WO2010134314A1 - Photocurable heat-curable resin composition, dry film and cured product of the composition, and printed wiring board utilizing those materials - Google Patents

Abstract

Disclosed are: a photocurable heat-curable resin composition which enables the formation of a cured coating film having PCT resistance, HAST resistance, electroless gold plating resistance and thermal shock resistance that are important properties for solder resists for semiconductor packages; a dry film and a cured product of the resin composition; and a printed wiring board having, formed thereon, a cured coating film (e.g., a solder resist) comprising those materials. Specifically disclosed is a photocurable heat-curable resin composition which is developable with an aqueous alkaline solution and comprises a carboxyl-group-containing resin having a photosensitive group (excluding a carboxyl-group-containing resin produced using an epoxy resin as a starting raw material), a photopolymerization initiator and a hydroxyl-group-containing elastomer.

Description

Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them

The present invention is a photocurable thermosetting resin composition that can be developed with an aqueous alkali solution, in particular, a solder resist composition that is photocured by ultraviolet exposure or laser exposure, its dry film and cured product, and these. The present invention relates to a printed wiring board having a cured film.

At present, some consumer printed wiring boards and most industrial printed wiring board solder resists are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density, and heat and / or light. Liquid development type solder resist that is final-cured (main-cured) by irradiation is used. In consideration of environmental problems, alkali development type photo solder resists that use an alkaline aqueous solution as the developer are the mainstream. Used in large quantities in the manufacture of plates. In addition, solder resists are also required to have improved workability and high performance in response to the recent increase in the density of printed wiring boards as electronic devices become lighter, thinner and shorter.

However, the current alkali development type photo solder resist still has problems in terms of durability. That is, the alkali resistance, water resistance, heat resistance and the like are inferior to those of conventional thermosetting type and solvent developing type. This is because the alkali-developable photo solder resist is mainly composed of a hydrophilic group in order to enable alkali development, and it is easy for chemicals, water, water vapor, etc. to permeate, resulting in reduced chemical resistance and resist film. This is thought to reduce the adhesion between copper and copper. As a result, the alkali resistance as chemical resistance is weak, especially in semiconductor packages such as BGA (Ball Grid Array) and CSP (Chip Scale Package), especially PCT resistance (pressure cooker test resistance) that should be called moisture heat resistance. ) Is necessary, but under such severe conditions, it is only several hours to several tens of hours. Further, in the HAST test (highly accelerated life test) in a state where a voltage is applied under humidification conditions, in most cases, a defect due to the occurrence of migration is confirmed within a few hours.

Also, in recent years, there is a tendency for the temperature applied to the package to become very high, such as the transition to surface mounting and the use of lead-free solder in consideration of environmental issues. Along with this, the reached temperature inside and outside of the package is remarkably high, and in the conventional liquid photosensitive resist, there is a problem that the coating film is cracked by thermal shock or peels off from the substrate and the sealing material, There is a need for improvement.

On the other hand, as a carboxyl group-containing resin used in a conventional solder resist, an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used. For example, Japanese Patent Laid-Open No. 61-243869 (Patent Document 1) discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, and a diluent. And a solder resist composition comprising an epoxy compound has been reported. Japanese Patent Laid-Open No. 3-250012 (Patent Document 2) adds (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin. Furthermore, a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed.

In general epoxy acrylate modified resins, the epoxy resin used as a raw material already contains a large amount of chlorine ion impurities, and it is very difficult to remove this after the epoxy acrylate modification. In addition, it is a known fact that an insulating material containing a chlorine ion impurity has poor insulation reliability.

JP 61-243869 (Claims) Japanese Patent Laid-Open No. 3-250012 (Claims)

The present invention has been made in view of the above-described problems of the prior art, and its main purpose is to have PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which are important as solder resists for semiconductor packages. It is providing the photocurable thermosetting resin composition which can form a cured film.
Furthermore, the object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable thermosetting resin composition, and a solder resist using the dry film and the cured product. An object of the present invention is to provide a printed wiring board on which a cured film such as the above is formed.

In order to achieve the above object, according to the present invention, a carboxyl group-containing resin (excluding a carboxyl group-containing resin starting from an epoxy resin), a photopolymerization initiator, and a hydroxyl group-containing elastomer are contained. A photocurable thermosetting resin composition that can be developed with an alkaline aqueous solution is provided.
The carboxyl group-containing resin preferably does not contain a hydroxyl group, and preferably has a photosensitive group. The hydroxyl group-containing elastomer is preferably a butadiene or isoprene derivative. In a preferred embodiment, the photocurable thermosetting resin composition of the present invention further contains a thermosetting component, and preferably for a solder resist containing a colorant.

