JP5520509B2 - Curable resin composition - Google Patents

Description

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

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

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

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

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

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

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

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

In order to achieve such an object, the curable resin composition of one embodiment of the present invention includes (A) a carboxyl group-containing resin that does not use an epoxy resin as a starting material, and (B) a carboxyl group-containing resin in one molecule. A composition containing a carboxyl group-containing photosensitive resin obtained by reacting a compound having both a cyclic ether group and an ethylenically unsaturated group, and a photopolymerization initiator , wherein (A) the epoxy resin is started The carboxyl group-containing resin not used as a raw material is at least one of the following resins (1) to (5) .
(1) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with an alkylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is a polybasic acid. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.
(2) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with a cyclic carbonate compound is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is polybasic. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride,
(3) A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin by polyaddition reaction of a diisocyanate compound and a diol compound.
(4) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound, a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule was added. Terminal group (meth) acrylated urethane resin containing carboxyl group.
(5) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule. In addition, terminal (meth) acrylated carboxyl group-containing urethane resin.

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

  In the curable resin composition of one embodiment of the present invention, the carboxyl group-containing resin (A) is obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide or a cyclocarbonate compound. It is preferable to obtain the reaction product by reacting an unsaturated group-containing monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.

  With such a configuration, water resistance is improved, excellent PCT resistance is obtained, and since chloride ion impurities are not included, excellent insulation reliability can be obtained.

  In the carboxyl group-containing photosensitive resin (B) in the curable resin composition of one embodiment of the present invention, a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is glycidyl (meth) acrylate, 4 Preferred is -hydroxybutyl acrylate glycidyl ether or 3,4-epoxycyclohexylmethyl methacrylate.

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

  In the carboxyl group-containing resin (A) in the curable resin composition of one embodiment of the present invention, the carboxyl group-containing resin is preferably photosensitive. With such a configuration, it can be used as a highly sensitive photocurable resin composition.

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

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

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

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

  And by using these hardened | cured materials 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, the curable resin composition has good workability, high sensitivity, and excellent PCT when used in, for example, a printed wiring board or a semiconductor package. Resistance and high insulation reliability can be obtained.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have obtained, as an essential component of the composition, a carboxyl group-containing resin that does not use an epoxy resin as a starting material, and a carboxyl that uses a carboxylic acid-containing resin as a starting material. It has been found that the above-described object can be achieved by combining the group-containing photosensitive resin, and the present invention has been completed. That is, the curable resin composition of the present invention is characterized by a combination of two kinds of carboxyl group-containing photosensitive resins contained therein.

  The carboxyl group-containing resin (A) can obtain excellent flexibility and elongation by, for example, chain extension by addition reaction between a compound having a phenolic hydroxyl group and an alkylene oxide or a cyclocarbonate compound. In addition, when an unsaturated group-containing monocarboxylic acid and a polybasic acid anhydride are added to a terminal hydroxyl group generated by the addition reaction of an alkylene oxide or a cyclocarbonate compound, the unsaturated group or the carboxyl group is the same side chain. Since it is not present above and is located at the end of each side chain, it has excellent reactivity. Moreover, it has excellent alkali developability due to the presence of a terminal carboxyl group separated from the main chain. In addition, it has excellent moisture absorption resistance because it has no or only a slightly reactive hydrophilic alcoholic hydroxyl group, so it has improved PCT resistance required for IC packages. It is estimated that it leads to. However, on the other hand, the adhesion to the base material and the support is weaker than other resins, and the obtained cured product cannot obtain sufficient electroless plating resistance and thermal shock resistance.

  On the other hand, the carboxyl group-containing photosensitive resin (B) improves flexibility by chain extension by addition reaction between a carboxyl group-containing resin and a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule. be able to. Moreover, since it has the photosensitive group of the terminal of a side chain, the outstanding photoreactivity can be obtained. In addition, due to the effect of the hydroxyl group generated during the addition reaction with the carboxyl group-containing resin, the adhesion to the substrate is improved, the electroless plating property is improved, and the thermal shock is improved along with the improvement in flexibility. It becomes possible to improve tolerance.

