JP2012212048A - Photo-curable thermosetting resin composition, dry film and cured product of the same, and printed wiring board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-curable thermosetting resin composition which has excellent storage stability at room temperature as a one liquid type resin composition and a dry film of the resin composition, and has excellent developability, solder heat resistance, insulation reliability, gold plating resistance and the like, and to provide a dry film and a cured product of the same, and a printed wiring board manufactured by forming a cured coating film such as a solder resist with the dry film and the cured product.SOLUTION: The photo-curable thermosetting resin composition which can be stored at normal temperature contains a carboxyl group-containing resin, a photoinitiator, and a plant-derived epoxy compound, preferably, the carboxyl group-containing resin has an acid number of 30-150 mgKOH/g and has a photopolymerizable group, particularly, an ethylenically unsaturated group, and the plant-derived epoxy compound is an epoxidized soybean oil and/or an epoxidized linseed oil.

Description

  The present invention relates to a photocurable thermosetting resin composition that can be developed with a dilute alkaline aqueous solution, in particular, a solder resist composition that is photocured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, and a film formed using them. The present invention relates to a printed wiring board having a cured film.

  With recent rapid progress in semiconductor components, electronic devices tend to be smaller, lighter, higher performance, and multifunctional. Following this trend, printed wiring boards are also becoming increasingly dense and surface-mounted. In the production of high-density printed wiring boards, photo solder resist is generally employed, and dry film type photo solder resist and liquid photo solder resist have been developed. Among these, in consideration of environmental problems, an alkali developing type photosensitive composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been proposed (Patent Document 1). reference).

The alkali-developable photosensitive composition exhibits alkali developability by containing a resin having a carboxyl group in the composition.
However, the carboxyl group is highly hydrophilic, and when a resin having a carboxyl group is used as a photosensitive insulating material such as a solder resist, the insulation reliability is likely to deteriorate.
Therefore, for the purpose of improving insulation reliability and solder heat resistance, a thermosetting component capable of crosslinking with a carboxyl group represented by a glycidyl compound is used.

Since the carboxyl group and the glycidyl group undergo a crosslinking reaction even at room temperature, the solder resist composition is generally a “two-pack type” in which the carboxyl group-containing compound and the glycidyl compound are separated.
However, the two-pack type solder resist has a short pot life after mixing as short as several hours to one day, and must be mixed immediately before the coating process. Furthermore, there is a problem that this mixing process takes time.

In order to compensate for the disadvantages of the two-component type, various one-component type photosensitive resin compositions have been studied.
For example, a photosensitive resin composition comprising a blocked isocyanate compound instead of a glycidyl compound and comprising a carboxyl group-containing resin, a photopolymerization initiator, a diluent, and an adhesion promoter has been proposed (see Patent Document 2). In addition, a photosensitive resin composition using an epoxy resin-encapsulated microcapsule that encapsulates a glycidyl compound in a thermally destructible film and latentizes the reaction between the carboxylic acid compound and the glycidyl compound at room temperature has been proposed (Patent Literature). 3).

JP 61-243869 (Claims etc.) JP 2001-305726 A (Claims etc.) JP 2010-128317 (Claims etc.)

  However, the photocurable thermosetting resin composition described in the above-mentioned patent document has problems that the heat resistance and insulation reliability of the cured coating film are insufficient or that the cost is increased.

Therefore, the present invention provides light having excellent storage stability at room temperature as a one-component resin composition and as a dry film, and having excellent developability, solder heat resistance, insulation reliability, gold plating resistance, and the like. An object is to provide a curable thermosetting resin composition.
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 photocurable thermosetting resin composition capable of being stored at room temperature, comprising a carboxyl group-containing resin, a photopolymerization initiator, and a plant-derived epoxy compound. Things are provided.
In a preferred embodiment, the acid value of the carboxyl group-containing resin is preferably 30 to 150 mgKOH / g, and preferably has a photopolymerizable group, particularly an ethylenically unsaturated group. Moreover, as said plant-derived epoxy compound, epoxidized soybean oil and epoxidized linseed oil are preferable from a versatility viewpoint.

Further, according to the present invention, a photocurable dry film obtained by applying and drying the photocurable thermosetting resin composition on a carrier film, the photocurable resin composition, or the dry film. There are also provided a cured product obtained by curing the resin, particularly a cured product obtained by photocuring on copper, and a cured product obtained by photocuring in a pattern.
Furthermore, according to the present invention, there is also provided a printed wiring board characterized by having a cured film obtained by photocuring the photocurable thermosetting resin composition or dry film in a pattern and then thermosetting. Is done.