Moreover, according to this invention, the photocurable thermosetting dry film obtained by apply | coating and drying the said photocurable thermosetting resin composition on a film is provided.
Furthermore, according to the present invention, there is provided a cured product obtained by photocuring the photocurable thermosetting resin composition or dry film, preferably by photocuring in a pattern with a light source having a wavelength of 350 to 410 nm. .
Furthermore, according to the present invention, the photocurable thermosetting resin composition or the dry film is photocured in a pattern by irradiation with active energy rays, preferably by direct drawing of ultraviolet rays, and then thermally cured. A printed wiring board having the resulting cured film is provided.

Since the photocurable thermosetting resin composition of the present invention uses a carboxyl group-containing resin that does not use an epoxy resin as a starting material as a component that can be developed with an alkaline aqueous solution, the contained chlorine ion impurity is remarkably reduced. The electrical properties of the resulting cured coating are improved. Further, since it contains a hydroxyl group-containing elastomer in combination with this, not only the flexibility of the cured coating film is improved, but also it is very effective for stress relaxation when the coating film is overcured. Therefore, by using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured film having PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance important as a solder resist for semiconductor packages.

Hereinafter, embodiments of the present invention will be described in detail.
The photocurable thermosetting resin composition of the present embodiment is characterized by containing a carboxyl group-containing resin not using an epoxy resin as a starting material, a photopolymerization initiator, and a hydroxyl group-containing elastomer.
As the carboxyl group-containing resin of this embodiment, conventionally known various carboxyl group-containing resins can be used as long as the carboxyl group-containing resin does not use an epoxy resin as a starting material. A carboxyl group-containing photosensitive resin having a bond is preferable in terms of photocurability and development resistance. Further, the unsaturated double bond of such a carboxyl group-containing resin is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, one or more ethylenically unsaturated groups per molecule as described later are used. It is necessary to use a compound having a group (photosensitive monomer) in combination.

As specific examples of such a carboxyl group-containing resin, for example, the following compounds (any of oligomers and polymers) are preferable.
(1) A plurality of phenols in one molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. Reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a reactive hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride such as maleic acid anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, or adipic acid anhydride.

(2) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound, molecules such as hydroxyalkyl (meth) acrylate A carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminally (meth) acrylated.

(5) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. A carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and then terminally (meth) acrylating.

(6) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(7) A polyfunctional oxetane resin as described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and the resulting primary hydroxyl group has phthalic anhydride, tetrahydrophthalic anhydride, One epoxy group in one molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate is added to a carboxyl group-containing polyester resin to which a dibasic acid anhydride such as hexahydrophthalic anhydride is added. A carboxyl group-containing photosensitive resin obtained by adding a compound having one or more (meth) acryloyl groups.

(8) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resins (1) to (7).
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

The carboxyl group-containing resin used in the present embodiment has a feature that the halide content is very low because an epoxy resin is not used as a starting material. The chlorine ion impurity content of the carboxyl group-containing resin used in the present invention is 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less.

Further, the carboxyl group-containing resin used in the present embodiment can easily obtain a resin not containing a hydroxyl group. In general, the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but it is known to significantly reduce moisture resistance. Below, the outstanding point of the carboxyl group-containing resin of this embodiment compared with the epoxy acrylate modified resin used for the general solder resist is demonstrated.

フ ェ ノ ー ル Phenol novolac resin without chlorine can be easily obtained. By partial acrylation of the phenol resin modified with alkylene oxide and introduction of an acid anhydride, a resin theoretically having no hydroxyl group in the range of double bond equivalent of 300 to 550 and acid value of 40 to 120 mgKOH / g. It is possible to obtain.

On the other hand, when all the epoxy groups of an epoxy resin synthesized from a similar phenol novolac resin are acrylated and acid anhydrides are introduced into all the hydroxyl groups, the acid value becomes very large with a double bond equivalent of 400 to 500, Even after exposure, a film having development resistance cannot be obtained. Furthermore, since the acid value is high, the water resistance is inferior, and the insulation reliability and PCT resistance are significantly reduced. That is, it is very difficult to completely eliminate the hydroxyl group from an epoxy acrylate resin derived from a similar phenol novolac type epoxy resin.

Moreover, urethane resin can also synthesize | combine easily the resin which does not contain a hydroxyl group by match | combining the equivalent of a hydroxyl group and an isocyanate group. The preferred resin is an isocyanate compound not using phosgene as a starting material, and a carboxyl group-containing resin having a chlorine ion impurity amount of 30 ppm or less synthesized from a raw material not using epihalohydrin, and more preferably synthesized so as not to theoretically contain a hydroxyl group. Resin.
From such a viewpoint, the carboxyl group-containing resins (1) to (5) shown as specific examples above can be particularly preferably used.

