TWI770369B - Alkali-developing photosensitive resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

The subject of this invention is to provide the alkali developing type photosensitive resin composition which maintains high heat resistance, and is excellent in solvent solubility, resolution, sensitivity, and adhesiveness. The solution is an alkali developing type photosensitive resin composition of the present invention, which is characterized by comprising: a carboxyl group-containing resin, a photobase generator, a thermosetting resin, and a filler, wherein the thermosetting resin comprises a biphenyl skeleton. The maleimide compound, and the aforementioned filler has a photoreactive or thermally reactive functional group on the surface.

Description

Alkali-developing photosensitive resin composition, dry film, cured product, and printed wiring board

The present invention relates to an alkali-developing photosensitive resin composition. Moreover, this invention also relates to the dry film, hardened|cured material, and printed wiring board using this alkali developing type photosensitive resin composition.

In recent years, with the reduction in size and weight of electronic equipment, multi-functionalization, and environmental compatibility, high-density packaging and thinning of printed wiring boards and the like are moving towards. In particular, since the solder resist for printed wiring boards is subjected to various thermal stresses during mounting, high reliability is required in the evaluation of HAST (Unsaturated Pressure Cooker Test) and TCT (Cooling and Thermal Cycle Test).

In order to improve high reliability, the photosensitive resin composition which added the maleimide compound, for example, has been proposed (for example, refer patent document 1). By adding a maleimide compound, high heat resistance can be imparted, and reliability can be improved. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-42711

[The problem to be solved by the invention]

However, the maleimide compound has poor solvent solubility, and when the maleimide compound is varnished, the solid content becomes very low. Therefore, the solid content of the photosensitive resin composition containing this varnished maleimide compound is reduced. Therefore, when the photosensitive resin composition is dried under normal conditions, the amount of the residual solvent in the dry film increases, which tends to cause problems in coatability and optical properties. In addition, since the maleimide compound is colored, when it is used in a photosensitive resin composition, it has a problem that it affects the deep curability and impairs the resolution. In addition, if the hardening of the deep part is insufficient, the interface between the resin and the copper is easily affected by humidification, etc., and there is a problem that the adhesion is lowered. In particular, when placed under high temperature and high humidity, moisture tends to penetrate into the interface between the resin and copper, resulting in a significant decrease in adhesion. In addition, in order to obtain high reliability, a large amount of filler is effective. However, as the filling amount of the filler increases, there is still a problem that the adhesiveness decreases.

Therefore, the objective of this invention is to provide the alkali developing type photosensitive resin composition which maintains high heat resistance, and is excellent in solvent solubility, resolution, sensitivity, and adhesiveness. [means to solve the problem]

The inventors of the present invention obtained maleiae having a biphenyl skeleton as a thermosetting resin by using a photobase generator in combination in an alkali-developing photosensitive resin composition comprising a carboxyl group-containing resin and a thermosetting resin. An amine compound and a filler having a photoreactive or thermally reactive functional group on the surface are the knowledge and knowledge that can solve the above-mentioned problems, and the present invention is based on the knowledge and knowledge.

That is, the alkali-developing photosensitive resin composition of the present invention is characterized by comprising: a carboxyl group-containing resin, a photobase generator, a thermosetting resin, and a filler, wherein the thermosetting resin comprises a maleic acid having a biphenyl skeleton. For imide compounds, the aforementioned fillers have photoreactive or thermally reactive functional groups on the surface.

In an aspect of the present invention, the photobase generator preferably has an oxime skeleton.

In the aspect of this invention, the compounding quantity of the said photobase generator is preferably 0.05 mass % or more and 0.7 mass % or less in conversion of solid content in the said alkali developing type photosensitive resin composition.

In the aspect of this invention, the compounding quantity of the said maleimide compound is preferably 0.3 mass % or more and 10 mass % or less in terms of solid content in the said alkali developing type photosensitive resin composition.

The dry film of another aspect of this invention is characterized by having a resin layer obtained by apply|coating the said alkali developing type photosensitive resin composition to a support film, and drying it.

A cured product of another aspect of the present invention is obtained by curing the alkali-developing photosensitive resin composition or the resin layer of the dry film.

A printed wiring board according to another aspect of the present invention is characterized by having the above-mentioned cured product. [Effect of invention]

According to the present invention, there is provided an alkali-developing-type photosensitive resin composition excellent in solvent solubility, resolution, sensitivity, and adhesion while maintaining high heat resistance. In particular, even in the case of highly filled fillers, an alkali-developing photosensitive resin composition excellent in adhesion can be provided. Moreover, the dry film and hardened|cured material using such an alkali-developing-type photosensitive resin composition can be provided. The alkali-developing photosensitive resin composition provided by the present invention can improve heat resistance and maintain adhesion, and can be expected to be suitable for applications such as automobiles of the next generation that require high temperature and high humidity resistance.

[Alkali developing type photosensitive resin composition] The alkali-developing-type photosensitive resin composition of the present invention will be described. The alkali-developing photosensitive resin composition of the present invention contains at least a carboxyl group-containing resin, a photobase generator, a thermosetting resin, and a filler, and may also contain a photosensitive monomer (reactive diluent), photopolymerization Other components such as initiators, colorants, organic solvents (non-reactive diluents), hardening catalysts, and additives. In the present invention, by using a photobase generator, a maleimide compound having a biphenyl skeleton as a thermosetting resin, and a filler having a photoreactive or thermally reactive functional group on the surface, it is possible to provide a high-maintenance filler. Alkali developing type photosensitive resin composition excellent in heat resistance, solvent solubility, resolution, sensitivity and adhesion. Hereinafter, each component which comprises the alkali developing type photosensitive resin composition of this invention is demonstrated.

[Carboxyl-containing resin] As the carboxyl group-containing resin, various conventionally known resins having a carboxyl group in the molecule can be used. The photosensitive resin composition can impart alkali developability to the photosensitive resin composition by including a resin having a carboxyl group. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable in terms of photocurability and development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. When only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond is used, in order to make a composition photosensitive, it is necessary to use together the photosensitive monomer mentioned later. As a specific example of the carboxyl group-containing resin, the compounds listed below (which may be either an oligomer or a polymer) can be mentioned.

(1) By combining unsaturated carboxylic acid such as (meth)acrylic acid with unsaturated group-containing styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Carboxyl-containing resin obtained by copolymerizing the compound; (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and carboxyl-containing groups such as dimethylolpropionic acid, dimethylolbutyric acid, etc. Diol compounds and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, phenolic Carboxyl-containing urethane resins obtained by addition polymerization of diol compounds such as hydroxyl and alcoholic hydroxyl compounds; (3) Using diisocyanate to mix with bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, joint phenol type epoxy resin, bisphenol A type epoxy resin Carboxyl group-containing photosensitive amines obtained by addition polymerization of (meth)acrylates of bifunctional epoxy resins such as phenolic epoxy resins or their partial acid anhydride denatured products, carboxyl group-containing diol compounds, and diol compounds carbamate resin; (4) In the synthesis of the resin in the above (2) or (3), a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule of hydroxyalkyl (meth)acrylate or the like is added , and the photosensitive urethane resin containing carboxyl group by terminal (meth)acrylation; (5) In the synthesis of the resin in the above (2) or (3), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added to have one isocyanate group and one or more isocyanate groups in the molecule. The (meth)acryloyl compound, and the terminal (meth)acrylation of the carboxyl group-containing photosensitive urethane resin; (6) A carboxyl group-containing photosensitive resin formed by reacting a bifunctional or more multifunctional (solid) epoxy resin with (meth)acrylic acid, and adding a dibasic acid anhydride to the hydroxyl group present in the side chain; (7) The polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of the bifunctional (solid) epoxy resin with epichlorohydrin is then reacted with (meth)acrylic acid, and a dibasic acid anhydride is added to the generated hydroxyl group to form The resulting photosensitive resin containing carboxyl group; (8) The bifunctional propylene oxide resin is reacted with dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid, and phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are added to the generated primary hydroxyl group. Carboxyl-containing polyester resins made from dibasic acid anhydrides such as (9) 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 (methyl) ) Monocarboxylic acid containing unsaturated groups such as acrylic acid is reacted, so that the alcoholic hydroxyl group of the obtained reaction product is then reacted with anhydrous maleic acid, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. The photosensitive resin containing carboxyl group obtained by the reaction of the polybasic acid anhydride, (10) The 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 and propylene oxide is further mixed with an unsaturated group-containing monocarboxylic acid Acid reaction, and the photosensitive resin containing carboxyl group obtained by reacting the obtained reaction product with polybasic acid anhydride; (11) 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 ethylidene carbonate and propylidene carbonate, and then with an unsaturated group-containing monocarboxylic acid react, and react the obtained reaction product with polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin; (12) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11) above. . In addition, in this specification, (meth)acrylate is a term collectively referring to acrylate, methacrylate, and these mixtures, and it is the same about other similar expressions.