  Therefore, as a resin used in combination with the carboxyl group-containing resin (A), a cured film that exhibits alkali developability, is effective for high sensitivity, has excellent adhesion to various base materials, and has excellent characteristics. The resin to be provided, that is, the carboxyl group-containing photosensitive resin (B) obtained by reacting a carboxyl group-containing resin with a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is used in combination.

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

  The curable resin composition of the present embodiment includes a carboxyl group-containing resin (A) that does not start with an epoxy resin. As such a carboxyl group-containing resin (A), from the viewpoint of photocurability and development resistance, the carboxyl group-containing resin is a carboxylic acid-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule. It is preferable. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. Specific examples are shown below.

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

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

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

  (4) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound, one hydroxyl group and one or more (meta) in a molecule such as hydroxyalkyl (meth) acrylate. ) A carboxyl group-containing urethane resin obtained by adding a compound having an acryloyl group and terminally (meth) acrylating it.

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

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

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

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

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

  In such a carboxyl group-containing resin (A), a phenol novolac resin free from chlorine can be easily obtained. The resulting phenol resin-derived polyol is partially acrylated, and an acid anhydride is introduced to the remaining hydroxyl group, whereby double bond equivalent 300-550, acid value In the range of 40 to 150, it is possible to obtain a resin that theoretically has no hydroxyl group. Moreover, the chlorine ion as an impurity at this time can be made into a very small state of 20 ppm or less.

 On the other hand, in epoxy acrylate modified resins used in general solder resists, it is possible to acrylate all epoxy groups of epoxy resins synthesized from similar phenol novolac resins and introduce acid anhydrides into the generated hydroxyl groups It is. However, many chlorine ions derived from epoxy resin remain, and there are very many hydroxyl groups generated when acrylated, and the acid value becomes very large even if all or partly modified with an acid anhydride. In other words, the hydroxyl group remains, the water resistance is poor, and the insulation reliability and PCT resistance are remarkably lowered. That is, it is very difficult to reduce chloride ions and hydroxyl groups from epoxy acrylate resins derived from similar phenol novolac epoxy resins.

  In addition, urethane resins can be easily synthesized by combining the equivalents of hydroxyl groups and isocyanate groups. 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 an epihalohydrin. Of these, the halogen content is preferably 0-30 ppm, and more preferably synthesized so as not to theoretically contain a hydroxyl group.

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

  In addition, as the carboxyl group-containing photosensitive resin (B) obtained by reacting a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule, which will be described later, the carboxyl group-containing compounds (1) to (6) described above are contained. A resin obtained by reacting a resin (A) with a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule can also be used.

  Such a carboxyl group-containing photosensitive resin (B) can be obtained by using an epoxy group synthesized by a method using a peracetic acid method instead of an epoxidation using an epihalohydrin. It is possible to further reduce the amount of chlorine ion impurities in the obtained carboxyl group-containing photosensitive resin (B). Furthermore, the amount of chlorine ion impurities can be reduced by using 3,4-epoxycyclohexylmethyl methacrylate.

 In addition, the carboxyl group-containing photosensitive resin (A) contains an unsaturated group in a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide or a cyclocarbonate compound. It is preferably obtained by reacting a monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.

  Examples of the compound having two or more phenolic hydroxyl groups in one molecule include catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylhydroquinone, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A and bisphenol F. Bisphenol S, biphenol, bixylenol, novolac-type phenol resin, novolac-type alkylphenol resin, bisphenol A novolak resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, polyvinylphenols, phenol Condensates of aromatics with phenolic hydroxyl groups, 1-naphthol or 2-naphthol with aromatic aldehydes , And the like compounds, but is not limited thereto. These phenolic hydroxyl group-containing compounds can be used alone or in admixture of two or more.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran. These alkylene oxides can be used alone or in admixture of two or more.

  As the cyclocarbonate compound, a known carbonate compound can be used, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate. Of these, 5-membered ethylene carbonate and propylene carbonate are preferable from the viewpoint of reactivity and supply system. These carbonate compounds can be used alone or in admixture of two or more.

