JP2010237576A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent workability and high sensitivity and obtaining high reliability concerning its cured matter when used in a printed wiring board or a semiconductor package for an example, and to provide its cured matter. <P>SOLUTION: The curable resin composition contains: a carboxylic group contained photosensitive resin obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting an unsaturated group contained mono-carboxylic acid with another reaction product obtained by reacting alkylene oxide or a cyclo carbonate compound with a phenolic resin; and a photopolymerization initiator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable resin composition used as a solder resist for printed wiring boards.

  Currently, some consumer printed wiring boards, and most industrial printed wiring board solder resists, from the viewpoint of high accuracy and high density, form an image by developing after irradiation with ultraviolet rays, heat and / or A liquid development type solder resist that is finish-cured (mainly cured) by light irradiation is used. In consideration of environmental problems, an alkali development type photo solder resist using a dilute alkaline aqueous solution as a developing solution has become the mainstream and is widely used (see, for example, Patent Document 1).

  In recent years, solder resists are required to have higher workability and higher performance in response to the increase in the density of printed wiring boards accompanying the reduction in the size of electronic devices. Recently, along with the downsizing, lightening, and high performance of electronic devices, downsizing of semiconductor packages and increasing the number of pins have been put into practical use, and mass production is progressing. For example, in order to obtain high reliability in semiconductor packages such as BGA (ball grid array) and CSP (chip size package), PCT (pressure cooker test) resistance, which is also referred to as moisture heat resistance, is required. Furthermore, from the viewpoint of productivity, the solder resist is also required to have reactivity with ultraviolet rays used for patterning, that is, high exposure sensitivity.

  However, the current state of the conventional liquid development type solder resist is only several hours to several tens of hours in the PCT resistance test. Also, when the package is mounted, moisture absorbed by the solder resist boils the moisture absorbed inside the package during reflow, causing cracks in the solder resist film inside the package and its surroundings, and sufficient crack resistance cannot be obtained. is there.

  On the other hand, in a conventional solder resist, an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used as a carboxylic acid-containing resin. Patent Document 1 describes a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound. ing. Moreover, in patent document 2, (meth) acrylic acid is added to the epoxy resin obtained by making epichlorohydrin react with the reaction product of a salicylaldehyde and monohydric phenol, and also polybasic carboxylic acid is added. A solder resist composition comprising a photosensitive resin obtained by reacting an acid or an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed.

  In general epoxy acrylate modified resins, the epoxy resin used as a raw material already contains a lot of chlorine ion impurities that deteriorate the insulation reliability of the insulating material. There is a problem that it is very difficult to remove.

JP-A 61-243869 Japanese Patent Laid-Open No. 3-250012

  The present invention has good workability, high sensitivity, and can provide excellent PCT resistance and high insulation reliability when used in a cured product such as a printed wiring board or a semiconductor package. An object is to provide a curable resin composition.

In order to achieve such an object, the curable resin composition of one embodiment of the present invention has the general formula (I) and the general formula (II).

  A reaction product obtained by reacting a phenol resin derived from more with an alkylene oxide or a cyclocarbonate compound is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is added to the resulting reaction product. It contains a carboxyl group-containing photosensitive resin obtained by reaction and a photopolymerization initiator.

  With such a configuration, the workability is good, the sensitivity is high, and when the cured product is used for, for example, a printed wiring board or a semiconductor package, excellent PCT resistance and high insulation reliability can be obtained. It becomes possible.

  Moreover, in the curable resin composition of 1 aspect of this invention, it is preferable that the acid value of carboxyl group-containing photosensitive resin is 30-150 mgKOH / g. By setting the oxidation within this range, alkali development is possible and sufficient development resistance can be obtained.

  In the curable resin composition of one embodiment of the present invention, the alkylene oxide is preferably ethylene oxide and / or propylene oxide.

  In the curable resin composition of one embodiment of the present invention, the cyclocarbonate compound is preferably ethylene carbonate and / or propylene carbonate.

  In the curable resin composition of one embodiment of the present invention, the unsaturated group-containing monocarboxylic acid is preferably acrylic acid and / or methacrylic acid.

  Furthermore, the curable resin composition of one embodiment of the present invention preferably contains a thermosetting component. With such a configuration, it can be used as a thermosetting resin composition that can be cured by heat.