The acid value of the carboxyl-containing resin is 40~150mgKOH/g. By setting the acid value of the carboxyl group-containing resin to be 40 mgKOH/g or more, alkali development becomes favorable. Moreover, it becomes easy to draw a favorable resist pattern by making an acid value 150 mgKOH/g or less. Preferably, it is 50-130 mgKOH/g.

The weight-average molecular weight of the carboxyl group-containing resin varies according to the resin skeleton, and is generally 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, tack-free performance and resolution can be improved. In addition, by setting the weight average molecular weight to be 150,000 or less, developability and storage stability can be improved. Preferably it is 3,000-100,000.

In the alkali-developing-type photosensitive resin composition, the compounding amount of the carboxyl group-containing resin is preferably 20 to 60 mass % in terms of solid content. By making it 20 mass % or more, the coating film strength can be improved. Moreover, by making it into 60 mass % or less, viscosity becomes suitable and workability improves. Preferably it is 25-50 mass %.

These carboxyl group-containing resins can be used without being limited to those listed above, and one type may be used alone, or a plurality of types may be mixed and used. Among them, carboxyl group-containing resins synthesized by using a compound having a phenolic hydroxyl group as a starting material as in the aforementioned carboxyl group-containing resins (10) and (11) can be suitably used because they are excellent in HAST resistance and PCT resistance.

[Photosensitive monomer] The compound used as a photosensitive monomer refers to a compound having an ethylenically unsaturated group in the molecule, and as the compound having an ethylenically unsaturated group in the molecule, for example, commonly known polyester (meth)acrylic acid can be mentioned. esters, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, and the like. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc.; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc. can be used Diacrylates of diols; acrylamides such as N,N-dimethyl acrylamide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide, etc.; Amino alkyl acrylates such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dimethicone Polyvalent alcohols such as pentaerythritol, para-hydroxyethyl isocyanurate, etc. or polyvalent ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts, etc. Acrylates; phenoxyacrylates, bisphenol A diacrylates, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol bicyclic Polyvalent acrylates of glycidyl ethers such as oxypropyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. However, it is not limited to the above, and the polyol can be directly acrylated from polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol, etc., or, through two At least one of isocyanates and urethane acrylates, melamine acrylates, and methacrylates corresponding to the aforementioned acrylates is appropriately selected and used. Such photosensitive monosystems can also be used as reactive diluents.

It can also be an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac epoxy resin with acrylic acid, or a hydroxyl group of the epoxy acrylate resin and pentaerythritol triacrylate or the like. As a photosensitive monomer, the epoxy urethane acrylate compound etc. which hydroxy acrylate and the diisocyanate lipid hemiurethane compound, such as isophorone diisocyanate, reacted are used. Such epoxy acrylate-based resins can improve photocurability without lowering dryness to the touch.

In the alkali-developing-type photosensitive resin composition, the compounding amount of the photosensitive monomer is preferably 0.2 to 60% by mass, more preferably 0.2 to 50% by mass, in terms of solid content. By making the compounding quantity of the compound which has an ethylenically unsaturated group 0.2 mass % or more, the photocurability of an alkali developing type photosensitive resin composition improves. Moreover, by making a compounding quantity into 60 mass % or less, the hardness of a coating film can be improved.

In the case of using a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond, it is necessary to use a compound having one or more ethylenically unsaturated groups in the molecule in order to make the composition photosensitive (photosensitive monomer). body), so it is especially effective.

[thermosetting resin] The thermosetting resin used in the present invention contains at least a maleimide compound having a biphenyl skeleton. By using the maleimide compound having a biphenyl skeleton as the thermosetting resin, high heat resistance can be maintained, and solvent solubility, resolution, sensitivity, and adhesion can be improved. Since the maleimide compound having a biphenyl skeleton has good solvent solubility, it can be varnished with a smaller amount of solvent than the maleimide compound having other skeletons. Therefore, the alkali-developing type photosensitive resin composition to which the maleimide compound having a biphenyl skeleton is added can maintain a high solid content of the whole. As a result, the dryness of the dry film is improved, and the residual solvent amount can be suppressed from being lowered. Moreover, although the maleimide compound which has a biphenyl skeleton is colored, it does not impair the resolution compared with the maleimide compound which has other skeletons. And by using together with a photobase generator, since a photobase generator is most suitable as a hardening catalyst of a maleimide compound, it becomes possible to provide higher heat resistance compared with other hardening catalysts. The reason for this is not clear, but is presumed as follows. That is, even in an alkali-developing photosensitive resin composition to which a maleimide compound having poor light transmittance is added, it is considered that a chain is caused by the alkali generated on the surface by irradiating the photobase generator to be blended with ultraviolet rays. Because of the reaction, the alkali can be efficiently generated even in the deep part. However, it is not necessarily the case that it is only at the stage of speculation. Adhesion, which has hitherto been a problem, is also improved by enhancing deep sclerosis. In particular, the decrease in adhesion under high temperature and high humidity is suppressed.

(式中，R可為相同亦可為相異，且係表示氫原子、碳數1~5之烷基、苯基等，n表示1＜n≦5之整數)。As a maleimide compound which has a biphenyl skeleton, the compound etc. which are represented by the following general formula (I) are mentioned, for example.

(In the formula, R may be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc., and n represents an integer of 1<n≦5).

The blending amount of the maleimide compound is preferably 0.3 mass % or more and 10 mass % or less, preferably 0.5 mass % or more and 8 mass % or less in terms of solid content in the alkali-developing photosensitive resin composition. , more preferably 1 mass % or more and 5 mass % or less. The adhesiveness to the base material forming material can be improved without impairing the heat resistance by making the above-mentioned compounding amount.

The thermosetting resin used in the present invention may contain other thermosetting components in addition to the above-mentioned maleimide compound. By adding other thermosetting components, heat resistance can be expected to improve. Examples of other thermosetting components used in the present invention include isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, polyfunctional epoxy compounds, polyfunctional epoxy Well-known conventional ones such as functional propylene oxide compounds and episulfide resins. Among these, a preferable thermal crosslinking component is a thermal compound having at least one of a plurality of cyclic ether groups and a plurality of cyclic thioether groups (hereinafter, abbreviated as cyclic (thio)ether groups) in one molecule. cross-linking components. There are many commercially available thermosetting components having such a cyclic (thio)ether group, and various properties can be imparted depending on the structure.

The thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is a cyclic ether group having a 3-, 4- or 5-membered ring in the molecule, or any one or two types of groups having a plurality of cyclic thioether groups For example, compounds having plural epoxy groups in the molecule, i.e., polyfunctional epoxy compounds, compounds having plural propylene oxide groups in the molecule, i.e., polyfunctional propylene oxide compounds, and plural sulfides in the molecule base compounds, namely episulfide resins, etc.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004, manufactured by Mitsubishi Chemical Corporation, EPICLON 840, EPICLON 840-S, EPICLON 850, EPICLON 1050, EPICLON 2055, manufactured by DIC Corporation. Epotote YD-011, YD-013, YD-127, YD-128 manufactured by Nippon Steel Chemical & Materials Co., Ltd., D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by The Dow Chemical Co., Ltd., Sumitomo Chemical Industry Co., Ltd. Bisphenol such as Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by the company, A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 manufactured by Asahi Kasei Industry Co., Ltd. (all are trade names) Type A epoxy resin; jERYL903 manufactured by Mitsubishi Chemical Corporation, EPICLON 152, EPICLON 165 manufactured by DIC Corporation, Epotote YDB-400, YDB-500 manufactured by Nippon Steel Chemical & Materials Co., Ltd., The Dow Chemical Company D.E.R.542 manufactured by Sumitomo Chemical Co., Ltd., Sumi-Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.E.R.711, A.E.R.714 manufactured by Asahi Kasei Industry Co., Ltd. (all are trade names) brominated epoxy resin; jER152, jER154 manufactured by Mitsubishi Chemical Corporation, D.E.N.431, D.E.N.438 manufactured by The Dow Chemical Company, EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC Corporation, Nippon Steel Chemical & Materials Co., Ltd. Epotote YDCN-701, YDCN-704 manufactured by Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H manufactured by Nippon Kayaku Co., Ltd., Sumitomo Chemical Industry Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by the company, A.E.R.ECN-235, ECN-299 manufactured by Asahi Kasei Industry Co., Ltd. (all are trade names) novolac epoxy resin; EPICLON manufactured by DIC Corporation 830. Bisphenol F-type epoxy resins such as jER807 manufactured by Mitsubishi Chemical Co., Ltd., Epotote YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel Chemical & Materials Co., Ltd. (all are trade names); Nippon Steel Epotote by Chemical & Materials Co., Ltd. Hydrogenated bisphenol A epoxy resins such as ST-2004, ST-2007, ST-3000 (trade name); jER604 manufactured by Mitsubishi Chemical Corporation, Epotote YH-434 manufactured by Nippon Steel Chemical & Materials Co., Ltd., Epoxypropylamine type epoxy resins such as Sumi-Epoxy ELM-120 (all trade names) manufactured by Sumitomo Chemical Co., Ltd.; alicyclic epoxy resins such as Ceroxide 2021 manufactured by Daicel Co., Ltd. (trade names) Epoxy resin; YL933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Corporation (all are trade names) trihydroxyphenylmethane epoxy resin; Mitsubishi Chemical Corporation The company's YL6056, YX4000, YL6121 (all trade names) and other phenolic or bisphenolic epoxy resins or their mixtures; EBPS-200 manufactured by Nippon Kayaku Co., Ltd. Bisphenol S type epoxy resin such as EPX-30, EXA-1514 (trade name) manufactured by DIC Co., Ltd.; Bisphenol A novolac epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation ; Tetraphenol ethane type epoxy resins such as jERYL931 (trade name) manufactured by Mitsubishi Chemical Co., Ltd.; Heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Nissan Chemical Industry Co., Ltd.; Nippon Oil Co., Ltd. Diglycidyl phthalate resin such as blemmer DGT manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Tetraglycidyl Tolyl ethane resin such as ZX-1063 manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Nippon Steel Chemical & Materials Co., Ltd. ESN-190, ESN-360 made by the company, HP-4032, EXA-4750, EXA-4700 made by DIC Co., Ltd. and other naphthyl-containing epoxy resins; HP7200, HP-7200H, etc. made by DIC Co., Ltd. Epoxy resin with pentadiene skeleton, soft and tough epoxy resin of EXA-4816, EXA-4822, EXA-4850 series; glycidyl methacrylic acid such as CP-50S, CP-50M manufactured by NOF Corporation Ester copolymerized epoxy resin; and copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, etc., but not limited to these. These epoxy resins may be used alone or in combination of two or more.

Examples of the polyfunctional propylene oxide compound include bis[(3-methyl-3-epoxypropylenemethoxy)methyl]ether, bis[(3-ethyl-3-epoxypropylenemethoxy)methyl] oxy)methyl]ether, 1,4-bis[(3-methyl-3-epoxypropanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-cyclo) Oxypropylmethoxy)methyl]benzene, (3-methyl-3-epoxypropylene)methacrylate, (3-ethyl-3-epoxypropylene)methacrylate, (3 -Methyl-3-epoxypropenyl)methmethacrylate, (3-ethyl-3-epoxypropanyl)methmethacrylate, or oligomers or copolymers of these, etc. In addition to functional propylene oxides, propylene oxide alcohol and phenolic resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixarene, etc. Diphenol aromatic hydrocarbons (Calix resorcinolarene), or semi-siloxane and other ethers of resins with hydroxyl groups, etc. In addition, for example, the copolymer of the unsaturated monomer which has a propylene oxide ring, and an alkyl (meth)acrylate, etc. are mentioned.

As an episulfide resin, YL7000 (bisphenol A type episulfide resin) etc. by Mitsubishi Chemical Corporation are mentioned, for example. Furthermore, by the same synthesis method, an episulfide resin or the like in which the oxygen atom of the epoxy group of the novolak-type epoxy resin is substituted with a sulfur atom is also used.

When the compounding amount of the thermosetting component having plural cyclic (thio)ether groups in the molecule is included in the composition, the amount of the thermosetting component having plural cyclic (thio) ether groups in the molecule is calculated in terms of solid content relative to the One equivalent of the carboxyl group of the carboxyl resin is preferably 0.3 equivalent or more, preferably in the range of 0.5 to 3.0 equivalent. By making the blending amount of the thermosetting component having plural cyclic (thio)ether groups in the molecule to 0.3 equivalent or more, carboxyl groups do not remain on the cured film, and heat resistance, alkali resistance, electrical insulation, etc. are further improved.

When using a thermosetting component having a plurality of cyclic (thio)ether groups in the molecule, it is preferable to mix a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.; dicyandiamide, benzyl dimethyl amine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N- Amine compounds such as dimethylbenzylamine, hydrazine compounds such as dihydrazine adipate, dihydrazine sebacate, etc.; phosphorus compounds such as triphenylphosphine, etc. Moreover, as a commercially available one, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., San-Apro Co., Ltd. U-CAT3513N (all are the trade names of dimethylamine compounds), DBU, DBN, U-CAT SA 102 (all are bicyclic amidine compounds and their salts) and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst of epoxy resin or propylene oxide compound, or one that promotes the reaction of either epoxy group or propylene oxide group with carboxyl group, it can be used alone It is also possible to use a combination of two or more. Also, for example, 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・isocyanuric acid adduct, 2,4-diamino-6-methyl S-triazine derivatives such as acryloxyethyl-S-triazine/isocyanuric acid adducts, etc., preferably these compounds which can also function as adhesion imparting agents are contacted with thermosetting agents. media together.

When a thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is contained in the composition, the amount of the thermosetting catalyst to be compounded in terms of solid content is relative to a component having a plurality of cyclic (thio)ether groups in the molecule. 0.1-20 mass parts is preferable with respect to 100 mass parts of thermosetting components, and 0.5-17.0 mass parts is more preferable.

[Photobase generator] A photobase generator is a compound which produces|generates 1 or more types of basic substances by changing a molecular structure by light irradiation, such as an ultraviolet-ray or a visible light. Any photobase generator can be used as long as it satisfies the above-mentioned content. Moreover, as a basic substance, a secondary amine and a tertiary amine are mentioned, for example. The basic substance is preferably one that can function as a catalyst for the addition reaction of the above-mentioned thermally reactive compound.

As a photobase generator, for example, an oxime ester compound, an α-aminoacetophenone compound, an oxyimide group, an N-methylated aromatic amino group, and an N-methylated aromatic amino group can be mentioned. , Substituent compounds of nitrobenzyl carbamate, alkoxybenzyl carbamate, etc. The photobase generator is preferably one that can also function as a photopolymerization initiator. For example, an oxime ester compound, an α-aminoacetophenone compound, etc. are mentioned. Among these, the oxime ester compound is preferable from the viewpoint of the photopolymerizability and storage stability of the composition. A photobase generator system may be used individually by 1 type, and may use 2 or more types together.

As the oxime ester compound, any compound that generates a basic substance by light irradiation can be used. Examples of commercially available products include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF JAPAN Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., Adeka Arkls NCI-831, Adeka Arkls NCI-831E, manufactured by Changzhou Qianqi Electronic New Material Co., Ltd. TR-PBG-304 et al.

