JP2009116111A - Photocurable resin composition, its cured product pattern, and printed wiring board with cured product pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-developable photocurable resin composition having high sensitivity to active energy rays, excellent in curability under exposure by direct drawing especially with laser light, excellent in developability, drying property to set to the touch, resistance to the heat of soldering, suitability to electroless gold plating, alkali resistance, PCT and PCBT resistances, and useful as a solder resist. <P>SOLUTION: The alkali-developable photocurable resin composition contains (A) a carboxylic acid-containing photosensitive resin containing a structure represented by general formula (I), (B) a photopolymerization initiator, and (C) a compound containing two or more ethylenically unsaturated groups in a molecule. In the formula, R<SP>1</SP>represents a hydrogen atom or a methyl group; R<SP>2</SP>represents a 2-6C linear, branched or cyclic alkyl; and R<SP>3</SP>represents an acid anhydride residue. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an alkali-developable photocurable resin composition that is excellent in sensitivity to active energy rays and is useful as a solder resist.

Recently, laser scanning exposure has become widespread as an exposure means for printed wiring board solder resist from the viewpoint of excellent alignment accuracy. In laser exposure, an image is formed while scanning a solder resist on a patterned wiring board without using a photomask, but a conventional solder resist has an appropriate exposure amount of 200 mJ / cm ² or more. There is a drawback that it takes a very long time for exposure, and a solder resist corresponding to laser exposure is required to have very high sensitivity.

  From such a background, a photosensitive composition capable of exhibiting high photopolymerization ability has been proposed (see, for example, Patent Document 1 and Patent Document 2). However, some of the photosensitive compositions that have been proposed so far can certainly exhibit high photopolymerization ability, but the sensitivity is not necessarily sufficient for laser direct exposure. In addition, the properties other than the sensitivity required for the photosensitive composition are not necessarily sufficient. Specifically, in the composition disclosed in Patent Document 1, only glycidyl methacrylate is exemplified as a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule used for forming a carboxyl group-containing photosensitive resin. However, not only is the sensitivity insufficient, but there is a tendency for the developability to deteriorate when the added amount is increased. On the other hand, when using caprolactone-modified acrylate, which is proposed in Patent Document 2 and chain-reacted with ε-caprolactone and molecularly extended, the sensitivity is high, but the dryness to touch is extremely poor, and the solder heat resistance is high. Sex was also insufficient.

Furthermore, the alkali development type photo solder resist still has problems in terms of durability. That is, the alkali developing type photo solder resist is inferior in chemical resistance, water resistance, heat resistance and the like as compared with conventional thermosetting type and solvent developing type. This is due to the fact that the alkali development type photo solder resist mainly contains a hydrophilic group in order to enable alkali development. Thereby, a chemical | medical solution, water, water vapor | steam etc. are easy to osmose | permeate, a chemical-resistant fall and the adhesiveness of a resist film and copper are reduced. As a result, alkali resistance as chemical resistance is weak, and especially in semiconductor packages such as BGA and CSP, PCT resistance (pressure cooker resistance) that should be called moisture heat resistance is necessary, but under such severe conditions Is currently only a few hours to a few dozen hours. In most cases, in the PCBT test in which a voltage is applied under the PCT condition, defects due to the occurrence of migration are confirmed within a few hours.
JP 2007-41502 (Claims) JP 2007-3590 A (Claims)

  The present invention has been developed in view of the above-mentioned problems, is highly sensitive to active energy rays, has excellent exposure curability by direct drawing, and developability, touch drying property, solder heat resistance. It is an object of the present invention to provide an alkali development type photo-curable resin composition that is excellent in resistance, electroless gold plating property, alkali resistance, PCT and PCBT resistance, and is useful as a solder resist.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have solved the above-described problems by using a specific carboxylic acid-containing photosensitive resin and combining it with other components. As a result, the present invention has been completed.

That is, the present invention includes (A) a carboxylic acid-containing photosensitive resin containing a structure represented by the general formula (I), (B) a photopolymerization initiator, and (C) two or more ethylenic groups in one molecule. An alkali-developable photocurable resin composition comprising a compound containing an unsaturated group:

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl having 2 to 6 carbon atoms, and R ³ represents an acid anhydride residue.

  Here, in one embodiment, the carboxylic acid-containing photosensitive resin is obtained by reacting (b) an unsaturated monocarboxylic acid with a compound containing two or more cyclic ether groups in one molecule; It can be obtained by further reacting (d) a compound containing a cyclic ether group and an ethylenically unsaturated group in one molecule with a resin reacted with a polybasic acid anhydride.

