JP5986157B2 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Description

  The present invention relates to a curable resin composition, a dry film, and a printed wiring board, and more specifically, a curable resin composition that is less likely to be decomposed or discolored by heat of the cured product, the dry film, and a print comprising the cured product. It relates to a wiring board.

  Due to rapid progress of semiconductor components in recent years, electronic devices tend to be smaller, lighter, higher performance, and multifunctional. Following this trend, printed wiring boards are also becoming increasingly dense and surface-mounted. In the production of high-density printed wiring boards, photo solder resist compositions are generally employed, and dry film type photo solder resist compositions and liquid photo solder resist compositions have been developed. Among these, in consideration of environmental problems, an alkali developing type photosensitive composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been proposed (Patent Document 1). -3 etc.)

  In the printed wiring board, applications that are directly mounted on LEDs that emit light with low power, such as backlights for liquid crystal displays of portable terminals, personal computers, televisions, etc., and light sources of lighting fixtures, have increased in recent years ( For example, see Patent Document 4). In addition, with the rise of smartphones and tablet PCs, IC packages are becoming increasingly lighter, thinner and smaller.

JP 61-243869 (Claims) JP-A-5-32746 (Claims) JP-A-11-288091 (Claims) JP 2007-249148 A (paragraphs 0002 to 0007)

  As the IC package becomes lighter, thinner, and shorter, heat is concentrated on the peripheral members of the IC package. Under such circumstances, a solder resist, which is an insulating film formed as a protective film on a printed wiring board, has a heat resistance in addition to the normally required characteristics such as solvent resistance, hardness, solder heat resistance, and electrical insulation. The characteristic which reduces peeling by discoloration and decomposition | disassembly at the time of using for the site | part which requires a mechanical load is calculated | required.

  Accordingly, an object of the present invention is to provide a curable resin composition that is less likely to decompose or discolor due to heat of a cured product, a dry film obtained from the composition, a cured product thereof, and a printed wiring board including the cured product. It is in.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formulated a carboxyl group-containing resin obtained by adding an acid anhydride having a carbon number of 9 or more to a polyol compound, resulting in the heat of the cured product. It has been found that deterioration such as decomposition and discoloration can be remarkably suppressed.

  That is, the curable resin composition of the present invention contains (A) a carboxyl group-containing resin obtained by adding an acid anhydride having 9 or more carbon atoms to a polyol compound, and (B) a photopolymerization initiator. It is characterized by.

  The curable resin composition of the present invention preferably further contains (C) a thermosetting component.

  In the curable resin composition of the present invention, the polyol compound preferably has a photosensitive group.

  In the curable resin composition of the present invention, the (A) carboxyl group-containing resin is preferably not derived from an epoxy resin.

  In the curable resin composition of the present invention, the acid anhydride having 9 or more carbon atoms is preferably a dibasic acid anhydride having an alicyclic structure.

  The dry film of the present invention is obtained by coating and drying the curable resin composition on a film.

  The cured product of the present invention is obtained by curing the curable resin composition or the dry film by irradiation with active energy rays.

  The printed wiring board of the present invention comprises the cured product.

  According to the present invention, it is possible to provide a curable resin composition with less decomposition and discoloration due to heat of a cured product, a dry film obtained from the composition, a cured product thereof, and a printed wiring board including the cured product. it can.

  The curable resin composition of the present invention contains (A) a carboxyl group-containing resin obtained by adding an acid anhydride having 9 or more carbon atoms to a polyol compound, and (B) a photopolymerization initiator. It is what. Hereinafter, each component of the curable resin composition of the present invention will be described.

[(A) Carboxyl group-containing resin obtained by adding an acid anhydride having 9 or more carbon atoms to a polyol compound]
(A) A carboxyl group-containing resin obtained by adding an acid anhydride having 9 or more carbon atoms to a polyol compound (hereinafter also simply referred to as “(A) carboxyl group-containing resin”) is a variety of conventionally known polyol compounds, It can be obtained by adding conventionally known acid anhydrides having 9 or more carbon atoms. By adding an acid anhydride having 9 or more carbon atoms, compared with the case of adding an acid anhydride having 8 or less carbon atoms such as tetrahydrophthalic anhydride, a cured product with less deterioration (decomposition, discoloration) due to heat is obtained. It can be set as the curable resin composition which can be obtained. Although the detailed mechanism is not clear, by adding an acid anhydride having 9 or more carbon atoms, the number of carbons in the structure increases and the structure becomes bulky, which contributes to improvement in heat resistance. Conceivable. Such a cured product is excellent in reducing deterioration due to light. Further, the presence of the carboxyl group makes the resin composition alkali developable.

