JP6379697B2 - Curable resin composition, cured product and curing agent - Google Patents

Description

  The present invention relates to a curing agent, a curable resin composition containing the curing agent, particularly a curable resin composition for forming a solder resist used in a printed wiring board, and a dry film and a printed wiring board using the same. About.

  In recent years, curable resin compositions for resin insulation layers such as solder resist have also been improved in performance and workability in response to the increase in the density of printed wiring boards as electronic devices (electronic devices) become lighter, thinner and shorter. Is required. In particular, electric control of a motor vehicle, in particular, a drive unit is progressing, and a printed wiring board is often mounted in a place with a high environmental temperature such as an engine room and its surroundings. In-vehicle printed wiring boards are exposed to a high temperature of 80 ° C. to 150 ° C. for a long period of time depending on the mounting location. Therefore, the high-performance solder resist used for in-vehicle printed wiring boards is excellent. Heat resistance is required.

  An example of a material suitable for such a solder resist is a bismaleimide compound. Although bismaleimide compounds are resins with excellent heat resistance, flame retardancy, dielectric properties, etc., known bismaleimide compounds that do not exhibit curing reactivity with epoxy resins are used in combination with epoxy curable resins, There was a problem of insufficient heat resistance. Therefore, an amine-modified bismaleimide compound obtained by reacting an amino group of a monoamine compound such as aminophenol with an unsaturated N-substituted maleimide group of a bismaleimide compound may be used in combination with an epoxy-curable curable resin. It has been proposed (Patent Document 1). However, since the compound does not have sufficient alkali developability, it is insufficient as a solder resist material, particularly a solder resist material required for a printed wiring board having a miniaturized circuit in recent years.

  It has also been proposed to use a bismaleimide compound modified with an amine compound having a carboxy group such as aminobenzoic acid in combination with an epoxy curable resin (Patent Document 2). However, the compound has a low thermal decomposition temperature, and heat resistance to lead-free solder that has been required in recent years has been demanded.

JP 2012-166515 A JP 2007-302843 A

  Therefore, the problem to be solved by the present invention is that a polyvalent carboxy group-containing compound capable of obtaining a cured product excellent in alkali developability and heat resistance, a curable resin composition containing the compound, and a solder resist formation It is providing the dry film and printed wiring board using a composition and the said curable resin composition.

  As a result of various investigations, the inventors of the present application have found that a polyvalent carboxy group-containing compound obtained by reacting a monoamine adduct of bismaleimide with an acid anhydride is used as a curing agent. It discovered that the hardened | cured material which expresses developability was obtained, and came to solve the said subject.

  That is, the present invention provides a polyvalent carboxy group-containing compound (A) obtained by reacting bismaleimide (A1) with monoamine (A2) and then reacting with acid anhydride (A3), and curable resin (B). The curable resin composition containing this.

  Furthermore, this invention relates to the hardened | cured material formed by hardening | curing the said curable resin composition.

  Furthermore, this invention relates to the curable resin composition for solder resist formation containing the said curable resin composition.

  Furthermore, this invention relates to the dry film which has a curable resin layer containing the said curable resin composition.

  Furthermore, this invention relates to the printed wiring board which has a resin insulating layer formed by thermosetting the curable resin layer containing the said curable resin composition.

  Furthermore, the present invention is a laminated structure having a substrate and a plurality of resin insulation layers formed on the substrate, and the resin insulation layer in contact with the substrate among the plurality of resin insulation layers is: It is related with the laminated structure characterized by being a layer formed from the said curable resin composition.

  Furthermore, the present invention provides the following general formula (3)

（式中、Ｒ^１は芳香環または脂肪族炭化水素を有する二価の有機基であり、Ｒ^３は下記一般式（４）

(In the formula, R ¹ is a divalent organic group having an aromatic ring or an aliphatic hydrocarbon, and R ³ is represented by the following general formula (4):

（ただし、＊は結合手であり、Ｒ^２は芳香環を有する一価の有機基であり、Ｒ^６はカルボキシ基及び環状構造を有する一価の有機基である。）であらわされる二価の有機基であり、Ｒ^４は一般式（４）又は下記一般式（５）

(However, * is a bond, R ² is a monovalent organic group having an aromatic ring, and R ⁶ is a monovalent organic group having a carboxy group and a cyclic structure.) It is an organic group, and R ⁴ is represented by the general formula (4) or the following general formula (5).

で表される二価の有機基である。）で表される多価カルボキシ基含有化合物、および該多価カルボキシ基含有化合物からなる硬化剤に関する。

It is a bivalent organic group represented by these. And a curing agent comprising the polyvalent carboxy group-containing compound.

  According to the present invention, a polyvalent carboxy group-containing compound capable of obtaining a cured product excellent in heat resistance and alkali developability, a curable resin composition containing the compound, a composition for forming a solder resist, and the curing described above. A dry film and a printed wiring board using the conductive resin composition can be provided.

It is a FT-IR chart figure of the polyvalent carboxy group containing compound obtained in Example 1 of the present invention.