According to the photocurable thermosetting resin composition of the present invention, the storage stability at room temperature is good as a one-component resin composition and as a dry film, and developability, solder heat resistance, and insulation reliability. Cured products having excellent properties such as properties and gold plating resistance.
Therefore, the photocurable thermosetting resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.

As described above, the photocurable thermosetting resin composition of the present invention is characterized in that a plant-derived epoxy compound is used in combination with a carboxyl group-containing resin and a photopolymerization initiator.
According to the study by the present inventors, such a photocurable thermosetting resin composition is excellent in storage stability at room temperature, and can be stored at room temperature as a one-component resin composition, and developability. It is possible to provide a resin composition excellent in solder heat resistance, insulation reliability, gold plating resistance, and the like. Furthermore, since plant raw materials are used as the thermosetting component, it is possible to provide an environmentally friendly resin composition.
Hereinafter, each component of the photocurable thermosetting resin composition of the present invention will be described in detail.

As the carboxyl group-containing resin, conventionally known various carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting a crosslinking reaction, adhesion and alkali developability can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and development resistance as a photosensitive composition for performing alkali development. The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof, and is preferably a carboxyl group-containing (meth) acrylate having an ethylenically unsaturated group. In addition, when using only the carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, the photosensitivity having a plurality of ethylenically unsaturated groups in the molecule described later. It is necessary to use a compound (photopolymerizable monomer) in an amount necessary for photocuring.
As specific examples of the carboxyl group-containing resin, the following compounds (any of oligomers and polymers) are preferable.

  (1) 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. A carboxyl group-containing photosensitive resin obtained by reacting a compound having one or more ethylenically unsaturated groups and one epoxy group in a molecule.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryl groups in the molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

  (5) During the synthesis of the resin of the above (2) or (3), one isocyanate group and one or more (meth) acryl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

  (6) (Meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride such as

  (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (8) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenolic compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is treated with maleic anhydride. Carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as tetrahydrophthalic anhydride, trimellitic anhydride and pyromellitic anhydride.

(9) The resin of the above (1) to (8) further has one epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing photosensitive resin obtained by adding a compound.
In the present specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  Among these, the resins mentioned in (1), (2), modified products thereof (4) and (5), and (8) can be used without using an epoxy compound (resin) made of epichlorohydrin as a raw material. Since a carboxylic acid-containing resin can be synthesized, it is particularly preferable from the viewpoint of halogen-free. In addition, even if it is an epoxy compound (resin), halogen-free can also be achieved by using the epoxy compound (resin) which does not use epichlorohydrin.

  In addition, the carboxyl group-containing resin used in the present invention has a mother skeleton such as novolak, bisphenol A, bisphenol F and the like described in the above (6), (7), and (8) from the viewpoint of heat resistance. A carboxyl group-containing photosensitive resin obtained by adding a dibasic acid anhydride represented by tetrahydrophthalic acid anhydride to a compound derived from a compound having an aromatic skeleton is preferred, but from the viewpoint of storage stability, A carboxyl group-containing resin derived by polymerization of an unsaturated carboxylic acid such as (meth) acrylic acid was better. This is because the carboxyl group of the polycarboxylic acid resin derived from the unsaturated carboxylic acid is milder in reactivity with the epoxy group than the carboxyl group derived from the aforementioned acid anhydride, so that the storage stability is improved. It is thought that it was excellent.

  Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

  The acid value of the carboxyl group-containing resin is suitably in the range of 30 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and particularly preferably 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 30 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds, so that the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group containing resin changes with resin frame | skeletons, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. 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.

The carboxyl group-containing resin is not limited to those listed above, and can be used alone or in combination of two or more.
The amount of such carboxyl group-containing resin is 60 wt% or less, preferably 10 to 50 wt% of the total amount of the composition.

  The photopolymerization initiator used in the present invention is at least selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. One type of photoinitiator can be used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルで表し、ｎは０か１の整数である。） Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like as commercially available products. . Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(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). A 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 number 1). Alkyl group having 1 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Group 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, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Represents an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene , Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.)

