JP5439256B2 - Photo-curable thermosetting resin composition - Google Patents

Description

  The present invention relates to a photocurable thermosetting resin composition used as a solder resist for a printed wiring board, and more particularly to a dilute alkali development type photocurable thermosetting resin composition suitable for a resist for an IC package. .

  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. A liquid development type photo solder resist that is finish-cured by irradiation (main curing) is used. For such a solder resist, an alkali developing type using a dilute alkaline aqueous solution as a developing solution has become the mainstream in consideration of environmental problems, and is used in large quantities in the actual production of printed wiring boards. 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. In general, an alkali development type photo solder resist mainly contains a hydrophilic group in order to enable alkali development, and chemicals, water, water vapor, etc. can easily permeate, resulting in reduced chemical resistance and resist film. It is considered that the adhesion between copper and copper is lowered. As a result, alkali resistance as chemical resistance is weakened, and PCT resistance (pressure cooker test resistance), which can be called moisture and heat resistance, is particularly good in semiconductor packages such as BGA (ball grid array) and CSP (chip scale package). ) Is necessary, but under such severe conditions, it is only several hours to several tens of hours. Also, in most cases in the HAST test (highly accelerated life test) in a state where a voltage is applied under humidification conditions, defects due to the occurrence of migration have been confirmed within a few hours.

  In recent years, there is a tendency for the temperature applied to the package to become extremely high, such as the use of lead-free solder due to the shift to surface mounting and consideration of environmental problems. Along with this, the temperature reached inside and outside of the package is remarkably increased, and the conventional liquid photosensitive resist is improved due to the problem that the coating film cracks due to thermal shock or peels off from the substrate or sealing material. It has been demanded.

  On the other hand, an epoxy acrylate modified resin derived by modification of an epoxy resin is generally used as a carboxyl group-containing resin in a conventional solder resist. For example, a solder resist composition comprising 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, a diluent and an epoxy compound is disclosed (for example, (See Patent Document 1).

  In addition, (meth) acrylic acid is added to the epoxy resin obtained by reacting the reaction product of salicylaldehyde and monohydric phenol with epichlorohydrin, and polybasic carboxylic acid or its anhydride is further reacted. A solder resist composition composed of a photosensitive resin, a photopolymerization initiator, an organic solvent, and the like is disclosed (see, for example, Patent Document 2). However, the carboxyl group-containing resins used in these conventional solder resist compositions have poor electrical characteristics.

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

  The present invention is a dilute alkali development type light suitable for obtaining a cured film excellent in adhesion of a substrate, chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless gold plating resistance, electrical insulation, etc. An object is to provide a curable thermosetting resin composition.

  In order to achieve the above object, according to one aspect of the present invention, alkali development is possible containing a carboxyl group-containing photosensitive resin having a structure represented by the following general formulas (1) to (4) and a photopolymerization initiator. A photocurable thermosetting resin composition is provided. With such a configuration, a cured film having excellent substrate adhesion, chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless gold plating resistance, electrical insulation, and the like can be obtained.

（式（１）中、Ｒ^１は下記式（２）の基を示し、Ｒ^２はメチル基またはＯＲ^１基を示し、ｎ＋ｍ＝１．５〜４．０、ｎ＝０〜４．０、ｍ＝０〜４．０、ｌ＝０〜３、ｋ＝０．３〜１０．０、ｎ：ｍ＝１００：０〜０：１００である。）

(In the formula (1), R ¹ represents a group of the following formula (2), R ² represents a methyl group or an OR ¹ group, n + m = 1.5 to 4.0, n = 0 to 4.0, m = 0 to 4.0, l = 0 to 3, k = 0.3 to 10.0, n: m = 100: 0 to 0: 100.)

（式（２）中、Ｒ^３は水素またはメチル基を示し、Ｒ^４は下記式（３）あるいは（４）の基または水素を示す。）

(In formula (2), R ³ represents hydrogen or a methyl group, and R ⁴ represents a group or hydrogen of the following formula (3) or (4).)

（式（３）中、Ｒ^５は水素またはメチル基を示す。）

(In formula (3), R ⁵ represents hydrogen or a methyl group.)

（式(４)中のＸは酸無水物残基を表す。）

(X in the formula (4) represents an acid anhydride residue.)

  Moreover, according to 1 aspect of this invention, the photocurable thermosetting film obtained by apply | coating and drying said photocurable thermosetting resin composition on a film is provided. By using such a dry film, a resist layer can be easily formed without applying a photocurable resin composition on a substrate.

  Moreover, according to 1 aspect of this invention, the hardened | cured material obtained by hardening said photocurable thermosetting resin composition or film by active energy ray irradiation and / or a heating is provided. In such a cured product, a cured product having excellent chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless gold plating resistance, electrical insulation, and the like can be obtained.

  Moreover, according to 1 aspect of this invention, the printed wiring board provided with the hardened | cured material obtained by hardening said photocurable thermosetting resin composition or film by active energy ray irradiation and / or a heating is provided. Is done. Thereby, the highly reliable printed wiring board which has the said characteristic can be provided.

  According to the photocurable thermosetting resin composition of the present invention, the workability is excellent, and in the cured product, adhesion to the substrate, chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless It is excellent in gold plating resistance, electrical insulation and the like, and can be advantageously applied to, for example, the formation of resists for IC packages, such as solder resists for printed wiring boards.

