KR101174983B1 - Curable resin composition - Google Patents

Abstract

The present invention has good workability, high sensitivity, and a curable resin composition capable of obtaining excellent PCT resistance and high insulation reliability when used in a cured product thereof, for example, in a printed wiring board or a semiconductor package, and its hardness. Deliver the cargo.
Curable resin composition WHEREIN: The carboxyl group-containing resin which does not use an epoxy resin as a starting material, the carboxyl group-containing photosensitive resin obtained by making the compound which has a cyclic ether group and ethylenically unsaturated group together in 1 molecule react with a carboxyl group-containing resin, and contains a photoinitiator do.

Description

Curable Resin Composition {CURABLE RESIN COMPOSITION}

This invention relates to curable resin composition used as a soldering resist of a printed wiring board, etc., for example.

At present, in some high-precision, high-density, solder resists of some commercial printed wiring boards and most industrial printed wiring boards, a liquid phase phenomenon in which an image is formed by developing after irradiation with ultraviolet rays and the final curing (main curing) is performed by heat and / or light irradiation. Type solder resists are used. And from consideration to environmental problems, the alkali developing type photo solder resist which uses dilute alkali aqueous solution as a developing solution becomes mainstream, and is used widely (for example, refer following patent document 1).

In recent years, in order to cope with the increase in density of printed wiring boards due to light and shorter electronic devices, workability and high performance are required for solder resists. In recent years, with the miniaturization, light weight, and high performance of electronic devices, miniaturization and multi-pinning of semiconductor packages have been put into practical use, and mass production has been advanced. For example, in semiconductor packages such as BGA (ball grid array) and CSP (chip size package), in order to obtain high reliability, PCT (pressure cooker test) resistance, which should also be referred to as moisture and heat resistance, is particularly required. Furthermore, in terms of productivity, it is required to have responsiveness to ultraviolet rays or the like, that is, high exposure sensitivity, used in patterning even in solder resists.

However, the conventional liquid developing solder resist can only withstand a few hours to several tens of hours in the PCT resistance test. In addition, when the package is mounted, moisture absorbed in the package during the reflow due to moisture absorption of the solder resist boils, causing cracks in the solder resist film inside the package and its periphery, and thus sufficient crack resistance is not obtained.

On the other hand, in the conventional soldering resist, epoxy acrylate modified resin induced by modification of an epoxy resin is generally used as carboxylic acid containing resin. In patent document 1, the soldering resist composition containing the photosensitive resin which added the acid anhydride, the photoinitiator, the diluent, and the epoxy compound to the reaction product of a novolak-type epoxy compound and unsaturated monobasic acid is described. Moreover, in following patent document 2, (meth) acrylic acid is added to the epoxy resin obtained by making epichlorohydrin react with the reaction product of salicylic aldehyde and monohydric phenol, and also polybasic carboxylic acid or its anhydride is added. The soldering resist composition containing the photosensitive resin obtained by making it react, a photoinitiator, an organic solvent, etc. is disclosed.

In general, epoxy acrylate-modified resins are mostly epoxy resins used as raw materials already contain a large amount of chlorine-ion impurities that degrade the insulation reliability of the insulating material, it is very difficult to remove chlorine-ion impurities after the epoxy acrylate modification. There is a problem.

Japanese Patent Publication No. 61-243869 Japanese Patent Laid-Open No. 3-250012

An object of the present invention is to provide a curable resin composition capable of obtaining excellent PCT resistance and high insulation reliability when used in a printed wiring board or a semiconductor package, for example, while having good workability and high sensitivity. It is done.

In order to achieve this object, the curable resin composition of one aspect of the present invention is a carboxyl group-containing resin that does not use (A) an epoxy resin as a starting material, and (B) a cyclic ether group and an ethylenically unsaturated group in one molecule of the carboxyl group-containing resin. It is characterized by containing a carboxyl group-containing photosensitive resin obtained by making the compound which has together react, and a photoinitiator.

Such a structure makes it possible to obtain excellent PCT resistance and high insulation reliability when used in printed wiring boards or semiconductor packages, for example, in the cured product thereof while having good workability and high sensitivity.

Moreover, in curable resin composition of 1 aspect of this invention, carboxyl group-containing resin (A) is unsaturated to the reaction product obtained by making the compound which has two or more phenolic hydroxyl groups, and the alkylene oxide or the cyclocarbonate compound in 1 molecule react. It is preferable to make group-containing monocarboxylic acid react, and to obtain polybasic acid anhydride by making reaction product obtained react.

By such a structure, since water resistance improves and excellent PCT tolerance is obtained, since it does not contain chloride ion impurity, the outstanding insulation reliability can be obtained.

Moreover, in the carboxyl group-containing photosensitive resin (B) in curable resin composition of 1 aspect of this invention, the compound which has a cyclic ether group and ethylenically unsaturated group together in 1 molecule is glycidyl (meth) acrylate, 4-hydroxy It is preferable that it is butyl acrylate glycidyl ether or 3, 4- epoxycyclohexyl methyl methacrylate.

By such a configuration, the sensitivity and the adhesion are improved, and excellent PCT resistance and electroless plating resistance can be obtained.

Moreover, in carboxyl group-containing resin (A) in curable resin composition of 1 aspect of this invention, it is preferable that carboxyl group-containing resin is photosensitive. By this structure, it can be used as a highly sensitive photocurable resin composition.

Moreover, in curable resin composition of 1 aspect of this invention, it is preferable to contain a thermosetting component. By such a structure, it can be used as a thermosetting resin composition which can be hardened by heat.

Moreover, in curable resin composition of 1 aspect of this invention, it is preferable to contain a coloring agent. By containing a coloring agent, when used as a soldering resist for printed wiring boards, concealability, such as a circuit, can be acquired.

Moreover, this curable resin composition is apply | coated to a base material, it can harden | cure by active energy ray irradiation and / or heating, and it can be set as hardened | cured material. In such hardened | cured material, when used for a printed wiring board or a semiconductor package, it becomes possible to obtain high reliability.

Moreover, such a curable resin composition is apply | coated and dried to a carrier film, and can be used as a photocurable thermosetting dry film. By setting it as such a dry film, a resist layer can be formed easily, without apply | coating. Moreover, this dry film is adhere | attached on a base material, it can harden | cure by active energy ray irradiation and / or heating, and it can be set as hardened | cured material. In such hardened | cured material, when used for a printed wiring board or a semiconductor package, it becomes possible to obtain high reliability.

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

According to one aspect of the present invention, in the curable resin composition, while having good workability and high sensitivity, the cured product thereof has excellent PCT resistance and high insulation reliability when used in, for example, a printed wiring board or a semiconductor package. It is possible to obtain.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the above-mentioned subject, as an essential component of a composition, the present inventors found carboxyl group-containing resin which does not use an epoxy resin as a starting material, and carboxyl group-containing photosensitive resin which uses a carboxylic acid-containing resin as a starting material. By combining with the present inventors, the present invention has been found to be able to achieve the above object. That is, the curable resin composition of this invention is characterized by the combination of 2 types of carboxyl group-containing photosensitive resin contained here.

A carboxyl group-containing resin (A) can obtain the outstanding flexibility and elongation by chain extension by addition reaction of the compound which has a phenolic hydroxyl group, and an alkylene oxide or a cyclocarbonate compound, for example. Moreover, when addition of an unsaturated group containing monocarboxylic acid and addition of a polybasic acid anhydride are performed to the terminal hydroxyl group produced by the addition reaction of an alkylene oxide or a cyclocarbonate compound, each unsaturated group and a carboxyl group do not exist on the same side chain, respectively. Since it is located at the end of the side chain, it has excellent reactivity. In addition, it has excellent alkali developability due to the presence of terminal carboxyl groups separated from the main chain. In addition, since it does not have or has only a small hydrophilic alcoholic hydroxyl group with low reactivity, since it has excellent hygroscopic resistance, it is estimated that it will lead to the improvement of PCT tolerance required for an IC package. However, on the other hand, adhesiveness with a base material and a support body is weak compared with other resin, and sufficient electroless-plating resistance and cold-heat shock resistance cannot be obtained in the obtained hardened | cured material.

On the other hand, carboxyl group-containing photosensitive resin (B) can improve flexibility by chain extension by addition reaction of carboxyl group-containing resin and the compound which has cyclic ether group and ethylenically unsaturated group together in 1 molecule. Moreover, since it has a photosensitive group of a side chain terminal, the outstanding photoreactivity can be obtained. Moreover, the adhesiveness with a base material improves by the effect of the hydroxyl group produced | generated at the time of addition reaction with a carboxyl group-containing resin, electroless plating property becomes favorable, and it becomes possible to improve cold-heat shock resistance by improving flexibility. .

Therefore, as resin used together with carboxyl group-containing resin (A), resin which shows alkali developability, is effective for high sensitivity, and is excellent in adhesiveness with various base materials, and provides the cured film which has the outstanding characteristic, ie, carboxyl group-containing It is used combining the carboxyl group-containing photosensitive resin (B) obtained by making resin react with the compound which has a cyclic ether group and ethylenically unsaturated group together in 1 molecule.

