KR20200137946A - Alkaline developing photosensitive resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

[Task] Providing an alkali developing type photosensitive resin composition excellent in solvent solubility, resolution, sensitivity, and adhesion while maintaining high heat resistance. [Solution means] The alkali developing photosensitive resin composition according to the present invention contains a carboxyl group-containing resin, a photobase generator, a thermosetting resin and a filler, and the thermosetting resin contains a maleimide compound having a biphenyl skeleton, It is characterized in that the filler has a photoreactive or thermally reactive functional group on its surface.

Description

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

The present invention relates to an alkali developing photosensitive resin composition. Further, the present invention also relates to a dry film, a cured product, and a printed wiring board using the alkali developing photosensitive resin composition.

In recent years, along with miniaturization and weight reduction, multifunctionalization, and environmental response of electronic devices, high-density mounting and thinning of printed wiring boards and the like have been promoted. In particular, since various thermal stresses are applied to a solder resist for a printed wiring board during mounting, high reliability in evaluation such as HAST (unsaturated pressure cooker test) or TCT (cold heat cycle test) is required.

In order to improve high reliability, a photosensitive resin composition to which a maleimide compound is added has been proposed (see, for example, Patent Document 1). High heat resistance can be imparted by addition of the maleimide compound, and reliability can be improved.

Japanese Patent Publication No. 2011-42711

However, the maleimide compound has poor solvent solubility, and the solid content when the maleimide compound is varnished is very low. Therefore, the solid content of the photosensitive resin composition containing this varnished maleimide compound is lowered. Therefore, when the photosensitive resin composition is dried under normal conditions, the amount of residual solvent in the dry film increases, and problems tend to occur in coating properties and optical properties. In addition, since the maleimide compound is colored, it is a problem to affect the deep curing property and impair the resolution when used in a photosensitive resin composition. In addition, if curing of the core is not sufficient, it is also a problem that the interface between the resin and copper is susceptible to influences such as humidification, and the adhesion is deteriorated. In particular, when left to stand at high temperature and high humidity, moisture enters the interface between the resin and copper, and the adhesion is greatly reduced.

In order to obtain more high reliability, high filling of the filler is effective. However, there is a problem that adhesiveness decreases with an increase in the amount of the filler in the filler.

Accordingly, an object of the present invention is to provide an alkali developing type photosensitive resin composition excellent in solvent solubility, resolution, sensitivity and adhesion while maintaining high heat resistance.

The inventors of the present invention, in an alkali developing photosensitive resin composition containing a carboxyl group-containing resin and a thermosetting resin, a photobase generator, a maleimide compound having a biphenyl skeleton as a thermosetting resin, and a photoreactive or thermally reactive functional group on the surface The knowledge that the said subject can be solved was acquired by using together the filler which has. The present invention is based on this knowledge.

That is, the alkali developing photosensitive resin composition according to the present invention contains a carboxyl group-containing resin, a photobase generator, a thermosetting resin, and a filler,

The thermosetting resin contains a maleimide compound having a biphenyl skeleton,

It is characterized in that the filler has a photoreactive or thermally reactive functional group on its surface.

In an aspect of the present invention, it is preferable that the photobase generator has an oxime skeleton.

In an aspect of the present invention, it is preferable that the amount of the photobase generator to be blended is 0.05% by mass or more and 0.7% by mass or less in terms of solid content in the alkali developing photosensitive resin composition.

In an aspect of the present invention, it is preferable that the blending amount of the maleimide compound is 0.3% by mass or more and 10% by mass or less in terms of solid content in the alkali developing photosensitive resin composition.

A dry film according to another aspect of the present invention is characterized by having a resin layer obtained by applying and drying the alkali developing type photosensitive resin composition to a support film.

A cured product according to another aspect of the present invention is characterized in that it 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 cured product.

According to the present invention, it is possible to provide 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 high filling of the filler, an alkali developing type photosensitive resin composition having excellent adhesion can be provided. In addition, a dry film and a cured product using such an alkali developing photosensitive resin composition can be provided. The alkali-development type photosensitive resin composition provided by the present invention, which can maintain adhesion while improving heat resistance, can be expected to adapt to applications such as vehicle mounting that require next-generation high-temperature, high-humidity resistance.

[Alkaline developing photosensitive resin composition]

The alkali developing photosensitive resin composition according to the present invention will be described. The alkali developing photosensitive resin composition according to the present invention contains at least a carboxyl group-containing resin, a photobase generator, a thermosetting resin and a filler, and includes a photosensitive monomer (reactive diluent), a photopolymerization initiator, a colorant, an organic solvent (non-reactive diluent), Other components, such as a curing catalyst and an additive, may be further included. 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, solvent solubility and resolution are maintained while maintaining high heat resistance. It is possible to provide an alkali developing type photosensitive resin composition having excellent properties, sensitivity and adhesion. Hereinafter, each component constituting the alkali developing type photosensitive resin composition according to the present invention will be described.

[Carboxyl group-containing resin]

As the carboxyl group-containing resin, various conventionally known resins having a carboxyl group in the molecule can be used. When the photosensitive resin composition contains a resin having a carboxyl group, alkali developability can be imparted to the photosensitive resin composition. Particularly, a photosensitive resin containing a carboxyl group having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. It is preferable that the ethylenically unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photosensitive, it is necessary to use a photosensitive monomer described later in combination. As a specific example of a carboxyl group-containing resin, the compound (all oligomer or polymer may be sufficient) enumerated below is mentioned.

