JP2019179201A - Curable resin composition, dry film and cured product thereof, and printed wiring board including the same - Google Patents

Abstract

To provide a highly sensitive curable resin composition that has both of heat resistance of a rigid substrate SR and flexibility of an FPC SR and accommodates a direct drawing method.SOLUTION: A curable resin composition contains (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) a photosensitive monomer, the (B) photopolymerization initiator containing (B1) an oxime ester photopolymerization initiator and (B2) a titanocene photopolymerization initiator, the (C) photosensitive monomer containing (C1) an alkylene oxide-added bifunctional photosensitive monomer, (C2) an alkanediol skeleton-containing bifunctional photosensitive monomer, and (C3) a photosensitive monomer having three or more functional groups.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, a dry film and a cured product thereof, and a printed wiring board using them.

  For electronic devices typified by smartphones and personal computers, printed wiring boards equipped with electronic elements having various functions are used. As a conventional printed wiring board, a printed wiring board employing a rigid base material called a rigid substrate has been used. However, as electronic devices have become smaller and more multifunctional, spaces for storing printed wiring boards in electronic devices have become narrower. As a countermeasure, a flexible printed wiring board (FPC), which is a printed wiring board that can be bent, has been adopted.

  Conventional FPCs are mainly used for the purpose of connecting rigid boards, but it has become necessary to mount more electronic elements as the functionality of electronic devices increases. Therefore, a rigid flexible printed wiring board (RFPC) has been devised as an FPC capable of mounting components. In order to mount the components, since the printed wiring board undergoes a process such as solder reflow, it is necessary to form a solder resist (SR) in order to protect the printed wiring board from heat at that time. The conventional SR for rigid substrates has high heat resistance, but since the rigid substrate itself is rigid, flexibility is not required. In addition, since the FPC mainly has a purpose of connecting rigid substrates, the FPC SR needs flexibility but does not require high heat resistance.

  Recently, an exposure method mainly used as a method for forming an SR pattern is a contact exposure method in which a negative film is brought into contact with an SR dry coating film to irradiate ultraviolet rays, and a desired SR without using a negative film. The pattern shape has been changed to a non-contact direct drawing method in which ultraviolet rays are directly irradiated (see Patent Document 1).

  Compared with the contact exposure method, the direct drawing method does not require a negative film, the shape to be exposed with digital data can be easily set or changed, and the exposure can be automatically corrected even when the substrate is deformed. There are advantages such as. On the other hand, in order to cope with the direct drawing method, it takes much time for exposure unless the SR is more sensitive than the conventional one.

JP 2009-86414 A

  As described above, the solder resist used in the RFPC, which is an FPC on which components can be mounted, is required to have the heat resistance of the rigid board SR and the flexibility of the FPC SR. However, the conventional rigid substrate SR has poor flexibility, while the FPC SR has poor heat resistance. Moreover, the SR developed so far has insufficient sensitivity to cope with the direct drawing method.

  Accordingly, an object of the present invention is to provide a high-sensitivity curable resin composition that has both the heat resistance of the SR for rigid substrates and the flexibility of the SR for FPCs and is compatible with the direct drawing method.

  As a result of intensive studies aimed at solving the above problems, the present inventors have completed the present invention.

That is, the present invention is a curable resin composition containing (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) a photosensitive monomer,
(B) The photopolymerization initiator includes (B1) an oxime ester photopolymerization initiator and (B2) a titanocene photopolymerization initiator,
(C) The photosensitive monomer includes (C1) a bifunctional photosensitive monomer to which an alkylene oxide is added, (C2) a bifunctional photosensitive monomer having an alkanediol skeleton, and (C3) a trifunctional or higher functional photosensitive monomer. It is a curable resin composition.

  (B) The photopolymerization initiator may further contain (B3) an α-aminoacetophenone photopolymerization initiator.

  (C1) The average addition amount of alkylene oxide per mole of carbon-carbon double bonds in the bifunctional photosensitive monomer to which alkylene oxide is added may be 4 moles or more.

  (C2) The bifunctional photosensitive monomer having an alkanediol skeleton may be a bifunctional photosensitive monomer having an alkanediol skeleton having 4 or more carbon atoms.

  (C3) The trifunctional or higher functional photosensitive monomer may be a trifunctional or higher functional photosensitive monomer to which 1 mol or more of alkylene oxide and / or lactone is added.

  Moreover, this invention is a cured film obtained by performing at least any one of thermosetting and photocuring the said curable resin composition or the dry film obtained by apply | coating and drying this to a film.

  Furthermore, this invention is a printed wiring board provided with the said cured film.

  According to the present invention, it is possible to provide a curable resin composition excellent in developability, photosensitivity, adhesion, solder heat resistance, and flexibility.

  Hereinafter, although the curable resin composition of this invention is demonstrated concretely, this invention is not limited to these at all.

  In addition, when an isomer exists in the described compound, all isomers that can exist can be used in the present invention unless otherwise specified.

  In the present specification, (meth) acrylic acid is a generic term for acrylic acid, methacrylic acid and a mixture thereof, and (meth) acrylate is a term generically used for acrylate, methacrylate and a mixture thereof. The same applies to other similar expressions.

[(A) Carboxyl group-containing resin]
The curable resin composition of the present invention contains (A) a carboxyl group-containing resin. Since the carboxyl group-containing resin has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

  As the carboxyl group-containing resin, a known resin can be used as long as it has a carboxyl group in the molecule. Moreover, carboxyl group-containing resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The carboxyl group-containing resin is preferably a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule from the viewpoint of photocurability and development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. By using a carboxyl group-containing resin having an ethylenically unsaturated double bond, it becomes easy to make the composition photocurable.

  Specific examples of the carboxyl group-containing resin include the following compounds (any of oligomers and polymers).

  (I) 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.

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

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

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

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

  (VI) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain.

  (VII) A carboxyl obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group Group-containing photosensitive resin.

  (VIII) Two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid on a bifunctional oxetane resin. A carboxyl group-containing polyester resin to which an acid anhydride is added.

  (IX) an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.

  (X) Reaction product obtained by reacting a compound obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

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

  (XII) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (I) to (XI).

  (A) The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film is good and the alkali development is good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed part by the developer can be suppressed, so that the line is thinner than necessary, or in some cases, the developer without distinguishing between the exposed part and the unexposed part The resist pattern can be satisfactorily drawn by suppressing dissolution and peeling.

  (A) The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

(A) Among the carboxyl group-containing resins, the polyfunctional epoxy resin used for the synthesis of the resin is a bisphenol A structure, a bisphenol F structure, a bisphenol AD structure, a biphenol structure, a biphenol novolak structure, a bisxylenol structure, a biphenyl novolak structure, and A polyfunctional epoxy resin having one or more partial structures selected from the group consisting of urethane structures or a carboxyl group-containing resin that is a hydrogenated compound thereof is preferred from the viewpoint of low warpage and bending resistance of the resulting cured product.
Among the carboxyl group-containing resins having a urethane structure, a carboxyl group-containing urethane resin obtained by using a diisocyanate in which an isocyanate group is not directly bonded to a benzene ring is used as a component having an isocyanate group (including a diisocyanate). Since there is no change, it is effective for concealment and has little UV absorption, it is preferable because it has excellent resolution when used as an alkali-developable composition.

  The blending amount of the (A) carboxyl group-containing resin is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, further preferably 20 to 60% by mass, and particularly preferably 30 to 30% by mass based on the total amount of the resin composition. 50% by mass. When it is in this range, the coating film strength is good, the viscosity of the composition is moderate, and the coating property and the like can be improved.

[(B) Photopolymerization initiator]
The curable resin composition of the present invention contains (B) a photopolymerization initiator. Here, the (B) photopolymerization initiator includes (B1) an oxime ester photopolymerization initiator and (B2) a titanocene photopolymerization initiator. (B) The photopolymerization initiator preferably further contains (B3) an α-aminoacetophenone photopolymerization initiator. The (B) photopolymerization initiator may contain (B4) another photopolymerization initiator.