Hereinafter, the curable resin composition of this embodiment is demonstrated in detail.

In curable resin composition of this embodiment, carboxyl group-containing resin (A) which does not use an epoxy resin as a starting material is included. As such carboxyl group-containing resin (A), it is preferable that a carboxyl group-containing resin is carboxylic acid containing photosensitive resin which has an ethylenically unsaturated double bond in a molecule | numerator from a photocurability and developability resistance. The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. The specific example thereof is shown below.

(1) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups with an alkylene oxide such as ethylene oxide and propylene oxide in a molecule, and a polybasic anhydride is added to the reaction product obtained. Carboxyl group containing photosensitive resin obtained by making it react.

(2) Polybasic acid anhydride to the reaction product obtained by making unsaturated group containing monocarboxylic acid react with the reaction product obtained by making the compound which has two or more phenolic hydroxyl groups in 1 molecule, and cyclic carbonate compounds, such as ethylene carbonate and a propylene carbonate, react. Carboxyl group containing photosensitive resin obtained by making it react.

(3) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A terminal carboxyl group-containing urethane resin formed by making an acid anhydride react with the terminal of the urethane resin by polyaddition reaction of diol compounds, such as A type | system | group alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group, and alcoholic hydroxyl group.

(4) During the synthesis of the carboxyl group-containing urethane resin by the polyaddition reaction of the diisocyanate, the carboxyl group-containing dialcohol compound and the diol compound, one hydroxyl group and at least one (meth) in a molecule such as hydroxyalkyl (meth) acrylate. The carboxyl group-containing urethane resin which added the compound which has acryloyl group, and was terminal (meth) acrylated.

(5) During the synthesis of the carboxyl group-containing urethane resin by the polyaddition reaction of the diisocyanate with the carboxyl group-containing dialcohol compound and the diol compound, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule is added to the terminal ( (Meth) acrylated carboxyl group-containing urethane resin.

(6) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

In addition, (meth) acrylate generically refers to acrylate, methacrylate, and mixtures thereof, and the same also applies to other similar expressions below.

Since such carboxyl group-containing resin (A) does not use an epoxy resin as a starting material, it has the characteristic that content of chlorine ion impurity is very small. Chlorine ion impurity content of carboxyl group-containing resin (A) is 0-100 ppm, More preferably, it is 0-50 ppm, More preferably, it is 0-30 ppm.

Moreover, such a carboxyl group-containing resin (A) is also characterized by being a resin that does not contain a hydroxyl group. In general, the presence of a hydroxyl group also has excellent characteristics such as improvement of adhesion by hydrogen bonding, but is known to significantly lower moisture resistance.

In such carboxyl group-containing resin (A), the phenol novolak resin without chlorine content can be obtained easily. Then, this is alkyl oxide-modified, and partially acrylates the obtained phenol resin-derived polyol and introduces an acid anhydride to the remaining hydroxyl group, thereby theoretically having no hydroxyl group in the range of double bond equivalence 300 to 550 and acid value 40 to 150. It is possible to obtain a resin. In addition, the chlorine ion as an impurity at this time can be made into the very few states 20 ppm or less.

On the other hand, in the epoxy acrylate modified resin used for the general soldering resist, it is possible to acrylate all the epoxy groups of the epoxy resin synthesize | combined with the similar phenol novolak resin, and to introduce | transduce an acid anhydride into the produced hydroxyl group. However, a large amount of chlorine ions derived from epoxy resins remain, and a large amount of hydroxyl groups are produced when acrylated, and even if all or partly denatures to an acid anhydride, the acid value becomes very large or the hydroxyl groups remain, resulting in poor water resistance, insulation reliability, Significantly lowers PCT resistance. That is, it is very difficult to reduce chlorine ions and hydroxyl groups from epoxy acrylate resins derived from similar phenol novolac epoxy resins.

Moreover, the urethane resin can also easily synthesize | combine resin which does not contain a hydroxyl group by combining the equivalent of a hydroxyl group and an isocyanate group. Among these, it is preferable to synthesize | combine from the isocyanate compound which does not use phosgene as a starting material, and the raw material which does not use epihalohydrin. In these, it is preferable that halogen amount is 0-30 ppm, and it is more preferable to synthesize | combine so that a hydroxyl group may not be included in theory.

In addition, resins obtained by copolymerization generally have very few chlorine ion impurities, and show excellent insulation reliability.

Moreover, as a carboxyl group-containing photosensitive resin (B) obtained by making the compound which has a cyclic ether group and ethylenically unsaturated group together in 1 molecule mentioned later, 1 molecule with respect to the carboxyl group-containing resin (A) of above-mentioned (1)-(6) What reacted the compound which has a cyclic ether group and ethylenically unsaturated group together in the inside can also be used.

Chlorine of the carboxyl group-containing photosensitive resin (B) obtained by using such a carboxyl group-containing photosensitive resin (B) synthesized by a method using peracetic acid method rather than epoxidation using epihalohydrin in the introduction of an epoxy group at the time of synthesis. It is possible to further reduce the amount of ionic impurities. In addition, by using 3,4-epoxycyclohexylmethyl methacrylate, it becomes possible to reduce the amount of chlorine ion impurities.

The carboxyl group-containing photosensitive resin (A) is obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups with an alkylene oxide or a cyclocarbonate compound in one molecule. It is preferable that it is obtained by making a polybasic acid anhydride react with a reaction product.

Examples of the compound having two or more phenolic hydroxyl groups in one molecule include catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylcatechol, t-butylhydroquinone, pyrogallol, fluoroglucinol, Bisphenol A, bisphenol F, bisphenol S, biphenol, bixylenol, novolak-type phenol resin, novolak-type alkylphenol resin, novolak resin of bisphenol A, dicyclopentadiene type phenol resin, Xylok type Phenol resins, terpene-modified phenol resins, polyvinylphenols, condensates of phenols with aromatic aldehydes having phenolic hydroxyl groups, and condensates of 1-naphthol or 2-naphthol with aromatic aldehydes, but are not limited thereto. It doesn't happen. These phenolic hydroxyl group containing compounds can be used individually or in mixture of 2 or more types.

Ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran etc. are mentioned as alkylene oxide. These alkylene oxides can be used individually or in mixture of 2 or more types.

A well-known carbonate compound can be used as a cyclocarbonate compound, For example, ethylene carbonate, a propylene carbonate, butylene carbonate, 2, 3- carbonate propyl methacrylate, etc. are mentioned. Among these, 5-membered ring ethylene carbonate and propylene carbonate are preferable from the viewpoint of reactivity and supply system. These carbonate compounds can be used individually or in mixture of 2 or more types.

The alkylene oxide or cyclocarbonate compound can be modified to a resin having an alcoholic hydroxyl group from the phenolic hydroxyl group by addition reaction using a basic catalyst to the phenolic hydroxyl group of the compound having the phenolic hydroxyl group. As addition amount at this time, it is preferable that it is the range of 0.3-1.5 mol per equivalent of phenolic hydroxyl group. When the addition amount is less than 0.3 mol, the reaction with the unsaturated group-containing monocarboxylic acid or polybasic acid anhydride described later becomes difficult, and the photosensitivity and the solubility in the diluted alkaline aqueous solution are lowered. On the other hand, when addition amount exceeds 1.5, water resistance will fall by ether bond produced, and electrical insulation, HAST tolerance, etc. will fall. More preferably, it is the range of 0.8-1.2 mol, More preferably, it is the range of 0.9-1.1 mol.

As an unsaturated group containing monocarboxylic acid, acrylic acid, methacrylic acid, or hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di ( Hydroxyl group-containing acrylates such as meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adducts And unsaturated dibasic acid anhydride adducts. Among these, acrylic acid and / or methacrylic acid are particularly preferable. These unsaturated group containing monocarboxylic acids can be used individually or in combination of 2 or more types.

As polybasic acid anhydride, methyltetrahydro phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, nad acid anhydride, 3,6- endomethylenetetrahydro phthalic anhydride, methylendomethylene tetrahydro phthalic anhydride, tetra Alicyclic dibasic acid anhydrides such as bromo phthalic anhydride; Aliphatic or aromatic dibasic anhydrides such as succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, or biphenyltetracarboxylic dianhydride, diphenyl Aliphatic or aromatic tetrabasic dianhydrides, such as ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride Can be. These polybasic acid anhydrides can be used individually or in combination of 2 or more types.

The carboxyl group-containing photosensitive resin (B) used in the curable resin composition of the present embodiment is obtained by reacting a carboxyl group-containing resin with a compound having a cyclic ether group and an ethylenically unsaturated group in one molecule.

