Curable resin composition, cured material, and related products

Abstract

To provide a curable resin composition from which a cured product that has high elastic modulus, high heat resistance, and excellent dielectric characteristics can be obtained.SOLUTION: A curable resin composition contains an active ester resin (A), and a resin (B) having a polymerizable unsaturated group, in which the active ester resin (A) contains: a compound (a1) that contains one phenolic hydroxyl group in the molecular structure; a phenolic hydroxyl group-containing resin (a2) containing a phenolic hydroxyl group-containing compound (a2-1) and a divinyl compound (a2-2) as essential reactive raw materials; and an aromatic polycarboxylic acid or an acid halide thereof (a3), as essential reactive raw materials.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to curable resin compositions, cured products, and articles. [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 the 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). In addition to solder resists, curable resin compositions are also widely used in fields such as inks, paints, coatings, adhesives, and optical components.

[0004] Furthermore, in recent years, it has been proposed to form solder resist films using an inkjet method. When forming solder resist films using an inkjet method, development is unnecessary, making it possible to reduce the number of steps, time, and consumables compared to the alkaline-developable liquid photoresist method described above. Inkjet inks must be low viscosity and not thickened, but there was a problem that reducing viscosity would significantly reduce the physical properties such as heat resistance and chemical resistance required for solder resist. In response to this, epoxy acrylate, which is made by acrylatening a part of epoxy resin and can be cured by ultraviolet light or heat, has been proposed as a material that can be used with inkjet methods. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Special Publication No. 1-54390 [Overview of the project] [Problems that the invention aims to solve]

[0006] On the other hand, in order to improve the reliability of the implementation, the solder resist film is required to have excellent heat resistance, and furthermore, it is important that it is highly elastic in order to accommodate miniaturization and thinning. 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.

[0007] In response to these requirements, the aforementioned epoxy acrylates have a high dielectric constant due to the presence of hydroxyl groups generated by the acrylate formation of epoxy resins, making them difficult to use in high-frequency applications. Furthermore, cured products obtained by curing conventional curable resin compositions containing alkali-soluble photosensitive resins have inferior heat resistance and dielectric properties, and there is room for improvement.

[0008] Therefore, an object of the present invention is to provide a curable resin composition capable of solving the above problems of the prior art and obtaining a cured product having high heat resistance, high elastic modulus, and excellent dielectric properties (low dielectric constant and low dielectric tangent). Another object of the present invention is to provide a cured product having high heat resistance, high elastic modulus, and excellent dielectric properties, and an article having a coating film made of such a cured product.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that a cured product obtained by curing a curable resin composition containing a specific active ester resin (A) and a resin (B) having a polymerizable unsaturated group has high heat resistance, high elastic modulus, and excellent dielectric properties, and thus have completed the present invention. That is, the gist of the present invention for solving the above problems is as follows.

[0010] [1] A curable resin composition containing an active ester resin (A) and a resin (B) having a polymerizable unsaturated group, wherein the active ester resin (A) is characterized in that an aromatic compound (a) having two hydroxyl groups at adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound having two or more carboxyl groups and / or its acid halide or esterified product (c) are essential reaction raw materials.

[0011] [2] The curable resin composition according to [1], wherein the aromatic compound (a) is at least one compound selected from the group consisting of the following general formulas (1) to (3).

[0012]

Chemical formula

[0013] [3] A curable resin composition according to any one of [1] to [2], further comprising a photopolymerization initiator.

[0014] [4] A cured product characterized by being obtained by curing a curable resin composition described in any one of [1] to [3].

[0015] An article characterized by having a coating film made of the cured product described in [5] [4]. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a curable resin composition that can produce a cured product with high heat resistance, high elastic modulus, 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 with high heat resistance, high elastic modulus, and excellent dielectric properties, and an article having a coating film made of such a cured product. [Modes for carrying out the invention]

[0017] The curable resin compositions, cured products, and articles of the present invention will be described in detail below, based on their embodiments.

