JP2010266819A - Photocurable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using those materials - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable thermosetting resin composition which can form a cured film having PCT durability, HAST durability, electroless gold plating durability, and cold-heat shock resistance, which are important as a solder resist for a semiconductor package, and to provide a dry film and a cured product of the composition, and a printed wiring board having a cured film such as a solder resist of the composition formed thereon. <P>SOLUTION: The photocurable thermosetting resin composition is developable with an alkali aqueous solution and includes: (A) a carboxyl group-containing resin (excepting a carboxyl group-containing resin derived from an epoxy resin as a start material); (B) a photopolymerization initiator; and (C) a hydroxyl group-containing elastomer. Preferably, the composition further includes (D) a thermosetting component, and preferably further includes (G) a colorant. Preferably, the carboxyl group-containing resin does not contain a hydroxyl group, and more preferably, the resin further includes a photosensitive group. The hydroxyl group-containing elastomer is preferably butadiene or an isoprene derivative. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

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

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

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

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

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

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

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

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

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

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

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

As specific examples of the carboxyl group-containing resin (A) that can be used in the present invention, compounds listed below (any of oligomers and polymers) may be preferable.
(1) 2 or more in one molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes Reaction obtained by reacting a monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.

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

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

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

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

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

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

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

  Since the carboxyl group-containing resin (A) used in the present invention does not use an epoxy resin as a starting material, it has a feature that the halide content is very low. The chlorine ion impurity content of the carboxyl group-containing resin used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.

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

A phenol novolak resin free from chlorine can be easily obtained. Resin that has no hydroxyl group in the range of double bond equivalent 300-550, acid value 40-120 mgKOH / g by partial acrylation of phenol resin modified with alkyl oxide and introduction of acid anhydride It is possible to obtain
On the other hand, if all the epoxy groups of an epoxy resin synthesized from a similar phenol novolac resin are acrylated and acid anhydrides are introduced into all the hydroxyl groups, the acid value becomes very large at double bond equivalents of 400 to 500. Even after exposure, a coating film having development resistance cannot be obtained. Furthermore, since the acid value is high, the water resistance is inferior, and the insulation reliability and PCT resistance are significantly reduced. That is, it is very difficult to completely eliminate the hydroxyl group from an epoxy acrylate resin derived from a similar phenol novolac type epoxy resin.

Moreover, urethane resin can also synthesize | combine easily the resin which does not contain a hydroxyl group by match | combining the equivalent of a hydroxyl group and an isocyanate group. The preferred resin is an isocyanate compound not using phosgene as a starting material and a carboxyl group-containing resin having a chlorine ion impurity amount of 0 to 30 ppm synthesized from a raw material not using epihalohydrin, and more preferably so as not to theoretically contain a hydroxyl group. It is a synthesized resin.
From such a viewpoint, the carboxyl group-containing resins (1) to (5) previously shown as specific examples can be particularly preferably used.

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

  On the other hand, the carboxyl group-containing resin (6) is obtained by reacting glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, or copolymerizing glycidyl methacrylate as an unsaturated group-containing compound. There is a concern that the amount of chlorine ion impurities increases. Moreover, an epoxy acrylate modified raw material can also be used as a diol compound in the synthesis of a urethane resin. Although chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.

Since the carboxyl group-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with an aqueous alkali solution becomes possible.
The acid value of the carboxyl group-containing resin (A) is desirably in the range of 40 to 150 mgKOH / g, and more preferably in the range of 40 to 130 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when it exceeds 150 mgKOH / g, dissolution of the exposed area by the developing solution proceeds, so that the line becomes thinner than necessary Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeleton, generally what is in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The compounding quantity of such carboxyl group-containing resin (A) is 20-60 mass% in all the compositions, Preferably it is 30-50 mass%. When the amount is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity becomes high and the coating property and the like deteriorate, which is not preferable.

（式中、
Ｒ^１は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^２は、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ^５及びＲ^６は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、
Ｒ^７及びＲ^８は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基若しくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^７及びＲ^８の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい）。 As the photopolymerization initiator (B), an oxime ester photopolymerization initiator (B1) having a group represented by the following general formula (I), an α-amino having a group represented by the following general formula (II) One or more photopolymerization initiators selected from the group consisting of an acetophenone photopolymerization initiator (B2) and an acylphosphine oxide photopolymerization initiator (B3) having a group represented by the following formula (III): Preferably to use

(Where
R ¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). Which may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (carbon number) May be substituted with 1 to 6 alkyl groups or phenyl groups),
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group. Represents one group, provided that one of R ⁷ and R ⁸ represents an R—C (═O) — group (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms).