  As the (B1) oxime ester photopolymerization initiator, for example, a photopolymerization initiator having two oxime ester groups in the molecule can be suitably used. Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (1).

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

  In particular, in the general formula (1), X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, and Ar is a bond, phenylene, naphthylene, Preferably it is thiophene or thienylene.

  As the compound represented by the general formula (1), the following compounds are particularly preferable.

  Moreover, as a preferable carbazole oxime ester compound, a compound represented by the following general formula (2) can also be exemplified.

In Formula (2), R1 represents a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, or a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms.
R2 represents a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
R3 may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms which may be substituted with a phenyl group, or an alkoxy group having 1 to 4 carbon atoms. Represents a good benzyl group.
R4 represents a nitro group or an acyl group represented by X—C (═O) —. X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula (i), which may be substituted with an alkyl group having 1 to 4 carbon atoms.

Examples of (B1) oxime ester photopolymerization initiators include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
Commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, Adekaoptomer N-1919, NCI-831 manufactured by ADEKA, and the like.

  (B1) Other examples of the oxime ester photopolymerization initiator include JP-A No. 2004-359639, JP-A No. 2005-097141, JP-A No. 2005-220097, JP-A No. 2006-160634, and JP-A No. 2006-160634. Examples thereof include carbazole oxime ester compounds described in JP 2008-094770 A, JP 2008-509967 A, JP 2009-040762 A, and JP 2011-80036 A.

  (B1) It is preferable that the compounding quantity of an oxime ester photoinitiator shall be 0.01-10 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing resin. When the amount is 0.01 parts by mass or more, the photocurability is good and the coating properties such as chemical resistance are good. On the other hand, when the amount is 10 parts by mass or less, light absorption on the surface of the coating film is improved, and deep curability is improved. More preferably, it is 0.5-5 mass parts.

  (B2) The titanocene-based photopolymerization initiator is an organic Ti compound having two or more unsubstituted or substituted cyclopentadienyl anions as η5-ligands. When it has another ligand, the kind and number of other ligands are not particularly limited.

  The substituent of cyclopentadienyl is not particularly limited, and examples thereof include a halo group, an alkyl group, and a halogenated alkyl group. In addition, cyclopentadienyl having a substituent includes a polycyclic structure such as indene.

  Examples of (B2) titanocene photopolymerization initiators include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) titanium diiodide, and bis (cyclopenta). Dienyl) titanium difluoride, bis (cyclopentadienyl) titanium chlorobromide, bis (cyclopentadienyl) titanium methoxy chloride, bis (cyclopentadienyl) titanium ethoxy chloride, bis (cyclopentadienyl) titanium phenoxycyclolide , Bis (cyclopentadienyl) titanium dimethoxide, bis (cyclopentadienyl) titanium diphenoxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- ( H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium, and the like. It is done. Commercially available products include Omnirad 784 manufactured by IGM Resins.

  (B2) It is preferable that the compounding quantity of a titanocene type photoinitiator shall be 0.01-10 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing resin. When the amount is 0.01 parts by mass or more, the photocurability is good and the coating properties such as chemical resistance are good. On the other hand, in the case of 10 parts by mass or less, deep part curability is improved, and a photocured coating film having a good shape after development is obtained. More preferably, it is 0.1-5 mass parts.

  The ratio (MB2 / MB1) of the blending amount (MB2) of (B2) titanocene photopolymerization initiator to the blending amount (MB1) of (B1) oxime ester photopolymerization initiator is not particularly limited. The ratio may be 0.2 or more, 0.4 or more, 0.6 or more, 0.8 or more, or 1 or more. The ratio may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.

Examples of (B3) α-aminoacetophenone photopolymerization initiators include 2-dimethylamino-2-methyl-1-phenylpropane-1-one, 2-diethylamino-2-methyl-1-phenylpropane-1- ON, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- ( 4-ethylphenyl) -2-methylpropan-1-one, 2-dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-dimethyl Amino-2-methylpropan-1-one, 2-dimethylamino-1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino 2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, 2-dimethylamino-2- [ (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like.
As a commercial item, Omnirad (Omnirad) 907, Omnirad (Omnilad) 369EG, etc. by IGM Resins are mentioned.

  (B3) When it contains an α-aminoacetophenone photopolymerization initiator, the blending amount is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. In the case of 0.01 parts by mass or more, photocurability is good, and deterioration of coating film properties such as solder heat resistance can be suppressed. On the other hand, in the case of 15 parts by mass or less, outgas is reduced and contamination in the heating furnace can be suppressed. More preferably, it is 0.5-10 mass parts.

  When (B3) α-aminoacetophenone photopolymerization initiator is contained, (B3) blending amount of (B3) α-aminoacetophenone photopolymerization initiator with respect to blending amount (MB1) of oxime ester photopolymerization initiator ( The ratio of MB3) (MB3 / MB1) is not particularly limited. The ratio may be 0.4 or more, 0.6 or more, 0.8 or more, 1 or more, or 1.2 or more. The ratio may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less.

  When (B3) α-aminoacetophenone photopolymerization initiator is contained, (B3) blending amount of (B3) α-aminoacetophenone photopolymerization initiator (MB3) relative to blending amount (MB2) of titanocene photopolymerization initiator (MB3) ) Ratio (MB3 / MB1) is not particularly limited. The ratio may be 0.4 or more, 0.6 or more, 0.8 or more, 1 or more, or 1.2 or more. The ratio may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less.

  (B4) Other photopolymerization initiators include, for example, acylphosphine oxide photopolymerization initiators (bisacylphosphine oxide photopolymerization initiators and monoacylphosphine oxide photopolymerization initiators), and acetophenone photopolymerization initiators. Initiator, hydroxyacetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzoin alkyl ether photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, anthraquinone photopolymerization initiator, ketal Examples include photopolymerization initiators, benzoate photopolymerization initiators, and tertiary amine compound photopolymerization initiators.

  Examples of the bisacylphosphine oxide photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide and bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide. Bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine Fin oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- ( 2,4,6-trimethylbenzoyl - phenyl phosphine oxide, and the like.

  Examples of the monoacylphosphine oxide photopolymerization initiator include 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, and methyl 2,4,6-trimethylbenzoylphenylphosphinate. Examples include esters, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.

  As commercial products of acylphosphine oxide photopolymerization initiators (bisacylphosphine oxide photopolymerization initiators and monoacylphosphine oxide photopolymerization initiators), Omnirad TPO, Omnirad (manufactured by IGM Resins) Omnirad) 819.

  Examples of the acetophenone photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

  Examples of the hydroxyacetophenone photopolymerization initiator include ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate, 1-hydroxy-cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and the like.

  Examples of the benzoin photopolymerization initiator include benzoin and benzyl.

  Examples of the benzoin alkyl ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

  Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like. Can be mentioned.

  Examples of the anthraquinone photopolymerization initiator include anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone and the like. It is done.

  Examples of the ketal photopolymerization initiator include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Examples of the benzoate photopolymerization initiator include ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, p-dimethylbenzoic acid ethyl ester, and the like.

  Specific examples of the tertiary amine compound photopolymerization initiator include ethanolamine compounds and compounds having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure manufactured by Nippon Soda Co., Ltd.). MABP), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and other dialkylaminobenzophenones, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4 Dialkylamino group-containing coumarin compounds such as -methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), -Dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylaminobenzoic acid 2 -Ethylhexyl (Esolol 507 manufactured by Van Dyk) and the like.

  As the tertiary amine compound photopolymerization initiator, a compound having a dialkylaminobenzene structure is preferable. Among these, dialkylaminobenzophenone compounds, dialkylamino group-containing coumarin compounds and ketocoumarins having a maximum absorption wavelength in the range of 350 to 450 nm are particularly preferable.

  In addition to the above-described photopolymerization initiator, phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like can be mentioned.

  (B4) When it contains another photoinitiator, it is preferable that the compounding quantity is 0.01-15 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing resin.

  (B) It is preferable that the total compounding quantity of a photoinitiator is 1 to 35 mass parts with respect to 100 mass parts of carboxyl group-containing resin. In the case of 35 parts by mass or less, it is possible to suppress a decrease in deep part curability due to light absorption.