  In addition, (d) the compound containing a cyclic ether group and an ethylenically unsaturated group in one molecule may be 4-hydroxybutyl acrylate glycidyl ether.

The (B) photopolymerization initiator includes an oxime ester photopolymerization initiator (B-1) including a structure represented by the general formula (II) and an aminoacetophenone including a structure represented by the general formula (III). 1 type, or 2 or more types selected from the group consisting of a series photopolymerization initiator (B-2) and an acylphosphine oxide photopolymerization initiator (B-3) containing a structure represented by the general formula (IV) Can be a mixture of:

In General Formulas (II) to (IV), R ¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), or 1 to 20 carbon atoms. A linear, branched or cyclic alkyl group (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), 5 to 5 carbon atoms An cycloalkyl group having 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one Which may be substituted with the above hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or Represents a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ³ and R ⁴ each independently represents a linear, branched or cyclic alkyl group or arylalkyl group having 1 to 12 carbon atoms,
R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ are bonded to form a cyclic alkyl ether group. You may,
R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (halogen atom, alkyl group, or alkoxy group). Or an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms). However, the case where both R ⁷ and R ⁸ are R—C (═O) — groups is excluded.

  Further, the resin composition of the present invention may further contain (D) a thermosetting component.

  The resin composition of the present invention may be a solder resist further containing (E) a colorant.

  In another aspect, the present invention is a photocurable dry film obtained by applying the photocurable resin composition of the present invention to a carrier film and drying it.

  In another aspect, the present invention is a cured product pattern formed using a resin layer comprising the photocurable resin composition, wherein the pattern formation is performed by irradiation with active energy rays. It is a thing putter. Here, the pattern formation by active energy ray irradiation may be by direct drawing using active energy rays having a wavelength of 350 nm to 410 nm.

  Moreover, this invention is a printed wiring board which comprises the said hardened | cured material pattern on a copper layer in another aspect.

Hereinafter, each component of the photocurable resin composition of the present invention will be described in detail.
The carboxylic acid-containing photosensitive resin (A) contained in the photocurable resin composition of the present invention includes a structure represented by the general formula (I), and further contains a carboxylic acid in the molecule.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl having 2 to 6 carbon atoms, and R ³ represents an acid anhydride residue.

  The carboxylic acid-containing photosensitive resin (A) of the present invention is a part of the carboxylic acid produced from the carboxylic acid-containing photosensitive resin (A ′) obtained by reacting, for example, a hydroxyl group-containing resin with a polybasic acid anhydride to form a half ester. (D) It is obtained by reacting a compound containing a cyclic ether group and an ethylenically unsaturated group in one molecule.

  As the carboxylic acid-containing photosensitive resin (A ′) half-esterified with an acid anhydride, (a) a compound containing two or more cyclic ether groups in one molecule is reacted with (b) an unsaturated monocarboxylic acid. Then, (c) a resin obtained by reacting a polybasic acid anhydride is preferable, and specific examples thereof include the resins listed below.

(1) Carboxylic acid-containing photosensitivity obtained by reacting a polyfunctional epoxy compound (a) with an unsaturated monocarboxylic acid (b) and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride (c) resin,
(2) Polyfunctional epoxy compound (a), unsaturated monocarboxylic acid (b), at least one alcoholic hydroxyl group in one molecule, and one reactivity other than the alcoholic hydroxyl group that reacts with the epoxy group A carboxylic acid-containing photosensitive resin obtained by reacting a reaction product with a compound having a group with a saturated or unsaturated polybasic acid anhydride (c),
(3) A polyfunctional oxetane compound (a) having at least two oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid (b), and the primary hydroxyl group in the resulting modified oxetane resin. Examples thereof include, but are not limited to, carboxylic acid-containing photosensitive resins obtained by reacting saturated or unsaturated polybasic acid anhydrides (c), and other hydroxyl group-containing polymers such as polyol derivatives. And a hydroxyl group- and carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic acid anhydride. Among these, the above (1), (2) and (3) already have an unsaturated double bond and are preferred from the viewpoint of photosensitivity.