The oxime ester photopolymerization initiator having a group represented by the general formula (I) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (IV), Examples include compounds represented by the following general formula (V) and compounds represented by the following general formula (VI). Among these, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (IV) and a compound represented by the formula (V) are more preferable.

（式中、
Ｒ^９は、水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基（アルコキシル基を構成するアルキル基の炭素数が２以上の場合、アルキル基は１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、又はフェノキシカルボニル基を表し、
Ｒ^１０、Ｒ^１２は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^１１は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表す。）

(Where
R ⁹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or an alkoxy having 2 to 12 carbon atoms. Carbonyl group (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and has one or more oxygen atoms in the middle of the alkyl chain. Or a phenoxycarbonyl group,
R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted). )

（式中、
Ｒ^１３及びＲ^１４は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、
ｎは０〜５の整数を表す。）

(Where
R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 12 carbon atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n represents an integer of 0 to 5. )

  Examples of commercially available oxime ester photopolymerization initiators having a group represented by the general formula (I) include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  Examples of the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (II) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Examples thereof include oxides and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

The blending amount of such a photopolymerization initiator (B) is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). desirable. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (B) becomes violent and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester photopolymerization initiator having a group represented by the formula (I), the blending amount is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is desirable to select from 20 parts by mass, more preferably from 0.01 to 5 parts by mass.

  Other photopolymerization initiators, photoinitiator assistants, and sensitizers that can be suitably used in the photocurable thermosetting resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketals. Examples thereof include compounds, benzophenone compounds, xanthone compounds, and tertiary amine 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, and 1,1-dichloroacetophenone.

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

  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, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, 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.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

  Of the above, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as

  The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (A). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is. When the amount of the tertiary amine compound is 0.1 parts by mass or less, there is a tendency that a sufficient sensitizing effect cannot be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

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 in a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (A). When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  The hydroxyl group-containing elastomer (C) used in the photocurable thermosetting resin composition of the present invention not only improves the flexibility of the resulting cured coating film, but also greatly reduces the stress during solder resist overcuring. It is valid. Such a hydroxyl group-containing elastomer (C) can be used without particular limitation as long as it is a compound having a hydroxyl group at a side chain or at the terminal, for example, a hydroxyl group-containing acrylic elastomer, a hydroxyl group-containing polyester elastomer, a hydroxyl group-containing compound. Examples thereof include polyester urethane elastomers, hydroxyl group-containing urethane elastomers, cellulose derivative elastomer resins, and polylactic acid elastomers. Particularly preferable examples include polybutadiene elastomers, polyisoprene elastomers and derivatives thereof.

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

  The amount of the hydroxyl group-containing elastomer (C) is suitably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more, with respect to 100 parts by mass of the carboxyl group-containing resin (A). , 50 parts by mass or less. When the amount is less than 5 parts by mass, the effect of the hydroxyl group-containing elastomer is not confirmed. On the other hand, when the amount exceeds 60 parts by mass, the tackiness of the coating film may be deteriorated or the development may be poor.

  Furthermore, a thermosetting component (D) can be added to the photocurable thermosetting resin composition of the present invention in order to impart heat resistance. Examples of the thermosetting component (D) used in the present invention include blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and melamine derivatives. Any known and commonly used thermosetting resin can be used. Among these, a preferable thermosetting component (D) is a thermosetting component having two or more 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 (D) having a cyclic (thio) ether group, and various properties can be imparted depending on their structures. Furthermore, the hydroxyl group of the hydroxyl group-containing elastomer (C) is reacted with a hydroxyl group produced by a reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group), or further, the hydroxyl groups are reacted with each other. By incorporating it into a strong three-dimensional network, its characteristics can be maximized, so it is extremely flexible by using amino resins, isocyanates, and blocked isocyanates that can easily react with hydroxyl groups or carboxyl groups. A cured product can be obtained.

  The thermosetting component (D) having two or more cyclic (thio) ether groups in such a molecule is either a three-, four- or five-membered cyclic ether group or a cyclic thioether group in the molecule. Or a compound having two or more two types of groups, for example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1), at least two oxetanyl in the molecule And a compound having a group, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D-3).

  Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Toto, manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Corporation A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names) Tetraphenylolethane type epoxy Fatty; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resins such as ZX-1063 manufactured by Nippon Steel Chemical Co., Ltd .; Naphthalene groups such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink and Chemicals, Inc. Containing epoxy resin; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200, HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by Nippon Oil & Fats Co., Ltd. Cyclohexyl maleimide and glycidyl methacrylate Relate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), etc. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, novolak-type epoxy resins, modified novolak-type epoxy resins, heterocyclic epoxy resins, bixylenol-type epoxy resins or mixtures thereof are particularly preferable.

  Examples of the polyfunctional oxetane compound (D-2) 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- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, 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 (D-3) having two or more cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd. and YSLV-120TE manufactured by Toto Kasei Co., Ltd. Etc. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). It is -2.5 equivalent, More preferably, it is the range used as 0.8-2.0 equivalent. When the blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in heat resistance, alkali resistance, electricity This is not preferable because the insulating property is lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

  Furthermore, examples of the thermosetting component (D) 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 Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM, (above, manufactured by Sanwa Chemical Co., Ltd.) and the like.
The said thermosetting component can be used individually or in combination of 2 or more types.

  In addition, the photocurable thermosetting resin composition of the present invention includes two or more 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. Compound (E) having can be added. Such a compound (E) having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound (E-1), Or the compound which has 2 or more blocked isocyanate groups in 1 molecule, ie, a blocked isocyanate compound (E-2), etc. are mentioned.

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

  The blocked isocyanate group contained in the blocked isocyanate compound (E-2) is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily inactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound (E-2), an addition reaction product of the isocyanate compound (c) and the isocyanate blocking agent (d) is used. Examples of the isocyanate compound (c) that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound (c), 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 (d) include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactams such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam. Blocking agents; active methylene-based 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, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agents; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocking agents such as methyleneimine and propyleneimine Can be mentioned.

  The blocked isocyanate compound (E-2) 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), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals), etc. Is mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compound (E) having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used alone or in combination of two or more.
The compounding amount of the compound (E) having two or more isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). More preferably, a ratio of 2 to 70 parts by mass is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.

  A urethanization catalyst (F) can be added to the photocurable thermosetting resin composition of the present invention in order to accelerate the curing reaction of hydroxyl groups, carboxyl groups and isocyanate groups. As urethanization catalyst (F), tin-based catalyst (F-1), metal chloride (F-2), metal acetylacetonate salt (F-3), metal sulfate (F-4), amine compound (F) It is preferable to use one or more urethanization catalysts selected from the group consisting of -5) and / or amine salts (F-6).

  Examples of the tin catalyst (F-1) include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

  The metal chloride (F-2) is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobaltous chloride, ferrous nickel chloride, ferric chloride, etc. Is mentioned.

  The metal acetylacetonate salt (F-3) is a metal acetylacetonate salt composed of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, Examples thereof include iron acetylacetonate.

  The metal sulfate (F-4) 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 (F-5) 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-H Roxyethyl) -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-hydroxy) Ethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl And ru-N ', N'-bis (2-hydroxypropyl) amine, melamine and / or benzoguanamine.

  Examples of the amine salt (F-6) 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 (F) is sufficient at a normal quantitative ratio, and for example, preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass of the carboxyl group-containing resin (A). 0.5 to 10.0 parts by mass.

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

  The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, a carboxyl group-containing resin (A) or a thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule. Preferably it is 0.1-20 mass parts with respect to 100 mass parts, More preferably, it is 0.5-15.0 mass parts.

  The photocurable resin composition of this invention can mix | blend (G) a coloring agent. As the colorant, conventionally known colorants such as red (G-1), blue (G-2), green (G-3), yellow (G-4) can be used, and pigments, dyes, Any of pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant (G-1):
Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Index (CI; issued by The Society of Dyers 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, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

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

Green colorant (G-3):
Similarly, there are phthalocyanine, anthraquinone, and perylene types as green colorants. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

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

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The blending ratio of the colorant (G) as described above is not particularly limited, but is preferably 0 to 10 parts by weight, particularly preferably 0.1 to 100 parts by weight of the carboxyl group-containing resin (A). A proportion of 5 parts by weight is sufficient.

  The compound (H) having two or more ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present invention is photocured by irradiation with active energy rays and contains the carboxyl group. The resin (A) is insolubilized in an aqueous alkali solution or assists insolubilization. As such a compound, conventionally 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 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl Aminoalkyl acrylates such as acrylates; 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 acrylate of glycidyl ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate Not limited to the above, but also acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and / or the above acrylates And methacrylates corresponding to the above.

