JP2008189803A - Photocurable or thermosetting resin composition, cured product thereof, dry film and thin package board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable or thermosetting resin composition excellent in soldering heat resistance, adhesivity, electrical insulation and HAST (highly accelerated steam and temperature) resistance, each required as a solder resist and a resist for a package board, and capable of giving a warpage-free package board of low cure shrinkage, and to provide a cured product, dry film, etc. made from the resin composition. <P>SOLUTION: The photocurable (photosensitive) or thermosetting resin composition comprises (A) a carboxyl-containing photosensitive resin obtained by reacting a polybasic acid anhydride (c) on a reaction product of a polynuclear epoxy compound (a) and an unsaturated group-containing monocarboxylic acid (b), (B) a carboxyl-containing urethane (meth)acrylate compound, (C) a photopolymerization initiator, (D) a thermosetting component having, in one molecule, two or more cyclic ether groups and/or cyclic thioether groups, (E) a diluent and (F) a curing catalyst. This resin composition (A) is to be used in producing its cured product, dry film, etc. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photocurable / thermosetting resin composition useful for manufacturing a package substrate for a semiconductor device, and a cured product thereof.

  Recent electronic devices, as represented by mobile phones, tend to be smaller, lighter, higher performance, and multifunctional, and in response to this, semiconductor integrated circuits (hereinafter referred to as ICs) used in these electronic devices. However, there is a demand for higher integration, smaller size, and thinner thickness. In response to such demands, packages that house semiconductor ICs are also IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc. using a lead frame and a sealing resin. Instead, an IC package called BGA (Ball Grid Array) or CSP (Chip Scale Package) using an insulating substrate coated with a solder resist and a sealing resin has appeared. In such a package, ball-shaped solder is arranged on the entire surface of an insulating printed circuit board coated with a solder resist, and an IC chip is fused on the other surface, and wire bonding or bumping is performed on the printed circuit board. Electrical connection with terminals or circuits is made, and the IC chip is sealed with resin.

As described above, the IC package having such a structure is required to be small and thin. As a result, the core material for forming the printed circuit board on which the IC chip is mounted is also required to be thin. For example, in a package called UT-CSP, that is, an ultra thin chip scale package, a glass epoxy substrate having a thickness of 30 to 60 μm is used as a core material. As a manufacturing process of such an IC package, both sides of the core material constituting the substrate, that is, the surface to which the solder balls are fixed, and the other surface on which the wiring for connection with the input / output terminal of the IC chip is formed. Then, after applying a resist ink so as to cover the portions excluding these solder balls and wiring patterns, this is cured to form an insulating protective film. However, when the substrate is extremely thin as described above, the substrate is warped or undulated due to curing shrinkage during baking of the resist applied to the surface of the core material, which causes a problem during chip mounting. Further, the IC package manufacturing process includes a process of exposing the printed circuit board to a high temperature of, for example, 170 to 270 ° C., such as a molding process or a soldering process. For this reason, the resist material is required to have high heat resistance such as solder heat resistance and high reliability such as electrical characteristics and PCT characteristics (pressure cooker test).
Further, as the core material becomes thinner, warping due to curing shrinkage of the resist has become a problem. When such a core material is used, a roll-to-roll method is used, and a dry film type solder resist from the viewpoint of workability, reliability, film thickness accuracy, and smoothness. Is required. In addition, such a dry film type solder resist is supplied in the form of a sheet or a roll, and it is necessary to include a resin component excellent in flexibility and film-forming property in the resin composition due to the characteristics in the form. is there.

Conventionally, in order to prevent warping and waviness of a printed circuit board, as a solder resist ink having a low curing shrinkage during sintering, a photosensitive resin composition containing a urethane (meth) acrylate compound having excellent flexibility is known. (See Patent Document 1). However, although the solder resist using this photosensitive resin can prevent warping and undulation of the printed circuit board, it cannot withstand the high temperature heat treatment in the manufacturing process of the IC package described above, and the necessary electrical characteristics cannot be obtained. There are drawbacks.
Conventionally, a terminal unsaturated compound of a reaction product of a compound having at least one carboxyl group and two hydroxyl groups in one molecule, a diol compound, and a polyisocyanate compound has a polymerizable unsaturated group in one molecule. A solder resist containing a photosensitive resin obtained by reacting a compound having a carboxyl group and at least one hydroxyl group has been proposed (see Patent Document 2). However, such a photosensitive resin also has a problem that it lacks the heat resistance necessary for the high-temperature heat treatment as described above.
On the other hand, a photosensitive resin composition for a solder resist having excellent heat resistance, adhesion, and electrical insulation has been known (see Patent Document 3). This resin is excellent in heat resistance, adhesion, and electrical insulation, and was useful for a conventional package substrate using a core material having a certain thickness, but for the extremely thin core material as described above. It was difficult to satisfy the demand for preventing warpage and undulation.
JP 2002-229201 A (Claims) JP 2003-192760 A (Claims) JP 2001-278947 A (Claims)

  The present invention has been made in view of the above-mentioned problems of the prior art, and its purpose is to provide solder resist, particularly solder heat resistance, adhesion, electrical insulation, and HAST resistance necessary as a resist for a semiconductor package substrate. An object of the present invention is to provide a photocurable / thermosetting resin composition that can provide a substrate that is excellent and has little curing shrinkage and no warp even for an extremely thin core material, a cured product thereof, and a dry film.

In order to achieve the above object, as a basic aspect of the present invention,
(A) A carboxyl obtained by reacting a polybasic acid anhydride (c) with a reaction product of a polynuclear epoxy compound (a) represented by the following general formula (1) and an unsaturated group-containing monocarboxylic acid (b) Group-containing photosensitive resin,
(B) a carboxyl group-containing urethane (meth) acrylate compound,
(C) a photopolymerization initiator,
(D) A photocurable thermosetting resin composition comprising a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in one molecule, and (E) a diluent. Things are provided.
In addition, in the above composition,
(F) The photocurable thermosetting resin composition characterized by containing a curing catalyst is provided.
As another embodiment, a photocurable / thermosetting dry film having a carrier film and a photocurable / thermosetting resin layer made of the photocurable / thermosetting resin composition formed on the carrier film. Is provided. The dry film may have a peelable cover film on the photocurable / thermosetting resin layer.