  Examples of the compound (a) having two or more cyclic ether groups in one molecule used for the synthesis of the carboxylic acid-containing photosensitive resin (A) of the present invention include various known and conventional epoxy resins such as bisphenol A type epoxy. Resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, cresol novolak type Glycidyl ether compounds such as epoxy resin, brominated phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin; terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycy Glycidyl ester compounds such as ester, triglycidyl isocyanurate, N, N, N ′, N′-tetraglycidylmetaxylenediamine, N, N, N ′, N′-tetraglycidylbisaminomethylcyclohexane, N, N-di Glycidylamine compounds such as glycidylaniline; copolymer resins of glycidyl (meth) acrylate and other polymerizable monomers, oxetane resins, copolymer resins of oxetane-containing (meth) acrylates and polymerizable monomers thereof, etc. . Among these, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin are preferable because they can provide a cured film having high sensitivity and excellent heat resistance. Furthermore, a cresol novolac type epoxy resin having a softening point of 60 ° C. or more is more preferable because it is excellent in dryness to touch.

  These polyfunctional epoxy compounds can be used alone or in combination of two or more.

  In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  Examples of the unsaturated monocarboxylic acid (b) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, and the like. Or two or more types can be used in combination.

  Examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride An acid, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned, These can be used individually or in combination of 2 or more types.

As a compound (d) containing a cyclic ether group and an ethylenically unsaturated group in one molecule, 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxypropyl (meth) Acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether, hydroxycyclohexyl Examples include (meth) acrylate glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether is particularly preferably used.
The addition amount of the compound (d) containing a cyclic ether group and an ethylenically unsaturated group in one molecule is preferably 5% equivalent to 40% equivalent, more preferably 10%, relative to the acid anhydride residue. Equivalent to 30% equivalent. When the added amount is 5% equivalent or more, it is preferable from the viewpoint of increasing sensitivity and improving electroless gold plating resistance. On the other hand, when it exceeds 40% equivalent, the maximum development life is shortened or the dryness to the touch is deteriorated. Is not preferable.

Modification by the compound (d) is essential for forming the structure represented by the general formula (I). The effect was confirmed to be synergistic with the increase in sensitivity due to improved crosslink density, alkali resistance, PCT and PCBT resistance. These effects are also obtained with glycidyl methacrylate or glycidyl acrylate, which is a compound containing a cyclic ether group and an ethylenically unsaturated group in one molecule. As the amount increases, the developability deteriorates, and when the added amount is reduced, the effect of increasing the sensitivity is reduced. However, the compound of the present invention in which a compound containing a cyclic ether group and an ethylenically unsaturated group is added to one molecule having an appropriate fatty chain has good developability even when the addition amount is improved, and high sensitivity and PCT. In addition, it is considered that PCBBT resistance has been improved. On the other hand, when the R ² component of Chemical Formula 1 is a long-chain alkyl having 7 or more carbon atoms, it is not preferable because the dryness to touch becomes worse or the developability becomes worse.

  Since the carboxylic acid-containing photosensitive resin (A) as described above has a number of free carboxyl groups in the side chain of the backbone polymer, alkali development is possible.

  Moreover, the acid value of the said carboxylic acid containing photosensitive resin (A) becomes like this. Preferably it is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. If the acid value of the carboxylic acid-containing photosensitive resin (A) is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so the line is more than necessary. In some cases, it is not preferable because it becomes thin or dissolves and peels off with a developer without distinction between an exposed portion and an unexposed portion, and it becomes difficult to draw a normal resist pattern.

  The weight-average molecular weight of the carboxylic acid-containing photosensitive resin (A) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. preferable. When the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, and the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The blending ratio of such a carboxylic acid-containing photosensitive resin (A) is preferably 20 to 60 mass%, more preferably 30 to 50 mass%, based on the total mass of the resin composition. When the amount is less than the above range, the coating film strength may decrease, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity may be increased or the coating property may be deteriorated.

  In the present invention, in addition to the carboxylic acid-containing photosensitive resin (A), a known and commonly used carboxylic acid resin, particularly preferably a photosensitive carboxylic acid resin, can be added.

Next, the photopolymerization initiator (B) will be described.
As a photoinitiator (B), the oxime ester type photoinitiator (B-1) containing the structure represented by the following general formula (II), the structure represented by the following general formula (III) (alpha) 1 type selected from the group consisting of an aminoacetophenone photopolymerization initiator (B-2) and an acylphosphine oxide photopolymerization initiator (B-3) containing a structure represented by the following general formula (IV) Or two or more photopolymerization initiators are preferably used.

