 5,000, preferably 200 to 2,000.
It is. When the unsaturated equivalent is 100 or less, it is difficult to synthesize an unsaturated resin having an acid group. On the other hand, when it is more than 5,000, photocurability decreases. The acid value of these resins is 20 to 300, preferably 30 to 200. If the acid value is less than 20, water dilution and development become impossible, while if it is more than 300, the water solubility of the photocured film becomes high, and the development resistance becomes poor.

The photopolymerizable resin (a) which can be diluted with water is obtained by neutralizing the carboxyl groups of the resins (1) to (6) with an amine compound.

As the amine compound to be used, conventionally known ones can be used.
Secondary amines are difficult to use because they easily cause a Michael addition reaction with unsaturated groups. Therefore, in the present invention, it is preferable to use a tertiary amine. As the tertiary amine compound, for example, triethylamine, tributylamine, N-
Examples include, but are not limited to, methylmorpholine, dimethylethanolamine, methyldiethanolamine, triethanolamine, dimethylaminoethyl (meth) acrylate, and the like.

The amount of the neutralizing agent is 0.1 to 1 equivalent of the carboxyl group contained in the skeleton of the photopolymerizable resin (a).
To 1.2 equivalents, more preferably 0.7 to 1.0 equivalent.
The range of equivalents. If the amount of the neutralizing agent is less than 0.1 equivalent, the photopolymerizable resin (a) cannot be diluted with water, while if it is more than 1.2 equivalent, the thermal curing of the oxazoline group-containing compound with the oxazoline group is inhibited. There is a problem.

The photopolymerization initiator (b) which can be used in the present invention is a conventionally known one, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, diethoxyacetophenone, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1
-Hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butanone, 2,4
6-trimethylbenzoyldiphenylphosphine oxide, benzophenone, methyl O-benzoylbenzoate, hydroxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4
-Diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4,6-tris (trichloromethyl) -S
-Triazine, 2-methyl-4,6-bis (trichloro) -S-triazine, 2- (4-methoxyphenyl)
-4,6-bis (trichloromethyl) -S-triazine and the like.

These photopolymerization initiators may be used alone or
More than one kind can be mixed and used, and the compounding amount is preferably in the range of 0.1 to 10% by weight based on the above-mentioned photopolymerizable resin (a).

In order to accelerate the photopolymerization reaction by these photopolymerization initiators, a photosensitization accelerator may be used in combination with the photopolymerization initiator. Examples of the photosensitizer that can be used in combination include alkylphosphine compounds such as triphenylphosphine and thioether compounds such as β-thiodiglycol. Each of these photosensitizers can be used alone or in combination of two or more. The compounding amount is preferably in the range of 0.1 to 30% by weight based on the above-mentioned photopolymerizable resin (a).

The oxazoline group-containing compound (c) used in the present invention includes, for example, 2,2'-bis (2-oxazoline), 2,2'-methylene-bis (2-oxazoline), 2,2'- Ethylene-bis (2-oxazoline), 2,2'-trimethylene-bis (2-oxazoline), 2,2'-tetramethylene-bis (2-oxazoline), 2,2'-hexamethylene-bis (2- Oxazoline), 2,2'-octamethylene-bis (2-oxazoline), 2,2'-decamethylene-bis (2-oxazoline), 2,2'-p-phenylene-bis (2-oxazoline), 2, 2'-m-phenylene-bis (2-
Oxazoline), 2,2'-o-phenylene-bis (2
-Oxazoline), 2,2'-cyclohexylene-bis (2-oxazoline), 2,2'-diphenylene-bis (2-oxazoline), 2,2'-bis (4-methyl-
2-oxazoline), 2,2'-bis (4,4'-dimethyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4 '-
Diethyl-2-oxazoline), 2,2'-bis (4-
Propyl-2-oxazoline), 2,2'-bis (4-
Butyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl- 2-oxazoline), 2,2'-m-
Phenylene-bis (4-methyl-2-oxazoline),
2,2'-m-phenylene-bis (4,4'-dimethyl-2-oxazoline), bis- (2-oxazolinylcyclohexane) sulfide, bis- (2-oxazolinylnorbornane) sulfide, and the like. Can be.

Also, 2-vinyl-2-oxazoline, 2
-Vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- Homopolymers and copolymers of oxazoline group-containing unsaturated monomers such as 5-methyl-2-oxazoline can also be mentioned as oxazoline group-containing compounds.