  As a result of intensive studies in view of the above problems, the inventors of the present invention have found that a photocurable resin containing a carboxyl group-containing photosensitive resin having a structure represented by the following general formulas (1) to (4) and a photopolymerization initiator. It has been found that the above problems can be achieved by using a thermosetting resin composition, and the present invention has been completed.

（式（１）中、Ｒ^１は下記式（２）の基を示し、Ｒ^２はメチル基またはＯＲ^１基を示し、ｎ＋ｍ＝１．５〜４．０、ｎ＝０〜４．０、ｍ＝０〜４．０、ｌ＝０〜３、ｋ＝０．３〜１０．０、ｎ：ｍ＝１００：０〜０：１００である。）

(In the formula (1), R ¹ represents a group of the following formula (2), R ² represents a methyl group or an OR ¹ group, n + m = 1.5 to 4.0, n = 0 to 4.0, m = 0 to 4.0, l = 0 to 3, k = 0.3 to 10.0, n: m = 100: 0 to 0: 100.)

（式（２）中、Ｒ^３は水素またはメチル基を示し、Ｒ^４は下記式（３）あるいは（４）の基または水素を示す。）

(In formula (2), R ³ represents hydrogen or a methyl group, and R ⁴ represents a group or hydrogen of the following formula (3) or (4).)

（式（３）中、Ｒ^５は水素またはメチル基を示す。）

(In formula (3), R ⁵ represents hydrogen or a methyl group.)

（式(４)中のＸは酸無水物残基を表す。）

(X in the formula (4) represents an acid anhydride residue.)

  The carboxyl group-containing photosensitive resin having the structure represented by the general formulas (1) to (4) is excellent in flexibility and elongation by chain extension by reaction addition of a phenol resin and an alkylene oxide or cyclocarbonate. In addition, unsaturated group-containing monocarboxylic acid and polybasic acid anhydride are added to the terminal hydroxyl group generated by the addition reaction of alkylene oxide or cyclocarbonate, and the unsaturated group or carboxyl group is on the same side chain. Since it does not exist and is located at the end of each side chain, it has excellent reactivity. Furthermore, it has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain.

  Moreover, since the said carboxyl group containing photosensitive resin does not contain a hydrophilic alcoholic hydroxyl group substantially, it is excellent in moisture absorption resistance. In general, the presence of a hydroxyl group has excellent characteristics such as improved adhesion due to hydrogen bonding, but it is known to significantly reduce moisture resistance. Therefore, in the carboxyl group-containing photosensitive resin of this embodiment, moisture resistance can be improved by not containing a hydroxyl group substantially. And improvement of PCT tolerance is attained by improvement in moisture resistance.

  Further, when considering the phenol skeleton of the precursor of the carboxyl group-containing photosensitive resin of the present embodiment, the hydroxyl group equivalent is larger than that of normal phenol or cresol type novolac resin. That is, the cured product derived from the precursor of the carboxyl group-containing photosensitive resin of the present embodiment has better flexibility than general novolak resins. Accordingly, the composition derived from the precursor of the carboxyl group-containing photosensitive resin of the present embodiment improves the thermal shock resistance and PCT resistance of the resulting cured product as compared with general novolak resins. It is possible.

  Therefore, the photocurable thermosetting resin composition of the present embodiment is excellent in workability, and by selective exposure, development and finish curing of the coating film, adhesion, chemical resistance, electroless gold plating resistance, A cured film having excellent thermal shock resistance, PCT resistance, electrical insulation and the like can be obtained.

Hereinafter, the photocurable thermosetting resin composition of the present embodiment will be described in detail.
First, the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (1) to (4) constituting the photocurable thermosetting resin composition of the present embodiment can be easily obtained by the following method. .
[1] Carboxyl group-containing product obtained by reacting a reaction product obtained by reacting a phenol resin and an alkylene oxide with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride Photosensitive resin.
[2] A carboxyl group obtained by reacting a reaction product obtained by reacting a phenol resin and a cyclocarbonate compound with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride. Contains photosensitive resin.

  Thus, the carboxyl group-containing photosensitive resin of this embodiment is obtained using a phenol resin as a starting material. Since the phenol resin which hardly contains chloride ion impurities can be easily obtained, the chloride ion impurity concentration in the obtained carboxyl group-containing photosensitive resin can be suppressed. It is preferable that the chloride ion impurity content of such a carboxyl group-containing photosensitive resin is 100 ppm or less. More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less.

Moreover, the carboxyl group containing photosensitive resin which does not contain a hydroxyl group substantially by such a method can be obtained. Note that “substantially free of hydroxyl groups” means that a trace amount of hydroxyl groups is allowed.
As described above, it is possible to exhibit excellent insulation reliability and PCT resistance by suppressing chlorine ion impurities in the carboxyl group-containing photosensitive resin and substantially not including a hydroxyl group.