Further, a cured product obtained by curing the photocurable / thermosetting resin composition or the dry film by irradiation with active energy rays and / or heating, and a predetermined circuit pattern In a printed wiring board in which a solder resist film as a permanent protective film is formed on a circuit board having a conductor layer, the solder resist film is the photocurable / thermosetting resin composition, or a cured coating film of the dry film. There is provided a printed wiring board characterized by comprising:

The active energy ray-curable resin of the present invention is a linear polynuclear epoxy acrylate compound containing regularly different types of aromatic rings, particularly an alternating copolymer in which a biphenyl skeleton and a naphthalene skeleton having a high softening point are alternately copolymerized. Since the polybasic acid anhydride adduct of the linear polynuclear epoxy acrylate compound of the type, the photocurable / thermosetting resin composition of the present invention contained as a photocurable component is a photocurable, alkali developable or basic group. In addition to excellent adhesion to materials, it has excellent heat resistance, water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexibility, PCT resistance, and the like. Therefore, since it is excellent in solder heat resistance, adhesion, electrical insulation, and HAST resistance, it can be used for package substrates such as QFP, BGA, and CSP that require high insulation reliability.
In addition, since the photocurable / thermosetting resin composition or dry film of the present invention can provide a substrate with little curing shrinkage and no warpage, it can also cope with TAB, T-BGA, T-CSP, and UT-CSP. .

As a result of intensive studies to solve the above problems, the present inventors have (A) a reaction between a polynuclear epoxy compound (a) represented by the following general formula (1) and an unsaturated group-containing monocarboxylic acid (b). A carboxyl group-containing photosensitive resin obtained by reacting the product with a polybasic acid anhydride (c),
(B) a carboxyl group-containing urethane (meth) acrylate compound,
(C) a photopolymerization initiator,
(D) A photocurable thermosetting resin composition comprising a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in one molecule, and (E) a diluent. The present inventors have found that a product is excellent in solder heat resistance, adhesion, electrical insulation and HAST resistance, and can provide a substrate with little curing shrinkage and no warpage, thereby completing the present invention.

  That is, the reaction product of the polynuclear epoxy compound (a) represented by the general formula (1) and the unsaturated group-containing monocarboxylic acid (b), which is excellent in solder heat resistance, adhesion, electrical insulation and HAST resistance. A carboxyl group-containing photosensitive resin (A) obtained by reacting a polybasic acid anhydride (c), and the carboxyl group-containing urethane (meth) acrylate compound (B) capable of providing a substrate with little curing shrinkage and no warpage. It has been found that the object of the present invention can be achieved without degrading the properties of each other by the combined use.

In order to achieve the above object, the blending ratio of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B) is blended at a ratio of 85:15 to 15:85. Is preferred.
When emphasizing solder heat resistance, adhesion, electrical insulation, and HAST resistance, the ratio of the carboxyl group-containing photosensitive resin (A) is increased within the above range, and emphasis is placed on the characteristic that there is little curing shrinkage and no warpage. When it does, what is necessary is just to make the ratio of the said carboxyl group-containing urethane (meth) acrylate compound (B) high within the said range.

When the ratio of the carboxyl group-containing photosensitive resin (A) is higher than 85% by mass, the warpage is deteriorated, and conversely, when it is lower than 15% by mass, the heat resistance is deteriorated.
In addition, in this specification, a carboxyl group-containing urethane (meth) acrylate compound is a term that collectively refers to a carboxyl group-containing urethane acrylate compound, a carboxyl group-containing urethane methacrylate compound, and a mixture thereof. It is the same.

Hereafter, the structural component of the photocurable thermosetting resin composition of this invention is demonstrated in detail.
First, the active energy ray-curable resin of the present invention will be described. The polynuclear epoxy compound (a) represented by the general formula (1) includes an aromatic epoxy compound having two glycidyl groups in one molecule (hereinafter referred to as a bifunctional aromatic epoxy compound) and 2 in one molecule. Using an aromatic alcohol having one phenolic hydroxyl group (hereinafter referred to as a bifunctional aromatic alcohol) as a raw material, using a known etherification catalyst as described later, polymerization is carried out alternately in a solvent or in the absence of a solvent. The known alcoholic secondary hydroxyl group is epihalohydrin, aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene. In the presence of an alkali metal hydroxide such as caustic soda.

  Next, an unsaturated group-containing monocarboxylic acid is added to the polynuclear epoxy compound (a) represented by the general formula (1) in the presence or absence of an organic solvent described later, a polymerization inhibitor such as hydroquinone or oxygen, And 80 ° C. in the presence of a reaction catalyst such as a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, and a phosphorus compound such as triphenylphosphine. By reacting at ~ 130 ° C, an epoxy acrylate compound is obtained.

  Furthermore, by reacting the polybasic acid anhydride with the alcoholic hydroxyl group of the epoxy acrylate compound produced by the above reaction, the active energy ray-curable resin of the present invention is obtained. In this reaction, the polybasic acid anhydride The amount used is such that the ratio of anhydride groups to the alcoholic hydroxyl groups in the epoxy acrylate compound is 99: 1 to 1:99, and preferably the acid value of the generated active energy ray-curable resin is 50 to 50. The added amount is 120 mg KOH / g. The reaction is usually performed at 50 to 130 ° C. in the presence or absence of an organic solvent described later. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, or a phosphorus compound such as triphenylphosphine is added as a catalyst. May be.

Examples of the bifunctional aromatic epoxy compound include biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type dithiol having an aromatic ring represented by the following formulas (2) to (5). By using one monomer component in an alternating copolymer with at least one bifunctional aromatic alcohol such as glycidyl ether, an epoxy compound excellent in strength, heat resistance, electrical insulation and the like of the cured product can be obtained.