[0018] (Explanation of terms) Unless otherwise specified in this specification, the following definitions of terms apply.

[0019] 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.

[0020] 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.

[0021] In this specification, "aralkyl group" refers to, for example, a benzyl group, a diphenylmethyl group, a biphenyl group, a naphthylmethyl group, and the like.

[0022] 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.

[0023] In this specification, "halogen atoms" include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] <Curable resin composition> The curable resin composition of this embodiment contains an active ester resin (A) and a resin (B) having polymerizable unsaturated groups. The curable resin composition of this embodiment is characterized in that the active ester resin (A) uses as essential reaction raw materials an aromatic compound (a) having two hydroxyl groups in adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound and / or its acid halide or esterified product (c) having two or more carboxyl groups.

[0029] In the curable resin composition of this embodiment, by using an activated ester resin (A) made from an aromatic compound (a) having two hydroxyl groups in adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound and / or its acid halide or esterified product (c) having two or more carboxyl groups as reaction raw materials, high heat resistance, moderately high elastic modulus, reduced dielectric constant and dielectric loss tangent, and improved dielectric properties are obtained. The reason why such properties are obtained is not entirely clear, but by using the aromatic compound (a) having two hydroxyl groups in adjacent positions on an aromatic ring (e.g., catechol) as a raw material for the activated ester, ester groups based on the two hydroxyl groups of the aromatic compound (a) having two hydroxyl groups in adjacent positions on an aromatic ring are formed in adjacent positions on the aromatic ring (e.g., a benzene ring), the crosslinking points of the cured product are adjacent, and molecular motion is inhibited by the steric hindrance, resulting in high heat resistance and high elastic modulus.

[0030] (Activated ester resin (A)) The curable resin composition of this embodiment contains an activated ester resin (A). The activated ester resin (A) is Aromatic compounds (a) having two hydroxyl groups in adjacent positions on the aromatic ring, • Aromatic monohydroxy compounds (b), and (c) Aromatic compounds having two or more carboxyl groups and / or acid halides or esters thereof It is characterized by using as an essential reaction raw material.

[0031] [Aromatic compounds having two hydroxyl groups in adjacent positions on an aromatic ring (a)] The active ester of the present invention is characterized by being obtained by reacting an aromatic compound (a) having two hydroxyl groups at adjacent positions on an aromatic ring (hereinafter sometimes referred to as "aromatic compound (a)"). The phrase "two hydroxyl groups at adjacent positions on an aromatic ring" means "two hydroxyl groups bonded to two adjacent carbon atoms on an aromatic ring."

[0032] Furthermore, it is preferable that the active ester of the present invention is at least one compound selected from the group consisting of the following general formulas (1) to (3) as the aromatic compound (a). In this compound, since hydroxyl groups are adjacent to each other on the aromatic ring, the ester groups contained in the resulting active ester are also adjacent to each other, and the crosslinking points of the cured product obtained using the active ester are adjacent to each other. This steric hindrance inhibits molecular motion, which is preferable as it allows for the expression of high heat resistance and high modulus of elasticity.

[0033] [ka]

[0034] In the above formulas (1) to (3), R is preferably an independent hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group include a methyl group, ethyl group, propyl group, butyl group, allyl group, and benzyl group. In particular, from the viewpoint of high heat resistance and low dielectric loss tangent, it is preferable that the group be unsubstituted, and from the viewpoint of low dielectric constant, it is preferable that the group be a butyl group.

[0035] In the above formulas (1) to (3), n is preferably an integer between 0 and 4, and more preferably an integer between 0 and 1. When n is within the above range, high heat resistance, low dielectric loss tangent, and low dielectric constant are obtained, which is preferable.

[0036] In the above formulas (1) to (3), m is preferably an integer between 0 and 2, and more preferably an integer between 0 and 1. When m is within the above range, high heat resistance, low dielectric loss tangent, and low dielectric constant are obtained, which is desirable.

