Curable resin composition, cured product, insulating material, and resist member

Abstract

To provide a curable resin composition which has high developability and can give a cured product having a low elastic modulus, high adhesion to an adjacent member, and excellent dielectric characteristics.SOLUTION: The curable resin composition contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group. The active ester resin (A) uses as essential reaction raw materials: a compound (a1) having one phenolic hydroxyl group in a molecular structure; a phenolic hydroxyl group-containing resin (a2) using a phenolic hydroxyl group-containing compound (a2-1) and a divinyl compound (a2-2) as essential reaction raw materials; and an aromatic polycarboxylic acid or an acid halide thereof (a3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, a cured product, an insulating material, and a resist member. [Background technology]

[0002] Traditionally, solder resist has been widely used as a material to prevent solder from adhering to areas other than the mounting area when soldering electronic components onto printed circuit boards, and to form a coating that semi-permanently prevents oxidation and corrosion of the wiring. One technique for forming such solder resist patterns is the photoresist method, which can accurately form fine patterns. Among these, the alkali-developable liquid photoresist method has become the mainstream, particularly due to environmental considerations.

[0003] For example, as an alkali-soluble photosensitive resin used in an alkali-developable liquid photoresist method, a reaction product (acid pendant type epoxy acrylate) obtained by reacting a novolac-type epoxy resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride is widely used, and a solder resist film is formed from a curable resin composition containing this alkali-soluble photosensitive resin (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 1-54390 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Meanwhile, printed circuit boards are constantly being miniaturized, multilayered, and integrated into a single board in order to achieve higher density, and the mounting method is also shifting towards surface mount technology (SMT). As a result, there is a growing demand for solder resist films to be finer, have high Tg (high heat resistance), high resolution, high precision, and high reliability. Furthermore, in order to achieve high reliability, the solder resist film must have excellent adhesion to adjacent components (such as copper foil), and it is also important that it has low elasticity so that it can conform to the adjacent components. Furthermore, with the increasing speed of transmitted signals, and the use of high frequencies (gigahertz band), there is a demand for solder resist films exhibiting low dielectric constant and low dielectric loss tangent, from the perspective of minimizing time delay.

[0006] In response to these requirements, conventional curable resin compositions containing alkali-soluble photosensitive resins have insufficient developability, and the cured products obtained by curing these curable resin compositions have a high elastic modulus, poor adhesion to adjacent members, and poor dielectric properties, leaving room for improvement.

[0007] Therefore, the object of the present invention is to solve the problems of the above-mentioned prior art and to provide a curable resin composition that has high developability, low elastic modulus, high adhesion to adjacent members (such as copper foil), and excellent dielectric properties (low dielectric constant and dielectric loss tangent) that can be obtained as a cured product. Furthermore, a further objective of the present invention is to provide a cured product, an insulating material, and a resist member that have a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties. [Means for solving the problem]

[0008] As a result of diligent research to solve the above problems, the present inventors have found that by blending a specific active ester resin (A) and a resin (B) having acidic groups and polymerizable unsaturated groups into a curable resin composition, the developability of the curable resin composition is improved, and the cured product obtained by curing such a curable resin composition has a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties, thus completing the present invention. In other words, the gist of the present invention that solves the above problems is as follows.

[0009] [1] Contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group, A curable resin composition characterized in that the active ester resin (A) is a compound (a1) having one phenolic hydroxyl group in its molecular structure, a phenolic hydroxyl group-containing resin (a2) using a phenolic hydroxyl group-containing compound (a2-1) and a divinyl compound (a2-2) as essential reaction raw materials, and an aromatic polycarboxylic acid or its acid halide (a3) ​​as essential reaction raw materials.

[0010] [2] The number of moles of hydroxyl groups in compound (a1) having one phenolic hydroxyl group in the molecular structure (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2) OH ) and the ratio [(a1 OH ) / (a2 OH A curable resin composition according to [1], wherein the ratio is 10 / 90 to 75 / 25.

[0011] [3] The number of moles of hydroxyl groups in compound (a1) having one phenolic hydroxyl group in the molecular structure (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2) OH The curable resin composition according to [1] or [2], wherein the total of (a) and (a3) ​​is 0.95 to 1.05 moles per mole of the total carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or its acid halide (a3).

[0012] [4] The curable resin composition according to any one of [1] to [3], wherein the active ester resin (A) has a weight-average molecular weight (Mw) of 600 to 5,000.

[0013] [5] The curable resin composition according to any one of [1] to [4], wherein the mass ratio of the solid content of the active ester resin (A) and the resin having the acid group and polymerizable unsaturated group (B) [(A) / (B)] is 5 / 95 to 50 / 50.

[0014] [6] A curable resin composition according to any one of [1] to [5], further comprising a photopolymerization initiator.

[0015] [7] A curable resin composition according to any one of [1] to [6], further comprising a curing agent.

[0016] [8] A cured product characterized by being obtained by curing a curable resin composition described in any one of [1] to [7].

[0017] An insulating material characterized by comprising any one of the curable resin compositions described in [9] [1] to [7].

[0018] A resist member characterized by comprising any one of the curable resin compositions described in [1] to [7]. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a curable resin composition that can produce a cured product with high developability, low elastic modulus, high adhesion to adjacent members (such as copper foil), and excellent dielectric properties (low dielectric constant and dielectric loss tangent). Furthermore, according to the present invention, it is possible to provide a cured product, an insulating material, and a resist member that have a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties. [Modes for carrying out the invention]

[0020] The curable resin composition, cured product, insulating material, and resist member of the present invention will be described in detail below based on embodiments thereof.

[0021] (Explanation of terms) Unless otherwise specified in this specification, the following definitions of terms apply.

[0022] In this specification, "alkyl group" refers to, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an (n-)heptyl group, an (n-)octyl group, an (n-)nonyl group, an (n-)decyl group, an (n-)undecyl group, an (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclononyl group.

[0023] In this specification, examples of "aryl group" include phenyl group, naphthyl group, phenalenyl group, phenantrenyl group, anthryl group, azulenyl group, indenyl group, indanyl group, tetralinyl group, and the like. Furthermore, the hydrogen atoms of the aromatic ring in the "aryl group" may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

[0024] In this specification, "aralkyl group" refers to, for example, a benzyl group, a diphenylmethyl group, a biphenyl group, a naphthylmethyl group, and the like.

[0025] In this specification, examples of "alkoxy group (alkyloxy group)" include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group, and the like.

[0026] In this specification, "halogen atoms" include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.

[0027] In this specification, examples of "alkylene group" include methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, propylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, and the like.

[0028] In this specification, "monovalent hydrocarbon group" refers, for example, to the alkyl group described above, and one or more -CH2- in the alkyl group may be substituted with -O- or -S- so as not to be adjacent to each other, or one or more -CH2-CH2- in the alkyl group may be substituted with -CH=CH- so as not to be adjacent to each other.

[0029] In this specification, "divalent hydrocarbon group" refers, for example, to the alkylene group described above. In the alkylene group, one or more -CH2- groups may be substituted with -O- or -S- groups such that they are not adjacent to each other, or one or more -CH2-CH2- groups may be substituted with -CH=CH- groups such that they are not adjacent to each other.

[0030] In this specification, "(meth)acrylate" means acrylate and / or methacrylate. In this specification, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, in this specification, "(meth)acrylic" means acrylic and / or methacrylic.

[0031] <Curable resin composition> The curable resin composition of this embodiment contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group. In the curable resin composition of this embodiment, the active ester resin (A) is characterized by having a compound (a1) having one phenolic hydroxyl group in its molecular structure, a phenolic hydroxyl group-containing resin (a2) using a phenolic hydroxyl group-containing compound (a2-1) and a divinyl compound (a2-2) as essential reaction raw materials, and an aromatic polycarboxylic acid or its acid halide (a3) ​​as essential reaction raw materials.

[0032] The curable resin composition of this embodiment contains a resin (B) having acidic groups and polymerizable unsaturated groups, and therefore exhibits high photosensitivity and high developability. Furthermore, developability relates to the contrast between the exposed and unexposed areas, and "high developability" means that the above contrast is sufficiently high. One reason for low developability is that when a curable resin composition applied to a substrate is dried and then exposed, the unexposed areas remain after (alkaline) development due to heating during drying, which reduces the contrast. Therefore, in this specification, developability is evaluated by the drying control range (minutes), as described in the examples below. This drying control range defines the range of drying conditions (drying time) in which development defects are unlikely to occur due to drying of the coating film, etc. Therefore, even if the drying time is extended, if development residue is unlikely to occur (i.e., if the drying control range is large), it is considered that high developability is achieved.

[0033] Furthermore, in the curable resin composition of this embodiment, by using an activated ester resin (A) that uses a phenolic hydroxyl group-containing resin (a2) that uses a divinyl compound (a2-2) as a reaction raw material, the polarity of the cured product obtained by curing the curable resin composition is reduced, thereby lowering the dielectric constant and dielectric loss tangent, and improving the dielectric properties. Furthermore, the activated ester resin (A) using a phenolic hydroxyl group-containing resin (a2) with a divinyl compound (a2-2) as a reaction raw material has a low curing shrinkage rate, so the cured product obtained by curing the curable resin composition of this embodiment has high adhesion to adjacent members (copper foil, etc.). Furthermore, the cured product obtained by curing a curable resin composition containing an active ester resin (A) and a resin (B) having an acidic group and a polymerizable unsaturated group is not excessively hard and has a low elastic modulus.

[0034] (Activated ester resin (A)) The curable resin composition of this embodiment contains an activated ester resin (A). The activated ester resin (A) is • Compounds having one phenolic hydroxyl group in their molecular structure (a1), • A phenolic hydroxyl group-containing resin (a2) using a phenolic hydroxyl group-containing compound (a2-1) and a divinyl compound (a2-2) as essential reaction raw materials, and • Aromatic polycarboxylic acids or their acid halides (a3) This is an essential reaction raw material.

[0035] --A compound (a1) having one phenolic hydroxyl group in its molecular structure-- The compound (a1) having one phenolic hydroxyl group in its molecular structure can be any aromatic compound having one hydroxyl group on its aromatic ring, and its other specific structures are not particularly limited. The compound (a1) having one phenolic hydroxyl group in its molecular structure may be used alone or two or more may be used in combination. Specifically, the compound (a1) having one phenolic hydroxyl group in its molecular structure can be phenol or a phenol compound having one or more substituents on the aromatic nucleus of phenol, naphthol or a naphthol compound having one or more substituents on the aromatic nucleus of naphthol, anthracenol or anthracenol compound having one or more substituents on the aromatic nucleus of anthracenol, and the like. Substituents on the aromatic nucleus include, for example, aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups; alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; phenyl, naphthyl, and anthryl groups, and aryl groups on which the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc. are substituted on these aromatic nuclei; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl groups, and aralkyl groups on which the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc. are substituted on these aromatic nuclei. Among these, naphthol compounds are preferred because they result in active ester resins with low curing shrinkage and excellent dielectric properties in the cured product, and 1-naphthol or 2-naphthol are particularly preferred.

[0036] --Phenolic hydroxyl group-containing resin (a2)-- Regarding the phenolic hydroxyl group-containing resin (a2), the phenolic hydroxyl group-containing compound (a2-1) can be any aromatic compound having a hydroxyl group on an aromatic ring, and other specific structures are not particularly limited. Specifically, examples include the same compounds as those exemplified as the compound (a1) having one phenolic hydroxyl group in its molecular structure, and compounds having multiple phenolic hydroxyl groups in their molecular structure (polyfunctional phenols) can also be used. Here, examples of compounds having multiple phenolic hydroxyl groups in their molecular structure include hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, polyhydroxynaphthylene ether, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and the like. Furthermore, the phenolic hydroxyl group-containing compound (a2-1) may be used alone or in combination of two or more types. Among these, naphthol compounds are preferred because they result in active ester resins with low curing shrinkage and excellent dielectric properties in the cured product, and 1-naphthol or 2-naphthol are particularly preferred.