In addition, as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, a 3,4-epoxy is used with respect to the carboxyl group-containing resin (6) obtained by copolymerization with the unsaturated group-containing compound shown above. A carboxyl group-containing photosensitive resin obtained by reacting cyclohexylmethyl (meth) acrylate can be suitably used because it uses alicyclic epoxy and has few chloride ion impurities.

On the other hand, the carboxyl group-containing resin (6) is reacted with glycidyl (meth) acrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, or glycidyl (meth) as an unsaturated group-containing compound. Those obtained by copolymerizing acrylates have a concern that the amount of chlorine ion impurities increases.

Also, an epoxy acrylate-modified raw material can be used as a diol compound in the synthesis of a urethane resin. Although chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.

Since the carboxyl group-containing resin as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with an alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mgKOH / g. When the acid value is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary. It is difficult to draw a normal resist pattern due to dissolution and peeling with a developer without distinction between the unexposed area and the unexposed area. More preferably, it is in the range of 40 to 130 mgKOH / g.

In addition, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000 in general. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is in the range of 5,000 to 100,000.

The blending amount of such a carboxyl group-containing resin is 20 to 60% by mass in the entire composition. When it is less than the above range, the coating film strength is lowered. On the other hand, when the amount is larger than the above range, the viscosity is increased or the coating property is decreased. More preferably, it is 30 to 50% by mass.

As the photopolymerization initiator used in the present embodiment, an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator can be used. Of these, it is preferable to use at least one of them.

Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by Adeka, Adeka Arcles NCI-831, and the like as commercially available products. .

In addition, a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used. Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (1). .

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom), substituted with an alkyl group having a C 1-8 alkyl group or a dialkylamino group. Alkyl groups having 8 to 8 alkoxy groups, halogen groups, phenyl groups, phenyl groups (alkyl groups having 1 to 17 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, amino groups, alkyl groups having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthrylene, thienylene, (Furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, n is an integer of 0 or 1)

Particularly, in the formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is preferably phenylene, naphthylene, or thienylene.

The blending amount of such oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.

Specific examples of the α-aminoacetophenone photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like can be mentioned. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.

Specific examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Japan.

The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount is less than 0.01 parts by mass, the photocurability on copper is similarly insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, if it exceeds 15 parts by mass, a sufficient effect of reducing the outgas cannot be obtained, and light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 10 parts by mass.

In addition, as a photopolymerization initiator, a photoinitiator assistant and a sensitizer that can be suitably used for the photocurable resin composition of the present embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, Examples include benzophenone compounds, tertiary amine compounds, and xanthone compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. A dialkylamino group-containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure® DMB manufactured by International Bio-Synthetics), 4-dimethylamino Ethyl benzoate (n-butoxy) (Quantacure® BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate ( Examples include Esolol® 507 manufactured by Van Dyk.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by including a thioxanthone compound, it is possible to improve deep curability.

The compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.

As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to obtain a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the coating film by the tertiary amine compound becomes violent, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.

The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the total amount exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

The hydroxyl group-containing elastomer used in the photocurable thermosetting resin composition of the present embodiment not only improves the flexibility of the resulting cured coating film, but is also very effective for stress relaxation during solder resist overcuring. In other words, it was revealed that it is excellent in PCT resistance. Such a hydroxyl group-containing elastomer can be used without particular limitation as long as it is a compound having a hydroxyl group at the side chain or terminal, for example, a hydroxyl group-containing acrylic elastomer, a hydroxyl group-containing polyester elastomer, a hydroxyl group-containing polyester urethane type Examples include elastomers, hydroxyl group-containing urethane elastomers, cellulose derivative elastomer resins, and polylactic acid elastomers. Particularly preferable examples include polybutadiene elastomers, polyisoprene elastomers and derivatives thereof.

Specific examples of the hydroxyl group-containing elastomer include hydroxyl group-terminated liquid polybutadiene (Poly bd, manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl group-terminated liquid isoprene (Poly ip, manufactured by Idemitsu Kosan Co., Ltd.), and hydroxyl group-terminated polyolefin-based polyol (Epol, Idemitsu Kosan Co., Ltd.). Product), hydroxyl-terminated liquid polybutadiene water additive (Polytail H, manufactured by Mitsubishi Chemical Corporation), and the like.

The blending amount of such a hydroxyl group-containing elastomer is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 5 parts by mass, the effect of the hydroxyl group-containing elastomer is not confirmed. On the other hand, when it exceeds 60 parts by mass, the tackiness of the coating film may be deteriorated and the development may be poor. More preferably, it is 10 to 50 parts by mass.

Furthermore, a thermosetting component can be added to the photocurable thermosetting resin composition of the present embodiment in order to impart heat resistance.
Examples of thermosetting components used in this embodiment include blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like. These known thermosetting resins can be used. Among these, a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.