  The curable resin composition of the present invention comprises a polyvalent carboxy group-containing compound (A) obtained by reacting bismaleimide (A1) and monoamine (A2) and then reacting with acid anhydride (A3), and curing. It contains the functional resin (B).

  The polyvalent carboxy group-containing compound (A) of the present invention is obtained by reacting bismaleimide (A1) with monoamine (A2) and then reacting with acid anhydride (A3).

  As the bismaleimide (A1), any compound having at least two unsaturated N-substituted maleimide groups in the molecular structure can be used. For example, the following general formula (1)

（式中、Ｒ^１は芳香環または脂肪族炭化水素を有する二価の有機基である）で表されるビスマレイミド化合物を好ましいものとして例示することができる。当該Ｒ^１は、耐熱性に優れる点から芳香環を有する二価の有機基であることがより好ましい。ここでＲ^１の芳香環または脂肪族炭化水素を有する二価の有機基としては、アルキレン基、シクロアルキレン基、単環式または多環式のアリーレン基、またはそれらの基が２価の原子団（たとえばアルキレン基やシクロアルキレン基、酸素原子、硫黄原子、スルホン基、スルフィニル基、ジスルフィド基、カルボニル基など）によって結合された２価の基が好ましい構造として挙げれる。

A preferable example is a bismaleimide compound represented by the formula (wherein R ¹ is a divalent organic group having an aromatic ring or an aliphatic hydrocarbon). The R ¹ is more preferably a divalent organic group having an aromatic ring from the viewpoint of excellent heat resistance. Here, as the divalent organic group having an aromatic ring or aliphatic hydrocarbon of R ¹ , an alkylene group, a cycloalkylene group, a monocyclic or polycyclic arylene group, or a group in which these groups are a divalent atomic group A preferable structure is a divalent group bonded by (for example, an alkylene group, a cycloalkylene group, an oxygen atom, a sulfur atom, a sulfone group, a sulfinyl group, a disulfide group, or a carbonyl group).

  Specific examples of the bismaleimide compound used in the present invention include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3- (2-methylphenylene)] bismaleimide, N, N ′-[1,3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) Bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimide) Phenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ke , Bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3- Bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) Phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2- Bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [[4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4, 4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phene Nyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) ) Phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4 -(4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4- Maleimidophenoxy) -α, α-dimethylbenzyl] benze 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethyl Benzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3 , 5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 4-methyl- , 3-phenylene bismaleimide, poly phenyl methane maleimide. These maleimide compounds may be used as a mixture of two or more may be used alone. Among these, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis (4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, polyphenylmethanemaleimide, and Bis (4-maleimidophenyl) sulfone is preferred. From the viewpoint of high reaction rate and higher heat resistance, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl] sulfide, bis (4-maleimidophenyl) ) Disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred, and bis (4-maleimidophenyl) is inexpensive. Methane and N, N ′-(1,3-phenylene) bismaleimide are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.

  As the monoamine (A2) used in the present invention, any compound can be used as long as it is a compound having one primary amino group in the molecular structure. For example, the following general formula (2)

（式中、Ｒ^２は芳香環を有する一価の有機基である）で表されるアミン化合物を好ましいものとして例示することができる。ここで、Ｒ^２としては、水酸基、カルボキシ基、スルホン基、ハロゲン原子および炭素原子数１〜５の範囲のアルキル基から成る群から選ばれる１以上の置換基を有していても良い、単環式または多環式のアリール基が挙げられ、さらに具体的には、以下の一般式（２．１）

A preferable example is an amine compound represented by the formula (wherein R ² is a monovalent organic group having an aromatic ring). Here, R ² may have one or more substituents selected from the group consisting of a hydroxyl group, a carboxy group, a sulfone group, a halogen atom, and an alkyl group having 1 to 5 carbon atoms. And a cyclic or polycyclic aryl group. More specifically, the following general formula (2.1)

（式中、Ｒ^７は水素原子、水酸基、カルボキシ基またはスルホン基を示し、Ｒ^８は水素原子、炭素原子数１〜５のアルキル基、ハロゲン原子、水酸基、カルボキシ基またはスルホン基を示し、ｎ及びｍは２〜４の整数である）で表されるアミン化合物を例示することができる。

(Wherein R ⁷ represents a hydrogen atom, a hydroxyl group, a carboxy group or a sulfone group; R ⁸ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxy group or a sulfone group; And m is an integer of 2 to 4).

  Specific examples of the monoamine used in the present invention include aniline, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o- Aminobenzene sulfonic acid, m-aminobenzene sulfonic acid, p-aminobenzene sulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. are mentioned. Among these, solubility and yield of synthesis From the viewpoint of m-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and from the viewpoint of heat resistance, m-aminophenol and p-aminophenol are more preferable. M-aminophenol is particularly preferable because of its low toxicity.

  The acid anhydride (A3) used in the present invention is any compound as long as it has at least two carboxy groups in the molecular structure and the carboxy group is dehydrated in the molecule to form an acid anhydride. For example, aromatic dicarboxylic acid anhydride, alicyclic dicarboxylic acid anhydride, aromatic tricarboxylic acid anhydride, alicyclic tricarboxylic acid anhydride, aromatic tetracarboxylic acid anhydride, alicyclic Tetracarboxylic acid anhydrides can be mentioned as preferred, and alicyclic dicarboxylic acid anhydrides and alicyclic tricarboxylic acid anhydrides having an alicyclic structure from the standpoint of excellent solvent solubility and storage stability during drying. And alicyclic tetracarboxylicsan anhydrides are more preferable.