[(C) Photosensitive monomer]
The curable resin composition of the present invention contains (C) a photosensitive monomer. Here, (C) the photosensitive monomer includes (C1) a bifunctional photosensitive monomer to which alkylene oxide is added, (C2) a bifunctional photosensitive monomer having an alkanediol skeleton, and (C3) a trifunctional or higher functional photosensitive monomer. Including. The (C) photocurable monomer may contain (C4) another photocurable monomer.

  Here, the photosensitivity means having a carbon-carbon multiple bond (double bond and triple bond). One carbon-carbon double bond has the same meaning as monofunctional photosensitivity. One carbon-carbon triple bond has the same meaning as bifunctional photosensitivity. That is, one carbon-carbon triple bond and two carbon-carbon double bonds are equivalent in photosensitivity. In the present invention, the carbon-carbon triple bond is treated as two carbon-carbon double bonds. In this sense, the bifunctional photosensitive monomer means a compound having two carbon-carbon double bonds in one molecule. Similarly, a trifunctional or higher functional photosensitive monomer means a compound having three or more carbon-carbon double bonds in one molecule.

  Although the present invention is not limited, a typical example of the (C) photocurable monomer is a compound having a carbon-carbon double bond derived from (meth) acrylic acid.

  (C1) The bifunctional photosensitive monomer to which alkylene oxide is added has bifunctional photosensitivity, and it is sufficient that at least a part of the molecule is modified with alkylene oxide. The modified part by alkylene oxide may have a repeating structure.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

  The average addition amount of alkylene oxide is not particularly limited. Since a cured coating film having sufficient flexibility can be obtained, the lower limit is preferably 4 moles or more and 5 moles or more per mole of carbon-carbon double bonds. On the other hand, since tackiness is unlikely to deteriorate, the upper limit is preferably 15 mol or less and 10 mol or less per mol of carbon-carbon double bonds.

  (C1) The molecular weight of the bifunctional photosensitive monomer to which alkylene oxide is added is preferably 400 to 2,000, and more preferably 500 to 1,500.

  Examples of the bifunctional photosensitive monomer to which (C1) alkylene oxide is added include, for example, bifunctional (meth) acrylates of alkylene oxide adduct diols of bisphenol (including hydrogenated) and alkylene oxide adduct diols of diols. Bifunctional photosensitive monomers, such as bifunctional (meth) acrylate, are mentioned.

  Examples of bisphenol (including hydrogenated ones) include hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol A, and bisphenol F.

  Examples of the diol include alkanediol, cycloalkane having a hydroxy group and / or a hydroxyalkyl group. More specifically, cyclohexanedimethanol, hexanediol, ethylene glycol, propylene glycol, neopentyl glycol and the like can be mentioned.

  (C1) The blending amount of the bifunctional photosensitive monomer to which alkylene oxide is added is preferably 1 part by weight to 40 parts by weight, more preferably 3 parts by weight with respect to 100 parts by weight of the (A) carboxyl group-containing resin. It is 30 mass parts, More preferably, it is the range of 5 mass parts-20 mass parts. By setting it as this range, the dry coating film with favorable softness | flexibility, tackiness, and photocurability can be obtained.

  (C2) The bifunctional photosensitive monomer having an alkanediol skeleton means a compound having the same structure as the compound that has obtained a structure in which the alkanediol has photosensitivity via a hydroxy group. As a matter of course, if the structure of the compound is the same, it does not depend on the production method. The bond via a hydroxy group is not limited, but typically includes an ether bond, an ester bond, and a urethane bond.

  One or both of two hydroxy groups of the alkanediol skeleton may form the above bond to obtain a photosensitive structure. Preferably both of the two hydroxy groups form the bond. At this time, it is preferable that both of the two hydroxy groups each form a bond having a monofunctional photosensitivity. As a matter of course, the structure and bond type having monofunctional photosensitivity may be the same or different.

  A typical example of the photosensitive structure is a structure derived from (meth) acrylic acid.

  (C2) A typical example of the bifunctional photosensitive monomer having an alkanediol skeleton includes a compound in which the hydroxy group of the alkanediol skeleton and the carboxy group of (meth) acrylic acid form an ester bond. Moreover, the compound in which the hydroxy group of alkanediol skeleton and the hydroxy group which hydroxyalkyl (meth) acrylate has is ether-bonded is mentioned.

  (C2) The carbon number of the alkanediol skeleton of the bifunctional photosensitive monomer having an alkanediol skeleton is not particularly limited. The lower limit is preferably 2 or more, 4 or more, 5 or more. If the carbon number of the alkanediol skeleton is equal to or greater than the lower limit, sufficient gold plating resistance can be obtained. On the other hand, the upper limit is 12 or less and 10 or less. If the number of carbons of the alkanediol skeleton is not more than the upper limit value, tackiness is unlikely to deteriorate.

  (C2) The molecular weight of the bifunctional photosensitive monomer having an alkanediol skeleton is preferably 40 to 300, more preferably 50 to 250.

  The alkane part of the alkanediol skeleton may be branched, but is preferably a straight chain.

  Examples of the alkanediol skeleton include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3 -Pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6- Hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,4-heptanediol, 1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, 1,2-octane Diol, 1,3-octanediol, 1,4-octanediol, 1,5-octanediol, 6-octanediol, 1,7-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,3-nonanediol, 1,4-nonanediol, 1,5-nonanediol, 1,6 -Nonanediol, 1,7-nonanediol, 1,8-nonanediol, 1,9-nonanediol, 1,2-decanediol, 1,3-decanediol, 1,4-decanediol, 1,5- Decanediol, 1,6-decanediol, 1,7-decanediol, 1,8-decanediol, 1,9-decanediol, 1,10-decanediol, 1,2-undecanediol, 1,3-undecane Diol, 1,4-undecanediol, 1,5-undecanediol, 1,6-undecanediol, 1,7-undecanediol, 1,8-un Candiol, 1,9-undecanediol, 1,10-undecanediol, 1,11-undecanediol, 1,2-dodecanediol, 1,3-dodecanediol, 1,4-dodecanediol, 1,5-dodecane Diol, 1,6-dodecanediol, 1,7-dodecanediol, 1,8-dodecanediol, 1,9-dodecanediol, 1,10-dodecanediol, 1,11-dodecanediol, 1,12-dodecanediol Examples include the alkanediol skeleton derived from the origin.

  (C2) More specifically, as the bifunctional photosensitive monomer having an alkanediol skeleton, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,2-pentanediol di (meth) acrylate, 1, 3-pentanediol di (meth) acrylate, 1,4-pentanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,3- Hexanediol di (meth) acrylate, 1,4-hexanediol (Meth) acrylate, 1,5-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,2-heptanediol di (meth) acrylate, 1,3-heptanediol di (meth) ) Acrylate, 1,4-heptanediol di (meth) acrylate, 1,5-heptanediol di (meth) acrylate, 1,6-heptanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate 1,2-octanediol di (meth) acrylate, 1,3-octanediol di (meth) acrylate, 1,4-octanediol di (meth) acrylate, 1,5-octanediol di (meth) acrylate, 1 , 6-Octanediol di (meth) acrylate, 1,7-octanedi Di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-nonanediol di (meth) acrylate, 1,3-nonanediol di (meth) acrylate, 1,4-nonanediol di ( (Meth) acrylate, 1,5-nonanediol di (meth) acrylate, 1,6-nonanediol di (meth) acrylate, 1,7-nonanediol di (meth) acrylate, 1,8-nonanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,3-decanediol di (meth) acrylate, 1,4-decanediol di (meth) acrylate, 1,5-decanediol di (meth) acrylate, 1,6-decanediol di (meth) acrylate Rate, 1,7-decanediol di (meth) acrylate, 1,8-decanediol di (meth) acrylate, 1,9-decanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-undecanediol di (meth) acrylate, 1,3-undecanediol di (meth) acrylate, 1,4-undecanediol di (meth) acrylate, 1,5-undecanediol di (meth) acrylate, 1, 6-undecanediol di (meth) acrylate, 1,7-undecanediol di (meth) acrylate, 1,8-undecanediol di (meth) acrylate, 1,9-undecanediol di (meth) acrylate, 1,10- Undecanediol di (meth) acrylate, 1,11-undecane All di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, 1,3-dodecanediol di (meth) acrylate, 1,4-dodecanediol di (meth) acrylate, 1,5-dodecanediol di ( (Meth) acrylate, 1,6-dodecanediol di (meth) acrylate, 1,7-dodecanediol di (meth) acrylate, 1,8-dodecanediol di (meth) acrylate, 1,9-dodecanediol di (meth) Examples include acrylate, 1,10-dodecanediol di (meth) acrylate, 1,11-dodecanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, and the like.

