JPH06138655A - Photosensitive thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive thermosetting resin compsn. for solder resist and a solder resist compsn. excellent in developing property, adhesion property, electric insulating property, heat resistance to soldering, and plating resistance. CONSTITUTION:This compsn. is obtd. by compounding the following compds. (A)-(D) as essential components. (A) Photosensitive prepolymer having at least two ethylene-type unsatd. bonds in one molecule, (B) photopolymn. initiator, (C) photopolymerizable vinyl monomers and/or org. solvent as a diluent, and (D) at least one of (1) phenoxy resin, (2) reaction product of phenoxy resin and polyvalent carboxylic acid and/or its anhydride, and (3) mixture of these. Further, if necessary, (E) thermosetting resin and/or crosslinking agent is incorporated into the photosensitive thermosetting resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to printed wiring board manufacturing,
The present invention relates to a novel photosensitive thermosetting resin composition and solder resist composition which are used for precision metal processing, materials for printing plates and the like, and are particularly useful as solder resists for printed wiring boards.

[0002]

2. Description of the Related Art A solder resist is intended to prevent adhesion of solder to a portion other than necessary when soldering components to a printed wiring board and to protect a circuit. Various properties such as heat resistance, solvent resistance, alkali resistance, acid resistance and plating resistance are required.

The initial type of solder resist used was an epoxy melamine type thermosetting type, but there were problems such as solder heat resistance, chemical resistance and plating resistance, and it was an industrial printed wiring board. For use, for example, Japanese Patent Publication No. 51-14044 discloses an improved epoxy resin type thermosetting type, which has become the mainstream. In addition, since productivity is important for printed wiring boards for consumer use, for example, Japanese Patent Publication No. 61-48.
A fast-curing ultraviolet-curing type as disclosed in Japanese Patent Publication No. 800 is mainly used. However, the ultraviolet curable type has a problem of internal curability in a thick film, and also has poor solder heat resistance, and therefore cannot be used for an industrial printed wiring board. In addition, these use screen printing as a method for forming a solder resist pattern, but the solder resist pattern is compatible with the high density of printed wiring boards and the surface mounting of components due to the recent trend toward lighter, thinner, and smaller electronic devices. However, there is a problem in bleeding and embeddability between circuits, and it is no longer possible to function as a solder resist film.

Therefore, dry film type photo solder resists and liquid photo solder resists have been developed. As the dry film type solder resist, for example, a dry film containing urethane di (meth) acrylate described in JP-A-57-55914, a cyclic polymer compound having a specific glass transition temperature, and a sensitizer is used. A photosensitive resin composition for a film is disclosed. However, when these dry film type photo solder resists are used for high density printed wiring boards, solder heat resistance and adhesion are not sufficient.

On the other hand, as the liquid photo solder resist, for example, British Patent Application Publication GB-2032939A is used.
A photopolymerizable coating composition containing a solid or semi-solid reaction product of a polyepoxide and an ethylenically unsaturated carboxylic acid, an inert inorganic filler, a photopolymerization initiator and a volatile organic solvent described in JP It is disclosed. However, in this case, since only the ultraviolet curing component is used and heat curing is not used together, there are problems such as adhesion to a printed wiring board, solder heat resistance, and electrical insulation.

In consideration of such thermosetting property, Japanese Unexamined Patent Publication (Kokai) No. 60-208377 discloses a reaction product of a phenol novolac type epoxy resin with an unsaturated monobasic acid and a cresol novolac type epoxy resin. A resin composition for a solder resist ink containing a partial reaction product with a saturated monobasic acid, an organic solvent, a photopolymerization initiator and an amine curing agent is disclosed. In this case, heat curing is also used by leaving an epoxy group in the molecule. However, since the photosensitive groups are reduced by the amount of the epoxy groups remaining, the curability by ultraviolet rays is lowered, and it is difficult to leave a large amount of epoxy groups remaining, and the characteristics as a solder resist cannot be satisfied.

