JPH1143533A - Resin composition, permanent resist resin composition, and their cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having a high sensitivity and resolu tion and an excellent resistance against solvent and plating, by including a photosensitive prepolymer having a specific carboxyl group, a diluent, a photopol ymerization initiator, and a thermosetting component. SOLUTION: This composition is obtained by including (A) 10-80 wt.% photosensitive prepolymer (preferably average molecular weight of 10,000-100,000, acid value of 70150 mg-KOH/g-solid) having a carboxyl group obtained by the reaction of (a) a product by the reaction of one mole of an epoxy resin having two or more epoxy groups in its molecule (preferably cresol novolak-type epoxy resin), 0.80-0.99 mole of (meth)acrylic acid based on epoxy equivalent, and 0.01-0.2 mole of a dibasic acid (e.g. succinic acid) with (b) a polybasic acid anhydride (e.g. succinic acid anhydride), (B) 5-80 wt.% diluent (e.g. carbitol acetate), (C) 0.1-30 wt.% photopolymerization initiator (e.g. acetophenone), and (D) 5-40 pts.wt. of a thermosetting component (e.g. epoxy resin) per 1 pt.wt. of the prepolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition useful as a permanent resist for circuit boards, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, printed wiring boards are manufactured by using a copper-clad laminate and by a subtractive method in which unnecessary portions of a copper foil circuit are removed by etching. It has drawbacks that it is difficult to form a wiring board, and that small-diameter flu holes and via holes cannot be uniformly formed by electroplating. Is the current situation.

On the other hand, recently, a full-available method in which an adhesive layer is formed on a laminate made of an insulating base material and a circuit and a through hole are formed thereon by electroless plating has been receiving attention. In this method, the conductor pattern accuracy is determined only by the transfer accuracy of the plating resist, and since the conductor portion is formed only by electroless plating, even with a substrate having a high aspect ratio through hole, uniform through hole plating with high throwing power can be achieved. It is possible to do. Until now, the additive method, which has been considered suitable for general consumer use, has begun to be put into practical use as an industrial, high-density, high-multilayer substrate manufacturing process.

[0004]

Generally, in an additive method for manufacturing a substrate for consumer use, a plating resist pattern is transferred by a screen printing method. However, in order to manufacture a printed wiring board having high-density wiring, ,
It is necessary to form a plating resist pattern by photolithography, that is, to employ a photo-additive method using a photoresist. Photoresists suitable for photo-additive methods include sensitivity, resolution,
In addition to the inherent properties of photoresist such as developability, the following properties are required. Development is limited to 1,1,1-trichloroethane-based organic solvent or alkaline aqueous solution, so that it can be developed by any of them, it can withstand electroless plating performed for a long time under high temperature and high alkaline conditions, plating After processing, have excellent solder resist properties as permanent resist, 260 in soldering process
It has heat resistance to withstand temperatures around ℃ and solvent resistance to organic solvents for cleaning flux used at the time of soldering, and furthermore, it does not stop the thermal reliability of the entire substrate even when laminated. . At present, photoresists that can be used in the additive method are commercially available, but their performance is not yet satisfactory.

Accordingly, an object of the present invention is to form a resist with high pattern accuracy by a photographic method by development using an alkaline aqueous solution, sufficiently withstand the electroless copper plating solution of the full additive method, and A permanent resist functional composition that has heat resistance to withstand temperatures around 260 ° C in the soldering process and solvent resistance to organic solvents that clean flux used during soldering, and is used without removing it to the final product And a cured product thereof.

[0006]

In order to achieve the above object, a resin composition, a permanent resist resin composition for a printed wiring board, and a cured product thereof according to the present invention have the following composition, and are used as a permanent resist. It is characterized in that it has excellent characteristics and that a printed wiring board using the resist resin composition can be manufactured.

That is, the present invention relates to (1) an epoxy resin (a) having at least two epoxy groups in one molecule and 0.80 to 0.99 mol of (meth) acrylic acid per epoxy equivalent of (a). A reaction product (d) of the acid (b) with 0.01 to 0.2 mol of a dibasic acid and / or its anhydride (c) and a reaction product of a polybasic anhydride (e) A resin composition containing a photosensitive prepolymer (A) having a certain carboxyl group, a diluent (B), a photopolymerization initiator (C), and a thermosetting component (D); and (2) an epoxy resin (a). The resin composition according to (1), which is a novolak type epoxy resin; (3) the resin composition according to (1), wherein the epoxy resin (a) is a trisphenolmethane type epoxy resin; A resist as described in any of the above items (1) to (3) Resin composition, (5)
The present invention relates to a cured product of the resin composition according to any one of (1) to (4).