  Specific examples of acid anhydrides used in the present invention include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride. , Succinic anhydride, dodecenyl succinic anhydride, dichloromaleic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, naphthalene-1,2,4-tricarboxylic anhydride Product, biphenyl-3,3 ', 4,4'-tetracarboxylic acid anhydride, biphenyl-2,3,3', 4'-tetracarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3 , 4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-trica Boronic acid-2,3-anhydride, pyromellitic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic Acid dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetra Carboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1, 2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 2,7-dichloronaphthalene-1, , 5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,3,9,10-tetra Carboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4 -Dicarboxypheny ) Ether dianhydride, ethylene glycol bisaan hydrotrimellitate, propylene glycol bisaan hydrotrimellitate, butanediol bisaanhydro trimellitate, hexamethylene glycol bisaan hydrotrimellitate, polyethylene glycol bisahydrotrimellitate Examples include melitrate, polypropylenelene glycol bisanhydro trimellitate, and other alkylene glycol bisan hydroxy trimellitate.

  The polycarboxyl group-containing compound (A) of the present invention is reacted with bismaleimide (A1) and monoamine (A2) in the presence or absence of an organic solvent (step 1), and then the bismaleimide obtained And a reaction product of monoamine with an acid anhydride (A3) (step 2).

  First, bismaleimide (A1) and monoamine (A2) are reacted in the presence of an organic solvent (step 1).

  Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran. Aromatic solvents such as toluene, xylene and mesitylene; S atom-containing solvents such as dimethyl sulfoxide; N atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Ethylene glycol dialkyl ethers such as dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol Polyethylene glycol dialkyl ethers such as rudiethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate Ethylene glycol monoalkyl ether acetates such as: diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether Polyethylene glycol monoalkyl ether acetates such as cetate and triethylene glycol monobutyl ether acetate; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, Polypropylene glycol dialkyl ethers such as dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol Polypropylene glycol monoalkyl ether acetates such as monoethyl ether acetate and tripropylene glycol monobutyl ether acetate; copolymer polyether glycol dialkyl ethers such as low molecular weight ethylene-propylene copolymer; copolymer polyether glycol monoacetate Monoalkyl ethers; copolymerized polyether Alkyl esters of glycol; and copolymerization monoalkyl esters monoalkyl ethers polyether glycol. These organic solvents can be used alone or in combination of two or more. In these, the solvent which does not contain an alcoholic hydroxyl group from a viewpoint of suppressing a side reaction is preferable. Further, acetates, dimethylformamide and dimethylacetamide are preferable from the viewpoint of solubility, and acetates are more preferable from the viewpoint of low toxicity. Although there is no restriction | limiting in particular as the usage-amount of an organic solvent, It is 0.5-100 mass parts normally with respect to 100 mass parts of total mass which match | combined the raw material bismaleimide (A1) and monoamine (A2), Preferably Is 0.5 to 70 parts by mass, more preferably 0.5 to 50 parts by mass.

  Furthermore, in step 1, a reaction catalyst can be arbitrarily used as necessary, and is not particularly limited. Examples of reaction catalysts include acidic compounds such as acetic anhydride and acetic acid, amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. 1 type (s) or 2 or more types can be mixed and used. Although there is no restriction | limiting in particular in the usage-amount of a catalyst, Usually 0.001-5 mass parts is used if needed with respect to 100 mass parts of total mass which added the raw material bismaleimide (A1) and monoamine (A2). It is preferable to do this.

  In step 1, the use ratio of bismaleimide (A1) and monoamine (A2) to be added to the reaction system as a raw material is preferably in the range of 0.3 to 1.0 equivalent of the amino group with respect to 1 equivalent of the maleimide group. A range of 0.5 to 1.0 equivalent is more preferable.

  In Step 1, the reaction can be carried out in the range of 50 to 250 ° C., and is preferably carried out in the range of 70 to 180 ° C. from the viewpoint of reaction rate and prevention of side reactions. At that time, the monoamine (A2) may be added to the reaction system containing the bismaleimide (A1) at a time or in several portions, or may be added successively in small portions and reacted while stirring. In particular, when an aliphatic monoamine is used, the latter is preferable from the viewpoint of suppressing side reactions.

  Further, in step 2, the organic solvent is added to the reaction system containing the reaction product of bismaleimide and monoamine obtained in step 1 as necessary, and then the acid anhydride (A3) is divided at once or several times. Or may be added successively to the reaction system little by little and allowed to react with stirring. The reaction temperature in step 2 can be carried out in the range of 50 to 250 ° C., and is preferably carried out in the range of 70 to 180 ° C. from the viewpoint of reaction rate and prevention of side reactions. In Step 2, the ratio of the acid anhydride (A3) used is such that the acid anhydride group is in the range of 0.1 to 1.0 equivalent with respect to 1 equivalent of the secondary amino group produced by the reaction product of bismaleimide and monoamine. Preferably, the range of 0.5-1.0 equivalent is more preferable.