[0037] Furthermore, it is preferable to use a compound containing a catechol skeleton (catechol compound) as the aromatic compound (a), and more preferably a catechol compound such as catechol or tert-butylcatechol. The resulting cured product can have high heat resistance, low dielectric properties (low dielectric constant, low dielectric loss tangent), and high elastic modulus, which is desirable. By introducing a catechol skeleton based on the aromatic compound (a) into the active ester, the ester groups in the active ester form adjacent structures on the same aromatic ring. Compared to conventional designs, this increases steric hindrance and suppresses molecular motion, resulting in a cured product with low dielectric properties (low dielectric constant, low dielectric loss tangent) and high elastic modulus.

[0038] The catechol mentioned above is a dihydroxybenzene having hydroxyl groups at the 1st and 2nd positions, and may also be a catechol compound having an alkyl group such as a methyl group as a substituent on the aromatic ring of the catechol.

[0039] Furthermore, from the viewpoint of imparting high heat resistance, it is preferable to use a catechol compound that does not have substituents on the aromatic ring (for example, catechol). Also, from the viewpoint of low dielectric properties, it is preferable to use a catechol compound such as catechol having a tertiary butyl group (tertiary butylcatechol), or a catechol compound with 4 to 10 carbon atoms in the alkyl group. If the number of carbon atoms is 4 or more, sufficient low dielectric properties can be achieved, and if the number of carbon atoms is 10 or less, a decrease in reactivity due to steric hindrance during the synthesis of the active ester can be prevented, which is preferable.

[0040] The aromatic compound (a) may be used alone, or multiple compounds with different positions of alkyl groups such as methyl groups may be used in combination.

[0041] [Aromatic monohydroxy compounds (b)] The present invention is characterized by being obtained by reacting with an aromatic monohydroxy compound (b). By using the aromatic monohydroxy compound (b), the resulting active ester can be controlled by the aromatic monohydroxy compound (b) acting as a terminal encapsulant during the synthesis of the active ester, thereby optimizing the viscosity of the active ester.

[0042] The aromatic monohydroxy compound (b) is not particularly limited, but examples include alkylphenols such as phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, and tert-butylphenol; aralkylphenols such as o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrene-phenol, and 4-(α-cumyl)phenol; and naphthol compounds such as α-naphthol (1-naphthol) and β-naphthol (2-naphthol). These may be used individually or in combination of two or more. Among these, tert-butylphenol and α-naphthol are preferred because they yield cured products with excellent heat resistance and dielectric properties (low dielectric properties).

[0043] [Aromatic compounds having two or more carboxyl groups and / or acid halides or esters thereof (c)] The present invention is characterized by being obtained by reacting an aromatic compound having two or more carboxyl groups and / or an acid halide or esterified product thereof (c) (hereinafter sometimes referred to as "aromatic compound, etc. (c)"). Using the aforementioned aromatic compound, etc. (c) yields a cured product with excellent heat resistance, which is preferable.

[0044] The aromatic compound (c) is not particularly limited, but examples include compounds having two or more carboxyl groups, etc., on a substituted or unsubstituted aromatic ring. "Carboxyl groups, etc." refers to carboxyl groups; halogenated acyl groups such as acyl fluoride groups, acyl chloride groups, and acyl bromide groups; alkyloxycarbonyl groups such as methyloxycarbonyl groups and ethyloxycarbonyl groups; and aryloxycarbonyl groups such as phenyloxycarbonyl groups and naphthyloxycarbonyl groups. When a halogenated acyl group is present, the aromatic compound is an acid halide; when an alkyloxycarbonyl group or aryloxycarbonyl group is present, the aromatic compound may be an ester. Of these, the aromatic compound preferably has a carboxyl group, an acyl halogenated group, or an aryloxycarbonyl group; more preferably has a carboxyl group and an acyl halogenated group; and even more preferably has a carboxyl group, an acyl chloride group, or an acyl bromide group.