  (C2) The blending amount of the bifunctional photosensitive monomer having an alkanediol skeleton is preferably 1 part by mass to 40 parts by mass, and more preferably 3 parts by mass to 30 parts with respect to 100 parts by mass of the (A) carboxyl group-containing resin. It is in the range of 5 parts by mass to 20 parts by mass, more preferably 5 parts by mass. By setting it as this range, the dry coating film with favorable gold-plating tolerance, tack property, and photocurability can be obtained.

  The ratio (MC2 / MC1) of the blending amount (MC2) of the (C2) bifunctional photosensitive monomer having an alkanediol skeleton to the blending amount (MC1) of the (C1) alkylene oxide added bifunctional photosensitive monomer is particularly limited. There is no. The ratio may be 0.2 or more, 0.4 or more, 0.6 or more, 0.8 or more, or 1 or more. The ratio may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.

  (C3) The trifunctional or higher functional monomer can be of any structure as long as it is trifunctional or higher.

  A typical example is a compound in which a compound having a photosensitive structure such as (meth) acrylate is bonded to a polyol compound having three or more hydroxy groups. As a matter of course, if the structure of the compound is the same, it does not depend on the production method. The bond via a hydroxy group is not limited, but typically includes an ether bond, an ester bond, and a urethane bond.

  Among these, a tri- or higher functional photosensitive monomer to which 1 mol or more of alkylene oxide and / or lactone is added is preferable. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Examples of the lactone include caprolactone.

  (C3) The molecular weight of the tri- or higher functional photosensitive monomer is preferably 500 to 3,000, and more preferably 600 to 2,500.

  (C3) More specifically, trifunctional or higher functional photosensitive monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( And (meth) acrylate compounds with trimethylolpropane, pentaerythritol, dipentaerythritol or alkylene oxide and / or lactone adduct of dipentaerythritol.

  (C3) The blending amount of the trifunctional or higher functional monomer is preferably 1 part by weight to 40 parts by weight, more preferably 3 parts by weight to 30 parts by weight, with respect to 100 parts by weight of the (A) carboxyl group-containing resin. More preferably, it is the range of 5 mass parts-20 mass parts. By setting it as this range, the dry coating film with favorable heat resistance, a softness | flexibility, and photocurability can be obtained.

  The ratio (MC3 / MC1) of the blending amount (MC3) of (C3) trifunctional or higher functional monomer to the blending amount (MC1) of bifunctional photosensitive monomer to which (C1) alkylene oxide is added is not particularly limited. The ratio may be 0.2 or more, 0.4 or more, 0.6 or more, 0.8 or more, or 1 or more. The ratio may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.

  The ratio (MC3 / MC2) of the blending amount (MC3) of (C3) trifunctional or higher functional monomer to the blending amount (MC2) of (C2) alkanediol skeleton is not particularly limited. The ratio may be 0.2 or more, 0.4 or more, 0.6 or more, 0.8 or more, or 1 or more. The ratio may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.

  Photosensitive monomers other than the above may be contained as (C4) other photosensitive monomers.

  (C4) The blending amount of the other photosensitive monomer is preferably 1 part by weight to 40 parts by weight, more preferably 3 parts by weight to 30 parts by weight, and still more preferably, with respect to 100 parts by weight of the (A) carboxyl group-containing resin. Is in the range of 5 to 20 parts by weight. By setting it as this range, the dry coating film with favorable heat resistance, a softness | flexibility, and photocurability can be obtained.

  (C) The total compounding amount of the photocurable monomer is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 80 parts by mass, and still more preferably, with respect to 100 parts by mass of the (A) carboxyl group-containing resin. Is in the range of 20 to 60 parts by weight. By setting it as this range, the dry coating film with favorable tack property and photocurability can be obtained.

[(D) filler]
(D) A well-known and usual inorganic or organic filler can be used for a filler. In particular, barium sulfate, silica, hydrotalcite and talc are preferably used.

  (D) The average particle diameter of the filler is not particularly limited as long as it can be used as a filler. A preferable average particle diameter is 0.1 μm to 30 μm, more preferably 0.1 μm to 10 μm, as an average particle diameter obtained from a volume average particle size distribution measurement result measured by a laser diffraction particle size distribution measuring device. is there.

  The blending amount of (D) filler is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and further preferably 30 to 70 parts by mass with respect to 100 parts by mass of (A) carboxyl group-containing resin. It is a range. By setting it within this range, a cured coating film having excellent heat resistance and physical strength can be obtained.

[(E) Epoxy resin]
(E) If an epoxy resin has an epoxy group, a well-known and usual thing can be used.

  Examples of the epoxy resin include JER828 manufactured by Mitsubishi Chemical Corporation, Epototo YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., Araldite GY240, Araldite GY250, Araldite GY260, Araldite GY261, Araldite GY266, Araldite GY2600, manufactured by Huntsman. Bisphenol A type epoxy resin such as Epicron 840, Epicron 850, (trade name) manufactured by DIC; Hydrogenated bisphenol F type epoxy resin such as Epototo YDF-170, YDF-175 (trade name) manufactured by Toto Kasei; DIC; Bisphenol F type epoxy resin such as Epicron 830, Epicron 830-S, Epicron 835, JER807 made by Mitsubishi Chemical Co., Ltd. (all trade names); Epototo ST-3000 made by Toto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin; celoxide 2021 manufactured by Daicel Chemical Industries, araldite CY175, CY179 manufactured by Asahi Ciba Co., Ltd. (both trade names); JER152, DIC manufactured by Mitsubishi Chemical Corporation Phenol novolac type epoxy resin such as Epicron N-730 (both trade names) manufactured by Mitsubishi Chemical Co., Ltd. JER604 (trade name) glycidylamine type epoxy resins manufactured by Mitsubishi Chemical Co., Ltd. Epolide PB3600 and Epolide PB4700 (both products) Name) polybutadiene epoxy resin; JER834, JER1001, JER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 1050, Epicron 2055 manufactured by DIC, Epototo YD-011, YD-013 manufactured by Tohto Kasei Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Araldite GT6063, Araldite GT6064, Araldite GT681, Araldite GT681, Araldite GT6072, Araldite GT6072, Araldite GT684, Araldite GT6072, Araldite GT6072 GT7077, Araldite GT16099; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); JER154 manufactured by Mitsubishi Chemical Corporation, D.C. E. N. 431, D.D. E. N. 438, Epicron N-770, Epicron N-865 manufactured by DIC, Epotot YDPN-638, YDCN-700-3, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN- manufactured by Toto Kasei 704A, Araldite ECN1280-1 manufactured by Huntsman, Araldite ECN 9699, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumy-Epoxy ESCN manufactured by Sumitomo Chemical Co., Ltd. -195X, ESCN-220, A.A. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both trade names); bisphenol F type epoxy resins such as TDF-2004 made by Toto Kasei Co., Ltd. and Araldite XPY306 made by BASF Japan; Hydrogenated bisphenol A type epoxy resin such as Etototo 4000D (trade name) manufactured by Toto Kasei Co., Ltd .; AER4001, AER4152, and AER4004 (all are trade names) manufactured by Asahi Kasei Co., Ltd., Epototo YH- manufactured by Toto Kasei Co., Ltd. 434, Araldite MY720 manufactured by Asahi Ciba, Sumic-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (both are trade names); Araldite CY-350 (trade name) manufactured by Asahi Ciba Japan; Hydantoin type epoxy resin such as Mitsubishi Chemical YL-933, Dow Chemical's EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical YL-6056, YX-4000, YL-6121 (any Or a mixture thereof; Nippon Kayaku EBPS-200, Asahi Denka Kogyo EPX-30, DIC EXA-1514 (trade name), etc. Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as JER157S (trade name) manufactured by Mitsubishi Chemical Corporation; TetraLite 163 manufactured by Mitsubishi Chemical Corporation, Araldite 163 manufactured by Asahi Ciba Co., Ltd. (all trade names) Phenylolethane type epoxy resin; Araldite PT810 manufactured by Asahi Ciba, Nissan Chemical Heterocyclic epoxy resins such as TEPIC made by Sangyo Co., Ltd. (both trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Nippon Steel Naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Kagaku Co., HP-4032, EXA-4750, and EXA-4700 manufactured by DIC; dicyclopentadiene skeletons such as HP-7200 and HP-7200H manufactured by DIC Epoxy resin having: Glycidyl methacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by NOF Corporation; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like, but is not limited thereto Absent. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  (E) The compounding quantity of an epoxy resin becomes like this. Preferably it is 5-100 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is 10-80 mass parts, More preferably, it is 30-70 mass parts. Range. By setting it within this range, a cured coating film having excellent heat resistance and physical strength can be obtained.