  The alkylene oxide or cyclocarbonate compound can be modified from a phenolic hydroxyl group to a resin having an alcoholic hydroxyl group by addition reaction with the phenolic hydroxyl group of the compound having a phenolic hydroxyl group using a basic catalyst. . The addition amount at this time is preferably in the range of 0.3 to 1.0 mol per equivalent of phenolic hydroxyl group. When the addition amount is less than 0.3 mol, a reaction with an unsaturated group-containing monocarboxylic acid or polybasic acid anhydride described later hardly occurs, and the photosensitivity and solubility in a dilute alkaline aqueous solution are lowered. On the other hand, if the addition amount exceeds 1.0, water resistance decreases due to the generated ether bond, and electrical insulation, HAST resistance and the like decrease. More preferably, it is the range of 0.8-5 mol, More preferably, it is the range of 1.0-3 mol.

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

  Polybasic acid anhydrides include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro Alicyclic dibasic acid anhydrides such as phthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, etc. Aliphatic or aromatic dibasic acid anhydride, or biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride , Benzophenone Tet Aliphatic or aromatic tetrabasic acid dianhydrides such as lacarboxylic acid dianhydride may be mentioned. These polybasic acid anhydrides can be used alone or in combination of two or more.

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

  The carboxyl group-containing resin used in such a carboxyl group-containing photosensitive resin (B) is a resin containing a carboxyl group in the molecule. In particular, from the viewpoint of photocurability and development resistance, a carboxylic acid-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. Specific examples are shown below.

  (1) Obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and a reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

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

  (3) A carboxyl group-containing resin obtained by copolymerization of (meth) acrylic acid and an unsaturated group-containing material.

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

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

  (6) A terminal (meth) acrylated carboxylic acid-containing urethane resin by adding a compound having one hydroxyl group and one or more (meth) acryl groups in the molecule during the synthesis of the resin of (4) or (5).

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

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

  (9) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Functional carboxyl group-containing resin.

  (10) A carboxylic acid-containing polyester resin obtained by reacting a difunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

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

  Examples of the compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, and 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 or glycidyl (meth) Examples include acrylates and 3,4-epoxycyclohexylmethyl acrylate. Among these, from the aspects of reactivity and supply system, one epoxy group and one or more glycidyl (meth) acrylate or 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, etc. in one molecule A compound having a (meth) acryl group is preferred. These compounds can be used alone or in combination of two or more.

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

The blending ratio of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing photosensitive resin (B) is appropriately set according to the purpose, but the carboxyl group-containing photosensitive resin (A) is carboxylated. The group-containing photosensitive resin (B) is preferably blended at a ratio of 70:30 to 30:70. When the blending ratio of the carboxyl group-containing photosensitive resin (A) is less than 30,
Furthermore, the total acid value of these carboxyl group-containing photosensitive resins (A) and (B) is desirably in the range of 30 to 150 mgKOH / g. When the acid value after blending the carboxyl group-containing photosensitive resins (A) and (B) is lower than 30 mg KOH / g, the solubility in an aqueous alkali solution is lowered, and development of the formed coating film becomes difficult. On the other hand, if the concentration is higher than 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line fades more than necessary, or dissolution and peeling occurs with the developer without distinction between the exposed portion and the unexposed portion. It may be difficult to draw a resist pattern. More preferably, it is 40-110 mgKOH / g.

  In the present invention, a known carboxylic acid resin can be used in combination. However, it can be used for various purposes, such as adjusting the balance of photoreactivity and developability. Generally, when epoxy resin is used as a starting material, chloride ion impurities Since contamination increases, it is desirable to use them in consideration of them.

Further, as the photopolymerization initiator, an oxime ester photopolymerization initiator having a group represented by the following general formula (I), an α-aminoacetophenone photopolymerization having a group represented by the following general formula (II) It is preferable to use one or more photopolymerization initiators selected from the group consisting of an initiator and an acylphosphine oxide photopolymerization initiator having a group represented by the following formula (III).