  Furthermore, the curable resin composition of one embodiment of the present invention preferably contains a colorant. By containing a colorant, when used as a solder resist for a printed wiring board, it is possible to obtain a concealing property such as a circuit.

  Furthermore, such a curable resin composition can be applied to a substrate and cured by irradiation with active energy rays and / or heating to obtain a cured product. In such a cured product, for example, when used for a printed wiring board or a semiconductor package, high reliability can be obtained.

  Moreover, such a curable resin composition can be applied to a carrier film and dried to be used as a curable dry film. By using such a dry film, a resist layer can be easily formed without coating. Furthermore, this dry film can be attached to a substrate and cured by irradiation with active energy rays and / or heating to obtain a cured product. In such a cured product, for example, when used for a printed wiring board or a semiconductor package, high reliability can be obtained.

  And by using these hardened | cured material for a printed wiring board, it becomes possible to obtain high reliability, such as PCT tolerance.

  According to one aspect of the present invention, the curable resin composition has good workability, high sensitivity, and excellent PCT when used in, for example, a printed wiring board or a semiconductor package. Resistance and high insulation reliability can be obtained.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have obtained a carboxyl group-containing photosensitivity starting from a bisphenol A-formaldehyde type phenol resin or a salicylaldehyde type phenol resin as an essential component of the composition. It has been found that the above-described object can be achieved by using a resin, and the present invention has been completed.

  This carboxyl group-containing photosensitive resin can obtain excellent flexibility and elongation by chain extension by reaction addition of bisphenol A-formaldehyde type phenol resin, salicylaldehyde type phenol resin and alkylene oxide or cyclocarbonate compound. it can. In addition, when an unsaturated group-containing monocarboxylic acid and a polybasic acid anhydride are added to a terminal hydroxyl group generated by the addition reaction of an alkylene oxide or a cyclocarbonate compound, the unsaturated group or the carboxyl group is the same side chain. Since it is not present above and is located at the end of each side chain, it has excellent reactivity. Moreover, it has excellent alkali developability due to the presence of a terminal carboxyl group separated from the main chain. In addition, it has excellent moisture absorption resistance because it has no or only a slightly reactive hydrophilic alcoholic hydroxyl group, so it has improved PCT resistance required for IC packages. It is estimated that it leads to.

  In addition, compared with conventional cresol type novolac resins, the skeletons of bisphenol A-formaldehyde type phenol resin and salicylaldehyde type phenol resin are flexible, so that the thermal shock resistance can be improved. It becomes possible.

  Hereinafter, the curable resin composition of the present invention will be described in detail.

  First, specifically, the carboxyl group-containing photosensitive resin having a bisphenol A-formaldehyde skeleton constituting the curable resin composition of the present invention can be easily obtained by the following method.

  (1) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a bisphenol A-formaldehyde type phenol resin and / or a salicylaldehyde type phenol resin with an alkylene oxide. The polybasic acid anhydride is reacted.

  (2) A reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a reaction product obtained by reacting a bisphenol A-formaldehyde type phenol resin and / or a salicylaldehyde type phenol resin with a cyclocarbonate compound. Is reacted with a polybasic acid anhydride.

  The carboxyl group-containing photosensitive resin in the present embodiment is a reaction product obtained by reacting bisphenol A-formaldehyde type phenol resin and salicylaldehyde type phenol resin as starting materials. These phenol resins can be easily obtained with almost no chloride ion impurities. The chlorine ion impurity content of the carboxyl group-containing photosensitive resin is 0-100 ppm, more preferably 0-50 ppm, still more preferably 0-30 ppm.

  Further, such a carboxyl group-containing photosensitive resin is also characterized in that it is a resin that does not contain a hydroxyl group. In general, the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but it is known to significantly reduce moisture resistance.

  The carboxyl group-containing photosensitive resin obtained in (1) and (2) may be reacted with a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule. As such a compound, glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, or 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of reactivity and supply.

  (Meth) acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  The addition amount of such a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is preferably 5% equivalent to 40% equivalent to the carboxyl group. When the added amount is less than 5% equivalent, sufficient sensitivity increase and improvement of the solder resist characteristics cannot be obtained, and when it exceeds 40% equivalent, the maximum development life is shortened and the dryness to the touch is deteriorated. More preferably, it is 10% equivalent to 30% equivalent.