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

  The compounding quantity of the compound (H) which has two or more ethylenically unsaturated groups in such a molecule | numerator is 5-100 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably 1 to 70 parts by mass. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

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

  Furthermore, the photocurable thermosetting resin composition of the present invention 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 invention can 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, 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 invention is organic for the synthesis of the carboxyl group-containing resin (A) and for the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. Solvents can be used.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , 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 invention includes In order to prevent oxidation, (1) the radical scavenger (J-1) or / and (2) the generated peroxide that invalidates the generated radical is decomposed into harmless substances, and no new radical is generated. An antioxidant (J) such as a peroxide decomposing agent (J-2) can be added.

  Specific examples of the antioxidant (J-1) acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t. -Butyl-p-cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-) phenolic compounds such as t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (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 152, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Special Product name).

  Specific examples of the antioxidant (J-2) acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, di And sulfur compounds such as stearyl 3,3′-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 (J) can be used individually by 1 type or in combination of 2 or more types.

  In general, the polymer material absorbs light, which causes decomposition / degradation. Therefore, the photo-curing thermosetting resin composition of the present invention has the above-mentioned antioxidant in order to take a countermeasure against stabilization against ultraviolet rays. In addition to the agent, an ultraviolet absorber (K) can be used.

  Examples of the ultraviolet absorber (K) 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.

The ultraviolet absorber (K) may be a commercially available product, 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 Specialty Chemicals, Inc., trade name) and the like.
Said ultraviolet absorber (K) can be used individually by 1 type or in combination of 2 or more types, The photocurable thermosetting resin composition of this invention is used together with the said antioxidant (J). The molded product obtained from the product can be stabilized.

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

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, and 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) s of 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, PMP, DPMP, and TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (manufactured by Showa Denko KK).

  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) Sunetto AF), 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 invention, 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 group-containing benzotriazole, silane coupling agents and the like.

  The photocurable thermosetting resin composition of the present invention may 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 and conventional additives such as copper damage prevention agents such as those based on triazine and triazine thiols can be blended.

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

  The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying) at a temperature of about 60 to 100 ° C. 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. Furthermore, in the case of a composition containing the thermosetting component (D), for example, by heating and curing at a temperature of about 140 to 180 ° C., the carboxyl group of the carboxyl group-containing resin (A), A thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups in the molecule reacts to have various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. An excellent cured coating film can be formed. Even when the thermosetting component (D) is not contained, the heat treatment causes the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure to undergo thermal radical polymerization, resulting in coating film characteristics. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

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

After applying the photocurable thermosetting resin composition of the present invention and evaporating and drying as follows, 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. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

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

  The photo-curable thermosetting resin composition of the present invention is not a liquid and directly applied to a substrate, but also a dry resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance. It can also be used in the form of a film. The case where the photocurable thermosetting resin composition of this invention is used as a dry film is shown below.

  The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by 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 alkali-developable photo-curable thermosetting resin composition is uniformly applied to a carrier film or cover film with a thickness of 10 to 150 μm with a blade coater, lip coater, comma coater, film coater, etc. and dried. Formed.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. 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.

Synthesis example 1
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 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 raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
Next, 293.0 g of the resulting novolak-type cresol resin 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, thermometer and air. A reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained 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 resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-1.

Synthesis example 2
In a 5-liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 1,245 g of polycaprolactone diol (PLACEL208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, a dihydroxyl compound having a carboxyl group Dimethylolpropionic acid 201 g, polyisocyanate 777 g isophorone diisocyanate, hydroxyl group-containing (meth) acrylate 2-hydroxyethyl acrylate 119 g, p-methoxyphenol and di-t-butyl-hydroxytoluene each 0 .5 g was added. The mixture was stopped by heating to 60 ° C. while stirring, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C., and the reaction is terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) has disappeared in the infrared absorption spectrum. A viscous liquid urethane acrylate compound was obtained. The volatile content was adjusted to 50% by mass using carbitol acetate. A resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as varnish A-2.

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

Comparative Synthesis Example 1
Orthocresol novolak type epoxy resin (manufactured by Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups) (diethylene glycol monoethyl ether acetate 600 g) Total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. Hereinafter, this is referred to as Varnish R-1.