  When a catalyst is used after completion of the reaction, the catalyst can be removed by neutralization, water washing, adsorption, or the like, if necessary. When a solvent is used, the solvent can be distilled off.

The polyvalent carboxy group-containing compound (A) of the present invention thus obtained usually shows a colorless to brown solid resinous or liquid state, and crystallizes in some cases.
When the hue of the polyvalent carboxy group-containing compound of the present invention is poor, the hue may be improved by hydrogenation in the presence of a hydrogenation catalyst. The hydrogenation catalyst used in that case is preferably one containing an iron group element such as nickel or a platinum group element such as palladium, rhodium or platinum as an active component, and more preferably one having an active component held on a carrier. .
Further, the carboxy group equivalent of the polyvalent carboxy group-containing compound of the present invention is not particularly limited, but when used as a curing agent described later, it is in the range of 200 to 1200 [g / eq] from the viewpoint of heat resistance. Further, from the viewpoint of alkali developability of the blend, it is preferably in the range of 350 to 750 [g / eq].

  Moreover, although the polyvalent carboxy group-containing compound of the present invention is not essential, it may be derived from a monoamine compound and have a hydroxyl group in the compound. When the polyvalent carboxy group-containing compound of the present invention has a hydroxyl group in the molecule, the hydroxyl group equivalent is not particularly limited, but when used as a curing agent described later, the heat resistance and alkali developability of the formulation are more. From the viewpoint of improvement, the range is preferably 200 to 1200 [g / eq], and more preferably 350 to 750 [g / eq].

Further, the melt viscosity of the polyvalent carboxy group-containing compound of the present invention is not particularly limited, but when used as a curing agent described later, the molding time of the cured product can be shortened and an arbitrary shape can be imparted. From the viewpoint, the molecular weight is preferably 300 to 10,000, and more preferably 330 to 5,000.
The polyvalent carboxy group-containing compound of the present invention thus obtained is, for example, the following general formula (3)

（式中、Ｒ^１は芳香環または脂肪族炭化水素を有する二価の有機基であり、Ｒ^３は下記一般式（４）

(In the formula, R ¹ is a divalent organic group having an aromatic ring or an aliphatic hydrocarbon, and R ³ is represented by the following general formula (4):

（ただし、＊は結合手であり、Ｒ^２は芳香環を有する一価の有機基であり、Ｒ^６はカルボキシ基及び環状構造を有する一価の有機基である。）であらわされる二価の有機基であり、Ｒ^４は一般式（４）又は下記一般式（５）

(However, * is a bond, R ² is a monovalent organic group having an aromatic ring, and R ⁶ is a monovalent organic group having a carboxy group and a cyclic structure.) It is an organic group, and R ⁴ is represented by the general formula (4) or the following general formula (5).

で表される二価の有機基である。）で表される構造を有するものが得られ、さらに、このうち、硬化性樹脂に優れた硬化性を付与することができる点で下記一般式（３．１）

It is a bivalent organic group represented by these. ), And among them, the following general formula (3.1) is given in that it can impart excellent curability to the curable resin.

（式中、Ｒ^１、Ｒ^２およびＲ^６は前記と同様の定義である）で表される構造を有するものが好ましいものとして挙げられる。
当該多価カルボキシ基含有化合物は、硬化性樹脂の硬化剤として使用することができ、例えば、以下の成分とともに使用することができる。

Those having a structure represented by the formula (wherein R ¹ , R ² and R ⁶ are as defined above) are preferred.
The polyvalent carboxy group-containing compound can be used as a curing agent for a curable resin, and can be used, for example, with the following components.

  Next, the curable resin (B) can be used without particular limitation as long as it is a resin curable by heating or active energy rays. For example, epoxy resin, melamine resin, benzoguanamine resin, melamine derivative A well-known curable resin such as an amino resin such as a benzoguanamine derivative, a blocked isocyanate compound, a cyclocarbonate compound, a polyfunctional oxetane compound, an episulfide resin, a bismaleimide, a carbodiimide resin, or a cyanate resin can be exemplified as a preferable one. Of these, an epoxy resin is preferred.

  More specifically, examples of the epoxy resin include novolac type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) It has a glycidyl group and / or an epoxycyclohexane structure Epoxy resins) include solid or liquid epoxy resins such as, but not limited thereto.

  In the curable resin composition of the present invention, the composition ratio of the polyvalent carboxy group-containing compound (A) and the curable resin (B) is not particularly limited, but from the viewpoint of excellent heat resistance and moist heat resistance, It is preferable that the epoxy group of the curable resin (B) is in a range of 1.0 to 2.0 equivalents relative to 1 equivalent of the carboxyl group of the polyvalent carboxyl group-containing compound (A), and further alkali developable. From the viewpoint, it is more preferably in the range of 1.0 to 1.5 equivalents.