The carboxyl group-containing resin used in such carboxyl group-containing photosensitive resin (B) is resin containing a carboxyl group in a molecule | numerator. In particular, in view of photocurability and developability, a carboxylic acid-containing photosensitive resin having an ethylenically unsaturated double bond in a molecule is preferable. The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. A specific example is shown below.

(1) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide, propylene oxide, and the like. Carboxyl group containing photosensitive resin obtained by making it react.

(2) Polybasic acid anhydride to the reaction product obtained by making unsaturated group containing monocarboxylic acid react with the reaction product obtained by making the compound which has two or more phenolic hydroxyl groups in 1 molecule, and cyclic carbonate compounds, such as ethylene carbonate and a propylene carbonate, react. Carboxyl group containing photosensitive resin obtained by making it react.

(3) Carboxyl group-containing resin obtained by copolymerization of (meth) acrylic acid and an unsaturated group containing thing.

(4) Carboxylic acid containing urethane resin by polyaddition reaction of diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound.

(5) Photosensitive carboxylic acid containing urethane resin by polyaddition reaction of diisocyanate, bifunctional epoxy (meth) acrylate, or its partial acid anhydride modified substance, and a carboxyl group-containing dialcohol compound and a diol compound.

(6) Carboxylic acid-containing urethane resin which terminal (meth) acrylated by adding the compound which has one hydroxyl group and 1 or more (meth) acryl group in a molecule | numerator during synthesis | combination of resin of (4) or (5).

(7) The carboxylic acid-containing urethane resin which terminal (meth) acrylated by adding the compound which has one isocyanate group and one or more (meth) acryl groups in a molecule | numerator during the synthesis | combination of resin of (4) or (5).

(8) Photosensitive carboxyl group-containing resin which made (meth) acrylic acid react with bifunctional and polyfunctional (solid) epoxy resin, and added dibasic acid anhydride to the hydroxyl group which exists in a side chain.

(9) The photosensitive carboxyl group which the (meth) acrylic acid reacted with the polyfunctional epoxy resin which further epoxidized the hydroxyl group of bifunctional (solid) epoxy resin with epichlorohydrin, and added the dibasic acid anhydride to the produced hydroxyl group is contained. Suzy.

(10) A carboxylic acid-containing polyester resin in which dicarboxylic acid is reacted with a bifunctional oxetane resin and dibasic acid anhydride is added to the produced primary hydroxyl group.

And the carboxyl group-containing photosensitive resin (B) of this embodiment is formed by adding the compound which has cyclic ether group and ethylenically unsaturated group together in 1 molecule with respect to resin shown to these (1)-(10).

As a compound which has a cyclic ether group and ethylenically unsaturated group together in 1 molecule, 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxypropyl (Meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate Glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl methyl acrylate, etc. are mentioned. Among them, one epoxy group and one in one molecule such as glycidyl (meth) acrylate or 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate in terms of reactivity and supply system. Preference is given to compounds having at least two (meth) acryl groups. These compounds may be used alone or in combination of two or more.

It is preferable that the addition amount of the compound which has a cyclic ether group and ethylenically unsaturated group together in such one molecule is 5 to 40% equivalent with respect to an acid anhydride residue. When the addition amount is less than 5% equivalent, a sufficient increase in sensitivity and an improvement in electroless gold plating resistance are not obtained. When the addition amount exceeds 40% equivalent, the maximum developing life is shortened and the touch drying property is deteriorated. More preferably, they are 10% equivalent-30% equivalent.

Although the compounding ratio of such carboxyl group-containing photosensitive resin (A) and carboxyl group-containing photosensitive resin (B) is suitably set according to the objective, it is 70: 30-30: carboxyl group-containing photosensitive resin (B) with respect to carboxyl group-containing photosensitive resin (A). It is preferable to mix | blend in the ratio of 70. When the compounding ratio of carboxyl group-containing photosensitive resin (A) is less than 30, alkali developability will fall and it is unpreferable.

Moreover, it is preferable that the sum total acid value of these carboxyl group-containing photosensitive resin (A) and (B) exists in the range of 30-150 mgKOH / g. When the acid value after the compounding of the carboxyl group-containing photosensitive resins (A) and (B) is lower than 30 mgKOH / g, solubility in an aqueous alkali solution is lowered, and development of the formed coating film becomes difficult. On the other hand, if it is higher than 150 mgKOH / g, since the dissolution of the exposed portion by the developing solution proceeds, the line becomes thinner than necessary, or is melted and peeled off by the developing solution without distinguishing between the exposed portion and the unexposed portion, making it difficult to draw a normal resist pattern. There may be a case. More preferably, it is 40-110 mgKOH / g.

Moreover, in this invention, it is also possible to use well-known carboxylic acid resin together. However, although it can be used for various purposes, such as adjusting the photoreactivity, developability balance, etc., in general, when an epoxy resin is used as a starting material, since chlorine ion impurity increases, it is used after considering these. It is desirable to.

Moreover, as a photoinitiator, the oxime ester system photoinitiator which has group represented by following formula (1), the (alpha)-amino acetophenone system photoinitiator which has group represented by following formula (2), and / or the acyl group which has group represented by following formula (3) It is preferable to use 1 or more types of photoinitiators selected from the group which consists of a pin oxide type photoinitiator.

Wherein R ¹ may be substituted with a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), or an alkyl group having 1 to 20 carbon atoms with one or more hydroxyl groups, May have one or more oxygen atoms in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (can be substituted with one or more hydroxyl groups, and at least one oxygen atom in the middle of the alkyl chain May be substituted), 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 ³ and R ⁴ are each independently , An alkyl group having 1 to 12 carbon atoms or an arylalkyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkylether group having two bonds, and R ⁷ and R ⁸ are each independently To 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, provided that one of R ⁷ and R ⁸ is RC (= O) -group, where R can be represented by a hydrocarbon group of 1 to 20 carbon atoms.

Here, as an oxime ester type photoinitiator which has group represented by General formula (1), Preferably, 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by following General formula (4), the compound represented by following General formula (5), and the following The compound represented by General formula (6) is mentioned.

(Wherein 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, and a carbon having 2 to 12 carbon atoms). An alkoxycarbonyl group (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbonyl group , R ¹⁰ , R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (can be substituted with one or more hydroxyl groups, the middle of the alkyl chain May be substituted with one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (alkyl group having 1 to 6 carbon atoms or a phenyl group). R ¹¹ 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 (can be substituted with one or more hydroxyl groups, and May have one or more oxygen atoms in the middle), 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 or a phenyl group having 1 to 6 carbon atoms)

(Wherein, R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, R ¹⁵ , R ¹⁶ , R ^17, and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 5) Among these, 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by the formula (4) and the compound represented by the formula (5) are more preferable. As a commercial item, CGI-325, Irgacure OXE01, Irgacure OXE02, etc. made by Ciba Specialty Chemicals, etc. are mentioned. These oxime ester photoinitiators can be used individually or in combination of 2 or more types.

As the α-aminoacetophenone-based photopolymerization initiator having a group represented by the formula (2), for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-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, etc. are mentioned. As a commercial item, Irgacure 907, Irgacure 369, Irgacure 379 by Ciba Specialty Chemicals, etc. are mentioned.

And as an acyl phosphine oxide type photoinitiator which has group represented by General formula (3), 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6- trimethyl benzoyl)-phenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide etc. are mentioned. As a commercial item, Lucirin TPO by BASF Corporation, Irgacure 819 by Ciba Specialty Chemicals Corporation, etc. are mentioned.

The compounding quantity of such a photoinitiator can be suitably set in 0.01-30 mass parts with respect to 100 mass parts of mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). If it is less than 0.01 mass part, since the photocurability on copper is inadequate and a coating film peels off or coating film properties, such as chemical resistance, fall, it is unpreferable. On the other hand, when it exceeds 30 mass parts, the light absorption in the soldering resist coating film surface of a photoinitiator will become severe, and there exists a tendency for core part hardenability to fall. More preferably, it is the range of 0.5-15 mass parts.

In addition, in the case of the oxime ester type photoinitiator which has group represented by General formula (1), it is preferable that the compounding quantity shall be 0.01-20 mass parts with respect to 100 mass parts of mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). . More preferably, it is 0.01-5 mass parts.

In addition, as a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for curable resin composition of this embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, k An acid compound, a tertiary amine compound, and the like.

Here, as a benzoin compound, a benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether is mentioned specifically ,.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone. Can be.

As an anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, and 1-chloro anthraquinone are mentioned specifically ,.

Specific examples of the thioxanthone compound include 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, and 2,4-diisopropyl thioxanthone. Can be mentioned.

Specifically as a ketal compound, acetophenone dimethyl ketal and benzyl dimethyl ketal are mentioned, for example.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4 -Benzoyl-4'-propyldiphenyl sulfide is mentioned.