[0045] The aforementioned aromatic ring is not particularly limited, but examples include monocyclic aromatic rings, fused aromatic rings, ring-aggregated aromatic rings, and aromatic rings linked by alkylene chains.

[0046] The aforementioned aromatic compounds, etc. (c) are not particularly limited, but include benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; benzenetricarboxylic acids such as trimellitic acid and 5-allyltrimellitic acid; naphthalenedicarboxylic acids such as naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1,4-dicarboxylic acid, and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; triazinecarboxylic acids such as 1,3,5-triazine-2,4,6-tricarboxylic acid; and acid halides and esters thereof. Of these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferred, isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, and 1,3,5-benzenetricarbonyltrichloride are more preferred, and bis(chlorocarbonyl)benzene such as isophthalic acid chloride and terephthalic acid chloride, and 1,3,5-benzenetricarbonyltrichloride are even more preferred.

[0047] Of the above, from the viewpoint of obtaining good heat resistance and dielectric properties of the resulting cured product, as well as the ease of industrial availability and workability of the raw materials, it is preferable that the aromatic compound has a monocyclic aromatic ring, or an aromatic compound has a fused aromatic ring, and more preferably benzenedicarboxylic acid, benzenetricarboxylic acid, naphthalenedicarboxylic acid, or their acid halides, more preferably benzenedicarboxylic acid, naphthalenedicarboxylic acid, or their acid halides, and even more preferably isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, or their acid halides. The above aromatic compound(c) may be used alone or in combination of two or more.

[0048] As described above, the active ester resin (A) used in the present invention requires an aromatic compound (a) having two hydroxyl groups in adjacent positions on the aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound and / or its acid halide or esterified product (c) having two or more carboxyl groups as essential reaction raw materials. However, any other optional reaction raw material may be an aromatic compound having multiple hydroxyl groups on the aromatic ring (excluding the aromatic compound (a) having two hydroxyl groups in adjacent positions on the aromatic ring). Here, examples of aromatic compounds having multiple hydroxyl groups on the aromatic ring include hydroquinone, resorcinol, 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, these compounds may be used individually or in combination of two or more types.

[0049] The active ester of the present invention functions as a curing agent for epoxy resins and the like, and can impart high heat resistance, low dielectric properties (low dielectric constant, low dielectric loss tangent), and high elastic modulus to the cured product obtained using the active ester, which is a preferred embodiment.

[0050] By using the active ester of the present invention, a cured product with low dielectric properties, high heat resistance, and excellent high modulus of elasticity can be obtained, which is a preferred embodiment. The reason for this is not entirely clear, but by introducing a catechol skeleton based on the aromatic compound (a) into the active ester, the ester groups in the active ester form adjacent structures on the same aromatic ring. Compared to conventional designs, this increases steric hindrance and suppresses molecular motion, resulting in a cured product with low dielectric properties (low dielectric constant, low dielectric loss tangent) and a high modulus of elasticity.

[0051] As for the active ester, from the viewpoint of having a better balance with handling properties when preparing the curable resin composition described later, and with the heat resistance and dielectric properties of the cured product, it is preferable that the softening point of the active ester is 200°C or lower, more preferably 180°C or lower, even more preferably 160°C or lower, and particularly preferably 140°C or lower.

[0052] The reaction with the aromatic compound (a), the aromatic monohydroxy compound (b), and the aromatic compound etc. (c) (hereinafter sometimes referred to as "starting material compound") is not particularly limited, but for example, the aromatic compound (a) and the aromatic monohydroxy compound (b) may be mixed and dissolved, and then the aromatic compound etc. (c) may be mixed and dissolved, and the reaction may be carried out in the presence of an alkaline catalyst at a temperature of 60°C or lower for a reaction time of 1 to 24 hours. Examples of alkaline catalysts that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, etc. These may be used individually or in combination of two or more. Among these, sodium hydroxide or potassium hydroxide is preferred because of its high reaction efficiency. These catalysts may also be used as 3 to 30% by mass aqueous solutions. In addition, to increase the reaction efficiency, an interlayer transfer catalyst may be used. Examples include alkylammonium salts and crown ethers. These may be used individually or in combination of two or more.