  As such a biphenol type, bixylenol type, bisphenol type or naphthalene type diglycidyl ether, it is possible to use, for example, a biphenol compound, a bixylenol compound, a bisphenol compound, or a product produced from the reaction of dihydroxynaphthalene and epichlorohydrin. it can. Commercially available epoxy compounds can also be used. For example, as biphenol type diglycidyl ether, trade name “Epicoat YL-6056” manufactured by Yuka Shell Epoxy Co., Ltd., and bixylenol type diglycidyl ether can be used. Bisphenol A such as “Araldite # 260” and “Araldite # 6071” manufactured by Asahi Chiba Co., Ltd. as bisphenol-type diglycidyl ether, such as “Epicoat YX-4000” manufactured by Yuka Shell Epoxy Co., Ltd. Type epoxy compound or bisphenol F type epoxy compound such as “Epicron 830S” trade name manufactured by Dainippon Ink and Chemicals, Inc. or bisphenol S such as “Epicron EXA1514” trade name manufactured by Dainippon Ink and Chemicals, Inc. Type epoxy compound, naphthalene type diglycidyl The ether, Dainippon Ink & Chemicals Co., Ltd. under the trade name of "Epiclon HP-4032 (D)" and the like can be mentioned, these can be used alone or in combination of two or more.

  The bifunctional aromatic alcohol used in the present invention is characterized by its structure, and an aromatic ring having a symmetric structure or a rigid structure can be used in order to increase heat resistance. Examples of such compounds include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene and the like. Dihydroxynaphthalene derivatives, biphenol derivatives such as bixylenol and biphenol, bisphenol derivatives such as bisphenol A, bisphenol F, bisphenol S and alkyl group-substituted bisphenol, hydroquinone derivatives such as hydroquinone, methylhydroquinone and trimethylhydroquinone, etc. These can be used alone or in combination of two or more.

  As a catalyst used for the reaction of a bifunctional aromatic epoxy compound and a bifunctional aromatic alcohol, a phosphine, an alkali metal compound, or an amine in which a glycidyl group and a phenolic hydroxyl group react quantitatively is used alone or in combination. Are preferably used. Other catalysts are not preferable because they react with an alcoholic hydroxyl group produced by the reaction between a glycidyl group and a phenolic hydroxyl group to form a gel.

Examples of phosphines include trialkyl phosphines such as tributyl phosphine and triphenyl phosphine, and salts of these with oxides.
Examples of the alkali metal compound include hydroxides, halides, alcoholates, amides, and the like of alkali metals such as sodium, lithium and potassium, and these can be used alone or in combination of two or more.

  Examples of the amines include aliphatic or aromatic primary, secondary, tertiary, and quaternary amines, and these can be used alone or in combination of two or more. Specific examples of amines include triethanolamine, N, N-dimethylpiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide and the like.

  These catalysts are preferably used in the range of 0.001 to 1 part by mass, preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the charged amount of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol. The reason for this is that if the amount of the catalyst used is less than 0.001 part by mass, the reaction takes time and is not economical. On the other hand, if it exceeds 1 part by mass, the reaction is fast and difficult to control. .

  The bifunctional aromatic epoxy resin compound and the difunctional aromatic alcohol are preferably reacted in a temperature range of 130 ° C. to 180 ° C. in an inert gas stream or in the air under the catalyst.

  The polynuclear epoxy compound (a) represented by the general formula (1) is a bifunctional aromatic epoxy compound and a bifunctional aroma in the presence of an alkali metal hydroxide in a known solvent as described later. It can produce by making the alcoholic hydroxyl group and epihalohydrin in the reaction product with an aromatic group react.

  Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepiiodohydrin, and the like.

  In the polynuclear epoxy compound (a) represented by the general formula (1), the amount of the epihalohydrin used is 1 equivalent of an alcoholic hydroxyl group in the reaction product of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol. About 0.1 times equivalent or more may be used. However, the use of an amount exceeding 15 times equivalent to 1 equivalent of hydroxyl group is not preferable because volume efficiency is deteriorated.

  Examples of the solvent include known solvents such as aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene. The amount of the solvent used is preferably 5 to 300% by mass with respect to the reaction product of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol. The reason for this is that if the amount is less than 5% by mass, the reaction between the alcoholic hydroxyl group and the epihalohydrin becomes slow. On the other hand, if it exceeds 300% by mass, the volumetric efficiency is deteriorated.

  Further, as the alkali metal hydroxide, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, and caustic soda is particularly preferable. The amount of the alkali metal hydroxide used is 0.5 to 2 times equivalent to 1 equivalent of alcoholic hydroxyl group to be epoxidized in the reaction product of the bifunctional aromatic epoxy compound and the difunctional aromatic alcohol. It is preferable to do.

  The reaction temperature between the alcoholic hydroxyl group and the epihalohydrin in the reaction product of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol is preferably 20 to 100 ° C. The reason for this is that if the reaction temperature is less than 20 ° C., the reaction slows down and a long-time reaction is required. On the other hand, if the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable.

  The reaction between the alcoholic hydroxyl group and the epihalohydrin in the reaction product of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol is performed by reacting with dimethyl sulfoxide, a quaternary ammonium salt, or 1,3-dimethyl-2-imidozoline. It can also be carried out by adjusting the amount of the alkali metal hydroxide in the presence of the alkali metal hydroxide. At that time, alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, and cyclic ether compounds such as tetrahydrofuran may be used in combination.

  Examples of quaternary ammonium salts that can be used include tetramethylammonium chloride, tetramethylammonium bromide, trimethylammonium chloride, etc., and the amount used is 1 equivalent of the hydroxyl group to be epoxidized of the epoxy resin used as a raw material. 0.3-50g is preferable. When the amount is less than 0.3 g with respect to 1 equivalent of the hydroxyl group to be epoxidized, the reaction between the alcoholic hydroxyl group of the epoxy resin used as a raw material and epihalohydrin is slow, and a long-time reaction is required, which is not preferable. On the other hand, when the amount exceeds 50 g with respect to 1 equivalent of the hydroxyl group to be epoxidized, the increased amount of curing is almost lost and the cost is not preferred.