Specifically as a tertiary amine compound, For example, an ethanolamine compound, the compound which has a dialkylaminobenzene structure, for example, 4,4'- dimethylamino benzophenone (Nissocure MABP by Nippon Soda Co., Ltd.), 4 Dialkylaminobenzophenone, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one, such as 4, 4- diethylamino benzophenone (EAB by Hodogaya Chemical Co., Ltd.) (7) Dialkylamino group-containing coumarin compounds such as-(diethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Gayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (international bio-synthetics) Quantacure DMB, 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics Co., Ltd.), p-dimethylaminobenzoic acid isoamyl ethyl ester (Nippon Kaya Co., Ltd.) Gayacure DMBI), 2-ethylhexyl 4-dimethylaminobenzoic acid (Ban Die) Esolol 507 by Van Dyk, and 4,4'- diethylamino benzophenone (EAB by Hodogaya Chemical Co., Ltd.) are mentioned.

Among these, thioxanthone compounds and tertiary amine compounds are preferable. It is preferable that a thioxanthone compound is contained in the composition of this embodiment from the point of deep-hardening, Especially, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2 Thioxanthone compounds, such as a 4-4-isoiso thioxanthone, are more preferable.

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 mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). When the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product. More preferably, it is 10 mass parts 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 in view of low toxicity.

The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has little coloration because the maximum absorption wavelength is in the ultraviolet region, and reflects the color of the color pigment itself using a color pigment as well as a colorless transparent photosensitive composition. It is possible to provide a colored solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

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 mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). If the compounding quantity of a tertiary amine compound is less than 0.1 mass part, it will become difficult to acquire sufficient sensitization effect. On the other hand, when it exceeds 20 mass parts, the light absorption in the surface of the dry solder resist coating film by a tertiary amine compound will become deep, and there exists a tendency for deep-part sclerosis | hardenability to fall. More preferably, it is 0.1-10 mass parts.

These photoinitiators, photoinitiator, and sensitizer can be used individually or as a mixture of 2 or more types.

It is preferable that the total amount of such a photoinitiator, a photoinitiator, and a sensitizer will be 35 mass parts or less with respect to 100 mass parts of mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

In addition, the following additives can be used.

<< chain transfer agent >>

In this embodiment, in order to improve the sensitivity, known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as the chain transfer agent. Specific examples include chain transfer agents having carboxyl groups such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; Chain transfer agents having hydroxyl groups such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol and the like.

Moreover, a polyfunctional mercaptan type compound can be used, Although it is not specifically limited, For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulphur Aromatic thiols such as aliphatic thiols such as a feed, xylylenedimercaptan, 4,4'-dimercaptodiphenyl sulfide, and 1,4-benzenedithiol; Ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris ( Poly (mercaptoacetates) of polyhydric alcohols such as mercaptoacetate), pentaerythritol tetrakis (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), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3 Poly (3-mercaptopropionate) of polyhydric alcohols such as mercaptopropionate); 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, Poly (mercaptobutyrate), such as 3H, 5H) -trione and pentaerythritol tetrakis (3-mercaptobutyrate), can be used.

Moreover, as a heterocyclic compound which has a mercapto group which functions as a chain transfer agent, For example, mercapto-4-butyrolactone (nickname: 2-mercapto-4-butanolide), 2-mercapto-4-methyl 4-butyrolactone, 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-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam , N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam and 2-mercapto-6- Hexanolactam etc. are mentioned.

Especially as a heterocyclic compound which has a mercapto group which is a chain transfer agent which does not impair developability of a photocurable resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, Preference is given to 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents can use together single or 2 types or more.

"diluent"

Moreover, a diluent may be used in order to insolubilize a carboxyl group-containing resin in aqueous alkali solution by photocuring by active energy ray irradiation, or to help insolubilization. As such a diluent, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric alcohols such as ethylene oxide adducts or propylene oxide adducts; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine acrylate, and / or each methacrylate corresponding to the acrylate.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, in the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin further, Epoxy urethane acrylate compounds etc. which reacted the half urethane compound of diisocyanate, such as isophorone diisocyanate, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

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

<< thermosetting ingredient >>

A thermosetting component can be added to impart heat resistance. As the thermosetting component used in the present embodiment, an amine resin such as melamine resin, benzoguanamine resin, bismaleimide, benzoxazine compound, oxazoline compound, carbodiimide resin, block isocyanate compound, cyclocarbonate compound, Known thermosetting resins such as functional epoxy compounds, polyfunctional oxetane compounds, episulfide resins and melamine derivatives can be used. Especially preferred are thermosetting components having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

The thermosetting component having two or more cyclic (thio) ether groups in such a molecule is a compound having at least two or three or more groups of 3, 4 or 5 membered cyclic ether groups or cyclic thioether groups in the molecule, for example For example, a compound having at least two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound, a compound having at least two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound, a compound having two or more thioether groups in a molecule, That is, episulfide resin etc. are mentioned.

Examples of the polyfunctional epoxy compound include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Epiclone 840, Epiclone 850, and Epiclone manufactured by Dainippon Ink & Chemical Co., Ltd. 1050, Epiclone 2055, Efototo YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., DER317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd., Ciba Specialty Chemical Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Bisphenol A type epoxy resins, such as AER330, AER331, AER661, and AER664, which are all manufactured by high school company; Epicoat YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclone 152, Epiclone 165, manufactured by Dainippon Ink & Chemicals Co., Ltd., Efototo YDB-400, YDB-500, manufactured by Toto Kasei Co., Ltd., DER542, manufactured by Dow Chemical Co., Ltd. Brominated epoxy resins, such as Araldide 8011 by Shiba Specialty Chemicals, Sumitomo Chemical Co., Ltd., Sumiepoxy ESB-400, ESB-700, Asahi Kasei Kogyo AER711, and AER714 (all brand names); Epicoat 152, Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., Epiclone N-730, Epiclone N-770, Epiclone N- 865, Efototo YDCN-701, YDCN-704, Arodaide ECN1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307 by Nippon Kayaku Co., Ltd. -201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumier epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN-299 Novolak-type epoxy resins, such as (all are brand names); Epiclone 830, manufactured by Dainippon Ink Industries, Inc., Epicoat 807, manufactured by Japan Epoxy Resin Co., Ltd., Efototo YDF-170, YDF-175, YDF-2004, manufactured by Tohto Kasei Co., Ltd., Aral, manufactured by Ciba Specialty Chemicals, Inc. Bisphenol F-type epoxy resins, such as DID XPY306 (all are brand names); Hydrogenated bisphenol A type epoxy resins such as Efototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; Epicoat 604, manufactured by Japan Epoxy Resin Co., Ltd., Efototo YH-434, manufactured by Toto Kasei Co., Ltd., Araldide MY720, manufactured by Ciba Specialty Chemicals, Sumitomo Chemical Co., Ltd., Sumiepoxy ELM-120, etc. Glycidyl amine epoxy resins; Hydantoin type epoxy resins, such as Araldide CY-350 (brand name) by the Ciba Specialty Chemicals company; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldide CY175 manufactured by Ciba Specialty Chemicals, Inc. (CY179), and the like; Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Co., Ltd. (both trade names); Bixylenol type or biphenol type epoxy resins, such as YL-6056, YX-4000, and YL-6121 (all are brand names) by the Japan epoxy resin company, or mixtures thereof; Bisphenol S-type epoxy resins, such as EBPS-200 by Nippon Kayaku Co., Ltd., EPX-30 by Asahi Denka Kogyo Co., Ltd., and EXA-1514 (brand name) by Dainippon Ink & Chemicals Co., Ltd .; Bisphenol A novolak-type epoxy resins, such as Epicoat 157S (brand name) by the Japan epoxy resin company; Tetraphenylolethane type epoxy resins, such as Epicoat YL-931 by the Japan epoxy resin company, Araldide 163 by Ciba Specialty Chemicals, Inc. (all are brand names); Heterocyclic epoxy resins, such as Araldide PT810 by Ciba Specialty Chemicals Co., Ltd. and TEPIC by Nissan Chemical Industries, Ltd. (all are brand names); Diglycidyl phthalate resins such as Bremmer DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Shinnitetsu Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink & Chemicals Co., Ltd .; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals, Incorporated; Glycidyl methacrylate copolymer type epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd .; Furthermore, copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Toto Kasei Co., Ltd.), and the like. However, it is not limited to these. These epoxy resins may be used alone or in combination of two or more. Especially among these, a novolak-type epoxy resin, a heterocyclic epoxy resin, a bisphenol-A epoxy resin, or a mixture thereof is preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether and 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylic Latex, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, calix arenes, calyx resorcinrenes, or seals Ether ether with resin which has hydroxyl groups, such as a sesquioxane, etc. are mentioned. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound which has a 2 or more cyclic thioether group in a molecule | numerator, bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used using the same synthesis method.