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that

  The blending amount of such an oxime ester photopolymerization initiator is preferably 0.02 to 10 wt% of the total amount of the composition. When it is less than 0.02 wt%, 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 10 wt%, light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered.

  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 BASF Japan.

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

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.5 to 15 wt% of the total amount of the composition. If it is less than 0.5 wt%, 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, when it exceeds 15 wt%, the effect of reducing the outgas cannot be obtained, and the light absorption on the surface of the solder resist coating film becomes intense and the deep curability tends to be lowered.

  Other photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photocurable thermosetting resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketals. Examples thereof include compounds, 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, and 2,4-diisopropylthioxanthone.

  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′-propyl. And diphenyl sulfide.

  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.). Dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4 Dimethylamino group-containing coumarin compounds such as -methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (International Bio-Synthetics) Quantacur DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 4 -Dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 manufactured by Van Dyk), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  Of the above photopolymerization initiator, photoinitiator assistant and sensitizer, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  The amount of such a thioxanthone compound is preferably 15 wt% or less of the total amount of the composition. When the blending amount of the thioxanthone compound exceeds 15 wt%, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 wt% 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 and is in the ultraviolet region, so it is less colored and uses not only a colorless and transparent photosensitive composition but also a colored pigment, which reflects the color of the colored pigment itself. A colored solder resist film can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  As a compounding quantity of such a tertiary amine compound, it is preferable to set it as 0.1-15 wt% of the whole composition amount. When the compounding amount of the tertiary amine compound is less than 0.1 wt%, a sufficient sensitizing effect tends not to be obtained. If it exceeds 15 wt%, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to be lowered.

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 it 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, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer 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 plant-derived epoxy compound is not particularly limited as long as the unsaturated group of the vegetable oil is epoxidized. Among these, epoxidized soybean oil and epoxidized castor oil are preferable from the viewpoint of versatility. Examples of commercially available products include Adeka Sizer D-32, Adeka Sizer D-55, Adeka Sizer O-130P, Adeka Sizer O-180A (all manufactured by ADEKA).

  The reaction between a general glycidyl compound and an active proton compound proceeds with β-cleavage and α-cleavage of the glycidyl compound, but most of them are β-cleavage. This is believed to be due to reactivity and steric hindrance. On the other hand, the epoxy group of the plant-derived epoxy compound is an epoxy structure derived from a double bond as described above, and the structure is an internal epoxy structure, which is less reactive than a general glycidyl compound. It is considered that excellent storage stability can be obtained. Furthermore, since the plant-derived epoxy compound does not use an epihalohydrin used for the synthesis of a general glycidyl compound, excellent results were obtained from a halogen-free viewpoint.

  The blending amount of the plant-derived epoxy compound is preferably in the range of 5 to 100 parts by mass, more preferably in the range of 10 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the plant-derived epoxy compound is less than 5 parts by mass, there is a concern about deterioration of various properties such as heat resistance. On the other hand, when it exceeds 100 parts by mass, the plant-derived epoxy compound remains and the coating strength decreases. Since it is considered, it is not preferable.

  The photocurable thermosetting resin composition of the present invention can contain other thermosetting components in addition to the plant-derived epoxy compound in order to impart heat resistance. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, bismaleimides, and oxazines. Known and commonly used thermosetting resins such as compounds, oxazoline compounds and carbodiimide compounds can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in the molecule.

  Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a plurality of thioether groups in the molecule The compound which has this, ie, an episulfide resin etc. are mentioned.