(1) 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,

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate polyols, polyether polyols , Polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, carboxyl group-containing urethane resin by polyaddition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group ,

(3) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin (Meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing photosensitive urethane resin by a polyaddition reaction of a carboxyl group-containing dialcohol compound and a diol compound,

(4) During the synthesis of the resin of (2) or (3), a compound having one hydroxyl group and one or more (meth)acryloyl groups is added in a molecule such as hydroxyalkyl (meth)acrylate, and the terminal ( Meth) acrylated carboxyl group-containing photosensitive urethane resin,

(5) Compounds having one isocyanate group and one or more (meth)acryloyl groups in a molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of (2) or (3) above. A photosensitive urethane resin containing a carboxyl group obtained by adding to the terminal (meth)acrylate,

(6) a carboxyl group-containing photosensitive resin in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin to add dibasic anhydride to a hydroxyl group present in the side chain,

(7) A photosensitive resin containing a carboxyl group obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin epoxidized with epichlorohydrin in addition to the hydroxyl group of a bifunctional (solid) epoxy resin, and adding dibasic anhydride to the resulting hydroxyl group. ,

(8) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional oxetane resin, and the resulting primary hydroxyl group is dibasic, such as phthalic anhydride, tetrahydro phthalic anhydride, and hexahydro phthalic anhydride. Carboxyl group-containing polyester resin to which an acid anhydride was added,

(9) Compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, in an epoxy compound having a plurality of epoxy groups in one molecule, and unsaturation such as (meth)acrylic acid Carboxyl group obtained by reacting a group-containing monocarboxylic acid and reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with respect to the alcoholic hydroxyl group of the obtained reaction product. Containing photosensitive resin,

(10) A monocarboxylic acid containing an unsaturated group is reacted 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 and propylene oxide, and a polybasic acid anhydride is added to the reaction product. Carboxyl group-containing photosensitive resin obtained by reaction,

(11) A monocarboxylic acid containing an unsaturated group is reacted with a reaction organism obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, and polybasic acid anhydride is added to the resulting reaction product. Carboxyl group-containing photosensitive resin obtained by reaction,

(12) Carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule of the resins (1) to (11).

And the like. In addition, in this specification, (meth)acrylate is a term generically referring to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

It is preferable that the acid value of the carboxyl group-containing resin is 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing resin is 40 mgKOH/g or more, the alkali phenomenon is improved. Further, by setting the acid value to 150 mgKOH/g or less, it is possible to easily draw a good resist pattern. More preferably, it is 50 to 130 mgKOH/g.

Although the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferably 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, the dry-to-touch performance and resolution can be improved. Further, by setting the weight average molecular weight to 150,000 or less, developability and storage stability can be improved. More preferably, it is 3,000 to 100,000.

The blending amount of the carboxyl group-containing resin is preferably 20 to 60 mass% in terms of solid content in the alkali developing photosensitive resin composition. By setting it as 20 mass% or more, the coating film strength can be improved. Moreover, by setting it as 60 mass% or less, viscosity becomes moderate and workability improves. More preferably, it is 25-50 mass %.

These carboxyl group-containing resins are not limited to those listed above, and can be used, and one type may be used alone, or multiple types may be mixed and used. Among them, in the case of the carboxyl group-containing resins (10) and (11), a carboxyl group-containing resin synthesized by using a compound having a phenolic hydroxyl group as a starting material can be suitably used because it has excellent HAST resistance and PCT resistance.

[Photosensitive monomer]

As a compound used as a photosensitive monomer, it refers to a compound having an ethylenically unsaturated group in the molecule, and as a compound having an ethylenically unsaturated group in the molecule, for example, commonly known polyester (meth)acrylate, polyether (meth)acrylate , Urethane (meth)acrylate, carbonate (meth)acrylate, epoxy (meth)acrylate, and the like. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; Acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts, etc. Polyhydric acrylates; Polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol, or urethane acrylate through diisocyanate, and It can be appropriately selected and used from at least any one of each of the methacrylates corresponding to the acrylate. Such a photosensitive monomer can also be used as a reactive diluent.

Epoxy acrylate resin in which acrylic acid is reacted with polyfunctional epoxy resin such as cresol novolak type epoxy resin, or hydroxyacrylate such as pentaerythritol triacrylate and isophorone in the hydroxyl group of the epoxy acrylate resin An epoxy urethane acrylate compound obtained by reacting a half urethane compound of diisocyanate such as diisocyanate, etc. may be used as the photosensitive monomer. Such an epoxy acrylate resin can improve photocurability without lowering dry to touch.

The blending amount of the photosensitive monomer is preferably 0.2 to 60 mass%, more preferably 0.2 to 50 mass% in terms of solid content in the alkali developing photosensitive resin composition. When the compounding amount of the compound having an ethylenically unsaturated group is 0.2% by mass or more, the photocurability of the alkali developing photosensitive resin composition is improved. Moreover, the coating film hardness can be improved by making the compounding quantity 60 mass% or less.

The photosensitive monomer is particularly effective in the case of using a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond, since it is necessary to use a compound having at least one ethylenically unsaturated group in the molecule (photosensitive monomer) in order to make the composition photosensitive. Do.

[Thermosetting resin]

The thermosetting resin used in the present invention contains at least a maleimide compound having a biphenyl skeleton. By using a maleimide compound having a biphenyl skeleton as a thermosetting resin, it is possible to improve solvent solubility, resolution, sensitivity and adhesion while maintaining high heat resistance. Since the maleimide compound having a biphenyl skeleton has good solvent solubility, varnishing can be performed with a smaller amount of solvent compared to maleimide compounds having other skeletons. Therefore, the alkali developing type photosensitive resin composition to which the maleimide compound having a biphenyl skeleton was added can maintain a high solid content as a whole. As a result, the drying property of the dry film becomes high, and the amount of residual solvent can be suppressed low. In addition, although the maleimide compound having a biphenyl skeleton is colored, the resolution is not impaired compared to maleimide compounds having other skeletons. Further, by using in combination with a photobase generator, since the photobase generator is optimal as a curing catalyst for the maleimide compound, it becomes possible to impart higher heat resistance compared to other curing catalysts. Although the reason is not clear, it thinks as follows. In other words, even in the alkali-development type photosensitive resin composition to which a maleimide compound having poor light transmittance is added, the base generated on the surface causes a chain reaction by irradiating the photobase generator to be mixed with ultraviolet light, and the base is efficiently generated even in the deep part. I think it is a š statement. However, it is an area of speculation to the last, and not necessarily. By improving the hardenability of the core, the adhesion, which has been a problem so far, is also improved. In particular, the decrease in adhesion at high temperature and high humidity is suppressed.

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, respectively, and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and the like, and n represents an integer of 1<n≤5.)

The blending amount of the maleimide compound is preferably 0.3% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 8% by mass or less, further preferably in terms of solid content in the alkali developing photosensitive resin composition. It is 1 mass% or more and 5 mass% or less. By setting it as the above compounding amount, it is possible to improve the adhesion to the substrate-forming material without impairing heat resistance.