  The carboxyl group-containing photosensitive resin has a high molecular weight to some extent in order to exhibit excellent film forming performance and film physical properties. In the carboxyl group-containing resin used in the present embodiment, n + m shown in the general formula (1) is preferably in the range of 1.5 to 4.0. If n + m of the carboxyl group-containing photosensitive resin is 1.5 or less, a carboxyl group-containing photosensitive resin having a precisely controlled structure cannot be obtained, and if it is 4.0 or more, dissolution by alkali development becomes difficult. This is not preferable because the development residue may be generated. The optimum n of the carboxyl group-containing photosensitive resin used in this embodiment is about 2.5 to 4.0.

  Since the carboxyl group-containing photosensitive resin of this embodiment has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible. Moreover, it is preferable that the acid value is the range of 50-200 mgKOH / g. When the acid value is less than 50 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, the exposed portion is dissolved by the developing solution, so that the line becomes thinner than necessary. Dissolving and peeling with a developer without distinction between unexposed areas makes it difficult to draw a normal resist pattern. More preferably, it is 50-150 mgKOH / g.

  Moreover, although the weight average molecular weight of the carboxyl group-containing photosensitive resin of this embodiment changes with resin frame | skeletons, what is generally in the range of 1,000-20,000 is preferable. If the weight average molecular weight is less than 1,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 20,000, developability may be remarkably deteriorated and storage stability may be inferior. More preferably, it is 1,000-10,000.

  It is preferable that the compounding quantity of such a carboxyl group-containing photosensitive resin is 20-60 mass% in the whole 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 30-50 mass%.

  The phenol resin used for the carboxyl group-containing photosensitive resin of the present embodiment has a biphenyl skeleton, a phenylene skeleton, or both skeletons, and the phenolic hydroxyl group-containing compound is phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethyl By using hydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc., it becomes possible to derive phenol resins having various skeletons. In other words, various molecular designs can be performed in consideration of the target properties.

  Examples of the alkylene oxide used in the carboxyl group-containing photosensitive resin of the present embodiment include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran. Preferably, ethylene oxide and propylene oxide are priced and supplied. Good from the aspect. These alkylene oxides can be used alone or in admixture of two or more.

  Moreover, as a cyclocarbonate compound, a well-known carbonate compound can be used, for example, ethylene carbonate, propylene carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate, etc. are mentioned, Preferably 5-membered-ring ethylene carbonate, propylene carbonate Is good in terms of reactivity and supply system. These carbonate compounds can be used alone or in admixture of two or more.

These alkylene oxides or cyclocarbonate compounds can be converted from phenolic hydroxyl groups to alcoholic groups by addition reaction to the phenolic hydroxyl groups of the corresponding phenol resins of the resin having the structure represented by the general formula (1) using a basic catalyst. It can be modified into a resin having a hydroxyl group.
The addition amount of the alkylene oxide or the cyclocarbonate compound is preferably in the range of 0.3 to 10 mol per equivalent of the phenolic hydroxyl group. When the addition amount is less than the above range, a reaction with an unsaturated group-containing monocarboxylic acid or polybasic acid anhydride described later hardly occurs, and the photosensitivity and solubility in a dilute alkaline aqueous solution are lowered. On the other hand, when the addition amount exceeds the above range, the water resistance is lowered due to the generated ether bond, and the electrical insulation property, HAST resistance and the like are lowered. More preferably, it is the range of 0.8-5 mol, More preferably, it is the range of 1.0-3 mol.

  Examples of unsaturated group-containing monocarboxylic acids include (meth) acrylic acid, or further, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, penta Examples include unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adduct. More preferred is (meth) acrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.

  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.

  Polybasic acid anhydrides include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydroanhydride Alicyclic dibasic acid anhydrides such as phthalic acid and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, etc. Aliphatic or aromatic dibasic acid anhydride, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, Benzophenone tetra Aliphatic or aromatic tetrabasic acid dianhydride, such as carboxylic acid dianhydride and the like, can be used one or two or more of these.

  Examples of the photopolymerization initiator used in the photocurable thermosetting resin composition of the present embodiment include an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide system. One or more photopolymerization initiators selected from the group consisting of photopolymerization initiators can be used.

  Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, N-1919 manufactured by Adeka, and Adeka Arcles NCI-831. 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 (5). .

（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、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、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−ジイルを表し、ｎは０又は１の整数である。）
特に式中、Ｘ、Ｙが、それぞれ、メチル基又はエチル基であり、Ｚはメチル又はフェニルであり、ｎは０であり、Ａｒは、フェニレン、ナフチレン、又はチエニレンであることが好ましい。

(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 Substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents 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, and n is an integer of 0 or 1.)
In particular, 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.

  It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of said carboxyl group-containing resin. When it 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 0.5-3 mass parts.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 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. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba 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-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Lucilin TPO manufactured by BASF, 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 it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5-10 mass parts.

  In addition, as a photopolymerization initiator, a photoinitiator assistant, and a sensitizer that can be suitably used for the photocurable thermosetting resin composition of the present embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, Examples include ketal 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′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4, Dialkylaminobenzophenone such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Bio-Synthetics), 4-dimethylamino Nobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  Of these, 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.

  It is preferable that the compounding quantity of such a thioxanthone compound is 20 mass parts or less with respect to 100 mass parts of said 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. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored, and use colored pigments as well as colorless and transparent photosensitive compositions, and colors that reflect the color of the colored pigments themselves It becomes possible to provide a solder resist film. 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.