As an example of using an epoxy resin in combination,
JP-A-49-107333 discloses a photosensitive resin composition comprising an unsaturated compound having two terminal ethylene groups, a polymerization initiator, a compound containing at least two epoxy groups and a compound containing at least two carboxyl groups. However, it is based on an acrylic linear polymer containing a (meth) acrylic group and has low solder heat resistance and solvent resistance. Further, if the ratio of the epoxy resin is increased, the photocurability is lowered, the resistance of the exposed portion to the developing solution is apt to be lowered, the development cannot be carried out for a long time, and the unexposed portion is likely to be left undeveloped. In addition, there is a problem in appearance such as whitening of the resist film when soldering is performed using a water-soluble flux that has been widely used in recent years. Also,
There is no resistance to various electrolytic / electroless plating.

In Japanese Patent Publication No. 1-54390, as a photo solder resist which can be developed with an alkaline aqueous solution, a reaction product of a novolac type epoxy resin, an unsaturated monobasic acid and a polybasic acid anhydride, a polyfunctional epoxy resin and a diluent. , A composition comprising a photopolymerization initiator is disclosed. However, even with this composition, it is difficult to balance the physical properties such as tackiness, storage stability, and heat resistance of solder, and all the properties as a solder resist have not been satisfied.

[0009]

The object of the present invention is to have both excellent developability and sensitivity, and to have excellent adhesion and good appearance even after a process such as soldering in the presence of various fluxes at a high temperature. Another object of the present invention is to provide a photosensitive thermosetting resin composition having resistance to various electrolytic / electroless plating.

Further, in addition to the above-mentioned excellent characteristics, a cured coating film excellent in electric insulation, moisture resistance, solder heat resistance and the like required for a solder resist can be obtained, which is particularly suitable for manufacturing printed wiring boards and the like. An object is to provide a suitable photosensitive thermosetting resin composition and solder resist composition.

[0011]

Means for Solving the Problems The present inventor has conducted research to solve the above problems and completed a photosensitive thermosetting resin composition. That is, the present invention provides the following (A) to (D) (A) a photosensitive prepolymer having at least two ethylenically unsaturated bonds in one molecule, (B) a photopolymerization initiator, and (C) a diluent. Photopolymerizable vinyl monomer and /
Or, a photosensitive heat-curable resin containing as an essential component an organic solvent, (D) at least a phenoxy resin, a reaction product of a phenoxy resin and a polycarboxylic acid and / or an anhydride thereof, or a mixture of both. Resin composition, and a solder resist composition containing or not (E) a thermosetting resin and / or a crosslinking agent in the composition.

A coating film can be formed by applying the photosensitive thermosetting resin composition of the present invention to the entire surface of a circuit-formed printed wiring board by screen printing, curtain coating, spin coating, spraying or the like. Then, the pattern can be formed by directly irradiating the laser beam or selectively exposing the unexposed portion with a developing solution through an actinic ray such as a high pressure mercury lamp or a metal halide lamp through a photomask on which the pattern is formed.

The photosensitive prepolymer (A) having at least two ethylenically unsaturated bonds in one molecule used in the present invention includes, for example, a polyfunctional epoxy resin such as cresol novolac epoxy resin and an unsaturated monocarboxylic acid. A reaction product of all and / or partial esterification product of polybasic acid, reaction product of carboxyl group or carboxylic acid anhydride group-containing polymer and hydroxyl group-containing (meth) acrylate, and the like,
Various compounds widely known so far can be used.

Next, as the photopolymerization initiator (B), benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether and benzoin alkyl ethers, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2 -Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl "-2-morphonopropan-1-one, N, N
-Acetophenones such as dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, anthraquinones such as 2-aminoanthraquinone, 2,4-dimethyl Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and the like, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone and methylbenzophenone,
There are benzophenones such as 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone and Michler's ketone, and xanthones, which can be used alone or in combination of two or more kinds. Further, the photopolymerization initiator (B) is a known conventional initiator such as benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate or tertiary amines such as triethylamine and triethanolamine. The photosensitizer may be used alone or in combination of two or more kinds.

The preferred range of the amount of the photopolymerization initiator (B) used is 0.2 to 30 parts by weight, preferably 2 to 20 parts by weight, relative to 100 parts by weight of the photosensitive prepolymer (A). .