Furthermore, the hydroxyl group of the above-mentioned hydroxyl group-containing elastomer is made strong by reacting with a hydroxyl group produced by a reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group), or by reacting the hydroxyl groups with each other. By incorporating it into a three-dimensional network, its characteristics can be maximized, and therefore a cured product that has been given considerable flexibility by using amino resins, isocyanates, or blocked isocyanates that can easily react with hydroxyl groups or carboxyl groups. Can be obtained.

Such a thermosetting component having a plurality of cyclic (thio) ether groups in one molecule is either one or two of three, four or five-membered cyclic ether groups or cyclic thioether groups in one molecule. A compound having at least a plurality of epoxy groups in one molecule, that is, a polyfunctional epoxy compound, a compound having at least a plurality of oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound, Examples thereof include a compound having a plurality of thioether groups in the molecule, that is, a polyfunctional episulfide resin.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055 manufactured by DIC, Epototo YD-011, YD manufactured by Toto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. A. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175 manufactured by Toto Kasei -2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); Hydrogenation of Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Toto Kasei Co., Ltd. Bisphenol A type epoxy resin; jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Name) glycidylamine type epoxy resin; Hydantoin-type epoxy resins such as Arapide CY-350 (trade name) manufactured by Japan; alicyclic epoxy such as Celoxide 2021 manufactured by Daicel Chemical Industries, Araldide CY175 and CY179 manufactured by Ciba Japan Resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resins or mixtures thereof; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd. Bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; Tetraphenylol such as jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Japan Co., Ltd. (all trade names) Ethane type epoxy resin; manufactured by Ciba Japan Heterocyclic epoxy resins such as Rudide PT810, TEPIC manufactured by Nissan Chemical Industries (all trade names); Diglycidyl phthalate resins such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidyl such as ZX-1063 manufactured by Tohto Kasei Xylenoylethane resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphtalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP- manufactured by DIC Epoxy resins having a dicyclopentadiene skeleton such as 7200 and HP-7200H; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; and a copolymer epoxy of cyclohexylmaleimide and glycidyl methacrylate Resin; Epoxy-modified polybutadiene rubber Derivatives (e.g., manufactured by Daicel Chemical Industries, PB-3600, etc.), CTBN modified epoxy resin (e.g., Tohto Kasei Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, novolak-type epoxy resins, modified novolak-type epoxy resins, heterocyclic epoxy resins, bixylenol-type epoxy resins or mixtures thereof are particularly preferable.

Polyfunctional oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, poly (P-hydroxystyrene), cardo bisphenol S, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

Examples of the polyfunctional episulfide resin include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in one molecule is in the range of 0.6 to 2.5 equivalents relative to 1 equivalent of carboxyl group of the carboxyl group-containing resin. Is preferred. When the blending amount is less than 0.6 equivalent, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like are deteriorated. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dried coating film, thereby reducing the strength of the coating film. More preferably, it is in the range of 0.8 to 2.0 equivalents.

Furthermore, examples of thermosetting components that can be suitably used include melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are the methylol groups of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx-290 Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw-750LM (Above, manufactured by Sanwa Chemical Co., Ltd.).
These thermosetting components can be used alone or in combination of two or more.

In addition, the photocurable thermosetting resin composition of the present embodiment has a plurality of isocyanate groups or blocked isocyanate groups in one molecule in order to improve the curability of the composition and the toughness of the resulting cured film. The compound having can be added. Such a compound having an isocyanate group or blocked isocyanate group in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having a plurality of blocked isocyanate groups in one molecule. That is, a blocked isocyanate compound etc. are mentioned.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As such an isocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam. Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is done.

The blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, while when it exceeds 100 parts by mass, the storage stability is lowered. More preferably, it is 2 to 70 parts by mass.

A urethanization catalyst can be added to the photocurable thermosetting resin composition of the present embodiment in order to accelerate the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group. As the urethanization catalyst, it is possible to use one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. preferable.

Examples of the tin-based catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

The metal chloride is a metal chloride made of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.

The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Can be mentioned.

The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include copper sulfate.

Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N′- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl -N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ) -N, N ′, N ″, N ″ -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ″, N ″ -tetramethyldiethylenetriamine, N, N, N′-trimethyl -N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1 -(2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imida 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′- Aminopropyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxy) Ethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, N'-bis (2-hydroxypropyl) amine, melamine and / or benzoguanamine and the like can be mentioned.

Examples of the amine salt include DBU (1,8-diaza-bicyclo [5,4,0] undecene-7) organic acid salt.

The amount of these urethanization catalysts to be blended is a normal quantitative ratio, for example, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts per 100 parts by weight of carboxyl group-containing resin. 0 parts by mass.

When using a thermosetting component having a plurality of cyclic (thio) ether groups in one molecule, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts can also be used. Is also used in combination with the above thermosetting catalyst.