[0053] The above reaction is preferably carried out in an organic solvent because it allows for easier reaction control. Examples of organic solvents used here include hydrocarbon solvents such as pentane and hexane, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ether solvents such as diethyl ether and tetrahydrofuran, acetate 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.

[0054] The reaction ratio of the aforementioned raw material compounds can be appropriately changed according to the desired molecular design, but in particular, from the viewpoint of reducing unreacted end products and excess reaction materials, the ratio of aromatic compound (a) to 1 mole of aromatic monohydroxy compound (b) is preferably in the range of 0.5 to 5 moles, more preferably 1 to 4 moles, and even more preferably 2 to 3 moles. Furthermore, the ratio of aromatic compound (c) to 1 mole of aromatic monohydroxy compound (b) is preferably in the range of 0.5 to 5 moles, more preferably 1 to 4 moles, and even more preferably 2 to 3 moles.

[0055] After the reaction is complete, if an aqueous solution is used in the presence of an alkaline catalyst, the reaction solution is allowed to stand and separate to remove the aqueous layer. The remaining organic layer is washed with water, and this washing is repeated until the aqueous layer becomes nearly neutral (pH 7). This reduces the inorganic salt content that adversely affects the insulating properties, thereby obtaining the active ester of the present invention. After the reaction is complete, the excess raw material compounds are removed by drying under heating and reduced pressure to obtain a high-purity active ester.

[0056] The functional group equivalent of the active ester of the present invention is preferably in the range of 100 to 500 g / equivalent, more preferably in the range of 110 to 400 g / equivalent, and even more preferably in the range of 120 to 300 g / equivalent, because when the total number of aromatic ester groups in the active ester structure is taken as the number of functional groups of the active ester, a cured product with excellent curability, low dielectric constant and dielectric loss tangent (low dielectric properties) can be obtained.

[0057] The number-average molecular weight (Mn) of the active ester of the present invention is preferably 500 to 3000, and more preferably 600 to 2000. A number-average molecular weight (Mn) of 500 or more is preferable because it exhibits excellent dielectric properties and heat resistance. On the other hand, a number-average molecular weight (Mn) of 3000 or less is preferable because it exhibits excellent moldability.

[0058] --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 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and also preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less, from the viewpoint of improving the developability and dielectric properties in a balanced manner while increasing the elastic modulus.

[0059] (Resin having polymerizable unsaturated groups (B)) The curable resin composition of this embodiment contains a resin (B) having polymerizable unsaturated groups. The resin (B) only needs to have polymerizable unsaturated groups; its other specific structure or molecular weight is not particularly limited, and a wide variety of resins can be used. It is preferable that the resin (B) having polymerizable unsaturated groups does not have acidic groups.

[0060] Examples of polymerizable unsaturated groups in the 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.

[0061] Examples of the polymerizable unsaturated resin (B) include the following [1] to [6]: [1] Epoxy resin having polymerizable unsaturated groups (B1), [2] Urethane resin having polymerizable unsaturated groups (B2), [3] Acrylic resin having polymerizable unsaturated groups (B3), [4] Amidoimide resin having polymerizable unsaturated groups (B4), [5] Acrylamide resin having polymerizable unsaturated groups (B5), [6] Ester resin having polymerizable unsaturated groups (B6), These are some examples. Among these, epoxy resins having polymerizable unsaturated groups (B1), acrylic resins having polymerizable unsaturated groups (B3), amide-imide resins having polymerizable unsaturated groups (B4), acrylamide resins having polymerizable unsaturated groups (B5), and ester resins having polymerizable unsaturated groups (B6) are preferred, with epoxy resins having polymerizable unsaturated groups (B1) being particularly preferred. The effects of the present invention are most pronounced when the active ester resin (A) is combined with epoxy resins having polymerizable unsaturated groups (B1). Furthermore, as the resin having polymerizable unsaturated groups (B), the epoxy resins having polymerizable unsaturated groups described in Synthesis Example 4 and Synthesis Example 5 described in the examples below are even more preferred, and the effects of the present invention are most pronounced when these epoxy resins having polymerizable unsaturated groups are used.