(式中，X₁ 表示氫原子、碳數1~17之烷基、碳數1~8之烷氧基、苯基、苯基(被碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基之烷基胺基或二烷基胺基所取代)、萘基(被碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基之烷基胺基或二烷基胺基所取代)，Y₁ 、Z係各自表示、氫原子、碳數1~17之烷基、碳數1~8之烷氧基、鹵素基、苯基、苯基(被碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基之烷基胺基或二烷基胺基所取代)、萘基(被碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基之烷基胺基或二烷基胺基所取代)、蒽基、吡啶基、苯並呋喃基、苯並噻吩基，Ar表示碳數1~10之伸烷基、伸乙烯基、伸苯基、伸聯苯基、伸吡啶基、伸萘基、噻吩、伸蒽基、伸噻吩基、伸呋喃基、2,5-吡咯-二基、4,4’-茋-二基、4,2’-苯乙烯-二基，n為0或1之整數)Moreover, the compound which has two oxime ester groups in a molecule|numerator can also be used suitably, and the oxime ester compound which has a carbazole structure represented by following general formula (II) is specifically mentioned.

(in the formula, X ₁ represents 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 (by an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms) alkoxy group, amine group, alkylamino group or dialkylamine group with an alkyl group of 1 to 8 carbon atoms), naphthyl (substituted by an alkyl group of 1 to 17 carbon atoms, an alkyl group of 1 to 8 carbon atoms) alkoxy group, amine group, alkylamino group or dialkylamine group having an alkyl group with 1 to 8 carbon atoms), Y ₁ and Z represent each, a hydrogen atom, an alkane with 1 to 17 carbon atoms group, alkoxy group with 1~8 carbon atoms, halogen group, phenyl group, phenyl group (alkyl group with 1~17 carbon atoms, alkoxy group with 1~8 carbon number, amine group, with 1~8 carbon atoms Alkylamine group or dialkylamine group of the alkyl group), naphthyl (substituted by alkyl group of carbon number 1~17, alkoxy group of carbon number 1~8, amine group, with carbon number 1~8 Alkylamino group or dialkylamino group of the alkyl group), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents alkylene, vinylidene, phenylene, biphenylene, pyridyl, naphthylene, thiophene, anthracenyl, thienyl, furanyl, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-styrene-diyl, n is an integer of 0 or 1)

In particular, it is an oxime ester compound in which X ₁ and Y ₁ in the above formula are methyl or ethyl respectively, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylidene. better.

As a preferable carbazole oxime ester compound, the compound which can be represented by the following general formula (III) is mentioned.

(式中，R₃ 表示碳原子數1~4之烷基，或，可被硝基、鹵素原子或碳原子數1~4之烷基所取代之苯基。 R₄ 表示碳原子數1~4之烷基、碳原子數1~4之烷氧基，或，可被碳原子數1~4之烷基或烷氧基所取代之苯基。 R₅ 表示可被氧原子或硫原子所連結，且也可被苯基所取代之碳原子數1~20之烷基、可被碳原子數1~4之烷氧基所取代之苄基。 R₆ 表示硝基，或，X₂ -C(=O)-所示之醯基。 X₂ 表示可被碳原子數1~4之烷基所取代之芳基、噻吩基、嗎啉基、硫苯基，或，下述式(IV)所示之構造)。

(In the formula, R ₃ represents an alkyl group with 1 to 4 carbon atoms, or a phenyl group that may be substituted by a nitro group, a halogen atom or an alkyl group with 1 to 4 carbon atoms. R ₄ represents a carbon number of 1 to 4 An alkyl group of 4, an alkoxy group of 1 to 4 carbon atoms, or a phenyl group that can be substituted by an alkyl group of 1 to 4 carbon atoms or an alkoxy group. R ₅ represents an oxygen atom or a sulfur atom. Linked to and may be substituted by phenyl with an alkyl group having 1 to 20 carbon atoms, or by a benzyl group with an alkoxy group having 1 to 4 carbon atoms. R ₆ represents a nitro group, or X ₂ - The acyl group represented by C(=O)-. X ₂ represents an aryl group, a thienyl group, a morpholinyl group, a thiophenyl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, or, the following formula (IV ) shown in the structure).

Others can be cited such as Japanese Patent Laid-Open No. 2004-359639, Japanese Patent Laid-Open No. 2005-097141, Japanese Patent Laid-Open No. 2005-220097, Japanese Patent Laid-Open No. 2006-160634, and Japanese Patent Laid-Open No. 2008-094770 , JP 2008-509967 A, JP 2009-040762 A, JP 2011-80036 A carbazole oxime ester compound, etc.

The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cracks are caused in the molecule to generate a basic substance (amine) that acts as a hardening catalyst. Specific examples of the α-aminoacetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-benzyl-2 -Dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-[4-(4-Mosyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, etc. As a commercial item, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379, etc. made by IGM Resins can be mentioned, for example.

Specific examples of the compound having an acyloxyimino group include O,O'-succinic acid benzophenone oxime, O,O'-succinic acid naphthyl phenyl ketone oxime, and benzophenone Oxime acrylate-styrene copolymer, etc.

Specific examples of the compound having an N-carboxylated aromatic amine group and an N-carboxylated aromatic amine group include, for example, di-N-(p-carbamoylamino)diphenylmethane, diphenylmethane, -N(p-Acetylamino)diphenylmethane, Di-N-(p-benzoylamino)diphenylmethane, 4-Methylaminostilbene, 4-Acetylamine stilbene, 2,4-dimethylaminostilbene, 1-methylaminostilbene, 1-acetylaminonaphthalene, 1,5-dimethylaminonaphthalene, 1 -Methylaminoanthracene, 1,4-dimethylaminoanthracene, 1-acetylaminoanthracene, 1,4-dimethylaminoanthraquinone, 1,5-dimethylaminoanthracene Aminoanthraquinone, 3,3'-dimethyl-4,4'-dimethylaminoaminobiphenyl, 4,4'-dimethylaminoaminobenzophenone, etc.

Specific examples of compounds having a nitrobenzyl carbamate group and an alkoxybenzyl carbamate group include, for example, bis{{(2-nitrobenzyl)oxy}carbonyl}bis Aminodiphenylmethane, 2,4-bis{(2-nitrobenzyl)oxy}stilbene, bis{{(2-nitrobenzyloxy)carbonyl}hexan-1,6-di Amine, m-stub amine {{(2-nitro-4-chlorobenzyl)oxy}amide} and so on.

As other photobase generators, for example, WPBG-018 (trade name: 9-anthrylmethyl N,N'-diethylcarbamate), WPBG-027 (trade name: (E)-1) can also be used -[3-(2-Hydroxyphenyl)-2-propenyl]piperidine), WPBG-082 (trade name: guanidine 2-(3-benzylphenyl)propionate), WPBG-140 (trade name: 1-(anthraquinone-2-yl)ethylimidazole carboxylate) and the like. In addition, Japanese Patent Laid-Open No. 11-71450, International Publication No. 2002/051905, International Publication No. 2008/072651, Japanese Patent Laid-Open No. 2003-20339, Japanese Patent Laid-Open No. 2003-212856, and Japanese Patent Laid-Open No. 2003 can also be used. -344992 Gazette, JP 2007-86763 A, JP 2007-231235 A, JP 2008-3581 A, JP 2008-3582 A, JP 2009-280785 A, JP 2009-080452 A, JP 2010-95686 A, JP 2010-126662 A, JP 2010-185010 A, JP 2010-185036 A, JP 2010- Japanese Patent Laid-Open No. 186054, Japanese Patent Laid-Open No. 2010-186056, Japanese Patent Laid-Open No. 2010-275388, Japanese Patent Laid-Open No. 2010-222586, Japanese Patent Laid-Open No. 2010-084144, Japanese Patent Laid-Open No. 2011-107199, Japanese Patent Laid-Open No. 2010-222586 Photobase generators described in documents such as Japanese Patent Laid-Open No. 2011-236416 and Japanese Patent Laid-Open No. 2011-080032.

It is preferable that the compounding quantity of a photobase generator is 0.05 mass % or more and 0.7 mass % or less in conversion of solid content in an alkali-developing-type photosensitive resin composition. By making the said compounding quantity, the photocurability on copper becomes more reliable, the coating film characteristics, such as chemical resistance, are improved, and halo etc. are hard to generate|occur|produce, and the resolution becomes favorable.