Further, Epocross WS- manufactured by Nippon Shokubai Co., Ltd.
Polymers containing an oxazoline group such as 500, K2020E and RAS-1005 can also be mentioned.

These oxazoline group-containing compounds can be used alone or as a mixture of two or more kinds. The compounding amount thereof is 0.3 to 2.0 with respect to 1 equivalent of the carboxyl group of the photopolymerizable resin (a). The range of the equivalent is preferable, and in other ranges, the chemical resistance and heat resistance decrease.

The water-soluble or water-dispersed resist composition of the present invention is used in order to further improve its fluidity.
If necessary, a hydrophilic solvent (eg, isopropanol, n-butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol, methyl ether, dioxane, tetrahydrofuran, etc.) can be added. The amount of the hydrophilic solvent used is desirably within a range of 300 parts by weight or less based on 100 parts by weight of the photopolymerizable resin (a) component.

The resist composition of the present invention comprising the above-mentioned components (a) to (c) is added with a polymer other than the photopolymerizable resin (a) in order to improve the performance such as photocurability and mechanical strength of the cured film. It is also possible to appropriately adjust the coating film performance by blending a resin having a unsaturated group, a polymerizable unsaturated monomer or the like in a range of 100 parts by weight or less based on 100 parts by weight of the photopolymerizable resin (a).

Examples of the polymerizable unsaturated group-containing resin include a resin obtained by condensing (meth) acrylic acid with a polyester;
Examples include unsaturated group-containing polyurethane resins, unsaturated group-containing epoxy resins, unsaturated group-containing phosphorus-containing epoxy resins, unsaturated group-containing acrylic resins, unsaturated group-containing silicone resins, and unsaturated group-containing melamine resins.

As the polymerizable unsaturated monomer, as a monofunctional polymerizable monomer, for example, styrene, methyl (meth)
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Aronix M11
0 (manufactured by Toa Gosei Co., Ltd.), N-methylol (meth) acrylamide, dimethylaminoethyl (meth) acrylate,
N-vinyl-2-pyrrolidone and the like can be mentioned.

As the bifunctional polymerizable monomer, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, Kayarad HX-220,620, R-60
4, MANDA (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

As the polymerizable monomer having three or more functional groups, for example, trimethylolpropane tri (meth) acrylate,
Trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene isocyanurate Oxide-modified triacrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

Other additives include reactive resins such as color pigments, extender pigments, rust preventive pigments, dyes, thermoplastic resins, melamine / formaldehyde resins, urea / formaldehyde resins, xylene / formaldehyde resins, and isocyanate group-containing compounds. And various additives (leveling agent, antifoaming agent, anti-sagging agent, etc.). As the coloring pigment, extender pigment, rust-preventive pigment and dye, those usually used in the field of ink and paint can be used.
It can be blended in an amount of not more than 00 parts by weight, preferably not more than 200 parts by weight.

When the resin composition of the present invention is used for a solder resist or the like, a catalyst for heat curing and other additives may be added as necessary. Examples of the catalyst for thermosetting include alkali metals (such as sodium and lithium), alkaline earth metals (such as calcium and magnesium), and metals selected from nickel, copper, molybdenum, lead, iron, chromium, manganese, tin, and cobalt. Hydroxides, organic acid salts, chelate compounds, and alkoxides. Further, an onium salt such as an ammonium salt, a sulfonium salt, an oxonium salt, an iodonium salt, a phosphonium salt, a nitronium salt, a nitrosonium salt, and a diazonium salt can be used as a catalyst for promoting a crosslinking reaction between an oxazoline group and a carboxylic acid. The addition amount of these curing catalysts is preferably 10 parts by weight or less, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the photopolymerizable resin (a) component.

The thus obtained resist composition of the present invention is applied on a substrate by a usual method such as spray coating, roll coating, dip coating, silk screen printing and the like.
After the solvent is removed from the uncured coating film at a temperature of 50 to 100 ° C., actinic rays such as ultraviolet rays are irradiated through a film (photomask) having a pattern drawn on the coating film for 10 minutes.
２，2,000 mJ / cm ² , preferably 50-1,000 mJ / c
It is cured by irradiation with m ² .

As the exposure machine, those conventionally used for actinic rays such as ultraviolet rays can be used, and examples thereof include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and a metal halide lamp.