  The polyol compound is not particularly limited as long as it is a bifunctional or higher functional polyol compound. Examples of bifunctional polyol compounds include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, spiroglycol, dioxane Glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol, 3-methylpentanediol, hexamethylene glycol Octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A ethylene oxide modified compound, bisphenol A Pyrene oxide modified compound, ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, copolymeric polyether polyol of ethylene oxide and propylene oxide, carbonate diol, and the like.

  Examples of the tri- or higher functional polyol compound include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, and their ethylene oxides, A propylene oxide modified product is also included. As the polyol compound having an aromatic ring, ethylene oxide of a trifunctional or higher phenol compound, (meth) acrylic acid adduct of a modified propylene oxide; bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type epoxy resin, etc. (Meth) acrylic acid adducts of bifunctional or higher functional epoxy resins; phenoxy resins and the like, and polyol compounds having an oxetane ring include dicarboxylic acid adducts of polyfunctional oxetane resins and have a heterocyclic ring Examples of the polyol compound include Sake manufactured by Shikoku Kasei Co., Ltd. A polyol compound can be used individually by 1 type or in combination of 2 or more types.

  The polyol compound preferably has a photosensitive group. Examples of the photosensitive group include a (meth) acryloyl group. Furthermore, the polyol compound having a photosensitive group is obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide, and (a) a group that reacts with a hydroxyl group and an ethylenic group. A polyol compound obtained by reacting a compound having an unsaturated group, or a polyol compound obtained by reacting (c) a carboxyl group-containing photosensitive compound with (b) a cyclic ether compound is preferred.

  Examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol F, bisphenol S, and these novolaks, phenol novolacs, cresol novolacs, and derivatives thereof.

As the compound (a) having a group that reacts with a hydroxyl group and an ethylenically unsaturated group, acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, Examples include α-cyanocinnamic acid, cinnamic acid, and half ester compounds of saturated or unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule. Examples of (meth) acrylates having a hydroxyl group for producing a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adduct. Examples of the dibasic acid anhydride for producing the half ester compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydro And phthalic anhydride. Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in admixture of two or more.
Alternatively, a compound having isocyanate and ethylenic unsaturation in one molecule may be used, and commercially available products include Karenz MOI, Karenz MOI-EG, Karenz AOI, and Karenz BEI manufactured by Showa Denko KK. Further, at this time, a product obtained by reacting one terminal of (meth) acrylate having one hydroxyl group and diisocyanate may be used.

  The (b) cyclic ether compound is a compound having a plurality of three, four or five-membered cyclic (thio) ether groups in the molecule, for example, a compound having a plurality of epoxy groups in the molecule, Examples thereof include a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin.

  The (c) carboxyl group-containing photosensitive compound is a compound having a carboxyl group and an ethylenically unsaturated group, and examples thereof include acrylic acid, methacrylic acid, and derivatives thereof.

  Examples of the acid anhydride having 9 or more carbon atoms include aliphatic acid anhydrides such as methyltetrahydrophthalic acid anhydride, highmic acid anhydride, methylhymic acid anhydride, cyclohexanetricarboxylic acid anhydride, and the like. Examples thereof include trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride and the like, which are acid anhydrides. From the viewpoint of easy addition reaction with polyol, the acid anhydride having 9 or more carbon atoms is preferably an aliphatic acid anhydride. Here, as an acid anhydride having 9 or more carbon atoms, a dibasic acid anhydride is preferable from the viewpoint of reactivity with a thermosetting component, and a dibasic acid anhydride having an alicyclic structure is particularly preferable. The acid anhydride having 9 or more carbon atoms preferably has 9 to 15 carbon atoms, and more preferably 9 to 11 carbon atoms, from the viewpoint of heat resistance. The acid anhydride having 9 or more carbon atoms can be used alone or in combination of two or more.

  A known method may be used as a method for adding an acid anhydride having 9 or more carbon atoms to the polyol compound, and is not particularly limited. For example, the reaction is usually performed at about 50 to 150 ° C. in the presence or absence of an organic solvent as described later in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and oxygen. At this time, as required, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine, naphthenic acid, laurin Metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium such as acid, stearic acid, oleic acid, and octoenoic acid may be added as a catalyst. The amount ratio of the polyol compound part and the acid anhydride having 9 or more carbon atoms in the addition reaction is preferably such that the acid value of the produced (A) carboxyl group-containing resin is 20 to 200 mgKOH / g, A quantitative ratio of 150 mgKOH / g is more preferable.