You may use a photopolymerization initiator, a photoinitiator auxiliary agent, or a sensitizer together with the said photobase generator. Examples of photopolymerization initiators, photoinitiating assistants, or sensitizers include acylphosphine compounds, titanocene compounds, benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and dibenzoyl compounds. Ketone compounds, tertiary amine compounds, and xanthene compounds, etc. Moreover, among acetophenone compounds, α-hydroxyacetophenone, α-methoxyacetophenone, etc. are mentioned, for example. Especially with phosphine oxidation using 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl-yl)-phenylphosphine oxide, etc. Compounds are preferred. As a commercial item, Omnirad TPO (made by IGM Resins) etc. are mentioned, for example. Moreover, a photoinitiator, a photoinitiator, or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

Furthermore, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb specific wavelengths, their sensitivity may be lowered depending on the situation, and they may function as ultraviolet absorbers. However, these are not used only for the purpose of improving the sensitivity of the composition. In response to the need to absorb light of a specific wavelength, the photoreactivity of the surface can be improved, the line shape and opening of the resist can be changed into vertical, tapered, and reverse tapered shapes, and the processing accuracy of line width or opening diameter can be improved at the same time.

[filler] The filler used in the present invention is characterized by having a photoreactive or thermally reactive functional group on the surface. By using such a filler, high heat resistance and adhesiveness can be further improved by reaction with a carboxyl group-containing resin or a thermosetting resin.

The filler used in the present invention is a surface treatment agent with a photoreactive or thermally reactive functional group. For example, the inorganic filler can be treated with a photoreactive or thermally reactive functional group as a coupling agent for an organic group. surface.

As the inorganic filler, for example, silica, hydrotalcite, talc, clay, barium sulfate, barium titanate, titanium oxide, aluminum oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, Neuburg silica can be used earth), glass powder, natural mica, synthetic mica, iron oxide, asbestos, aluminosilicate, calcium silicate, etc. Among these, silica is preferred.

As a photoreactive group, an acryl group, a methacryl group, a vinyl group, a cyclic ether group, a cyclic sulfide group, etc. are mentioned, for example. Among these, at least one of a (meth)acryloyl group and a vinyl group is preferable.

Examples of the thermally reactive group include a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, a propylene oxide group, a mercapto group, a methoxymethyl group, a methoxyethyl group, and an ethoxy group. Methyl, ethoxyethyl, oxazolinyl, etc. Among these, at least one of an amino group and an epoxy group is preferable.

As the coupling agent, a coupling agent capable of introducing the above-mentioned photoreactive group or thermally reactive group to the filler can be used. As the coupling agent, for example, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. Among these, silane coupling agents are preferred.

In the alkali-developing photosensitive resin composition, the compounding amount of the filler is preferably 20 mass % or more and 80 mass % or less, preferably 30 mass % or more and 60 mass % or less, in terms of solid content. The strength and rigidity of the cured product can be improved by making the above-mentioned compounding amount.

[Colorant] A coloring agent may be contained in an alkali-developing-type photosensitive resin composition. As the colorant, known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. However, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferable to contain no halogen.

Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridine. As the pyridone series, specifically, those with a color index (C.I.; issued by The Society of Dyers and Colourists) numbered as follows are exemplified.

Examples of the monoazo-based red colorants include 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. Moreover, as a disazo type red coloring agent, Pigment Red 37, 38, 41 etc. are mentioned, for example. Moreover, as a monoazo lake-based red colorant, for example, Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1 can be mentioned. , 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68, etc. Moreover, as a benzimidazolone type red coloring agent, Pigment Red 171, 175, 176, 185, 208 etc. are mentioned, for example. Moreover, as a perylene type red colorant, Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224 etc. are mentioned, for example. Further, examples of the diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, 272, and the like. Moreover, as a condensed azo type red colorant, Pigment Red 220, 144, 166, 214, 220, 221, 242 etc. are mentioned, for example. Moreover, as an anthraquinone type red coloring agent, Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207, etc. are mentioned, for example. Moreover, as a quinacridone type red coloring agent, Pigment Red Red 122, 202, 206, 207, 209 etc. are mentioned, for example.

Examples of blue colorants include phthalocyanine-based and anthraquinone-based colorants, and pigment-based compounds such as those classified in Pigment, for example, Pigment Blue 15, 15:1, 15:2, 15:3, 15 : 4, 15: 6, 16, 60. As the dye system, for example, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based colorants. For example, as anthraquinone-based yellow colorants Examples of the agent include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, and the like. As an isoindolinone type yellow coloring agent, Pigment Yellow 110, 109, 139, 179, 185 etc. are mentioned, for example. As a condensed azo type yellow coloring agent, Pigment Yellow 93, 94, 95, 128, 155, 166, 180 etc. are mentioned, for example. As a benzimidazolone type yellow coloring agent, Pigment Yellow 120, 151, 154, 156, 175, 181 etc. are mentioned, for example. Moreover, as a monoazo-based yellow colorant, for example, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75 can be mentioned. , 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. Also, as disazo yellow colorants, pigment yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc.

In addition, colorants such as purple, orange, brown, and black can also be added. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet (Pigment Violet) 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, carbon black, etc.

[Organic solvents] For the purpose of preparing the composition, or adjusting the viscosity at the time of coating on a substrate or a support film, an organic solvent may be blended in the alkali-developing photosensitive resin composition. As the organic solvent, ketones such as methyl ethyl ketone, cyclohexanone, etc.; aromatic hydrocarbons such as toluene, stubble, tetramethylbenzene, etc.; cellosolve, methyl cellosolve, butyl cellosolve, Carbitol, Methyl Carbitol, Butyl Carbitol, Propylene Glycol Monomethyl Ether, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Diethyl Ether, Diethylene Glycol Monomethyl Ether Acetate, Tripropylene Glycol Glycol ethers such as monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate Esters of acid esters, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, solvent stone Well-known and usual organic solvents, such as a petroleum solvent, such as naphtha. These organic solvent systems may be used individually by 1 type, and may be used in combination of 2 or more types.

[other ingredients] In the alkali-developing photosensitive resin composition, if necessary, components such as flame retardant, adhesion promoter, antioxidant, ultraviolet absorber, and dispersant can be further blended. These systems can use those known in the field of electronic materials. In addition, at least one of defoaming agents and leveling agents such as polysiloxane, fluorine, and polymer systems, silane coupling agents such as imidazole, thiazole, and triazole, rust inhibitors, fluorescent agents, etc., can be used. At least one of known and commonly used additives such as brighteners.

The alkali-developing photosensitive resin composition can be used as a dry film, or can be used as a liquid. Moreover, when using it as a liquid state, it may be a one-component property or a two-component property or more.

[use] The alkali-developing photosensitive resin composition of the present invention can be suitably used for forming a solder resist layer of a printed wiring board, and is particularly suitable for forming a solder resist layer for IC packaging.

[Dry film] The alkali-developing photosensitive resin composition of the present invention is in the form of a dry film including a support (carrier) film and a resin layer formed on the support film and composed of the alkali-developing photosensitive resin composition. During dry film formation, the alkali-developing photosensitive resin composition of the present invention can be diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate viscosity, and a comma coater, a blade coater, a lip coater can be used to adjust the viscosity. Coater (lip coater), rod coater (rod coater), squeeze coater (squeeze coater), reverse coater (reverse coater), transfer roll coater (Transfer roll coater), gravure coater, spray The film can be obtained by coating the carrier film with a uniform thickness by machine, etc., and drying it at a temperature of 50~130°C for 1~30 minutes. The thickness of the coating film is not particularly limited. Generally, the film thickness after drying is 1-150 μm, preferably 10-60 μm.

As the support film, any known ones can be used without particular limitation, and for example, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamide films, etc. can be suitably used. Films made of thermoplastic resins such as amide imide films, polypropylene films, and polystyrene films. Among these, polyester films are preferable from the viewpoints of heat resistance, mechanical strength, handleability, and the like. Moreover, the laminated body of these films can also be used as a support film.

In addition, from the viewpoint of improving the mechanical strength, the thermoplastic resin film described above is preferably a film extending in a uniaxial direction or a biaxial direction.

The thickness of the support film is not particularly limited, and can be, for example, 10 μm to 150 μm.

After the resin layer of the alkali-developing photosensitive resin composition of the present invention is formed on the support film, a peelable cover film is laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. good. As the peelable protective film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used, and when peeling the protective film, as long as the adhesive force between the resin layer and the support film is higher than that of the resin layer The adhesive force with the protective film is still small.