The compounding quantity of the thermosetting component which has two or more cyclic (thio) ether groups in these molecules is 0.6-2.5 equivalents of cyclic (thio) ether group with respect to 1 equivalent of carboxyl groups of the mixture of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). Is preferably. When the compounding quantity of the thermosetting component which has two or more cyclic (thio) ether groups in a molecule | numerator is less than 0.6, a carboxyl group will remain in a soldering resist film, and heat resistance, alkali resistance, electrical insulation, etc. will fall. On the other hand, when it exceeds 2.5 equivalent, the low molecular weight cyclic (thio) ether group remains in a dry coating film, and the intensity | strength of a coating film, etc. fall. More preferably, it is 0.8-2.0 equivalent.

<< thermosetting catalyst >>

When using the thermosetting component which has two or more cyclic (thio) ether group in such a molecule, it is preferable to contain a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenyl are Imidazole derivatives such as midazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic dihydrazide and sebacic acid dihydrazide; As commercially available things, such as phosphorus compounds, such as a triphenylphosphine, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole type compound), acid by Shikoku Kasei Kogyo Co., Ltd. Aprosa-made U-CAT3503N, U-CAT3502T (all are brand names of the block isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compound and its salt), etc. are mentioned. In particular, it is not limited to these, What is necessary is just to accelerate | stimulate reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group. You may use these individually or in mixture of 2 or more types. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid S-triazine derivatives, such as an addition product, can also be used. It is more preferable to use the compound which also functions as these adhesive imparting agents together with a thermosetting catalyst.

The compounding quantity of these thermosetting catalysts should just be a normal quantity ratio, for example, the mixture of a carboxyl group-containing resin (A) and a carboxyl group-containing photosensitive resin (B), or the thermosetting component which has 2 or more cyclic (thio) ether group in a molecule | numerator. It is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts. More preferably, it is 0.5-15.0 mass parts.

<< isocyanate derivative >>

Moreover, in curable resin composition of this embodiment, in order to improve the hardenability of the photosensitive resin composition and the toughness of the cured film obtained, the compound which has two or more isocyanate groups or blocked isocyanate groups can be added in 1 molecule. 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 a compound having two or more blocked isocyanate groups in one molecule, that is, a block isocyanate compound Etc. can be mentioned.

As a polyisocyanate 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-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. Moreover, the adduct, biuret, and isocyanurate body of the above-mentioned isocyanate compound are mentioned.

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

As a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, an isocyanurate type, a biuret type, an adduct type, etc. are mentioned. 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-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.

As an isocyanate blocking agent, For example, phenol type blocking agents, such as phenol, cresol, xylenol, chlorophenol, and ethyl phenol; lactam block agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; Active methylene blockers 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, glycol Alcohol blocking agents such as butyl acid, diacetone alcohol, methyl lactate and ethyl lactate; Oxime blocking agents such as formaldehyde oxime, acetaldehyde, acetoxime, methyl ethyl ketoxime, diacetyl monooxime and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; Acid amide block agents such as acetic amide and benzamide; Imide block agents such as succinic acid imide and maleic acid imide; Amine blocking agents such as xyldine, aniline, butylamine and dibutylamine; Imidazole blockers such as imidazole and 2-ethylimidazole; And imine-based blocking agents such as methyleneimine and propyleneimine.

Such block isocyanate compounds may be commercially available, for example, smidule BL-3175, BL-4165, BL-1100, BL-1265, death module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117 Desmosam 2170, Desmosam 2265 (more than Sumitomo Bayer urethane company make, brand name), colonate 2512, colonate 2513, colonate 2520 (more, Nippon Polyurethane high school company make, brand name), B-830, B- 815, B-846, B-870, B-874, B-882 (made by Mitsui Takeda Chemical, make, brand name), TPA-B80E, 17B-60PX, E402-B80T (made by Asahi Kasei Chemicals make, brand name), etc. are mentioned. Can be. In addition, the smead BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compound which has two or more isocyanate groups or blocked isocyanate groups in such one molecule can be used individually by 1 type or in combination of 2 or more types.

It is preferable that the compounding quantity of the compound which has two or more isocyanate groups or a blocked isocyanate group in 1 molecule is 1-100 mass parts with respect to 100 mass parts of mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). In the case of less than 1 mass part, sufficient toughness of a coating film is not acquired, and when it exceeds 100 mass parts, storage stability falls. More preferably, it is the ratio of 2-70 mass parts.

<< urethanization catalyst >>

In addition, a urethanization catalyst can be added to curable resin composition of this embodiment in order to accelerate hardening of a hydroxyl group and an isocyanate group. As the urethane-forming catalyst, it is preferable to use at least one urethane-forming catalyst selected from the group consisting of tin catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds and / or amine salts.

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

Examples of the metal chlorides include chlorides of metals composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, for example, cobalt chloride, nickel nickel chloride, and ferric chloride.

As the metal acetylacetonate salt, as the acetylacetonate salt of a metal consisting of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate and the like Can be.

As a metal sulfate, copper sulfate etc. are mentioned as a sulfate of the metal which consists of Cr, Mn, Co, Ni, Fe, Cu, or Al.

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-dimethyl Aminoethoxyethanol, 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) isopropane Olamine, 2-aminoquinuclidin, 3-aminoquinuclidin, 4-aminoquinuclidin, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1- (2'-hydroxy Propyl) imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- (2'-hydroxyethyl) -2-methyl Imidazole, 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) Amines, 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 and / Or benzoguanamine etc. are mentioned.

As an amine salt, the organic acid salt type | system | group amine salt of DBU (1,8- diaza-bicyclo [5,4,0] undecene-7), etc. are mentioned, for example.

A compounding quantity of a urethanation catalyst may be sufficient as a normal quantity ratio, For example, with respect to 100 mass parts of mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B), 0.1-20.0 mass parts is more preferable. Preferably from 0.5 to 10.0 parts by mass.

<< melamine derivative >>

Moreover, a melamine derivative, a benzoguanamine derivative, etc. are mentioned as a thermosetting component. For example, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned. In addition, the alkoxy methylated melamine compound, the alkoxy methylated benzoguanamine compound, the alkoxy methylated glycoluril compound and the alkoxy methylated urea compound are the respective methylol melamine compounds, the methylol benzoguanamine compounds, the methylol glycoluril compounds and the methylol urea compounds. Obtained by converting a methylol group into an alkoxymethyl group. It does not specifically limit about the kind of this alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. In particular, melamine derivatives having a concentration of 0.2% or less of formalin, which is human or environmentally friendly, are preferable.

As these commercial items, for example, Cymel 300, East 301, East 303, East 370, East 325, East 327, East 701, East 266, East 267, East 238, East 1141, East 272, East 202, East 1156 , Copper 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300 (above, Mitsui Cyanamid Co., Ltd.), Nikalac Mx-750, copper Mx-032, copper Mx-270, copper Mx- 280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30 HM, Mw-390, Mw -100 LM, copper Mw-750 LM (above, Sanwa Chemical Co., Ltd.), etc. are mentioned.

These thermosetting components can be used individually or in combination of 2 or more types.

<< adhesion grant agent >>

In addition, in the curable composition of this embodiment, in order to improve adhesiveness between layers or adhesiveness with a base material, an adhesion imparting agent can be used. Specifically, for example, benzoimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Kagaku) Excel M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto by the Kogyo Co., Ltd. -5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

"coloring agent"

Moreover, a coloring agent can be mix | blended. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. However, from the viewpoint of reducing the environmental load and the effect on the human body, it is preferable not to contain a halogen.

(Blue colorant)

Phthalocyanine type and anthraquinone type can be mentioned as a blue coloring agent. Among these, Pigment Blue 15, Pigment, which is labeled with a compound classified as Pigment in the pigment system, specifically, the following color index (CI; issued by The Society of Dyers and Colourists) 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 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 Blue 70, etc. can be used. In addition to these, a metal substituted or unsubstituted phthalocyanine compound can also be used.

(Green colorant)

Similar 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 and the like can be used. In addition to these, a metal substituted or unsubstituted phthalocyanine compound can also be used.

(Yellow colorant)

Examples of the yellow colorant include anthraquinones, isoindolinones, condensed azos, benzimidazolones, monoazos, and disazos. Specifically, the following can be used.

As an anthraquinone type, solvent yellow 163, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202, etc. are used.

As the isoindolinone series, Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185 and the like are used.

As the condensed azo system, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180 and the like are used.

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

As a monoazo system, 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 and the like are used.

As the disazo system, pigment yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and the like are used.

(Red colorant)

Examples of the red colorant include monoazo, disazo, monoazo lakes, benzimidazolones, perylenes, diketopyrrolopyrroles, condensed azos, anthraquinones and quinacridones. Specifically, the following can be used.

As a monoazo system, 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 and the like are used.

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

As a monoazo lake system, 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 and the like.

As the benzimidazolone system, Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208 and the like are used.

As the perylene system, 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 and the like are used.

As the diketopyrrolopyrrole system, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272 and the like are used.

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

As an anthraquinone type, Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207 and the like are used.

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, coloring agents such as purple, orange, brown, and 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, and C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73, C.I. Pigment Brown 23, C.I. Pigment Brown 25, 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 mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). More preferably, it is 0.1-5 mass parts.