[(F) Colorant]
(F) As the colorant, conventionally known colorants such as red, blue, green, yellow, purple, orange, brown, white, black and the like can be used, and any of pigments, dyes, and pigments may be used. Specifically, the color index (CI; issued by The Society of Dyers and Colorists) number is given. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.

<Red colorant>
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Examples of color index numbers are listed.

Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14,15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188,193, 210, 245, 253, 258, 266, 267, 268, 269;
Disazo: Pigment Red 37, 38, 41;
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1, 68;
Benzimidazolone series: Pigment Red 171, Pigment Red 175, PigmentRed 176, Pigment Red 185, Pigment Red 208;
Perylenes: Solvent Red 135, Solvent Red 179, Pigment Red123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224;
Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272;
Condensed Azo: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242;
Anthraquinone series: Pigment Red 168, Pigment Red 177, PigmentRed 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207;
Kinacridone series: Pigment Red 122, Pigment Red 202, PigmentRed 206, Pigment Red 207, Pigment Red 209.

<Blue colorant>
Blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds include those classified as Pigment. Specifically, those with the following color index numbers are listed. Can do.
Pigment Blue: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60;
Dye type: Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. Can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

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

<Yellow colorant>
Examples of the yellow colorant include monoazo series, disazo series, condensed azo series, benzimidazolone series, isoindolinone series, anthraquinone series, and the like, and specific examples include the following colorants.
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;
Condensed azo: 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;
Isoindolinone: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185;
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

<Purple colorant, orange colorant, brown colorant>
Specific examples of purple colorant, orange colorant, and brown colorant include Pigment Violet 19,23, 29, 32, 36, 38, 42; Solvent Violet 13, 36; CIPigment Orange 1, CIPigment Orange 5, CIPigment Orange 13, CIPigment Orange 14, CIPigment Orange 16, CIPigment Orange 17, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 38, CIPigment Orange 40, CIPigment Orange 43, CIPigment Orange 46, CIPigment Orange 49, CIPigment Orange 49 51, CIPigment Orange 61, CIPigment Orange 63, CIPigment Orange 64, CIPigment Orange 71, CIPigment Orange 73; CI Pigment Brown 23, CI Pigment Brown 25, and the like.

<White colorant>
Examples of the white colorant include zinc oxide shown in CIPigment White 4, titanium oxide shown in CIPigment White 6, and zinc sulfide shown in CIPigment White 7. Particularly preferable from the viewpoint of coloring power and non-toxicity. For example, TR-600, TR-700, TR-750, TR-840, Ishihara Sangyo R-550, R-580, R-630, R-820, CR-50 manufactured by Fuji Titanium Industry Co., Ltd. , CR-60, CR-90, CR-97, rutile titanium oxide such as KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd., TA-100, TA-200, TA- manufactured by Fuji Titanium Industry Co., Ltd. 300, TA-500, A100, A220 manufactured by Ishihara Sangyo Co., Ltd., an anatase type titanium oxide such as KA-15, KA-20, KA-35, KA-90 manufactured by Titanium Industrial Co., Ltd.

<Black colorant>
Examples of black colorants include carbon black pigments such as CIPigment Black 6, 7, 9 and 18; graphite pigments such as CIPigment Black 8, 10 and the like; and CIPigment Black 11, 12 and 27 etc. Iron oxide pigments: For example, iron oxide of Toda Kogyo KN-370, Mitsubishi Materials 13M titanium black, anthraquinone pigments such as CIPigment Black 20, CIPigment Black 13, 25 and 29 etc. Cobalt oxide pigments, copper oxide pigments such as CIPigment Black 15 and 28, manganese pigments such as CIPigment Black 14 and 26, antimony oxide pigments such as CIPigment Black 23, CIPigment Examples of suitable pigments include nickel oxide pigments such as Black 30 and the like, perylene pigments represented by CIPigment Black 31 and 32, molybdenum sulfide and bismuth sulfide. These pigments are used alone or in appropriate combination. Particularly preferred is carbon black. For example, carbon black, M-40, M-45, M-50, MA-8, MA-100 manufactured by Mitsubishi Chemical Corporation, and perylene pigments are low among organic pigments. Effective for halogenation.

  A coloring agent can be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of a coloring agent is not specifically limited, Preferably it is 0.01-10 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is 0.1-7 mass parts. However, in the case of a white colorant, it is preferably 50 to 300 parts by mass, more preferably 70 to 250 parts by mass with respect to (A) 100 parts by mass of the carboxyl group-containing resin.

  As described above, by setting the curable resin composition of the present invention to black, a curable resin composition having excellent concealability can be obtained. In order to blacken, the curable resin composition of the present invention may contain only a black colorant as a colorant, but as described above, it is more excellent in concealment property despite excellent resolution. It is preferable to contain 1 or more types of coloring agents other than a black coloring agent and a black coloring agent from the curable resin composition obtained. By blackening with the combination of the colorants, the exposure light for photocuring becomes difficult to be absorbed by the colorant while having sufficient blackness, and the photocuring proceeds sufficiently so that resolution is improved. It is also considered excellent. An example of the combination of the colorants is a combination of carbon black and at least one of a blue colorant and a red colorant, and preferably a combination of carbon black, a blue colorant and a red colorant.

  When blackening only with a black colorant, it is preferable to use a perylene-based black colorant from the viewpoint of resolution.

  Moreover, it can also blacken by the combination of 2 or more types of colorants other than a black colorant.

  Specific examples of each colorant used in combination of two or more colorants other than the black colorant include those described above.

[Other ingredients]
The curable resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired.

  As other components, known additives generally used in curable resin compositions, such as flame retardants, coupling agents, elastomers, adhesion promoters, antioxidants, ultraviolet absorbers, thermal polymerization inhibitors, etc. You may mix | blend.

[Flame retardants]
For the curable resin composition of the present invention, it is preferable to use a conventionally known flame retardant for the purpose of improving the flame retardancy of the resulting cured product. From the viewpoint of the environment, a flame retardant containing no halogen is preferred. As the flame retardant, for example, a phosphorus-containing compound or aluminum hydroxide, magnesium hydroxide, hydrotalcite, boehmite, or the like, which is an inorganic filler that imparts flame retardancy to the curable resin composition, may be blended. Of the flame retardants, phosphorus-containing compounds are preferred. A flame retardant may be used individually by 1 type, and may use 2 or more types together.

  Examples of the phosphorus-containing compound include those known as organic phosphorus flame retardants. Among such organic phosphorus flame retardants, preferred are phosphoric acid esters and condensed phosphoric acid esters, phosphorus element-containing (meth) acrylates, phosphorus-containing compounds having phenolic hydroxyl groups, cyclic phosphazene compounds, phosphazene oligomers, phosphines. Examples include acid metal salts and compounds represented by the following general formula (3).