The curable resin composition of this invention can add a well-known photoinitiator (C) suitably as needed. Examples of the photopolymerization initiator include an oxime ester photopolymerization initiator having an oxime ester group, an alkylphenone photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a titanocene light. One or more photopolymerization initiators selected from the group consisting of polymerization initiators can be suitably used.
The compounding amount when such an oxime ester photopolymerization initiator is used is excellent in photocurability and resolution, improves adhesion and PCT resistance, and further has chemical resistance such as electroless gold plating resistance. From the point which can obtain the outstanding soldering resist, it is preferable to set it as 0.01-5 mass% of the whole composition, and it is more preferable to set it as 0.25-3 mass%.
By setting it as 0.01-5 mass%.
From the same point, the blending amount in the case of using an alkylphenone photopolymerization initiator is preferably 0.2 to 30% by mass, and more preferably 2 to 20% by mass based on the total composition.

  From the same point, the blending amount in the case of using an α-aminoacetophenone photopolymerization initiator or an acylphosphine oxide photopolymerization initiator is preferably 0.1 to 25% by mass of the whole composition. More preferably, it is 20 mass%.

  Also, as a photopolymerization initiator, Irgacure 389 manufactured by BASF Japan can be suitably used. The suitable compounding quantity of Irgacure 389 is 0.1-20 mass% of the whole composition, and also 1-15 mass% is suitable.

  A titanocene photopolymerization initiator such as Irgacure 784 can also be suitably used. The suitable compounding quantity of a titanocene type photoinitiator is 0.01-5 mass% of the whole composition, and also 0.01-3 mass% is suitable.

  By setting these photopolymerization initiators in suitable amounts, they are excellent in photocurability and resolution, improved in adhesion and PCT resistance, and also in chemical resistance such as electroless gold plating resistance. Solder resist can be used.

  In the curable resin composition of the present invention, in addition to the photopolymerization initiator, a photoinitiation assistant and a sensitizer can be used as necessary. Photoinitiators and sensitizers that can be suitably used in the curable resin composition include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. Can be mentioned.

  These photoinitiator aids and sensitizers can be used alone or as a mixture of two or more. The total amount of such photoinitiator aid and sensitizer is preferably 30% by mass or less of the entire composition. If it exceeds 30% by mass, the deep curability tends to decrease due to light absorption.

  Diluent (D) can be appropriately added to the curable resin composition as necessary. As the diluent (D), a compound having an ethylenically unsaturated group in the molecule is preferably blended. A compound having an ethylenically unsaturated group in the molecule can be photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the photosensitive resin composition of the present invention in an alkaline aqueous solution. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide , N-methylolacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate, or their ethylene oxide adducts, propylene oxide adducts Or polyvalent acrylates such as ε-caprolactone adduct; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyacid acrylates of sidyl ether; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And at least one of the methacrylates corresponding to the acrylate.

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

  A compound having an ethylenically unsaturated group in the molecule as described above may be used alone or in combination of two or more. In particular, a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable from the viewpoint of photoreactivity and resolution, and a compound having two ethylenically unsaturated groups in one molecule is used. And the linear thermal expansion coefficient of hardened | cured material falls, and since generation | occurrence | production of peeling at the time of PCT is reduced, it is preferable.

  When the diluent is used in the curable resin composition of the present invention, the photo-curing property is improved, the pattern formation is improved by alkali development after irradiation with active energy rays, and the solubility in a dilute aqueous alkali solution is improved. Is improved, and the impact resistance of the coating film tends to be improved, so 2 to 50% by mass of the entire composition is preferable.

  The curable resin composition of this invention can add a hardening accelerator suitably as needed. Examples of the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole and 1-methylimidazole, tertiary amines such as benzyldimethylamine and N, N-dimethylaniline, tetramethylammonium chloride, and benzyltriethylammonium chloride. Quaternary ammonium salts such as tetra-n-butylphosphonium o, o-diethyl phosphorodithionate, phosphonium salts such as tetrabutylphosphonium benzotriazolate, metal salts such as zinc octylate and zinc stearate, zinc acetylacetone, Examples thereof include metal complexes such as benzoylacetone zinc.

  When the curing accelerator is used in the curable resin composition of the present invention, the blending amount is preferably 0.01 to 8% by mass, and more preferably 0.1 to 5% by mass. A blending amount of the curing accelerator of 0.01% by mass or more is preferable because a sufficient effect can be obtained. Moreover, if the compounding quantity of a hardening accelerator is 8 mass% or less, since transparency and heat resistance of the hardened | cured material obtained can be maintained, it is preferable.

The curable resin composition of this invention can add an inorganic filler suitably as needed. An inorganic filler is used in order to suppress the curing shrinkage of the cured product of the curable resin composition and improve properties such as adhesion and hardness. Examples of inorganic fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and nitriding Examples thereof include silicon and aluminum nitride.
The average particle size of the inorganic filler is preferably 5 μm or less. The blending ratio is preferably 75% by mass or less, more preferably 0.1 to 60% by mass of the entire composition. When the blending ratio of the inorganic filler exceeds 75% by mass, the viscosity of the composition increases, and the applicability may decrease, or the cured product of the curable resin composition may become brittle.