The compounding amount of these thermosetting catalysts is sufficient in a normal quantitative ratio, for example, for 100 parts by mass of a thermosetting component having a carboxyl group-containing resin or a plurality of cyclic (thio) ether groups in one molecule. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

The photocurable resin composition of the present embodiment can contain a colorant. As the colorant, known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant:
Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Indexes (CI; issued by The Society of Dyers and Colorists) are listed.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, 175, 176, 185, 208.
Perylene series: Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224.
Diketopyrrolopyrrole type: Pigment Red 254, 255, 264, 270, 272.
Condensed azo series: Pigment Red 144, 166, 214, 220, 221, 242.
Anthraquinone series: Pigment Red 168, 177, 216, Solvent Red 52, 149, 150, 207.
Quinacridone series: Pigment Red 122, 202, 206, 207, 209.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds include those classified as Pigments, specifically, the following: Pigment Blue: 15 : 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60.
Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, 136 etc. can be used as the dye system. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, the green colorant includes phthalocyanine, anthraquinone, and perylene, and specifically, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, 108, 147, 193, 199, 202.
Isoindolinone series: Pigment Yellow 110, 109, 139, 179, 185.
Condensed azo type: Pigment Yellow 93, 94, 95, 128, 155, 166, 180.
Benzimidazolone series: Pigment Yellow 120, 151, 154, 156, 175, 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

Other colorants such as purple, orange, brown and black may be added for the purpose of adjusting the color tone. Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38 , 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, Pigment Black 1, 7, etc.

The blending amount of these colorants is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.

The compound having a plurality of ethylenically unsaturated groups in one molecule used in the photocurable thermosetting resin composition of the present embodiment is photocured by irradiation with active energy rays to convert the carboxyl group-containing resin into an alkali. It helps insolubilize or insolubilize in an aqueous solution. As such a compound, known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like can be used. Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate Aminoalkyl acrylates such as relates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone Polyvalent acrylates such as adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Multivalent acrylates of glycidyl ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate Not limited to the above, but also acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and / or the above acrylates. Corresponding methacrylates are exemplified.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. The epoxy urethane acrylate compound etc. which made the half urethane compound react are mentioned. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

The compounding amount of the compound having a plurality of ethylenically unsaturated groups in one molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays. On the other hand, when it exceeds 100 mass parts, the solubility with respect to alkaline aqueous solution falls, and a coating film becomes weak. A ratio of 1 to 70 parts by mass is more preferable.

In the photocurable thermosetting resin composition of the present embodiment, a filler can be blended as necessary in order to increase the physical strength of the coating film. As such a filler, known inorganic or organic fillers can be used, but barium sulfate, spherical silica, and talc are particularly preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of these fillers is preferably 200 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the compounding amount exceeds 200 parts by mass, the viscosity of the composition increases, printability is reduced, and the cured product becomes brittle. More preferred is 0.1 to 150 parts by mass, and particularly preferred is 1 to 100 parts by mass.

Furthermore, the photocurable thermosetting resin composition of the present embodiment can use a binder polymer for the purpose of improving dryness to touch and improving handling properties. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.

Furthermore, the photocurable thermosetting resin composition of the present embodiment can further use other elastomers for the purpose of imparting flexibility and improving the brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used. In addition, resins in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.

Furthermore, the photocurable thermosetting resin composition of the present embodiment uses an organic solvent for the synthesis of a carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. can do.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, the photocurable thermosetting resin composition of the present embodiment is used. Such as radical scavengers that invalidate the generated radicals to prevent oxidation and / or peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals. Antioxidants can be added.

Specific examples of the antioxidant that acts as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-t-butyl-p-cresol. 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'-di-t-butyl-4- Phenolic compounds such as hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-te Ramechiru 4-piperidyl) - sebacate, amine compounds such as phenothiazine and the like.

The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN Japan brand name, product name) and the like.

Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3. And sulfur compounds such as' -thiodipropionate.

The peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer TPS (Sumitomo Chemical). Company name, product name) and the like.
These antioxidants can be used alone or in combination of two or more.

In general, since the polymer material absorbs light and thereby decomposes and deteriorates, the photocurable thermosetting resin composition of the present embodiment has the above-described oxidation in order to take a countermeasure against stabilization against ultraviolet rays. In addition to the inhibitor, an ultraviolet absorber can be used.

Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and the like. Is mentioned.

Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like.

Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (manufactured by Ciba Japan, trade name) and the like.

These ultraviolet absorbers can be used singly or in combination of two or more, and stabilization of a molded product obtained from the photocurable thermosetting resin composition of the present embodiment by using in combination with the above antioxidant. Can be planned.