As the diluent (C) used in the present invention, a photopolymerizable vinyl monomer and / or an organic solvent can be used. Typical photopolymerizable vinyl monomers include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, and glycol monolayers such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Alternatively, diacrylates, acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N,
Aminoalkyl acrylates such as N-dimethylaminoethyl acrylate, polyhydric alcohols such as trimethylolpropane and pentaerythritol, or polyhydric acrylates of adducts of ethylene oxide or propylene oxide, phenoxy acrylate, phenoxy ethyl acrylate, and other phenols Or acrylates such as ethylene oxide or propylene oxide adducts thereof, acrylates of glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and / or methacrylates corresponding to the above acrylates.

Examples of the organic solvent include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and tetramethylbenzene, methyl cellosolve, methyl carbitol, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate and the above. Esters such as acetic acid esterification products of glycol ethers,
Examples include alcohols such as ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane, and petroleum-based solvents such as petroleum naphtha and solvent naphtha.

The diluent (C) is used alone or as a mixture of two or more kinds, and the preferable range of the amount of use is 20 to 25 relative to 100 parts by weight of the photosensitive prepolymer (A).
It is 0 part by weight, preferably 30 to 200 parts by weight.

The purpose of use of the diluent is to dilute the photosensitive prepolymer in the case of a photopolymerizable vinyl-based monomer so that it can be easily applied and to enhance the photopolymerizability. In the case of an organic solvent. The reason for this is that the photosensitive prepolymer is dissolved and diluted, whereby it is applied as a liquid and then dried to form a film. Therefore, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the coating film is used depending on the diluent used.

Next, as the phenoxy resin (D), Phenotote YP-40, YP-50, manufactured by Tohto Kasei,
YP-60, Union Carbide PKHC, PKH
Known and commonly used phenoxy resins such as H and PKHJ can be used. The phenoxy resin can be used by dispersing it in the solid state, or can be used after being dissolved in the diluent (C).

On the other hand, as the reaction product of the phenoxy resin and the polycarboxylic acid and / or its anhydride, the polycarboxylic acid or its anhydride is allowed to act on the phenoxy resin in the diluent (C). You can get it. By introducing a carboxyl group into the phenoxy resin, the developability when developing with an alkaline solution is further improved. Examples of the polycarboxylic acid or anhydride thereof include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, itaconic acid, chlorendic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid. Acid, methyltetrahydrophthalic acid, trimellitic acid and pyromellitic acid, etc.
Alternatively, the anhydrides corresponding to each of these can be used alone or in combination of two or more kinds.

The mixing ratio of the photosensitive prepolymer to the (D) phenoxy resin, the reaction product of the phenoxy resin and the polycarboxylic acid or its anhydride, or at least one of the both is 97: 3 to. 1
It is 0:90, preferably 90:10 to 30:70.
When the value of the ratio of photosensitive prepolymer / (D) is 19 or less, the adhesion, solder heat resistance, electrical characteristics, and kick resistance are insufficient, and the coating film is not formed when soldering with a water-soluble flux. There are problems in appearance such as whitening, and the effects of the present invention cannot be fully exhibited. On the other hand, when the value of the ratio is 1/9 or more, development becomes difficult.

The photosensitive thermosetting resin composition of the present invention may contain barium sulfate, barium titanate, silicon oxide powder, if necessary, for the purpose of improving properties such as adhesion and hardness.
Fine powder silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide,
Known and commonly used inorganic fillers such as aluminum hydroxide and mica powder can be used, and the compounding ratio thereof is 0 to 100% by weight, preferably 5 to 60% by weight of the photosensitive thermosetting resin composition. If necessary, phthalocyanine blue,
Known colorants such as phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc., known conventional heat polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, asbestos, orben. Adhesive imparting agents such as well-known and commonly used thickeners such as Benton, silicone-based, fluorine-based, polymer-based defoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents, etc. Known and commonly used additives such as can be used.

In the photosensitive thermosetting resin composition of the present invention, a known and customary (E) thermosetting resin and a cross-linking agent can be used for the purpose of improving the properties such as heat resistance, moisture resistance and electrolytic corrosion resistance. . As the thermosetting resin, a combination of a known and commonly used epoxy resin such as bisphenol A, bisphenol F, bisphenol S, phenol novolac, cresol novolac type and a known commonly used epoxy curing agent such as amine type and acid anhydride type, melamine resin, Amino resins such as urea resins and guanamine resins and their derivatives, and phenol resins can be used. Further, as the crosslinking agent, amines, isocyanates, blocked isocyanates,
An oxazoline derivative or the like can be used.