[0062] --Epoxy resin with polymerizable unsaturated groups (B1)-- Examples of the epoxy resin (B1) having polymerizable unsaturated groups include epoxy (meth)acrylate resins obtained by reacting epoxy resin with an unsaturated monobasic acid and, if necessary, a polybasic acid anhydride; and epoxy (meth)acrylate resins having urethane groups obtained by reacting epoxy resin with an unsaturated monobasic acid, a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polybasic acid anhydride. Although polybasic acid anhydrides can be used as reaction raw materials for resin (B1) as described above, it is preferable not to use them. The resin (B1) has polymerizable unsaturated groups, but preferably does not have acid groups. Furthermore, it is preferable that the epoxy resin (B1) having polymerizable unsaturated groups has polymerizable unsaturated groups and epoxy groups in the same molecular chain. When the epoxy resin (B1) having polymerizable unsaturated groups has polymerizable unsaturated groups and epoxy groups in the same molecular chain, the epoxy groups react with the active ester groups of the active ester resin (A), and the effects of the present invention are more pronounced.

[0063] Examples of the epoxy resins mentioned above include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol copolymer novolac-type epoxy resins, naphthol-cresol copolymer novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, oxazolidone-type epoxy resins, and the like. These epoxy resins may be used individually or in combination of two or more types.

[0064] 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.

[0065] Examples of the aforementioned unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the aforementioned unsaturated monobasic acid can also be used. Furthermore, an unsaturated monobasic acid can be represented by the following general formula (4):

[0066] [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, Y41 is a hydrogen atom or a methyl group. Compounds represented by ] can also be used. Unsaturated monobasic acids may be used alone or in combination of two or more.

[0067] Examples of the polyoxyalkylene chains include polyoxyethylene chains and polyoxypropylene chains. Examples of the (poly)ester chain include the following general formula (5):

[0068] [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):

[0069] [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 ].

[0070] Examples of the polybasic acid anhydrides include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides. The polybasic acid anhydrides may be used individually or in combination of two or more types.

[0071] 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.

[0072] Examples of the polyisocyanate compound 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; the following general formula (7):

[0073] [Chemical formula] [In the above general formula (7), R 72 and R 73 each independently represent either a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R 71 each independently represents an alkyl group having 1 to 4 carbon atoms, k 71 is 0 or an integer of 1 to 3, and n 71 is an integer of 1 or more.], a polymethylene polyphenyl polyisocyanate having a repeating structure represented by these; and isocyanurate-modified products, biuret-modified products, allophanate-modified products, etc. of these. The polyisocyanate compound may be used alone or in combination of two or more.

[0074] Examples of the hydroxyl group-containing (meth)acrylate compounds 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.

[0075] The method for producing the epoxy resin (B1) having polymerizable unsaturated groups is not particularly limited and can be any method. The production of the epoxy resin (B1) having polymerizable unsaturated groups may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed.

[0076] 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."

[0077] 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.

[0078] --Urethane resin (B2) having polymerizable unsaturated groups-- Examples of the urethane resin (B2) having polymerizable unsaturated groups include those obtained by reacting polyisocyanate compounds, (meth)acrylate compounds having hydroxyl groups, and, if necessary, polyol compounds and / or polybasic acid anhydrides. Although polybasic acid anhydrides can be used as reaction raw materials for resin (B2) as described above, it is preferable not to use them. It is preferable that the resin (B2) has polymerizable unsaturated groups but does not have acid groups.