  It is preferable that the compounding quantity of such a tertiary amine compound is 0.1-20 mass parts with respect to 100 mass parts of said 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 dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts. 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.

  Furthermore, in the photocurable thermosetting resin composition of the present embodiment, in addition to the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (1) to (4), various properties such as developability and tackiness are provided. In order to adjust the balance of characteristics, carboxyl-containing resins as listed below may be used in combination.

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

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

(3) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group such as (meth) acrylic acid Polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the resulting reaction product by reacting with the contained monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting a product.

(4) 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.

(5) 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 is added to an unsaturated group-containing compound such as (meth) acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a carboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.

(6) 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.

(7) During 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, a molecule 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.

(8) During 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.

(9) 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.

(10) A carboxyl group-containing polyester obtained by reacting a difunctional acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a polyfunctional oxetane resin described later, and adding a dibasic acid anhydride to the resulting primary hydroxyl group Carboxyl group-containing photosensitivity obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate to the resin. Resin.

(11) 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 resin of (1) to (10).

  Among these carboxyl group-containing resins, as described above, it is particularly preferable to use a carboxyl group-containing resin that does not use an epoxy resin as a starting material because of its very low chlorine ion impurity.

  Furthermore, a thermosetting component can be added to the photocurable thermosetting resin composition of the present embodiment in order to impart heat resistance. Specific examples of thermosetting components include block isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. Resin 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.

  Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule contains either one of the three-, four- or five-membered cyclic ether groups or cyclic thioether groups or two types of groups in the molecule. 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, and a plurality of thioether groups in the molecule. A compound having the same, that is, an episulfide resin.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto 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 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 Company D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400 and 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 manufactured by DIC, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., Araldide ECN1235, Araldide ECN1273, Araldide ECN1299 manufactured by Ciba Japan 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, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175 manufactured by Toto Kasei Co., YDF- 2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd. Type A epoxy resin: jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as 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. Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; 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 epoxy resin jER157S (trade name); Tetraphenylolethane type such as jERYL-931 from Japan Epoxy Resin, Araldide 163 from Ciba Japan Co., Ltd. (all trade names) Epoxy resin; Aral made by Ciba Japan Id PT810, a heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries (all trade names); a diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; a tetraglycidyl xyleno such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. Irethane resin; Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700 and other naphthalene group-containing epoxy resins; DIC Corporation HP-7200, HP-7200H Epoxy resins having a dicyclopentadiene skeleton such as CP-50S and CP-50M glycidyl methacrylate copolymer epoxy resins manufactured by Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene Rubber derivatives (eg Iseru Chemical Co. 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.

  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 novolak resin, poly (P-hydroxystyrene), cardo bisphenol , 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 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.

  As for the compounding quantity of the thermosetting component which has a some cyclic | annular (thio) ether group in such a molecule | numerator, 0.6-2.5 equivalent is preferable with respect to 1 equivalent of carboxyl groups of the said carboxyl group-containing resin. When the blending amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation and the like are lowered. 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 0.8-2.0 equivalent.

  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, 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 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid), Nikarak 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 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 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 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 phenol 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 And alcohol-based blocking agents such as ethyl lactate; oxime-based 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 It is.

The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur 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 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals Corp.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.
These 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 coating film toughness cannot be obtained. On the other hand, when it exceeds 100 mass parts, storage stability falls. More preferably, it is 2-70 mass parts.

  A urethanization catalyst can be added to the photocurable thermosetting resin composition of the present embodiment in order to accelerate the curing reaction of hydroxyl groups, carboxyl groups, and isocyanate groups. 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) imidazole 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-hydroxyethyl) 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 or / and benzoguanamine etc. are mentioned.

Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5,4,0] undecene-7).
The compounding amount of the urethanization catalyst is sufficient at a normal quantitative ratio, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 with respect to 100 parts by mass of the carboxyl group-containing resin. Part by mass.

  When using a thermosetting component having a plurality of cyclic (thio) ether groups in the 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. 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. Is also used in combination with the above thermosetting catalyst.

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

  The photocurable thermosetting 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.

  Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Index (CI; Issued by The Society of Dyer's and Colorists) number.

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 220, 144, 166, 214, 220, 221, 242.
Anthraquinone series: Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207.
Quinacridone series: Pigment Red 122, 202, 206, 207, 209.

Blue colorant:
Blue colorants include phthalocyanine and anthraquinone, and pigments include compounds classified as Pigment, specifically, Pigment Blue 15, 15: 1 , 15: 2, 15: 3, 15: 4, 15: 6, 16, 60. Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 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, 193, 147, 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.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
For example, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI 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 mixing ratio 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 the 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 ether such as methylolpropane triglycidyl ether and triglycidyl isocyanurate ; Not limited to the above, polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols and other acrylates and melamine acrylates that are directly acrylated or urethane acrylated via diisocyanate, and / or the above acrylates And methacrylates.

  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 amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, and the compounding amount is 5 parts by mass. If it is less than the range, 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. More preferably, it is 1-70 mass parts.

  The photocurable thermosetting resin composition of the present embodiment can contain a filler 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, and barium sulfate, spherical silica and talc, and Neuburg Silyce earth are particularly preferable. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can also be used as a filler.