  When the polynuclear epoxy compound (a) represented by the general formula (1) is reacted with the unsaturated group-containing monocarboxylic acid (b) to obtain an unsaturated epoxy acrylate, the compound represented by the general formula (1) is used. In the polynuclear epoxy compound, an unsaturated group-containing monocarboxylic acid is blended at a ratio of 0.8 to 1.3 mol with respect to 1 mol of the epoxy group contained in the compound, and in an inert solvent or without solvent, The reaction is carried out in the presence of air, preferably by heating to 60 to 150 ° C, preferably 70 to 130 ° C. In order to prevent gelation due to polymerization during the reaction, it is preferable to use known and commonly used polymerization inhibitors such as hydroquinones such as methylhydroquinone and hydroquinone; and benzoquinones such as p-benzoquinone and p-toluquinone. In order to shorten the reaction time, it is preferable to use an esterification catalyst. Examples of the esterification catalyst include tertiary amines such as N, N-dimethylaniline, pyridine, triethylamine, and hydrochlorides or bromates thereof. Quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; sulfonic acids such as paratoluenesulfonic acid; sulfonium salts such as dimethyl sulfoxide and methyl sulfoxide; phosphines such as triphenylphosphine and tri-n-butylphosphine A known and commonly used metal halide such as lithium chloride, lithium bromide, stannous chloride and zinc chloride can be used. As the inert solvent, for example, toluene, xylene and the like can be used.

  Representative examples of the unsaturated group-containing monocarboxylic acid (b) include acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and trimethylolpropane. Unsaturated dibasic acid anhydrides of hydroxyl group-containing acrylates such as di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, (meth) acrylic acid caprolactone adduct Examples include adducts. Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in admixture of two or more.

  The polybasic acid anhydride (c) is reacted with the alcoholic hydroxyl group of the epoxy acrylate compound produced by the reaction to obtain the carboxyl group-containing photosensitive resin (A) of the present invention. In this reaction, the polybasic acid anhydride (c) is obtained. The amount of the acid anhydride (c) used is suitably such that the ratio of anhydride groups is 99: 1 to 1:99 with respect to the alcoholic hydroxyl groups in the reaction product, and is 50 to 200 mgKOH / g, preferably 50. It is desirable to have an acid value in the range of ~ 120 mg KOH / g. When the acid value of the carboxyl group-containing photosensitive resin (A) is lower than 50 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated, and development of the formed coating film becomes difficult. On the other hand, if it is higher than 200 mgKOH / g, the surface of the exposed area is developed regardless of the exposure conditions, which is not preferable.

The reaction is usually performed at 50 to 130 ° C. in the presence or absence of an organic solvent described later in the presence of a polymerization inhibitor such as hydroquinone or oxygen. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, 2-
An imidazole compound such as ethyl-4-methylimidazole or a phosphorus compound such as triphenylphosphine may be added as a catalyst.

  Examples of the polybasic acid anhydride (c) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, Cycloaliphatic dibasic anhydrides such as methylendomethylenetetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, anhydrous Aliphatic or aromatic dibasic acid anhydrides such as trimellitic acid, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, Pyromellitic anhydride, benzofu Mentioned Non aliphatic tetracarboxylic dianhydride or aromatic tetracarboxylic acid dianhydride may be used one or two or more of these. Among these, alicyclic dibasic acid anhydrides are particularly preferable.

  The number average molecular weight of the carboxyl group-containing photosensitive resin (A) of the present invention is 400 to 10,000, preferably 500 to 7,000, more preferably 500 to 3,000. When the number average molecular weight of the active energy ray-curable resin is less than 400, the toughness of the obtained cured product is not sufficient, and when it exceeds 10,000, the solubility in a solvent is lowered, which is not preferable.

  Next, the carboxyl group-containing urethane (meth) acrylate compound (B), which is the second feature of the present invention, comprises a hydroxyl group-containing (meth) acrylate compound (d), a dimethylolalkanoic acid (e), and a diisocyanate compound ( Obtained by reacting a compound obtained by reacting f) and / or a hydroxyl group-containing (meth) acrylate compound (d), dimethylolalkanoic acid (e), diisocyanate compound (f), and polymer polyol (g). The compound having an acid value of 30 to 100 mgKOH / g.

  Since the carboxyl group-containing urethane (meth) acrylate compound (B) is basically a carboxyl group-containing photosensitive resin having a linear urethane bond, it has flexibility and warpage due to curing shrinkage. There is an effect of reducing.

  The hydroxyl group-containing (meth) acrylate compound (d) used for the synthesis of the carboxyl group-containing urethane (meth) acrylate compound (B) is basically a (meth) acrylate compound (d-) having one hydroxyl group. 1) or (meth) acrylate (d-2) having two hydroxyl groups.

  Examples of the (meth) acrylate compound (d-1) having one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include methylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and a reaction product of glycidyl (meth) acrylate and (meth) acrylic acid. Such a (meth) acrylate compound having one hydroxyl group is added to the terminal of the carboxyl group-containing urethane (meth) acrylate compound of the present invention and functions as a terminator for stopping molecular growth.

On the other hand, as a (meth) acrylate (d-2) having two hydroxyl groups, a bifunctional epoxy (meth) acrylate compound obtained by adding (meth) acrylic acid to a bifunctional epoxy compound, or a bifunctional oxetane compound, A bifunctional oxetane (meth) acrylate compound to which (meth) acrylic acid is added may be mentioned.
Specifically, (meth) acrylates of bifunctional epoxy resins with aromatic rings such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, and bixylenol type epoxy resin Is preferred. The molecular weight of these bifunctional epoxy (meth) acrylates is preferably in the range of 450 to 2,000 from the viewpoint of cured coating film characteristics.

  The dimethylol alkanoic acid (e) is a compound having a tertiary carboxyl group and two primary hydroxyl groups, specifically, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolhexane. An acid etc. are mentioned. Among these, dimethylolpropionic acid and dimethylolbutanoic acid are preferable from the viewpoint of characteristics of the cured coating film.

  Examples of the diisocyanate compound (f) include phenylene diisocyanate, toluylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, trimethylphenylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. . Among these, isophorone diisocyanate is particularly preferable because the reaction can be easily controlled.

  For the synthesis of the carboxyl group-containing urethane (meth) acrylate compound (B) used in the photocurable / thermosetting resin composition of the present invention, a polymer polyol (g) is further used in order to reduce curing shrinkage. May be.