In the present invention, a photosensitive prepolymer (A) having a carboxyl group is used. Component (A) is an epoxy resin (a) having at least two epoxy groups in one molecule and 0.80 to 0.8 per epoxy equivalent of (a).
99 moles of (meth) acrylic acid (b) and 0.01-0.
A reaction product (d) with 2 mol of a dibasic acid or its anhydride (c) and a polybasic anhydride (e), wherein at least two epoxy groups are present in one molecule; 0.80 per epoxy equivalent of epoxy resins (a) and (a)
0.99 mol of (meth) acrylic acid (b) and 0.01
It can be obtained by reacting .about.0.2 mol of a dibasic acid and / or its anhydride (c), and then reacting this reactant (d) with a polybasic anhydride (e). Specific examples of the epoxy compound (a) having at least two or more epoxy groups in one molecule include, for example, novolak-type epoxy resins (for example, phenols such as phenol, cresol, halogenated phenol and alkylphenol, and formaldehyde). Novolaks obtained by reaction in the presence of an acidic catalyst and epichlorohydrin and / or
Or those obtained by reacting with methyl epichlorohydrin. Commercial products include Nippon Kayaku Co., Ltd., EOC
N-103, EOCN-104S, EOCN-102,
EOCN-1027, EPPN-201, BREN-
S: DEN-431, DEN-4 manufactured by Dow Chemical Company
39; N-730, N, manufactured by Dainippon Ink and Chemicals, Inc.
-770, N-865, N-665, N-673, VH
-4150 etc.), bisphenol type epoxy resins (for example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin and / or methyl epichlorohydrin, bisphenol A or bisphenol A product obtained by reacting the diglycidyl ether of F with the condensate of the above bisphenols and epichlorohydrin and / or methyl epichlorohydrin, etc. Commercially available products are Yuko Shell Epoxy Co., Ltd., Epicoat 1004, Epicoat 1002, Epicoat 4002. , Epicoat 4004
etc. ), Trisphenolmethane-type epoxy resin (for example, those obtained by reacting with epichlorohydrin and / or methylepichlorosiderin such as trisphenolmethane, triscresol methane, etc.) Commercial products include Nippon Kayaku Co., Ltd. Made, EPPN-501, EPPN
-502 and the like. ) Tris (2,3-epoxypropyl) isocineurate, biphenyl diglycidyl ether, others, manufactured by Daicel Chemical Industries, Ltd., Celloxide 202
1: EPOMIC VG-31 manufactured by Mitsui Petrochemical Industries, Ltd.
01; Yuka Shell Epoxy Co., Ltd., E-1031S;
Alicyclic epoxy resins such as EPB-13 and EPB-27 manufactured by Nippon Soda Co., Ltd., and copolymerized epoxy resins (for example, manufactured by Nippon Oil & Fats Co., Ltd., which is a copolymer of glycidyl methacrylate, styrene and methylstyrene, CP-50M, CP
-50S, or a copolymer of glycidyl methacrylate and cyclohexylmaleimide, etc.). Alternatively, other examples include an epoxy resin having a special structure. Particularly preferred are, for example, cresol novolak type epoxy resin, phenol novolak type epoxy resin, trisphenolmethane type epoxy resin and the like.

The reactant (d) contains at least 2 molecules per molecule.
0.80 to 0.99 mol of (meth) acrylic acid (b) and 0.01 to 0.2 mol of dibasic acid or anhydride thereof per epoxy equivalent of epoxy resin (a) having two epoxy groups ( c) can be obtained by reacting.

Next, the (meth) acrylic acid (b) is
Acrylic acid or methacrylic acid.

Specific examples of the dibasic acid or its anhydride (c) include, for example, succinic acid, maleic acid, adipic acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methyl Examples thereof include dibasic acids such as hexahydrophthalic acid and anhydrides thereof.