  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 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. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used.

  Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl-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 contains an organic solvent for the synthesis of the 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 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 , 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. In order to prevent oxidation, radical scavengers that invalidate the generated radicals and / or peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals, etc. An antioxidant 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, 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) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6) Tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.

  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-68, ADK STAB LA-87 (above, manufactured by 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 5100, TINUVIN 5100 Product name).

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

  The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilyzer TPS (Sumitomo Chemical) Company name, product name).

Said antioxidant can be used individually by 1 type or in combination of 2 or more types.
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 the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. 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'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-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 (above, manufactured by Ciba Japan, trade name) and the like.

  These ultraviolet absorbers can be used singly or in combination of two or more, and the molded product obtained by using in combination with the above-described antioxidant can be stabilized.

  In the photocurable thermosetting resin composition of the present embodiment, known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, etc. can be used as chain transfer agents in order to improve sensitivity. . Examples of the chain transfer agent include 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, mercaptopropanediol, Chain transfer agents having a hydroxyl group such as 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, cyclopentanethiol Le, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  A polyfunctional mercaptan-based compound can be used and is 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, aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (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 ( Poly (mercaptobutyrate) s such as 1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mertapbutyrate) 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 (above, Showa Denko Co., Ltd.) etc. can be mentioned.

  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- 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 (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd .: trade name Disnet DB) , And 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: DYSNET AF), etc. And the like.

  In particular, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2 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. , 4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole are preferred. 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 adhesion between layers or adhesion between the photosensitive resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 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 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, and phenothiazine, 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 with an organic solvent, for example, on the substrate, dip coating method, flow coating method, roll coating method, 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. 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 and a plurality of cyclic groups in the molecule ( A thermosetting component having a thio) ether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. 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.

  As a substrate, in addition to a printed circuit board and a flexible printed circuit board in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin, Glass fabric / 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 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).

  After applying the photocurable thermosetting resin composition of the present embodiment and evaporating and drying it as described below, the obtained coating film is exposed (irradiated with active energy rays). 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. Moreover, although the exposure amount changes with film thickness etc., generally it is 5-500 mJ / cm < ² >, Preferably it is 5-300 mJ / 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. .

  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 photocurable thermosetting resin composition of the present embodiment is a liquid having a solder resist layer formed by previously applying a solder resist to a film of polyethylene terephthalate or the like in addition to a method of directly applying it to a substrate in a liquid state. It can also be used in the form of a 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 then dried. Formed.

  As the cover film, a polyethylene film, a polypropylene film, or the like can be used.

  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.

<Resin synthesis example 1>
A 1 L autoclave is charged with 313.2 g of a biphenyl aralkyl resin (hydroxyl equivalent: 232 g / eq) obtained by a condensation reaction of orthocresol and 4,4-bis (chloromethyl) biphenyl, 3.13 g of potassium hydroxide, and 344.1 g of toluene. The solution was stirred and dissolved while raising the temperature to 130 ° C. Next, 87.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 4.11 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 296 g / eq and a resin content of 54.8% was obtained.

  The obtained propylene oxide adduct solution 718.0 g, 4-methoxyphenol 0.36 g, toluene 459.6 g, acrylic acid 28.8 g, and methanesulfonic acid 12.1 g were charged into a 2 L glass flask, and a temperature of 100 to 110 ° C. The esterification reaction was carried out for 6 hours. The water produced | generated by reaction was distilling 7.2g of water as an azeotrope with toluene. Then, it cooled to room temperature and neutralized with 51.8 g of 15% potassium hydroxide aqueous solution. Further, the acrylate resin solution was purified by washing once with 5% saline and three times with pure water. The resin content in the solution was 36.1%.

  While distilling off toluene of 1083.4 g of purified acrylate resin solution, it was replaced with 196.9 g of diethylene glycol monoethyl ether acetate, 133.5 g of tetrahydrophthalic anhydride, 0.23 g of 4-methoxyphenol, 2.26 g of triphenylphosphine. And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 93 mgKOH / g, and n + m = 2.1 shown in the general formula (1). This is designated as resin solution A-1.

<Resin synthesis example 2>
To a 1 L autoclave, a biphenyl-phenylene co-condensation resin (hydroxyl equivalent 215 g / eq, average 3) obtained by co-condensation reaction of ortho-cresol with 4,4-bis (chloromethyl) biphenyl and 4,4-bis (chloromethyl) benzene .7 nuclei) 370.0 g, potassium hydroxide 3.70 g, and toluene 370.0 g were charged and stirred and dissolved while heating to 130 ° C. Next, 111.9 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 4.85 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 278 g / eq and a resin content of 56.9% was obtained.

  80 L of the resulting propylene oxide adduct solution, 0.42 g of 4-methoxyphenol, 563.9 g of toluene, 46.4 g of acrylic acid, and 14.1 g of methanesulfonic acid were charged into a 2 L glass flask, and a temperature of 100 to 110 ° C. The esterification reaction was carried out for 6 hours. The water produced by the reaction was an azeotrope with toluene, and 11.6 g of water was distilled off. Then, it cooled to room temperature and neutralized with 60.4 g of 15% potassium hydroxide aqueous solution. Further, the acrylate resin solution was purified by washing once with 5% saline and three times with pure water. The resin content in the solution was 37.1%.