  The curable resin composition of the present invention further includes, as optional components, an organic solvent, an elastomer, a mercapto compound, a colorant, an antioxidant, an ultraviolet absorber, an adhesion promoter, a polymerization inhibitor, fine silica, organic bentonite, Thickeners such as montmorillonite, at least one of defoamers and leveling agents such as silicones, fluorines and polymers, silane coupling agents such as imidazole, thiazole and triazoles, rust preventives, You may mix | blend well-known additives, such as flame retardants, such as phosphorus compounds, such as a phosphinate, a phosphoric acid ester derivative, and a phosphazene compound, and a block copolymer.

  In the curable resin composition of the present invention, an organic solvent can be used for the preparation of the resin composition or for the viscosity adjustment for application to a substrate or a carrier film. Organic solvents for preparing such resin compositions or for adjusting the viscosity for application to a substrate or carrier film include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates. And esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, for example, 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 Glycol ethers such as monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether Esters such as acetate and propylene glycol butyl ether acetate; ethanol, pro Nord, ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; can be exemplified petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, a petroleum-based solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used 2 or more types as a mixture.

  The dry film of the present invention has a curable resin layer formed by applying and drying the curable resin composition of the present invention. The dry film of the present invention can be used by laminating the curable resin layer so as to be in contact with the substrate.

  In the dry film of the present invention, the curable resin composition is uniformly applied to the carrier film by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater, and dried to form the curable resin layer described above. Preferably, it can be produced by laminating a cover film thereon. The cover film and the carrier film may be the same film material or different films.

  In the dry film of the present invention, as the film material for the carrier film and the cover film, any known materials used for the dry film can be used.

  As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.

  As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but it is preferable that the adhesive force with the curable resin layer is smaller than that of the carrier film.

  The film thickness of the curable resin layer on the carrier film of the present invention is preferably 100 μm or less, and more preferably in the range of 5 to 50 μm.

  The printed wiring board of the present invention is preferably produced using the curable resin layer of the present invention constituting the dry film of the present invention. For example, it is preferable to form a resin insulating layer by laminating a dry film including a curable resin layer and heating and curing the film at a temperature of about 140 to 180 ° C., for example.

  In the printed wiring board of the present invention, a resin insulating layer is formed by directly applying and drying a curable resin composition on a substrate by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater. Can be obtained.

The resin insulating layer of the printed wiring board of the present invention can be patterned by irradiating a semiconductor laser such as a CO ₂ laser or a UV-YAG laser. Moreover, a hole can be opened with a CO ² laser, a UV-YAG laser, or a drill. When the resin insulation layer consists of multiple holes, the hole is a through hole that can be connected to any layer of the resin insulation layer (through hole), but it is a partial hole for the purpose of conduction between the inner circuit and the surface of the resin insulation layer (conformal via) ) Can be opened.

  After drilling, in order to remove the residue (smear) existing on the inner wall and bottom of the hole and to develop an anchor effect with the conductor layer (the metal plating layer to be formed thereafter), a rough surface with fine irregularities For the purpose of forming a chemical surface, treatment with a commercially available desmear solution (roughening agent) or a solution containing an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. Do.

  Next, a circuit is formed by a subtractive method or a semi-additive method in the hole from which the residue has been removed with a desmear liquid or the surface of the film roughened into fine irregularities. In any method, after electroless plating or electrolytic plating, or after both plating, heat treatment (about 80 to 180 ° C. for about 10 to 60 minutes for the purpose of removing stress of metal and improving strength) Annealing treatment may be performed.

  There is no restriction | limiting in particular as metal plating used here, such as copper, tin, solder, nickel, and it can also be used in combination. Moreover, it is also possible to substitute metal sputtering etc. instead of the plating used here.

  In addition, when the resin insulating layer is formed by a dry coating film obtained by applying and drying a photosensitive curable resin layer or a curable resin composition, the curable resin layer or dry coating formed on the substrate (substrate) is used. The film is selectively exposed by an active energy ray or directly by a laser direct exposure machine through a photomask having a pattern formed by a contact method (or a non-contact method). In the curable resin layer and the dried coating film, the exposed portion (the portion irradiated with the active energy ray) is cured.

  As an exposure machine used for active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer), an exposure device equipped with a metal halide lamp, and an (ultra) high-pressure mercury lamp An exposure apparatus equipped with an LED, an exposure apparatus equipped with an LED, or an exposure apparatus equipped with a mercury short arc lamp can be used.

As the active energy ray, it is preferable to use light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, radicals can be efficiently generated from the photopolymerization initiator. Further, the exposure amount varies depending the thickness or the like, generally 5~500mJ / cm ^2, preferably be in the range of 10 to 300 mJ / cm ^2.

  As the direct drawing device, for example, those manufactured by Nippon Orbotech Co., Ltd., Pentax Co., Ltd., Oak Co., Ltd., Dainippon Screen Co., Ltd., etc. can be used, and the active energy ray has a maximum wavelength of 350 to 410 nm. Any device may be used as long as the device emits light.

  Then, by exposing the curable resin layer and the dried coating film in this manner to cure the exposed portion (the portion irradiated by the active energy ray), the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0. Development is performed with a 3 to 3 wt% sodium carbonate aqueous solution), and a pattern is formed on the curable resin layer and the dried coating film.