  In formula (3), R5, R6 and R7 each independently represent a substituent other than a halogen atom.

  In the general formula (3), R5 and R6 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R7 has 1 to 1 carbon atoms optionally substituted with a hydrogen atom or a cyano group. It is preferably 4 alkyl groups, 2,5-dihydroxyphenyl groups, or 3,5-di-t-butyl-4-hydroxyphenyl groups, but is not limited thereto.

  Commercially available products of the phosphorus-containing compound represented by the general formula (3) include HCA, SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sanko).

  The phosphorus element-containing (meth) acrylate is preferably a compound having a phosphorus element and having a plurality of (meth) acryloyl groups in the molecule. Specifically, R5 and R6 in the general formula (3) are used. In which R 7 is a hydrogen atom and R 7 is a (meth) acrylate derivative. Generally, it can be synthesized by a Michael addition reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a known and commonly used polyfunctional (meth) acrylate monomer.

  Examples of the (meth) acrylate monomer include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyania. Polyhydric alcohols such as nurate or polyvalent acrylates such as ethylene oxide adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxides of these phenols Polyvalent acrylates such as adducts; and urethane acrylates of the above polyalcohols; Polyglycerides of glycidyl ethers such as diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and at least one of melamine acrylate and methacrylates corresponding to the acrylate Is mentioned.

  The phosphorus-containing compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, does not deteriorate electrical characteristics due to hydrolysis, and has high solder heat resistance. Further, as an appropriate combination, when an epoxy resin is used among thermosetting resins, there is an advantage that it does not bleed out after curing because it reacts with the epoxy group and is taken into the network. Among the phosphorus-containing compounds having a phenolic hydroxyl group, preferred are those in which R7 in the general formula (3) is a phenyl group substituted with a hydroxyl group. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.

  Phosphorus-containing compounds that are oligomers or polymers have the advantage that there is little decrease in bendability due to the influence of the alkyl chain, and there is no bleedout after curing due to the large molecular weight. Commercially available products include M-Ester-HP manufactured by Sanko Co., Ltd. and phosphorus-containing Byron 337 manufactured by Toyobo Co., Ltd.

  As the phosphazene oligomer, a phenoxyphosphazene compound is effective, and there are a substituted or unsubstituted phenoxyphosphazene oligomer or a trimer, a tetramer, and a pentamer, and there are liquid and solid powders. It can be preferably used. Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical. Among these, a phenoxyphosphazene oligomer substituted with an alkyl group or a polar group such as a hydroxyl group or a cyano group is preferable because it has high solubility in a carboxyl group-containing resin and does not cause problems such as recrystallization even when added in a large amount.

  In addition, as another phosphazene oligomer, at least one of a phosphorus element-containing dicarboxylic acid represented by the following general formula (4) and an anhydride thereof and an acrylate compound are reacted, and one or more in the molecule. It is a compound containing (meth) acrylate.

  Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R8 and R9 in the general formula (4) include, for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, Examples thereof include a cycloalkyl group and a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, pentyl group, isopentyl group, and tertiary pentyl group. Examples of the alkenyl group having 1 to 6 carbon atoms such as hexyl group include vinyl group, allyl group, 3-butenyl group, isobutenyl group, 4-pentenyl group, and 5-hexenyl group. The hydrocarbon group having 1 to 6 carbon atoms may be branched or substituted.

  Examples of the phosphorus element-containing dicarboxylic acid or anhydride thereof include compounds obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with itaconic acid and anhydrides thereof. Thing etc. are mentioned.

As the acrylate compound, an acrylate compound having a functional group that reacts with a carboxyl group or a carboxylic acid anhydride of the dicarboxylic acid or an anhydride thereof is preferable. An acrylate residue can be added by such a reaction. Such an acrylate compound may be a monofunctional acrylate containing one (meth) acrylate group in the molecule or a polyfunctional acrylate containing two or more (meth) acrylate groups in the molecule. Examples of the functional group include an epoxy group, a hydroxyl group, and an amino group. Examples of the acrylate compound having an epoxy group include glycidyl (meth) acrylate and 2-methyl-2,3-epoxypropyl (meth) acrylate. Examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Examples of the acrylate compound having an amino group include diethylaminoethyl acrylate. Among the functional groups, an epoxy group and a hydroxyl group are more preferable.
A conventionally known reaction method can be used as the reaction method for adding with the functional group.

  Examples of the phosphazene oligomer include mono- or bifunctional phosphazene oligomers obtained by reacting a phosphorus element-containing dicarboxylic acid of the general formula (4) synthesized as described above with glycidyl methacrylate, and the general formula (4 ), A bifunctional phosphazene oligomer obtained by reacting a phosphorus element-containing dicarboxylic acid with hydroxy (meth) acrylate and, if necessary, a dialcohol.

  The amount of the acrylate compound added to the phosphorus element-containing dicarboxylic acid represented by the general formula (4) or its anhydride is not particularly limited, but the phosphorus concentration of the phosphazene oligomer is in the range of 2% to 7%. It is preferable to adjust to an acrylate compound.

By using the phosphorus element-containing dicarboxylic acid represented by the general formula (4) or its anhydride, a phosphazene oligomer having both ends acrylated can be easily obtained. By using the terminal acrylated phosphazene oligomer obtained in this way, it is excellent in flexibility and low warpage, and can be obtained a flame retardant coating that does not cause bleeding out during high temperature pressing. A flame curable resin composition can be obtained.
The phosphazene oligomer is preferably a bifunctional phosphorus element-containing acrylate from the viewpoints of flexibility and low warpage. When the phosphazene oligomer is bifunctional, the heat resistance is good and the decrease in flexibility can be suppressed.
Moreover, the said phosphazene oligomer may be used individually by 1 type, and may use 2 or more types together.

  Moreover, by using a phosphinic acid metal salt, flame retardance can be improved without impairing the flexibility of the cured coating. By using such a phosphinic acid metal salt excellent in heat resistance, the bleed-out of the flame retardant can be suppressed in the hot press during mounting.

  Specific examples of the phosphinic acid constituting the phosphinic acid metal salt include phosphinic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1, 4- (dimethylphosphinic acid), methylphenylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid and mixtures thereof.

  Examples of the metal component constituting the phosphinate include calcium, magnesium, aluminum, zinc, bismuth, manganese, sodium, and potassium. Of these, calcium, magnesium, aluminum and zinc are preferable.

  Commercially available phosphinic acid metal salts include EXOLIT OP 930, EXOLIT OP 935 and the like manufactured by Clariant.

  A phosphorus containing compound may be used individually by 1 type, and may use 2 or more types together. The compounding quantity of a phosphorus containing compound is 5-150 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing resin, Preferably it is 10-80 mass parts. When the amount is 150 parts by mass or less, the bending properties and the like of the obtained cured coating film are good.

  Aluminum hydroxide may be untreated surface, using a silane coupling agent having a vinyl group or an epoxy group at its end, stearic acid, oleic acid, phosphoric acid ester, etc. Also good. Examples of commercially available aluminum hydroxides include Showa Denko Hijilite H42M, Hijilite H42S, Hijilite H42T, Hijilite H42ST-V, Nippon Light Metal Co., Ltd. B1403, B1403ST, B1403T, and the like.

  Magnesium hydroxide may be a natural product or a synthetic product, and may be untreated, a silane coupling agent having a vinyl group or an epoxy group at its terminal, stearic acid, You may use what was surface-treated with oleic acid, phosphoric acid ester, etc. As a commercial item of magnesium hydroxide, Kyowa Chemical Co., Ltd. Kisuma 5A, Kisuma 5B, Kisuma 5E, Kisuma 5J, Kisuma 5P, Kisuma 5L, Albemarle Magnifin H5, Magnifin H7, Magnifin H10, etc. are mentioned.