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

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

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

上記表１に示す結果から明らかなように、エポキシ樹脂を出発原料としないカルボキシル基含有樹脂（Ａ−１，Ａ−２）を用いた実施例１、２の光硬化性熱硬化性樹脂組成物は、エポキシ樹脂を出発原料としたカルボキシル基含有感光性樹脂（Ｒ−１，Ｒ−２，Ｒ−３）を用いた比較例１〜３の光硬化性熱硬化性樹脂組成物と比較して、著しくハロゲン量が少ないことが明らかとなった。

As is clear from the results shown in Table 1, the photocurable thermosetting resin compositions of Examples 1 and 2 using a carboxyl group-containing resin (A-1, A-2) that does not use an epoxy resin as a starting material. Compared with the photocurable thermosetting resin compositions of Comparative Examples 1 to 3 using a carboxyl group-containing photosensitive resin (R-1, R-2, R-3) starting from an epoxy resin. It was revealed that the amount of halogen was extremely small.

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

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 Co., Ltd.), washed with water, and dried, and then the photocurable thermosetting resin composition of the examples and comparative examples. The product was applied to the entire surface by a screen printing method, and dried for 60 minutes in an 80 ° C. hot air circulation drying oven. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and remains when developing (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) in 60 seconds. When the step tablet pattern is 7 steps, the optimum exposure was set.

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

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

<Tackiness>
The compositions of Examples and Comparative Examples were applied on the entire 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, and the film was pressure-bonded with ORW HMW-GW20 under reduced pressure conditions for 1 minute, and then the sticking state of the film when the negative film was peeled was evaluated according to the following criteria.
○: When peeling off the film, there is no resistance at all and no mark is left on the coating film.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

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

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

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

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

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

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

<Cold shock resistance>
The evaluation board | substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced. The obtained evaluation substrate was subjected to a 1000 cycle resistance test using a thermal shock tester (manufactured by ETAC Co., Ltd.), with -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-shaped electrodes (line / space = 50 microns / 50 microns) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high temperature / humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 12V was charged, and the in-chamber HAST test was done for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.
○: 10 ⁸ Ω or more △: 10 ⁶ to 10 ⁸ Ω
×: 10 ⁶ Ω or less

Examples 14-21 and Comparative Examples 7-9
Each composition of Examples 3, 5, 6, 8, 9, 10, 11, 13 and Comparative Examples 4, 5, 6 prepared at the blending ratios shown in Table 2 was diluted with methyl ethyl ketone and applied onto a PET film. And it dried at 80 degreeC for 30 minutes, and formed the photosensitive resin composition layer of thickness 20 micrometers. Furthermore, the cover film was bonded together on it and the dry film was produced, and it was set as Examples 14-21 and Comparative Examples 7-9, respectively.

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

前記表３及び表４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（電気特性）を兼ね備えた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 Tables 3 and 4, the photo-curable thermosetting resin composition of the present invention has the PCT resistance, the thermal shock resistance, the HAST characteristics (electrical characteristics) required for the solder resist for semiconductor packages. ) Was found to be useful as a photocurable thermosetting resin composition.

Claims (10)

(A) Carboxyl group-containing resin (however, excluding carboxyl group-containing resin starting from epoxy resin),
(B) A photopolymerization initiator, and (C) a photocurable thermosetting resin composition that can be developed with an aqueous alkaline solution, comprising a hydroxyl group-containing elastomer.   The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin (A) does not contain a hydroxyl group.   The photocurable thermosetting resin composition according to claim 1 or 2, wherein the carboxyl group-containing resin (A) has a photosensitive group.   The photocurable thermosetting resin composition according to any one of claims 1 to 3, wherein the hydroxyl group-containing elastomer (C) is butadiene or an isoprene derivative.   Furthermore, (D) a thermosetting component is contained, The photocurable thermosetting resin composition as described in any one of Claims 1 thru | or 4 characterized by the above-mentioned.   The photocurable thermosetting resin composition according to any one of claims 1 to 5, which is further used for a solder resist containing a colorant (G).   A photocurable thermosetting dry film obtained by applying and drying the photocurable thermosetting resin composition according to any one of claims 1 to 6 on a carrier film.   The hardened | cured material obtained by photocuring the photocurable thermosetting resin composition as described in any one of the said Claims 1 thru | or 6, or the dry film of the said Claim 7.   The cured product according to claim 8, wherein the cured product is obtained by photocuring in a pattern with a light source having a wavelength of 350 nm to 410 nm.   After photocuring the photocurable thermosetting resin composition according to any one of claims 1 to 6 or the dry film according to claim 7 in a pattern by irradiation with active energy rays, A printed wiring board having a cured film obtained by thermosetting.