"filling"

Moreover, a filler can be mix | blended as needed in order to raise the physical strength of the coating film, etc. As such a filler, known inorganic or organic fillers can be used, but barium sulfate, spherical silica and talc are particularly preferably used. In addition, metal hydroxides such as titanium oxide, metal oxides and aluminum hydroxide can also be used as extender pigment fillers in order to obtain a white appearance and flame retardancy. In addition, nanocryl (NANOCRYL; trade name) manufactured by Hanse-Chemie, in which nanosilica is dispersed in a compound having at least one ethylenically unsaturated group or the polyfunctional epoxy resin (D-1), XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade name) and Hanse Chemical Co., Ltd. (nanopox; brand name) XP 0516, XP 0525, XP 0314 (all product class names) may also be used. These fillers may 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 (A). When the compounding quantity of a filler exceeds 300 mass parts, the viscosity of a photosensitive composition becomes high, printability falls, or hardened | cured material becomes weak. More preferably, it is 0.1-300 mass parts, Especially preferably, it is 0.1-150 mass parts.

Binder Polymer

In addition, a binder polymer can be used for the purpose of improving the touch dryness, the handleability, and the like. For example, polyester type polymer, polyurethane type polymer, polyester urethane type polymer, polyamide type polymer, polyesteramide type polymer, acrylic type polymer, cellulose type polymer, polylactic acid type polymer, phenoxy clock polymer, etc. can be used. These binder polymers can be used alone or as a mixture of two or more thereof.

Elastomer

Moreover, an elastomer can be used for the purpose of providing flexibility, improving the fragility of hardened | cured material, etc. For example, polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers can be used. Moreover, the resin etc. which modified | denatured the epoxy group of one part or all part of the epoxy resin which has a various skeleton with both terminal carboxylic acid modified butadiene- acrylonitrile rubber can also be used. Furthermore, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl-containing polybutadiene-based elastomers, hydroxyl-containing isoprene-based elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more thereof.

<< organic solvent >>

Moreover, the organic solvent can be used for the synthesis | combination of carboxyl group-containing photosensitive resin (A), adjustment of a composition, or 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, and petroleum solvents. 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 ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or as a mixture of two or more thereof.

<< antioxidant >>

Since most of the polymer material is oxidatively deteriorated serially once after oxidation has started, resulting in a decrease in the function of the polymer material, in the curable resin composition of the present embodiment, (1) the radicals generated in order to prevent oxidation are invalidated. It is possible to add an antioxidant such as a radical scavenger and / or (2) a peroxide decomposing agent which decomposes the generated peroxide into a harmless substance and prevents generation of new radicals.

As antioxidant which functions as a radical trapping agent, as a specific compound, hydroquinone, 4-t- butylcatechol, 2-t- butyl hydroquinone, hydroquinone monomethyl ether, 2, 6- di-t- butyl- p-cresol, 2 , 2-methylene-bis- (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'di-t-butyl-4 Phenolic compounds such as -hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6, And amine compounds such as 6-tetramethyl-4-piperidyl) -sebacate and phenothiazine.

Antioxidant which functions as such a radical trapping agent can use a commercially available thing, For example, Adeka stab AO-30, Adeka stab AO-330, Adeca stab AO-20, Adeka stab LA- 77, Adeka stab LA-57, Adeka stab LA-67, Adeka stab LA-68, Adeka stab LA-87 (above, Asahi Denka Co., brand name), Irganox (IRGANOX) 1010, Irganox 1035, Irganox 1076, Irganox 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Specialty Chemicals Co., Ltd.) Manufacture, brand name), etc. are mentioned.

As antioxidant which functions as a peroxide decomposition agent, As a specific compound, Phosphorus type compounds, such as a triphenyl phosphite, a pentaerythritol tetralauryl thio propionate, a dilauryl thiodipropionate, a distearyl 3,3'- thi Sulfur type compounds, such as an odys propionate, etc. are mentioned.

Antioxidant which functions as such a peroxide decomposer can use a commercially available thing, For example, Adeka Stave TPP (Asahi Denka Co., brand name), Mark AO-412S (Adeka Agus Chemical Co., Ltd. brand name), Smillizer TPS (Sumitomo Chemical Co., Ltd. brand name) etc. are mentioned.

These antioxidant can be used individually by 1 type or in combination of 2 or more types.

<< ultraviolet absorbent >>

Since the polymer material absorbs light and thus causes decomposition and deterioration, the curable resin composition of the present embodiment can use a ultraviolet absorber in addition to an antioxidant in order to stabilize the ultraviolet ray.

Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives. Examples of specific benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'- Dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; Examples of specific 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 and the like; Examples of specific benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- ( 2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole; As an example of a specific triazine derivative, hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, etc. are mentioned.

As a ultraviolet absorber, a commercially available thing can be used, For example, tinuvin PS, tinubin 99-2, tinubin 109, tinubin 384-2, tinubin 900, tinubin 928, tinubin 1130, tinubin 400, tea Nuvin 405, Tinuvin 460, Tinuvin 479 (above, Ciba Specialty Chemicals make, brand name), etc. are mentioned.

These ultraviolet absorbers can be used individually by 1 type or in combination of 2 or more types, and can be stabilized of the molded object obtained from the curable resin composition of this embodiment by using together with the antioxidant mentioned above.

In addition, the curable resin composition of this embodiment may further contain known thixotropy-imparting agents such as known thermal polymerization inhibitors, finely divided silica, organic bentonite, montmorillonite, and hydrotalcite, silicon-based, fluorine-based, and polymer-based polymers. Known additives such as antifoaming agents and / or leveling agents, silane coupling agents such as imidazole-based, thiazole-based, triazole-based, antioxidants, and rust-preventing agents can be blended.

The thermal polymerization inhibitor may be used to prevent thermal polymerization or polymerisation of the polymerizable compound over time. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydroxybenzophenone. Cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl-6-t Butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and chelate with Al Etc. can be mentioned.

The curable resin composition of this embodiment comprised in this way is adjusted to the viscosity suitable for an application | coating method with an organic solvent, for example, and it is an immersion coating method, a flow coating method, a roll coating method, the bar coater method, and screen printing on a base material. And coating by a method such as curtain coating or the like.

And a tack free coating film is formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC. At this time, the volatilization drying is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (a method having a heat source of an air heating method by steam) such that the hot air in the dryer is countercurrently contacted, and from the nozzle to the support. Spraying)).

Moreover, a resin insulating layer can be formed by apply | coating curable resin composition on a carrier film, drying, winding up as a film, forming a dry film, and bonding this on a base material.

At this time, as a base material in which a coating film is formed or a dry film is bonded, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine polyethylene PPO Copper clad laminates for high frequency circuits using cyanate esters are used. Copper clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. have.

In addition, by contact type (or non-contact method), pattern exposure (irradiation of active energy rays) is performed by an active energy ray selectively by exposure or a laser direct exposure machine, selectively via a photomask in which the pattern was formed.

As an exposure apparatus used for active energy ray irradiation, a direct drawing apparatus (for example, the laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer) can be used. For example, products, such as those manufactured by Nippon Orbotech Co., Ltd. and Pantax Co., Ltd., can be used, and any device can be used as long as the device emits a laser light having a maximum wavelength of 350 to 410 nm.

As an active energy ray, as long as the maximum wavelength is the laser beam in the range of 350-410 nm, both a gas laser and a solid laser can also be used. In addition, the exposure amount thereof varies depending on the film thickness and the like, but can generally be in the range of 5 to 200 mJ / cm ² , preferably 5 to 100 mJ / cm ² , more preferably 5 to 50 mJ / cm ² . have.

Then, by exposing in this manner, the exposed portion (the portion irradiated with the active energy ray) is cured, and the unexposed portion is developed with a dilute alkali aqueous solution (for example, an aqueous solution of 0.3 to 3% sodium carbonate) to thereby form a resist pattern. Is formed.

At this time, the developing method may be an immersion method, a shower method, a spray method, a brush method, or the like. As a developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like may be used. Can be.

Further, for example, by heating at a temperature of about 140 to 180 ° C and thermosetting, the carboxyl group of the mixture of the carboxyl group-containing resin (A) and the carboxyl group-containing photosensitive resin (B), two or more cyclic ether groups and / or in the molecule A thermosetting component having a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesion, and electrical properties.

Thus, in curable resin composition, when it contains a carboxyl group-containing resin (A), a carboxyl group-containing photosensitive resin (B), a photoinitiator, a diluent, a thermosetting component, a coloring agent, etc. as needed, the outstanding alkali developability and excellent work | work Sex and mass production can be obtained. In addition, by selectively exposing and developing the coating film obtained by coating this, and performing final hardening as needed, hardened | cured material excellent in adhesiveness, chemical-resistance, electroless gold plating resistance, cold shock resistance, PCT resistance, electrical insulation, etc. Can be obtained, and high reliability can be provided by using this hardened | cured material for a printed wiring board.