The developing treatment can be carried out by spraying water or diluted alkaline water onto the resist coating film surface to wash out the uncured portion of the coating film. As the diluted alkaline water, those which can neutralize the free carboxyl groups present in the coating film and make them water-soluble, such as sodium carbonate, caustic soda and caustic potable water, can be used. For example, in the case of a sodium carbonate aqueous solution, a concentration of 0.1 to 5% by weight is appropriate. If it is less than 0.1% by weight, development is difficult, and if it is more than 5% by weight, the image area may be undesirably damaged.

After the photocuring, the coated plate developed and treated
By performing heat treatment at 180 ° C. for 10 to 60 minutes, the amine in the coating film is desorbed to cause hydrophobicity, and at the same time, the reaction between the carboxyl group and the oxazoline group in the resin, polymerization of the remaining unsaturated group, An addition reaction between the hydroxyl group and the hydroxyl group occurs,
Since a coating film having a high crosslinking density is formed, heat resistance and chemical resistance are improved.

When the resist composition of the present invention is used to form a resist film having a pattern such as an etching resist, the uncured coating film can be developed with harmless water or a dilute alkaline aqueous solution. Can be solved. Further, the resist film obtained by the method of the present invention has excellent adhesiveness to a substrate, heat resistance, chemical resistance and impact resistance, and therefore can be used as a solder resist, a plating resist, an interlayer insulating material and the like.

[0038]

The present invention will be described more specifically with reference to the following examples. Hereinafter, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Production Example 1 of Photopolymerizable Resin 110 parts of normal butyl methacrylate, 300 parts of methyl methacrylate, 158 parts of styrene, 43 parts of acrylic acid
A mixture of 2 parts and 30 parts of α, α 'azobisisobutyronitrile was added dropwise to 700 parts of propylene glycol monomethyl ether kept at 115 ° C. over 3 hours in a nitrogen gas atmosphere. After the dropwise addition, the mixture was stirred at 115 ° C. for 3 hours (resin acid value: 327). Next, 4 parts of tetramethylammonium bromide, 497 parts of glycidyl methacrylate, and 1 part of hydroquinone were added to the resin solution, and reacted for 5 hours while blowing air (unsaturated equivalent 436, resin acid value 92). This resin solution was cooled to room temperature, 253 parts of triethylamine was added, and the mixture was stirred to obtain a resin solution A.
This resin solution could be diluted with water to an arbitrary concentration. Production Example 2 A mixture of 150 parts of normal butyl methacrylate, 150 parts of methyl methacrylate, 188 parts of styrene, 512 parts of glycidyl acrylate and 30 parts of α, α 'azobisisobutyronitrile was mixed under a nitrogen gas atmosphere under a nitrogen atmosphere.
It was added dropwise over 3 hours to 700 parts of carbitol acetate maintained at 5 ° C. After the addition, the mixture was stirred at 115 ° C. for 3 hours. Next, 4 parts of tetramethylammonium bromide, 288 parts of acrylic acid and 1 part of hydroquinone were added, and the mixture was reacted for 5 hours while blowing air. The reaction solution was further added with 608 parts of tetrahydrophthalic anhydride and reacted for 5 hours (unsaturated equivalent 482, resin acid value 117). The resin solution was cooled to room temperature, and N-methylmorpholine 404 was added.
Was added and stirred to obtain a resin liquid B. This resin solution could be diluted with water to an arbitrary concentration.

Production Example 3 In a flask equipped with a reflux condenser equipped with a water separator, 192 parts of trimellitic anhydride, 888 parts of phthalic anhydride, 730 parts of adipic acid, 416 parts of neopentyl glycol,
A mixed solution consisting of 248 parts of ethylene glycol and 0.5 part of dibutyltin oxide was left at room temperature for 24 hours.
The temperature was raised to 0 ° C. Next, 150 parts of xylene was added, and a condensation reaction was performed for 3 hours while maintaining the temperature at 240 ° C. under xylene reflux to obtain a polyester (resin acid value 231). After cooling to room temperature, 1,000 parts of propylene glycol monomethyl ether, 426 parts of glycidyl methacrylate and 1 part of hydroquinone are added, and the mixture is blown at 60 ° C. while blowing air.
For 5 hours (unsaturated equivalent 967, resin acid value 12
9). This resin solution was cooled to room temperature, 534 parts of dimethylethanolamine was added, and the mixture was stirred to obtain a resin solution C.
This resin solution could be diluted with water to an arbitrary concentration.