(Wherein R1 represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (It may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R2 may be a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom). Preferably), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), and 5 to 8 carbon atoms. A cycloalkyl group of Represents an alkanoyl group having 2 to 20 prime atoms or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R3 and R4 each independently represents an alkyl having 1 to 12 carbon atoms. R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded, and R7 and R8 each independently represent 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 R7 and R8 Is an R—C (═O) — group (wherein R may be a hydrocarbon group having 1 to 20 carbon atoms).

Here, the oxime ester photopolymerization initiator having a group represented by the general formula (I) is preferably 2- (acetyloxyiminomethyl) thioxanthene-9- represented by the following formula (IV). on,

Compound represented by the following general formula (V)

(In the formula, R9 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Or R10 and R12 each independently represents a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), An alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain); ), A cycloalkyl group having 5 to 8 carbon atoms, 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 R11 is A hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups) May have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms). Which may be substituted with an alkyl group or a phenyl group)),
Compound represented by the following general formula (VI)

(In the formula, R13 and R14 each independently represent an alkyl group having 1 to 12 carbon atoms, and R15, R16, R17 and R18 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) thioxanthen-9-one represented by formula (IV) and a compound represented by formula (V) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

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

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

  The blending amount of such a photopolymerization initiator is appropriately set in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the mixture of the carboxyl group-containing resin (A) and the carboxyl group-containing photosensitive resin (B). can do. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes intense, and the deep curability tends to decrease. More preferably, it is the range of 0.5-15 mass parts.

  In the case of the oxime ester photopolymerization initiator having a group represented by the formula (I), the blending amount is 100 parts by mass of a mixture of the carboxyl group-containing resin (A) and the carboxyl group-containing photosensitive resin (B). It is preferable to set it as 0.01-20 mass parts with respect to. More preferably, it is 0.01-5 mass parts.

  In addition, examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the curable resin composition of the present embodiment include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. Examples thereof include compounds, xanthone compounds, and tertiary amine compounds.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

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

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

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

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

  Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyl. Mention may be made of diphenyl sulfide.

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

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present embodiment preferably contains a thioxanthone compound from the viewpoint of deep curable properties, among which 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl. A thioxanthone compound such as thioxanthone is 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 parts by mass or less.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable.

  Here, as the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity.

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

  As a compounding quantity of such a tertiary amine compound, it is 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). preferable. When the compounding amount of the tertiary amine compound is less than 0.1 parts by mass, it is difficult to obtain a sufficient sensitizing effect. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts.

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

  The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is 35 parts by mass or less with respect to 100 parts by mass of the mixture of the carboxyl group-containing resin (A) and the carboxyl group-containing photosensitive resin (B). It is preferable that it is the range which becomes. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  Furthermore, the following additives can be used.

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

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

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

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

<Diluent>
In addition, a diluent can be used for photocuring by irradiation with active energy rays to insolubilize or assist insolubilization of the carboxyl group-containing resin in an alkaline aqueous solution. Such diluents include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyhydric alcohols or polyhydric acrylates such as these ethylene oxide adducts or propylene oxide adducts; polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols Acrylates; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

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

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

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

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

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

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

  Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The compounding amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is equivalent to 1 equivalent of carboxyl group of the mixture of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). On the other hand, it is preferable that it is 0.6-2.5 equivalent. When the amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. Decreases. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dried coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8-2.0 equivalent.

《Thermosetting catalyst》
When using a thermosetting component having two or more cyclic (thio) ether groups in such a molecule, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and those that are commercially available ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (all dimethylamine block isocyanate compounds manufactured by San Apro) Product names), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. In particular, it is not restricted to these, What is necessary is just a thermosetting catalyst of an epoxy resin or an oxetane compound, or what accelerates | stimulates the reaction of an epoxy group and / or an oxetanyl group, and a carboxyl group. These may be used alone or in admixture of two or more. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used. It is more preferable to use a compound that also functions as an adhesion-imparting agent in combination with a thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, a mixture of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B), or two or more cyclic rings in the molecule. It is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of thermosetting components which have a (thio) ether group. More preferably, it is 0.5-15.0 mass parts.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The compounding amount of the urethanization catalyst is sufficient in an ordinary quantitative ratio. For example, it is preferably 0.1 with respect to 100 parts by mass of the mixture of the carboxyl group-containing resin (A) and the carboxyl group-containing photosensitive resin (B). ˜20.0 parts by mass, more preferably 0.5 to 10.0 parts by mass.