Known and commonly used binder resins such as copolymers of ethylenically unsaturated compounds such as acrylic acid esters and polyester resins synthesized from polyhydric alcohols and saturated or unsaturated polybasic acid compounds. and,
Polyester (meth) acrylates synthesized from polyhydric alcohols, saturated or unsaturated polybasic acid compounds and glycidyl (meth) acrylate, and polyhydric alcohols, diisocyanates and hydroxyl group-containing (meth) acrylates Known and commonly used photosensitive oligomers such as urethane (meth) acrylates can also be used within a range that does not affect various properties as a solder mask.

The developing solution for forming the solder resist pattern after exposing the photosensitive thermosetting resin composition through a photomask is different depending on the selection of the photosensitive prepolymer (A), but as an organic solvent. Is cyclohexanone, xylene, tetramethylbenzene, butyl cellosolve, butyl carbitol, propylene glycol monomethyl ether, cellosolve acetate, propanol, propylene glycol, trichloroethane,
Trichlorethylene, modified trichloroethane (Etana IR manufactured by Asahi Kasei Kogyo, Three One EX manufactured by Toagosei Kagaku Kogyo)
-R, Kanto Dene Kogyo Co., Ltd. candentriethane SR-A, Asahi Glass Resorsolve V-5) and / or organic solvent and / or potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate An alkaline aqueous solution of ammonia, amines, etc. can be used.

[0027]

EXAMPLES The present invention will be specifically described below with reference to production examples, examples and comparative examples, but the present invention is not limited thereto. In addition, "part" and "%" are
All are by weight unless otherwise noted.

[0028]

[Production Example 1] Cresol novolac type epoxy resin having an epoxy equivalent of 214 (Epiclon N-6 manufactured by Dainippon Ink and Chemicals, Inc.
80) 107 parts, carbitol acetate 62 parts, and solvent naphtha 30 parts are put in a three-necked flask equipped with a stirrer and a condenser, heated and melted at 90 ° C., and stirred. Next, 40 parts of acrylic acid, 0.1 part of hydroquinone, and 0.68 part of dimethylbenzylamine were added, and the mixture was stirred and reacted at 110 ° C. for 24 hours. After cooling the reaction mixture to 100 ° C., 37 parts of tetrahydrophthalic anhydride was added, and the mixture was stirred and reacted for 4 hours to obtain a varnish having an acid value of 50 mgKOH / g (Resin a-1).

[0029]

[Production Example 2] 85 parts of a phenoxy resin (YP-50 manufactured by Tohto Kasei) having a molecular weight of about 8000, carbitol acetate 1
Add 71 parts to a three-necked flask equipped with a stirrer and a condenser, heat and melt at 80 ° C., and stir. Next, 55 parts of trimellitic anhydride was added and reacted with stirring at 100 ° C. for 6 hours to obtain a varnish having an acid value of 103 mgKOH / g (resin a-
2).

[0030]

Example 1 Resin (a-1) obtained in Production Example 1 (solid content 66.7%) 50 parts Dipentaerythritol hexaacrylate 3 parts Irgacure 907 (CIBA-GEIGY photopolymerization initiator) 3 parts Epicoat 157 (Epoxy resin made of oiled shell epoxy) 24 parts Dicyandiamide 1 part PKHH (phenoxy resin made by Union Carbide) 10 parts Barium sulfate 30 parts Phthalocyanine green 2 parts Floren AC-326F (Kyoeisha's oil and fat defoamer) 2 parts Carbitol acetate 3 Parts Solvent Naphtha 1 part After preliminarily kneading the above-mentioned blending components, they were kneaded 3 times with a three-roll mill to prepare a photosensitive thermosetting resin composition. This photosensitive thermosetting resin composition was applied to the entire surface of the copper clad laminate by a screen printing method, put in a hot air circulation oven, dried at 80 ° C. for 20 minutes and cooled to room temperature to obtain a dried coating film. Next, a photomask on which a pattern was formed was brought into contact with the coating film surface, and exposure was performed using a metal halide lamp manufactured by Oak Manufacturing Co., Ltd. Next, using 1% sodium carbonate aqueous solution as a developing solution, development was carried out for 1 minute, washing with water and drying. Next, it was placed in a hot air circulation furnace heated to 180 ° C. and post-cured for 30 minutes to form a solder resist pattern. (A) of this composition:
(D) was 75:25.