  By using such a carboxyl group-containing photosensitive resin, since it has many free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible. Moreover, it is preferable that the acid value of carboxyl group-containing photosensitive resin is the range of 30-150 mgKOH / g. When it is lower than 30 mgKOH / g, the solubility in an aqueous alkali solution is lowered, and development of the formed coating film becomes difficult. On the other hand, if the concentration is higher than 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line fades more than necessary, or dissolution and peeling occurs with the developer without distinction between the exposed portion and the unexposed portion. It may be difficult to draw a resist pattern. And it causes the appearance defect and the deterioration of electrical characteristics.

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

  It is preferable that the compounding quantity of such a carboxyl group-containing photosensitive resin is 20-60 mass% in the whole composition. When it is less than 20% by mass, the coating film strength is lowered. On the other hand, when it is more than 60% by mass, the viscosity becomes high, and the coating property and the like are lowered. More preferably, it is 30-50 mass%.

The bisphenol A-formaldehyde type phenol resin and the salicylaldehyde type phenol resin are not particularly limited as long as they have the structures of the general formulas (I) and (II).

As the resin having the skeleton of the general formula (I), for example, BPA-D manufactured by Meiwa Kasei Co., Ltd. can be used. Moreover, as resin which has frame | skeleton of general formula (II), MEH-7500 by Meiwa Kasei Co., Ltd. can be used, for example.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and the like, and ethylene oxide and propylene oxide are preferable from the viewpoint of price and supply system. Moreover, as a cyclocarbonate compound, a well-known carbonate compound can be used, For example, ethylene carbonate, propylene carbonate, butylene carbonate, 2, 3-carbonate propyl methacrylate, etc. are mentioned. Among these, 5-membered ethylene carbonate and propylene carbonate are preferable from the viewpoint of reactivity and supply system. These alkylene oxides and cyclocarbonate compounds can be used alone or in admixture of two or more.

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

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

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

As the photopolymerization initiator, an oxime ester photopolymerization initiator having a group represented by the general formula (III), an α-aminoacetophenone photopolymerization initiator having a group represented by the following general formula (IV), Alternatively, it is preferable to use one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (V).

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

The oxime ester photopolymerization initiator having a group represented by the general formula (III) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (VI),

Compound represented by general formula (VII)

(In the formula, R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 carbon atoms. To 12 alkoxycarbonyl groups (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 one or more oxygen atoms in the middle of the alkyl chain) Or R ¹⁰ and R ¹² are each independently a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom may be substituted). Good), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and have one or more oxygen atoms in the middle of the alkyl chain) A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and 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), an alkyl group having 1 to 20 carbon atoms (which is substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 1 carbon atoms). 6 may be substituted with an alkyl group or a phenyl group).
Compound represented by general formula (VIII)

(In the formula, R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or 1 to 1 carbon atoms. 6 represents an alkyl group, and n represents an integer of 0 to 5). Among these, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by general formula (VI) and a compound represented by formula (VII) 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.

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

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

  It is preferable that the compounding quantity of such a photoinitiator is 0.01-30 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes intense, and the deep curability tends to decrease. More preferably, it is the range of 0.5-15 mass parts. In addition, in the case of the oxime ester photopolymerization initiator having a group represented by the formula (III), the blending amount is 0.01% with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin for the same reason. It is more preferable to set it as -20 mass parts. More preferably, it is the range of the range of 0.01-5 mass parts.

  In addition, photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photosensitive composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, A xanthone compound, a tertiary amine compound, etc. can be mentioned.

  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-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide. Can be mentioned.

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

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present embodiment preferably contains a thioxanthone compound from the viewpoint of deep sclerosis, and in particular, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl. Thioxanthone compounds such as thioxanthone are preferred.

  As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of carboxyl group-containing photosensitive resin. If it exceeds 20 parts by mass, the thick film curability is lowered, leading to an increase in the cost of the product. More preferably, the ratio is 10 parts by mass or less.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and 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 quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin. When the compounding amount of the tertiary amine compound is less than 0.1 parts by mass, it is difficult to obtain a sufficient sensitizing effect. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is a ratio of 0.1 to 10 parts by mass.

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

  The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  Furthermore, the following arbitrary components can be blended.

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

  A polyfunctional mercaptan-based compound can be used and is not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide. Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohol such as erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 ( Poly (mercaptobutyrate) s such as 1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mertabutbutyrate) can be used.