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

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

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

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

《Colorant》
Furthermore, 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 dyes may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental burden and affecting the human body.

(Blue colorant)
Examples of the blue colorant include phthalocyanine series and anthraquinone series. Of these, compounds classified as pigments in the pigment system, specifically, the following color index (CI; issued by The Society of Dyers and Colorists) numbers are attached. Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, and the like can be used.

  In addition, in the dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

(Green colorant)
Similarly, examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

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

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

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

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

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

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

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

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

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

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

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

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

  Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, etc. are used as the perylene system.

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

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

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

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

  In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone. Specific examples of such coloring agents include Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 2 5, C.I. pigment black 1, C.I. pigment black 7, and the like.

  Although such a coloring agent is mix | blended suitably, it is 10 mass parts or less with respect to 100 mass parts with respect to 100 mass parts of mixtures of carboxyl group-containing resin (A) and carboxyl group-containing photosensitive resin (B). It is preferable to do. More preferably, it is 0.1-5 mass parts.

《Filler》
Furthermore, in order to increase the physical strength and the like of the coating film, a filler can be blended as necessary. As such a filler, known inorganic or organic fillers can be used, and in particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. Moreover, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin (D-1), XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) manufactured by Hanse-Chemie, Inc. XP 0516, XP 0525, XP 0314 (all are product grades) Name) can also be used. These fillers can be used alone or in combination of two or more.

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

<< Binder polymer >>
Furthermore, a binder polymer can be used for the purpose of improving dryness to touch and improving handling properties. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyesteramide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.

<Elastomer>
Furthermore, an elastomer can be used for the purpose of imparting flexibility and improving brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeletons with the both terminal carboxylic acid modified butadiene-acrylonitrile rubber | gum can also be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.

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

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

"Antioxidant"
In many polymer materials, once oxidation starts, oxidative degradation occurs one after another in a chain, resulting in functional degradation of the polymer material. Therefore, in order to prevent oxidation in the curable resin composition of this embodiment ( 1) Oxidation of radical scavengers that invalidate the generated radicals and / or (2) peroxide decomposers that decompose the generated peroxides into innocuous substances and prevent the generation of new radicals. An inhibitor can be added.

  Specific examples of antioxidants that function as radical scavengers include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p- Cresol, 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′di-tert-butyl-4) -Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6- And amine compounds such as tetramethyl-4-piperidyl) -sebacate and phenothiazine.

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

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

  As such an antioxidant that acts as a peroxide decomposer, commercially available products can be used. For example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical, product) Name), Sumilizer TPS (manufactured by Sumitomo Chemical, trade name), and the like.

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

<Ultraviolet absorber>
Since the polymer material absorbs light and thereby decomposes and deteriorates, the curable resin composition of the present embodiment includes an ultraviolet absorber in addition to the antioxidant in order to stabilize the ultraviolet ray. Can be used.

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

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

  These ultraviolet absorbers can be used alone or in combination of two or more. By using in combination with the above-described antioxidant, the stability of the molded product obtained from the curable resin composition of the present embodiment can be improved. Can be achieved.

  In addition, the curable resin composition of the present embodiment may further include a known thermal polymerization inhibitor, a known thixotropic agent such as fine silica, organic bentonite, montmorillonite, hydrotalcite, silicone, fluorine Addition of known additives such as antifoaming agents and / or leveling agents such as olefins and polymers, silane coupling agents such as imidazole, thiazole and triazole, antioxidants and rust inhibitors be able to.

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

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

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

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

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

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

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

As the active energy ray, either a gas laser or a solid laser may be used as long as it has a maximum wavelength in the range of 350 to 410 nm. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2.