In addition to the maleimide compound, the thermosetting resin used in the present invention may contain other thermosetting components. By adding another thermosetting component, it can be expected that the heat resistance is improved. Other thermosetting components used in the present invention include isocyanate compounds, block isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. Known and common things such as are mentioned. Among these, a preferred thermal crosslinking component is a thermal crosslinking component having at least any 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. There are many commercially available thermosetting components having these cyclic (thio) ether groups, and various properties can be imparted depending on their structure.

The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of groups of either or two types of 3, 4 or 5 membered cyclic ether groups or cyclic thioether groups in the molecule, for example, a molecule Compounds having a plurality of epoxy groups in the molecule, i.e., 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, episulfide resin, etc. I can.

As a polyfunctional epoxy compound, for example, Mitsubishi Chemical Corporation jER 828, jER 834, jER 1001, jER 1004, DIC Corporation EPICLON 840, EPICLON 840-S, EPICLON 850, EPICLON 1050, EPICLON 2055 , Nippon Seitetsu Chemical & Materials Co., Ltd.'s Epototo YD-011, YD-013, YD-127, YD-128, Dow Chemical's DER317, DER331, DER661, DER664, Sumitomo Ga Of the sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Kaku High School Co., Ltd., AER330, AER331, AER661, AER664 manufactured by Asahi Kasei High School Co., Ltd. (all brand names) Bisphenol A type epoxy resin; JER YL903 manufactured by Mitsubishi Chemical Co., Ltd., EPICLON 152, EPICLON 165 manufactured by DIC Corporation, Nippon Seitetsu Chemical & Materials Co., Ltd. Epotto YDB-400, YDB-500, Dow Chemical DER542 , Sumitomo Chemical Co., Ltd. Sumiepoxy ESB-400, ESB-700, Asahi Kasei High School Co., Ltd. AER711, AER714, etc. (all are brand names) brominated epoxy resins; JER 152, jER 154 manufactured by Mitsubishi Chemical Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical, EPICLON N-730, EPICLON N-770 manufactured by DIC Corporation, EPICLON N-865, Nippon Seitetsu Chemical & Materials Epotto YDCN-701, YDCN-704 manufactured by Nippon Kayaku Corporation, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, Sumitomo manufactured by Nippon Kayaku Corporation Novolac-type epoxy resins such as Sumiepoxy ESCN-195X, ESCN-220 manufactured by Kagaku Kogyo Kogyo, AERECN-235, ECN-299 manufactured by Asahi Kasei Kogyo Corporation (all are brand names); Bisphenols such as EPICLON 830 manufactured by DIC Corporation, jER 807 manufactured by Mitsubishi Chemical Corporation, and Epotto YDF-170, YDF-175, YDF-2004 manufactured by Nippon Seitetsu Chemical & Materials Corporation (all brand names) F type epoxy resin; Hydrogenated bisphenol A type epoxy resins such as Nippon Seitetsu Chemical & Material Co., Ltd. Epototo ST-2004, ST-2007, and ST-3000 (trade name); Glee from Mitsubishi Chemical Co., Ltd. jER 604, Nippon Seitetsu Chemical & Materials Co., Ltd. Epototo YH-434, Sumitomo Chemical Co., Ltd.'s Sumiepoxy ELM-120, etc. (all brand names) Cidylamine type epoxy resin; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Co., Ltd. (brand name); Trihydroxyphenylmethane type epoxy resins such as YL933 manufactured by Mitsubishi Chemical Co., Ltd., T.E.N. manufactured by Dow Chemical, EPPN-501, and EPPN-502 (all are brand names); Bixylenol-type or biphenol-type epoxy resins such as YL6056, YX4000, and YL6121 (all brand names) manufactured by Mitsubishi Chemical Co., Ltd. or mixtures thereof; Bisphenol S-type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Corporation, EPX-30 manufactured by Asahi Tenka Kogyo, and EXA-1514 (brand name) manufactured by DIC Corporation; Bisphenol A novolac type epoxy resins such as jER 157S (brand name) manufactured by Mitsubishi Chemical Co., Ltd.; Tetraphenylolethane type epoxy resins such as jER YL931 (trade name) manufactured by Mitsubishi Chemical Co., Ltd.; Heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Nissan Chemical Industry Co., Ltd.; Diglycidyl phthalate resins such as Blemmer DGT manufactured by Nippon Yushi Co., Ltd.; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Nippon Seitetsu Chemical & Material Co., Ltd.; Naphthalene-containing epoxy resins such as ESN-190, ESN-360, manufactured by Nippon Seitetsu Chemical & Material Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation; Epoxy resins having dicyclopentadiene skeletons, such as HP-7200 and HP-7200H manufactured by DIC Corporation, and epoxy resins that are flexible and strong in the EXA-4816, EXA-4822, and EXA-4850 series; Glycidyl methacrylate copolymerized epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd.; Further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate may be mentioned, but the present invention is not limited thereto. These epoxy resins may be used alone or in combination of two or more.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, and 1,4-bis[( 3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methylacrylic Rate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxetanyl)methylmethacrylate and their In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetane alcohol and novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes or silsesquioxane Etherified products with resins having a hydroxyl group such as the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, etc. may be mentioned.

Examples of the episulfide resin include YL7000 (bisphenol A episulfide resin) manufactured by Mitsubishi Chemical Corporation. Further, an episulfide resin obtained by substituting a sulfur atom for an oxygen atom in the epoxy group of a novolak type epoxy resin can also be used using the same synthesis method.

The blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin in terms of solid content when the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. , Preferably 0.3 equivalents or more, more preferably 0.5 to 3.0 equivalents. By setting the amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule to be 0.3 equivalent or more, no carboxyl groups remain in the cured film, and heat resistance, alkali resistance, electrical insulation, and the like are further improved.

In the case of using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to blend 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 and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic acid dihydrazide, and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. In addition, as a commercially available one, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of imidazole-based compounds) manufactured by Shikoku Chemicals Co., Ltd., manufactured by San Apro Co., Ltd. U-CAT 3513N (all are brand names of dimethylamine compounds), DBU, DBN, and U-CAT SA 102 (all bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, and any one that accelerates the reaction of the epoxy resin or the oxetane compound thermosetting catalyst, or the carboxyl group with at least one of the epoxy group and the oxetanyl group, alone or in combination of two or more It doesn't matter if you use it. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid S-triazine derivatives such as adducts may also be used, and compounds which also function as adhesion-imparting agents are preferably used in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is based on 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule in terms of solid content when the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. , Preferably 0.1 to 20 parts by mass, more preferably 0.5 to 17.0 parts by mass.