[0031]

Example 2 Resin (a-1) obtained in Production Example 1 50 parts Dipentaerythritol hexaacrylate 3 parts Irgacure907 3 parts Cymel 303 (Melamine resin manufactured by Mitsui Cyamide) 10 parts PKHH 30 parts Barium sulfate 30 parts Phthalocyanine green 2 parts Florene AC-326F 2 parts Carbitol acetate 3 parts Solvent naphtha 1 part The above-mentioned components were kneaded, coated, dried, developed and post-cured in the same manner as in Example 1 to form a solder resist pattern. The composition (A) :( D) was 50:
It was 50.

[0032]

Example 3 Resin (a-1) obtained in Production Example 1 50 parts Dipentaerythritol hexaacrylate 3 parts Irgacure907 3 parts Coronate 2513 (block polyurethane from Nippon Polyurethane Industry Co., Ltd.) 20 parts PKHH 50 parts Barium sulfate 30 parts Phthalocyanine Green 2 parts Floren AC-326F 2 parts Carbitol acetate 3 parts Solvent naphtha 1 part The above compounding ingredients were kneaded, coated, dried, developed and post-cured in the same manner as in Example 1 to form a solder resist pattern. The composition (A) :( D) was 38:
It was 62.

[0033]

Example 4 Resin (a-1) obtained in Production Example 1 50 parts Dipentaerythritol hexaacrylate 3 parts Irgacure907 3 parts Coronate 2513 20 parts Cymel 303 10 parts PKHH 60 parts Barium sulfate 30 parts Phthalocyanine green 2 parts Florene AC-326F 2 parts Carbitol acetate 3 parts Solvent naphtha 1 part The above components were kneaded, coated, dried, developed and post-cured in the same manner as in Example 1 to form a solder resist pattern. The composition (A) :( D) was 30:
It was 70.

[0034]

Example 5 Resin (a-1) obtained in Production Example 1 50 parts Dipentaerythritol hexaacrylate 3 parts Irgacure907 3 parts Epicoat 157 24 parts Dicyandiamide 1 part Resin (a-2) obtained in Preparation Example 2 40 parts Barium sulfate 30 parts Phthalocyanine green 2 parts Florene AC-326F 2 parts Carbitol acetate 3 parts Solvent naphtha 1 part The above compounding ingredients are kneaded, coated, dried, developed and post-cured in the same manner as in Example 1 to obtain a solder resist. A pattern was formed. The composition (A) :( D) was 50:
It was 50.

[0035]

Comparative Example Resin (a-1) obtained in Production Example 1 50 parts Dipentaerythritol hexaacrylate 3 parts Irgacure907 3 parts Epicoat 157 24 parts Dicyandiamide 1 part Barium sulfate 30 parts Phthalocyanine green 2 parts Florene AC-326F 2 parts Carbitol acetate 3 parts Solvent naphtha 1 part The above components were kneaded, coated, dried, developed and post-cured in the same manner as in Example 1 to form a solder resist pattern.

Table 1 shows the results of testing various properties of the solder resist resin compositions and solder resist patterns obtained in Examples 1 to 5 and Comparative Example. In addition, the test method and evaluation judgment of each performance of the following Table 1 are as follows.

[0037]

[Table 1]

1) Developability Test Each test piece was irradiated with ultraviolet rays at 500 mJ / cm 2 using an integrating photometer manufactured by Oak Manufacturing Co., Ltd. through a photomask, and the test piece was immersed for 1 minute while stirring the developing solution. Then, the state in which the unexposed portion was removed was visually observed. ⊚: Completely developed ○: Partially undeveloped portion on the surface Δ: Residual undeveloped ×: Almost undeveloped

2) Adhesion test Each of the samples was passed through a photomask, irradiated with ultraviolet rays of 500 mJ / cm2 using an integrating photometer manufactured by Oak Manufacturing Co., and immersed in the developing solution for 1 minute while stirring to develop it.
Post-cure was carried out under the condition of 30 ° C. for 30 minutes to prepare a test piece, and a cross-cut was put in a grid pattern according to the test method of JIS D0202, and then the state of peeling after a peeling test with cellophane tape was visually observed. ⊚: 100/100 with no peeling at all; ◯: 100/100 with a little peeling of the cross-cut portion Δ: 50/100 to 99/100 ×; 0/100 to 49/100

3) Pencil hardness test Each of the same test pieces as the adhesion test was JIS K
Hardness was measured according to the test method of 5400.