  Examples of the polyfunctional epoxy compound include jER (registered trademark) 828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, EHPE3150 manufactured by Daicel Chemical Industries, Epicron (registered trademark) 840 manufactured by DIC, Epicron 850, and Epicron 1050. , Epicron 2055, Epototo (registered trademark) YD-011, YD-013, YD-127, YD-128 manufactured by Nippon Steel Chemical Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, BASF Japan 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. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epototo YDB-400, YDB-500 manufactured by Nippon Steel Chemical Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by BASF Japan, Sumi-epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Nippon Steel Chemical Co., Ltd. Epotot YDCN-701, YDCN-704, BASF Japan Araldide ECN1235, Araldide ECN1273, Araldide ECN1299 , Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN (registered trademark) -201, EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Epoxy ESCN-195X, ESCN-220, A.A. E. R. ECN-235, ECN-299, etc. (both trade names) novolak epoxy resins; DIC Corporation Epicron 830, Mitsubishi Chemical Corporation jER807, Nippon Steel Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF -2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by BASF Japan (all trade names); water such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Nippon Steel Chemical Co., Ltd. Bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Nippon Steel Chemical Co., Ltd., Araldide MY720 manufactured by BASF Japan, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Product name) glycidylamine type epoxy resin; Araf made by BASF Japan Hydantoin type epoxy resin such as Dydo CY-350 (trade name); Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, araldide CY175, CY179 manufactured by BASF Japan, etc. (all trade names) YL-933 manufactured by Mitsubishi Chemical Corporation, T.M. manufactured by Dow Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Industrial Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Tetraphenylolethane type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Corporation, Araldide 163 manufactured by BASF Japan Co., Ltd. (all are trade names); BASF Japan Araldide PT810 (trade name) manufactured by Nissan, Nissan Heterocyclic epoxy resins such as TEPIC (registered trademark) manufactured by Kogyo Co .; diglycidyl phthalate resins such as Blemmer (registered trademark) DGT manufactured by Nippon Oil &Fats; Tetraglycidyl xylenoyl such as ZX-1063 manufactured by Nippon Steel Chemical Ethane resin; Naphthalene group-containing epoxy resin such as ESN-190, ESN-360, manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP-7200, HP-7200H manufactured by DIC, etc. Epoxy resin having dicyclopentadiene skeleton; CP-50S and CP-50M glycidyl methacrylate copolymer epoxy resin such as Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber Derivatives (eg Daicel Chemical Ltd. PB-3600, etc.), CTBN modified epoxy resin (e.g., Nippon Steel Chemical 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, epoxide-modified compounds by the peracetic acid method such as EHPE3150, PB-3600, and Celoxide 2021 (all manufactured by Daicel Chemical Industries, Ltd.) are preferable because they do not contain halogen ions as impurities.

  Examples of the polyfunctional oxetane compound 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 novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a 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 compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. 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 the molecule is preferably 0.1 to 1.5 equivalents relative to 1 equivalent of the carboxyl group in the composition, More preferably, a range of 0.2 to 1.0 equivalent is appropriate. When the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, This is not preferable because the strength of the resin decreases and the storage stability also deteriorates.

  Further, as another thermosetting component, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.

  As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. 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 such a 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 this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. 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-palerolactam, 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, milk Alcohol blocking agents such as methyl and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl 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 I can get lost.

  The blocked isocyanate compound may be commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS- 2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., product Name), B-830, B-815, B-846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei) Chemicals, product name)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.
In the case of blending such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule, the proportion of 1 wt% to 50 wt%, more preferably 2 to 40 wt% of the total amount of the composition is appropriate. It is. When the blending amount is less than 1 wt%, it is not preferable because sufficient toughness of the coating film cannot be obtained. On the other hand, when it exceeds 50 wt%, storage stability falls and it is not preferable.

  Furthermore, examples of other thermosetting components 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, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group 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 (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202. 1156, 1158, 1123, 1170, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak (registered trademark) 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, and the like (manufactured by Sanwa Chemical Co., Ltd.). The said thermosetting component can be used individually or in combination of 2 or more types.

  Moreover, the compound which has a carbodiimide group can be contained as another thermosetting component. By containing the compound which has a carbodiimide group, it can bridge | crosslink with the unreacted hydroxyl group and unreacted carboxyl group which remain | survive in hardened | cured material, and a coating-film intensity | strength can be improved. Furthermore, coating film deterioration due to hydrolysis of ester bonds can be suppressed.

  The compound having a carbodiimide group used in the present invention can be easily obtained from the market. Specific examples include Carbodilite V-03, Carbodilite V-06, Carbodilite 10M-SP, Carbodilite 9010, etc., manufactured by Nisshinbo Co., Ltd. Carbodilite series.

  The compounding amount of the compound having a carbodiimide group is 0.5 to 40 wt%, preferably 1 to 30 wt% of the total amount of the composition. When the compounding quantity of the compound which has a carbodiimide group is too much than the said range, since the intensity | strength of a coating film falls, it is unpreferable. On the other hand, when it is less than 0.5 wt%, the effect of hydrolysis resistance is impaired, which is not preferable.

  When using the thermosetting component which has a some cyclic | annular (thio) ether group in the said molecule | numerator, 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. Also, 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 and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The amount of these thermosetting catalysts to be blended is a normal quantitative ratio, and is preferably 0.1 to 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. It is 20 mass parts, More preferably, it is 0.5-15.0 mass parts.