[Photobase generator]

The photobase generator is a compound that changes its molecular structure by irradiation with light such as ultraviolet rays or visible light to generate one or more basic substances. Any substance can be used as long as the photobase generator satisfies the above. 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 thermally reactive compound.

As a photobase generator, for example, an oxime ester compound, α-aminoacetophenone compound, acyloxyimino group, N-formylated aromatic amino group, N-acylated aromatic amino group, nitrobenzyl carbamate group, alkoxybenzylcarba And compounds having a substituent such as a mate group. It is preferable that the photobase generator also functions as a photoinitiator. For example, an oxime ester compound, an α-aminoacetophenone compound, etc. are mentioned. Among these, oxime ester compounds are preferred from the viewpoint of storage stability in addition to the photopolymerization of the composition. A photobase generator may be used individually by 1 type, and may be used in combination of 2 or more types.

As the oxime ester compound, any compound that generates a basic substance by irradiation with light can be used. As a commercial item, BASF Japan Co., Ltd. Irgacure OXE01, Irgacure OXE02, ADEKA Co., Ltd. N-1919, Adeka Arcles NCI-831, Adeka Arcles NCI-831E, Changzhou Strong Electronic New Materials Corporation TR- PBG-304, etc. are mentioned.

Further, a compound having two oxime ester groups in the molecule can also be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (II) is mentioned.

(In the formula, X ₁ 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, an amino group, 1 to 8 carbon atoms) Alkylamino group having an alkyl group or substituted by dialkylamino group), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkylamino group or dialkyl having an alkyl group having 1 to 8 carbon atoms) Represents a substituted amino group), and Y ₁ , Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms, Substituted by an alkoxy group of 1 to 8, 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, an amino group, Substituted by an alkylamino group or dialkylamino group having an alkyl group having 1 to 8 carbon atoms), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene , Phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'- Represents styrene-diyl, n is an integer of 0 or 1)

In particular, in the above formula, X ₁ and Y ₁ are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, Ar is phenylene, naphthylene, thiophene, or thienylene oxime ester compounds are preferred. .

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

(In the formula, R ₃ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

R ₄ 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 or alkoxy group having 1 to 4 carbon atoms.

R ₅ represents a benzyl group which may be connected with an oxygen atom or a sulfur atom and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group.

R ₆ represents a nitro group or an acyl group represented by X ₂ -C(=O)-.

X ₂ represents an aryl group, thienyl group, morpholino group, thiophenyl group, or a structure represented by the following formula (IV) which may be substituted with an alkyl group having 1 to 4 carbon atoms.)

In addition, Japanese Patent Application Publication No. 2004-359639, Japanese Patent Application Publication No. 2005-097141, Japanese Patent Application Publication No. 2005-220097, Japanese Patent Application Publication No. 2006-160634, and Japanese Patent Application Publication 2008-094770 The carbazole oxime ester compounds described in Japanese Patent Publication No. 2008-509967, Japanese Patent Publication No. 2009-040762, Japanese Patent Application Publication No. 2011-80036, and the like are mentioned.

The α-aminoacetophenone compound has a benzoin ether bond in its molecule, and when it is irradiated with light, cleavage occurs in the molecule, and a basic substance (amine) exerting a curing catalyst action is produced. As an α-aminoacetophenone compound, 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 And N,N-dimethylaminoacetophenone. As a commercial item, IGM Resins company Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379, etc. are mentioned.

Specific examples of the compound having an acyloxyimino group include O,O'-succinate diacetophenone oxime, O,O'-succinate dinaphthophenone oxime, benzophenone oxime acrylate styrene copolymer, and the like.

Specific examples of the compound having an N-formylated aromatic amino group and an N-acylated aromatic amino group include, for example, di-N-(p-formylamino)diphenylmethane, di-N(p-aceethylamino)diphenyl Melan, di-N-(p-benzoamide) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1 -Acetylaminonaphthalene, 1,5-diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1 ,5-diformylaminoanthraquinone, 3,3'-dimethyl-4,4'-diformylaminobiphenyl, 4,4'-diformylaminobenzophenone, and the like.

Specific examples of the compound having a nitrobenzyl carbamate group and an alkoxybenzyl carbamate group include, for example, bis{{(2-nitrobenzyl)oxy}carbonyl}diaminodiphenylmethane, 2,4-di{(2 -Nitrobenzyl)oxy}toluylene, bis{{(2-nitrobenzyloxy)carbonyl}hexane-1,6-diamine, m-xylidine{{(2-nitro-4-chlorobenzyl)oxy}amide } And the like.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethylN,N'-diethylcarbamate), WPBG-027 (trade name: (E)-1-[3-(2-hydroxy) Phenyl)-2-propenoyl]piperidine), WPBG-082 (trade name: guanidinium 2-(3-benzoylphenyl) propionate), WPBG-140 (trade name: 1-(anthraquinone-2- 1) ethyl imidazole carboxylate) etc. can also be used.

In addition, Japanese Patent Laid-Open Publication No. Hei 11-71450, International Publication No. 2002/051905, International Publication 2008/072651, Japanese Patent Publication No. 2003-20339, Japanese Patent Publication No. 2003-212856, Japanese Patent Publication 2003-344992, JP 2007-86763, JP 2007-231235, JP 2008-3581, JP 2008-3582, JP 2009-280785, Japanese Patent Publication No. 2009-080452, Japanese Patent Publication No. 2010-95686, Japanese Patent Publication No. 2010-126662, Japanese Patent Publication No. 2010-185010, Japanese Patent Publication 2010-185036, Japanese Patent Publication 2010-186054, Japanese Patent Publication 2010-186056, Japanese Patent Publication 2010-275388, Japanese Patent Publication 2010-222586, Japanese Patent Publication A photobase generator described in documents such as 2010-084144, Japanese Patent Application No. 2011-107199, Japanese Patent Application No. 2011-236416, and Japanese Patent Application No. 2011-080032 can also be used.