[0037] The divinyl compound (a2-2) may be any compound having at least two vinyl groups (-CH=CH2) and capable of reacting with the phenolic hydroxyl group-containing compound (a2-1) to cause the phenolic hydroxyl group-containing compounds (a2-1) to bond together; other specific structures are not particularly limited. Furthermore, the divinyl compound (a2-2) may be used alone or in combination of two or more types. Among these, it is preferable that the compound has an aromatic ring or a cyclo ring in its molecular structure, as this results in an active ester resin with low curing shrinkage and excellent dielectric properties in the cured product. A more preferred specific structure of the divinyl compound (a2-2) is, for example, the following structural formulas (1-1) to (1-4): [ka] (In the formula, R 1 Each of the following is an independent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is 0 or an integer from 1 to 4. Y is an alkylene group with 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group. j is an integer from 1 to 4. Examples include compounds represented by any of the following.

[0038] R in the above structural formulas (1-1) to (1-4) 1 Each of these is independently one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group. Specifically, examples include aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups; alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; phenyl, naphthyl, and anthryl groups, and aryl groups in which the aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted on these aromatic nuclei; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl groups, and aralkyl groups in which the aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted on these aromatic nuclei.

[0039] Among the compounds represented by any one of the above structural formulas (1-1) to (1-4), the compound represented by the above structural formula (1-1) is preferable, since it provides an active ester resin having a low cure shrinkage and excellent dielectric properties in a cured product.

[0040] When a compound represented by any one of the above structural formulas (1-1) to (1-4) is used as the above divinyl compound (a2-2), the above phenolic hydroxyl group-containing resin (a2) is obtained such that the phenolic hydroxyl group-containing compound (a2-1) has the following structural formula (2): Chemical formula [in the formula, X is any of the following structural formulas (X-1) to (X-4): Chemical formula (wherein, R 1 each independently represent any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group; i is 0 or an integer of 1 to 4; Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group; and j is an integer of 1 to 4), which is a structural moiety represented by any one of the above], and has a molecular structure linked via the structural moiety (α) represented by the above.

[0041] In addition to the above phenolic hydroxyl group-containing compound (a2-1) and the above divinyl compound (a2-2), the above phenolic hydroxyl group-containing resin (a2) may use other compounds as reaction raw materials. Examples of the other compounds include various aldehyde compounds, such as compound (a2-2') which is a compound other than divinyl compound (a2-2) and capable of linking the phenolic hydroxyl group-containing compound (a2-1), and substituent-introducing agents (a2-3) for introducing aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, or aralkyl groups as substituents on the aromatic ring in the phenolic hydroxyl group-containing resin (a2-1).

[0042] When compound (a2-2') is used, the effects of low curing shrinkage and low dielectric loss tangent in the cured product are fully exhibited. Therefore, it is preferable that the amount of divinyl compound (a2-2) is 50% by mass or more, and preferably 80% by mass or more, relative to the total amount of divinyl compound (a2-2) and compound (a2-2').

[0043] Examples of the substituent introducing agents (a2-3) include phenylmethanol compounds, phenylmethyl halide compounds, naphthylmethanol compounds, naphthylmethyl halide compounds, and aralkyl group introducing agents such as styrene compounds.

[0044] The method for producing the phenolic hydroxyl group-containing resin (a2) is not particularly limited, but it is preferable to adjust the ratio of the reaction raw materials so that the number of phenolic hydroxyl groups per molecule is 2 or more. For example, it can be produced by using 2 to 10 moles of the phenolic hydroxyl group-containing compound (a2-1) per mole of the divinyl compound (a2-2), and heating and stirring under acid catalyst conditions at a temperature of about 80 to 180°C. The reaction may be carried out in an organic solvent if necessary. After the reaction is complete, the excess amount of the phenolic hydroxyl group-containing compound (a2-1) may be removed by distillation if desired. Alternatively, the unreacted phenolic hydroxyl group-containing compound (a2-1) in the reaction product may be used as is as a compound (a1) having one phenolic hydroxyl group in its molecular structure.

[0045] Examples of the acid catalyst include p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, sulfuric acid, hydrochloric acid, and oxalic acid. These may be used individually or in combination of two or more. The amount of acid catalyst added is preferably in the range of 0.01 to 10% by mass relative to the phenolic hydroxyl group-containing compound (a2-1).

[0046] Examples of the aforementioned organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used individually or as a mixture of two or more solvents.

[0047] As an example of the specific structure of the phenolic hydroxyl group-containing resin (a2), for example, when naphthol is used as the phenolic hydroxyl group-containing compound (a2-1) and divinylbenzene is used as the divinyl compound (a2-2), a structural example is shown in the following structural formula (2-1). Note that the following structural formula (2-1) is merely one example of the specific structure of the phenolic hydroxyl group-containing resin (a2) and does not exclude other resin structures.

[0048] [ka] [In equation (2-1), n ​​is an integer between 1 and 10. R is independently a hydrogen atom or the following structural formula (R-1): [ka] This is the structural part represented by [formula]. Furthermore, in equation (R-1), R is synonymous with R in equation (2-1) above, and m is an integer between 1 and 10.

[0049] Furthermore, commercially available divinylbenzene may contain some ethylstyrene. In this case, the structure represented by the following structural formula (R-2) may be partially introduced as R in the above structural formula (2-1). [ka]

[0050] The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (a2) is preferably in the range of 130 to 300 g / equivalent, as this results in an active ester resin with high solvent solubility that is easy to use in various applications.

[0051] --Aromatic polycarboxylic acids or their acid halides (a3)-- The aromatic polycarboxylic acid or its acid halide (a3) ​​is any aromatic compound that can react with a compound (a1) having one phenolic hydroxyl group in its molecular structure and a phenolic hydroxyl group in the phenolic hydroxyl group-containing resin (a2) to form an ester bond, and the specific structure is not particularly limited; any compound is acceptable. Specific examples include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, benzenetricarboxylic acids such as trimellitic acid, naphthalenedicarboxylic acids such as naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid, their acid halides, and compounds in which aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc., are substituted on the aromatic kernels. Examples of acid halides include acid chlorides, acid bromides, acid fluorides, and acid iodides. These may be used individually or in combination of two or more. In particular, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, or their acid halides, are preferred because they form active ester resins with high reaction activity and excellent curability.

[0052] --Manufacturing Method-- The activated ester resin (A) can be produced, for example, by heating and stirring reaction raw materials, which include a compound (a1) having one phenolic hydroxyl group in its molecular structure, the phenolic hydroxyl group-containing resin (a2), and the aromatic polycarboxylic acid or its acid halide (a3), in the presence of an alkaline catalyst at a temperature of approximately 40 to 65°C. The reaction may be carried out in an organic solvent if necessary. After the reaction is complete, the reaction product may be purified by washing with water or reprecipitation, if desired.

[0053] Examples of the aforementioned alkaline catalysts include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These may be used individually or in combination of two or more. They may also be used as an aqueous solution of about 3.0-30%. Among these, sodium hydroxide or potassium hydroxide, which have high catalytic activity, are preferred.

[0054] Examples of the aforementioned organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used individually or as a mixture of two or more solvents.

[0055] The reaction ratio of the compound (a1) having one phenolic hydroxyl group in its molecular structure, the phenolic hydroxyl group-containing resin (a2), and the aromatic polycarboxylic acid or its acid halide (a3) ​​can be appropriately changed according to the desired molecular design. In particular, the number of moles of hydroxyl groups in the compound (a1) having one phenolic hydroxyl group in its molecular structure (a1) is such that it is an active ester resin with high solvent solubility and is easy to use in various applications. OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2) OH ) and the ratio [(a1 OH ) / (a2 OH The ratio of ) is preferably 10 / 90 to 75 / 25, and more preferably 25 / 75 to 50 / 50.

[0056] Furthermore, the number of moles of hydroxyl groups in compound (a1) having one phenolic hydroxyl group in its molecular structure (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2) OHThe total amount of (a3) ​​is preferably 0.95 to 1.05 moles per mole of the total carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or its acid halide (a3).

[0057] --Ester compounds (a1-a3)-- The activated ester resin (A) may partially contain an ester compound (a1-a3) of a compound (a1) having one phenolic hydroxyl group in its molecular structure and the aromatic polycarboxylic acid or its acid halide (a3). The ester compound (a1-a3) can be produced as a component of the activated ester resin, for example, by adjusting the reaction ratio of the compound (a1) having one phenolic hydroxyl group in its molecular structure, the phenolic hydroxyl group-containing resin (a2), and the aromatic polycarboxylic acid or its acid halide (a3).

[0058] As an example of the specific structure of the ester compounds (a1-a3), for example, when a naphthol compound is used as the compound (a1) having one phenolic hydroxyl group in its molecular structure, and benzenedicarboxylic acid or its acid halide is used as the aromatic polycarboxylic acid or its acid halide (a3), a structural example is shown in the following structural formula (3). Note that the following structural formula (3) is merely one example of the specific structure of the ester compounds (a1-a3) and does not exclude diester compounds having other molecular structures.

[0059] [ka] (In the formula, R 2 Each of these groups is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and may be bonded to any carbon atom forming the naphthalene ring. p is 0 or an integer from 1 to 3.

[0060] When the activated ester resin (A) contains the ester compounds (a1-a3), the content is preferably less than 40% of the activated ester resin, and particularly preferably 10% or more and less than 35%, in order to obtain an activated ester resin with a low curing shrinkage rate and excellent curability.

[0061] The content of the ester compounds (a1-a3) in the active ester resin (A) is a value calculated from the area ratio of the GPC chart measured under the following conditions.

[0062] Measuring device: Tosoh Corporation "HLC-8320 GPC" Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40°C Developing solvent: tetrahydrofuran Flow rate 1.0mL / min Standard: In accordance with the measurement manual for "GPC-8320" mentioned above, the following monodisperse polystyrenes with known molecular weights were used. (Uses polystyrene) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation Tosoh Corporation's "F-10" F-20 manufactured by Tosoh Corporation Tosoh Corporation's "F-40" Tosoh Corporation's "F-80" Tosoh Corporation's "F-128" Sample: 50 μL of a tetrahydrofuran solution containing 1.0% by mass (based on resin solids content) filtered through a microfilter.

[0063] --Physical Properties-- The weight-average molecular weight (Mw) of the activated ester resin (A) is preferably in the range of 600 to 5,000, and particularly preferably in the range of 800 to 3,000, in order to obtain an activated ester resin with a low curing shrinkage rate. Here, the weight-average molecular weight (Mw) of the activated ester resin (A) is a polystyrene-converted value measured by GPC under the same conditions as when determining the content of the ester compounds (a1-a3).

[0064] The softening point of the activated ester resin (A) is preferably in the range of 80 to 180°C, and more preferably in the range of 85 to 160°C, as measured according to JIS K7234.

[0065] The functional group equivalent of the activated ester resin (A) is preferably in the range of 100 to 500 g / equivalent, more preferably in the range of 100 to 400 g / equivalent, and particularly preferably in the range of 200 to 300 g / equivalent, in order to obtain an activated ester resin with low curing shrinkage and excellent curability. Furthermore, the ester group equivalent of the activated ester resin (A) is preferably in the range of 200 to 500 g / equivalent, more preferably in the range of 200 to 400 g / equivalent, and particularly preferably in the range of 200 to 300 g / equivalent, in order to obtain an activated ester resin with low curing shrinkage and excellent curability. Here, the functional groups in the activated ester resin (A) refer to the ester bond sites and phenolic hydroxyl groups in the activated ester resin (A). The functional group equivalent and ester group equivalent of the activated ester resin (A) are values ​​calculated from the amount of reaction raw materials charged.

[0066] --Content-- The content of the active ester resin (A) in the total amount (100% by mass) of the curable resin composition of this embodiment is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of improving developability, adhesion, and dielectric properties in a balanced manner while lowering the elastic modulus.

[0067] (Resin (B) having acidic groups and polymerizable unsaturated groups) The curable resin composition of this embodiment contains a resin (B) having acidic groups and polymerizable unsaturated groups. The resin (B) only needs to have acidic groups and polymerizable unsaturated groups; its other specific structure or molecular weight is not particularly limited, and a wide variety of resins can be used.