  (A) The carboxyl group-containing resin may have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group from the viewpoint of making the curable resin composition of the present invention photocurable and developing resistance. Although preferred, only a carboxyl group-containing resin having no ethylenically unsaturated double bond can be used as the (A) carboxyl group-containing resin. (A) When the carboxyl group-containing resin does not have an ethylenically unsaturated bond, in order to make the composition photocurable, a compound having at least one ethylenically unsaturated group in the molecule (photosensitive compound ) Must be used in combination. As the ethylenically unsaturated double bond, those derived from (meth) acrylic acid or derivatives thereof are preferable. In this specification, (meth) acrylic acid is a generic term for acrylic acid, methacrylic acid and mixtures thereof, and the same applies to other similar expressions.

(A) The method for introducing an ethylenically unsaturated group into the carboxyl group-containing resin is not particularly limited. For example, a method of introducing a polyol compound having a (meth) acryloyl group and an acid anhydride having 9 or more carbon atoms by addition reaction, or a polyol compound is at least one of (meth) acrylic acid and (meth) acrylic acid derivatives On the other hand, after processing, the method of introduce | transducing by making addition reaction of an acid anhydride of 9 or more carbon atoms is mentioned. Examples of (meth) acrylic acid and (meth) acrylic acid derivatives include acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyanocinnamic Half ester compounds of acid, cinnamic acid, or saturated or unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule, (meth) acrylic monomers having an isocyanate group, Examples thereof include compounds having both a cyclic ether group and an ethylenically unsaturated group in one molecule.
In addition, when the (A) carboxyl group-containing resin is not derived from an epoxy resin, the insulation reliability is improved and it can be suitably used as a solder resist for a semiconductor package. Examples of the carboxyl group-containing resin not derived from the epoxy resin include a carboxyl group-containing resin derived from a phenol resin, a carboxyl group-containing urethane resin, and a carboxyl group-containing copolymer resin.

  Specific examples of the (A) carboxyl group-containing resin include the compounds listed below (any of oligomers and polymers), but are not limited thereto.

  (1) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid such as (meth) acrylic acid and adding a dibasic acid anhydride having 9 or more carbon atoms to a hydroxyl group present in the side chain. Here, the polyfunctional epoxy resin is preferably solid.

  (2) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin with a saturated monocarboxylic acid and adding a dibasic acid anhydride having 9 or more carbon atoms to a hydroxyl group present in the side chain. Here, the polyfunctional epoxy resin is preferably solid.

  (3) The polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride having 9 or more carbon atoms is added to the resulting hydroxyl group. Carboxyl group-containing resin. Here, the bifunctional epoxy resin is preferably solid.

  (4) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride having 9 or more carbon atoms to the resulting primary hydroxyl group.

  (5) obtained by reacting a polybasic acid anhydride having 9 or more carbon atoms with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide. Carboxyl group-containing resin.

  (6) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a saturated monocarboxylic acid, and carbon is added to the resulting reaction product. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride having a number of 9 or more.

  (7) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a product with a polybasic acid anhydride having 9 or more carbon atoms.

  (8) A reaction product obtained by reacting a compound obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a saturated monocarboxylic acid. A carboxyl group-containing resin obtained by reacting with a polybasic acid anhydride having 9 or more carbon atoms.

  (9) A polybasic acid anhydride having 9 or more carbon atoms is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. The carboxyl group-containing resin obtained by the above.

  (10) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride having 9 or more carbon atoms.

  (11) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a saturated monocarboxylic acid A carboxyl group-containing resin obtained by reacting an acid and reacting a polybasic acid anhydride having 9 or more carbon atoms with the alcoholic hydroxyl group of the obtained reaction product.

  (12) reacting an epoxy compound having a plurality of epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol; A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride having 9 or more carbon atoms with the alcoholic hydroxyl group of the obtained reaction product.

  (13) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Carboxyl group-containing resin obtained by reacting an unsaturated hydroxyl group-containing monocarboxylic acid such as acrylic acid and reacting a polybasic acid anhydride having 9 or more carbon atoms with the alcoholic hydroxyl group of the resulting reaction product .

  (14) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate A carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminally (meth) acrylated.

  (15) 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, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. A carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and then terminally (meth) acrylating.

  (16) 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.

  (17) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any of the resins (1) to (16) above A carboxyl group-containing resin formed by adding a group-containing compound.

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

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

  (A) A carboxyl group-containing resin can be used alone or in combination of two or more. Moreover, you may use together conventionally well-known carboxyl group-containing resin in the range which does not impair the effect of this invention. The blending amount of the (A) carboxyl group-containing resin is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, further preferably 20 to 60% by mass, and particularly preferably 30 to 50% in the entire composition. % By mass. In the case of 5 to 60% by mass, the coating film strength is good, the viscosity of the composition is moderate, and coatability and the like can be improved.