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

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

<Diluent>
In the present embodiment, a reactive diluent can be used as one that is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the carboxyl group-containing photosensitive resin 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 acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to these acrylates like.

  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.

  It is preferable that the compounding quantity of such a diluent shall be 5-100 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays. On the other hand, when it exceeds 100 mass parts, the solubility with respect to alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is a ratio of 5-70 mass parts.

《Thermosetting component》
A thermosetting component can be added to the photocurable resin composition of the present embodiment in order to impart heat resistance. The thermosetting component used in the present embodiment includes amine resins such as melamine resin and benzoguanamine resin, bismaleimide, benzoxazine compound, oxazoline compound, carbodiimide resin, blocked isocyanate compound, cyclocarbonate compound, polyfunctional epoxy compound, polyfunctional Known thermosetting resins such as oxetane compounds, episulfide resins, and melamine derivatives can be used. Particularly preferred are two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  Such a thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two of them. A compound having at least two epoxy groups in the molecule, that is, a compound having at least two oxetanyl groups in the molecule, ie, a polyfunctional oxetane Examples thereof include compounds and compounds having two or more thioether groups in the molecule, that is, episulfide resins.

  As the polyfunctional epoxy compound, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Tohto Kasei Co., Ltd. manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Dow Chemical Co., Ltd. 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 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., YDF -175, YDF-2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals (all are trade names); Epotot ST-2004, ST-2007, ST-3000 manufactured by Tohto 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., Sumitomo Chemical Co., Ltd. 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 (trade name) 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 are 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.

  Polyfunctional oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, poly (P-hydroxystyrene), cardo bisphenol , Calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having two or more cyclic thioether groups in the molecule 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 amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxylic acid-containing resin. preferable. When the blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in heat resistance, alkali resistance, electricity Insulation properties are reduced. 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, and thus the strength of the coating film is lowered. More preferably, it is the range used as 0.8-2.0 equivalent.

《Thermosetting catalyst》
When using a thermosetting component having two or more cyclic (thio) ether groups in such a molecule, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 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. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used. And it is preferable to use together the compound which functions also as an adhesive imparting agent with a thermosetting catalyst.

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

<Isocyanate derivative>
Furthermore, in the curable resin composition of this embodiment, in order to improve the curability of the photosensitive resin composition and the toughness of the resulting cured film, two or more isocyanate groups or blocked isocyanate in one molecule Compounds having groups can be added. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two in one molecule. Examples thereof include compounds having the above blocked isocyanate groups, that is, blocked isocyanate compounds.

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

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

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  A commercially available thing can be used for such a block isocyanate compound, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078. , TPLS-2117, desmotherm 2170, desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), coronate 2512, coronate 2513, coronate 2520 (above, Japan Polyurethane Industry Co., Ltd., trade name), B-830, B- 815, B-846, B-870, B-874, B-882 (trade name, manufactured by Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals Corp.), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  Such compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.

  The blending amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. . When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained. On the other hand, when the amount exceeds 100 parts by mass, the storage stability decreases. More preferably, it is the ratio of 2-70 mass parts.

《Urethaneization catalyst》
Furthermore, a urethanization catalyst can be added to the photocurable resin composition of the present embodiment in order to promote curing of hydroxyl groups and isocyanate groups. As the urethanization catalyst, it is preferable to use one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. .

  Examples of the tin-based catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

  The metal chloride is a metal chloride made of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.

  The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Can be mentioned.

  The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.

  Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N ′-( 2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N ′ -(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl-N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanolamine 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1- ( 2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′-aminopropyl) ) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxyethyl) Amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, N ′ -Bis (2-hydroxypropyl) amine, melamine or / and benzoguanamine etc. are mentioned.

  Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5,4,0] undecene-7).

  The compounding amount of such a urethanization catalyst is sufficient in an ordinary quantitative ratio, and for example, preferably 0.1 to 20 parts by mass, more preferably 0.00 with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. 5 to 10.0 parts by mass.

<Melamine derivative>
Furthermore, a melamine derivative, a benzoguanamine derivative, etc. can be added as a thermosetting component. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM, (manufactured by Sanwa Chemical Co., Ltd.) and the like.

  These thermosetting components can be used alone or in combination of two or more.

<Adhesive agent>
Furthermore, in the curable composition of the present embodiment, an adhesion imparting agent can be used in order to improve adhesion between layers or adhesion with a substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Co., Ltd.), 3 -Morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, Amino group-containing benzotriazole, silane coupling agent and the like.