[0068] Examples of acidic groups in the resin (B) include carboxyl groups, sulfonic acid groups, and phosphate groups. Among these, carboxyl groups are preferred as acidic groups because they exhibit excellent alkali developability.

[0069] Furthermore, examples of polymerizable unsaturated groups in resin (B) include (meth)acryloyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, styryl groups, styrylmethyl groups, maleimide groups, vinyl ether groups, and the like.

[0070] Examples of the resin (B) having the acid group and polymerizable unsaturated group include the following [1] to [6]: [1] Epoxy resin having acid groups and polymerizable unsaturated groups (B1), [2] Urethane resin having acidic groups and polymerizable unsaturated groups (B2) [3] Acrylic resin having acidic groups and polymerizable unsaturated groups (B3), [4] Amidoimide resin having acid groups and polymerizable unsaturated groups (B4), [5] Acrylamide resin having acidic groups and polymerizable unsaturated groups (B5), [6] Ester resin having acidic groups and polymerizable unsaturated groups (B6), These are some examples. Among these, epoxy resins having acidic groups and polymerizable unsaturated groups (B1) and amide-imide resins having acidic groups and polymerizable unsaturated groups (B4) are preferred, and a combination of an active ester resin (A) and epoxy resins having acidic groups and polymerizable unsaturated groups (B1) and / or amide-imide resins having acidic groups and polymerizable unsaturated groups (B4) is particularly preferred for achieving the effects of the present invention.

[0071] --Epoxy resin (B1) having acidic groups and polymerizable unsaturated groups-- Examples of the epoxy resin (B1) having acidic groups and polymerizable unsaturated groups include epoxy (meth)acrylate resins having acidic groups, which require epoxy resin (b1-1), unsaturated monobasic acid (b1-2), and polybasic acid anhydride (b1-3) as essential reaction raw materials, and epoxy (meth)acrylate resins having acidic groups and urethane bonds, which require epoxy resin (b1-1), unsaturated monobasic acid (b1-2), polybasic acid anhydride (b1-3), polyisocyanate compound (b1-4), and (meth)acrylate compound (b1-5) having hydroxyl groups as reaction raw materials.

[0072] The epoxy resin (b1-1) is not particularly limited in its specific structure, as long as it has multiple epoxy groups in the resin. Examples of the epoxy resin (b1-1) include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, biphenol type epoxy resin, hydrogenated biphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol copolymer novolac type epoxy resin, naphthol-cresol copolymer novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, and the like. The epoxy resin (b1-1) may be used alone or in combination of two or more types.

[0073] Examples of the bisphenol-type epoxy resins include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the hydrogenated bisphenol type epoxy resins include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Examples of the biphenol-type epoxy resins include 4,4'-biphenol-type epoxy resin, 2,2'-biphenol-type epoxy resin, tetramethyl-4,4'-biphenol-type epoxy resin, and tetramethyl-2,2'-biphenol-type epoxy resin. Examples of the hydrogenated biphenol-type epoxy resins include hydrogenated 4,4'-biphenol-type epoxy resins, hydrogenated 2,2'-biphenol-type epoxy resins, hydrogenated tetramethyl-4,4'-biphenol-type epoxy resins, and hydrogenated tetramethyl-2,2'-biphenol-type epoxy resins.

[0074] Examples of the unsaturated monobasic acid (b1-2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, etc. Acid halides and esters of the unsaturated monobasic acid can also be used. Furthermore, the following general formula (4) applies to the unsaturated monobasic acid (b1-2): [ka] [In the above general formula (4), X 41 X represents an alkylene chain, polyoxyalkylene chain, (poly)ester chain, aromatic hydrocarbon chain, or (poly)carbonate chain having 1 to 10 carbon atoms. 41 The hydrogen atoms in the structure may be substituted with halogen atoms or alkoxy groups, Y 41 is a hydrogen atom or a methyl group. Compounds represented by ] can also be used. The molecular weight of the compound represented by the above general formula (4) is preferably in the range of 100 to 500, and more preferably in the range of 150 to 400. The unsaturated monobasic acid (b1-2) may be used alone or in combination of two or more.

[0075] Examples of the polyoxyalkylene chains include polyoxyethylene chains and polyoxypropylene chains. Examples of the (poly)ester chain include the following general formula (5): [ka] [In the above general formula (5), R 51 and R 52 This represents an alkylene group with 1 to 10 carbon atoms, n 51 represents an integer from 1 to 5. Examples include (poly)ester chains represented by ]. Examples of the aromatic hydrocarbon chains include phenylene chains, naphthylene chains, biphenylene chains, phenylnaphthylene chains, or binaphthylene chains. Hydrocarbon chains having aromatic rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings as partial structures can also be used. Examples of the (poly)carbonate chain include the following general formula (6): [ka] [In the above general formula (6), R 61 This represents an alkylene group with 1 to 10 carbon atoms, n 61 represents an integer from 1 to 5. An example is a (poly)carbonate chain represented by ].

[0076] Examples of the polybasic acid anhydrides (b1-3) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, acid halides of aliphatic polybasic acid anhydrides, acid halides of alicyclic polybasic acid anhydrides, and acid halides of aromatic polybasic acid anhydrides.

[0077] Examples of the aliphatic polybasic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid. Furthermore, the aliphatic polybasic acid anhydride may have either linear or branched aliphatic hydrocarbon groups, and may also have unsaturated bonds in its structure. In this specification, the alicyclic polybasic acid anhydride is defined as one in which the acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is irrelevant. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and the acid anhydride of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid. Examples of the aforementioned aromatic polybasic acid anhydrides include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0078] The polybasic acid anhydrides (b1-3) may be used individually or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic acid anhydride are preferred from the viewpoint of more effectively improving photosensitivity, developability, and adhesion.

[0079] Examples of the polyisocyanate compounds (b1-4) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; and the following general formula (7): [ka] [In the above general formula (7), R 72 and R 73 Each of these independently represents either a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 71 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and k 71 n is an integer between 0 and 3, and n 71 is an integer greater than or equal to 1. Examples include polymethylene polyphenyl polyisocyanates having a repeating structure represented by ]; isocyanurate modified versions, biuret modified versions, allophanate modified versions, etc. The polyisocyanate compounds (b1-4) may be used individually or in combination of two or more.

[0080] Examples of the hydroxyl group-containing (meth)acrylate compounds (b1-5) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Furthermore, polyoxyalkylene modified compounds, in which polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains are introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds, in which a polylactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, can also be used. Among these, those with a molecular weight of 1,000 or less are preferred from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. In addition, if the hydroxyl group-containing (meth)acrylate compound (b1-5) is an oxyalkylene modified compound or a lactone modified compound, it is preferable that the weight-average molecular weight (Mw) is 1,000 or less. The hydroxyl group-containing (meth)acrylate compound (b1-5) may be used alone or in combination of two or more types.

[0081] The method for producing the epoxy resin (B1) having the acid group and polymerizable unsaturated group is not particularly limited and can be produced by any method, but it is preferable to use epoxy resin (b1-1), unsaturated monobasic acid (b1-2), and polybasic acid anhydride (b1-3) as essential reaction raw materials, or to use epoxy resin (b1-1), unsaturated monobasic acid (b1-2), polybasic acid anhydride (b1-3), polyisocyanate compound (b1-4), and (meth)acrylate compound (b1-5) having a hydroxyl group as reaction raw materials. Here, the epoxy resin (B1) may be produced by reacting all the reaction raw materials at once, or by reacting the reaction raw materials sequentially. Among these, it is preferable to react the epoxy resin (b1-1) and unsaturated monobasic acid (b1-2) first, and then react the polybasic acid anhydride (b1-3), as this allows for easy control of the reaction. The reaction can be carried out, for example, by reacting an epoxy resin (b1-1) with an unsaturated monobasic acid (b1-2) in the presence of a basic catalyst at a temperature range of 100 to 150°C, then adding a polybasic acid anhydride (b1-3) to the reaction system and reacting at a temperature range of 80 to 140°C. In the production of the epoxy resin (B1) having the acid group and polymerizable unsaturated group, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed.

[0082] The reaction ratio of the epoxy resin (b1-1) to the unsaturated monobasic acid (b1-2) is preferably in the range of 0.9 to 1.1 moles of unsaturated monobasic acid (b1-2) per mole of epoxy groups in the epoxy resin (b1-1). Furthermore, the reaction ratio of the polybasic anhydride (b1-3) is preferably in the range of 0.2 to 1.0 mole per mole of epoxy groups in the epoxy resin (b1-1).

[0083] Examples of the aforementioned organic solvents include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; and carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanone. Examples of organic solvents include alcohol solvents such as propylene glycol monomethyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils such as soybean oil, linseed oil, rapeseed oil, and safflower oil; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents may be used individually or in combination of two or more. Furthermore, commercially available organic solvents can also be used, such as ENEOS Corporation's "Spindle Oil No. 1", "Solvent No. 3", "Solvent No. 4", "Solvent No. 5", "Solvent No. 6", "Naphthezol H", "Alken 56NT", "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", "AF Solvent No. 7", Mitsubishi Chemical Corporation's "Diadol 13", "Dialen 168"; Nissan Chemical Corporation's "F Oxocol", "F Oxocol 180"; Idemitsu Kosan Co., Ltd.'s "Supersol LA35", "Supersol LA38"; ExxonMobil Examples include Chemical's "Exsol D80," "Exsol D110," "Exsol D120," "Exsol D130," "Exsol D160," "Exsol D100K," "Exsol D120K," "Exsol D130K," "Exsol D280," "Exsol D300," and "Exsol D320." The amount of the organic solvent used is preferably in the range of 0.1 to 5 times the total mass of the reaction raw materials, as this ensures good reaction efficiency.

[0084] Examples of the basic catalysts include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc.; trioctylmethylammonium chloride, tri Examples include quaternary ammonium salts such as octylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octyolate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistanoxane; organometallic compounds such as zinc octyolate and bismuth octyolate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. Alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. The basic catalyst may be used alone or in combination of two or more types. The amount of the basic catalyst added is preferably in the range of 0.001 to 5 parts by mass per 100 parts by mass of the total reaction raw materials.

[0085] The acid value of the epoxy resin (B1) having the acid group and polymerizable unsaturated group is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. In this specification, the acid value of the resin (B) having the acid group and polymerizable unsaturated group is the value measured by the neutralization titration method of JIS 0070 (1992).

[0086] --Urethane resin (B2) having acidic groups and polymerizable unsaturated groups-- The urethane resin (B2) having the acid group and polymerizable unsaturated group is, for example, a resin obtained by reacting a polyisocyanate compound (b1-4), a hydroxyl group-containing (meth)acrylate compound (b1-5), a carboxyl group-containing polyol compound (b2-1), and, if necessary, a polybasic acid anhydride (b1-3) and a polyol compound other than the carboxyl group-containing polyol compound (b2-2); polyisocyanate compound (b1-4) and hydroxyl group-containing (meth)acrylate compound. Examples include resins obtained by reacting acrylate compounds (b1-5) with polybasic acid anhydrides (b1-3) and, if necessary, polyol compounds other than carboxyl group-containing polyol compounds (b2-2) (b2-2); or resins obtained by reacting epoxy resin (b1-1) with unsaturated monobasic acid (b1-2), polybasic acid anhydrides (b1-3), polyisocyanate compounds (b1-4), and hydroxyl group-containing (meth)acrylate compounds (b1-5).

[0087] Examples of the carboxyl group-containing polyol compound (b2-1) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The carboxyl group-containing polyol compound can be used alone or in combination of two or more.

[0088] Examples of polyol compounds other than the carboxyl group-containing polyol compound (b2-1) (b2-2) include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various polyol compounds; and lactone modified compounds obtained by introducing (poly)lactone structures into the molecular structure of the various polyol compounds. The polyol compounds other than the carboxyl group-containing polyol compound can be used individually or in combination of two or more.

[0089] The method for producing the urethane resin (B2) having the acid group and polymerizable unsaturated group is not particularly limited and may be produced by any method. In producing the urethane resin having the acid group and polymerizable unsaturated bond, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed.