In General Formulas (II) to (IV), R ¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), or 1 to 20 carbon atoms. A linear, branched or cyclic alkyl group (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), 5 to 5 carbon atoms An cycloalkyl group having 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one Which may be substituted with the above hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or Represents a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ³ and R ⁴ each independently represents a linear, branched or cyclic alkyl group or arylalkyl group having 1 to 12 carbon atoms,
R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ are bonded to form a cyclic alkyl ether group. You may,
R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (halogen atom, alkyl group, or alkoxy group). Or an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms). However, the case where both R ⁷ and R ⁸ are R—C (═O) — groups is excluded.

As the oxime ester photopolymerization initiator (B-1) having a structure represented by the general formula (II), 2- (acetyloxyiminomethyl) thioxanthene represented by the following formula (V) is preferable. -9-On:

Compounds represented by the following general formula (VI):

(Where
R ⁹ is a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, or an alkanoyl group having 2 to 12 carbon atoms. Group, an alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and 1 in the middle of the alkyl chain) Which may have more than one oxygen atom), or a phenoxycarbonyl group,
R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear or branched chain having 1 to 20 carbon atoms, or A cyclic alkyl group (which may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, a carbon number Represents an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ¹¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. (It may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a C5-C8 cycloalkyl group, a C2-C20 An alkanoyl group or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group) is represented. And a compound represented by the following general formula (VII):

(Where
R ¹³ , R ¹⁴ and R ¹⁹ each independently represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
m and n each independently represents an integer of 0 to 5. )
Is mentioned.

  Among these, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by formula (V) and a compound represented by formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

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

Acylphosphine oxide photopolymerization initiators having a structure represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Bis (2,6-
And dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  The blending ratio of such a photopolymerization initiator (B) is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). It can be selected from the range of parts by mass. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (B) becomes violent and the deep curability tends to decrease, which is not preferable.

  In the case of the oxime ester photopolymerization initiator including the structure represented by the formula (II), the blending ratio is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A). It is desirable to select from 20 parts by mass, more preferably from 0.01 to 5 parts by mass.

  In the composition of the present invention, photopolymerization initiators other than the above-mentioned compounds, photopolymerization initiation assistants, and sensitizers can be used, for example, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketals. Examples thereof include compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

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

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

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

  Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

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

  Of the above, thioxanthone compounds and tertiary amine compounds are preferred. The inclusion of a thioxanthone compound is preferable from the viewpoint of deep curable properties, and among these, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferable.

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

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

  As a compounding ratio of such a tertiary amine compound, it is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). It is. When the mixing ratio of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

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

  The total amount of such photopolymerization initiator (B), photopolymerization initiation assistant, and sensitizer is in a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). It is preferable. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  Next, the compound (C) having two or more ethylenically unsaturated groups in the molecule will be described.

  The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays and contains the ethylenically unsaturated groups. The carboxylic acid-containing photosensitive resin (A) is insolubilized or assists insolubilization in an alkaline aqueous solution. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric alcohols or polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglyceride Jill ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

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

  The compounding ratio of the compound (C) having two or more ethylenically unsaturated groups in the molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). The ratio is more preferably 5 to 70 parts by mass. When the blending ratio is less than 1 part by mass, the photocurability is lowered, and pattern formation by alkali development after irradiation with active energy rays becomes difficult, which is not preferable. On the other hand, when it exceeds 100 mass parts, since the solubility with respect to aqueous alkali solution falls and a coating film tends to become weak, it is unpreferable.

Next, the thermosetting component (D) will be described.
A thermosetting component (D) can be added to the photocurable resin composition of the present invention in order to impart heat resistance. Particularly preferred is a thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  As the thermosetting component (D) having two or more cyclic (thio) ether groups in such a molecule, either a three-, four- or five-membered cyclic ether group or a cyclic thioether group is included in the molecule. Examples thereof include compounds having two or more groups of one or two types. For example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1), at least 2 in the molecule. Examples thereof include a compound having two or more oxetanyl groups, that is, a polyfunctional oxetane compound (D-2), a compound having two or more cyclic thioether groups in the molecule, that is, an episulfide compound (D-3).