[Photopolymerization initiator]
Examples of the photopolymerization initiator include an oxime ester photopolymerization initiator having an oxime ester group, an alkylphenone photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a titanocene system. One or more photopolymerization initiators selected from the group consisting of photopolymerization initiators can be suitably used. The oxime ester-based initiator is preferable because the addition amount is small and outgassing is suppressed, which is effective in PCT resistance and crack resistance.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０か１の整数である。） Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

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

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that

（式中、Ｒ^１は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。
Ｒ^２は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。
Ｒ^３は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。
Ｒ^４は、ニトロ基、または、Ｘ−Ｃ（＝Ｏ）−で表されるアシル基を表す。Ｘは、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式で示される構造を表す。）

Moreover, the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.

(In the formula, R ¹ represents an alkyl group or a nitro group, a halogen atom or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ² represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
R ³ may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl group.
R ⁴ represents a nitro group or an acyl group represented by X—C (═O) —. X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms. )

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

The blending amount of such an oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass and preferably 0.25 to 3 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferred.
By setting the content to 0.01 to 5 parts by mass, a cured film having excellent photocurability and resolution, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance is obtained. be able to. In particular, when the amount is 5 parts by mass or less, light absorption on the coating film surface becomes intense, and it is possible to suppress a decrease in deep part curability.

  Examples of commercially available alkylphenone photopolymerization initiators include α-hydroxyalkylphenone types such as Irgacure 184, Darocur 1173, Irgacure 2959, and Irgacure 127 manufactured by BASF Japan.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 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 BASF Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.

The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferably, it is 20 parts by mass.
By being 0.1 to 25 parts by mass, a cured film having excellent photocurability and resolution, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance is obtained. be able to. In particular, when it is 25 parts by mass or less, an effect of reducing outgas is obtained, and further, light absorption on the surface of the coating film becomes intense, and it is possible to suppress a decrease in deep part curability.

  In addition, Irgacure 389 manufactured by BASF Japan can be suitably used as a photopolymerization initiator. The suitable compounding quantity of Irgacure 389 is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, More preferably, it is 1-15 mass parts.

A titanocene photopolymerization initiator such as Irgacure 784 can also be suitably used. The suitable compounding quantity of a titanocene type photoinitiator is 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing resin, and a more suitable compounding quantity is 0.01-3 mass parts. .
By setting these photopolymerization initiators in suitable amounts, they are excellent in photocurability and resolution, improved in adhesion and PCT resistance, and also in chemical resistance such as electroless gold plating resistance. Solder resist can be used. Moreover, in the case of a suitable blending amount, an effect of reducing outgas is obtained, and further, light absorption on the surface of the coating film becomes intense, so that it is possible to suppress a decrease in deep curability.

  The photosensitive resin composition can use a photoinitiator and a sensitizer in addition to the photopolymerization initiator. Photoinitiators, photoinitiators, and sensitizers that can be suitably used for photosensitive resin compositions include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and tertiary amine compounds. And xanthone 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, 1,1-dichloroacetophenone, and the like.

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

  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′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4, Dialkylaminobenzophenone such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Bio-Synthetics), 4-dimethylamino Nobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  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 said carboxyl group-containing resin. When the blending amount of the thioxanthone compound is 20 parts by mass or less, the thick film curability is improved and the cost of the product is reduced. 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, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength in the range of 350 to 450 nm, and ketocoumarins are particularly preferable. .

  As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored, and use colored pigments as well as colorless and transparent photosensitive compositions, and colors that reflect the color of the colored pigments themselves It becomes possible to provide a solder resist. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin. When the compounding amount of the tertiary amine compound is 0.1 parts by mass or more, a sufficient sensitizing effect can be obtained. On the other hand, when the amount is 20 parts by mass or less, light absorption on the surface of the dried coating film by the tertiary amine compound becomes violent, and it is suppressed that the deep part curability is lowered. 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 preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. It can suppress that deep part curability falls by these light absorption as it is 35 mass parts or less.

[(C) thermosetting component]
It is preferable to mix | blend (C) thermosetting component with the curable resin composition of this invention. It can be expected that heat resistance is improved by adding a thermosetting component. (C) Any known thermosetting component can be used. For example, known thermosettings such as melamine resin, benzoguanamine resin, melamine derivative, amino resin such as benzoguanamine derivative, isocyanate compound, blocked isocyanate compound, cyclocarbonate compound, epoxy compound, oxetane compound, episulfide resin, bismaleimide, carbodiimide resin, etc. Ingredients can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio) ether groups in the molecule. A compound having a plurality of epoxy groups, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, a polyfunctional episulfide resin, etc. It is done.

  Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Diglycidyl Taleate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives; CTBN-modified epoxy resins and the like can be mentioned, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, novolak type epoxy resins, bisphenol type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, biphenol novolac type epoxy resins, naphthalene type epoxy resins or mixtures thereof are particularly preferable.

  Examples of the polyfunctional oxetane compound 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- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxystyrene), cardo-type bis Phenol ethers, calixarenes, calix resorcin arenes or etherified products such as the 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 a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. 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 a plurality of cyclic (thio) ether groups in such a molecule is 0.6 to 2.5 equivalents with respect to 1 equivalent of carboxyl group of (A) carboxyl group-containing resin. preferable. When the blending amount is 0.6 equivalent or more, the carboxyl group hardly remains in the cured product, and the heat resistance, alkali resistance, electrical insulation and the like are good. On the other hand, when the amount is 2.5 equivalents or less, the low molecular weight cyclic (thio) ether group hardly remains in the dry coating film, and the strength of the coating film is good. More preferably, it is 0.8-2.0 equivalent.

  Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.

  As the isocyanate compound, a polyisocyanate compound can be blended. Examples of the polyisocyanate compound include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and Aromatic polyisocyanates such as 2,4-tolylene dimer; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as heptane triisocyanate; and adducts of the isocyanate compounds listed above, Yuretto body and isocyanurate products thereof.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example. As an isocyanate block agent, for example, phenol block agent; lactam block agent; active methylene block agent; alcohol block agent; oxime block agent; mercaptan block agent; acid amide block agent; imide block agent; Examples include amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents.

  As for the compounding quantity of such a polyisocyanate compound or a block isocyanate compound, 1-100 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group-containing resin. When the amount is 1 part by mass or more, sufficient toughness of the coating film is obtained. On the other hand, when it is 100 parts by mass or less, the storage stability is good. More preferably, it is 2-70 mass parts.

  (C) As for the compounding quantity of a thermosetting component, 10-100 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group-containing resin.

(Photosensitive compound containing acrylic group or methacryl group)
The curable resin composition of the present invention preferably contains a photosensitive compound containing an acryl group or a methacryl group (hereinafter also simply referred to as “photosensitive compound”). Any known compound can be used as the photosensitive compound. A compound having an acryl group or a methacryl group in the molecule is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the curable resin of the present invention or the carboxyl group resin in an alkaline aqueous solution. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide , N-methylolacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate, or their ethylene oxide adducts, propylene oxide adducts Or polyhydric acrylates such as ε-caprolactone adduct; polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyacid acrylates of sidyl ether; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And / or methacrylates corresponding to the acrylate. Among the photosensitive compounds, from the viewpoint of versatility, polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, or ε- Polyvalent acrylates such as caprolactone adducts are preferred.

  A photosensitive compound can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use together other conventionally well-known photosensitive compounds in the range which does not impair the effect of this invention. 1-50 mass parts is preferable with respect to 100 mass parts of said (A) component, and, as for the compounding quantity of a photosensitive compound, 5-40 mass parts is more preferable. When the amount is 1 part by mass or more, sufficient patterning by exposure is obtained. In the case of 50 parts by mass or less, the tackiness of the dried coating film is good.

(Filler)
An inorganic filler can be blended in the curable resin composition of the present invention. An inorganic filler is used in order to suppress the curing shrinkage of the cured product of the curable resin composition and improve properties such as adhesion and hardness. Examples of inorganic fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and nitriding Examples thereof include silicon and aluminum nitride.

  The average particle size of the inorganic filler is preferably 5 μm or less. The blending ratio is preferably 75% by mass or less, more preferably 0.1 to 60% by mass based on the total solid content of the curable resin composition. When the blending ratio of the inorganic filler is 75% by mass or less, the viscosity of the composition does not become too high, the coating property is good, and the cured product of the curable resin composition is difficult to become brittle. Moreover, an organic filler can be mix | blended with the curable resin composition of this invention as a filler.

(Coloring agent)
The curable resin composition of the present invention can contain a colorant. As the colorant, conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments may be used. Specific examples include color index (CI; issued by The Society of Dyers and Colorists) number. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.

  Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Examples of blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment. Similarly, the green colorant includes metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based materials. Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the white colorant include rutile type, anatase type titanium oxide and the like. Black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. Examples thereof include pigments, molybdenum sulfide, and bismuth sulfide. In addition, a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.

  Although the compounding quantity of a coloring agent is not specifically limited, It is preferable to set it as 10 mass parts or less with respect to 100 mass parts of (A) carboxyl group-containing resin. More preferably, it is 0.1-5 mass parts.