The reaction between the epoxy resin (a), the (meth) acrylic acid (b) and the dibasic acid or its anhydride (c) is based on the equivalent of (meth) ) Acrylic acid (b) is 0.8 to 0.99 mol, preferably 0.9 to 0.95 mol, and dibasic acid or anhydride (c) is 0.01 to 0.2 mol, preferably Are reacted at 0.05 to 0.1 mol. The reaction is carried out by simultaneously charging and reacting the epoxy resin (a), (meth) acrylic acid (b) and dibasic acid or its anhydride (c) (method A), and the epoxy resin (a) and (meth) There is a method (method B) in which the reaction of acrylic acid (b) is carried out by charging dibasic acid or its anhydride (c) at a reaction rate of about 50 to 80%.

When the amount of the dibasic acid or anhydride (c) used is 0.2 mol or more, the molecular weight is increased, and the viscosity may be too high or gelation may occur.
If the amount used is less than 0.01 mol, the molecular weight does not become sufficiently large, and the heat resistance, plating solution resistance, photosensitivity and the like are insufficient.

The component (A) of the present invention is prepared by simultaneously charging and reacting the components (a), (b) and (c).
Method) or the reaction of component (a) with component (b)
% By increasing the molecular weight by charging the component (c) at a reaction rate of (%) (method B), thereby having excellent properties such as heat resistance, plating solution resistance, and photosensitivity.

At the time of the reaction in both methods (A) and (B), ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol dimethyl ether, dipropylene Glycol ethers such as propylene glycol diethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha Organic solvents such as petroleum solvents such as acryloyl morpholine, isobornyl (meth) acrylate, dicyclopentadiene mono (meth) acrylate,
Hydrogenated dicyclopentadiene mono (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, nonambiol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, isocyanurate di (meth) acrylate, isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Acrylate, pentaerythritol tri (meth)
It is preferable to use a photopolymerizable reactive diluent such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta and hexa (meth) acrylate, and ditrimethylolpropanetetra (meth) acrylate. To further promote the reaction, a catalyst (for example, triphenylphosphine, benzyldimethylamine, methyltriethylammonium chloride,
It is preferable to use triphenylstibine or the like.
In order to prevent gelation during the reaction, it is preferable to use a polymerization inhibitor (for example, hydroquinone, methylhydroquinone, methoquinone, phenothiazine, etc.). The reaction temperature is 60 to 150 ° C. in both the method (A) and the method (B). The reaction time is preferably 5 to 40 hours. Such a reactant (d) can be obtained.

Next, reactant (d) and polybasic anhydride (e) (for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride) Acid, methylendomethylenetetrahydrophthalic anhydride, trimellitic acid, pyromellitic acid, etc.) are reacted with the reactant (d).
It is preferable to react 0.1 to 1.0 equivalent of the above-mentioned polybasic anhydride (e) per equivalent of the hydroxyl group with respect to the hydroxyl group contained therein. The reaction temperature is preferably from 60 to 150C. The reaction time is preferably 1 to 10 hours.

The average molecular weight of the thus obtained photosensitive prepolymer having a carboxyl group (A) of the present invention is preferably 10,000 to 100,000, particularly preferably 1.5 to 50,000. The acid value (mgKOH / g) of the solid content is 70 to 15
0 is preferable, and 80 to 110 is particularly preferable.

The amount of the photosensitive prepolymer (A) having a carboxyl group contained in the composition of the present invention is 1% in the composition.
It is preferably from 0 to 80% by weight, particularly preferably from 15 to 60% by weight.

Specific examples of the diluent (B) include, for example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve and methyl carbyl. Tall, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol ethers such as dipropylene glycol diethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, esters such as carbitol acetate, ethanol, propanol, Alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; stones such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Solvent, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , Polyethylene glycol di (meth) acrylate, N, N-
Dimethyl acrylamide, melamine (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, glycerin diglycidyl ether di (meth) Acrylate, isobornyl (meth) acrylate, or hexanediol,
Photopolymerizable reactivity of polyhydric alcohols such as trimethylolpropane, pentaerythritol ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, and polyhydric (meth) acrylates of ethylene oxide or propylene oxide adduct thereof. Diluents and the like can be mentioned.

The diluent (B) is used alone or as a mixture of two or more, and the amount of the diluent (B) contained in the composition of the present invention is not limited to a specific range. In the composition, it is preferably from 5 to 80% by weight, particularly preferably from 10 to 70% by weight.