The thickness of the protective film is not particularly limited, and can be, for example, 10 μm to 150 μm.

[hardened product] The cured product of the present invention is obtained by curing the alkali-developing photosensitive resin composition of the present invention or the resin layer of the dry film of the present invention.

[Printed Wiring Board] The printed wiring board of the present invention has a cured product obtained from the alkali-developing photosensitive resin composition of the present invention or the resin layer of the dry film. As a method for producing a printed wiring board of the present invention, for example, the alkali-developing photosensitive resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the above-mentioned organic solvent, and is applied to a substrate by dip coating, casting, etc. After coating by methods such as coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried at a temperature of 60~100°C ( temporary drying) to form a non-stick resin layer. In addition, in the case of a dry film, after the resin layer is brought into contact with the base material by a laminator or the like and bonded to the base material, the carrier film is peeled off to form the resin layer on the base material.

As the above-mentioned base material, for example, a printed wiring board or a flexible printed wiring board in which a circuit is formed by copper or the like in advance, for example, paper phenol, paper epoxy, glass cloth epoxy, etc. can be mentioned. Glass polyimide, glass cloth/non-woven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin, polyethylene, phenylene ether, polyphenylene oxide, cyanide Materials such as copper-clad laminates for high-frequency circuits such as acid esters, copper-clad laminates of all grades (FR-4, etc.), others such as metal substrates, polyimide films, polyethylene terephthalate Film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.

The lamination of the dry film on the substrate is preferably carried out under pressure and heating using a vacuum laminator or the like. By using this type of vacuum laminator, when using a circuit-formed substrate, even if the surface of the circuit substrate has irregularities, the dry film will still adhere to the circuit substrate, so no air bubbles will be mixed in, and there will be no concave parts on the surface of the substrate. The buried hole property is also improved. The pressure conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120°C.

The volatilization drying system that is carried out after coating the alkali-developing photosensitive resin composition of the present invention can use, for example, a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. The method of hot air countercurrent contact in the dryer and the method of blowing to the support body through the nozzle) are carried out.

After the resin layer is formed on the substrate, it is selectively exposed by active energy rays through a photomask with a predetermined pattern formed, and the unexposed portion is developed by a dilute aqueous alkaline solution to form a pattern of the cured product. In the case of a dry film, a patterned hardened product is formed on the substrate by peeling the support film from the dry film and developing after exposure. Moreover, as long as it is a range which does not impair the characteristics, the support film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed.

Furthermore, after irradiating the cured product with active energy rays, heat curing (for example, 100 to 220° C.) is performed, or after heat curing, active energy rays are irradiated, or only heat curing is applied to complete the final curing (main curing). ) to form a cured film excellent in various properties such as adhesion and hardness.

As the exposure machine used for the above-mentioned active energy ray irradiation, any device equipped with a high-pressure mercury-vapor lamp, an ultra-high-pressure mercury-vapor lamp, a metal halide lamp, a mercury short-arc lamp, etc. to irradiate ultraviolet rays in the range of 350 to 450 nm may be used, and a direct A drawing device (eg, a laser direct image drawing device that draws an image directly with a laser by means of CAD data from a computer). As the light source or laser light source of the direct drawing machine, the one with the maximum wavelength in the range of 350~450nm is suitable. The exposure amount for forming the image varies according to the film thickness, etc., but generally it can be made in the range of 10 to 1000 mJ/cm ² , preferably in the range of 20 to 800 mJ/cm ² .

When forming a recoat film of the alkali-developing photosensitive resin composition of the present invention, it is subjected to alkali development by performing alkali development after exposure. As the developing method, it can be carried out by, for example, dipping, spraying, spraying, brushing, etc. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicon Aqueous alkali solutions of sodium, ammonia, amines, etc. Among these, sodium carbonate is preferable from the viewpoint of reducing the environmental load. Moreover, as a density|concentration, 0.3-3 mass % is preferable. [Example]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

(Synthesis example 1) <Synthesis of carboxyl group-containing resin varnish 1> A novolac cresol resin (trade name "Shonol CRG951", manufactured by Aike Industries) was introduced into an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device. Co., Ltd. product, OH equivalent: 119.4) 119.4 parts by mass, 1.19 parts by mass of potassium hydroxide, and 119.4 parts by mass of toluene, and the system was heated while substituting nitrogen in the system with stirring. Next, 63.8 parts by mass of propylene oxide was gradually dropped, and the reaction was carried out at 125 to 132° C. and 0 to 4.8 kg/cm ² for 16 hours. Then, it was cooled to room temperature, and 1.56 parts by mass of 89% phosphoric acid was added and mixed to the reaction solution to neutralize potassium hydroxide to obtain a phenolic aldehyde having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.). Propylene oxide reaction solution of cresol resin. This is based on the average addition of 1.08 moles of propylene oxide per 1 equivalent of phenolic hydroxyl groups.

293.0 parts by mass of the propylene oxide reaction solution of the obtained novolac cresol resin, 43.2 parts by mass of acrylic acid, 11.53 parts by mass of methanesulfonic acid, 0.18 parts by mass of methylhydroquinone, and 252.9 parts by mass of toluene were introduced into a mixer equipped with a stirrer, a thermometer and air. The reactor was blown into the tube, air was blown in at a rate of 10 ml/min, and the reaction was carried out at 110°C for 12 hours while stirring. 12.6 parts by mass of water was distilled off as an azeotrope with toluene from the water produced by the reaction. Then, it cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 mass parts of 15% sodium hydroxide aqueous solutions, and it washed with water next. Then, toluene was substituted with 118.1 parts by mass of diethylene glycol monoethyl ether acetate using an evaporator, and was distilled off to obtain a novolac-type acrylate resin solution. Next, 332.5 parts by mass of the obtained phenolic acrylate resin solution and 1.22 parts by mass of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing pipe, and air was blown in at a rate of 10 ml/min, stirring and simultaneously. 60.8 parts by mass of tetrahydrophthalic anhydride was gradually added, it was made to react at 95-101 degreeC for 6 hours, and it was taken out after cooling. In this way, a photosensitive carboxyl group-containing resin varnish 1 having a solid content of 65% and an acid value of the solid content of 87.7 mgKOH/g was obtained.

(Synthesis example 2) <Synthesis of carboxyl group-containing resin varnish 2> 220 parts of cresol novolac epoxy resin (manufactured by DIC Co., Ltd., registered trademark "EPICLON N-695, epoxy equivalent: 220) was placed in a four-neck flask equipped with a stirrer and a reflux cooler, and carbitol ethyl acetate was added. 214 parts of acid esters were heated and dissolved. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95-105° C., and acrylic acid was slowly dripped. 72 parts were reacted for 16 hours. The reaction product was cooled to 80 to 90° C., 106 parts of tetrahydrophthalic anhydride were added and reacted for 8 hours, and then taken out after cooling. By this operation, 65% of solid content and solids were obtained. Photosensitive carboxyl-containing resin varnish 2 with an acid value of 100 mgKOH/g.

(Synthesis example 3) <Synthesis of carboxyl group-containing resin varnish 3> In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110° C., and 174.0 parts by mass of methacrylic acid and ε-caprolactone were added dropwise over 3 hours. Ester-modified methacrylic acid (average molecular weight 314) 174.0 parts by mass, methyl methacrylate 77.0 parts by mass, 222.0 parts by mass of dipropylene glycol monomethyl ether, and t-butylperoxy 2-ethyl as a polymerization catalyst A mixture of 12.0 parts by mass of hexanoic acid ester (manufactured by NOF Corporation, Perbutyl O) was further stirred at 110° C. for 3 hours to deactivate the polymerization catalyst to obtain a resin solution. After cooling this resin solution, 289.0 parts by mass of Cyclomer M100 manufactured by Daicel Co., Ltd., 3.0 parts by mass of triphenylphosphine, and 1.3 parts by mass of hydroquinone monomethyl ether were added, and epoxy resin was carried out by heating up to 100° C. and stirring. The ring-opening addition reaction of the base was carried out to obtain a photosensitive carboxyl group-containing resin varnish 3 with a solid content of 45.5% and an acid value of the solid matter of 79.8 mgKOH/g.