《Colorant》
Furthermore, a coloring agent can be mix | blended in the curable resin composition of this embodiment. As the colorant, known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

(Blue colorant)
Examples of the blue colorant include phthalocyanine series and anthraquinone series. Of these, compounds classified as pigments in the pigment system, specifically, the following color index (CI; issued by The Society of Dyers and Colorists) numbers are attached. 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, and the like can be used.

  In addition, in the dye system, 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 these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

(Green colorant)
Similarly, examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series. 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 these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

(Yellow colorant)
Examples of yellow colorants include anthraquinone, isoindolinone, condensed azo, benzimidazolone, monoazo, and disazo. Specifically, the following can be used.

  As an anthraquinone, Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202, and the like are used.

  Examples of isoindolinone compounds include Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, and Pigment Yellow 185.

  Examples of condensed azo compounds include Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, and Pigment Yellow 180.

  As the benzimidazolone series, Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 and the like are used.

  As monoazo series, 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, etc. are used.

  Examples of the disazo group include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, and the like.

(Red colorant)
Examples of the red colorant include monoazo, diazo, monoazo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specifically, the following can be used.

  Monoazo series includes 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, etc. are used.

  As the disazo system, Pigment Red 37, 38, 41 or the like is used.

  Monoazo lakes include 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 etc. are used.

  Examples of benzimidazolone-based compounds include Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, and Pigment Red 208.

  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, etc. are used as the perylene system.

  Examples of the diketopyrrolopyrrole include Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, and Pigment Red 272.

  As the condensed azo system, Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242 are used.

  Examples of anthraquinone include Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207, and the like.

  As the quinacridone system, Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, and the like are used.

  In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone. Specific examples of such colorants include 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 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 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 2 5, C.I. pigment black 1, C.I. pigment black 7, and the like.

  Although such a coloring agent is mix | blended suitably, it is preferable to set it as 10 mass parts or less with respect to 100 mass parts of carboxyl group-containing photosensitive resin or a thermosetting component. More preferably, it is 0.1-5 mass parts.

《Filler》
Furthermore, in order to increase the physical strength and the like of the coating film, a filler can be blended as necessary. As such a filler, known inorganic or organic fillers can be used, and in particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. Moreover, 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 are product grade names), NANOPOX (trade name) manufactured by Hanse-Chemie, Inc. XP 0516, XP 0525, XP 0314 (all are product grades) Name) can also be used. These fillers can be used alone or in combination of two or more.

  It is preferable that the compounding quantity of these fillers is 300 mass parts or less with respect to 100 mass parts of carboxyl group-containing photosensitive resin. When the compounding quantity of a filler exceeds 300 mass parts, the viscosity of a photosensitive composition will become high, printability will fall, or hardened | cured material will become weak. More preferably, it is 0.1-300 mass parts, Most preferably, it is 0.1-150 mass parts.

"Organic solvent"
Furthermore, an organic solvent can be used for the synthesis | combination of a carboxyl group-containing photosensitive resin, the adjustment of a composition, or the viscosity adjustment for apply | coating to a board | substrate or a carrier film.

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

"Antioxidant"
In many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, the photocurable resin composition of the present embodiment is used to prevent oxidation. (1) radical scavengers that invalidate the generated radicals and / or (2) peroxide decomposers that decompose the generated peroxides into harmless substances and prevent new radicals from being generated Antioxidants can be added.

  Specific examples 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-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′di-tert-butyl-4) -Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6 , 6-tetramethyl-4-piperidyl) -sebacate, amine compounds such as phenothiazine, and the like.

  As such an antioxidant acting as a radical scavenger, commercially available products can be used. For example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 152, TINUVIN 292, (The above is a product name, manufactured by Ciba Specialty Chemicals Co., Ltd.).

  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.

  A commercially available antioxidant can be used as the peroxide decomposing agent. For example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.) , Sumilyzer TPS (product name) manufactured by Sumitomo Chemical Co., Ltd.

  These antioxidants can be used alone or in combination of two or more.

<Ultraviolet absorber>
Since the polymer material absorbs light and thereby decomposes and deteriorates, the photocurable resin composition of the present invention is not limited to the above-described antioxidant, but an ultraviolet absorber in order to take measures against stabilization against ultraviolet rays. Can be used.

  Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. 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, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc .; specific examples of benzotriazole derivatives include 2- (2′- Hydroxy-5'-t-butylphenyl) Zotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy -3 ', 5'-di-tert-amylphenyl) benzotriazole; Examples of specific triazine derivatives include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

  Commercially available UV absorbers can be used, such as TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460. TINUVIN 479 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).

  These ultraviolet absorbers can be used singly or in combination of two or more, and by using in combination with the above-described antioxidant, a molded product obtained from the photocurable resin composition of the present embodiment. Can be stabilized.

  In addition, the photo-curable resin composition of the present embodiment may further include a known thixotropic agent such as a known thermal polymerization inhibitor, fine silica, organic bentonite, montmorillonite, hydrotalcite, silicone, Formulated with known additives such as defoamers and / or leveling agents such as fluorine and polymer, silane coupling agents such as imidazole, thiazole and triazole, antioxidants and rust inhibitors can do.

  The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound. 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.

  The curable resin composition of the present embodiment configured as described above is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and is formed on a substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater. It is applied by a method such as a method, a screen printing method or a curtain coating method.

  And the tack-free coating film is formed by carrying out the volatile drying (temporary drying) of the organic solvent contained in a composition at the temperature of about 60-100 degreeC. At this time, the volatile drying is supported by a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (a method provided with a heat source of an air heating method using steam in a countercurrent contact with hot air in the dryer and a nozzle. Can be performed using a method of spraying on the body).

  Alternatively, a curable resin composition may be applied onto a carrier film, dried and wound up as a film to form a dry film, and this may be laminated on a substrate to form a resin insulation layer. Good.

  At this time, as a base material on which a coating film is formed or a dry film is laminated, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy All grades (FR-4, etc.) of copper clad laminates, such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate esters, etc., other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer board, etc. can be mentioned.

  Further, by a contact type (or non-contact type), pattern exposure (irradiation of active energy rays) is selectively performed by an active energy ray through a photomask on which a pattern is formed, or by exposure or a laser direct exposure machine.

  As an exposure apparatus used for active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can be used. For example, a device manufactured by Nippon Orbotech, Pentax, or the like can be used, and any device that oscillates laser light having a maximum wavelength of 350 to 410 nm may be used.

As the active energy ray, either a gas laser or a solid laser may be used as long as it has a maximum wavelength in the range of 350 to 410 nm. 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.

  And by exposing in this way, an exposed part (part irradiated with the active energy ray) is cured, and an unexposed part is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a resist pattern is formed.

  At this time, the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developer is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicic acid. Alkaline aqueous solutions such as sodium, ammonia and amines can be used.

  Further, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing photosensitive resin has two or more cyclic ether groups and / or cyclic thioether groups in the molecule. 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.

  Thus, in the curable resin composition, bisphenol A-formaldehyde, a carboxyl group-containing photosensitive resin having a salicylaldehyde type phenol skeleton, and a photopolymerization initiator, and, if necessary, a diluent, a thermosetting component, a coloring By containing an agent and the like, excellent alkali developability, excellent workability, and mass productivity can be obtained. Furthermore, the coating film obtained by applying this is selectively exposed, developed, and finish-cured as necessary, so that adhesion, chemical resistance, electroless gold plating resistance, thermal shock resistance, PCT A cured product excellent in resistance, electrical insulation and the like can be obtained, and high reliability can be imparted by using the cured product for a printed wiring board.

(Resin synthesis example 1)
Into an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120) 0 g, 1.20 g of potassium hydroxide and 120.0 g of toluene were charged, and the system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours.

  Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1%, and the hydroxyl value was 182.2 g / eq. A propylene oxide reaction solution of bisphenol A-formaldehyde type phenol resin was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

  293.0 g of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring.

  12.6 g of water produced by the reaction was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.

  Next, 332.5 g of the obtained novolak acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%. . This is designated as resin solution A-1.

(Resin synthesis example 2)
A reaction kettle was charged with 120 parts of bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate. The reaction was started by heating to 150 to 160 ° C., and then continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system.

  Then, it cooled to room temperature and a hydroxyl group equivalent was 182.2 g / eq. A propylene carbonate reaction product of bisphenol A-formaldehyde type phenol resin was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.

  After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.6 parts of water produced by the reaction was distilled as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.

  Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%. Obtained. This is designated as resin solution A-2.