Specific examples of the photopolymerization initiator (C) include acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, cycloloacetophenone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-propane-1-
On, 2-benzyl-2-dimethylamino-1- (4-
Acetophenones such as morpholinophenyl) -butanone-1, benzophenone, 2-chlorobenzophenone,
p, p-bisdiethylaminobenzophenone, P, P-
Bisdiethylaminobenzohenone, 4-benzoyl-
Benzophenones such as 4'-methyldiphenyl sulfide; benzoin ethers such as benzyl, benzoin, benzoin methyl ether and benzoin isobutyl ether; ketals such as benzyl dimethyl ketal; thioxanthone; 2-chlorothioxanthone; 2,4-diethylthioxanthone; -Thioxanthones such as isopropylthioxanthone, anthraquinone, 2,4,5-
Triarylimidazole dimer, 2,4,6-tris-S-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned. These polymerization initiators (c) can be used alone or in combination of two or more.

In the present invention, the amount of the component (C) is preferably from 0.1 to 30% by weight, particularly preferably from 1 to 20% by weight in the composition.

Next, specific examples of the thermosetting component (D) include amino resins such as epoxy resins, butoxylated melamine resins, methoxylated melamine resins, and benzoguanamine-based co-condensation resins. Of these, epoxy resins are particularly preferred. Typical examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, and rubber modified epoxy resin. , Tris (2,3-epoxypropyl) isocyanurate, diphenyl diglycidyl ether, tetramethyl diphenyl diglycidyl ether, and the like. When using these epoxy resins, it is preferable to use a curing agent. Specific examples of the curing agent include a known epoxy curing agent such as a melamine derivative, an imidazole derivative, dicyandiamide, and a phenol derivative. It is preferable that such a thermosetting component is blended in an amount of 5 to 40 parts by weight based on the photosensitive prepolymer (A). The resulting cured coating film may not have sufficient electrical properties such as heat resistance, solvent resistance, acid resistance, adhesion, insulation resistance, etc. If it exceeds this, the photosensitivity and developability will decrease.

The resin composition of the present invention may contain an inorganic powder for the purpose of improving heat resistance and adjusting fluidity, and typical examples thereof include amorphous silica and amorphous powder. Silica, high-purity crystalline silica, talc, clay, titanium oxide, calcium carbonate, aluminum hydroxide, alumina, barium sulfate, hydrated silicate, antimony trioxide, magnesium carbonate, mica powder, aluminum silicate, magnesium silicate, and the like.

The resin composition of the present invention may further contain a coloring agent, a silicone compound or an acrylate copolymer, if necessary.
Leveling agents such as fluorine-based surfactants, adhesion promoters such as silane coupling agents, thixotropic agents such as Aerosil, and polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butyl catechol, and phenothiazine, Various additives such as an antihalation agent, a flame retardant, an antifoaming agent, and an antioxidant may be added.

The resin composition of the present invention comprises the components (A) to (D), other inorganic powders and various additives,
The mixture is mixed with a three-roll mill or the like, for example, for 0.5 hour to disperse the solid content, thereby completing a dispersion. The resin composition thus obtained was applied to a thickness of 10 to 150 μm (liquid thickness) on a printed circuit board by screen printing, curtain coating, roll coating, spin coating, dip coating, or the like. Later, 6
After drying at 0 to 80 ° C. for 15 to 60 minutes, a volatile film such as an organic solvent is volatilized, and then a negative film of a desired circuit pattern is brought into close contact with the dried coating film. Irradiate radiation. Then, the negative film is removed, and the coating film in the non-exposed area is removed by developing with a diluted alkaline aqueous solution as a developing solution, but the coating film in the exposed portion remains without being removed because it is light-cured. As the diluted alkaline aqueous solution at this time, a 0.5 to 5% by weight aqueous solution of sodium carbonate is generally used, but other alkaline solutions can also be used. Then at 130-160 ° C. for 20
A cured product can be obtained by heat curing with a hot air dryer or the like for 90 minutes.

The resin composition of the present invention is preferably used as a solder resist for a circuit board such as a printed circuit board or a permanent resist such as an interlayer insulating layer, but is not limited thereto. Applicable to application.