Production Example 4 1,000 parts of Epicoat 190s80 (cresol novolac type epoxy resin; epoxy equivalent: 200), 2.5 parts of hydroquinone and 10 parts of tetraethylammonium bromide were dissolved in 1,000 parts of carbitol acetate and heated to 100 ° C. 360 parts of acrylic acid was dropped over 3 hours while heating and blowing air. After dripping, 1
Stirred at 00 ° C. for 5 hours. To this reaction solution, 770 parts of hexahydrophthalic anhydride was added and reacted for 5 hours (unsaturated equivalent 426, resin acid value 132). The resin solution was cooled to room temperature, 715 parts of dimethylaminoethyl acrylate was added, and the mixture was stirred to obtain a resin solution D. This resin solution could be diluted with water to an arbitrary concentration.

Production Example 5 In a flask equipped with a reflux condenser with a water separator, N
-646 parts of methylpyrrolidone and 142 parts of trimethylhexamethylenediamine were mixed, followed by addition of 230 parts of pyromellitic acid, and the temperature was raised to 160 ° C over 3 hours. 70 g of toluene was added, and the mixture was refluxed at 160 ° C. to perform a dehydration reaction for 5 hours. Thereafter, the temperature was raised to 200 ° C. to remove the solvent from toluene.

After cooling to 60 ° C., 1 part of hydroquinone,
Add 42 parts of glycidyl methacrylate and blow in air
The reaction was carried out for 5 hours while watching (unsaturated equivalent 1,400,
Fatty acid value 41). The resin solution is cooled to room temperature,
Add 45 parts of nolamine and stir to obtain resin liquid E
Was. This resin solution could be diluted with water to an arbitrary concentration. Example 1 Photopolymerizable unsaturated resin liquid A of Production Example 1 (solid content) 100 parts Photopolymerization initiator Irgacur 907 (manufactured by Ciba Geigy) 5 parts 2,2'-m-phenylene-bis (2-oxazoline) 30 parts The above composition The material was diluted with deionized water to a 30% solution.
Using an electrostatic spray coater, the copper thickness is 35μm
Painted on copper-clad laminate (300 x 250 x 1.6mm)
And dried for 10 minutes in a hot air drier at 80 ° C.
Was obtained. Next, at room temperature 22 ° C,
Negative = 100 / 100μm pattern negative film
Adhere to this coated plate with a vacuum device and use a 3kw ultra-high pressure mercury lamp
Use 100mJ / cm^TwoAfter exposure, 25 ° C, 1% sodium carbonate
And developed with an aqueous solution. The coated plate is further heated to 140 ° C.
Bake for 10 minutes in air dryer. Then, at 55 ° C, pH
8.7 ammonium chloride / ammonia aqueous solution at pressure 2
kg / cm^TwoThe copper was etched by spraying. Then water
After washing, cured film at 50 ℃, 3% caustic soda aqueous solution
It was removed to obtain a printed wiring board.

Example 2 A printed wiring board was obtained by performing the same process as in Example 1 except that the resin liquid C of Production Example 3 was used instead of the resin liquid A of Example 1.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that, instead of 2,2'-m-phenylene-bis (2-oxazoline), 20 parts of Epicoat 828 (a resin manufactured by Yuka Shell Co.) was blended. Performed the same processing as in Example 1.

Comparative Example 2 A composition was prepared in the same manner as in Example 2 except that, instead of 2,2'-m-phenylene-bis (2-oxazoline), 20 parts of Epicoat 828 (Poxy resin manufactured by Yuka Shell) was used. Performed the same processing as in Example 2.

The resist films obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were tested for developability, etching resistance and peeling, and the results are shown in Table 1.

[0048]

[Table 1]

Test Method Water Dilution Stability: Changes in properties after standing at room temperature for one day were evaluated.

：: no change in properties ×: two-phase separation Developability: using a 1% aqueous sodium carbonate solution as a developing solution on the exposed resist film at 25 ° C. and a spray pressure of 25 kg / c
Spraying was performed for 60 seconds under the condition of m ² .

：: no film residue, Δ: some film residue,
×: not developed Etching resistance: The state of the resist film when copper was etched by spraying an aqueous solution of ammonium chloride and ammonia at 55 ° C. and pH 8.7 with a pressure of 2 kg / cm ² was evaluated.

：: Good Δ: Partial dissolution ×: Total dissolution Peelability: Peelability of the resist film when the test piece after etching was dipped in a 3% aqueous solution of caustic soda at 50 ° C. was evaluated.