In addition, the photocurable thermosetting resin composition of the present embodiment uses known N phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, etc. as chain transfer agents in order to improve sensitivity. Can do. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclope Tanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

Polyfunctional mercaptan compounds can be used and are not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythri Poly (mercaptoacetate) s of polyhydric alcohols such as tetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, poly (mercaptobutyrate) s such as pentaerythritol tetrakis (3-mertabutbutyrate) can be used.

Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz- NR1 (manufactured by Showa Denko KK) and the like can be mentioned.

Further, as a heterocyclic compound having a mercapto group that acts as a chain transfer agent, for example, mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto- 4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl -2-Mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2 , 4,6-trimercapto-s-triazine (Sankyo Kasei Co., Ltd .: trade name: Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (Sankyo Chemical Co., Ltd .: trade name: Disnet DB) , And 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd., trade name: DISNET AF) And the like.

In particular, mercaptobenzothiazole, 3-mercapto-4-methyl-4H is a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable thermosetting resin composition of the present embodiment. Preferred are -1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, and 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents can be used alone or in combination of two or more.

In the photocurable thermosetting resin composition of the present embodiment, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.), 3- Morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino Examples include group-containing benzotriazoles and silane coupling agents.

The photocurable thermosetting resin composition of the present embodiment can further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary. Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics. In addition, thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, and bisphenols Known additives such as copper damage preventing agents such as triazine and triazine thiol can be blended.

The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound contained in the photocurable thermosetting resin composition of the present embodiment. Examples of such thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride Phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, Examples include picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, nitroso compound, chelate of nitroso compound and Al, and the like.

The photocurable thermosetting resin composition of the present embodiment is adjusted to a viscosity suitable for the coating method using, for example, the above organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying). . Thereafter, the contact pattern (or non-contact pattern) is selectively exposed with an active energy ray through a photomask on which a pattern is formed, or directly exposed with a pattern using a laser direct exposure machine. A resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution. Further, in the case of a composition containing a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin in the composition and one molecule A thermosetting component having a plurality of cyclic (thio) ether groups reacts to form a cured coating film having excellent characteristics such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. it can. In addition, even when it does not contain a thermosetting component, by performing heat treatment, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

Examples of the base material include printed circuit boards and flexible printed circuit boards that are pre-formed with a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

Volatile drying performed after applying the photocurable thermosetting resin composition of the present embodiment is a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, or the like (having a heat source of an air heating method using steam). And a method in which the hot air in the dryer is brought into countercurrent contact and a method in which the hot air is blown onto the support from the nozzle).

Exposure (irradiation of active energy rays) is performed on the coating film thus obtained. In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp.
As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure amount varies depending on the film thickness and the like, but can be generally in the range of 5 to 200 mJ / cm ² , preferably 5 to 100 mJ / cm ² , more preferably 5 to 50 mJ / cm ² .
As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

As the developing method, dipping method, shower method, spray method, brush method, etc. can be used, and as the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia An alkaline aqueous solution such as amines can be used.

The photo-curable thermosetting resin composition of the present embodiment has a solder resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance, in addition to the method of directly applying to a substrate in a liquid state. It can also be used in the form of a dry film. The case where the photocurable thermosetting resin composition of this embodiment is used as a dry film is shown below.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali-developable photocurable thermosetting resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
For the solder resist layer, the photocurable thermosetting resin composition of the present embodiment is uniformly applied to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. A cured coating film can be formed by exposing, developing, and heat-curing the formed solder resist layer in the same manner as described above. The carrier film may be peeled off either before exposure or after exposure.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

<Synthesis Example 1>
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 119.4 g of a novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4), 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
Next, 293.0 g of the resulting novolak-type cresol resin propylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air. A reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolak acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-1.

<Synthesis Example 2>
In a 5-liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, 1,245 g of polycaprolactone diol (PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, and dihydroxy compound as a dihydroxyl compound having a carboxyl group 201 g of methylol propionic acid, 777 g of isophorone diisocyanate as a polyisocyanate, 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and 0.5 g each of p-methoxyphenol and di-t-butyl-hydroxytoluene I put them one by one. The mixture was stopped by heating to 60 ° C. while stirring, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C. to confirm that the isocyanate group absorption spectrum (2280 cm ⁻¹ ) has disappeared in the infrared absorption spectrum. A viscous liquid urethane acrylate compound was obtained. The volatile content was adjusted to 50% using carbitol acetate. A resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as varnish A-2.

<Synthesis Example 3>
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate as a polymerization initiator (Japan) 21.4 g (trade name; Perbutyl O) manufactured by Yushi Co., Ltd. was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Placcel FM1: manufactured by Daicel Chemical Industries) were added to the bis (4 -T-Butylcyclohexyl) peroxydicarbonate (trade name; Parroyl TCP, manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise over 3 hours together with 21.4 g, and further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. Obtained. The reaction was performed under a nitrogen atmosphere.
Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer A200) and 3.6 g of dimethylbenzylamine as a ring-opening catalyst were added to the obtained carboxyl group-containing copolymer resin. Then, 1.80 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, heated to 100 ° C., and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000, and a solid content of 54% was obtained. Hereinafter, this is referred to as varnish A-3.