  At this time, as a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. Further, as the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.

  Furthermore, the curable resin layer is heated to a temperature of, for example, about 140 to 180 ° C. and thermally cured, whereby the carboxy group of the polyvalent carboxy group-containing compound (A) and the curable resin (B) react, A resin insulating layer (pattern) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and insulation reliability can be formed.

  The total film thickness of the resin insulating layer in the printed wiring board of the present invention is preferably 100 μm or less, and more preferably in the range of 5 to 50 μm.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using composite materials such as fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate ester, A polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  The resin insulation layer which the printed wiring board of this invention has is suitable as a permanent film, and especially suitable as a soldering resist or an interlayer insulation material.

  The laminated structure of the present invention has a base material and a plurality of resin insulating layers formed on the base material, and at least one of the plurality of resin insulating layers is made of the curable resin composition of the present invention. Any insulating resin layer may be used.

  The basic structure of the laminated structure of the present invention may be any general structure. For example, the insulating resin layer (L1) provided in contact with the substrate (S) and the surface layer, that is, the outermost layer, 2 The thing which has a layer is mentioned. Another layer may be provided between the insulating resin layer (L1) and the surface layer. For example, the insulating resin layer (L1) and the resin insulating layer (L2) may be alternate layers without providing other layers. For example, the insulating resin layer (L1) / resin insulating layer (L2) / insulating resin layer (L1) / resin insulating layer (L2) may be used.

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

(Synthesis Example 1)
In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet, 295 parts by mass of diethylene glycol monoethyl ether acetate (EDGAc), 197 parts by mass of N, N-dimethylacetamide (DMAc), 4,4′-diphenylmethane bismaleimide ( Daiwa Kasei Kogyo Co., Ltd., “BMI-1000”) 400 parts by mass and p-aminophenol 243 parts by mass were added, heated to 120 ° C. over 150 minutes under nitrogen flow in the liquid, and reacted for 90 minutes. . To this reaction vessel, 339 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride (Shin Nippon Rika Co., Ltd., “Licacid TH”) was added, and the reaction was continued at 120 ° C. for 4.5 hours. Thereafter, the FT-IR spectrum of the resin was measured and it was confirmed that there was no change in the spectrum. Then, 710 parts by mass of EDGAc was added, and the mixture was heated to 140 ° C. and decompressed to remove DMAc. After completion of the distillation, 197 parts by mass of EDGAc was added and cooled to obtain a resin solution (A-1) having a nonvolatile content of 45%. The FT-IR spectrum of the obtained compound is shown in FIG.

(Synthesis Example 2)
In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet, 279 parts by mass of diethylene glycol monoethyl ether acetate (EDGAc), 186 parts by mass of N, N-dimethylacetamide (DMAc), 4,4′-diphenylmethane bismaleimide ( Daiwa Kasei Kogyo Co., Ltd., “BMI-1000”), 400 parts by mass and 208 parts by mass of aniline were added, and the temperature was raised to 120 ° C. over 150 minutes under nitrogen flow in the liquid, and the reaction was carried out for 5 hours. To this reaction vessel, 339 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride (Shin Nippon Rika Co., Ltd., “Licacid TH”) was added, and the reaction was continued at 120 ° C. for 4.5 hours. Thereafter, the FT-IR spectrum of the resin was measured and it was confirmed that there was no change in the spectrum. Then, 668 parts by mass of EDGAc was added, and the mixture was heated to 140 ° C. and decompressed to remove DMAc. After completion of the distillation, 186 parts by mass of EDGAc was added and cooled to obtain a resin solution (A-2) having a nonvolatile content of 45%.

(Synthesis Example 3)
In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet, 295 parts by mass of diethylene glycol monoethyl ether acetate (EDGAc), 197 parts by mass of N, N-dimethylacetamide (DMAc), 4,4′-diphenylmethane bismaleimide ( Daiwa Kasei Kogyo Co., Ltd., “BMI-1000”) 400 parts by mass and 243 parts by mass of m-aminophenol were added, heated to 120 ° C. over 150 minutes under a nitrogen flow in the liquid, and reacted for 3 hours. . To this reaction vessel, 339 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride (Shin Nippon Rika Co., Ltd., “Licacid TH”) was added, and the reaction was continued at 120 ° C. for 4.5 hours. Thereafter, the FT-IR spectrum of the resin was measured and it was confirmed that there was no change in the spectrum. Then, 710 parts by mass of EDGAc was added, and the mixture was heated to 140 ° C. and decompressed, and DMAc was distilled off. After completion of the distillation, 197 parts by mass of EDGAc was added and cooled to obtain a resin solution (A-3) having a nonvolatile content of 45%.