(Organic solvent)
In the curable resin composition of the present invention, an organic solvent can be used for the synthesis of the carboxyl group-containing resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. . Examples of the organic solvent 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, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate , Propylene glycol ethyl ether acetate, propylene glycol butyl ether Esters such as cetate; Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha is there. Such an organic solvent can be used individually by 1 type or in combination of 2 or more types.

(Other optional ingredients)
In the curable resin composition of the present invention, if necessary, a cyanate compound, an elastomer, a mercapto compound, a thermosetting catalyst, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, Polymerization inhibitors, copper damage inhibitors, antioxidants, rust inhibitors, UV absorbers, fine silica, organic bentonite, montmorillonite and other thickeners, silicone-based, fluorine-based, polymer-based antifoaming agents and / or Alternatively, components such as leveling agents, silane coupling agents such as imidazole, thiazole, and triazole, flame retardants such as phosphorus compounds such as phosphinates, phosphate ester derivatives, and phosphazene compounds can be blended. As these, those known in the field of electronic materials can be used.

  The curable resin composition of the present invention is a material that is less likely to be deteriorated by heat, and can be used for a long period of time as a protective film without being decomposed and peeled even when used in a part that is subjected to a thermal load. The cured coating film which consists of a thing can be provided. The curable resin composition of the present invention is useful for forming a pattern layer of a printed wiring board, and is particularly useful as a material for a solder resist or an interlayer insulating layer. Moreover, since there is little discoloration, it can be used as a protective film for the LED illumination member without impairing the reflectance for a long period of time.

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

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

  After the curable resin composition of the present invention is formed on the carrier film, a peelable cover film may be laminated on the film surface for the purpose of preventing dust from adhering to the film surface. preferable. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

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

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

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

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

  By exposing the coating film obtained after applying the curable resin composition of the present invention and evaporating and drying the solvent to the exposed portion (irradiation of active energy rays), the exposed portion (the portion irradiated by the active energy rays) ) Is cured. Further, by a contact method (or a non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution.

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

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

  The glass transition temperature (Tg) of the cured product of the present invention is preferably 100 ° C. or higher, and more preferably 110 ° C. or higher. When the glass transition temperature (Tg) is 100 ° C. or higher, PCT resistance and HAST resistance are further improved.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

(Synthesis Example 1)
Orthocresol novolak type epoxy resin [DICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups (total number of aromatic rings)): 600 g of diethylene glycol monoethyl ether acetate 0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. Into the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride were charged, and reacted at 110 ° C. for 4 hours. After cooling, a carboxyl group-containing resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained. This is designated as resin solution 1.

(Synthesis Example 2)
In the same manner as in Synthesis Example 1 except that 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride was replaced with 498 g (3.0 mol) of methyltetrahydrophthalic anhydride, A carboxyl group-containing resin solution having a partial acid value of 89 mgKOH / g and a solid content of 65% was obtained. This is designated as Resin Solution 2.

(Synthesis Example 3)
In an autoclave equipped with a thermometer, a nitrogen introducing device / alkylene oxide introducing device and a stirring device, 119.4 g of a novolac-type cresol resin (Shornol CRG951, OH equivalent: 119.4, manufactured by Showa Denko KK), 1.19 g of potassium hydroxide Then, 119.4 g of toluene was charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A 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 the obtained novolak-type cresol resin alkylene oxide reaction solution, 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. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained 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, 71.2 g of methyl-5-norbornene-2,3-dicarboxylic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A carboxyl group-containing resin solution having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. This is designated as resin solution 3.

(Synthesis Example 4)
In the same manner as in Synthesis Example 3 except that 71.2 g of methyl-5-norbornene-2,3-dicarboxylic acid anhydride was replaced with 66.4 g of methyltetrahydrophthalic anhydride, the acid value of the solid substance was 88 mgKOH / g, A carboxyl group-containing resin solution having a nonvolatile content of 71% was obtained. This is designated as resin solution 4.

(Synthesis Example 5)
After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide in 400 parts of a bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 parts of 98.5% NaOH at 100 ° C. with stirring were added to 100 parts. Added over 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, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% NaOH was added at 70 ° C. The reaction was carried out for 1 hour. After completion of the reaction, washing was performed twice with 200 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 diethylene glycol monoethyl ether acetate are heated and stirred at 90 ° C., and the reaction mixture Was dissolved. 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, 1305 parts (7.86 mol) of methyltetrahydrophthalic anhydride and 423 parts of diethylene glycol monoethyl ether acetate were added to this, heated to 95 ° C., reacted for about 6 hours, and a solid content acid value of 100 mg KOH / g. A resin solution having a solid content of 65% was obtained. This is designated as resin solution 5.