The blending amount of the photobase generator is preferably 0.05% by mass or more and 0.7% by mass or less in terms of solid content in the alkali developing photosensitive resin composition. By setting it as the said compounding amount, the photocurability on copper becomes more reliable, coating properties, such as chemical resistance, are improved, and halation etc. hardly generate|occur|produce, and resolution also becomes better.

In combination with the above-described photobase generator, a photoinitiator, a photoinitiation aid, or a sensitizer may be used. As a photoinitiator, photoinitiation aid or sensitizer, acylphosphine compound, titanocene compound, benzoin compound, anthraquinone compound, thioxanthone compound, ketal compound, benzophenone compound, tertiary amine compound, xanthone compound, etc. Can be lifted. Further, among the acetophenone compounds, α-hydroxyacetophenone and α-methoxyacetophenone may be mentioned. In particular, it is preferable to use acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. As a commercial item, Omnirad TPO (made by IGM Resins) etc. are mentioned. Moreover, a photoinitiator, a photoinitiator, or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

Further, since these photopolymerization initiators, photoinitiation aids, and sensitizers absorb specific wavelengths, the sensitivity is lowered in some cases and may function as an ultraviolet absorber. However, they are not used solely for the purpose of improving the sensitivity of the composition. By absorbing light of a specific wavelength as needed, it improves the photoreactivity of the surface, changes the line shape and opening of the resist into vertical, tapered, and inverse tapered shapes, and improves the processing precision of the line width and opening diameter. I can.

[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 adhesion can be further improved by reaction with a carboxyl group-containing resin or a thermosetting resin.

The filler used in the present invention can be obtained by treating the surface of the inorganic filler with a surface treating agent having a photoreactive or thermally reactive functional group, for example, a coupling agent having a photoreactive or thermally reactive functional group as an organic group. .

Examples of inorganic fillers include silica, hydrotalcite, talc, clay, barium sulfate, barium titanate, titanium oxide, aluminum oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, Neuburg silica, glass powder, natural mica, synthetic Mica, iron oxide, mineral wool, aluminum silicate, calcium silicate, etc. can be used. Among these, silica is preferable.

Examples of the photoreactive group include acryloyl group, methacryloyl group, vinyl group, cyclic ether group, and cyclic thioether group. Among these, at least any 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, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group, and the like. . Among these, at least any one of an amino group and an epoxy group is preferable.

As the coupling agent, a coupling agent capable of introducing the above photoreactive group or thermally reactive group into the filler can be used. As a coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, etc. can be used, for example. Among these, a silane coupling agent is preferable.

The blending amount of the filler is preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 60% by mass or less in terms of solid content in the alkali developing photosensitive resin composition. By setting it as the said compounding amount, the strength and rigidity of a hardened|cured material can be improved.

[coloring agent]

The colorant may be contained in the alkali developing photosensitive resin composition. As the colorant, known colorants such as red, blue, green, and yellow can be used, and any of a pigment, a dye, and a dye may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body.

Examples of the red colorant include monoazo-based, disazo-based, azolake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, quinacridone-based, and the like. The same color index (CI; published by The Society of Dyers and Colorists) number is attached.

As a monoazo-based red colorant, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. are mentioned. Moreover, pigment red 37, 38, 41, etc. are mentioned as a disazo type red colorant. In addition, as a monoazo lake-based red colorant, Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53 :1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68, and the like. Moreover, pigment red 171, 175, 176, 185, 208, etc. are mentioned as a benzimidazolone type red colorant. Moreover, solvent red 135, 179, pigment red 123, 149, 166, 178, 179, 190, 194, 224 etc. are mentioned as a perylene-type red colorant. Moreover, pigment red 254, 255, 264, 270, 272, etc. are mentioned as a diketopyrrolopyrrole type red colorant. In addition, pigment red 220, 144, 166, 214, 220, 221, 242, etc. are mentioned as a condensed azo red colorant. Further, examples of the anthraquinone-based red colorant include Pigment Red 168, 177, 216, and Solvent Red 149, 150, 52, 207, and the like. Moreover, pigment red 122, 202, 206, 207, 209 etc. are mentioned as a quinacridone type red colorant.

Examples of the blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as pigments. For example, Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60. As the dye system, solvent blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

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

In addition, colorants such as purple, orange, brown, and black may 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 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, CI 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. are mentioned.

[Organic solvents]

The alkali developing type photosensitive resin composition can be blended with an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or support film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether Glycol ethers such as acetate and tripropylene glycol monomethyl ether; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; Known and common organic solvents such as petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha can be used. These organic solvents can be used alone or in combination of two or more.

[Other ingredients]

Components such as a flame retardant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and a dispersant may be further added to the alkali developing photosensitive resin composition as necessary. These can use materials known in the field of electronic materials. In addition, at least any one of antifoaming agents and leveling agents such as silicone-based, fluorine-based, polymer-based, etc., at least any of known and commonly used additives such as silane coupling agents such as imidazole-based, thiazole-based, and triazole-based, rust inhibitors, and optical brighteners One can be combined.

The alkali developing photosensitive resin composition may be used as a dry film, or may be used as a liquid. In addition, when used as a liquid, one liquid or two or more liquids may be used.

[Usage]

The alkali developing photosensitive resin composition according to the present invention can be suitably used for forming a solder resist layer of a printed wiring board, and can be particularly suitably used for forming a solder resist layer for an IC package.

[Dry film]

The alkali developing photosensitive resin composition of the present invention can also be in the form of a dry film provided with a support (carrier) film and a resin layer comprising the alkali developing photosensitive resin composition formed on the support film. In dry film formation, the alkali developing photosensitive resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, The film can be obtained by applying a gravure coater or a spray coater to a uniform thickness on a carrier film and drying for 1 to 30 minutes at a temperature of usually 50 to 130°C. There is no restriction|limiting in particular with respect to the coating film thickness, In general, the film thickness after drying is suitably selected in the range of 1 to 150 micrometers, Preferably it is 10 to 60 micrometers.

As the supporting film, any known one can be used without particular limitation. For example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a thermoplastic resin such as a polystyrene film can be used. The included film can be used suitably. Among these, a polyester film is preferable from the viewpoints of heat resistance, mechanical strength, and handling properties. In addition, a laminate of these films can also be used as a supporting film.

In addition, it is preferable that the thermoplastic resin film as described above is a film stretched in a uniaxial direction or a biaxial direction from the viewpoint of improving mechanical strength.