  While distilling out 1270.0 g of the purified acrylate resin solution with toluene, 263.5 g of diethylene glycol monoethyl ether acetate was substituted, 143.6 g of tetrahydrophthalic anhydride, 0.44 g of 4-methoxyphenol, 2.20 g of triphenylphosphine And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 86 mgKOH / g, and n + m = 2.7 shown in the general formula (1). This is designated as resin solution A-2.

<Resin synthesis example 3>
In a 1 L autoclave, 400.3 g of biphenyl aralkyl resin (hydroxyl equivalent 197 g / eq, average number of nuclei 3.1) obtained from the co-condensation reaction of cresol, hydroquinone and 4,4-bis (chloromethyl) biphenyl, potassium hydroxide 4.01 g and 402.3 g of toluene were charged and dissolved by stirring while raising the temperature to 130 ° C. Next, 132.1 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 5.26 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 261 g / eq and a resin content of 56.5% was obtained.

  909.7 g of the resulting propylene oxide adduct solution, 0.49 g of 4-methoxyphenol, 664.3 g of toluene, 56.8 g of acrylic acid, and 14.7 g of methanesulfonic acid were charged into a 2 L glass flask, and a temperature of 100 to 110 ° C. The esterification reaction was carried out for 6 hours. 14.2 g of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting acrylate resin solution was neutralized with 57.2 g of 15% potassium hydroxide solution, washed once with 5% brine and three times with pure water to purify the acrylate resin solution. . The resin content in the solution was 33.8%.

  While purifying 1527.5 g of the purified acrylate resin solution while distilling off toluene, it was replaced with 292.4 g of diethylene glycol monoethyl ether acetate. Tetrahydrophthalic anhydride 166.6 g, 4-methoxyphenol 0.29 g, triphenylphosphine 1.95 g And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 90 mgKOH / g, and n + m = 2.1 shown in the general formula (1). This is designated as resin solution A-3.

<Resin synthesis example 4>
In a 1 L autoclave, 400.0 g of cresol aralkyl resin (hydroxyl equivalent: 188 g / eq, average number of nuclei: 4.6) obtained from cresol and 1,4-bischloromethylbenzene, 4.00 g of potassium hydroxide, 399.9 g of toluene The solution was stirred and dissolved while raising the temperature to 130 ° C. Next, 138.4 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Then, it cooled to room temperature and added 5.24g of 85% phosphoric acid to the reaction solution, and neutralized potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 252 g / eq and a resin content of 56.8% was obtained.

  A 2 L glass flask was charged with 920.0 g of the resulting propylene oxide adduct solution, 0.51 g of 4-methoxyphenol, 704.9 g of toluene, 71.0 g of acrylic acid, and 15.3 g of methanesulfonic acid, and a temperature of 100 to 110 ° C. The esterification reaction was carried out for 6 hours. 17.7 g of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting acrylate resin solution was neutralized with 59.6 g of 15% potassium hydroxide solution, washed once with 5% saline and three times with pure water to purify the acrylate resin solution. . The resin content in the solution was 36.2%.

  While purifying 1550.0 g of the purified acrylate resin solution with toluene, 309.9 g of diethylene glycol monoethyl ether acetate was substituted, and tetrahydrophthalic anhydride 162.0 g, 4-methoxyphenol 0.31 g, triphenylphosphine 2.07 g And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 82 mgKOH / g, and n + m = 3.6 shown in the general formula (1). This is designated as Resin Solution A-4.

<Resin synthesis example 5>
In a 1 L autoclave, 400.0 g of cresol aralkyl resin (hydroxyl equivalent 180 g / eq, average number of nuclei 3.3) obtained from cresol and 1,4-bischloromethylbenzene, 4.00 g of potassium hydroxide, 402.1 g of toluene The solution was stirred and dissolved while raising the temperature to 130 ° C. Next, 144.6 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Then, it cooled to room temperature and added 5.24g of 85% phosphoric acid to the reaction solution, and neutralized potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 243 g / eq and a resin content of 57.5% was obtained.

  A 2 L glass flask was charged with 920.0 g of the resulting propylene oxide adduct solution, 0.52 g of 4-methoxyphenol, 737.2 g of toluene, 78.5 g of acrylic acid, and 15.6 g of methanesulfonic acid, and a temperature of 100 to 110 ° C. The esterification reaction was carried out for 6 hours. 19.6 g of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting acrylate resin solution was neutralized with 60.7 g of 15% potassium hydroxide solution, washed once with 5% saline and three times with pure water to purify the acrylate resin solution. . The resin content in the solution was 37.0%.

  While purifying 1550.0 g of toluene in the purified acrylate resin solution, it was replaced with 315.0 g of diethylene glycol monoethyl ether acetate, 161.6 g of tetrahydrophthalic anhydride, 0.32 g of 4-methoxyphenol, 2.10 g of triphenylphosphine. And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 80 mgKOH / g, and n + m = 2.3 shown in the general formula (1). This is designated as Resin Solution A-5.