[0090] The organic solvent can be the same as the organic solvent described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the organic solvent can be used alone or in combination of two or more types. Furthermore, the basic catalyst can be the same as the basic catalyst described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the basic catalyst can be used alone or in combination of two or more types.

[0091] --Acrylic resin (B3) having acidic groups and polymerizable unsaturated groups-- Examples of the acrylic resin (B3) having the acid group and polymerizable unsaturated group include a reaction product obtained by introducing a (meth)acryloyl group by further reacting an acrylic resin intermediate obtained by polymerizing an acrylic resin intermediate having a reactive functional group such as a hydroxyl group, carboxyl group, isocyanate group, or glycidyl group with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups, or a resin obtained by reacting a polybasic acid anhydride (b1-3) with the hydroxyl group in the reaction product.

[0092] The acrylic resin intermediate may be copolymerized with other polymerizable unsaturated group-containing compounds as needed, in addition to the (meth)acrylate compound (α). Examples of these other polymerizable unsaturated group-containing compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobolonyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These other polymerizable unsaturated group-containing compounds may be used individually or in combination of two or more.

[0093] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but from the viewpoint of reactivity, the following combinations are preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more types.

[0094] The method for producing the acrylic resin (B3) having the acidic group and polymerizable unsaturated group is not particularly limited and can be any method. The production of the acrylic resin (B3) having the acidic group and polymerizable unsaturated group may be carried out in an organic solvent if necessary, and a basic catalyst may also be used if necessary.

[0095] The organic solvent can be the same as the organic solvent described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the organic solvent can be used alone or in combination of two or more types. Furthermore, the basic catalyst can be the same as the basic catalyst described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the basic catalyst can be used alone or in combination of two or more types.

[0096] The acid value of the acrylic resin (B3) having the acid group and polymerizable unsaturated group is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of more effectively improving photosensitivity, developability, and adhesion.

[0097] --Amido-imide resin (B4) having acidic groups and polymerizable unsaturated groups-- Examples of the amide-imide resin (B4) having the acid group and polymerizable unsaturated group include those obtained by reacting an amide-imide resin (b4-1) having an acid group and / or an acid anhydride group with a (meth)acrylate compound (b1-5) having a hydroxyl group and / or a (meth)acrylate compound (b4-2) having an epoxy group, and, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group.

[0098] The amide-imide resin (b4-1) having acid groups and / or acid anhydride groups may have only one of them, or both. From the viewpoint of reactivity and reaction control with (meth)acrylate compounds (b1-5) having hydroxyl groups or epoxy compounds having (meth)acryloyl groups, it is preferable that the amide-imide resin (b4-1) has acid anhydride groups, and more preferably that it has both acid groups and acid anhydride groups. The solid content acid value of the amide-imide resin (b4-1) is preferably in the range of 60 to 350 mgKOH / g when measured under neutral conditions, i.e., conditions in which the acid anhydride groups are not ring-opened. On the other hand, it is preferable that the measured value is in the range of 61 to 360 mgKOH / g when measured under conditions in which the acid anhydride groups are ring-opened, such as in the presence of water.

[0099] Examples of the amide-imide resin (b4-1) include those obtained using a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3) as reaction raw materials. Furthermore, if necessary, the amide-imide resin (b4-1) can also be obtained by using a polybasic acid in addition to the polyisocyanate compound (b1-4) and polybasic acid anhydride (b1-3) as reaction raw materials.

[0100] As the aforementioned polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of polybasic acids include dicarboxylic acids, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile having a carboxyl group in its molecule can also be used. The polybasic acid can be used alone or in combination of two or more.

[0101] The epoxy group-containing (meth)acrylate compound (b4-2) can be any compound with a molecular structure containing both a (meth)acryloyl group and an epoxy group; the specific structure is not particularly limited, and a wide variety of compounds can be used. Examples include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, as well as mono(meth)acrylate compounds of diglycidyl ether compounds such as hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The epoxy group-containing (meth)acrylate compound can be used alone or in combination of two or more.

[0102] Furthermore, the specific structure or manufacturing method of the amide-imide resin (b4-1) having the acid group and / or acid anhydride group is not particularly limited, and general amide-imide resins can be widely used. Preferably, the amide-imide resin (b4-1) having the acid group and / or acid anhydride group is obtained using a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3) as reaction raw materials.

[0103] Furthermore, as the polyisocyanate compound (b1-4), since a curable resin composition with high solvent solubility can be obtained, alicyclic diisocyanate compounds or modified thereof, aliphatic diisocyanate compounds or modified thereof are preferred, and alicyclic diisocyanate or its isocyanurate modified, aliphatic diisocyanate or its isocyanurate modified are more preferred. Preferably, the ratio of the total mass of alicyclic diisocyanate compounds or their modified counterparts to that of aliphatic diisocyanate compounds or their modified counterparts in the total mass of the polyisocyanate compounds (b1-4) is 70% by mass or more, and more preferably 90% by mass or more. Furthermore, when using an alicyclic diisocyanate compound or a modified version thereof in combination with an aliphatic diisocyanate compound or a modified version thereof, it is preferable that the mass ratio of the two (alicyclic diisocyanate compound or modified version thereof / aliphatic diisocyanate compound or modified version thereof) is in the range of 30 / 70 to 70 / 30.

[0104] The amide-imide resin (B4) having acid groups and polymerizable unsaturated groups can also be used in combination with other reaction materials in addition to the reaction materials of the amide-imide resin (b4-1) having acid groups and / or acid anhydride groups, the hydroxyl group-containing (meth)acrylate compound (b1-5), and / or epoxy group-containing (meth)acrylate compound (b4-2), depending on the desired resin performance. In this case, it is preferable that the total mass ratio of the components (b4-1) to (b4-2) in the total mass of the reaction materials for the resin (B4) having acid groups and polymerizable unsaturated groups be 80% by mass or more, and more preferably 90% by mass or more.

[0105] The method for producing the amide-imide resin (B4) having acid groups and polymerizable unsaturated groups is not particularly limited and can be any method. For example, it may be produced by reacting all the reaction materials, including the amide-imide resin (b4-1) having acid groups and / or acid anhydride groups, and the hydroxyl group-containing (meth)acrylate compound (b1-5) and / or epoxy group-containing (meth)acrylate compound (b4-2), all at once, or by reacting the reaction materials sequentially. For example, the reaction between the amide-imide resin (b4-1) having acid groups and / or acid anhydride groups and the hydroxyl group-containing (meth)acrylate compound (b1-5) can be carried out by heating and stirring at a temperature of about 80 to 140°C in the presence of a suitable basic catalyst. In the production of the amide-imide resin (B4) having acid groups and polymerizable unsaturated groups, it may be carried out in an organic solvent as needed, and a basic catalyst or an acidic catalyst may be used as needed.

[0106] The organic solvent can be the same as the organic solvent described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the organic solvent can be used alone or in combination of two or more types. Furthermore, the basic catalyst can be the same as the basic catalyst described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the basic catalyst can be used alone or in combination of two or more types. Examples of the acidic catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Solid acid catalysts having strong acids such as sulfonyl groups can also be used. These acidic catalysts can be used individually or in combination of two or more.

[0107] The acid value of the amide-imide resin (B4) having the acid group and polymerizable unsaturated group is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of more effectively improving photosensitivity, developability, and adhesion.

[0108] --Acrylamide resin (B5) having acidic groups and polymerizable unsaturated groups-- Examples of the acrylamide resin (B5) having the acid group and polymerizable unsaturated group include a resin obtained by reacting a phenolic hydroxyl group-containing compound (b5-1), an alkylene carbonate (b5-2a) or alkylene oxide (b5-2b), an N-alkoxyalkyl (meth)acrylamide compound (b5-3), a polybasic acid anhydride (b1-3), and optionally an unsaturated monobasic acid (b1-2) as reaction raw materials.

[0109] The phenolic hydroxyl group-containing compound (b5-1) refers to a compound having at least one phenolic hydroxyl group in its molecule. Examples of phenolic hydroxyl group-containing compounds (b5-1) include compounds represented by any of the following general formulas (8.1) to (8.5), reaction products using an aromatic polyhydroxy compound (b5-4) and a compound represented by any of the following general formulas (9.1) to (9.5) as essential reaction raw materials, or novolac-type phenolic resins using one or more aromatic polyhydroxy compounds (b5-4) or other compounds (b5-5) having one phenolic hydroxyl group in their molecule as reaction raw materials.

[0110] [ka] [In the above general formulas (8.1) to (8.5), R 81 ~R 84 and R 87 Each of these independently represents one of the following: an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. 85 and R 86 Each of these independently represents a hydrogen atom or a methyl group, and j 81 ~j 84 and j 87 Each of these independently represents an integer of 0 or 1 or more, preferably an integer between 0 and 3, and more preferably 0 or 1. 81 ~k 84 and k 87 Each of these independently represents an integer of 1 or greater, preferably 2 or 3. Furthermore, the positions of substituents on the aromatic rings in the above general formulas (8.1) to (8.5) are arbitrary. For example, in the naphthalene ring of general formula (8.2), the substituent may substitute for any hydrogen atom on the ring; in general formula (8.3), it may substitute for any hydrogen atom on the benzene ring present in one biphenyl molecule; in general formula (8.4), it may substitute for any hydrogen atom on the benzene ring present in one aralkyl molecule; and in general formula (8.5), it may substitute for any hydrogen atom on the benzene ring present in one molecule. The number of substituents in one molecule is j. 81 ~j 84 , j 87 and k 81 ~k 84 , k 87 This indicates that...

[0111] [ka] [In the above general formulas (9.1) to (9.5), h 91 represents 0 or 1, R 91 ~R 96 Each of these independently represents one of the following: a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, k 91 ~k 96 Each of these independently represents either 0 or an integer from 1 to 4, and Z 91 ~Z 96 Each of these independently represents one of the following: a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group, Y 91 n represents one of the following: an alkylene group with 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group. 91 [This represents an integer between 1 and 4.] The compounds represented by the above general formulas (9.1) to (9.5) can be used individually or in combination of two or more.

[0112] Examples of the aromatic polyhydroxy compounds (b5-4) include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, bisphenol, and compounds having one or more substituents on these aromatic nuclei. Furthermore, examples of substituents on the aromatic nucleus include monovalent aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups; alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; phenyl, naphthyl, and anthryl groups, and aryl groups on which these aromatic nuclei are substituted with the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc.; phenyloxy and naphthyloxy groups, and aryloxy groups on which these aromatic nuclei are substituted with the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc.; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl groups, and aralkyl groups on which these aromatic nuclei are substituted with the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc. These aromatic polyhydroxy compounds can be used individually or in combination of two or more. Among these, compounds that do not contain halogens are preferred because they yield resins having acidic groups and polymerizable unsaturated groups with high insulating reliability.

[0113] The aforementioned compounds having one phenolic hydroxyl group in the molecule (b5-5) can be any aromatic compound having one hydroxyl group on the aromatic nucleus. Examples include phenol or phenol compounds having one or more substituents on the aromatic nucleus of phenol, naphthol or naphthol compounds having one or more substituents on the aromatic nucleus of naphthol, anthracenol or anthracenol compounds having one or more substituents on the aromatic nucleus of anthracenol, etc. Examples of substituents on the aromatic nucleus include monovalent aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, aralkyl groups, etc., with specific examples of each being as described above. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.

[0114] Examples of the novolac-type phenolic resin include resins obtained by reacting one or more compounds having one phenolic hydroxyl group in their molecule with an aldehyde compound under acidic catalyst conditions. Examples of the aldehyde compounds include formaldehyde; alkyl aldehydes such as acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, pentylaldehyde, and hexylaldehyde; hydroxybenzaldehydes such as salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, and 3,4-dihydroxybenzaldehyde; and 2-hydroxy-3-methoxybenzaldehyde and 3-hydroxy-4-methoxybenzaldehyde. Examples include aldehydes, benzaldehydes having both a hydroxyl group and an alkoxy group, such as 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxynaphthaldehydes such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and 6-hydroxy-2-naphthaldehyde; and halogenated benzaldehydes such as bromobenzaldehyde. The aldehyde compounds can be used individually or in combination of two or more.