  In the photocurable thermosetting resin composition of the present invention, 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 benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione. , 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, vinyltriazine, silane coupling agent and so on.

  The photocurable thermosetting resin composition of the present invention can contain a compound having a plurality of ethylenically unsaturated groups in the molecule. The compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays, and the curable resin of the present invention or the carboxyl group resin is obtained. Insolubilizes or helps insolubilize in an aqueous alkali solution. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate 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, N Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate Aminoalkyl acrylates such as alcohols; 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 Polyvalent acrylates of glycidyl ethers such as methylolpropane triglycidyl ether, triglycidyl isocyanurate; Not limited to the above, it corresponds to 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. Each methacrylate is mentioned.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of the compound which has several ethylenically unsaturated groups in such a molecule | numerator is 1-70 wt% in the solid content of a composition, More preferably, it is 5-60 wt%, The said carboxyl group containing photosensitive resin and When using together, the ratio of 5-100 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin, More preferably, the ratio of 5-70 mass parts is suitable. 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, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

  The curable resin composition of the present invention can contain a colorant. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. Specific examples include those to which the following color index numbers (CI; issued by The Society of Dyers and Colorists) are attached. 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 red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Is mentioned.
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, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

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

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. 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, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 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.

In addition, a colorant such as purple, orange, brown, or 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, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The mixing ratio of the colorant as described above is not particularly limited, but 5 wt% or less, more preferably 0.1 to 3 wt% is sufficient in the solid content of the composition.

  In the photocurable thermosetting resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity. . 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.

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 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- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

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

Hydrotalcite may be added to the photocurable thermosetting resin composition of the present invention for the purpose of improving the insulation reliability. Commercial products of hydrotalcites include: Kyowa Chemical Industry Co., Ltd .; Alkamizer, DHT-4A, Kyoward 500, Kyoward 1000, Sakai Chemical Co., Ltd. STABIACE series HT-1, HT-7, HT-P etc. are mentioned.
Particularly preferred are synthetic hydrotalcites having an average particle size of 2 μm or less, more preferably 1 μm or less. Further, these hydrotalcites can be used in the anhydrous state as they are in the form of hydrates or after baking.

  The blending amount of hydrotalcites is preferably 0.1 to 30 wt% of the total amount of the composition. The range is preferably 0.5-30 wt%, more preferably 0.1-25 wt%. If the blending amount of hydrotalcites is more than the above range, the viscosity and thixotropy of the composition will be too high, the printability may be lowered, and the cured product may become brittle, which is not preferable. On the other hand, if it is less than 0.1 wt%, the effect of electrode corrosion resistance is impaired, which is not preferable.

  Many of the polymer materials once oxidize start to undergo oxidative degradation one after another, leading to a decrease in the function of the polymer material. Therefore, the photocurable thermosetting resin composition of the present invention is oxidized. To prevent this, (1) radical scavengers that invalidate the generated radicals and / or (2) peroxide decomposition that decomposes the generated peroxide into harmless substances and prevents the generation of new radicals. An antioxidant such as an agent can be added.

  Examples of the antioxidant acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 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-hydroxybenzyl)- Phenolic compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4 -Piperidyl) -amine compounds such as sebacate and phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB (registered trademark) 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-68, Adekastab LA-87 (all manufactured by ADEKA), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 152 And TINUVIN 5100 (both manufactured by BASF Japan Ltd.).

Examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipro Sulfur compounds such as pionate can be mentioned.
The peroxide decomposing agent may be a commercially available one. For example, Adeka Stub TPP (manufactured by ADEKA), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer (registered trademark) TPS (manufactured by Sumitomo Chemical Co., Ltd.) Etc.
The above antioxidants can be used individually by 1 type or in combination of 2 or more types.

The photocurable thermosetting resin composition of the present invention can use an ultraviolet absorber in addition to the antioxidant.
Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.

  Examples of the benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2 , 4-dihydroxybenzophenone and the like.

  Examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl- Examples include 4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

  Examples of the benzotriazole derivatives include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′- Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, Examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole.

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

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

  The ultraviolet absorbers as described above can be used singly or in combination of two or more, and can be obtained from the photocurable thermosetting resin composition of the present invention by using in combination with an antioxidant. Stabilization of the molded product can be achieved.