(Comparative Synthesis Example 1)
In the same manner as in Synthesis Example 1, except that 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride was replaced with 456.0 g (3.0 mol) of tetrahydrophthalic anhydride, A carboxyl group-containing resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained. This is designated as resin solution 6.

(Comparative Synthesis Example 2)
71.2 g of methyl-5-norbornene-2,3-dicarboxylic acid anhydride was added to tetrahydrophthalic anhydride 60. The acid value of the solid substance was 88 m in the same manner as in Synthesis Example 3 except that 8 g was used.
A carboxyl group-containing resin solution having gKOH / g and a nonvolatile content of 71% was obtained. This is designated as resin solution 7.

( Reference Examples 1, 2, 5, Examples 3, 4 and Comparative Examples 1, 2)
It mix | blended in the ratio (mass part) shown in Table 1 with the various component shown in following Table 1, Then, it premixed with the stirrer and knead | mixed with the 3 roll mill, and prepared curable resin composition. For each resin solution, the carbon number of the acid anhydride added to the polyol compound is 10 for resin solution 1, 9 for resin solution 2, 10 for resin solution 3, 9 for resin solution 4, 9 for resin solution 5, The resin solution 6 is 8 and the resin solution 7 is 8.

＊１：α−アミノアセトフェノン系光重合開始剤（ＢＡＳＦジャパン社製Ｉｒｇｃｕｒｅ
９０７）
＊２：ノボラック型エポキシ樹脂（日本化薬社製ＲＥ−３０６）
＊３：ジペンタエリスリトールヘキサアクリレート（日本化薬社製ＫＡＹＡＲＡＤ ＤＰ
ＨＡ）
＊４：硫酸バリウム（堺化学社製Ｂ−３０）
＊５：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊６：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １４７

* 1: α-aminoacetophenone photopolymerization initiator (Irgcure manufactured by BASF Japan Ltd.)
907)
* 2: Novolac epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd.)
* 3: Dipentaerythritol hexaacrylate (KAYARAD DP manufactured by Nippon Kayaku Co., Ltd.)
HA)
* 4: Barium sulfate (B-30 manufactured by Sakai Chemical Co., Ltd.)
* 5: C.I. I. Pigment Blue 15: 3
* 6: C.I. I. Pigment Yellow 147

About the curable composition of the reference example shown in Table 1, an Example, and a comparative example, performance evaluation and characteristic evaluation were performed with the evaluation method shown below. The evaluation results are shown in Table 2.

<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water and dried, and then the curable resin compositions of the above examples and comparative examples were applied to the entire surface by a screen printing method, and a hot air circulation drying oven at 80 ° C. And dried for 60 minutes. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the pattern of the step tablet remaining when performing in seconds was 7 steps, the optimum exposure amount was set.

Characteristic evaluation substrate manufacturing procedure:
The compositions of Reference Examples, Examples and Comparative Examples shown in Table 1 were applied on the entire surface of the patterned copper foil substrate so as to have a dry film thickness of about 20 μm by screen printing, and dried at 80 ° C. for 30 minutes. Allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa. Obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<PCT resistance (adhesion, discoloration resistance)>
About the evaluation board | substrate, the electroless gold plating process was performed on the conditions of nickel 5micrometer and gold | metal 0.05micrometer using the electroless nickel plating bath and electroless gold plating bath of a commercial item. Place the electroless gold-plated evaluation substrate in a high-pressure, high-humidity bath at 121 ° C, 2 atm and 100% humidity for 100 hours, observe the state change of the solder resist, and evaluate the adhesion and discoloration resistance according to the following evaluation criteria. did.
Adhesiveness ○: No noticeable swelling.
Δ: Slightly peeled off.
X: There is peeling.
Discoloration resistance ○: No discoloration.
×: Discolored.

<HAST resistance (insulation reliability)>
Using a comb-type electrode pattern of line / space = 50/50 μm, an evaluation substrate was produced under the above conditions, and the insulation reliability (electrode corrosivity) was evaluated.
The evaluation method was that this comb-shaped electrode was 121 ° C., 97% R.D. H. A bias voltage of DC 30 V was applied under the heating and humidifying conditions, and the time until insulation deterioration was measured. Here, when the electric resistance value fell below 1 × 10 ⁻⁶ Ω, it was determined that the insulation was deteriorated. The evaluation criteria are as follows.
◎: Time to insulation degradation is 300 hours or more ○: Time to insulation degradation is 200 hours to less than 300 hours △: Time to insulation degradation is 100 hours to less than 200 hours ×: Insulation degradation Less than 100 hours

<HAST resistance (discoloration resistance)>
In the HAST test, the discoloration of the test substrate after 300 hours from the application of the bias voltage was confirmed. The evaluation criteria are as follows.
○: No discoloration.
×: Discolored.