  Examples of the polyfunctional epoxy compound (D-1) include, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, manufactured by Dainippon Ink & Chemicals, Inc. Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Corporation A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB- manufactured by Tohto Kasei Co., Ltd. 500, D.C. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical Co., Ltd. 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF -175, YDF-2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals (all trade names); Epotot ST-2004, ST-2007, ST-3000 manufactured by Toto Kasei Hydrogenated bisphenol A type epoxy resin, such as Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., and Sumitomo Chemical Industries Epoxy ELM-120 etc. All are trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty Chemicals Alicyclic epoxy resins such as Araldide CY175, CY179, etc. (both trade names) manufactured by YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin; Epicoat YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. Name) Tetraphenylolethane type Poxy resin; Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene groups such as HP-4032, EXA-4750 and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; In addition, cyclohexylmaleimide and glycidyl Methacrylate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), etc. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the episulfide compound (D-3) include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The blending ratio of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0 with respect to 1 equivalent of the carboxyl group of the carboxylic acid-containing photosensitive resin (A). .6 to 2.5 equivalents, and more preferably 0.8 to 2.0 equivalents. When the blending ratio of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6 equivalent, it causes a carboxyl group to remain in the solder resist film. It is not preferable because heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film may decrease.

  When using a thermosetting component (D) for the photocurable resin composition of this invention, it is preferable to use a thermosetting catalyst together. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and those that are commercially available ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (both dimethylamine block isocyanate compounds manufactured by San Apro) Product names), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. However, it is not particularly limited to these, as long as it is a thermosetting catalyst for an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group and a carboxyl group, and may be used alone or in combination of two or more. You may mix and use. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending ratio of these thermosetting catalysts is sufficient at a normal quantitative ratio, and for example, preferably 0.1 to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A) or thermosetting component (D). It is 20 mass parts, More preferably, it is 0.5-15.0 mass parts.

Next, the colorant (E) that can be used in the photocurable resin composition of the present invention will be described.
A coloring agent can be mix | blended with the photocurable resin composition of this invention. As the colorant, conventionally known colorants such as red, blue, green, yellow and black can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen and an azo compound from the viewpoint of reducing environmental burden and affecting the human body.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: 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.

  The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, as the green colorant, there are phthalocyanine type and anthraquinone type, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. . In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.

  Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

  Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

  Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

  Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

  Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.

  Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.

  Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

  Disazo: Pigment Red 37, 38, 41.

  Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.

  Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

  Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

  Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

  Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.

  Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

  Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

  In addition, colorants such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone.

  Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Rack 1, there is a C.I. Pigment Black 7 and the like.

  Although the specific blending ratio of the colorant is influenced by the type of the colorant used and the type of other additives, it cannot be generally stated, but the carboxylic acid-containing photosensitivity of the photosensitive resin composition of the present invention. It is preferable to mix 0 to 5 parts by mass with respect to 100 parts by mass of the resin (A). More particularly preferred colorants that can be used at 0.05 to 3 parts by weight are blue and green phthalocyanine, anthraquinone, yellow anthraquinone, red diketopyrrolopyrrole, anthraquinone, and It does not contain a halogen atom. Further, pigment-based blue and green are preferable from the viewpoint of heat resistance, and dye-based blue, green, and red colorants are preferable from the viewpoint of sensitivity and resolution.

  The photocurable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, publicly known and commonly used inorganic or organic fillers can be used, and barium sulfate, spherical silica and talc are particularly preferably used. Furthermore, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin (D-1), XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names) and NANOOX (trade name) XP 0516, XP 0525, XP 0314 (all product grades) manufactured by Hanse-Chemie Name) etc. can also be used. These may be used alone or in combination of two or more.

  The blending ratio of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). 150 parts by mass. When the blending ratio of the filler exceeds 300 parts by mass, the viscosity of the photosensitive composition is increased, the printability may be lowered, and the cured product may be brittle, which is not preferable.

  Further, the photocurable resin composition of the present invention is an organic solvent for the synthesis of the carboxylic acid-containing photosensitive resin (A) and for the preparation of the composition, or for adjusting the viscosity for application to a substrate or carrier film. Can be used.

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

  The photo-curable resin composition of the present invention may further contain, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, finely divided silica, organic bentonite, and montmorillonite. Known and commonly used thickeners, silicone-based, fluorine-based and polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, etc. The known and conventional additives such as can be blended.

  The photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the 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. After coating by a curtain coating method or the like, a tack-free coating film is formed by volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Alternatively, the resin insulating layer can be formed by applying the composition of the present invention on a carrier film, drying it to obtain a dry film, and laminating the wound film on a substrate.

  The coating film obtained as described above, or the resin layer on the carrier film (along with the “coating film”, these are referred to as “resin layer”) is exposed by irradiation with active energy rays, and an exposed portion (active The portion irradiated by the energy rays is cured.