[0028]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

(Synthesis Example of Photosensitive Prepolymer (A) Having Carboxyl Group) Synthesis Example 1 o-cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent) (220) 2200 g (10 equivalents), acrylic acid 641 g (8.9 mol), methylhydroquinone 1.7
g, tetrahydrophthalic anhydride 76 g (0.5 mol),
1361 g of carbitol acetate and 583.7 g of solvent naphtha were charged and heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 14.5 g of triphenylphosphine, heated to 100 ° C., reacted for about 32 hours, and when the acid value (mg KOH / g) became 3.0 or less, then 60 ° C. The mixture was cooled to 1089 g (7.16 mol) of tetrahydrophthalic anhydride, 508.2 g of carbitol acetate and 217.8 g of solvent naphtha, and reacted at 95 ° C. for 10 hours to obtain a photosensitive prepolymer having a carboxyl group (A). −
1) was obtained. The average molecular weight of the product (solid content) was about 20,000 and the acid value (solid content, mgKOH / g) was 100.

Synthesis Example 2 1785 g (10 equivalents) of trisphenol methane type epoxy resin (EPPN-503, Nippon Kayaku Co., Ltd., softening point 81.5 ° C., epoxy equivalent 178.5), 691.7 g of acrylic acid ( 9.6 mol), 707.6 g of carbitol acetate and 1.7 g of methylhydroquinone were charged and heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., 10.6 g of triphenylphosphine was charged, and the mixture was heated to 100 ° C. to obtain an acid value (mg
When the (KOH / g) became 85, 22.8 g (0.15 mol) of tetrahydrophthalic anhydride was charged, the reaction was continued, and when the acid value (mgKOH / g) became 3.0 or less, then 60 After cooling to 87.degree. C., 870.4 g (5.73 mol) of tetrahydrophthalic anhydride, 870.8 g of carbitol acetate and 676.4 g of solvent naphtha were charged and reacted at 95.degree. C. for 10 hours to obtain a photosensitive prepolymer having a carboxyl group. Polymer (A-2) was obtained. The average molecular weight of the product (solid content) was about 15,000, and the acid value (solid content, mgKOH / g) was 95.

(Synthesis Example for Comparative Example) Synthesis Example 3 2,200 g (10 equivalents) of o-cresol novolak type epoxy resin (EOCN-104S, Nippon Kayaku Co., Ltd., softening point 92 ° C., epoxy equivalent 220) , Acrylic acid 7
13.4 g (9.9 mol), methylhydroquinone 1.
7 g, 1359 g of carbitol acetate and 583.6 g of solvent naphtha were charged, and heated and stirred at 90 ° C.
The reaction mixture was dissolved. Then, the reaction solution was cooled to 60 ° C., and 14.6 g of triphenylphosphine was charged and 10
Heat to 0 ° C. and react for about 32 hours, acid value (mgKOH /
g) is 3.0 or less, then cooled to 60 ° C. and 1087.9 g of tetrahydrophthalic anhydride (7.1
6 mol), 410 g of carbitol acetate and 176 g of solvent naphtha, and reacted at 95 ° C. for 10 hours to obtain a carboxyl-containing photosensitive prepolymer (A).
-3) was obtained. The average molecular weight of the product (solids) is about 7
At 500, the acid value (solid content, mgKOH / g) was 100.

Examples 1 and 2 Comparative Example 1 A permanent resist resin composition was mixed, dispersed and kneaded in accordance with the composition shown in Table 1 (the numerical values are parts by weight). The obtained composition was applied on a laminate at a thickness of 30 μm, dried at 80 ° C. for 60 minutes, then brought into contact with a negative mask on the resist, and irradiated with ultraviolet rays using an ultra-high pressure mercury lamp. The unexposed portion is treated with 1.5% Na ₂ CO ₃ aqueous solution 6
Development was performed for 0 second at a spray pressure of 2.0 kg / cm ² .
(It can be heat-treated before development.)
After irradiating the entire surface with ultraviolet rays, a heat treatment was performed at 150 ° C. for 30 minutes. This was immersed in an electroless copper plating solution at 70 ° C. for 10 hours to form an electroless copper plating film of about 20 μm, thereby producing an additive-processed multilayer printed wiring board. Table 1 shows the results of evaluating the resist characteristics in the process of obtaining the additive multilayer printed wiring board in this manner.