○: peeled within 10 seconds Δ: peeled within 10 to 30 seconds ×: 30 seconds or more Example 3 100 parts of photopolymerizable unsaturated resin liquid B (solid content) 100 parts Photopolymerization initiator Irgacur 907 (manufactured by Ciba Geigy) 5 parts 2-isopropenyl-2-oxazoline homopolymer (molecular weight: about 10,000) 30 parts Phthalocyanine green 0.5 part Talc 50 parts Lead octylate 0.1 part Modaflow (manufactured by Monsanto) 0.5 part The above composition The material was diluted with deionized water to a 40% solution.
Using an electrostatic spray coater, the copper thickness is 35μm
Printed glass epoxy board (1.6mm)
Thickness) and dried with a hot air drier at 80 ° C. for 15 minutes to obtain a smooth photosensitive film having a thickness of 30 μm. Next, a negative photomask film was adhered to the coated plate with a vacuum device, and
After exposure to 300mJ / cm ² using a 0kw ultra-high pressure mercury lamp,
A coated plate developed with a 1% aqueous sodium carbonate solution at 25 ° C.
It was baked for 30 minutes in a hot air dryer at 0 ° C. to obtain a solder resist film.

[0054] except that the resin solution D Production Example 4 instead of Example 4 Resin solution B is to obtain a solder resist film in the same manner as in Example 3.

Comparative Example 3 In Example 3, epicoat 1 was used instead of 2-isopropenyl-2-oxazoline homopolymer (molecular weight: about 10,000).
A solder resist film was obtained in the same manner as in Example 3 except that a composition containing 20 parts of 009 (epoxy resin manufactured by Yuka Shell Co., Ltd.) was used.

COMPARATIVE EXAMPLE 4 In Example 4, Nikarac M was used instead of 2-isopropenyl-2-oxazoline homopolymer (molecular weight: about 10,000).
A solder resist film was obtained in the same manner as in Example 3, except that a composition containing 20 parts of W-30 (an amino resin manufactured by Sanwa Chemical Co., Ltd.) was used.

Table 2 shows the results of tests performed on the solder resist films obtained in Examples 3 and 4, and Comparative Examples 3 and 4.

[0058]

[Table 2]

Test method Solder heat resistance: Sample was treated with aqueous flux CF330V
H (manufactured by Tamura Kaken Co., Ltd.), dried with hot air at 80 ° C. for 5 minutes, and then immersed in a 260 ° C. solder bath for 10 seconds. The (flux treatment-drying-immersion) step was defined as one cycle, and this cycle was performed three times, and the adhesion was evaluated. Adhesion was measured according to JIS K5400 8.5.2 (19
90) In accordance with the test method of
Zero cross-cuts were cut, and a cellophane adhesive tape was closely adhered to this portion and instantaneously peeled off. The evaluation was made based on the number of squares that did not peel off.

◎: 100 ○: 99 to 95 △: 9
4 to 50 pieces ×: less than 50 Acid resistance: After immersing the test piece in 10% sulfuric acid at 20 ° C. for 1 hour, make a cross cut in a grid pattern, adhere the cellophane adhesive tape, peel off instantly, and remove the resist. Was evaluated for peeling.

：: No peeling Δ: Slight peeling X: Peeling Adhesion: According to the test method of JIS D-0202, a cross cut was made in a grid pattern, and a cellophane adhesive tape was adhered and peeled off instantaneously. Peeling was evaluated.

：: No peeling Δ: Slight peeling ×: Peeling Insulation resistance: An evaluation board was prepared using a JIS Z 3197, 2-type G-10 comb test pattern, and 100
V, the insulation resistance after applying for 1 minute was measured.

Electrocorrosion: JIS Z3197, type 2 G-
An evaluation board is created using a 10-type comb-shaped test pattern,
Applying a bias voltage of DC100V, 40 ° C, 90%
R. H. The presence or absence of the dentite after 500 hours was confirmed in the constant temperature and humidity chamber.