  Specifically, contact exposure (or non-contact method), exposure with active energy rays selectively through a photomask on which a pattern is formed, or pattern exposure by direct drawing of active energy rays using a laser direct exposure machine or the like, The unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution) to form a resist pattern. Furthermore, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxylic acid-containing resin (A) and two or more cyclic ether groups and / or cyclic thioether groups in the molecule are obtained. The thermosetting component which it has reacts and can form the cured coating film excellent in various characteristics, such as heat resistance, chemical resistance, moisture absorption resistance, adhesiveness, and an electrical property.

  High frequency circuit using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO / cyanate ester, etc. Examples include materials such as copper clad laminates, and copper graded laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates and the like.

  The volatile drying performed after the application of the photocurable resin composition of the present invention includes a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. And a method of spraying the hot air against the support from a nozzle).

As the exposure apparatus used for the active energy ray irradiation, an ultraviolet irradiation device and a direct drawing device (a direct imaging device that draws an image by direct active energy ray irradiation using CAD data from a computer) can be used. As the active energy ray, a laser beam having a maximum wavelength in the range of 350 to 410 nm, or a light source that emits light by discharge of mercury vapor, for example, a short arc lamp or a (super) high pressure mercury lamp may be used. Either gas laser or solid state laser may be used. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Hitachi Via Mechanics, Fujifilm, Dainippon Screen Manufacturability, ORC Manufacturing, etc. can be used, and the maximum wavelength is 350 to 410 nm. Any device may be used as long as the device uses a light source that oscillates laser light or emits light by discharge of mercury vapor, for example, a short arc lamp or a (super) high pressure mercury lamp.

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

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

<Synthesis of carboxylic acid-containing photosensitive resin>
Resin synthesis example 1: Synthesis example of carboxylic acid-containing photosensitive resin (varnish (A-1)) having a structure of 4-hydroxybutyl acrylate glycidyl ether A stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction pipe In a 2 liter separable flask, 197 g of diene glycol monoethyl ether acetate and 214 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), acrylic acid 72 g (1.0 mol) and 0.29 g of hydroquinone were charged and stirred at 100 ° C. with stirring to obtain a uniform solution. Next, 0.86 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, further 0.23 g of triphenylphosphine was added, the temperature was raised to 120 ° C., and the reaction was further performed for 12 hours. The obtained reaction solution was charged with 197 g of Solvesso 150 and 144 g (0.95 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 4 hours. Furthermore, 40.05 g (0.2 mol) of 4-hydroxybutyl acrylate glycidyl ether and 45.9 g of propylene glycol methyl ether acetate were added to the resulting reaction solution, and the mixture was heated to 110 ° C. with stirring, and kept at 110 ° C. for 6 hours. The reaction continued. When the reaction product was cooled to room temperature, a viscous solution was obtained. In this way, a solution of a carboxylic acid-containing photosensitive resin (A) having a nonvolatile content of 52% by mass and a solid content acid value of 90 mgKOH / g was obtained. Hereinafter, this carboxylic acid-containing photosensitive resin solution is referred to as varnish (A-1).

Comparative Synthesis Example 1 (Varnish (R-1))
700 g of diethylene glycol monoethyl ether acetate and 1070 g of orthocresol novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) (number of glycidyl groups (fragrance) Total number of rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged and heated to 100 ° C. with stirring to obtain a uniform solution. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and further 1.6 g of triphenylphosphine was added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. To the obtained reaction solution, 562 g of aromatic hydrocarbon (Sorvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 87 mgKOH / g and a solid content of 65%. This is called varnish (R-1).

Comparative Synthesis Example 2 (Varnish (R-2))
1070 g of diethylene glycol monoethyl ether acetate and orthocresol novolak type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) (glycidyl group number (aromatic Total number of rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged and heated to 100 ° C. with stirring to obtain a uniform solution. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and further 1.6 g of triphenylphosphine was added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. To the obtained reaction solution, 535 g of aromatic hydrocarbon (Sorvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. Furthermore, 71.0 g (0.5 mol) of glycidyl methacrylate was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 103 mgKOH / g and a solid content of 65%. This is called varnish (R-2).