<Comparative Synthesis Example 1>
In a 1 L autoclave, 400.0 g of cresol aralkyl resin (hydroxyl equivalent: 190 g / eq, average number of nuclei: 5.4) obtained from cresol and 1,4-bischloromethylbenzene, 4.00 g of potassium hydroxide, 400.0 g of toluene The solution was stirred and dissolved while raising the temperature to 130 ° C. Next, 137.0 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Then, it cooled to room temperature and added 5.24g of 85% phosphoric acid to the reaction solution, and neutralized potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 254 g / eq and a resin content of 57.5% was obtained.

  90 L of the resulting propylene oxide adduct solution, 0.50 g of 4-methoxyphenol, 694.2 g of toluene, 69.2 g of acrylic acid, and 15.0 g of methanesulfonic acid were charged into a 2 L glass flask, and a temperature of 100 to 110 ° C. The esterification reaction was carried out for 6 hours. 17.3 g of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting acrylate resin solution was neutralized with 58.4 g of 15% potassium hydroxide solution, washed once with 5% saline and three times with pure water to purify the acrylate resin solution. . The resin content in the solution was 36.5%.

  While distilling off 1500.0 g of the purified acrylate resin solution, 301.7 g of diethylene glycol monoethyl ether acetate, 156.4 g of tetrahydrophthalic anhydride, 0.30 g of 4-methoxyphenol, 2.01 g of triphenylphosphine And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 81 mgKOH / g, and n + m = 4.4 shown in the general formula (1). This is designated as resin solution R-1.

<Comparative Synthesis Example 2>
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 C RG951”, OH equivalent: 119.4) Then, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased 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.

  293.0 g of the resulting novolak-type cresol resin alkylene 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, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours with stirring. 12.6 g of water was distilled from the water produced by the reaction 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 added to diethylene glycol monoethyl ether acetate 118. The solvent was distilled off while replacing with 1 g to obtain a novolak acrylate resin solution.

  Next, 332.5 g of the obtained novolac 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 carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. This is designated as resin solution R-2.

<Comparative Synthesis Example 3>
Orthocresol novolak type epoxy resin (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 g of diethylene glycol monoethyl ether acetate 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 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. Hereinafter, this is referred to as a resin solution R-3.

  Using the resin solution of the above synthesis example, the various components shown in Table 1 are blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photosensitive for a solder resist. A functional resin composition was prepared. Here, when the degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.

＊１：ビフェニルノボラック型エポキシ樹脂(NC-3000HCA75:日本化薬社製)
＊２：ビスフェノール型エポキシ樹脂(YSLV-80XY：東都化成社製)
＊３：エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム) (イルガキュア OXE 02:チバ・ジャパン社製)
＊４：2-メルカプトベンゾチアゾール
＊５：酸化防止剤（チバ・ジャパン社製）
＊６：B-30 (堺化学社製)
＊７：SO-E3（アドマテックス社製）
＊８：ハイドロタルサイト（協和化学工業社製）
＊９：C.I.Pigment Blue 15:3
＊１０：C.I.Pigment Yellow147
＊１１：ジエチレングリコールモノエチルエーテールアセテート
＊１２：ジペンタエリスリトールヘキサアクリレート

* 1: Biphenyl novolac type epoxy resin (NC-3000HCA75: manufactured by Nippon Kayaku Co., Ltd.)
* 2: Bisphenol type epoxy resin (YSLV-80XY: manufactured by Toto Kasei)
* 3: Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure OXE 02: manufactured by Ciba Japan)
* 4: 2-mercaptobenzothiazole * 5: Antioxidant (manufactured by Ciba Japan)
* 6: B-30 (manufactured by Sakai Chemical Co., Ltd.)
* 7: SO-E3 (manufactured by Admatechs)
* 8: Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 9: CIPigment Blue 15: 3
* 10: CIPigment Yellow147
* 11: Diethylene glycol monoethyl ether acetate * 12: Dipentaerythritol hexaacrylate

[Examples 1-8, Comparative Examples 1-4]
About the composition of the Example shown in Table 1, and a comparative example, performance evaluation and characteristic evaluation were performed with the evaluation method shown below. The evaluation results are shown in Table 2.
Performance evaluation:
<Optimum exposure amount>
A circuit pattern board having a copper thickness of 18 μm was subjected to a copper surface roughening treatment (MEC etch bond CZ-8100 manufactured by MEC), washed with water and dried, and then the photocurable thermosetting resins of Examples and Comparative Examples shown in Table 1 The composition was applied to the entire surface by a screen printing method and dried for 60 minutes in a hot air circulating drying oven at 80 ° C. to obtain a dried coating film of about 20 μm. Then, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and a step remaining when development (30 ° C., 0.2 MPa, 1% aqueous sodium carbonate solution) is performed in 90 seconds. When the tablet pattern was 7 steps, the optimum exposure was set.

<Tackiness>
Each photocurable resin composition was coated on the front surface of a patterned copper foil substrate by screen printing, 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, pressure-bonded under a reduced pressure condition by ORC (HMW-GW20) for 1 minute, and then the state of sticking of the film when the negative film was peeled was evaluated.
○: There is a slight resistance when the film is peeled off, and a slight mark can be confirmed on the coating film. Δ: There is a slight resistance when the film is peeled off, and the coating film is clearly marked. ×: The film is peeled off. Sometimes there is great resistance and the coating is clearly marked

<Maximum development life>
The compositions of Examples and Comparative Examples shown in Table 1 were applied on the entire surface of a patterned copper foil substrate so as to have a dry film thickness of about 20 μm by screen printing, dried at 80 ° C. and dried for 20 to 80 minutes. The substrate was taken out every minute and allowed to cool to room temperature. This substrate was 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, and the maximum allowable drying time in which a dry coating film did not remain was judged as the maximum development life. In addition, after the development processing, a development residue is confirmed to be present on the copper that is slightly confirmed on the copper.