The thickness of the supporting film is not particularly limited, but may be, for example, 10 μm to 150 μm.

After forming the resin layer of the alkali-developable photosensitive resin composition of the present invention on the support film, in addition, for the purpose of preventing dust from adhering to the surface of the resin layer, a peelable protection on the surface of the resin layer (cover ) It is preferable to laminate the film. As the peelable protective film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. When peeling the protective film, the resin layer and the resin layer are It is sufficient that the protective film has a smaller adhesive force.

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

[Hardened cargo]

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 a resin layer of a dry film. As a manufacturing method of the 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 organic solvent, and on a substrate, a dip coating method or a flow coating method After applying by a method such as a method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100°C to dry to touch. To form a resin layer. Further, in the case of a dry film, a resin layer is formed on the substrate by peeling the carrier film after bonding on the substrate so that the resin layer is in contact with the substrate by a laminator or the like.

As the substrate, in addition to a printed wiring board or a flexible printed wiring board previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin Copper-clad laminates for high frequency circuits made of polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. are used, and copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates and polyimide films. , Polyethylene terephthalate film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer plate, and the like.

The bonding of the dry film onto the substrate is preferably performed under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, when a circuit-formed substrate is used, even if there are irregularities on the circuit board surface, since the dry film adheres to the circuit board, there is no mixing of air bubbles, and the hole filling of the concave portion of the substrate surface is improved. . The pressurizing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120°C.

The volatilization drying performed after applying the alkali developing photosensitive resin composition of the present invention is a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. (with a heat source of an air heating method using steam, It can be carried out using a method of making hot air in countercurrent contact and a method of spraying the support from a nozzle).

After the resin layer is formed on the substrate, a pattern of a cured product is formed by selectively exposing with active energy rays through a photomask having a predetermined pattern, and developing the unexposed portion with a dilute alkali aqueous solution. In the case of a dry film, after exposure, the support film is peeled from the dry film and developed, thereby forming a patterned cured product on the substrate. Further, as long as the properties are not impaired, the supporting film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed.

In addition, by irradiating the cured product with active energy rays followed by heat curing (for example, 100 to 220°C), or by irradiating with active energy rays after heat curing, or final curing with only heat curing (main curing), adhesion and hardness It forms a cured film excellent in various properties such as.

As the 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, etc. may be mounted, and a device that irradiates ultraviolet rays in the range of 350 to 450 nm may be used. (For example, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer) can also be used. As the lamp light source or the laser light source of the direct writing machine, the maximum wavelength may be in the range of 350 to 450 nm. Light exposure for the image forming layer is therefore different from the thickness or the like, but in general can be within the 10 to 1000mJ / cm ^2, preferably in the range of 20 to a range of 800mJ / cm ^2.

The alkali developing photosensitive resin composition in the present invention is alkali developed by alkali development after exposure when forming a coating film. As the developing method, a dipping method, a shower method, a spray method, a brush method, etc. can be used, and as a developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used. I can. Among these, sodium carbonate is preferred from the viewpoint of reducing the environmental load. Moreover, it is preferable that it is 0.3-3 mass% as a concentration.

Example

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

(Synthesis Example 1)

<Synthesis of carboxyl group-containing resin varnish 1>

In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device and a stirring device, a novolac cresol resin (trade name ``Shonol CRG951'', manufactured by Aika Kogyo Co., Ltd., OH equivalent: 119.4) 119.4 parts by mass, potassium hydroxide 1.19 parts by mass and 119.4 parts by mass of toluene were introduced, and the inside of the system was replaced with nitrogen while stirring, followed by heating and heating. Then, 63.8 parts by mass of propylene oxide was gradually added dropwise, followed by reaction at 125 to 132°C and 0 to 4.8 kg/cm ² for 16 hours. Then, it cooled to room temperature, and 1.56 mass parts of 89% phosphoric acid was added to this reaction solution, and potassium hydroxide was neutralized, and the novolak type of 62.1% nonvolatile matter and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.) A propylene oxide reaction solution of cresol resin was obtained. This was obtained by adding an average of 1.08 mol of propylene oxide per equivalent of phenolic hydroxyl groups.

293.0 parts by mass of the propylene oxide reaction solution of the obtained novolak-type 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 reactor equipped with a stirrer, a thermometer and an air intake tube. Then, air was blown at a rate of 10 ml/min and reacted at 110° C. for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 parts by mass of water flowed out. Then, it cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 mass parts of 15% sodium hydroxide aqueous solution, and then washed with water. Then, it distilled off, replacing toluene with 118.1 parts by mass of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolac-type acrylate resin solution. Next, 332.5 parts by mass of the obtained novolac-type 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 intake tube, and air was blown at a rate of 10 ml/min. 60.8 parts by mass of hydrophthalic anhydride was gradually added, followed by reaction at 95 to 101°C for 6 hours, and then 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>

Put 220 parts of cresol novolak type epoxy resin (manufactured by DIC Corporation, registered trademark “EPICLON N-695, epoxy equivalent: 220) into a 4-neck flask equipped with a stirrer and reflux condenser, and add 214 parts of carbitol acetate to dissolve by heating Made it. Next, 0.1 part of hydroquinone and 2.0 parts of dimethylbenzylamine were added as a reaction catalyst as a polymerization inhibitor. The mixture was heated to 95 to 105°C, and 72 parts of acrylic acid were gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90°C, 106 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and then taken out after cooling. Thus, a photosensitive carboxyl group-containing resin varnish 2 having a solid content of 65% and an acid value of 100 mgKOH/g of a solid was obtained.

(Synthesis Example 3)

<Synthesis of carboxyl group-containing resin varnish 3>

In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent is heated to 110° C., and 174.0 parts by mass of methacrylic acid, ε-caprolactone-modified methacrylic acid (average molecular weight 314) 174.0 parts by mass, 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether, and t-butylperoxy2-ethylhexanoate as a polymerization catalyst (manufactured by Nichiyu Corporation, Perbutyl O ) A 12.0 parts by mass of a mixture was added dropwise over 3 hours, 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, heated to 100° C. and stirred to add ring opening of the epoxy group. The reaction was carried out to obtain a photosensitive carboxyl group-containing resin varnish 3 having a solid content of 45.5% and an acid value of 79.8 mgKOH/g of a solid.