[0115] Examples of the alkylene carbonate (b5-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of the curable resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better adhesion. The alkylene carbonate (b5-2a) can be used alone or in combination of two or more types.

[0116] Examples of the alkylene oxide (b5-2b) include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred from the viewpoint of the curable resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better adhesion. The alkylene oxide (b5-2b) can be used alone or in combination of two or more types.

[0117] Examples of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, and N-butoxyethyl(meth)acrylamide. Among these, N-methoxymethyl(meth)acrylamide is preferred from the viewpoint of the curable resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better adhesion. The N-alkoxyalkyl(meth)acrylamide compound (b5-3) can be used alone or in combination of two or more types.

[0118] When the N-alkoxyalkyl(meth)acrylamide compound (b5-3) is used as a reaction raw material for an acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, the equivalent ratio of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) to the polybasic acid anhydride (b1-3) [(b5-3) / (b1-3)] is preferably in the range of 0.2 to 7, and more preferably in the range of 0.25 to 6.7, from the viewpoint of the curable resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better adhesion.

[0119] The method for producing the acrylamide resin (B5) having the acid group and polymerizable unsaturated group is not particularly limited and can be produced by any method. For example, it may be produced by reacting all the reaction materials at once, or by reacting the reaction materials sequentially. In particular, a method is preferred in which the reaction is easily controlled, in which a phenolic hydroxyl group-containing compound (b5-1) is first reacted with an alkylene carbonate (b5-2a) or alkylene oxide (b5-2b) (for example, in the presence of a basic catalyst and at a temperature range of 100 to 200°C), then an unsaturated monobasic acid (b1-2) and / or an N-alkoxyalkyl (meth)acrylamide compound (b5-3) is reacted (for example, in the presence of an acidic catalyst and at a temperature range of 80 to 140°C), and finally a polybasic acid anhydride (b1-3) is reacted (for example, at a temperature range of 80 to 140°C).

[0120] The acrylamide resin (B5) having the acid group and polymerizable unsaturated group is a resin obtained from the above reaction raw materials. For example, the acrylamide resin (B5) may be a resin having a resin structure in which structural units are repeatedly formed from structural units (I) represented by the following general formula (10.1) and structural units (II) represented by the following general formula (10.2), or a resin having a resin structure in which structural units are repeatedly formed from structural units (III) represented by the following formula (10.3) and structural units (IV) represented by the following formula (10.4).

[0121] [ka] [In the above formula (10.1) or (10.2), R b2 and R b8 Each of these independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R b3 and R b9 Each of these independently represents one of the following: a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. 1 and n 2 Each of them independently represents either 1 or 2, R b4 and R b10Each of these independently represents a methylene group or a structural part represented by one of the following general formulas (11.1) to (11.5), and R b5 and R b6 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, however, R b5 and R b6 These may be linked together to form a saturated or unsaturated ring, R b11 R represents a divalent hydrocarbon group with 1 to 12 carbon atoms. b12 R represents a hydrogen atom or a methyl group. b1 and R b7 Each of them independently, R b3 and R b9 The group represented by, or the structural part (I) represented by formula (10.1) or the structural part (II) represented by formula (10.2), is marked with an asterisk (*) in R b4 or R b10 It is a connection point that is linked via [a certain mechanism].

[0122] [ka] [In the above general formula (10.3) or (10.4), R b2 and R b8 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R b3 and R b9 Each of these independently represents one of the following: a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. 3 and n 4 Each of them independently represents either 1 or 2, R b4 and R b10 Each of these independently represents a methylene group or a structural part represented by any of the following formulas (11.1) to (11.5), and R b5 and R b6 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, however, R b5 and R b6 These may be linked together to form a saturated or unsaturated ring, R b11 R represents a divalent hydrocarbon group with 1 to 12 carbon atoms. b12represents a hydrogen atom or a methyl group, R b1 and R b7 each independently represent a group represented by the aforementioned R b3 and the aforementioned R b9 , or a bonding point via which the structural moiety (III) represented by general formula (10.3) or the structural moiety (IV) represented by general formula (10.4) is linked through R b4 or R b10 marked with an asterisk *.]

[0123]

Chemical Formula

[0124]

Chemical Formula

[0125] The acid value of the acrylamide resin (B5) having the acid group and polymerizable unsaturated group is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of the curable resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better adhesion.

[0126] --Ester resin (B6) having acidic groups and polymerizable unsaturated groups-- Examples of ester resins (B6) having the acid group and polymerizable unsaturated group include resins obtained by reacting a phenolic hydroxyl group-containing compound (b5-1) with an alkylene oxide (b5-2b) or alkylene carbonate (b5-2a) with an unsaturated monobasic acid (b1-2) and a polybasic acid anhydride (b1-3).

[0127] As the alkylene oxide (b5-2b), the same type as the alkylene oxide described in the section above for "acrylamide resin (B5) having acidic groups and polymerizable unsaturated groups" can be used. Among these, ethylene oxide or propylene oxide is preferred from the viewpoint of more effectively improving photosensitivity, developability, and adhesion. The alkylene oxide (b5-2b) can be used alone or in combination of two or more types.

[0128] As the alkylene carbonate (b5-2a) mentioned above, the same type as the alkylene carbonate described in the section "Acrylamide resin having acidic groups and polymerizable unsaturated groups (B5)" above can be used. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of more effectively improving light sensitivity, developability, and adhesion. The alkylene carbonate (b5-2a) can be used alone or in combination of two or more types.

[0129] The method for producing the ester resin (B6) having the acidic group and polymerizable unsaturated group is not particularly limited and can be any method. The production of the ester resin having the acidic group and polymerizable unsaturated group may be carried out in an organic solvent as needed, and a basic catalyst and an acidic catalyst may be used as needed.

[0130] The organic solvent can be the same as the organic solvent described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the organic solvent can be used alone or in combination of two or more types. Furthermore, the basic catalyst can be the same as the basic catalyst described in the section "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)" above, and the basic catalyst can be used alone or in combination of two or more types. Furthermore, the acidic catalyst can be the same as the acidic catalyst described in the section above for "Amidimide resin having acidic groups and polymerizable unsaturated groups (B4)," and the acidic catalyst can be used alone or in combination of two or more types.

[0131] --Content-- The content of resin (B) having acid groups and polymerizable unsaturated groups in the total amount (100% by mass) of the curable resin composition of this embodiment is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and also preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of improving developability, adhesion, and dielectric properties in a balanced manner while lowering the elastic modulus.

[0132] Furthermore, in the curable resin composition of this embodiment, the mass ratio of solid content (non-volatile content) of the active ester resin (A) and the resin having acid groups and polymerizable unsaturated groups (B) [(A) / (B)] is preferably 5 / 95 to 50 / 50, and more preferably 10 / 90 to 30 / 70, from the viewpoint of improving developability, adhesion, and dielectric properties in a balanced manner while lowering the elastic modulus.

[0133] The curable resin composition of this embodiment may consist only of the active ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups, but may further contain photopolymerization initiators, curing agents, etc., as described later. The total solid content (non-volatile content) of the active ester resin (A) and the resin (B) having acid groups and polymerizable unsaturated groups in the total amount (100% by mass) of the curable resin composition of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of improving developability, adhesion, and dielectric properties in a balanced manner while lowering the elastic modulus.

[0134] (Photopolymerization initiator) The curable resin composition of this embodiment preferably further contains a photopolymerization initiator. The inclusion of a photopolymerization initiator in the curable resin composition facilitates the initiation of the photo-induced curing reaction (polymerization). The photopolymerization initiator may be used alone or in combination of two or more types.

[0135] The aforementioned photopolymerization initiator can be selected and used appropriately depending on the type of active energy ray used for irradiation. It may also be used in combination with photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds. Furthermore, the photopolymerization initiator is preferably a radical polymerization initiator.

[0136] Specific examples of the aforementioned photopolymerization initiators include, for example, alkylphenone-based photopolymerization initiators such as 1-hydroxycyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. Furthermore, specific examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthones and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and the like. Examples of commercially available photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Om Examples include "nirad-81" (manufactured by IGM), "KayaCure-DETX", "KayaCure-MBP", "KayaCure-DMBI", "KayaCure-EPA", "KayaCure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "ByCure-10", "ByCure-55" (manufactured by Stauffa Chemical), "Trigonal P1" (manufactured by Akzo), "Sandoz 1000" (manufactured by Sandoz), "Deep" (manufactured by Apjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0137] When using the aforementioned photopolymerization initiator, the amount of the photopolymerization initiator in the curable resin composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total solid content (non-volatile content) of the active ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups.

[0138] (Hardening agent) The curable resin composition of this embodiment preferably further contains a curing agent. The curability of the curable resin composition is improved by the inclusion of a curing agent. Examples of the curing agent include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenol resin curing agents, etc.), but epoxy resins are preferred among these.

[0139] The epoxy resin is not particularly limited, but preferably, for example, it is a curable resin that contains two or more epoxy groups in its molecule and can be cured by forming a crosslinking network with the epoxy groups. The epoxy resin is not particularly limited, but may include novolac type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolac type epoxy resin, β-naphthol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and biphenyl novolac type epoxy resin; aralkyl type epoxy resins such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, and phenol biphenyl aralkyl type epoxy resin; bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin; Examples include biphenyl-type epoxy resins such as phenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton; naphthalene-type epoxy resins; binaphthol-type epoxy resins; binaphthyl-type epoxy resins; dicyclopentadiene-type epoxy resins such as dicyclopentadienephenol-type epoxy resins; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and glycidylamine-type epoxy resins of diaminodiphenylsulfone; diglycidyl ester-type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester-type epoxy resins and glycidyl ester-type epoxy resins of hexahydrophthalic anhydride; and benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran.Of these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing phenol compounds are preferred, and among these, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are more preferred from the viewpoint of dielectric properties. The above epoxy resins may be used individually or in combination of two or more types.

[0140] The epoxy equivalent of the epoxy resin is preferably 120 to 400 g / eq, and more preferably 150 to 300 g / eq. A epoxy equivalent of 120 g / eq or more is preferred because it results in superior dielectric properties of the resulting cured product, while a epoxy equivalent of 400 g / eq or less is preferred because it provides an excellent balance between heat resistance and dielectric loss tangent of the resulting cured product. The softening point of the epoxy resin is preferably 20 to 200°C, and more preferably 40 to 150°C, from the viewpoint of improving light sensitivity, developability, dielectric properties, and adhesion in a balanced manner.

[0141] The amine curing agent is not particularly limited, but examples include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprendiamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, mensendiamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol. Examples of the acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexendicarboxylic anhydride. Examples of the phenol resin curing agents include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, triphenolmethane type resin, tetraphenolethane type resin, aminotriazine modified phenol resin, and the like. The other curing agents mentioned above may be used individually or in combination of two or more.

[0142] When using the curing agent described above, the curable resin composition of this embodiment preferably contains 10 to 40 parts by mass of the curing agent per 100 parts by mass of the total solid content (non-volatile content) of the active ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups. If the content is 10 parts by mass or more, the heat resistance and curability can be further improved, and if it is 40 parts by mass or less, a lower dielectric loss tangent and higher flexibility can be achieved.

[0143] (Optional addition ingredient) The curable resin composition of this embodiment may further contain optional additives, as long as it does not deviate from the purpose. Examples of optional additives include compounds having polymerizable unsaturated groups, curing accelerators, other resins, organic solvents, polymerization inhibitors, antioxidants, flame retardants, fillers, pigments, defoamers, viscosity modifiers, leveling agents, UV stabilizers, and storage stabilizers.