<Color retention>
The evaluation substrate was passed through a reflow furnace having a maximum temperature of 260 ° C. three times, and the change in the color of the cured coating film was observed and evaluated.
○: No discoloration.
X: Slightly discolored.

<Glass transition temperature>
The cured coating film was peeled off from the evaluation substrate, and the cured coating film was measured by thermomechanical analysis (DSC) according to the method described in “5.17.5 DSC method” of JIS C 6481: 1996.

From the results shown in Tables 1 and 2, it can be seen that in the case of the curable resin compositions of Reference Examples 1, 2, 5, and Examples 3 and 4 , there is little deterioration of the cured coating film due to heat. On the other hand, (A) Comparative Examples 1 and 2 using a carboxyl group-containing resin obtained by adding an acid anhydride having 8 carbon atoms to a polyol compound instead of a carboxyl group-containing resin is a deterioration of a cured coating film due to heat. Was remarkable.
Moreover, from the said result, it turns out that the curable resin composition of this invention has little deterioration of the cured coating film by a heat | fever, and is useful as members for printed wiring boards, such as a material of a soldering resist and an interlayer insulation layer. Moreover, since there is little discoloration, it can be used as a protective film for the LED illumination member without impairing the reflectance for a long period of time.

Claims (8)

(A) a polyol compound having 9 or more acid anhydride of carbon atoms in (except an acid anhydride represented by the following formula (1)) a carboxyl group-containing resin which is an adduct of,

(In Formula (1), R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, or a monovalent organic group, which may be the same or different from each other. Z is a nitrogen atom, or a carbon atom to which the substituent R is bonded, the substituent R, a hydrogen atom, a halogen atom, or a monovalent organic group, they may be being the same or different. Further, the R ¹ to R ⁴ and one of the substituents R may also form a cyclic structure via a coupling to one another.)
and,
(B) a photopolymerization initiator,
Containing
As the (A) a carboxyl group-containing resin which is a number of 9 or more acid anhydride adduct of carbon atoms in the polyol compound,
(5) a carboxyl group-containing resin which is a reaction of the compound and a reaction product and having 9 or more polybasic acid anhydrides carbon of an alkylene oxide having a plurality of phenolic hydroxyl groups in the molecule,
(6) a compound having a plurality of phenolic hydroxyl groups per molecule and reaction products of alkylene oxides and a reaction product of a saturated monocarboxylic acid, a reaction product of the number of 9 or more polybasic acid anhydrides carbon A certain carboxyl group-containing resin,
(7) a compound having a plurality of phenolic hydroxyl groups in the molecule and the reaction product of a reaction product with an unsaturated group-containing monocarboxylic acids with alkylene oxides, and having 9 or more polybasic acid anhydrides carbon A carboxyl group-containing resin as a reaction product ,
(8) reaction of the reaction product and the reaction product of a saturated monocarboxylic acid, and having 9 or more polybasic acid anhydrides carbon of the compound and a cyclic carbonate compound having a plurality of phenolic hydroxyl groups in the molecule A carboxyl group-containing resin,
(9) a plurality of compounds having a phenolic hydroxyl group and a cyclic carbonate compound with the carboxyl group-containing resin reaction product and a reaction product of the number of 9 or more polybasic acid anhydrides carbon in in the molecule,
(10) a reaction product of one reaction product of a compound having a plurality of phenolic hydroxyl groups in the molecule and a cyclic carbonate compound with an unsaturated group-containing monocarboxylic acid, and having 9 or more polybasic acid anhydrides carbon A carboxyl group-containing resin that is a reaction product of
(17) A carboxyl group-containing resin which is an adduct of a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule of the resin of any one of (5) to (10) above,
Any one of these is included, The curable resin composition characterized by the above-mentioned.   Furthermore, (C) thermosetting component is contained, The curable resin composition of Claim 1 characterized by the above-mentioned.   The curable resin composition according to claim 1, wherein the polyol compound has a photosensitive group.   The curable resin composition according to claim 1, wherein the (A) carboxyl group-containing resin is not derived from an epoxy resin.   The curable resin composition according to any one of claims 1 to 4, wherein the acid anhydride having 9 or more carbon atoms is a dibasic acid anhydride having an alicyclic structure.   A dry film obtained by applying and drying the curable resin composition according to any one of claims 1 to 5 on a film.   Hardened | cured material obtained by hardening | curing the curable resin composition as described in any one of Claims 1-5, or the dry film of Claim 6 by active energy ray irradiation.   A printed wiring board comprising the cured product according to claim 7.