As the polymer polyol (g), a diol compound that is difficult to be three-dimensional is basically preferred, but a triol may be added to give a branched structure.
Specific examples include polyether polyols, polyester polyols, polycarbonate polyols, and polybutadiene glycols.
In particular, polycarbonate polyols derived from diols or bisphenols and carbonates such as dimethyl carbonate are preferred from the standpoint of chemical resistance.

These hydroxyl group-containing (meth) acrylate compounds (d), the dimethylol alkanoic acid (e), the diisocyanate compound (f), or further, the polymer polyol (g) can be urethanized by a known and conventional method. Thus, the carboxyl group-containing urethane (meth) acrylate compound (B) used in the present invention can be synthesized.
Specifically, the equivalent ratio of isocyanate groups and hydroxyl groups is 0.8 to 1.05, and the acid value of the resulting carboxyl group-containing urethane (meth) acrylate compound (B) is 30 to 100 mgKOH / g. Prepare and react as follows. As reaction conditions, it is possible to synthesize by reacting at room temperature to 150 ° C., preferably 60 to 120 ° C. in a solvent-free or aprotic solvent using a metal catalyst that is difficult to be three-dimensional.
When the acid value of the carboxyl group-containing urethane (meth) acrylate compound (B) is less than 30 mgKOH / g, developability with a dilute aqueous alkali solution cannot be obtained, which is not preferable. On the other hand, when the acid value exceeds 100 mgKOH / g, development resistance cannot be obtained, and electroless plating resistance and the like are not preferable.

Since the photocurable / thermosetting resin composition of the present invention efficiently photocures the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B), ( C) A photopolymerization initiator is used.
Examples of the photopolymerization initiator (C) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Aminoacetophenones such as 2-methylan Anthraquinones such as laquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzyl and benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphine Phosphine oxides such as finate, (2- (acetyloxyiminomethyl) thioxanthen-9-one), (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)) and the like. .

  These publicly known photopolymerization initiators can be used alone or in combination of two or more. The blending ratio of the photopolymerization initiator (C) is 0. 0 with respect to 100 parts by mass of the total amount of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B). The appropriate amount is 01 to 30 parts by mass, but in the case of the above oxime photopolymerization initiator, 0.01 to 20 parts by mass, preferably 0.01 to 5 parts by mass is appropriate. When the amount of the photopolymerization initiator used is less than the above range, the photocurability is deteriorated.

  In addition, the photocurable / thermosetting resin composition of the present invention can contain a tertiary amine compound or a benzophenone compound as a photoinitiating aid. Examples of such tertiary amines include ethanolamines, 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2- Ethyl dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), ethyl 4-dimethylaminobenzoate (n-butoxy) Quantacure BEA manufactured by International Bio-Synthetics, isoamyl p-dimethylaminobenzoate Ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-Ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk), 4,4'-diethylaminobenzophenone (Hodogaya Chemical) Company made EAB), and the like. These known and commonly used tertiary amine compounds can be used alone or as a mixture of two or more. A particularly preferred tertiary amine compound is 4,4′-diethylaminobenzophenone, but is not particularly limited thereto, and absorbs light in the wavelength region of 300 to 420 nm and is used in combination with a hydrogen abstraction type photopolymerization initiator. As long as it exhibits a sensitizing effect, it is not limited to a photopolymerization initiator and a photoinitiator aid, and can be used alone or in combination.

The photocurable / thermosetting resin composition of the present invention is the thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in one molecule in order to improve the heat resistance of the cured product. (D) (hereinafter may be abbreviated as a cyclic (thio) ether compound).
Examples of the thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups in one molecule include three, four or five-membered cyclic ether groups in one molecule, or cyclic A compound having two or more thioether groups or two kinds of groups, for example, a compound having at least two epoxy groups in one molecule, that is, a polyfunctional epoxy compound (D-1), one molecule Examples thereof include compounds having at least two or more oxetane groups, that is, polyfunctional oxetane compounds (D-2), compounds having two or more thioether groups in one molecule, that is, episulfide resins.

  As the polyfunctional epoxy compound (D-1), for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epiklone 840, Epicron 850, Epicron 1050, manufactured by Dainippon Ink & Chemicals, Inc. , Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128, manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Corporation A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB- manufactured by Tohto Kasei Co., Ltd. 500, D.C. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical Co., Ltd. 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., YDF -175, YDF-2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals (all are trade names); Epotot ST-2004, ST-2007, ST-3000 manufactured by Tohto Kasei Hydrogenated bisphenol A type epoxy resin, such as Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumitomo Chemical Co., Ltd. Epoxy ELM-120 etc. All are trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty Chemicals Alicyclic epoxy resins such as Araldide CY175, CY179, etc. (both trade names) manufactured by YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin; Epicoat YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. Name) Tetraphenylolethane type Poxy resin; Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both are trade names); Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene groups such as HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; In addition, cyclohexylmaleimide and glycidyl Methacrylate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), etc. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane And novolac resin, poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

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

  The compounding amount of such a cyclic (thio) ether compound (D) is 1 equivalent of the total amount of carboxyl groups of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B). Is 0.5 to 2.0 equivalents, preferably 0.8 to 1.5 equivalents. When the amount of the cyclic (thio) ether compound (D) is less than the above range, the carboxyl group remains, which is not preferable because the heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when the above range is exceeded, the low molecular weight cyclic (thio) ether compound (D) remains, which is not preferable because the strength of the coating film decreases.

  Furthermore, the photocurable / thermosetting resin composition of the present invention is a composition of the synthesis and composition of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B). In order to improve photocurability, (E) diluent is used. As the diluent (E), an organic solvent (E-1) can be used as a non-reactive diluent, or a polymerizable monomer (E-2) can be used as a reactive diluent.