  The amount of the inorganic filler that imparts flame retardancy such as aluminum hydroxide or magnesium hydroxide is preferably 500 parts by mass or less, more preferably 0.1 parts per 100 parts by mass of the (A) carboxyl group-containing resin. ˜300 parts by mass, particularly preferably 0.1 to 150 parts by mass. When the compounding quantity of a filler is 500 mass parts or less, the viscosity of a curable resin composition does not become high too much, printability is favorable, and hardened | cured material becomes difficult to become weak.

[Coupling agent]
Any conventionally known coupling agent can be used in the present invention. The coupling agent can be selected from aluminate, titanate, zirconate, silane, and the like, and silane is most preferable.

  Examples of the aluminate coupling agent include acetoalkoxyaluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.

  Examples of titanate coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2-2 -Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like.

  Examples of the zirconate coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tributoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate and the like.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

  The addition amount of the coupling agent is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. More preferably, it is 0.1-3 mass parts. When the addition amount is 0.05 parts by mass or more, a sufficient wet dispersion effect can be obtained for the organic or inorganic filler, and when it is 5 parts by mass or less, a decrease in tackiness can be suppressed.

[Elastomer]
The curable resin composition of the present invention can be blended with an elastomer for the purpose of imparting flexibility to the resulting cured product and improving the brittleness of the cured product. Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. One type of elastomer may be used alone, or a mixture of two or more types may be used.

[Adhesion promoter]
In the curable resin composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the resin composition layer and the substrate. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, Examples include 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, and amino group-containing benzotriazole.

[Antioxidant]
In many polymer materials, once oxidation starts, oxidative degradation occurs one after another in a chain, resulting in a decrease in the function of the polymer material. Therefore, the curable resin composition of the present invention has a (1) ) Antioxidants such as radical scavengers that invalidate the generated radicals and / or (2) peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals. An agent can be added.

  Specific compounds of antioxidants that act as radical scavengers include hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′di-t-butyl-4-hydroxy Benzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione and the like, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-te And amine compounds such as tramethyl-4-piperidyl) -sebacate and 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 ADEKA, trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN S Japan 5100, manufactured by TINUVIN S ) And the like.

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

  The peroxide decomposing agent may be commercially available, for example, ADK STAB TPP (manufactured by ADEKA, trade name), Mark AO-412S (manufactured by ADEKA, trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd. Name).

[Ultraviolet absorber]
Since the polymer material absorbs light and thereby decomposes and deteriorates, the curable resin composition of the present invention contains an ultraviolet absorber in addition to the above-mentioned antioxidants in order to take a countermeasure against stabilization against ultraviolet rays. Can be used.

  Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone. And 2,4-dihydroxybenzophenone and the like; 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 benzotriazole derivatives include 2- (2'- Hydroxy-5'-tert-butylphenyl) benzotriazol 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy −3 ′, 5′-di-t-amylphenyl) benzotriazole; Examples of specific triazine derivatives include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by BASF Japan Ltd., trade name).
Said ultraviolet absorber may be used individually by 1 type, and can also be used in combination of 2 or more type. By using together with the above antioxidant, the cured coating obtained from the curable resin composition of the present invention can be stabilized.

[Thermal polymerization inhibitor]
The thermal polymerization inhibitor can be used to prevent unintentional thermal polymerization or temporal polymerization of the curable resin composition. Examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil. , Naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, 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.

[Organic solvent]
The curable resin composition of the present invention may use an organic solvent for the synthesis of the above (A) carboxyl group-containing resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. it can. A well-known thing can be used as an organic solvent. Moreover, an organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.

  Examples of ketone solvents include methyl ethyl ketone and cyclohexanone.

  Examples of the aromatic hydrocarbon solvent include toluene, xylene, tetramethylbenzene and the like.

  Examples of glycol ether solvents include cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether. Can be mentioned.

  Examples of the ester solvent include ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate and the like.

  Examples of alcohol solvents include ethanol, propanol, ethylene glycol, and propylene glycol.

  Examples of the aliphatic hydrocarbon solvent include octane and decane.

  Examples of the petroleum solvent include petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  The curable resin composition of the present invention is useful for forming a pattern layer of a printed wiring board and a flexible wiring board, and is particularly useful as a material for a solder resist or an interlayer insulating layer.

  The curable resin composition of this invention can also be made into the form of the dry film provided with the carrier film (support body) and the layer which consists of the said curable resin composition formed on this carrier film.

  When forming a dry film, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater. A film can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After the curable resin composition of the present invention is formed on the carrier film, a peelable cover film may be laminated on the film surface for the purpose of preventing dust from adhering to the film surface. preferable.

  As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the above organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Further, in the case of a dry film obtained by applying the above composition on a carrier film and drying and winding it as a film, after laminating the curable resin composition layer on the substrate with a laminator or the like The resin insulating layer can be formed by peeling off the carrier film.

  Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) and other polyimides using materials such as epoxy, fluorine, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. A film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, etc. can be mentioned.

  Volatile drying performed after the application of the curable resin composition of the present invention is performed by using a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like (with a steam-heated air source). Can be carried out by using a counter-current contact method and a method of spraying a nozzle on a support.

  When the curable resin composition of the present invention contains a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the (A) carboxyl group of the carboxyl group-containing resin, A thermosetting component reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

  In the case of containing a photopolymerization initiator and a photopolymerizable monomer, the exposed portion (active energy ray) is obtained by performing exposure (irradiation of active energy rays) on the coating film obtained after coating and volatile drying of the solvent. The portion irradiated by (3) is cured. Further, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, 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) can be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

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

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited by an Example and a comparative example. In addition, the part showing a compounding quantity is a mass part unless there is particular description.

  The compounds used in the examples are as follows.

(A) Carboxyl group-containing resin A-1: Bisphenol A type carboxyl group-containing resin, ZAR-2023H manufactured by Nippon Kayaku Co., Ltd., solid content 62 wt%, solid content acid value 101 mgKOH / g
A-2: Cresol novolak-type carboxyl group-containing resin, solid content 64 wt%, solid content acid value 84 mgKOH / g
A-3: Acrylic copolymer-based carboxyl group-containing resin, Cyclomer P (ACA) Z250 manufactured by Daicel Ornex, solid content 55 wt%, solid content acid value 125 mgKOH / g

(B) Photopolymerization initiator B1-1: Oxime ester photopolymerization initiator, Irgacure OXE02 manufactured by BASF
B1-2: Oxime ester photopolymerization initiator, Adeka optomer N-1919T manufactured by ADEKA
B2-1: Titanocene-based photopolymerization initiator, Omnirad manufactured by IGM Resins, Inc. 784
B2-2: Titanocene photopolymerization initiator, JMT784 manufactured by Yueyang Jinmao Technology Co., Ltd.
B3-1: α-Aminoacetophenone photopolymerization initiator, Omnirad 369E manufactured by IGM Resins
B3-2: α-aminoacetophenone photopolymerization initiator, Omnirad 379EG manufactured by IGM Resins

(C) Photosensitive monomer C1-1: Bifunctional photosensitive monomer to which alkylene oxide is added, NK ester BPE-900 manufactured by Shin-Nakamura Chemical Co., Ltd.
C1-2: bifunctional photosensitive monomer to which alkylene oxide is added, SR480 manufactured by Sartomer
C2-1: Bifunctional photosensitive monomer having an alkanediol skeleton, 1,9-nonanediol diacrylate C2-2: Bifunctional photosensitive monomer having an alkanediol skeleton, 1,2-ethylene glycol diacrylate C3-1: Trifunctional or higher photosensitive monomer, Aronix M-350 manufactured by Toa Gosei Co., Ltd.
C3-2: Trifunctional or higher photosensitive monomer, trimethylolpropane triacrylate C3-3: Trifunctional or higher photosensitive monomer, KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.