(Synthesis example 4) <Synthesis of silica particles coated with hydrated oxide of silicon and then coated with hydrated oxide of aluminum> Spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400nm) 50g of water slurry was heated to 70°C, and 1% of a 10% sodium silicate aqueous solution was added to the silica particles in terms of silica particles. Hydrochloric acid was added to this slurry to make the pH 4, and after aging for 30 minutes, the pH was maintained at 7±1 with hydrochloric acid, and 20% of 5% was added in terms of alumina (Al ₂ O ₃ ) relative to the silica particles. % sodium aluminate (NaAlO ₂ ) in water. Then, 20% sodium hydroxide water bath was added, pH was adjusted to 7, and it aged for 30 minutes. Then, the water washing slurry was filtered using a filter press, and vacuum-dried to obtain a solid matter of silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. Hereinafter, it is referred to as the solid substance A of the silica particles.

(Synthesis example 5) <Synthesis of barium particles coated with hydrated oxide of silicon and then coated with hydrated oxide of aluminum> After raising the temperature of an aqueous slurry of 50 g of barium sulfate particles to 70°C, with respect to the silica particles, two In terms of silica particle conversion, add 1% of 10% sodium silicate aqueous solution. Hydrochloric acid was added to this slurry to adjust the pH to 4 and aged for 30 minutes, and then the pH was maintained at 7±1 with hydrochloric acid, and 5% of alumina (Al ₂ O ₃ ) was added relative to the silica particles. 20% sodium aluminate (NaAlO ₂ ) in water. Then, a 20% sodium hydroxide water bath was added to adjust the pH to 7, and it was aged for 30 minutes. Then, the water washing slurry was filtered using a filter press, and vacuum-dried to obtain a solid substance of barium particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. Hereinafter, it is referred to as the solid substance B of barium particles.

(Synthesis Example 6) <Synthesis of filler 1> By uniformly dispersing 50 g of solid A of silica particles, 48 g of PMA as solvent, and 1 g of a silane coupling agent having a methacryloyl group (KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), filtering, washing with water, and vacuum drying were carried out. , and inorganic treatment was applied to obtain filler 1 surface-treated with methacryloylsilane.

(Synthesis Example 7) <Synthesis of filler 2> By uniformly dispersing 50 g of barium particle solid B, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacryloyl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), filtration, washing with water, vacuum drying, and applying Inorganic treatment to obtain filler 2 surface-treated with methacryloylsilane.

(Synthesis Example 8) <Synthesis of filler 3> 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm), 48 g of PMA as a solvent, and a silane coupling agent having a methacryloyl group (KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -503) 1 g is uniformly dispersed, filtered, washed with water, and dried in vacuum to obtain filler 3 surface-treated with methacryloylsilane.

(Synthesis Example 9) <Synthesis of filler 4> By uniformly dispersing 50 g of barium particle solid B, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), filtration, washing with water, vacuum drying, and applying inorganic The filler 4 surface-treated with methacryloylsilane is obtained by the treatment.

(Synthesis Example 10) <Synthesis of filler 5> 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm), 48 g of PMA as a solvent, and a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) ) 1g is uniformly dispersed, filtered, washed with water, and dried in vacuum to obtain filler 5 with epoxy silane surface treatment.

(Synthesis Example 11) <Synthesis of filler 6> 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm), 48 g of PMA as a solvent, and a silane coupling agent with an amine group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) 1 g is uniformly dispersed, filtered, washed with water, and dried in vacuum to obtain filler 6 surface-treated with aminosilane.

<Preparation of alkali-developing photosensitive resin composition> [Example 1] The carboxyl group-containing resin, photobase generator, photopolymerization initiator, thermosetting resin, filler, photosensitive monomer (reactive diluent), colorant, and hardening catalyst in the proportions shown in Table 1 (mass After mixing with a mixer, it was preliminarily mixed with a mixer, and then kneaded with a three-roll mill to prepare an alkali-developing-type photosensitive resin composition (solder resist) 1. Moreover, when the value of the compounding quantity in the table|surface is not specifically defined, it all represents the mass part of solid content.

[Examples 2 to 14] Except having changed the mixing|blending of each component as shown in Table 1, it carried out similarly to Example 1, and prepared the alkali developing type photosensitive resin composition 2-14.

[Comparative Examples 1 to 5] Except having changed the mixing|blending of each component as shown in Table 1, it carried out similarly to Example 1, and prepared the alkali developing type photosensitive resin composition 15-19.

※1：含羧基樹脂清漆1(合成例1) ※2：含羧基樹脂清漆2(合成例2) ※3：含羧基樹脂清漆3(合成例3) ※4：肟酯化合物(光鹼產生劑、BASF JAPAN股份有限公司製、Irgacure OXE02) ※5：WPBG-027(光鹼產生劑、和光純藥工業股份有限公司製、(E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine) ※6：醯膦氧化物化合物(光聚合起始劑、IGM Resins公司製、Omnirad TPO) ※7：馬來醯亞胺化合物1(具有下述式之骨架之化合物)

(上述式中，R表示氫原子，n為平均值且表示1.5)。 ※8：馬來醯亞胺化合物2(脂肪族骨架，KI化成股份有限公司製BMI-70) ※9：酚醛型環氧樹脂(176g/eq，陶氏化學公司製DEN431) ※10：變性酚醛型環氧樹脂(205g/eq，DIC股份有限公司製N870-75EA) ※11：填料1(無機處理及甲基丙烯醯基矽烷處理二氧化矽，合成例6) ※12：填料2(無機處理及甲基丙烯醯基矽烷處理鋇，合成例7) ※13：填料3(甲基丙烯醯基矽烷處理二氧化矽，合成例8) ※14：填料4(無機處理及環氧矽烷處理鋇，合成例9) ※15：填料5(環氧矽烷處理二氧化矽，合成例10) ※16：填料6(胺基矽烷處理二氧化矽，合成例11) ※17：球狀二氧化矽(無表面處理，平均粒徑：400nm ，電化股份有限公司製SFP-20M) ※18：硫酸鋇(無表面處理，堺化學工業股份有限公司製，沈降性鋇100) ※19：熱硬化觸媒(2,4,6-三巰基s-三嗪) ※20：感光性單體(二季戊四醇六丙烯酸酯) ※21：著色劑(藍色顏料，酞菁藍，C.I.顏料藍15：3) ※22：著色劑(黃色顏料，固美透黃(cromophtal yello)C.I.顏料黃147) ※23：熱硬化觸媒(三聚氰胺) ※24：熱硬化觸媒(二氰二醯胺)

※1: Carboxyl group-containing resin varnish 1 (Synthesis example 1) ※2: Carboxyl group-containing resin varnish 2 (Synthesis example 2) ※3: Carboxyl group-containing resin varnish 3 (Synthesis example 3) ※4: Oxime ester compound (photobase generator) , manufactured by BASF JAPAN Co., Ltd., Irgacure OXE02) *5: WPBG-027 (Photobase generator, manufactured by Wako Pure Chemical Industries, Ltd., (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl ]piperidine) *6: Phosphine oxide compound (photopolymerization initiator, manufactured by IGM Resins, Omnirad TPO) *7: Maleimide compound 1 (a compound having a skeleton of the following formula)

(In the above formula, R represents a hydrogen atom, and n is an average value and represents 1.5). *8: Maleimide compound 2 (aliphatic skeleton, BMI-70 manufactured by KI Chemical Co., Ltd.) *9: Novolak-type epoxy resin (176 g/eq, DEN431 manufactured by The Dow Chemical Company) *10: Denatured phenolic Type epoxy resin (205g/eq, N870-75EA manufactured by DIC Co., Ltd.) ※11: Filler 1 (inorganic treatment and methacrylosilane treatment silica, synthesis example 6) ※12: Filler 2 (inorganic treatment and methacryloylsilane-treated barium, synthesis example 7) ※13: Filler 3 (methacryloylsilane-treated silica, synthesis example 8) ※14: Filler 4 (inorganic and epoxysilane-treated barium, Synthesis example 9) *15: Filler 5 (epoxysilane-treated silica, synthesis example 10) *16: Filler 6 (aminosilane-treated silica, synthesis example 11) *17: Spherical silica (no Surface treatment, average particle size: 400nm, SFP-20M manufactured by Denka Co., Ltd.) ※18: Barium sulfate (without surface treatment, manufactured by Sakai Chemical Industry Co., Ltd., sedimentable barium 100) ※19: Thermosetting catalyst (2 ,4,6-trimercapto s-triazine) *20: Photosensitive monomer (dipentaerythritol hexaacrylate) *21: Colorant (blue pigment, phthalocyanine blue, CI pigment blue 15:3) *22: Colorant (yellow pigment, cromophtal yello CI Pigment Yellow 147) *23: Thermosetting catalyst (melamine) *24: Thermosetting catalyst (dicyandiamide)

＜Production of dry film＞ Alkali developing type photosensitive resin compositions 1 to 19 prepared in the above examples and comparative examples were respectively diluted with propylene glycol monomethyl ether acetate (PMA) to a suitable viscosity, and then a coating machine was used to dry the film. It apply|coated to PET film (T100:25 micrometers by Mitsubishi Chemical Corporation) so that the thickness might become 20 micrometers, and it dried at 80 degreeC for 30 minutes, and obtained the dry film.