4) Solder resistance test Each of the same test pieces as the adhesion test was JIS C
According to the test method of 6481, the state and adhesion of the coating film after being immersed in a solder bath at 260 ° C. for 15 seconds once were comprehensively evaluated. ⊚: No change observed ○: Slight change Δ: Significant change ×: Swelling or swelling drop off of the coating film

5) Solder leveler resistance test The same operation as in the solder resistance test was conducted except that a water-soluble flux was used as the flux, and after immersion in a solder bath for 10 minutes in warm water at 80 ° C., the state of the coating film was observed. did.

6) Resistance to Ni Plating The same test pieces as those used in the adhesion test were used with an electroless nickel plating solution ICP Nicoron manufactured by Okuno Seiyaku Kogyo.
The state of the coating film after plating for 30 minutes at a liquid temperature of 85 ° C. was evaluated in the same manner as in the solder resistance test.

7) Insulation Resistance Test Using JIS Z 3197, type 2 G-10 type comb test patterns, test pieces were prepared under the same conditions as in the adhesion test, respectively, and the test pieces were boiled under normal conditions and after boiling for 2 hours to 100.
The insulation resistance after applying V for 1 minute was measured.

As is clear from the results shown in Table 1 above,
The photosensitive thermosetting resin composition obtained in each example of the present invention has excellent developability, and the obtained solder resist pattern has various properties such as adhesion, hardness, solder heat resistance, and plating resistance. , Especially excellent resistance to water-soluble flux. On the other hand, when the phenoxy resin or the reaction product of the phenoxy resin and the polycarboxylic acid and / or the anhydride thereof is not blended as in Comparative Example, solder heat resistance,
Various properties required as a solder resist such as plating resistance and moisture resistance are inferior.

[0046]

EFFECT OF THE INVENTION Using a phenoxy resin or a photosensitive thermosetting resin composition according to the present invention using a reaction product of a phenoxy resin and a polycarboxylic acid and / or an anhydride thereof, exposure and development are carried out, Then, post-curing can be performed to form a solder resist pattern having excellent adhesion, electrical insulation, solder heat resistance, plating resistance, and the like. Further, it is possible to provide a coating film which is not whitened even when soldering with a water-soluble flux is performed and has an excellent appearance.

Claims (4)

[Claims] 1. The following (A) to (D) (A) a photosensitive prepolymer having at least two ethylenically unsaturated bonds in one molecule, (B) a photopolymerization initiator, and (C) as a diluent. Photo-polymerizable vinyl monomer and /
Alternatively, a photosensitive heat containing an organic solvent, and (D) a phenoxy resin, a reaction product of a phenoxy resin and a polycarboxylic acid and / or an anhydride thereof, or a mixture of the two, as essential components. Curable resin composition. 2. A photosensitive prepolymer and at least a phenoxy resin, a phenoxy resin and a polycarboxylic acid, and / or
Alternatively, the compounding ratio of the reaction product with the anhydride or one of the mixture of the both is 97: 3 to 10:90.
The photosensitive thermosetting resin composition according to claim 1, which is (weight-based solid content ratio). 3. The photosensitive thermosetting resin composition according to claim 1, which contains a thermosetting resin and / or a crosslinking agent. 4. The following (A) to (D) (A) a photosensitive prepolymer having at least two ethylenically unsaturated bonds in one molecule, (B) a photopolymerization initiator, and (C) as a diluent. Photo-polymerizable vinyl monomer and /
Or an organic solvent, (D) containing at least one essential component of a phenoxy resin, a reaction product of a phenoxy resin and a polycarboxylic acid and / or an anhydride thereof, or a mixture of both, and (E) A solder resist composition containing or not containing a thermosetting resin and / or a crosslinking agent.