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

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

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

  Thus, in the curable resin composition, the carboxyl group-containing resin (A), the carboxyl group-containing photosensitive resin (B), the photopolymerization initiator, and, if necessary, a diluent, a thermosetting component, a colorant, etc. By containing, excellent alkali developability, excellent workability, and mass productivity can be obtained. Furthermore, by selectively exposing and developing the coating film obtained by applying this, and performing finish curing as necessary, adhesion, chemical resistance, electroless gold plating resistance, thermal shock resistance, A cured product excellent in PCT resistance, electrical insulation and the like can be obtained, and high reliability can be imparted by using this cured product for a printed wiring board.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this embodiment is demonstrated concretely, it cannot be overemphasized that this invention is not limited to the following Examples.

(Resin synthesis example 1)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a novolac type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol C RG951”, OH equivalent: 119.4) 119 .4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours.

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

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

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

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

(Resin synthesis example 2)
1070 g of diethylene glycol monoethyl ether acetate and orthocresol novolak type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) (glycidyl group number (aromatic Total number of rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve.

  Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and further 1.6 g of triphenylphosphine was added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. To the obtained reaction solution, 535 g of aromatic hydrocarbon (Sorvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours.

  Furthermore, 71.0 g (0.5 mol) of glycidyl methacrylate was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 103 mgKOH / g and a solid content of 65%. . This is designated as resin solution A-2.

(Resin synthesis example 3)
To 700 g of diethylene glycol monoethyl ether acetate, 1070 g of orthocresol novolak type epoxy resin [Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] (glycidyl group number ( Total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve.

  Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and further 1.6 g of triphenylphosphine was added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. To the obtained reaction solution, 562 g of aromatic hydrocarbon (Sorvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours.

  Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 87 mgKOH / g and a solid content of 65%. This is designated as resin solution A-3.

(Resin synthesis example 4)
Into a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 197 g of diene glycol monoethyl ether acetate and 214 g of orthocresol novolac epoxy resin “EPICLON N-695” (glycidyl) Base number (total number of aromatic rings): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to be uniformly dissolved. Next, 0.86 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, then 0.23 g of triphenylphosphine was added, the temperature was raised to 120 ° C., and the reaction was further performed for 12 hours.

  The obtained reaction solution was charged with 197 g of Solvesso 150 and 144 g (0.95 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 4 hours. Furthermore, 40.05 g (0.2 mol) of 4-hydroxybutyl acrylate glycidyl ether and 45.9 g of propylene glycol methyl ether acetate were added to the obtained reaction solution, and the mixture was heated to 110 ° C. while stirring, and kept at 110 ° C. The reaction was continued for 6 hours.

  When the reaction product was cooled to room temperature, a viscous solution was obtained. Thus, a solution of a carboxyl group-containing resin (A) having a nonvolatile content of 52% by mass and a solid content acid value of 90 mgKOH / g was obtained. This is designated as Resin Solution A-4.

(Resin synthesis example 5)
An ortho cresol novolak type epoxy resin [Dainippon Ink Chemical Co., Ltd., EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups ( Total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve.

  Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This is designated as Resin Solution A-5.

(Comparative Synthesis Example 6)
400 parts of a bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide were dissolved, and 81.2 parts of 98.5% NaOH at 70 ° C. with stirring. Was added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours.

  Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% NaOH was added to 70 ° C. For 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water.

  After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C. 2900 parts (10 equivalents) of epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate are heated and stirred at 90 ° C. to dissolve the reaction mixture. did.

  Next, the reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mgKOH / g, solid content 65% A resin solution was obtained. This is designated as Resin Solution A-6.

Using the resin solution synthesized as described above, as shown in Table 1, various components were blended at predetermined ratios (mass parts), premixed with a stirrer, kneaded with a three-roll mill, and soldered. A photosensitive resin composition for resist was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

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

(Performance evaluation)
<Optimal exposure>
The circuit pattern substrates having a copper thickness of 35 μm were polished with buffalo, washed with water, dried and then applied to the entire surface by a screen printing method, and a hot air circulation drying oven at 80 ° C. For 60 minutes. After drying, it is exposed through a step tablet (Kodak No2) using an exposure device equipped with a high-pressure mercury lamp and a direct drawing device equipped with a semiconductor laser with a maximum wavelength of 355 nm, and developed (30 ° C., 0.2 MPa, 1% by mass carbonic acid). The optimal exposure amount was obtained when the step tablet pattern remained when the aqueous sodium solution was 60 seconds was 7 steps.