(Synthesis Example 4)

<Synthesis of silica particles coated with hydrated oxide of aluminum and then coated with hydrated oxide of silicon>

After 50 g of a water slurry of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm) was heated to 70°C, a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to this slurry, the pH was adjusted to 4, aged for 30 minutes, and a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles while the pH was maintained at 7±1. ₂ O ₃ ) 5% was added in terms of conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press, dried in vacuo, and solids of silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum were obtained. Hereinafter, it is referred to as solid substance A of silica particles.

(Synthesis Example 5)

<Synthesis of barium particles coated with hydrated oxide of aluminum after coating with hydrated oxide of silicon>

After the water slurry of 50 g of barium sulfate particles was heated to 70°C, a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to this slurry, the pH was adjusted to 4, and the pH was aged for 30 minutes, and a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles while maintaining the pH at 7±1. ₂ O ₃ ) 5% was added in terms of conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water through a filter press, dried in vacuo, and solids of barium particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum were obtained. Hereinafter, it is referred to as solid B of barium particles.

(Synthesis Example 6)

<Synthesis of filler 1>

50 g of the solid substance A of the silica particles, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed, followed by filtration, washing with water, and vacuum drying. It was added to obtain a filler 1 surface-treated with methacrylsilane.

(Synthesis Example 7)

<Synthesis of filler 2>

50 g of solid B of barium particles, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed, followed by filtration, washing with water, and vacuum drying. It was added to obtain a filler 2 surface-treated with methacrylsilane.

(Synthesis Example 8)

<Synthesis of filler 3>

Uniform dispersion of 50 g of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm), 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) And filtration, washing with water, and vacuum drying to obtain a filler 3 surface-treated with methacrylsilane.

(Synthesis Example 9)

<Synthesis of filler 4>

50 g of solid B of barium particles, 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.) were uniformly dispersed and added to inorganic treatment by filtration, washing with water, and vacuum drying. Thus, a filler 4 surface-treated with methacrylsilane was obtained.

(Synthesis Example 10)

<Synthesis of filler 5>

50 g of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm), 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.) were uniformly dispersed. , Filtration, washing with water, and vacuum drying to obtain a filler 5 surface-treated with epoxy silane.

(Synthesis Example 11)

<Synthesis of filler 6>

50 g of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm), 48 g of PMA as a solvent, and 1 g of a silane coupling agent having an amino group (KBM-573 manufactured by Shin-Etsu Chemical Corporation) were uniformly dispersed. , Filtration, washing with water, and vacuum drying to obtain a filler 6 surface-treated with aminosilane.

<Preparation of alkali developing photosensitive resin composition>

[Example 1]

After mixing a carboxyl group-containing resin, a photobase generator, a photopolymerization initiator, a thermosetting resin, a filler, a photosensitive monomer (reactive diluent), a colorant, and a curing catalyst in the ratio (parts by mass) shown in Table 1, premixed in a stirrer and then 3 It kneaded with an open roll mill, and the alkali developing type photosensitive resin composition (solder resist) 1 was prepared. In addition, the value of the blending amount in the table represents parts by mass of the solid content unless otherwise specified.

[Examples 2 to 14]

Alkali developing photosensitive resin compositions 2 to 14 were prepared in the same manner as in Example 1, except that the formulation of each component was changed as shown in Table 1.

[Comparative Examples 1 to 5]

Alkali developing photosensitive resin compositions 15 to 19 were prepared in the same manner as in Example 1, except that the formulation of each component was changed as shown in Table 1.

※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, 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: Acylphosphine oxide compound (photopolymerization initiator, IGM Resins, Omnirad TPO)

※7: Maleimide compound 1 (compound having a skeleton of the following formula)

(In the above formula, R represents a hydrogen atom, and n represents 1.5 as an average value.)

※8: Maleimide compound 2 (aliphatic skeleton, manufactured by K-I Kasei Co., Ltd., BMI-70)

※9: Novolac type epoxy resin (176g/eq, Dow Chemical, DEN431)

※10: Modified novolak type epoxy resin (205g/eq, DIC Corporation, N870-75EA)

※11: Filler 1 (inorganic treatment and methacrylsilane treatment silica, Synthesis Example 6)

※12: Filler 2 (inorganic treatment and methacrylsilane treatment barium, Synthesis Example 7)

*13: Filler 3 (methacrylsilane treated silica, Synthesis Example 8)

※14: Filler 4 (inorganic treatment and epoxy silane treatment barium, Synthesis Example 9)

※15: Filler 5 (epoxy silane treated silica, Synthesis Example 10)

※16: Filler 6 (aminosilane treated silica, Synthesis Example 11)

*17: Spherical silica (no surface treatment, average particle diameter: 400 nm, manufactured by Denka Corporation, SFP-20M)

※18: Barium sulfate (no surface treatment, manufactured by Sakai Chemical Co., Ltd., precipitated barium 100)

※19: Thermal curing catalyst (2,4,6-trimercapto-triazine)

※20: Photosensitive monomer (dipentaerythritol hexaacrylate)

※21: Colorant (blue pigment, phthalocyanine blue, C.I. pigment blue 15:3)

※22: Colorant (yellow pigment, chromophthal yellow, C.I. pigment yellow 147)

※23: Thermal curing catalyst (melamine)

※24: Thermal curing catalyst (dicyandiamide)

<Production of dry film>

After diluting the alkali developing photosensitive resin compositions 1 to 19 prepared in the above Examples and Comparative Examples to an appropriate viscosity with propylene glycol monomethyl ether acetate (PMA), respectively, using an applicator, the film thickness after drying was 20 μm. It applied to a PET film (Mitsubishi Chemical Co., Ltd. T100: 25 micrometers) so as to be, and it dried at 80 degreeC for 30 minutes, and obtained the dry film.

<Heat resistance>

The dry film was heat-laminated on a copper foil-attached substrate subjected to surface treatment (CZ8101B chemical solution, CZ roughening treatment at an etching rate of 1.0 µm) using a vacuum laminator. After exposing the pattern of a DMA measurement sample to the obtained laminated body, and peeling a PET film, a 30 degreeC 1 mass% Na ₂ CO ₃ aqueous solution was developed for 60 seconds on the condition of a spray pressure of 2 kg/cm ² . After development, light irradiation was performed on a UV conveyor with a cumulative amount of light of 2000 mJ/cm ^{2, followed} by heat curing in a drying furnace at 170° C. for 60 minutes to obtain a resist film. The resist film peeled off from this laminate was measured by DMA, and the glass transition point was measured from the temperature of the peak top of tan δ.