Characterization:
The compositions of Examples and Comparative Examples shown in Table 1 were applied on the entire surface of a patterned copper foil substrate so as to have a dry film thickness of about 20 μm by screen printing, dried at 80 ° C. for 30 minutes, and then released to room temperature. Chilled. 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% by volume 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% by volume 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. Δ: A little peeling occurs when the immersion for 10 seconds is repeated 3 times or more. X: The resist layer swells and peels within 3 times for 10 seconds.

<Electroless gold plating resistance>
About the evaluation board | substrate, the plating process was performed to the ball | bowl pad with an opening of 80 micrometers under the conditions of nickel 5 micrometers and gold | metal | money 0.05 micrometers using the commercially available electroless nickel plating bath and electroless gold plating bath. In the plated evaluation substrate, the presence or absence of peeling of the resist layer or the presence or absence of plating penetration was evaluated by tape peeling, and then the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: No penetration after plating, no peeling after tape peeling △: Whitening is confirmed after plating, but no peeling after tape peeling ×: Electroless gold plating not applied due to development residue

<PCT resistance>
Various evaluation substrates subjected to electroless gold plating in the same manner as the evaluation of electroless gold plating resistance can be obtained under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec). PCT resistance was evaluated according to the state of the coating film. The judgment criteria are as follows.
○: After 300 hours test, no swelling, peeling, discoloration, or dissolution Δ: When 168 hours testing elapsed, no swelling, peeling, discoloration, no dissolution ×: After 168 hours testing, swelling, peeling, discoloration, Elution is seen

<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 with 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 of less than 30% Δ: Crack generation rate of 30 to 50%
×: Crack occurrence rate of 50% or more

<HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-type electrodes (line / space = 30 microns / 30 microns) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high-temperature, high-humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 12V was charged, and the internal HAST test was done for various time. The insulation resistance value in the tank at various times was evaluated according to the following criteria.
○: After 300 hours, 10 ⁸ Ω or more Δ: When 168 hours have elapsed, 10 ⁸ Ω or more ×: When 168 hours have elapsed, 10 ⁸ Ω or less

[Examples 9 to 16]
Each composition of Examples 1-8 prepared with the compounding ratio shown in Table 1 was diluted with methyl ethyl ketone, applied onto a PET film, dried at 80 ° C. for 30 minutes, and a photosensitive resin composition layer having a thickness of 20 μm. Formed. Furthermore, the cover film was bonded together on it and the dry film was produced, and each was set as Examples 9-16.

<Dry film evaluation>
The cover film is peeled off from the dry film obtained as described above, the film is heat laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the above-mentioned coating film property evaluation. . 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 board | substrate which has the obtained cured film, performance evaluation and characteristic evaluation were performed with said evaluation method. The evaluation results are shown in Table 3.

表２及び表３に示す結果から明らかなように、本発明の光硬化性熱硬化性樹脂組成物は半導体パッケージ用ソルダーレジストに必要とされるＰＣＴ耐性、冷熱衝撃耐性、ＨＡＳＴ特性を兼ね備え、非常に信頼性の高いソルダーレジスト硬化塗膜が得られることが明らかとなり、光硬化性熱硬化性樹脂組成物として有用であることが認められた。

As is clear from the results shown in Table 2 and Table 3, the photo-curable thermosetting resin composition of the present invention has the PCT resistance, the thermal shock resistance, and the HAST characteristics required for the solder resist for semiconductor packages. It became clear that a highly reliable solder resist cured coating film was obtained, and was found to be useful as a photocurable thermosetting resin composition.

Claims (4)

A photocurable thermosetting resin composition comprising a carboxyl group-containing photosensitive resin having a structure represented by the following general formulas (1) to (4) and a photopolymerization initiator.

(In the formula (1), R ¹ represents a group of the following formula (2), R ² represents a methyl group or an OR ¹ group, n + m = 1.5 to 4.0, n = 0 to 4.0, m = 0 to 4.0, l = 0 to 3, k = 0.3 to 10.0, n: m = 100: 0 to 0: 100.)

(In the formula (2), R ³ represents hydrogen or a methyl group, and R ⁴ represents the following group (3) or (4) or hydrogen.)

(In formula (3), R ⁵ represents hydrogen or a methyl group.)

(X in the formula (4) represents an acid anhydride residue.)   A photocurable thermosetting film obtained by applying and drying the photocurable thermosetting resin composition according to claim 1 on a film.   A cured product obtained by curing the photocurable thermosetting resin composition according to claim 1 or the film according to claim 2 by irradiation with active energy rays and / or heating.   It comprises a cured product obtained by curing the photocurable thermosetting resin composition according to claim 1 or the film according to claim 2 by irradiation with active energy rays and / or heating. Printed wiring board.