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

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

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

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

○: When the film is peeled off, there is no resistance, but the coating film has a slight mark.

(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.

X: When the film is peeled off, there is resistance and the coating film is clearly marked.

(Characteristic test)
Each composition of the example and the comparative example is coated on the entire surface of the patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The solder resist pattern was exposed with an optimum exposure amount using an exposure apparatus having a high-pressure mercury lamp mounted on the substrate. Then, a 1% by mass sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under a spray pressure of 0.2 MPa / cm ² to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristic was evaluated as follows with respect to the obtained printed circuit board (evaluation board).

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

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

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

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

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

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

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5μm and gold 0.05μm, and tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.

A: No soaking or peeling is observed.

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

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

X: There is peeling after plating.

<PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film was determined. evaluated. Judgment criteria are as follows.

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

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

○: 10 ⁸ Ω or more Δ: 10 ⁶ to 10 ⁸ Ω
×: 10 ⁶ Ω or less

  Furthermore, a dry film was formed from the compositions of Examples and Comparative Examples and evaluated in the same manner.

<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, dried at 80 ° C. for 30 minutes, and a photosensitive resin composition layer having a thickness of 20 μm. Formed. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 12-16 and Comparative Examples 5 and 6, respectively.

Thereafter, the cover film was peeled off, the film was thermally laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the coating film property evaluation of the examples. After the exposure, the carrier film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa / cm ² to obtain a resist pattern.

This substrate was heat-cured for 60 minutes with a hot air dryer at 150 ° C., and then irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 3.

  From the results shown in Table 2 and Table 3, the curable resin composition of the present embodiment is a combination of two types of resins, so that the PC package resistance, the thermal shock resistance, and the electricity required for the solder resist for IC packages are used. It turns out that it has the characteristic.

Claims (10)

A carboxyl group-containing resin (A) not using an epoxy resin as a starting material;
A carboxyl group-containing photosensitive resin (B) obtained by reacting a carboxyl group-containing resin with a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule;
A photopolymerization initiator;
A curable resin composition containing
The carboxyl group-containing resin (A) that does not use the epoxy resin as a starting material is at least (1) a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with an alkylene oxide. A carboxyl group-containing photosensitive resin obtained by reacting a saturated carboxyl group-containing monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride,
(2) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with a cyclic carbonate compound is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is polybasic. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride,
(3) a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of the urethane resin by polyaddition reaction of a diisocyanate compound and a diol compound;
(4) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound, a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule was added. , Terminal (meth) acrylated carboxyl group-containing urethane resin, and
(5) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule. In addition, terminal (meth) acrylated carboxyl group-containing urethane resin,
A curable resin composition characterized by being one kind of resin .   The carboxyl group-containing resin (A) is obtained by reacting a compound obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide or a cyclocarbonate compound, into an unsaturated group-containing monocarboxylic acid. The curable resin composition according to claim 1, wherein the curable resin composition is obtained by reacting polybasic acid anhydride with the reaction product obtained.   In the carboxyl group-containing photosensitive resin (B), the compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, or 3, 4- The curable resin composition according to claim 1, which is epoxycyclohexylmethyl methacrylate.   The curable resin composition according to any one of claims 1 to 3, wherein in the carboxyl group-containing resin (A), the carboxyl group-containing resin is photosensitive.   Furthermore, a thermosetting component is contained, The curable resin composition of any one of Claims 1-4 characterized by the above-mentioned.   Furthermore, a coloring agent is contained, The curable resin composition of any one of Claims 1-5 characterized by the above-mentioned.   A cured product obtained by applying the curable resin composition according to any one of claims 1 to 6 to a substrate and curing it by irradiation with active energy rays and / or heating.   A dry film obtained by applying and drying the curable resin composition according to any one of claims 1 to 6 on a carrier film.   A cured product obtained by attaching the dry film according to claim 8 to a substrate and curing it by irradiation with active energy rays and / or heating.   A printed wiring board comprising the cured product according to claim 8 or 9.