Heat resistance was evaluated based on the following criteria, and the evaluation results are shown in Table 2.

[Evaluation standard]

(Double-circle): It was 180 degreeC or more.

○: It was 170 degreeC or more and less than 180 degreeC.

?: It was 160 degreeC or more and less than 170 degreeC.

X: It was less than 160 degreeC.

<Adhesion>

On the patterned copper foil substrate, the dry film was heated and laminated using a vacuum laminator. After exposing the entire surface of the obtained laminate to peel off the PET film, a 1 mass% Na ₂ CO ₃ aqueous solution at 30° C. was developed for 60 seconds under a spray pressure of 2 kg/cm ² . After development, light irradiation was performed on a UV conveyor with a cumulative amount of light of 2000 mJ/cm ^{2, followed} by heat curing in a drying furnace at 170° C. for 60 minutes to obtain a resist film. This laminate was treated in a high-temperature, high-humidity bath in an atmosphere of 130°C and 85% humidity. After the treatment, a crosscut was put in a checkerboard shape according to the test method of JIS D0202, and a peel test was performed with an adhesive tape, and the peeling of the resist layer was evaluated. The adhesion after HAST was evaluated based on the following criteria, and the evaluation results are shown in Table 2.

[Evaluation standard]

(Double-circle): It did not peel after 300 hours of HAST.

O: No peeling occurred after 200 hours of HAST.

?: It did not peel after 100 hours of HAST.

X: It peeled after 100 hours of HAST.

<Resolution>

A dry film having a thickness of 10 to 15 µm prepared by the above method was heated and laminated on a copper plated substrate subjected to surface treatment (CZ8101B chemical solution, CZ roughening treatment at an etching rate of 1.0 µm) by a vacuum laminator. This layered product was exposed with each opening pattern by a projection exposure machine. The exposure amount was adjusted with a step tablet (Photec 41 steps) so that the gloss sensitivity became 8 steps. Thereafter, a 30°C 1 mass% Na ₂ CO ₃ aqueous solution was developed for 60 seconds under a spray pressure of 2 kg/cm ² . The laminate was irradiated with ultraviolet rays on a UV conveyor furnace under conditions of a cumulative exposure amount of 2000 mJ/cm ² , and then heat-cured at 170°C for 60 minutes. The opening diameter of the obtained hardened|cured material was observed with SEM, and it evaluated whether there was occurrence of halation or undercut.

The resolution was evaluated according to the following criteria, and the evaluation results are shown in Table 2.

[Evaluation standard]

(Double-circle): A good opening diameter was obtained at 40 micrometers.

○: A good opening diameter was obtained at 50 µm.

?: A good opening diameter was obtained at 60 µm.

X: At 60 µm, a good opening diameter was not obtained or development was impossible.

<Sensitivity>

The dry film was heated and laminated 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 vacuum laminator. A 41-step step tablet was used for the obtained laminate, and exposure was performed with a projection exposure machine at an exposure amount of 10 remaining steps after development.

The sensitivity was evaluated according to the following criteria, and the evaluation results are shown in Table 2.

[Evaluation standard]

◎: 10 levels of remaining at exposure dose less than 150 mJ/cm ²

○: 10 stages remaining at exposure doses of 150 mJ/cm ² or more and less than 200 mJ/cm ²

△: 10 levels remaining at an exposure dose of 200 mJ/cm ² or more and less than 300 mJ/cm ²

×: 10 levels remaining at an exposure dose of 300 mJ/cm ² or more

<solvent solubility>

The weight of the glass plate preheated at 80°C for 30 minutes was measured (weight A). The dry film was heat-laminated on this glass using a vacuum laminator. After peeling off the supporting film of the dry film, the weight was measured (weight B). The produced glass plate with the dry film was dried at 80°C for 30 minutes. After cooling, the weight of the glass plate to which the dry film was attached was measured (weight C). It was calculated as residual solvent amount (%) = (B-C)/(B-A) x 100. Seven points were measured by these procedures, and the value which averaged 5 points excluding each point of a maximum value and a minimum value was made into the residual solvent amount.

The solvent solubility was evaluated according to the following criteria, and the evaluation results are shown in Table 2.

[Evaluation standard]

(Double-circle): The amount of residual solvent was less than 0.5%.

○: The amount of residual solvent was 0.5% or more and less than 1.5%.

X: The amount of residual solvent was 1.5% or more.

As apparent from the above experimental results, it was found that the photosensitive resin composition according to the present invention was excellent in solvent solubility, resolution, sensitivity and adhesion, while maintaining high heat resistance. In particular, it was found that even when the filler was highly charged, adhesion was excellent. In addition, Examples 1 to 12 and 14 using Irgacure OXE02 as a photobase generator are easier to manage during drying than in Example 13 using WPBG as a photobase generator, and storage of an alkali developing photosensitive resin composition The stability was also excellent.

Claims (7)

An alkali developing type photosensitive resin composition comprising a carboxyl group-containing resin, a photobase generator, a thermosetting resin, and a filler,
The thermosetting resin contains a maleimide compound having a biphenyl skeleton,
The alkali developing type photosensitive resin composition, characterized in that the filler has a photoreactive or thermally reactive functional group on its surface. The alkali developing type photosensitive resin composition according to claim 1, wherein the photobase generator has an oxime skeleton. The alkali developing type photosensitive resin composition according to claim 1 or 2, wherein the amount of the photobase generator is 0.05% by mass or more and 0.7% by mass or less in terms of solid content in the alkali developing type photosensitive resin composition. The alkali developing type photosensitive resin composition according to any one of claims 1 to 3, wherein the blending amount of the maleimide compound is 0.3% by mass or more and 10% by mass or less in terms of solid content in the alkali developing type photosensitive resin composition. . A dry film comprising a resin layer obtained by applying and drying the alkali developing photosensitive resin composition according to any one of claims 1 to 4 on a supporting film. A cured product obtained by curing the alkali developing type 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 comprising the cured product according to claim 6.