(Comparative Synthesis Example 1)
In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet, 563 parts by mass of diethylene glycol monoethyl ether acetate (EDGAc), 4,4′-diphenylmethane bismaleimide (Daiwa Kasei Kogyo Co., Ltd., “BMI-1000”) 400 Mass part and 60.9 parts by mass of p-aminophenol were added, the temperature was raised to 120 ° C. over 150 minutes under nitrogen flow in the liquid, the reaction was performed for 3 hours, and a resin solution (a-1 having a nonvolatile content of 45%) )

(Comparative Synthesis Example 2)
In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet, 563 parts by mass of diethylene glycol monoethyl ether acetate (EDGAc), 4,4′-diphenylmethane bismaleimide (Daiwa Kasei Kogyo Co., Ltd., “BMI-1000”) 400 Part by mass, 76.5 parts by mass of p-aminobenzoic acid were added, heated to 120 ° C. over 150 minutes under nitrogen flow in the liquid, reacted for 3 hours, and a resin solution (a- 2) was obtained.

(Calculation of epoxy curable substituent equivalent)
Of the carboxy group-containing compounds (A-1) to (A-3) obtained in Synthesis Examples 1 to 4 and the compounds (a-1) and (a-2) obtained in Comparative Synthesis Examples 1 and 2 The epoxy curable substituent equivalent was calculated from the theoretical structure.

(Preparation of resin composition)
The composition ratio shown in Table 2 was used to prepare curable resin compositions 1 to 6 by blending EDGAc so that the nonvolatile content (N.V) was finally 50 mass%.

(Measurement of glass transition temperature of film)
Preparation of measurement sample The curable resin compositions 1 to 6 were coated on a tin plate so that the film thickness after curing was 50 to 70 µm. Next, this coated plate was dried for 30 minutes with a dryer at 80 ° C. and then cured at 170 ° C. for 1 hour to prepare a cured coating film. After cooling to room temperature, the cured coating film was cut into 22 mm length × 6 mm width substrate. Was used as a sample for measurement.
Measuring method

The dynamic viscoelasticity of the measurement sample was measured under the following conditions, and the temperature of the maximum value of Tan δ of the obtained spectrum was defined as the glass transition temperature (Tg). The obtained results are shown in Table 2 as “Tg of film (° C.)”.
Measuring instrument: Leo Vibron RSA-II (manufactured by Rheometric)
Jig: Pull Chuck spacing: 20 mm
Measurement temperature: 25 ° C to 400 ° C
Measurement frequency: 1Hz
Temperature increase rate: 3 ° C / min

(Alkali developability)
The curable resin compositions 1 to 6 were coated on a tinplate substrate so that the film thickness after drying was 25 to 35 μm. Next, this coated plate was dried for a predetermined time with a dryer at 80 ° C. to prepare a test piece. This was shaken for 3 minutes in a 1% potassium carbonate aqueous solution at 30 ° C., then washed with tap water, and the remaining state of the coating film was visually observed to evaluate alkali developability. When all the coating films were dissolved, “◯”, when some remained, “△”, and when all remained, “×”. Those in which the coating film dissolves even with a longer drying time are excellent in alkali developability.

*表中の値は全て固形分あたり

* All values in the table are per solid content

In addition, the word in a table | surface is as follows N-680 ... DIC Corporation, a cresol novolak type epoxy resin, epoxy equivalent 212g / equivalent 2E4MZ ... 2-ethyl-4methylimidazole

Claims (12)

A polyvalent carboxy group-containing compound represented by the following general formula (3).

(In the formula, R ¹ is a divalent organic group having an aromatic ring or an aliphatic hydrocarbon, and R ³ is represented by the following general formula (4):

(However, * is a bond, R ² is a monovalent organic group having an aromatic ring, and R ⁶ is a monovalent organic group having a carboxy group and a cyclic structure.) It is an organic group, and R ⁴ is represented by the general formula (4) or the following general formula (5).

It is a bivalent organic group represented by these. ) The polyvalent carboxyl group equivalent of the carboxyl group-containing compound is 200 to 1200 [g / eq] polyvalent carboxyl group-containing compound of claim 1 wherein the range of. The molecular weight of the polyvalent carboxyl group-containing compound is in the range of 300 to 10,000 claim 1 or 2 multivalent carboxylated compound according. Bismaleimide (A1) represented by the following general formula (1);
After reacting the monoamine (A2) represented by the following general formula (2),
A method for producing a polyvalent carboxy group-containing compound in which an acid anhydride (A3) is reacted .

(Wherein R ¹ is a divalent organic group having an aromatic ring or an aliphatic hydrocarbon)

(Wherein R ² is a monovalent organic group having an aromatic ring) A curable resin composition comprising the polyvalent carboxy group-containing compound according to any one of claims 1 to 3 and an epoxy resin. Furthermore, the curable resin composition of Claim 5 containing a photoinitiator (C). Furthermore, the curable resin composition of Claim 5 or 6 containing a diluent (D). Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of Claims 5-7 . The curable resin composition for solder resist formation containing the curable resin composition as described in any one of Claims 5-7 . The dry film which has a curable resin layer containing the curable resin composition as described in any one of Claims 5-7 . The printed wiring board which has a resin insulating layer formed by thermosetting the curable resin layer containing the curable resin composition as described in any one of Claims 5-7 . It is a laminated structure which has a base material and the some resin insulation layer formed on this base material, Comprising: At least one layer of these resin insulation layers is any one of Claims 5-7. A layered structure formed of the curable resin composition described in 1.

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