Evaluation method (developability) ・ ・ ・: At the time of development, ink was completely removed and complete development was possible. ×: At the time of development, a small amount of residue remains, and there is a part that is not developed. (Light sensitivity) 21 steps of step tablets (manufactured by Stoffer) are adhered to the dried coating film, and the integrated light amount is 300 mJ / c.
Irradiation with ultraviolet rays of m ² is performed. Next, 1.5% Na ₂ CO
₍₃₎ Develop with an aqueous solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and confirm the number of steps of the coating film that has not been developed.
The following criteria were used: ○ ・ ・ ・ 9 steps or more △ ・ ・ ・ ・ 6 ~ 8 steps × ・ ・ ・ ・ 5 steps or less

(Solvent resistance) The cured resist film is made of acetone 2
It was immersed for 0 minutes and the condition was visually observed. ○ ・ ・ ・ ・ No change at all. ×: blisters and peeling occurred. (Plating resistance) ○ ・ ・ ・ ・ No change is observed in the electroless plating process. C: Discoloration, blistering, and peeling occurred in the electroless plating process. (Solder Heat Resistance) According to the test method of JIS C6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds three or two times, and the change in appearance was evaluated.

(Post-flux resistance)
It was rotated and the change in appearance was evaluated. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling and solder dipping of the cured film Note) Post flux used (rosin type): JIS
Use flux according to C 6481.

(Flux resistance for leveler) Dipping for 10 seconds was performed three times, and after immersing in boiling water for 10 minutes, the change in appearance was evaluated. ○ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling and solder dipping of the cured film Note) Flux for leveler used: manufactured by MEC Corporation ,
W-121

[0037]

Table 1 Example 1 Comparative Example 12 1 Photosensitive Prepolymer (A-1) Obtained in Synthesis Example 1 74.7 Photosensitive Prepolymer (A-2) Obtained in Synthesis Example 1 74.7 Obtained in Synthesis Example 1 Photosensitive prepolymer (A-3) 69 KAYARAD DPHA * 1 3.5 3.5 3.5 Irgacure 907 * 2 3.0 3.0 3.0 KAYACURE DETX-S * 3 0.5 0.5 0.5 EPPN-201 * 4 10.0 10.0 10.0 Carbitol acetate 10.0 10.0 10.0 Dioxide Silica 30 30 30 Aerosil 380 * 5 3 3 3 Phthalocyanine green (color pigment) 1.8 1.8 1.8 Dicyandiamide (epoxy hardener) 0.5 0.5 0.5 Developability ○ ○ ○ Photosensitivity ○ ○ △ Plating solution ○ ○ × Soldering heat resistance Post flux Resistance ○ ○ ○ Flux resistance for leveler ○ ○ △

Note) * 1 KAYARAD DPH
A: Nippon Kayaku Co., Ltd. mixture of dipentaerythritol penta and hexaacrylate. * 2 Irgacure 907: a photopolymerization initiator manufactured by Ciba-Geigy Corporation. * 3 KAYACURE DETX-S: Nippon Kayaku Co., Ltd. photopolymerization initiator. * 4 EPPN-201: a phenol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd. * 5 Aerosil 380: Japan Aerosil Co., Ltd.
Made, anhydrous silica

From the evaluation results shown in Table 1, the resin composition of the present invention is excellent in photosensitivity, and the cured product is excellent in plating solution resistance and heat resistance.

[0040]

The resin composition, the permanent resist resin composition and the cured product of the present invention have high sensitivity, high resolution, and
Despite easy development with dilute alkali aqueous solution, it has excellent solvent resistance, plating solution resistance to electroless plating performed for a long time under high temperature and high alkalinity conditions, and around 260 ° C. in the soldering process It is particularly suitable for manufacturing a printed wiring board having heat resistance to withstand the above temperatures.

Claims (5)

[Claims] 1. An epoxy resin (a) having at least two epoxy groups in one molecule and 0.80 to 0.99 mol of (meth) acrylic acid (b) per epoxy equivalent of (a)
Having a carboxyl group, which is a reaction product of a reaction product (d) of a polybasic acid anhydride (e) with a dibasic acid or its anhydride (c) in an amount of 0.01 to 0.2 mol. A resin composition containing a prepolymer (A), a diluent (B), a photopolymerization initiator (C), and a thermosetting component (D). 2. The resin composition according to claim 1, wherein the epoxy resin (a) is a novolak type epoxy resin. 3. The resin composition according to claim 1, wherein the epoxy resin (a) is a trisphenolmethane type epoxy resin. 4. The resin composition according to claim 1, which is a permanent resist for a circuit board. 5. A cured product of the resin composition according to claim 1.