Hereinafter, although an Example and a comparative example are shown and this embodiment is demonstrated concretely, of course, this invention is not limited to a following example.

(Resin synthesis example 1)

119.4 g of a novolak-type cresol resin (Showa Kobunshi Co., Ltd. make, brand name "Shonor CRG951", OH equivalence: 119.4) in the autoclave provided with the thermometer, the nitrogen introduction apparatus, the alkylene oxide introduction apparatus, and the stirring apparatus. 1.19 g of potassium hydroxide and 119.4 g of toluene were added thereto, and the inside of the system was nitrogen-substituted and heated to elevated temperature while stirring, and then 63.8 g of propylene oxide was slowly added dropwise to 0 to 4.8 kg / cm ² at 125 to 132 ° C. The reaction was carried out for 16 hours.

Thereafter, the mixture 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 propylene oxide reaction of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. A solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

293.0 g of the alkylene oxide reaction solution of the obtained novolac-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 introduced into a reactor equipped with a stirrer, a thermometer, and an air blown pipe, and then air Was blown at a rate of 10 ml / min and reacted at 110 ° C for 12 hours with stirring.

The water produced by the reaction flowed out of 12.6 g of an azeotropic mixture with toluene. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of an aqueous 15% sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate to obtain a novolak-type acrylate resin solution.

Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and the air was blown at a rate of 10 ml / min, followed by stirring. 60.8 g of tetrahydrophthalic anhydride was added gradually, and it was made to react at 95-101 degreeC for 6 hours. As a result, the acid value 88 mgKOH / g of solids and the carboxyl group-containing photosensitive resin of 71% of non volatile matter were obtained. Let this be resin solution A-1.

(Resin synthesis example 2)

To 685 g of diethylene glycol monoethyl ether acetate, orthocresol novolak type epoxy resin [Dainikbon ink Kagaku Kogyo Co., Ltd. make, EPICLON N-695, softening point 95 degreeC, epoxy equivalent 214, average functional number 7.6 1070 g (glycidyl group number (aromatic ring total number): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added thereto, and the resulting mixture was dissolved by heating and stirring to 100 ° C.

Subsequently, 4.3 g of triphenylphosphines were added, and it heated at 110 degreeC and made it react for 2 hours, Then, 1.6 g of triphenylphosphines were further added, it heated up at 120 degreeC, and reaction was further performed for 12 hours. 535 g of aromatic hydrocarbons (Solvesso 150) and 684 g (4.5 mol) of tetrahydro phthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours.

Furthermore, 71.0 g (0.5 mol) of glycidyl methacrylates were thrown into the obtained reaction liquid, and it reacted at 115 degreeC for 4 hours, and obtained the resin solution of 103 mgKOH / g of solid content acid value, and 65% of solid content. Let this be resin solution A-2.

(Resin synthesis example 3)

To 700 g of diethylene glycol monoethyl ether acetate, orthocresol novolak type epoxy resin (Dini Nippon Ink Chemical Co., Ltd. make, epiclon N-695, softening point 95 degreeC, epoxy equivalent 214, average functional number 7.6] 1070 g (glycidyl group number (aromatic ring total number): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and made it melt | dissolve uniformly.

Subsequently, 4.3 g of triphenylphosphines were added, and it heated at 110 degreeC and made it react for 2 hours, Then, 1.6 g of triphenylphosphines were further added, it heated up at 120 degreeC, and reaction was further performed for 12 hours. 562 g of aromatic hydrocarbon (Solvesso 150) and 684 g (4.5 mol) of tetrahydro phthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours.

Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylates were added to the obtained reaction liquid, and it reacted at 115 degreeC for 4 hours, and obtained the resin solution of solid content acid value 87 mgKOH / g, and solid content 65%. Let this be resin solution A-3.

(Resin synthesis example 4)

214 g of orthocresol novolak type epoxy resin "Epiclon N-695" in 197 g of diethylene glycol monoethyl ether acetate in a two-liter separation flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube. (Glycidyl group number (aromatic ring total number): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and made it melt | dissolve uniformly. Subsequently, 0.86 g of triphenylphosphine was added, and it heated at 110 degreeC and made it react for 2 hours, 0.23 g of triphenylphosphines were added, it heated up at 120 degreeC, and reaction was performed for 12 hours further.

197 g of Solvesso 150 and 144 g (0.95 mol) of tetrahydro phthalic anhydride were added to the obtained reaction liquid, and it reacted at 110 degreeC for 4 hours. Further, 40.05 g (0.2 mol) of 4-hydroxybutyl acrylate glycidyl ether and 45.9 g of propylene glycol methyl ether acetate were added to the obtained reaction solution, heated to 110 ° C. while stirring, and maintained at 110 ° C. for 6 hours. The reaction was continued.

When the reaction product was cooled to room temperature, a viscous solution was obtained. Thus, the solution of carboxyl group-containing resin (A) of 52 mass% of non volatile matters and 90 mgKOH / g of solid content values was obtained. Let this be resin solution A-4.

(Resin synthesis example 5)

To 600 g of diethylene glycol monoethyl ether acetate, ortho cresol novolak type epoxy resin (Dini Nippon Ink Chemical Co., Ltd. make, Epiclone N-695, softening point 95 degreeC, epoxy equivalent 214, average functional number 7.6] 1070 g (glycidyl group number (aromatic ring total number): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and made it melt | dissolve uniformly.

Subsequently, 4.3 g of triphenylphosphines were added, and it heated at 110 degreeC and made it react for 2 hours, and it heated up at 120 degreeC and performed reaction for further 12 hours. 415 g of aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydro phthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours, after cooling, solid content acid value 89 mgKOH / g, solid content 65 % Resin solution was obtained. Let this be resin solution A-5.

Comparative Synthesis Example 6

After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide, 400 parts of bisphenol F-type solid epoxy resins of the epoxy equivalent 800 and the softening point of 79 degreeC were added, and 88.5 parts of 98.5% NaOH at 70 degreeC was stirred over 100 minutes under stirring. After addition, reaction was further performed at 70 degreeC for 3 hours.

Subsequently, 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 parts of methyl isobutyl ketone, and further 30% NaOH 10 parts were added and it reacted at 70 degreeC for 1 hour. After completion of the reaction, water washing was performed twice with 200 parts of water.

Methyl isobutyl ketone was distilled off from the oil layer after oil-water separation, and 370 parts of epoxy resins (A-1) of epoxy equivalent 290 and softening point 62 degreeC were obtained. 2900 parts (10 equivalents) of epoxy resin (A-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were added thereto, and the reaction mixture was heated and stirred to 90 ° C.

Subsequently, the reaction liquid was cooled to 60 ° C, 16.7 parts of triphenylphosphine was added, heated to 100 ° C, and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were thrown in here, it heated at 95 degreeC, and it reacted for about 6 hours, and obtained the resin solution of 100 mgKOH / g of solid acid value, and 65% of solid content. Let this be resin solution A-6.

Using the resin solution synthesized in this way, various components were blended at a predetermined ratio (mass parts) as shown in Table 1, premixed in a stirrer, and then kneaded with a triaxial roll mill to form a photosensitive resin composition for solder resist. Was prepared. Here, when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grinding meter by Eriksen company, it was 15 micrometers or less.

* 1 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one

    (Irgacure 907: product of Ciba specialty chemicals company)

* 2 2,4-diethyl thioxanthone (KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd.)

* 3 2- (acetyloxyiminomethyl) thioxanthene-9-one

* 4 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (irgacure OXE 02: Ciba Specialty Chemical) Zusa made)

* 5 dipentaerythritol pentaacrylate (DPHA: manufactured by Nippon Kayaku Co., Ltd.)

* 6 modified novolac type epoxy resin (Epiclon N-865: manufactured by DIC Corporation)

* 7 Vixylenol type epoxy resin (YX-4000: Japan Epoxy Resin Co., Ltd.)

* 8 Methylated melamine resin (manufactured by Acid Chemical Co., Ltd.)

* 9 block isocyanate (made by Asahi Kasei Chemicals Co., Ltd.)

* 10 C.I. Pigment Blue 15: 3

* 11 C.I. Pigment Yellow 147

* 12 2-mercaptobenzothiazole

* 13 antioxidant (made by Ciba Specialty Chemicals)

* 14 B-30 (manufactured by Sakai Chemical Industries, Ltd.)

* 15 hydrotalcite (manufactured by Kyowa Kagaku Kogyo Co., Ltd.)

* 16 diethylene glycol monoethyl ether acetate

Thus, Examples 1-11 and Comparative Examples 1-4 which were obtained were evaluated as follows.

(Performance evaluation)

<Optimal exposure amount>

The curable resin composition of the said Example and the comparative example is buffed-roll-polished the circuit pattern board | substrate of 35 micrometers of copper thicknesses, and it washes with water, dries, and apply | coats it to the whole surface by the screen printing method, and it is a hot air circulation type drying furnace of 80 degreeC. Dry for 60 minutes. After drying, exposure was 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 developed (30 ° C., 0.2 MPa, 1). When the mass% sodium carbonate aqueous solution) was performed for 60 seconds, when the pattern of the remaining step tablet is 7 steps was made into the optimal exposure amount.