Examples of the organic solvent (E-1) include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc. Glycol ether acetates; ethyl acetate, butyl acetate and above Esters such as acetates of glycol ethers; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Such as petroleum-based solvents. Such an organic solvent (E-1) is used alone or as a mixture of two or more.
The blending amount of the organic solvent (E-1) is not particularly limited, and can be determined in consideration of the coating properties and securing the film thickness of the dried coating film, but the carboxyl group-containing photosensitive resin. (A) and 300 mass parts or less are preferable with respect to 100 mass parts of total amounts of the said carboxyl group-containing urethane (meth) acrylate compound (B).

  Examples of the polymerizable monomer (E-2) that is a reactive diluent include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, Mono- or diacrylates of glycols such as propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethyl acrylate, N, N- Aminoalkyl acrylates such as dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydro Polyhydric alcohols such as ethyl isocyanurate or polyacrylates such as these ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide additions of these phenols Acrylates such as glycerin; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, glycidyl ether acrylates such as triglycidyl isocyanurate; and melamine acrylate and / or methacrylates corresponding to the acrylate Etc. Among these, a polyfunctional (meth) acrylate compound which is a compound having two or more ethylenically unsaturated groups in the molecule is particularly preferable because of its excellent photocurability.

  Furthermore, polyfunctional epoxy resins such as bisphenol A, bisphenol F type epoxy resins, phenol and cresol novolac type epoxy resins, and epoxy acrylate resins obtained by reacting acrylic acid, and further to the hydroxyl groups of the epoxy acrylate resins, pentaerythritol triacrylate And epoxy urethane acrylate compounds obtained by reacting a half urethane compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding amount of the polymerizable monomer (E-2) is 120 with respect to 100 parts by mass of the total amount of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B). The ratio is 10 parts by mass or less, more preferably 10 parts by mass or less. When the blending amount exceeds 120 parts by mass, it is not preferable because electrical insulation and the like are deteriorated and the coating film becomes brittle.

The photocurable / thermosetting resin composition of the present invention includes two or more carboxyl groups in the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B) in the molecule. In order to accelerate the curing reaction of the thermosetting component (D) having a cyclic ether group and / or a cyclic thioether group, it is preferable to incorporate a (F) curing catalyst.
Examples of the curing catalyst (F) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine, etc. For example, Shikoku 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Seiko Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (all are dimethylamine block isocyanate compounds) Product name), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof). In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2 S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, Preferably, a compound that also functions as an adhesion-imparting agent is used in combination with the thermosetting catalyst as described above.

  The amount of the curing catalyst (F) is sufficient in a normal quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the total resin composition. The ratio of parts. When the blending amount of the curing catalyst (F) is less than the above range, the curing time becomes long, workability is lowered, and oxidation of the copper foil or the like becomes intense, which is not preferable. On the other hand, when the blending amount of the curing catalyst (F) exceeds the above range, it is not preferable because the electrical characteristics are lowered or the standing life after temporary drying is shortened.

  In addition, the photocurable / thermosetting resin composition of the present invention can be blended with an inorganic filler for the purpose of further improving properties such as adhesion, mechanical strength, and linear expansion coefficient of the cured product. For example, known and commonly used inorganic fillers such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc. Can be used. The blending ratio is 0 to 80% by mass of the resin composition.

  The photo-curable / thermosetting resin composition of the present invention is further known as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Conventional colorants, known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, etc., known conventional thickeners such as fine silica, organic bentonite, montmorillonite, silicone-based, fluorine-based In addition, known and conventional additives such as polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, and the like can be blended.

  The photocurable / thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the diluent (E), and a dip coating method, a flow coating method, a roll is formed on a circuit-formed substrate. It is tack-free by coating the entire surface by a method such as a coating method, bar coater method, screen printing method, curtain coating method and the like, and evaporating and drying (preliminary drying) the organic solvent contained in the composition at a temperature of 60 to 100 ° C. Can be formed. Then, the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask having a pattern formed, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a resist pattern is formed.

  Base materials used for the circuit-formed substrate include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO・ Copper-clad laminates of all grades (FR-4, etc.) using materials such as copper-clad laminates for high-frequency circuits using cyanate esters, etc., other polyimide films, PET films, glass substrates, ceramic substrates, A wafer board etc. can be mentioned.

As alkaline aqueous solution, alkaline aqueous solution, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, can be used.
Moreover, as an irradiation light source used for active energy ray irradiation, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, laser beams and the like can also be used as active energy rays.
The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  Further, for example, by heating to 140 to 180 ° C. and thermosetting, the carboxyl group-containing photosensitive resin (A) and the carboxyl group of the carboxyl group-containing urethane (meth) acrylate compound (B) The thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups in the molecule reacts to various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. It is possible to form a cured coating film excellent in