<Comparative Synthesis Example 1>
Orthocresol novolac epoxy resin (600 g, diethylene glycol monoethyl ether acetate (DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings): 5) 0.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction liquid, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value A resin solution having 89 mg KOH / g and a solid content of 65% was obtained. Hereinafter, this is referred to as varnish R-1.

<Comparative Synthesis Example 2>
Cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220) 2200 parts, dimethylolpropionic acid 134 parts, acrylic acid 648.5 parts, methylhydroquinone 4.6 parts, Calvi 1131 parts of tall acetate and 484.9 parts of solvent naphtha were charged, heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g. Next, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent naphtha are charged into this, heated to 95 ° C., reacted for about 6 hours, cooled, solid acid A resin solution of a carboxyl group-containing photosensitive resin having a value of 40 mgKOH / g and a nonvolatile content of 65% was obtained. Hereinafter, this is referred to as varnish R-2.

<Comparative Synthesis Example 3>
After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide in 400 parts of a bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 parts of 98.5% NaOH at 100 ° C. with stirring were added to 100 parts. Added over minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% NaOH is added, The reaction was carried out at 1 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After the oil / water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were charged, heated to 90 ° C., stirred and reacted. The mixture was dissolved. Next, the reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mg KOH / g, solid content 65 % Resin solution was obtained. Hereinafter, this is referred to as varnish R-3.

[Examples 1 and 2 and Comparative Examples 1 to 3]
Using the resin solutions obtained in each of the above synthesis examples, blended in various components and proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photocurable heat A curable resin composition was prepared. The obtained photocurable thermosetting resin composition was quantified in halide content (total of chloride and bromide) by using a flask combustion treatment ion chromatography method based on the JPCA standard. The results are also shown in Table 1.

[Remarks]
* 1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1,1- (O-acetyloxime) (Irgacure OXE02: manufactured by Ciba Japan)
* 2: Hydroxyl-terminated liquid polybutadiene (Poly bd: manufactured by Idemitsu Kosan Co., Ltd.)

As is apparent from the results shown in Table 1, the photocurable thermosetting resin compositions of Examples 1 and 2 using the carboxyl group-containing resins (A-1, A-2) not using an epoxy resin as a starting material are In comparison with the photocurable thermosetting resin compositions of Comparative Examples 1 to 3 using a carboxyl group-containing photosensitive resin (R-1, R-2, R-3) starting from an epoxy resin, It can be seen that the amount of halogen is extremely small.

[Examples 3 to 13, Comparative Examples 4 to 6]
Using the resin solution of the above synthesis example, blended in various components and proportions (parts by mass) shown in Table 2, premixed with a stirrer, kneaded with a three-roll mill, and photosensitive resin composition for solder resist Was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

[Remarks]
* 1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: manufactured by Ciba Japan)
* 2: 2,4-Diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1,1- (O-acetyloxime)
(Irgacure OX02: manufactured by Ciba Japan)
* 4: Hydroxyl-terminated liquid polybutadiene (Poly bd: manufactured by Idemitsu Kosan Co., Ltd.)
* 5: Hydroxyl-terminated liquid polyisoprene (Poly ip: manufactured by Idemitsu Kosan Co., Ltd.)
* 6: Hydroxyl-terminated liquid polyolefin (Epol: Idemitsu Kosan Co., Ltd.)
* 7: Epoxidized polybutadiene (manufactured by Daicel Chemical Industries)
* 8: Phenol novolac type epoxy resin (RE306CA90: manufactured by Nippon Kayaku Co., Ltd.)
* 9: Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.)
* 10: C.I. I. Pigment Blue 15: 3
* 11: C.I. I. Pigment Yellow 147
* 12: 2-mercaptobenzothiazole * 13: Antioxidant (Ciba Japan)
* 14: B-30 (manufactured by Sakai Chemical)
* 15: Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 16: Diethylene glycol monoethyl ether acetate * 17: Dipentaerythritol hexaacrylate * 18: Block isocyanate (manufactured by Asahi Kasei Chemicals)
* 19: Methylated melamine resin (Sanwa Chemical Co., Ltd.)

Performance evaluation:
<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 18 μm was subjected to a copper surface roughening treatment (MEC etch bond CZ-8100 manufactured by MEC Co., Ltd.), washed with water, dried, and then the photocurable thermosetting resins of Examples and Comparative Examples shown in Table 2 The composition was applied to the entire surface by a screen printing method, and dried for 60 minutes in a hot air circulation drying oven at 80 ° C. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and remains when developing (30 ° C., 0.2 MPa, 1% aqueous sodium carbonate solution) in 60 seconds. When the step tablet pattern is 7 steps, the optimum exposure was set.