[0144] --Compounds containing polymerizable unsaturated groups-- Examples of compounds having polymerizable unsaturated groups include (meth)acrylate compounds, specifically, aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantylmono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfurylacrylate; and benzyl(meth)acrylate, phenyl(meth)acrylate, and phenylbenzyl(meth)acrylate. Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds including phenoxy(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, benzylbenzyl(meth)acrylate, and phenylphenoxyethyl(meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various mono(meth)acrylate monomers; and lactone-modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the various mono(meth)acrylate compounds. Aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate. (meth)acrylate compounds; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the above-mentioned di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds obtained by introducing (poly)lactone structures into the molecular structure of the above-mentioned di(meth)acrylate compounds; Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene-modified tri(meth)acrylate compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the aliphatic tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the aliphatic tri(meth)acrylate compounds; Aliphatic poly(meth)acrylate compounds with four or more functions, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; aliphatic poly(meth)acrylate compounds with four or more functions, obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the aliphatic poly(meth)acrylate compounds; aliphatic lactone-modified poly(meth)acrylate compounds with four or more functions, obtained by introducing (poly)lactone structures into the molecular structure of the aliphatic poly(meth)acrylate compounds; Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate (meth)acrylate compounds having hydroxyl groups, such as acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropanedi(meth)acrylate, and ditrimethylolpropanetri(meth)acrylate; (poly)oxyalkylene modified compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the hydroxyl group-containing (meth)acrylate compounds; lactone modified compounds obtained by introducing a (poly)lactone structure into the molecular structure of the hydroxyl group-containing (meth)acrylate compounds; (Meth)acrylate compounds having an isocyanate group, such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; Examples include (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, as well as (meth)acrylate compounds having an epoxy group, such as mono(meth)acrylates of diglycidyl ether compounds of droxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The aforementioned polymerizable unsaturated compound may be used alone or in combination of two or more compounds.

[0145] --Curing accelerator-- The curing accelerator is not particularly limited, but examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, etc. The curing accelerator may be used alone or in combination of two or more types.

[0146] Examples of the phosphorus-based curing accelerators include organophosphine compounds such as triphenylphosphine, tributylphosphine, triparathylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organophosphine compounds such as trimethylphosphine and triethylphosphine; and phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, and tetrabutylphosphonium decanoate. Examples of the amine-based curing accelerators include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5,4,0]-undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN). The imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole. Examples include ethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and 2-methylimidazoline. Examples of the guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, and 1-phenylbiguanide. Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea. Of the curing accelerators mentioned above, it is preferable to use 2-ethyl-4-methylimidazole or N,N-dimethyl-4-aminopyridine (DMAP).

[0147] When using the curing accelerator, the content of the curing accelerator in the curable resin composition of this embodiment is preferably 0.01 to 5 parts by mass per 100 parts by mass of the total amount of solids (non-volatile content) of the active ester resin (A) and the resin (B) having acid groups and polymerizable unsaturated groups. If the content of the curing accelerator is 0.01 parts by mass or more, the curability can be more reliably improved. On the other hand, if the content of the curing accelerator is 5 parts by mass or less, the insulation reliability can be maintained at a sufficiently good level. From a similar viewpoint, the content of the curing accelerator is more preferably 0.1 parts by mass or more, and more preferably 5 parts by mass or less, per 100 parts by mass of the total amount of solids (non-volatile content) of the active ester resin (A) and the resin (B) having acid groups and polymerizable unsaturated groups.

[0148] --Other resins-- The aforementioned other resins are not particularly limited, but include maleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, cyanate ester resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallylbisphenol and triallyl isocyanurate, polyphosphate esters, and phosphate ester-carbonate copolymers. These other resins may be used individually or in combination of two or more. When using the aforementioned other resins, it is preferable that the content of the other resins in the curable resin composition of this embodiment is 50% by mass or less of the total.

[0149] --Organic Solvents-- The organic solvent may have the function of adjusting the viscosity of the curable resin composition. Specific examples of organic solvents are not particularly limited, but include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more types. When using the aforementioned organic solvent, the content of the organic solvent in the curable resin composition of this embodiment is preferably 90% by mass or less, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, based on the total amount (100% by mass) of the curable resin composition. An organic solvent content of 10% by mass or more is preferable because it provides excellent handling properties. On the other hand, an organic solvent content of 90% by mass or less is preferable from an economic standpoint.

[0150] --Polymerization inhibitor-- The polymerization inhibitors are not particularly limited, but include phenol compounds such as p-methoxyphenol (methoquinone), p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrene-phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; and quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone. Amine compounds such as melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrene-diphenylamine, reaction products of styrene-diphenylamine and 2,4,4-trimethylpentene, and reaction products of diphenylamine and 2,4,4-trimethylpentene; Thioether compounds such as phenothiazines, distearyl thiodipropionates, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], and ditridecane-1-yl=3,3'-sulfandiyldipropanoate; N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydrox Nitroso compounds such as siquinolin, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride; Phosphate compounds such as esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl=diphenyl=phosphite, diphenylisodecyl phosphite, triisodecyl=phosphite, and tris(2,4-di-tert-butylphenyl)phosphite; Zinc compounds such as bis(dimethyldithiocarbamate-κ(2)S,S')zinc, diethyldithiocarbamate zinc, and dibutyldithiocarbamate zinc; Nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel; Examples include sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, and 3,3'-distearyl thiodipropionate. The polymerization inhibitor may be used alone or in combination of two or more types.

[0151] --Antioxidant-- The antioxidant is not particularly limited, but compounds similar to those exemplified as polymerization inhibitors can be used. The antioxidant may be used alone or in combination of two or more.

[0152] Examples of commercially available polymerization inhibitors and antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumiriser BBM-S" and "Sumiriser GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0153] --Flame retardant-- The aforementioned flame retardant is not particularly limited, but examples include inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, halogen-based flame retardants, etc. The flame retardant may be used alone or in combination of two or more types.

[0154] The inorganic phosphorus-based flame retardant is not particularly limited, but examples include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate; and phosphate amides. The organophosphorus flame retardants mentioned above are not particularly limited, but include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, and stearyl acid phosphate. Phosphate esters such as isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, and (2-hydroxyethyl) methacrylate acid phosphate; diphenylphosphine such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; and 10-(2,5-dihydroxyphenyl)-10H-9-oxa Phosphorus-containing phenols such as -10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinnylhydroquinone, diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinnyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinnyl-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phos Examples include cyclic phosphorus compounds such as phaphenanthrene-10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the aforementioned phosphate esters, diphenylphosphine, or phosphorus-containing phenols with epoxy resins, aldehyde compounds, or phenolic compounds. The halogenated flame retardant is not particularly limited, but examples include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, and tetrabromophthalic acid.

[0155] When using the aforementioned flame retardant, the amount of flame retardant used in the resin composition of this embodiment is preferably 0.1 to 50 parts by mass per 100 parts by mass of the total solid content (non-volatile content) of the activated ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups. If the flame retardant content is 0.1 parts by mass or more, flame retardancy can be imparted more reliably. On the other hand, if the flame retardant content is 50 parts by mass or less, flame retardancy can be imparted while maintaining dielectric properties. From a similar viewpoint, the flame retardant content is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less, per 100 parts by mass of the total solid content (non-volatile content) of the activated ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups.

[0156] --Filler-- Examples of fillers include organic fillers and inorganic fillers. Organic fillers have functions such as improving elongation and improving mechanical strength. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and providing flame retardancy. The above-mentioned fillers may be used individually or in combination of two or more types.

[0157] The aforementioned organic filler is not particularly limited, but examples include polyamide particles. The inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. Of these, silica is preferred. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used as silica.

[0158] Furthermore, the filler may be surface-treated as needed. In this case, there are no particular limitations on the surface treatment agents that can be used, but aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc. The above-mentioned fillers may be used individually or in combination of two or more.

[0159] When using the filler, the amount of filler used in the resin composition of this embodiment is preferably 0.5 to 95 parts by mass per 100 parts by mass of the total solid content (non-volatile content) of the activated ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups. If the filler content is 0.5 parts by mass or more, the effect of the filler can be sufficiently imparted. On the other hand, if the filler content is 95 parts by mass or less, deterioration of moldability due to increased viscosity of the compound can be suppressed. From a similar viewpoint, the filler content is more preferably 5 parts by mass or more, and more preferably 80 parts by mass or less, per 100 parts by mass of the total solid content (non-volatile content) of the activated ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups.

[0160] The method for producing the curable resin composition of this embodiment is not particularly limited, and it can be produced by kneading the various components described above using a kneader such as a roll.

[0161] <Cured product> The cured product of this embodiment is characterized by being obtained by curing the above-described curable resin composition. The cured product of this embodiment has a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties, and can function suitably as an insulating material or a resist member. The cured product of this embodiment is preferably obtained by curing a curable resin composition by irradiating it with active energy rays.

[0162] Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When ultraviolet rays are used as the active energy rays, irradiation may be carried out under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere, in order to efficiently carry out the curing reaction by ultraviolet rays.

[0163] Specific sources of ultraviolet light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, and other ultraviolet lamps, as well as sunlight and LEDs. Among these, ultraviolet lamps are generally used from the standpoint of practicality and economic efficiency.

[0164] The integrated light intensity of the aforementioned active energy rays is not particularly limited, but is between 0.1 and 50 kJ / m 2 Preferably, it is 0.5 to 10 kJ / m³. 2 It is more preferable that the cumulative light intensity is within the above range. If the cumulative light intensity is within the above range, the occurrence of uncured areas can be sufficiently prevented or suppressed. The irradiation of the active energy ray may be performed in one stage or in two or more stages.

[0165] Another method for obtaining a cured product by curing the curable resin composition is, for example, heat curing. The heating temperature during heat curing is not particularly limited, but is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

[0166] Applications of the curable resin composition or cured product of this embodiment include printed circuit board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, and molded products obtained by curing the above composite materials. Among these various applications, in the applications of printed circuit board materials, insulating materials for circuit boards, and build-up adhesive films, it can be used as an insulating material for so-called electronic component-embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. Furthermore, taking advantage of the characteristics of the cured product, such as its excellent heat resistance and coating appearance, the curable resin composition or cured product of this embodiment can be suitably applied to semiconductor encapsulation materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, and build-up films, build-up substrates, multilayer printed circuit boards, fiber-reinforced composite materials, and molded products obtained by curing the above composite materials.

[0167] <Insulating materials> The insulating material of this embodiment is characterized by comprising the curable resin composition described above. Furthermore, it is preferable that the insulating material of this embodiment is obtained by curing the curable resin composition described above by irradiation with active energy rays. The insulating material of this embodiment has a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties.

[0168] Examples of insulating materials include the interlayer insulating material for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, insulating materials for circuit boards, and insulating materials for substrates for embedding electronic components. For example, a method for manufacturing a build-up substrate from the above-mentioned curable resin composition is a method consisting of the following three steps. The first step is to apply the curable resin composition, which is appropriately blended with rubber, fillers, etc., to a circuit board with a circuit formed on it using a spray coating method, a curtain coating method, etc., and then cure it. The second step is to then drill holes such as predetermined through-holes as needed, treat the surface with a roughening agent, wash the surface with hot water to form irregularities, and then plate it with a metal such as copper. The third step is to repeat these operations sequentially as desired to alternately build up and form a resin insulating layer and a conductor layer of a predetermined circuit pattern. It is preferable to drill the through-holes after the formation of the outermost resin insulating layer. The first step can be carried out not only by the solution coating method described above, but also by laminating a build-up film that has been pre-coated to a desired thickness and dried. Furthermore, the build-up substrate of the present invention can also be manufactured by forming a roughened surface and omitting the plating process by heating and pressing a resin-coated copper foil, on which the resin composition has been semi-cured, onto a wiring board on which a circuit has been formed, at 170-250°C.

[0169] <Resist material> The resist member of this embodiment is characterized by being made of the curable resin composition described above. The resist member can be obtained, for example, by applying the curable resin composition described above onto a substrate, drying it in a suitable temperature range of about 60 to 100°C, exposing it with active energy rays through a photomask on which a desired pattern has been formed, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing it in a temperature range of about 140 to 180°C. The resist member (resist film) of this embodiment has a low elastic modulus, high adhesion to adjacent members, and excellent dielectric properties. [Examples]

[0170] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to the following Examples in any way. Unless otherwise specified, the descriptions of "parts" and "%" in the Examples are based on mass. The GPC measurement conditions in the present Examples are as follows.