The case where the photocurable / thermosetting composition of the present invention is used as a dry film is shown below.
A photocurable / thermosetting dry film is a photocurable / thermosetting resin layer obtained by applying and drying a carrier film and the photocurable / thermosetting resin composition on a carrier film or a cover film, and a resin. It has a peelable cover film on the layer.
As the carrier film, a polyester film such as PET having a thickness of 10 to 150 μm, a polyimide film, or the like is used.
The photo-curing / thermosetting resin layer is uniformly applied to a carrier film or cover film with a thickness of 10 to 150 μm by using a blade coater, lip coater, comma coater, film coater, etc. And dried to form.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but it is preferable that the adhesive strength with the photocurable / thermosetting resin layer is smaller than that of the support film.
The cover film is peeled off, the photo-curing / thermosetting resin layer and the circuit-formed base material are stacked, and bonded together using a laminator, etc. to form a photo-curing / thermo-setting resin layer on the circuit-formed base material To do. The formed photocurable / thermosetting resin layer can be exposed, developed and heat cured in the same manner as described above to form a cured coating film. The carrier film may be peeled off either before exposure or after exposure.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Synthesis Example 1: Synthesis of carboxyl group-containing photosensitive resin of the present invention Hydroxyl equivalent in a reaction vessel equipped with a gas introduction tube, a stirrer, a cooling tube, a thermometer, and a dropping funnel for continuous dropping of an aqueous alkali metal hydroxide solution 224 parts of 80 g / equivalent 1,5-dihydroxynaphthalene and 1075 parts of bisphenol A type epoxy resin Epicoat 828 (Japan Epoxy Resin, Epoxy equivalent 189 g / equivalent) were charged at 110 ° C. with stirring in a nitrogen atmosphere. Dissolved. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C., and the mixture was reacted for about 90 minutes while maintaining the temperature at 150 ° C., and an epoxy equivalent of 452 g / equivalent epoxy compound ( 4-a) was obtained. Next, the temperature in the flask is cooled to 40 ° C., 1920 parts of epichlorohydrin, 1690 parts of toluene, and 70 parts of tetramethylammonium bromide are added, and the temperature is raised to 45 ° C. and maintained with stirring. Thereafter, 364 parts of a 48% aqueous sodium hydroxide solution was continuously added dropwise over 60 minutes, and then reacted for another 6 hours. After completion of the reaction, most of the excess epichlorohydrin and toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methyl isobutyl ketone was distilled from the organic solvent layer under reduced pressure to obtain a polynuclear epoxy compound (4-b) having an epoxy equivalent of 277 g / equivalent. When the obtained polynuclear epoxy compound (4-b) is calculated from the epoxy equivalent, about 1.59 of the 1.98 alcoholic hydroxyl groups in the epoxy compound (4-a) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%. Next, 277 parts of the polynuclear epoxy compound (4-b) is put into a flask equipped with a stirrer, a condenser tube and a thermometer, 290 parts of carbitol acetate is added, and heated to dissolve, 0.46 part of methylhydroquinone and triphenol 1.38 parts of phosphine was added and heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., and 129 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. The reaction was carried out by measuring the acid value and total oxidation of the reaction solution by potentiometry, followed by the obtained addition rate, and the reaction rate was 95% or more as the end point. The carboxyl group-containing active energy ray-curable resin (4-c) thus obtained had a solid content of 62% and an acid value of 100 mgKOH / g. Next, the active energy ray curable resins (2-a) and (4-c) are mixed in such a ratio that the solid matter becomes (2-a) :( 4-c) = 1: 1. The active energy ray-curable resin thus obtained had a solid content of 61% and an acid value of 100 mgKOH / g. Hereinafter, this reaction solution is referred to as varnish A.

Synthesis Example 2: Synthesis of urethane (meth) acrylate compound having a carboxyl group In a 5 L separable flask equipped with a thermometer, a stirrer, and a reflux condenser, polycaprolactone diol (PLACCEL 208, manufactured by Daicel Chemical Industries, molecular weight 830) was used as a polymer polyol. ) 1,245 g, dimethylolpropionic acid 201 g as a dihydroxyl compound having a carboxyl group, 777 g of isophorone diisocyanate as a polyisocyanate, 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and p-methoxyphenol And 0.5 g each of di-t-butyl-hydroxytoluene. The mixture was heated to 60 ° C. with stirring and stopped, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C., and the reaction is terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) has disappeared in the infrared absorption spectrum. A viscous liquid urethane acrylate compound was obtained. The non-volatile content was adjusted to 50% by mass using PMA. A urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained. Hereinafter, this reaction solution is referred to as varnish B.

Synthesis Example 3: Synthesis of general-purpose carboxyl group-containing photosensitive resin different from the present invention 330 g of cresol novolac type epoxy resin (Epicron N-695, manufactured by Dainippon Ink & Chemicals, Epoxy equivalent 220), gas introduction tube, stirring It put into the flask provided with the apparatus, the cooling pipe, and the thermometer, 340 g of PMA was added, and it heat-dissolved, and added hydroquinone 0.46g and triphenylphosphine 1.38g. This mixture was heated to 95 to 105 ° C., 108 g of acrylic acid was gradually added dropwise, and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 68 g of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. A carboxyl group-containing photosensitive resin having a solid acid value of 50 mgKOH / g and a nonvolatile content of 60% was obtained. Hereinafter, this reaction solution is referred to as Varnish C.

Examples 1-3 and Comparative Examples 1-3
The compounding components shown in Table 1 using varnish A, varnish B, and varnish C obtained in Synthesis Examples 1 to 3 were kneaded with a three-roll mill to obtain a photocurable / thermosetting resin composition. .

Performance evaluation:
<Dry film production>
Each of the photocurable and thermosetting resin compositions having the thermosetting properties in the alkali development types of Examples 1 to 3 and Comparative Examples 1 to 3 are each dried using an applicator so that the film thickness after drying is 30 μm. It was applied to a PET film (R310: 16 μm manufactured by Mitsubishi Polyester) and dried at 40-100 ° C. to obtain a dry film.
<Board fabrication>
After the circuit-formed FR-4 substrate was buffed, the film produced by the above method was 0.8 MPa, 80 ° C., 1 minute, 133.3 Pa using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho). An evaluation substrate was obtained by heat lamination under conditions.

(1) Solder heat resistance Using each of the above evaluation boards, Kodak No. A step tablet of 2 was applied to obtain an exposure amount of 6 steps. A negative pattern on which a solder resist pattern is drawn is applied to each of the evaluation substrates described above, and the resulting exposure amount is irradiated. Using a 1% by mass aqueous sodium carbonate solution at 30 ° C., development is performed with a developing machine having a spray pressure of 0.2 MPa Then, a pattern was formed. Then, it hardened at 150 degreeC for 60 minutes, and obtained the cured coating film.
A rosin flux was applied to the cured coating film and immersed in a solder bath at 260 ° C. for 30 seconds, and the state of the cured coating film was evaluated according to the following criteria.
○: The cured coating has no blistering, peeling or discoloration
Δ: Slightly blistered, peeled, or discolored on the cured coating
X: The cured coating has blistering, peeling, or discoloration