Comparative Synthesis Example 3 (Varnish (R-3))
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy Equivalent 220) 660 g, carbitol acetate 421.3 g, and solvent naphtha 180.6 g were introduced, heated and stirred at 90 ° C., and dissolved. Next, it is once cooled to 60 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone are added and reacted at 100 ° C. for 12 hours, and a reaction product having an acid value of 0.2 mgKOH / g. Got. This was charged with 241.7 g of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for 6 hours. As a result, a solution of a carboxylic acid-containing resin (A) having an acid value of 50 mg KOH / g, a double bond equivalent (g mass of resin per mole of unsaturated groups) of 400, and a weight average molecular weight of 7,000 was obtained. Hereinafter, this carboxylic acid-containing resin solution is referred to as varnish (R-3).

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

Performance evaluation <Optimum exposure amount>
Each of the prepared photocurable resin compositions is applied to the entire surface of a circuit pattern substrate having a copper thickness of 35 μm after polishing with buffalo, washed with water, dried, and then screen-printed to circulate at 80 ° C. Dry in an oven for 30 minutes. After drying, direct drawing device (Parbot 8000 made by Orbotech) equipped with a semiconductor laser with a maximum wavelength of 355 nm, direct drawing exposure machine equipped with a high-pressure mercury lamp (direct drawing exposure machine equipped with an ultra-high pressure mercury lamp lamp, Marculex made by Dainippon Screen) or high pressure Exposure through a step tablet (Kodak No 2) using an exposure apparatus equipped with a mercury lamp (ORC Co., Ltd. mounted with a mercury short arc lamp), and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) for 60 seconds The amount of exposure of the step tablet remaining at the time of 7 was determined as the optimum exposure amount when the pattern was 7 steps.

<Dry touch dryness>
Each of the prepared photocurable resin compositions is applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and pressure-bonded under reduced pressure with ORC (HMW680-GW20) for 1 minute, and then the sticking state of the film when the negative film was peeled off was evaluated.

○: The film peels without resistance.

(Triangle | delta): Although a film peels, a trace is attached to the coating film.

X: There is resistance when the film is peeled off, and the coating film has a clear mark.

<Maximum development life>
Each prepared said photocurable resin composition is apply | coated whole surface by screen printing on the copper foil board | substrate with which pattern formation was carried out, and it dries at 80 degreeC. From 20 minutes to 80 minutes after the start of the drying, the substrate is taken out every 10 minutes and allowed to cool to room temperature. The substrate was developed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. under a spray pressure of 2 kg / cm ² for 60 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.

Characteristic test:
(Preparation of coating film property evaluation board)
Each of the photocurable resin compositions is applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. This substrate is exposed to a solder resist pattern at an optimum exposure amount using a direct writing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 2 kg / cm ^2. Development was performed for 2 seconds to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.

○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.

(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.

X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the presence or absence of peeling of the resist layer or penetration of the plating is visually confirmed. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.

○ ^* : No soaking or peeling is observed.

○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.

Δ: Slight penetration after plating and peeling after tape peel.

X: There is peeling after plating.

<Alkali resistance>
The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes, and the infiltration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.

○: There is no penetration or dissolution, and no peeling is confirmed after the tape peel.

(Triangle | delta): There is no bleed-in and melt-out, and a slight peeling is recognized after a tape peel.

X: Permeation and dissolution, or peeling after tape peeling.

<PCT resistance>
The evaluation substrate was treated for 50 hours under the conditions of 121 ° C., saturation and 0.2 MPa using a PCT device (HEST SYSTEM TPC-412MD manufactured by ESPEC CORP.), And the state of the coating film was visually confirmed, and further the tape The peeling due to the peel was confirmed. Judgment criteria are as follows.

○: There is no penetration or dissolution, and no peeling is confirmed after the tape peel.

(Triangle | delta): There is no bleed-in and melt-out, and a slight peeling is recognized after a tape peel.

X: Permeation and dissolution, or peeling after tape peeling.

<PCBT resistance>
An evaluation board was produced under the above conditions using IPC B-25 comb-type electrode B coupon instead of the copper foil substrate, and a bias voltage of DC 30 V was applied to the comb-type electrode. System TPC-412MD) was used for 96 hours under the conditions of 121 ° C. and 97% humidity, and the presence or absence of discoloration or migration was evaluated. Judgment criteria are as follows.

○ ^* : No discoloration or migration.

○: Only slight discoloration or migration has occurred.

Δ: Discoloration or migration has occurred.

X: Discoloration is remarkable and migration reaches from one electrode to the other.