(Resin synthesis example 3)
A reaction kettle was charged with 120 parts of bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120), 0.6 part of triphenylphosphine and 96.9 parts of ethylene carbonate. While stirring, the temperature was raised to 150 to 160 ° C. to start the reaction, and then the reaction was continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system.

  Then, it cooled to room temperature and a hydroxyl group equivalent was 182.2 g / eq. A propylene carbonate reaction product of bisphenol A-formaldehyde type phenol resin was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.

  After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.

  Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 89 mgKOH / g and a nonvolatile content of 72%. Obtained. This is designated as resin solution A-3.

(Resin synthesis example 4)
While stirring 98 parts of salicylaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “MEH-7500”, OH equivalent: 98), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, the mixture was stirred. The reaction was started by heating to 150 to 160 ° C. and then continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system.

  Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 159.0 g / eq. A propylene carbonate reaction product of salicylaldehyde type phenol resin was obtained. This was equivalent to an average of 1.05 mol of propylene oxide added per equivalent of phenolic hydroxyl group.

  After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.8 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.

  Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 92 mgKOH / g and a nonvolatile content of 72%. Obtained. This is designated as Resin Solution A-4.

(Resin synthesis example 5)
Orthocresol novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (fragrance) Total number of rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C., reacted for 2 hours, heated to 120 ° C., and further reacted for 12 hours.

  To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This is designated as Resin Solution A-5.

(Resin synthesis example 6)
After dissolving 925 g of epichlorohydrin and 462.5 g of dimethyl sulfoxide in 400 g of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 g of 98.5% NaOH is added over 100 minutes at 70 ° C. with stirring. did. After the addition, the reaction was further carried out at 70 ° C. for 3 hours.

  Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 g of methyl isobutyl ketone, and further 10 parts of 30% NaOH was added at 70 ° C. The reaction was carried out for 1 hour. After completion of the reaction, washing was performed twice with 200 g of water. After oil-water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain 370 g of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C.

  2900 g (10 equivalents) of an epoxy resin, 720 g (10 equivalents) of acrylic acid, 2.8 g of methylhydroquinone, and 1950 g of carbitol acetate were charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 16.7 g of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g.

  Next, 786 g (7.86 mol) of succinic anhydride and 423 g of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, and a resin having a solid content acid value of 100 mgKOH / g and a solid content of 65%. A solution was obtained. This is designated as Resin Solution A-6.

Using these resin solutions, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photocurability for solder resist A resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer made from an Eriksen company.

* 1 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one
(Irga Caer 907: Ciba Specialty Chemicals)
* 2 2,4-Diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3 2- (Acetyloxyiminomethyl) thioxanthen-9-one * 4 Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-,
1- (0-acetyloxime)
(Irgacure OXE 02: Ciba Specialty Chemicals)
* 5 Dipentaerythritol pentaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 6 Modified novolac epoxy resin (EPICLON N-865: manufactured by DIC)
* 7 Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.)
* 8 Methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)
* 9 Block isocyanate (Asahi Kasei Chemicals)
* 10 CIPigment Blue 15: 3
* 11 CIPigment Yellow147
* 12 2-mercaptobenzothiazole * 13 Antioxidant (Ciba Specialty Chemicals)
* 14 B-30 (manufactured by Sakai Chemical Co., Ltd.)
* 15 Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.)
* 16 Epoxidized polybutadiene (manufactured by Daicel Chemical Industries, Ltd.)
* 17 Diethylene glycol monoethyl ether acetate Examples 1 to 13 and Comparative Examples 1 and 2 thus obtained were evaluated as follows.

(Performance evaluation)
<Optimal exposure>
The obtained curable resin compositions of Examples and Comparative Examples were subjected to circuit printing with a copper thickness of 35 μm after buffing, washed with water, dried and then applied to the entire surface by a screen printing method. It was dried for 60 minutes in a drying furnace. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp and a direct drawing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm, and development (30 ° C., 0.2 MPa, 1% by mass carbonic acid) The optimal exposure amount was obtained when the step tablet pattern remained when the aqueous sodium solution was 60 seconds was 7 steps.

<Developability>
The curable resin compositions of Examples and Comparative Examples were dried on a solid copper substrate by a screen printing method, applied to a thickness of about 25 μm, and dried for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, development was performed with a 1% by mass aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured with a stopwatch.