(2) Resistance to electroless gold plating In the same manner as described above, after exposure and development, thermosetting was performed to prepare an evaluation substrate. Each evaluation substrate was degreased by immersing in an acidic degreasing solution at 30 ° C. (manufactured by Nippon Macder Mid Co., Ltd., 20 vol% aqueous solution of Metex L-5B) for 3 minutes, and then immersed in running water for 3 minutes and washed with water. This evaluation substrate was immersed in an aqueous solution of 14.3 wt% ammonium persulfate for 3 minutes at room temperature, soft-etched, and then immersed in running water for 3 minutes and washed with water. The test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, and then immersed in running water for 30 seconds to 1 minute and washed with water. This evaluation substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes to give a catalyst, and then immersed in running water for 3 minutes and washed with water. The evaluation substrate to which the catalyst was applied was immersed in a nickel plating solution (manufactured by Meltex, 20 vol% aqueous solution of Melplate Ni-865M, pH 4.6) for 20 minutes to perform electroless nickel plating. After the evaluation substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was immersed in a gold plating solution at 95 ° C. (Meltex Co., Ourolectroless UP15 vol% and potassium gold cyanide 3 vol%, pH 6) for 10 minutes, followed by electroless gold plating, followed by running water It was immersed for 3 minutes in water and washed with water, and further immersed in warm water at 60 ° C. for 3 minutes and washed with hot water. After sufficiently washing with water, water was thoroughly drained and dried to obtain an evaluation substrate plated with electroless gold. Using the electroless gold-plated substrate as described above, a peel test using a cellophane adhesive tape was performed, and peeling and discoloration of the coating film were evaluated according to the following criteria.
○: No change is observed at all.
(Triangle | delta): The coating film peeled off only slightly or discoloration was recognized.
X: Peeling is recognized on the coating film.

(3) PCT resistance In the same manner as described above, after exposure and development, thermosetting was performed to prepare an evaluation substrate. This evaluation substrate was placed in a high-pressure, high-temperature, high-humidity tank at 121 ° C., 2 atm, and humidity 100% for 168 hours, and the state change of the cured coating film was evaluated. Evaluation was made according to the following evaluation criteria.
○: No peeling, discoloration or elution.
Δ: Any of peeling, discoloration, or elution.
X: Many peeling, discoloration, and elution are seen.

(5) Insulation after HAST test In the same manner as described above, the photocurable / thermosetting resin composition is applied to an FR-4 substrate on which comb-type electrodes (line / space = 50 microns / 50 microns) are formed. The whole surface was printed, exposed and developed, and then thermally cured to produce an evaluation substrate. This evaluation substrate was placed in a high-temperature and high-humidity tank in an atmosphere of 130 ° C. and 85% humidity, charged with a voltage of 5 V, and subjected to a HAST test for 168 hours. The electrical insulation after the HAST test was measured.
○: 10 ¹⁰ Ω or more Δ: 10 ¹⁰ to 10 ⁸ Ω
×: 10 ⁸ Ω or less

(6) Evaluation of warpage In the same manner as described above, the photocurable / thermosetting resin composition was printed on the entire surface of an FR-4 substrate having a substrate thickness of 60 microns, exposed and developed, and then evaluated by thermosetting. A substrate was produced. Using this evaluation substrate (400 mm × 300 mm) as a test piece, four corners of the test piece were measured on a plane, and the total of the values was measured as the amount of warpage deformation.
○: 20 mm or less Δ: 20 mm to 40 mm
×: 40 mm or more

The results of evaluating the photocurable and thermosetting resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 as described above are shown in Table 2 below.

As is apparent from Table 2, the photocurable / thermosetting resin composition of the present invention is required for solder resists and resists for package substrates, solder heat resistance, electroless gold plating resistance, PCT resistance, after HAST test. It can be seen that even if a thin plate used for a package substrate such as QFP, BGA, or CSP is used, there is little warpage.
On the other hand, Comparative Example 1 using a general-purpose carboxyl group-containing photosensitive resin and a carboxyl group-containing urethane (meth) acrylate compound (B) had large warpage, and was inferior in PCT resistance and insulation after the HAST test.
Further, Comparative Example 2 using only the carboxyl group-containing photosensitive resin (A) of the present invention was inferior in finger touch drying property and warped.
Furthermore, Comparative Example 3 using only the carboxyl group-containing urethane (meth) acrylate compound (B) was inferior in solder heat resistance.

Claims (10)

(A) A carboxyl obtained by reacting a polybasic acid anhydride (c) with a reaction product of a polynuclear epoxy compound (a) represented by the following general formula (1) and an unsaturated group-containing monocarboxylic acid (b) Group-containing photosensitive resin,
(B) a carboxyl group-containing urethane (meth) acrylate compound,
(C) a photopolymerization initiator,
(D) a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in one molecule, and (E) a diluent, a photocurable thermosetting resin composition object.

  The carboxyl group-containing urethane (meth) acrylate compound (B) is a compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound (d), a dimethylolalkanoic acid (e), and a diisocyanate compound (f). The acid value is 30-100 mgKOH / g, The photocurable thermosetting resin composition of Claim 1 characterized by the above-mentioned.   The carboxyl group-containing urethane (meth) acrylate compound (B) reacts the hydroxyl group-containing (meth) acrylate compound (d), dimethylolalkanoic acid (e), diisocyanate compound (f), and polymer polyol (g). The photocurable thermosetting resin composition according to claim 1, wherein the acid value is 30 to 100 mg KOH / g.   The photocurable / thermosetting resin composition according to claim 2 or 3, wherein the dimethylolalkanoic acid (e) is at least one of dimethylolpropionic acid and dimethylolbutanoic acid. .   The blending ratio of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B) is 85:15 to 15:85. The photocurable thermosetting resin composition as described in any one of these.   The photocurable / thermosetting resin composition according to any one of claims 1 to 4, further comprising (F) a curing catalyst.   A photocurable / thermosetting resin layer obtained by applying and drying the carrier film and the photocurable / thermosetting resin composition according to any one of claims 1 to 6 on the carrier film. A photocurable / thermosetting dry film.   The photocurable / thermosetting dry film according to claim 7, further comprising a peelable cover film on the photocurable / thermosetting resin layer.   By curing the photocurable / thermosetting resin composition according to any one of claims 1 to 6 or the dry film according to claim 7 or 8 by irradiation with active energy rays and heating. A cured product obtained.   The light according to any one of claims 1 to 6, wherein a solder resist film as a permanent protective film is formed on a circuit board having a conductor layer having a predetermined circuit pattern. A thin package substrate comprising a curable / thermosetting resin composition or a cured coating film of the dry film according to claim 7 or 8.