(D) Filler D-1: Barium sulfate, Variace B-30 manufactured by Sakai Chemical Industry Co., Ltd.
D-2: Fused silica, Fuse Rex WX manufactured by Tatsumori,
D-3: Aluminum hydroxide, Heidilite H-42M

(E) Epoxy resin E-1: Polybutadiene epoxy resin, Epolide PB3600 manufactured by Daicel Corporation, epoxy equivalent 200 g / eq
E-2: Bisphenol A type epoxy resin, Mitsubishi Chemical Corporation JER828, epoxy equivalent 189 g / eq
E-3: Phenol novolac type epoxy resin, DIC Corporation Epicron N-770, epoxy equivalent 188 g / eq
E-4: Isocyanate-modified epoxy resin, AER4001 manufactured by Asahi Kasei Corporation, epoxy equivalent 292 g / eq

(F) Colorant F-1: black pigment, carbon black,
F-2: Blue pigment, Pigment Blue 15
F-3: Yellow pigment, Pigment Yellow 147
F-4: Red pigment, C.I. I. Pigment Red 149

(Organic solvent)
Dipropylene glycol monomethyl ether (glycol ether organic solvent)

<Synthesis of cresol novolac-type carboxyl group-containing resin (A-2)>
Orthocresol novolac type epoxy resin [DICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups (total number of aromatic rings)): 600 g of diethylene glycol monoethyl ether acetate 0 mol), 360 g (5.0 mol) of acrylic acid, 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. Into the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride were charged, and reacted at 110 ° C. for 4 hours. After cooling, a cresol novolak-type carboxyl group-containing resin solution (A-2) having a solid content acid value of 84 mgKOH / g and a solid content of 64 wt% was obtained.

<Preparation of Resin Compositions of Examples and Comparative Examples>
Based on the component composition shown in Table 1, each component was blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a curable resin composition.

<Evaluation>
The performance of the resin composition thus obtained was evaluated based on the following evaluation method. These evaluation results are also shown in Table 1.

<Developability>
The composition of each of the above Examples and Comparative Examples was applied to the entire surface of the circuit pattern substrate having a copper thickness of 18 μm after buffing, washed with water, dried and then dried by screen printing so that the coating film thickness was 15 μm. And dried for 30 minutes, 40 minutes, and 50 minutes in a hot air circulating drying oven at 80 ° C. Next, development was performed for 60 seconds with a 1 wt% Na ₂ CO ₃ aqueous solution having a spray pressure of 0.2 MPa and a liquid temperature of 30 ° C. to evaluate the developability of the coating film.
○: The dry coating film was completely removed by development. Δ: The dry coating film remained slightly after development. ×: The dry coating film remained clearly after development.

<Optimum exposure amount>
The composition of each of the above Examples and Comparative Examples was applied to the entire surface of the circuit pattern substrate having a copper thickness of 18 μm after buffing, washed with water, dried and then dried by screen printing so that the coating film thickness was 15 μm. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. Next, using ORC DiIMPACT Mms60 equipped with a UV-LED lamp, exposure was performed through a Stoffer 41-step tablet, and development was performed for 60 seconds with a 1 wt% Na ₂ CO ₃ aqueous solution having a spray pressure of 0.2 MPa and a liquid temperature of 30 ° C. The exposure amount at which the pattern of the remaining step tablet was 6 steps was determined as the optimum exposure amount.

<Method for preparing test piece for evaluating film properties>
The compositions of each of the above Examples and Comparative Examples were applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Next, the solder resist pattern was exposed to the obtained substrate with an optimal exposure amount using an ORC DiIMPACT Mms60 equipped with a UV-LED lamp, and sprayed with a 1 wt% Na ₂ CO ₃ aqueous solution having a spray pressure of 0.2 MPa and a liquid temperature of 30 ° C. for 60 seconds. Development was performed to obtain a resist pattern. Furthermore, this board | substrate was heated for 60 minutes at 150 degreeC, and it hardened | cured, and obtained the test piece for coating-film characteristic evaluation.

<Evaluation>
The performance of the thus obtained test piece for coating film property evaluation was evaluated based on the following evaluation method. These evaluation results are also shown in Table 1.

<Appearance>
The appearance of the cured coating film obtained by the above-mentioned test piece preparation method for coating film property evaluation was visually evaluated.

<Adhesion>
Cross-cut the cured coating film obtained by the above-mentioned test piece preparation method for coating film property evaluation into a grid pattern according to JIS K 5600-5-6, and then perform a peeling test with a cellophane adhesive tape, and the rest of the grid pattern The number was evaluated according to the following criteria.
◎: Remaining number of grids is 91 or more and 100 or less ○: Remaining number of grids is 70 or more and 90 or less △: Remaining number of grids is 30 or more and 69 or less ×: Remaining number of grids is 29 or less

<Solder heat resistance>
After applying the rosin-based flux to the cured coating film obtained by the above-mentioned test piece preparation method for evaluating film characteristics, immersing it in a solder bath set at 260 ° C. in advance for 10 seconds, washing the flux with denatured alcohol, and then visually The swelling / peeling of the cured coating film was evaluated according to the following criteria.
○: There is no swelling or peeling in the cured coating film △: There is a slight swelling or peeling in the cured coating film ×: Clear swelling or peeling in the cured coating film

<Flexibility>
The compositions of the above Examples and Comparative Examples were applied to the entire surface of a 25 μm thick polyimide film (Kapton 100H manufactured by Toray DuPont) by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The obtained substrate is exposed to a resist pattern with an optimal exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed at a pressure of 0.2 MPa. Development was performed for 60 seconds to obtain a resist pattern, and this substrate was cured by heating at 150 ° C. for 60 minutes.
The obtained evaluation substrate was subjected to 180 ° folding by goblet folding several times, and the occurrence of cracks in the coating film at that time was observed visually and with a 200-fold optical microscope until cracks were generated. The number of bendings was measured and evaluated according to the following criteria.
A: The number of times of bending is 6 times or more.
○: The number of bending is 4 to 5 times.
(Triangle | delta): The frequency | count of bending is 2-3 times.
X: The number of times of bending is 0 to 1 times.

From the results shown in Table 1, the cured products of the curable resin compositions of Examples 1 to 25 can reduce the optimum exposure amount, and have good developability, adhesion, solder heat resistance, and flexibility. I understand that Moreover, it turned out that Example 1 thru | or 7 which contains the combination of C1-1, C2-1, C3-1 especially as a (C) photosensitive monomer has a better result in all the evaluation results.
On the other hand, Comparative Example 1 that does not contain B1 and B2 as photopolymerization initiators cannot reduce the optimum exposure amount. Of the three types of (C) photosensitive monomer of the present invention, Comparative Example 2 which does not contain two types had a very large optimum exposure amount, and was inferior in solder heat resistance and gold plating resistance. Moreover, the comparative exposure example 3 which does not contain 1 type among (C) 3 types of photosensitive monomers of this invention cannot reduce the optimal exposure amount, but was inferior in solder heat resistance.

Claims (7)

(A) a carboxyl group-containing resin;
(B) a photopolymerization initiator;
(C) a photosensitive monomer;
A curable resin composition containing
(B) The photopolymerization initiator includes (B1) an oxime ester photopolymerization initiator and (B2) a titanocene photopolymerization initiator,
(C) The photosensitive monomer includes (C1) a bifunctional photosensitive monomer to which an alkylene oxide is added, (C2) a bifunctional photosensitive monomer having an alkanediol skeleton, and (C3) a trifunctional or higher functional photosensitive monomer. Curable resin composition.   The curable resin composition according to claim 1, wherein the (B) photopolymerization initiator further comprises (B3) an α-aminoacetophenone photopolymerization initiator.   The average addition amount of alkylene oxide per mole of carbon-carbon double bonds in the bifunctional photosensitive monomer to which (C1) alkylene oxide has been added is 4 moles or more. 2. The curable resin composition according to item 1.   (C2) The bifunctional photosensitive monomer having an alkanediol skeleton is a bifunctional photosensitive monomer having an alkanediol skeleton having 4 or more carbon atoms. Curable resin composition.   (C3) The trifunctional or higher functional photosensitive monomer is a trifunctional or higher functional photosensitive monomer to which 1 mol or more of alkylene oxide and / or lactone is added. The curable resin composition described in 1.   The curable resin composition according to any one of claims 1 to 5 or a dry film obtained by applying and drying the curable resin composition on a film is obtained by performing at least one of thermosetting and photocuring. Cured coating. A printed wiring board provided with the cured film according to claim 6.