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

<Tackiness>
Each curable resin composition was applied onto the patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, pressure-bonded under a reduced pressure condition by ORC (HMW-GW20) for 1 minute, and then the state of sticking of the film when the negative film was peeled was evaluated.

○: When the film is peeled off, there is no resistance, but the coating film has a slight mark. Δ: When the film is peeled off, there is a slight resistance, and the coating film has a slight mark. X: Resistance when the film is peeled off. There are clear marks on the coating (characteristic test)
Each composition of Examples and Comparative Examples was applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and a 1% by weight sodium carbonate aqueous solution at 30 ° C. is developed for 90 seconds under a spray pressure of 0.2 MPa / cm ^2. A resist pattern was obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.

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

○: No change is observed Δ: Only a slight change ×: The coating film is swollen or swelled off <Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.

○: Peeling is not observed even if the immersion for 10 seconds is repeated 3 times or more. Δ: Slight peeling occurs when the immersion for 10 seconds is repeated 3 times or more. X: The resist layer swells and peels within 3 times for 10 seconds. Electroless gold plating>
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5 μm and gold 0.05 μm, and tape peeling is used to check whether the resist layer has been peeled off or plating has penetrated. 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 soaking is confirmed after plating, but no peeling after tape peeling △: Slight soaking is seen after plating, peeling is also seen after tape peeling ×: After plating There is peeling <PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film was determined. evaluated. Judgment criteria are as follows.

○: No swelling, peeling, discoloration, or elution △: Some swelling, peeling, discoloration, or elution ×: Many swelling, peeling, discoloration, or elution <Resistance to thermal shock>
The evaluation board | substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced. The obtained evaluation substrate was subjected to a 1000 cycle durability test using a thermal shock tester (manufactured by ETAC Co., Ltd.) with -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.

○: Crack generation rate of less than 30% △: Crack generation rate of 30-50%
×: Crack generation rate of 50% or more <HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-type electrodes (line / space = 50 microns / 50 microns) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high-temperature, high-humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 5V was charged, and the in-chamber HAST test was done for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.

○: 10 ⁸ Ω or more △: 10 ⁶ ~10 ⁸ Ω
×: 10 ⁶ Ω or less

<Evaluation of dry film>
The curable resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were 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. did. Furthermore, the cover film was bonded together and the dry film was produced, and it was set as Examples 14-20 and Comparative Examples 3 and 4, respectively.

Thereafter, 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 the examples. After the exposure, the carrier film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa / cm ² 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 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.

  From the results shown in Table 2 and Table 3, the curable resin composition of the present embodiment uses a bisphenol A-formaldehyde type phenol resin and a carboxy-containing photosensitive resin having a salicylaldehyde type phenol skeleton, so that IC can be obtained. It can be seen that it has both PCT resistance, thermal shock resistance, and electrical characteristics required for use in a solder resist for packages.

Claims (11)

Obtained by reacting a monocarboxylic acid containing an unsaturated group with a reaction product obtained by reacting a phenol resin derived from the general formula (I) and the general formula (II) with an alkylene oxide or a cyclocarbonate compound. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride;
A photopolymerization initiator;
A curable resin composition comprising:

  2. The curable resin composition according to claim 1, wherein the carboxyl group-containing photosensitive resin has an acid value of 30 to 150 mgKOH / g.   The curable resin composition according to claim 1, wherein the alkylene oxide is ethylene oxide and / or propylene oxide.   The curable resin composition according to any one of claims 1 to 3, wherein the cyclocarbonate compound is ethylene carbonate and / or propylene carbonate.   The curable resin composition according to any one of claims 1 to 4, wherein the unsaturated group-containing monocarboxylic acid is acrylic acid and / or methacrylic acid.   Furthermore, a thermosetting component is contained, The curable resin composition of any one of Claims 1-5 characterized by the above-mentioned.   Furthermore, a coloring agent is contained, The curable resin composition of any one of Claims 1-6 characterized by the above-mentioned.   A cured product obtained by applying the curable resin composition according to any one of claims 1 to 7 to a substrate and curing the composition by irradiation with active energy rays and / or heating.   The dry film obtained by apply | coating the curable resin composition of any one of the said Claims 1-7 to a carrier film, and drying.   A cured product obtained by attaching the dry film according to claim 9 to a substrate and curing it by irradiation with active energy rays and / or heating.   A printed wiring board comprising the cured product according to claim 9.