[0171] [GPC measurement conditions] Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation, Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate 1.0 mL / min Standard: In accordance with the measurement manual of the aforementioned "GPC-8320", the following monodisperse polystyrenes with known molecular weights were used. (Polystyrenes used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: 50 μL of a tetrahydrofuran solution containing 1.0% by mass (based on resin solids content) filtered through a microfilter.

[0172] (Synthesis Example 1: Synthesis of activated ester resin (A-1)) A flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer was charged with 209 parts by mass of 1-naphthol, 350 parts by mass of toluene, 47 parts by mass of divinylbenzene (DVB-810, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., with a divinylbenzene purity of 81% and containing 19% ethylstyrene), and 1 part by mass of p-toluenesulfonic acid monohydrate. The contents of the flask were heated to 115°C while stirring, and the reaction was carried out by stirring at 115°C for 1 hour. After the reaction was complete, 0.6 parts by mass of 49% sodium hydroxide aqueous solution was added to neutralize the mixture, then 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 250 parts by mass of a mixture (M-1) containing unreacted 1-naphthol and a phenolic hydroxyl group-containing resin. The hydroxyl group equivalent of the obtained mixture (M-1) was 177 g / equivalent, and the number of moles of hydroxyl groups in unreacted 1-naphthol (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 OH ) and the ratio [(a1 OH ) / (a2 OH The ratio was 1.45 / 1.41. Next, 147 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer, and dissolved while purging the system with reduced pressure nitrogen. Then, 250 parts by mass of the previously obtained mixture (M-1) were charged, and dissolved while purging the system with reduced pressure nitrogen. Here, the number of moles of hydroxyl groups in mixture (M-1) is 0.98 moles for every 1 mole of acid halide groups in isophthalic acid chloride. 0.5 g of tetrabutylammonium bromide was added, and while purging with nitrogen gas, the reaction system temperature was controlled to below 60°C, and 299 parts by mass of 20% sodium hydroxide aqueous solution were added dropwise over 3 hours. After the dropwise addition was complete, stirring was continued for 1 hour to allow the reaction to proceed. After the reaction was complete, the reaction mixture was allowed to stand and separated, and the aqueous layer was removed. Water was added to the remaining organic layer and stirred for about 15 minutes, then the mixture was allowed to stand and separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 320 parts by mass of activated ester resin (A-1). The functional group equivalent of activated ester resin (A-1) was 241 g / equivalent, and the softening point, measured according to JIS K7234, was 130°C. The weight-average molecular weight (Mw) of activated ester resin (A-1), calculated from the area ratio of the GPC chart, was 1236.

[0173] (Synthesis Example 2: Synthesis of activated ester resin (A-2)) A flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer was charged with 200 parts by mass of 1-naphthol, 350 parts by mass of toluene, 60 parts by mass of divinylbenzene (DVB-960, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 96% divinylbenzene purity, containing 4% ethylstyrene), and 1 part by mass of p-toluenesulfonic acid monohydrate. The contents of the flask were heated to 115°C while stirring, and the reaction was carried out by stirring at 115°C for 1 hour. After the reaction was complete, 0.6 parts by mass of 49% sodium hydroxide aqueous solution was added to neutralize the mixture, then 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 254 parts by mass of a mixture (M-2) containing unreacted 1-naphthol and a phenolic hydroxyl group-containing resin. The hydroxyl group equivalent of the resulting mixture (M-2) was 187 g / equivalent, and the number of moles of hydroxyl groups in unreacted 1-naphthol (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 OH ) and the ratio [(a1 OH ) / (a2 OH The ratio was 1.39 / 1.36. Next, 140 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer, and dissolved while purging the system with reduced pressure nitrogen. Then, 254 parts by mass of the previously obtained mixture (M-2) were charged, and dissolved while purging the system with reduced pressure nitrogen. Here, the number of moles of hydroxyl groups in mixture (M-2) is 0.98 moles for every 1 mole of acid halide groups in isophthalic acid chloride. 0.5 g of tetrabutylammonium bromide was added, and while purging with nitrogen gas, the reaction system was controlled to below 60°C, and 286 parts by mass of 20% sodium hydroxide aqueous solution were added dropwise over 3 hours. After the dropwise addition was complete, stirring was continued for 1 hour to allow the reaction to proceed. After the reaction was complete, the reaction mixture was allowed to stand and separated, and the aqueous layer was removed. Water was added to the remaining organic layer and stirred for about 15 minutes, then the mixture was allowed to stand and separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 320 parts by mass of activated ester resin (A-2). The functional group equivalent of activated ester resin (A-2) was 252 g / equivalent, and the softening point, measured according to JIS K7234, was 165°C. The weight-average molecular weight (Mw) of activated ester resin (A-2), calculated from the area ratio of the GPC chart, was 2772.

[0174] (Synthesis Example 3: Synthesis of Active Ester Resin (A-3)) A flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer was charged with 200 parts by mass of 1-naphthol, 350 parts by mass of toluene, 51 parts by mass of divinylbenzene (DVB-960, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 96% divinylbenzene purity, containing 4% ethylstyrene), and 1 part by mass of p-toluenesulfonic acid monohydrate. The contents of the flask were heated to 115°C while stirring, and the reaction was carried out by stirring at 115°C for 1 hour. After the reaction was complete, 0.6 parts by mass of 49% sodium hydroxide aqueous solution was added to neutralize the mixture, then 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 245 parts by mass of a mixture (M-3) containing unreacted 1-naphthol and a phenolic hydroxyl group-containing resin. The hydroxyl group equivalent of the resulting mixture (M-3) was 181 g / equivalent, and the number of moles of hydroxyl groups in unreacted 1-naphthol (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 OH ) and the ratio [(a1 OH ) / (a2 OH The ratio was 1.39 / 1.35. Next, 140 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer, and dissolved while purging the system with reduced pressure nitrogen. Then, 245 parts by mass of the previously obtained mixture (M-3) were charged, and dissolved while purging the system with reduced pressure nitrogen. Here, the number of moles of hydroxyl groups in mixture (M-3) is 0.98 moles for every 1 mole of acid halide groups in isophthalic acid chloride. 0.5 g of tetrabutylammonium bromide was added, and while purging with nitrogen gas, the reaction system was controlled to below 60°C, and 286 parts by mass of 20% sodium hydroxide aqueous solution were added dropwise over 3 hours. After the dropwise addition was complete, stirring was continued for 1 hour to allow the reaction to proceed. After the reaction was complete, the reaction mixture was allowed to stand and separated, and the aqueous layer was removed. Water was added to the remaining organic layer and stirred for about 15 minutes, then the mixture was allowed to stand and separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 312 parts by mass of activated ester resin (A-3). The functional group equivalent of activated ester resin (A-3) was 245 g / equivalent, and the softening point, measured according to JIS K7234, was 150°C. The weight-average molecular weight (Mw) of activated ester resin (A-3), calculated from the area ratio of the GPC chart, was 1377.

[0175] (Synthesis Example 4: Synthesis of Active Ester Resin (A-4)) A flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer was charged with 255 parts by mass of orthophenylphenol, 400 parts by mass of toluene, 49 parts by mass of divinylbenzene (DVB-810, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., with a divinylbenzene purity of 81% and containing 19% ethylstyrene), and 1 part by mass of p-toluenesulfonic acid monohydrate. The contents of the flask were heated to 115°C while stirring, and the reaction was carried out by stirring at 115°C for 1 hour. After the reaction was complete, 0.6 parts by mass of 49% sodium hydroxide aqueous solution was added to neutralize the mixture, then 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 295 parts by mass of a mixture (M-4) containing unreacted orthophenylphenol and a phenolic hydroxyl group-containing resin. The hydroxyl group equivalent of the resulting mixture (M-4) was 203 g / equivalent, and the number of moles of hydroxyl groups in the unreacted orthophenylphenol was (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 OH ) and the ratio [(a1 OH ) / (a2 OH The ratio was 1.50 / 1.45. Next, 151 parts by mass of isophthalic acid chloride and 800 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer, and dissolved while purging the system with reduced pressure nitrogen. Then, 295 parts by mass of the previously obtained mixture (M-4) were charged, and dissolved while purging the system with reduced pressure nitrogen. Here, the number of moles of hydroxyl groups in mixture (M-4) is 0.98 moles for every 1 mole of acid halide groups in isophthalic acid chloride. 0.5 g of tetrabutylammonium bromide was added, and while purging with nitrogen gas, the reaction system was controlled to below 60°C, and 308 parts by mass of 20% sodium hydroxide aqueous solution were added dropwise over 3 hours. After the dropwise addition was complete, stirring was continued for 1 hour to allow the reaction to proceed. After the reaction was complete, the reaction mixture was allowed to stand and separated, and the aqueous layer was removed. Water was added to the remaining organic layer and stirred for about 15 minutes, then the mixture was allowed to stand and separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 365 parts by mass of activated ester resin (A-4). The functional group equivalent of activated ester resin (A-4) was 267 g / equivalent, and the softening point, measured according to JIS K7234, was 94°C. The weight-average molecular weight (Mw) of activated ester resin (A-4), calculated from the area ratio of the GPC chart, was 1181.

[0176] (Synthesis Example 5: Synthesis of Activated Ester Resin (A-5)) A flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer was charged with 245 parts by mass of orthophenylphenol, 400 parts by mass of toluene, 49 parts by mass of divinylbenzene (DVB-810, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., with a divinylbenzene purity of 81% and containing 19% ethylstyrene), and 1 part by mass of p-toluenesulfonic acid monohydrate. The contents of the flask were heated to 115°C while stirring, and the reaction was carried out by stirring at 115°C for 1 hour. After the reaction was complete, 0.6 parts by mass of 49% sodium hydroxide aqueous solution was added to neutralize the mixture, then 400 parts by mass of toluene was added, and the mixture was washed three times with 200 parts by mass of water. Toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 300 parts by mass of a mixture (M-5) containing unreacted orthophenylphenol and a phenolic hydroxyl group-containing resin. The hydroxyl group equivalent of the resulting mixture (M-5) was 213 g / equivalent, and the number of moles of hydroxyl groups in the unreacted orthophenylphenol was (a1 OH ) and the number of moles of hydroxyl groups in the phenolic hydroxyl group-containing resin (a2 OH ) and the ratio [(a1 OH ) / (a2 OH The ratio was 1.44 / 1.41. Next, 145 parts by mass of isophthalic acid chloride and 800 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer, and dissolved while purging the system with reduced pressure nitrogen. Then, 300 parts by mass of the previously obtained mixture (M-5) were charged, and dissolved while purging the system with reduced pressure nitrogen. Here, the number of moles of hydroxyl groups in mixture (M-5) is 0.99 moles for every 1 mole of acid halide groups in isophthalic acid chloride. 0.5 g of tetrabutylammonium bromide was added, and while purging with nitrogen gas, the temperature in the reaction system was controlled to below 60°C, and 297 parts by mass of 20% sodium hydroxide aqueous solution were added dropwise over 3 hours. After the dropwise addition was complete, stirring was continued for 1 hour to allow the reaction to proceed. After the reaction was complete, the reaction mixture was allowed to stand and separated, and the aqueous layer was removed. Water was added to the remaining organic layer and stirred for about 15 minutes, then the mixture was allowed to stand and separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain 365 parts by mass of activated ester resin (A-5). The functional group equivalent of activated ester resin (A-5) was 278 g / equivalent, and the softening point, measured according to JIS K7234, was 102°C. The weight-average molecular weight (Mw) of activated ester resin (A-5), calculated from the area ratio of the GPC chart, was 1795.