  The photocurable thermosetting resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, publicly known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica, Neuburg silica clay particles, and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler is preferably 75 wt% or less, more preferably 0.1 to 60 wt% of the total amount of the composition. When the blending amount of the filler exceeds 75 wt% of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle.

  Furthermore, the photocurable thermosetting resin composition of the present invention is used for the synthesis of the carboxyl group-containing photosensitive resin, for the preparation of the composition, or for the viscosity adjustment for application to a substrate or a carrier film. Organic solvents can be used.

  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 , Such as propylene glycol butyl ether acetate, methyl 2-hydroxyisobutyrate Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  The photo-curable thermosetting resin composition of the present invention may further comprise a known conventional thickener such as a known thermal polymerization inhibitor, fine silica, organic bentonite, and montmorillonite, silicone, fluorine, Known additives such as molecular antifoaming agents and / or leveling agents, imidazole, thiazole and triazole silane coupling agents, antioxidants, rust inhibitors and the like can be blended. .

  The thermal polymerization inhibitor can be used for preventing thermal polymerization or polymerization with time of the polymerizable compound. Examples of the thermal polymerization inhibitor 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, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the 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 (temporary drying) at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, by contact type (or non-contact type), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to A resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution. Furthermore, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and the epoxy group of the epoxidized vegetable oil (or other thermosetting if included) The cyclic (thio) ether group of the reactive component can react to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, 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 laminate 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 invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (equipped with an air heating heat source using steam). And a method in which hot air in the dryer is brought into countercurrent contact and a method in which the hot air in the dryer is blown onto the support from the nozzle).

  As mentioned above, after apply | coating the photocurable thermosetting resin composition of this invention and evaporating and drying, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. 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. Further, the exposure amount varies depending the thickness or the like, generally 5~800mJ / cm ^2, preferably be in the range of 5~500mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The photo-curable thermosetting resin composition of the present invention is not a liquid and directly applied to a substrate, but also a dry resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance. It can also be used in the form of a film. The case where the photocurable thermosetting resin composition of this invention 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, for example, applying and drying an alkali-developable photocurable 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.
The solder resist layer is formed by uniformly applying an alkali-developable photocurable resin composition 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, and the like, and then drying. The
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. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

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

<Carboxyl group-containing photosensitive resin synthesis example 1>
Orthocresol novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (fragrance) Total number of rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. 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 solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This resin solution is referred to as A-1.

<Carboxyl group-containing photosensitive resin synthesis example 2>
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser was charged with methyl methacrylate, ethyl methacrylate, and methacrylic acid in a molar ratio of 1: 1: 2, and dipropylene glycol monomethyl ether as a solvent, AIBN was added as a catalyst and stirred at 80 ° C. for 4 hours under a nitrogen atmosphere to obtain a resin solution. This resin solution is cooled, methylhydroquinone as a polymerization inhibitor, tetrabutylphosphonium bromide as a catalyst, and glycidyl methacrylate is added at 20% by mole to the carboxyl group of the resin at 95 to 105 ° C. for 16 hours. And cooled and then taken out. The thus obtained photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group had a non-volatile content of 65%, a solid acid value of 120 mgKOH / g, and a Mw of about 20,000. Hereinafter, this resin solution is referred to as A-2.

Examples 1-4 and Comparative Examples 1-3
It mix | blended in the ratio (mass part) shown in Table 1 with the various components shown in the following Table 1, and after premixing with the stirrer, it knead | mixed with the 3 roll mill and prepared the photosensitive resin composition for soldering resists.

Performance evaluation:
<Storage stability at 20 ° C>
The resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 in Table 1 were stored in a dark place at 20 ° C. for 3 months, and the thickening rate after 3 months was measured. The evaluation criteria are as follows.
A: Thickening rate 0% to 100%.
(Triangle | delta): Thickening rate 100-200%.
X: Thickening rate 200% or more or gelation.

<Storage stability at 50 ° C>
The resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 in Table 1 were stored in a dark place at 50 ° C., and the thickening rate at the time of diameter was measured. When the thickening ratio exceeded 200%, it was determined that the product could not be used, and the time until the product was not used was measured.

<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water and dried, and then the photo-curable thermosetting resin compositions of the examples and comparative examples were applied to the entire surface by a screen printing method, and hot air at 80 ° C. It was dried for 60 minutes in a circulation drying oven. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the pattern of the step tablet remaining when performing in seconds was 7 steps, the optimum exposure amount was set.