○: no dentite generated Δ:
Example 5 Photopolymerizable unsaturated resin solution E (solid content) 100 parts Photopolymerization initiator Irgacur 907 (manufactured by Ciba Geigy) 5 parts 2,2'-tetramethylene-bis (2 -Oxazoline) 30 parts Trimethylolpropane triacrylate 30 parts Barita 100 parts The above composition was diluted with deionized water to make a 50% solution.
Using an electrostatic spray coating machine, paint on a glass epoxy board (0.2 mm thick) with a printed wiring of 35 μm thick and dry for 15 minutes in a hot air dryer at 80 ° C. A membrane was obtained. Next, a negative type photomask film was adhered to the coated plate with a vacuum device, exposed to 300 mJ / cm ² using a 10 kw ultrahigh pressure mercury lamp, and then the coated plate developed at 25 ° C. and a 1% aqueous sodium carbonate solution at 160 ° C. Baking was performed for 40 minutes with a hot air drier to obtain an interlayer insulating film. The surface of the interlayer insulating film was roughened by a known method, copper plating was performed, a pattern was formed, and an interlayer insulating film was formed thereon. This operation was repeated to obtain a multilayer substrate.

Comparative Example 5 A composition was prepared by blending Example 5 with 20 parts of EPPN-201 (a novolak type epoxy resin manufactured by Nippon Kayaku) in place of 2,2'-tetramethylene-bis (2-oxazoline). The same processing as in Example 5 was performed.

Table 3 shows the test results of the substrates obtained in Example 5 and Comparative Example 5.

[0067]

[Table 3]

Test method : Alkali resistance: A test piece was immersed in a 10% aqueous solution of sodium hydroxide at 20 ° C. for 1 hour, then cut in a grid pattern, adhered with a cellophane adhesive tape, and immediately peeled off. Peeling was evaluated.

：: No peeling Δ: Slight peeling X: Peeling Copper plating adhesion: The adhesion of copper plating formed on the interlayer insulating film was evaluated by a 90 ° peel test.

Example 6 Photopolymerizable unsaturated resin liquid D (solid content) 100 parts Photopolymerization initiator Irgacur 907 (manufactured by Ciba Geigy) 5 parts 2,2'-Hexamethylene-bis (2-oxazoline) 30 parts The composition was diluted with deionized water to make a 50% solution.
Using an electrostatic spray coating machine, paint on a glass epoxy substrate, dry with a hot air dryer at 80 ° C for 15 minutes,
An m-thick smooth photosensitive film was obtained. Next, a negative-type photomask film was adhered to the coated plate with a vacuum device and exposed to 300 mJ / cm ² using a 10 kw ultrahigh pressure mercury lamp.
The coated plate developed with the aqueous sodium carbonate solution was baked with a hot air drier at 160 ° C. for 40 minutes to obtain a plating resist pattern. Thereafter, electroless copper plating was performed by a known method to form a copper pattern.

Comparative Example 6 In Example 6, 2,2'-hexamethylene-bis (2
-Oxazoline) instead of YDF-2004 (Epoxy resin manufactured by Toto Kasei Co., Ltd.)
The same processing as in Example 5 was performed.

Table 4 shows the test results of the copper patterns obtained in Example 6 and Comparative Example 6.

[0073]

[Table 4]

Test method : Alkali resistance: A test piece was immersed in a 10% aqueous solution of sodium hydroxide at 70 ° C. for 1 hour, then cut in a grid pattern, adhered with a cellophane adhesive tape, and immediately peeled off. Peeling was evaluated.

：: No peeling, Δ: Slight peeling, ×: Peeling

[0076]

The resist composition of the present invention can be easily diluted with water, and a resist film to be formed can use water or a dilute alkaline aqueous solution as a developing solution. Excellent chemical resistance,
A resist film having heat resistance can be formed.

Claims (4)

[Claims] 1. A photopolymerizable resin containing (a) a polymerizable unsaturated group and a carboxyl group, wherein a part or all of the carboxyl group is neutralized with an amine compound; (b) a photopolymerization initiator; c) A resist composition for a printed wiring board, comprising a compound containing an oxazoline group. 2. The photopolymerizable resin (a) is 100 to 5,0
The resist composition according to claim 1, which has an unsaturated equivalent of 00 and an acid value of 20 to 300. 3. The composition according to claim 1, wherein the oxazoline group-containing compound (c) is blended in an amount of 0.3 to 2.0 equivalents of the oxazoline group to 1 equivalent of the carboxyl group of the photopolymerizable resin (a). Resist composition. 4. A step of applying the resist composition according to claim 1 to a substrate, a step of drying the substrate, a step of irradiating with an actinic ray through a photomask, a step of developing with water or dilute alkaline water, and A method for manufacturing a printed wiring board, comprising sequentially performing a step of heating a substrate after development.