[0177] (Synthesis Example 6: Production of Active Ester Resin (C-1)) In a flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer, 165 parts by mass of the addition product of dicyclopentadiene and phenol (hydroxyl group equivalent 165 g / equivalent, softening point 85°C), 72 parts by mass of 1-naphthol, and 630 parts by mass of toluene were charged and dissolved while purging the system with reduced pressure nitrogen. Next, 152 parts by mass of isophthalic acid chloride were charged and dissolved while purging the system with reduced pressure nitrogen. While controlling the temperature of the system to below 60°C with nitrogen gas purging, 300 parts by mass of 20% sodium hydroxide aqueous solution were added dropwise over 3 hours. After the addition was complete, stirring was continued for 1 hour to allow the reaction to proceed. After the reaction was complete, the reaction mixture was allowed to stand and separated, and the aqueous layer was removed. Water was added to the remaining organic layer and stirred for about 15 minutes, then the mixture was allowed to stand and separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, toluene and other substances were removed by distillation under heated and reduced pressure conditions to obtain the activated ester resin (C-1). The functional group equivalent of the activated ester resin (C-1) was 223 g / equivalent, and the softening point, measured according to JIS K7234, was 150°C.

[0178] (Synthesis Example 7: Synthesis of a resin (B-1) having acidic groups and polymerizable unsaturated groups) In a flask equipped with a thermometer, stirrer, and reflux condenser, 123 parts by mass of diethylene glycol monoethyl ether acetate was added, and 214 parts by mass of orthocresol novolac type epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, epoxy equivalent: 214 g / eq) was dissolved. After adding 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone, 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing in air. Next, 72 parts by mass of diethylene glycol monoethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110°C for 3 hours to obtain resin (B-1) having acidic groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-1) having acidic groups and polymerizable unsaturated groups was 65% by mass, and the solid content acid value was 80 mgKOH / g. The acid value was measured based on the neutralization titration method specified in JIS K 0070 (1992).

[0179] (Synthesis Example 8: Synthesis of resin (B-2) having acidic groups and polymerizable unsaturated groups) In a flask equipped with a thermometer, stirrer, and reflux condenser, 499.7 parts by mass of diethylene glycol monoethyl ether acetate was added, and 244.3 parts by mass of isocyanurate-modified isophorone diisocyanate (EVONIK "VESTANAT T-1890 / 100", NCO%=17.2%) and 192.0 parts by mass of trimellitic anhydride were dissolved. Then, 1.0 part by mass of dibutylhydroxytoluene was added. The mixture was reacted at 160°C for 6 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less. Next, 0.4 parts by mass of metoquinone was added as a thermal polymerization inhibitor, followed by 147.6 parts by mass of pentaerythritol polyacrylate mixture (Toagosei Co., Ltd. "Aronics M-306", hydroxyl value: 159.7 mg KOH / g) and 3.5 parts by mass of triphenylphosphine. The mixture was reacted at 110°C for 5 hours while blowing air into the mixture. Subsequently, 165.0 parts by mass of glycidyl methacrylate was added and the mixture was reacted at 110°C for 6 hours. Next, 110.4 parts by mass of succinic anhydride was added and the mixture was reacted at 110°C for 5 hours to obtain resin (B-2) having acidic groups and polymerizable unsaturated groups. The non-volatile content of this resin (B-2) was 62% by mass, and the solid content acid value was 80 mgKOH / g.

[0180] (Examples 1-20, Comparative Examples 1-2) The components were mixed in the proportions shown in Tables 1 and 2 below to obtain curable resin compositions (1) to (20) and (C1) to (C2). In Tables 1 and 2, the amounts of resins (B-1) and (B-2) having acidic groups and polymerizable unsaturated groups are the amounts as non-volatile content (solids). The following tests were performed on the resulting curable resin composition.

[0181] [Evaluation of alkaline developability] The curable resin compositions obtained in each example and comparative example were applied to a glass substrate to a thickness of 50 μm using an applicator, and then dried at 80°C for 50, 60, 70, 80, and 90 minutes to prepare samples with different drying times. These samples were developed with a 1% by mass sodium carbonate aqueous solution (alkaline aqueous solution) at 30°C for 180 seconds, and the drying time at 80°C for samples that left no residue on the substrate was evaluated as the drying control range (minutes). A longer drying control range (minutes) indicates higher developability.

[0182] [Method for measuring elastic modulus] The curable resin compositions obtained in the examples and comparative examples were applied to copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using a 50 μm applicator, and a metal halide lamp was used to cure the resin at a rate of 10 kJ / m². 2 After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour. The cured material was peeled off the copper foil to obtain test piece 1 (cured material). Using this test piece 1, the elastic modulus (MPa) was measured at a rate of 2 mm / min in accordance with JIS K7181. A smaller value indicates lower elasticity.

[0183] [Method for evaluating adhesion] Adhesion was evaluated by measuring peel strength. Specifically, the curable resin compositions obtained in the examples and comparative examples were applied to copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using a 50 μm applicator, and a metal halide lamp was used to measure 10 kJ / m². 2 After irradiation with ultraviolet light, the sample was heated at 160°C for 1 hour to obtain test piece 2 (cured material). This test piece 2 was cut to a size of 1 cm wide and 12 cm long, and the 90° peel strength (N / cm) was measured using a peel tester (A&D Tensilon, manufactured by A&D Corporation, peel speed 50 mm / min). A higher value indicates better adhesion.

[0184] [Method for measuring dielectric constant] The curable resin compositions obtained in each of the examples and comparative examples were applied onto a glass substrate using an applicator to a film thickness of 50 µm, and dried at 80°C for 30 minutes. Then, using a metal halide lamp at 10 kJ / m 2 of ultraviolet irradiation, followed by heating at 160°C for 1 hour to obtain a cured coating film. Subsequently, the cured coating film was peeled from the glass substrate to obtain a cured product. A test piece was obtained by storing the cured product in a room at a temperature of 23°C and a humidity of 50% for 24 hours, and the dielectric constant of the test piece at 1 GHz was measured by the cavity resonance method using a "Network Analyzer E8362C" manufactured by Agilent Technologies, Ltd.

[0185] [Measurement Method for Dielectric Loss Tangent] The curable resin compositions obtained in each of the examples and comparative examples were applied onto a glass substrate using an applicator to a film thickness of 50 µm, and dried at 80°C for 30 minutes. Then, using a metal halide lamp at 10 kJ / m 2 of ultraviolet irradiation, followed by heating at 160°C for 1 hour to obtain a cured coating film. Subsequently, the cured coating film was peeled from the glass substrate to obtain a cured product. A test piece was obtained by storing the cured product in a room at a temperature of 23°C and a humidity of 50% for 24 hours, and the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using a "Network Analyzer E8362C" manufactured by Agilent Technologies, Ltd.

[0186]

Table 1

[0187]

Table 2

[0188] *1 Active ester resin (A-1): an active ester resin obtained in Synthesis Example 1, which is an active ester resin produced using a phenolic hydroxyl group-containing resin (a2) prepared from divinyl compound (a2-2) as a reaction raw material, non-volatile content (solid content) = 100 mass% *2 Activated ester resin (A-2): Activated ester resin obtained in Synthesis Example 2, activated ester resin using phenolic hydroxyl group-containing resin (a2) with divinyl compound (a2-2) as a reaction raw material, non-volatile content (solids) = 100% by mass *3 Activated ester resin (A-3): Activated ester resin obtained in Synthesis Example 3, activated ester resin using phenolic hydroxyl group-containing resin (a2) with divinyl compound (a2-2) as a reaction raw material, non-volatile content (solids) = 100% by mass *4 Activated ester resin (A-4): Activated ester resin obtained in Synthesis Example 4, activated ester resin using phenolic hydroxyl group-containing resin (a2) with divinyl compound (a2-2) as a reaction raw material, non-volatile content (solids) = 100% by mass *5 Activated ester resin (A-5): Activated ester resin obtained in Synthesis Example 5, activated ester resin using phenolic hydroxyl group-containing resin (a2) with divinyl compound (a2-2) as a reaction raw material, non-volatile content (solids) = 100% by mass *6 Activated ester resin (C-1): Activated ester resin obtained in Synthesis Example 6, activated ester resin that does not use phenolic hydroxyl group-containing resin (a2) with divinyl compound (a2-2) as a reaction raw material, non-volatile content (solids) = 100% by mass *7 Resin having acidic groups and polymerizable unsaturated groups (B-1): Resin having acidic groups and polymerizable unsaturated groups obtained in Synthesis Example 7, epoxy resin having acidic groups and polymerizable unsaturated groups, non-volatile content (solids) = 65% by mass *8 Resin having acidic groups and polymerizable unsaturated groups (B-2): Resin having acidic groups and polymerizable unsaturated groups obtained in Synthesis Example 8, urethane resin having acidic groups and polymerizable unsaturated groups, non-volatile content (solids) = 62% by mass *9 Hardener: Orthocresol novolac type epoxy resin, manufactured by DIC Corporation, product name "EPICLON N-680", epoxy equivalent: 214 g / eq *10 Organic solvent: Diethylene glycol monoethyl ether acetate *11 Photopolymerization initiator: Omnirad 907, manufactured by IGM Resins.

[0189] Table 1 shows that the curable resin compositions of Examples 1 to 10 according to the present invention have higher developability compared to the curable resin composition of Comparative Example 1, which uses an active ester resin that does not use a phenolic hydroxyl group-containing resin (a2) as a reaction raw material, with a divinyl compound (a2-2) as the reaction raw material.

[0190] Furthermore, Table 2 shows that the cured products obtained by curing the curable resin compositions of Examples 11 to 20 according to the present invention have a lower elastic modulus, higher adhesion, and superior dielectric properties (lower dielectric constant and dielectric loss tangent) compared to the cured product of Comparative Example 2, which uses an active ester resin that does not use a phenolic hydroxyl group-containing resin (a2) with a divinyl compound (a2-2) as a reaction raw material. [Industrial applicability]

[0191] The curable resin composition and cured product of the present invention can be used as insulating materials, resist members, and the like.

Claims

1. It contains an active ester resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group, The activated ester resin (A) is a compound (a1) having one phenolic hydroxyl group in its molecular structure, a phenolic hydroxyl group-containing resin (a2) having two or more phenolic hydroxyl groups in its molecular structure, and an aromatic polycarboxylic acid or its acid halide (a3) ​​as essential reaction raw materials. The aforementioned divinyl compound (a2-2) has the following structural formula (1-1): 【Chemistry 1】 (In the formula, R1 is independently one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is 0 or an integer from 1 to 4.) This is a compound represented by the formula, The aromatic polycarboxylic acid or its acid halogen (a3) ​​is an aromatic dicarboxylic acid or its acid halogen, The ratio of the number of moles of hydroxyl groups (a1OH) in compound (a1) having one phenolic hydroxyl group in its molecular structure to the number of moles of hydroxyl groups (a2OH) in the phenolic hydroxyl group-containing resin (a2) [(a1OH) / (a2OH)] is between 10 / 90 and 75 / 25. The sum of the number of moles of hydroxyl groups (a1OH) in compound (a1) having one phenolic hydroxyl group in its molecular structure and the number of moles of hydroxyl groups (a2OH) in the phenolic hydroxyl group-containing resin (a2) is 0.95 to 1.05 moles per mole of the total carboxyl groups or acid halide groups in the aromatic polycarboxylic acid or its acid halide (a3). The activated ester resin (A) has a weight-average molecular weight (Mw) of 600 to 5,000. A curable resin composition characterized in that the mass ratio of solids between the activated ester resin (A) and the resin (B) having acidic groups and polymerizable unsaturated groups [(A) / (B)] is 5 / 95 to 50 / 50.

2. The curable resin composition according to claim 1, wherein the divinyl compound (a2-2) is divinylbenzene.

3. The curable resin composition according to claim 1, wherein the aromatic polycarboxylic acid or its acid halide (a3) ​​is isophthalic acid chloride.

4. The divinyl compound (a2-2) is divinylbenzene, The curable resin composition according to claim 1, wherein the aromatic polycarboxylic acid or its acid halide (a3) ​​is isophthalic acid chloride.

5. The curable resin composition according to claim 1, further containing a photopolymerization initiator.

6. The curable resin composition according to claim 1, further containing a curing agent.

7. A cured product characterized by being obtained by curing a curable resin composition according to any one of Claims 1 to 6.

8. An insulating material characterized by comprising the curable resin composition described in any one of Claims 1 to 6.

9. A resist member characterized by comprising the curable resin composition described in any one of Claims 1 to 6.

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