<Developability>
The photocurable thermosetting resin compositions of the examples and comparative examples were applied to a solid copper substrate by a screen printing method so that the film thickness after drying was about 25 μm, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.

<Dry touch dryness>
The photocurable thermosetting resin compositions of the examples and comparative examples were each coated on the patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and brought to room temperature. Allowed to cool. A PET film was pressed against this substrate, and then the sticking state of the film when the negative film was peeled off was evaluated. The judgment criteria are as follows.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark.
(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.

<Resolution>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm was applied to the photocurable thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water, drying and then applying by screen printing. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp. For the exposure pattern, a negative was used to draw a 20/30/40/50/60/70/80/90/100 μm line in the space. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and heat cured at 150 ° C. for 60 minutes to obtain a cured coating film. It determined using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times, and made this resolution.

Characteristic test:
The compositions of Examples and Comparative Examples 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. This substrate is exposed to a solder resist pattern at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was 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.

<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 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Infiltration and peeling are not seen.
Δ: Slight penetration is observed after plating, but does not peel off after tape peeling.
X: Slight penetration was observed after plating, and peeling was also observed after tape peeling.

<Alkali resistance>
The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at room temperature for 30 minutes, and soaking, dissolution of the coating film, and peeling by tape beer were confirmed. The judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.

<Electrode corrosion resistance (insulation reliability)>
A comb-type electrode pattern of line / space = 100/100 μm was used in place of the copper foil substrate, and an evaluation substrate was produced under the above conditions. H. A bias voltage of DC 30 V was applied under the above heating and humidification conditions, and the degree of dendrite generation after 500 hours was evaluated. The judgment criteria are as follows.
○: Dendrite generation is small.
X: Many dendrites are generated.

<Dry film production>
After appropriately diluting each of the photosensitive resin compositions for solder resists of Examples 1 and 2 and Comparative Example 1 with methyl ethyl ketone, using an applicator, a PET film (Toray FB-) was prepared so that the film thickness after drying was 30 μm. 50:16 μm) and dried at 40 to 100 ° C. to obtain a dry film.

<Board fabrication>
After the circuit-formed substrate is buffed, the dry film produced by the above method is pressurized using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho): 0.8 MPa, 70 ° C., 1 minute, vacuum degree The substrate (unexposed substrate) having an unexposed solder resist layer was obtained by heat lamination under the condition of 133.3 Pa. Each of the obtained substrates was tested in the same manner as in the above evaluation method for optimum exposure, developability, resolution, solder heat resistance, gold plating resistance, and alkali resistance.
The evaluation results are shown in Table 2.

  As is clear from the results shown in Table 2 above, the one-component resin composition of the present invention is excellent in storage stability, excellent in solder heat resistance, gold plating resistance, alkali resistance, and electrode corrosion resistance, and as a solder resist. Useful. On the other hand, in the case of Comparative Example 1 in which no thermosetting component was used, there was no problem in storage stability, but the characteristics were not satisfactory. On the other hand, in Comparative Examples 2 and 3 using a general-purpose epoxy resin that is not a plant-derived epoxy compound as a thermosetting component, there were no problems in various characteristics, but the storage stability was remarkably inferior.

Claims (7)

  A photocurable thermosetting resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, and a plant-derived epoxy compound.   The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin is a carboxyl group-containing resin having a photosensitive group.   2. The photocurable thermosetting resin composition according to claim 1, wherein the plant-derived epoxy compound comprises one or a combination of two or more of epoxidized soybean oil and epoxidized linseed oil.   The photocurable thermosetting resin composition according to claim 1, wherein the photocurable thermosetting resin composition is a solder resist that can be developed with a dilute aqueous alkali solution.   The photocurable dry film obtained by apply | coating and drying the photocurable thermosetting resin composition as described in any one of the said Claims 1 thru | or 3 to a film.   A photocurable thermosetting resin composition according to any one of claims 1 to 3 or a dry film obtained by applying and drying the photocurable thermosetting resin composition on a film, A cured product obtained by curing.   A photocurable thermosetting resin composition according to any one of claims 1 to 3, or a dry film obtained by applying and drying the photocurable thermosetting resin composition on a film, A printed wiring board having a cured film obtained by photocuring into a shape and then heat curing.