<Heat resistance> The surface-treated (CZ8101B chemical solution, CZ roughening treatment at an etching rate of 1.0 μm) was attached to the copper foil, and the above-mentioned dry film was heated and laminated on the substrate using a vacuum laminator. After exposing the pattern of the DMA measurement sample to the obtained laminate and peeling off the PET film, development was performed for 60 seconds using a 1 mass % Na ₂ CO ₃ aqueous solution at 30° C. under a spray pressure of 2 kg/cm ² . After image development, light irradiation was performed with a cumulative light amount of 2000 mJ/cm ² using a UV conveyor, and a resist film was obtained by thermal curing in a drying oven at 170° C. for 60 minutes. The resist film peeled from the laminate was measured by DMA, and the glass transition temperature was measured from the temperature of the peak top of tan delta. The heat resistance was evaluated using the following criteria, and the evaluation results are shown in Table 2. [Evaluation Criteria] ⊚: 180°C or higher. ○: 170°C or more and less than 180°C. △: 160°C or more and less than 170°C. ×: Less than 160°C.

<Adhesion> On the patterned copper foil substrate, the above-mentioned dry film was heated and laminated using a vacuum laminator. After exposing the entire surface of the obtained laminate and peeling off the PET film, development was performed for 60 seconds under the condition of a spray pressure of 2 kg/cm ² using a 1 mass % Na ₂ CO ₃ aqueous solution at 30°C. After image development, light irradiation was performed with a cumulative light amount of 2000 mJ/cm ² using a UV conveyor, and a resist film was obtained by thermal curing in a drying oven at 170° C. for 60 minutes. The laminate was processed in a high temperature and high humidity tank at 130°C and a humidity of 85%. After the treatment, according to the test method of JISD0202, a cross was cut into a checkerboard shape, and a peeling test using an adhesive tape was performed, and the peeling of the resist layer was evaluated. Adhesion after HAST was evaluated using the following criteria, and the evaluation results are shown in Table 2. [Evaluation Criteria] ⊚: No peeling after HAST 300 hours. ○: No peeling after HAST 200 hours. Δ: No peeling after HAST 100 hours. ×: Peeling occurs after HAST 100 hours.

<Resolution> On the copper-plated substrate subjected to surface treatment (CZ8101B chemical solution, CZ roughening treatment at an etching rate of 1.0 μm), a vacuum laminator is used to heat and laminate a dry film with a thickness of 10 to 15 μm made by the above method. membrane. This laminate was exposed with each opening pattern by a projection exposure machine. The exposure amount was adjusted so that the gloss sensitivity became 8 steps using a step tablet (Photec 41 steps). After that, development was performed for 60 seconds using a 1 mass % Na ₂ CO ₃ aqueous solution at 30° C. under the condition of a spray pressure of 2 kg/cm ² . The laminate was irradiated with ultraviolet rays under the condition of a cumulative exposure amount of 2000 mJ/cm ² in a UV conveying furnace, and then heat-hardened at 170° C. for 60 minutes. The opening diameter of the obtained cured product was observed by SEM, and the presence or absence of halo and undercut was evaluated. The resolution was evaluated using the following benchmarks, and the evaluation results are shown in Table 2. [Evaluation Criteria] ⊚: A good opening diameter was obtained at 40 μm. ○: A good opening diameter was obtained at 50 μm. Δ: A good opening diameter was obtained at 60 μm. ×: A good aperture diameter of 60 μm was not obtained, or development was not possible.

<Sensitivity> The above-mentioned dry film was heated and laminated using a vacuum laminator on a copper-plated substrate subjected to surface treatment (CZ8101B chemical solution, CZ roughening treatment at an etching rate of 1.0 μm). Using a 41-segment exposure grid table, the obtained laminate was exposed with a projection exposure machine at an exposure amount such that the number of remaining steps after development became 10 steps. The sensitivity was evaluated using the following criteria, and the evaluation results are shown in Table 2. [Evaluation criteria] ◎: The exposure amount is less than 150 mJcm ² and 10 steps remain ○: The exposure amount is 150 mJ/cm ² or more and less than 200 mJ/cm ² and 10 steps remain △: The exposure amount is 200 mJ/cm ² or more and less than 300 mJ/ cm ² with 10 remaining steps ×: Exposure is 300mJ/cm ² or more and 10 remaining steps

<Solvent Solubility> The weight (weight A) of the glass plate after air-fired at 80°C for 30 minutes was calculated and measured. The above-mentioned dry film was heat-laminated on this glass using a vacuum laminator. After peeling off the support film of the dry film, the weight (weight B) was measured. The prepared glass plate with the dry film was dried at 80°C for 30 minutes. After cooling, the weight of the glass plate with the dry film attached (weight C) was measured. The residual solvent amount was calculated using: residual solvent amount (%)=(B-C)/(B-A)×100. Seven points were measured in the order of these operations, and a value obtained by averaging five points after excluding each point of the maximum value and the minimum value was used as the residual solvent amount. Solvent solubility was evaluated using the following criteria, and the evaluation results are shown in Table 2. [Evaluation Criteria] ⊚: The residual solvent amount is less than 0.5%. ○: The residual solvent amount is 0.5% or more and less than 1.5%. ×: The residual solvent amount is 1.5% or more.

From the above-mentioned experimental results, it is clear that the photosensitive resin composition of the present invention maintains high heat resistance, and is excellent in solvent solubility, resolution, sensitivity, and adhesion. In particular, even in the case of a highly filled filler, the adhesion is excellent. In addition, compared with Example 13 using WPBG as the photobase generator, Examples 1 to 12 and 14 using Irgacure OXE02 as the photobase generator were easy to manage during drying, and the composition of the alkali developing type photosensitive resin was The preservation stability of things is also excellent.

Claims (7)

An alkali-developing photosensitive resin composition, characterized by comprising: a carboxyl group-containing resin, a photobase generator, a thermosetting resin, and a filler, wherein the thermosetting resin comprises the following general formula (I) Maleimide compounds with biphenyl skeleton, the aforementioned fillers have photoreactive or thermally reactive functional groups on the surface;

In the formula, R may be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n represents an integer of 1<n≦5. The alkali-developing photosensitive resin composition according to claim 1, wherein the photobase generator has an oxime skeleton. The alkali-developable photosensitive resin composition according to claim 1 or 2, wherein in the alkali-developable photosensitive resin composition, the compounding amount of the photobase generator is 0.05% by mass or more and 0.7% in terms of solid content. mass % or less. The alkali-developable photosensitive resin composition according to claim 1 or 2, wherein in the alkali-developable photosensitive resin composition, the maleimide compound The compounding quantity of a thing is 0.3 mass % or more and 10 mass % or less in conversion of solid content. A dry film characterized by having a resin layer obtained by applying the alkali-developing photosensitive resin composition according to any one of claims 1 to 4 on a support film and drying it. A cured product obtained by curing the alkali-developing photosensitive resin composition according to any one of claims 1 to 4, or the resin layer of the dry film according to claim 5. A printed wiring board characterized by having the hardened material as claimed in claim 6.