<Developability>
The photocurable thermosetting resin compositions of Examples and Comparative Examples shown in Table 2 were applied on a copper solid substrate by a screen printing method so that the film thickness after drying was about 25 μm, and hot air circulation at 80 ° C. It was made to dry for 30 minutes in a type drying oven. After drying, development was performed with a 1% aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured with a stopwatch.

<Maximum development life>
The photocurable thermosetting resin compositions of Examples and Comparative Examples shown in Table 2 were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., and every 10 minutes from 20 minutes to 80 minutes. The substrate was taken out and allowed to cool to room temperature. This substrate was developed with a 1% aqueous sodium carbonate solution at 30 ° C. for 60 seconds under the condition of a spray pressure of 0.2 MPa, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.

<Tackiness>
The photocurable thermosetting resin compositions of Examples and Comparative Examples shown in Table 2 were applied on the entire surface of the patterned copper foil substrate by screen printing and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. And allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and the film was pressure-bonded under reduced pressure for 1 minute with HMW-GW20 manufactured by ORC. Thereafter, the sticking state of the film when the negative film was peeled off was evaluated according to the following criteria.
○: When peeling off the film, there is no resistance at all and no mark is left on the coating film.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

Characteristic test:
The photocurable thermosetting resin compositions of Examples and Comparative Examples shown in Table 2 were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. . Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa. Obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling due to the tape peel was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off

<Alkali resistance>
The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling due to the tape peel was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5μm and gold 0.05μm, and tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Slight penetration was confirmed after plating, but there was no peeling after tape peeling.
Δ: Slight penetration was confirmed after plating, and peeling was also observed after tape peeling.
X: There is peeling after plating.

<PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HEST SYSTEM TPC-412MD manufactured by Espec Corp.), and the state of the coating film was evaluated. did. The judgment criteria are as follows.
○: No swelling, peeling, discoloration, or dissolution △: Some swelling, peeling, discoloration, or dissolution ×: Many swelling, peeling, discoloration, or dissolution

<Cold shock resistance>
The evaluation board | substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced. The obtained evaluation substrate was subjected to a 1000 cycle durability test using a thermal shock tester (manufactured by ETAC) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.
○: Crack generation rate less than 30% △: Crack generation rate 30-50%
×: Crack occurrence rate 50% or more

<HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-shaped electrodes (line / space = 50 microns / 50 microns) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high temperature / humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 12V was charged, and the in-chamber HAST test was done for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.
○: 10 ⁸ Ω or more △: 10 ⁶ to 10 ⁸ Ω
×: 10 ⁶ Ω or less

[Examples 14 to 21, Comparative Examples 7 to 9]
Each composition of Examples 3, 5, 6, 8, 9, 10, 11, 13 and Comparative Examples 4, 5, 6 prepared at the blending ratios shown in Table 2 was diluted with methyl ethyl ketone and applied onto a PET film. And it dried at 80 degreeC for 30 minutes, and formed the photosensitive resin composition layer of thickness 20 micrometers. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 14 to 21 and Comparative Examples 7 to 9, respectively.

<Dry film evaluation>
The cover film is peeled off from the dry film obtained as described above, the film is thermally laminated on the patterned copper foil substrate, and then under the same conditions as the substrate used for the coating film property evaluation of the above examples. Exposed. After the exposure, the carrier film was peeled off, and a 1% sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 4.

As is apparent from the results shown in Tables 3 and 4, the photo-curable thermosetting resin composition of the present invention has the PCT resistance, thermal shock resistance, HAST characteristics (electrical characteristics) required for the solder resist for semiconductor packages. It was recognized that it was useful as a photocurable thermosetting resin composition having

Claims (5)

1. A carboxyl group-containing resin having a photosensitive group (excluding a carboxyl group-containing resin starting from an epoxy resin),
   A photocurable thermosetting resin composition developable with an aqueous alkali solution, comprising a photopolymerization initiator and a hydroxyl group-containing elastomer.
2. The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin does not contain a hydroxyl group.
3. A photocurable thermosetting dry film obtained by applying and drying the photocurable thermosetting resin composition according to claim 1 or 2 on a film.
4. A photocurable thermosetting resin composition according to claim 1 or claim 2 or a dry film obtained by applying and drying the photocurable thermosetting resin composition on a film is laminated on a substrate. Cured product obtained by photocuring the coating film obtained by irradiation with active energy rays.
5. The photocurable thermosetting resin composition according to claim 1 or 2, or a dry film obtained by applying and drying the photocurable thermosetting resin composition on a film is irradiated with active energy rays. A printed wiring board having a cured film obtained by photocuring in a pattern and then thermosetting.