<Electrical characteristics>
An evaluation board was produced under the above conditions using IPC B-25 comb electrode B coupon instead of the copper foil substrate, and a bias voltage of DC 100 V was applied to the comb electrode, and a constant temperature of 85 ° C. and humidity 85%. The presence or absence of migration after 1,000 hours was confirmed in a constant humidity bath. The judgment criteria are as follows.

○: No change is observed at all.

Δ: Slightly changed.

×: Migration has occurred.

<Color of coating film>
The color of the cured product was judged visually.

The results are shown in Table 2.

Example 2
<Dry film evaluation>
The composition example used in Example 1 was diluted with methyl ethyl ketone, applied onto a PET film, and dried at 80 ° C. for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. Further, a cover film was laminated thereon to obtain a dry film. Then, the cover film was peeled off, the film was heat-laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the coating film property evaluation of Example 1. After the exposure, the carrier film was peeled off, and heat-cured for 60 minutes with a hot air dryer at 150 ° C. to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 3.

  As can be seen from the results shown in Tables 2 and 3 in Examples 1 and 2, the photocurable resin composition containing the carboxylic acid-containing photosensitive resin (A) of the present invention is a conventional resin. Compared with high sensitivity, it has excellent developability, dryness to touch, solder heat resistance, electroless gold plating resistance, alkali resistance, PCT resistance, and PCBT resistance, and is useful as a resist ink. In addition, the photocurable resin composition of the present invention can be applied with high sensitivity to monochromatic light such as i-line and h-line or laser light, and also to an ultraviolet light source such as a high-pressure mercury lamp. I understand.

Claims (10)

(A) a carboxylic acid-containing photosensitive resin having a structure represented by the general formula (I), (B) a photopolymerization initiator, and (C) a compound containing two or more ethylenically unsaturated groups in one molecule. A photocurable resin composition capable of alkali development, comprising:

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl having 2 to 6 carbon atoms, and R ³ represents an acid anhydride residue.   The (A) carboxylic acid-containing photosensitive resin is obtained by reacting (a) a compound containing two or more cyclic ether groups in one molecule with (b) an unsaturated monocarboxylic acid, and (c) polybasic. It is a carboxylic acid-containing photosensitive resin obtained by further reacting (d) a compound containing a cyclic ether group and an ethylenically unsaturated group in one molecule with a resin reacted with an acid anhydride. The photocurable resin composition capable of alkali development according to claim 1.   The alkali-developable photocurability according to claim 2, wherein the compound (d) containing a cyclic ether group and an ethylenically unsaturated group in one molecule is 4-hydroxybutyl acrylate glycidyl ether. Resin composition. The (B) photopolymerization initiator is an oxime ester photopolymerization initiator (B1) containing a structure represented by the following general formula (II), an aminoacetophenone series containing a structure represented by the following general formula (III) It is one or a mixture of two or more selected from the group consisting of a photopolymerization initiator (B2) and an acylphosphine oxide photopolymerization initiator (B3) containing a structure represented by the following general formula (IV). The photocurable resin composition capable of alkali development according to any one of claims 1 to 3, wherein:

In General Formulas (II) to (IV), R ¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), or 1 to 20 carbon atoms. A linear, branched or cyclic alkyl group (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), 5 to 5 carbon atoms An cycloalkyl group having 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one Which may be substituted with the above hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or Represents a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ³ and R ⁴ each independently represents a linear, branched or cyclic alkyl group or arylalkyl group having 1 to 12 carbon atoms,
R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ are bonded to form a cyclic alkyl ether group. You may,
R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (halogen atom, alkyl group, or alkoxy group). Or an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms). However, the case where both R ⁷ and R ⁸ are R—C (═O) — groups is excluded.   The alkali-developable photocurable resin composition according to any one of claims 1 to 4, further comprising (D) a thermosetting component.   Furthermore, (E) It is a soldering resist containing a coloring agent, The alkali-developable photocurable resin composition as described in any one of Claims 1 thru | or 5 characterized by the above-mentioned.   The photocurable dry film obtained by apply | coating the photocurable resin composition as described in any one of Claims 1 thru | or 6 to a carrier film, and drying.   It is a hardened material pattern formed using the resin layer which consists of a photocurable resin composition as described in any one of Claims 1 thru | or 6, Comprising: Pattern formation was performed by active energy ray irradiation. Hardened product pattern.   A cured product pattern in which pattern formation by active energy ray irradiation according to claim 8 is by direct drawing using an active energy ray having a wavelength of 350 nm to 410 nm.   The printed wiring board which comprises the hardened | cured material pattern of Claim 8 or 9 on a copper layer.