<Developing>

The curable resin composition of the said Example and the comparative example was apply | coated so that it might become about 25 micrometers after drying by the screen printing method on the board | substrate completely covered with copper, and it dried for 30 minutes in 80 degreeC hot air circulation type drying furnace. After drying, image development was performed by 1 mass% sodium carbonate aqueous solution, and time until the dry coating film was removed was measured with the stopwatch.

<Maximum developing life>

The composition of each Example and a comparative example is apply | coated completely by screen printing on the patterned copper foil board | substrate, it is dried at 80 degreeC, the board | substrate is taken out every 10 minutes from 20 minutes to 80 minutes, and it cools to room temperature. This board | substrate was developed for 60 second by the 1 mass% sodium carbonate aqueous solution of 30 degreeC on the conditions of spray pressure of 0.2 MPa, and the maximum allowable drying time which a residue does not remain was made into the maximum developing life.

<Tak Castle>

Each photocurable resin composition was apply | coated completely by screen printing on the patterned copper foil board | substrate, it dried for 30 minutes by the 80 degreeC hot air circulation type drying furnace, and cooled to room temperature. The negative film made from PET was placed on this substrate, and the resultant was pressed under reduced pressure for 1 minute with (HMW-GW20) manufactured by ORC Corporation, and then the adhesion state of the film when the negative film was peeled off was evaluated.

(Double-circle): When peeling a film, there is no resistance at all, and a trace does not remain in a coating film.

(Circle): There is no resistance at the time of peeling a film, but there are some marks on a coating film.

(Triangle | delta): When peeling off a film, there exists a little resistance and a trace has a little in a coating film.

X: When peeling a film, there exists resistance and a mark was made to a coating film surely.

(Characteristic test)

Each composition of an Example and a comparative example is apply | coated completely by screen printing on the patterned copper foil board | substrate, dried at 80 degreeC for 30 minutes, and cooled to room temperature. The soldering resist pattern was exposed by the optimal exposure amount using the exposure apparatus which mounted the high pressure mercury lamp on this board | substrate. And 30 mass degree 1 mass% sodium carbonate aqueous solution was developed for 90 ^{second on} the conditions of 0.2 MPa / cm <^2> of spray pressures, and the resist pattern was obtained. This board | substrate was irradiated with the ultraviolet-ray on the conditions of accumulated exposure amount 1000mJ / cm <^2> by UV conveyor, and it heats at 150 degreeC for 60 minutes, and hardened | cured. The characteristic was evaluated as follows about the obtained printed circuit board (evaluation board | substrate).

<Acid resistance>

Evaluation board was immersed for 30 minutes at room temperature in 10 vol% H ₂ SO ₄ aqueous solution, and visually observed as the dissolution of the infiltration or coating, which was then added to make the peeling of the tape peel.

○: no change is seen

△: very slightly changed

×: swelling or swelling drop in the coating film

<Alkali resistance>

The evaluation board | substrate was immersed in 10 volume% NaOH aqueous solution for 30 minutes at room temperature, the penetration and the elution of the coating film were visually confirmed, and peeling by tape peel was further confirmed.

○: no change is seen

△: very slightly changed

×: swelling or swelling drop in the coating film

Solder Heat Resistance

The evaluation board | substrate with which the rosin type flux was apply | coated was immersed in the solder tank set previously to 260 degreeC, and the flux was wash | cleaned with modified alcohol, and the swelling and peeling of the resist layer by visual observation were evaluated. The criteria are as follows.

(Circle): Peeling is not seen even if it repeats immersion 3 times or more for 10 second.

(Triangle | delta): When it immerses 3 times or more for 10 second, it peels a little.

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

Electroless Gold Plating Resistance

Using a commercially available electroless nickel plating bath and an electroless gold plating bath, plating was performed under conditions of 5 μm of nickel and 0.05 μm of gold, and the peeling of the resist layer and the penetration of plating were evaluated by visual inspection after tape peeling. . The criteria are as follows.

(Double-circle): Penetration and peeling are not seen.

(Circle): Penetration is confirmed a little after plating, but it does not peel after tape peeling.

(Triangle | delta): Penetration was seen very little after plating, and peeling was also seen after tape peeling.

X: There exists peeling after plating.

<PCT resistant>

The evaluation board | substrate which formed the soldering resist hardened coating film was processed by the PCT apparatus (HAST SYSTEM TPC-412MD made by SPECK Corporation) at 121 degreeC, saturated, and 0.2 MPa conditions for 168 hours, and the state of a coating film was evaluated. It was. The criteria are as follows.

○: no swelling, peeling, discoloration, elution

Δ: slight swelling, peeling, discoloration, elution

×: swelling, peeling, discoloration, elution

<Cold shock resistance>

□ Exclusion, ○ An evaluation board | substrate which has the soldering resist hardened coating film in which the exclusion pattern was formed was produced. The obtained evaluation board | substrate was subjected to 1000 cycles of resistance tests using a cold heat shock tester (manufactured by Eckett Co., Ltd.) at -55 ° C / 30 minutes to 150 ° C / 30 minutes. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged based on the following criteria.

○: less than 30% of crack occurrence rate

△: crack incidence 30 to 50%

X: 50% or more of crack incidence

<HAST attribute>

The soldering resist hardened coating film was formed in the BT board | substrate with which the comb-shaped electrode (line / space = 50 micrometer / 50 micrometer) was formed, and the evaluation board | substrate was manufactured. This evaluation board | substrate was put into the high temperature, high humidity tank in the atmosphere of 130 degreeC and 85% of humidity, the voltage of 5V was charged, and the in-house HAST test was done for 168 hours. The insulation resistance value in the tank after 168 hours was evaluated according to the following criteria.

○: 10 ⁸ Ω or more

△: 10 ⁶ to 10 ⁸ Ω

×: 10 ⁶ Ω or less

Moreover, the dry film was formed from the composition of the Example and the comparative example, and it evaluated similarly.

<Dry Film Evaluation>

Example 1-5 and Comparative Examples 1 and 2 prepared in Table 1 were diluted with methyl ethyl ketone, coated on a PET film, and dried at 80 ° C. for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. Furthermore, the cover film was bonded together on it, the dry film was produced, and each was set to Examples 12-16 and Comparative Examples 5 and 6.

Then, after peeling a cover film and thermally laminating | stacking a film on the patterned copper foil board | substrate, it exposed on the conditions similar to the board | substrate used for the coating-film characteristic evaluation of an Example. The carrier film was peeled off after exposure, and development was performed for 60 second in 30 degreeC 1 mass% sodium carbonate aqueous solution on the conditions of spray pressure of 0.2 MPa / cm <^2> , and the resist pattern was obtained.

After heat-hardening this board | substrate for 60 minutes with the 150 degreeC hot air dryer, UV irradiation was performed on the conditions of the integrated exposure amount of 1000 mJ / cm <^2> by the UV conveyor, and the test board | substrate was produced. The evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above about the test board | substrate which has the obtained hardened film. The results are shown in Table 3.

From the results shown in Tables 2 and 3, it can be seen that the curable resin composition of the present embodiment combines two kinds of resins together to have PCT resistance, cold shock resistance, and electrical properties required for the solder resist for IC packages.

Claims (7)

Obtained by making a unsaturated product containing monocarboxylic acid react with the reaction product obtained by making the compound which has two or more phenolic hydroxyl groups, and an alkylene oxide or a cyclocarbonate compound in 1 molecule react, and making polybasic acid anhydride react with the reaction product obtained, Carboxyl group-containing resin (A) which does not use epoxy resin as a starting material,
Carboxyl group-containing photosensitive resin (B) obtained by making a carboxyl group-containing resin react with the compound which has a cyclic ether group and ethylenically unsaturated group together in 1 molecule,
Photopolymerization initiator
Curable resin composition characterized by including the. delete The said carboxyl group-containing photosensitive resin (B) WHEREIN: The compound which has a cyclic ether group and ethylenically unsaturated group together in the said 1 molecule is glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycine. Curable resin composition characterized by the above-mentioned: diether or 3, 4- epoxycyclohexyl methyl methacrylate. The curable resin composition according to claim 1, further comprising a thermosetting component. The dry film obtained by apply | coating and drying the curable resin composition of any one of Claims 1, 3, and 4 to a film. The dry coating film obtained by apply | coating and drying the curable resin composition of any one of Claims 1, 3, and 4 on a base material, or the dry film formed by apply | coating and drying the said curable resin composition to a film is laminated | stacked on a base material Hardened | cured material obtained by hardening | curing the dry coating film obtained by active energy ray irradiation or heating, or active energy ray irradiation and heating. The hardened | cured material of Claim 6 is provided, The printed wiring board characterized by the above-mentioned.