[0079] The polyisocyanate compound, the (meth)acrylate compound having a hydroxyl group, and the polybasic acid anhydride are the same as those previously described with respect to resin (B1), etc.

[0080] Examples of the polyol compounds 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; lactone modified compounds obtained by introducing (poly)lactone structures into the molecular structure of the various polyol compounds, such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds may be used individually or in combination of two or more.

[0081] The method for producing the urethane resin (B2) having polymerizable unsaturated groups is not particularly limited and can be any method. In producing the urethane resin (B2) having polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed. In that case, the organic solvent and basic catalyst are the same as those described above for resin (B1), etc.

[0082] --Acrylic resin (B3) containing polymerizable unsaturated groups-- Examples of the polymerizable unsaturated acrylic resin (B3) include a reaction product obtained by polymerizing 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, and then further reacting it with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups to introduce a (meth)acryloyl group, or, if necessary, a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (B3), but it is preferable not to use them. The resin (B3) has polymerizable unsaturated groups, but it is preferable that it does not have acid groups.

[0083] The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) as well as other compounds having polymerizable unsaturated groups as needed. Examples of other compounds having polymerizable unsaturated groups 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. The other compounds having polymerizable unsaturated groups may be used individually or in combination of two or more.

[0084] 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 water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) may be used alone or in combination of two or more types.

[0085] The polybasic anhydride is the same as that described previously for resin (B1), etc.

[0086] The method for producing the acrylic resin (B3) having polymerizable unsaturated groups is not particularly limited and can be any method. In producing the acrylic resin (B3) having polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed. In that case, the organic solvent and basic catalyst are the same as those described above for resin (B1), etc.

[0087] --Amidoimide resin with polymerizable unsaturated groups (B4)-- Examples of the polymerizable unsaturated amide-imide resin (B4) include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or an epoxy group, and optionally with 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. It is preferable that the resin (B4) has polymerizable unsaturated groups but does not have acid groups.

[0088] The amide-imide resin having acid groups and / or acid anhydride groups may have only one of them, or both. However, from the viewpoint of reactivity and reaction control with (meth)acrylate compounds having hydroxyl groups and epoxy compounds having (meth)acryloyl groups, it is preferable that the amide-imide resin having acid groups 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 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.

[0089] Examples of amide-imide resins having acid groups and / or acid anhydride groups include those obtained using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials. In this case, the polyisocyanate compound and polybasic acid anhydride are the same as those previously described for resin (B1), etc. Although the polybasic acid anhydride can be used as a reaction raw material for resin (B4) as described above, it is preferable not to use it. Furthermore, as necessary, in addition to the polyisocyanate compound and polybasic acid anhydride, a polybasic acid can also be used as a reaction raw material for the amide-imide resin having acid groups and / or acid anhydride groups.

[0090] 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. These polybasic acids may be used individually or in combination of two or more.

[0091] The (meth)acrylate compound having a hydroxyl group is the same as that described above for resin (B1), etc.

[0092] Examples of the epoxy group-containing (meth)acrylate compounds include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The epoxy group-containing (meth)acrylate compounds may be used individually or in combination of two or more.

[0093] The method for producing the polymerizable unsaturated amide-imide resin (B4) is not particularly limited and can be any method. In producing the polymerizable unsaturated amide-imide resin (B4), the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed. In that case, the organic solvent and basic catalyst are the same as those described above for resin (B1), etc.

[0094] --Acrylamide resin with polymerizable unsaturated groups (B5)-- Examples of the polymerizable unsaturated acrylamide resin (B5) include those obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl(meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid. Although polybasic acid anhydrides can be used as reaction raw materials for resin (B5) as described above, it is preferable not to use them. The resin (B5) preferably has polymerizable unsaturated groups but does not have acid groups.

[0095] The aforementioned compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in its molecule. Examples of compounds having at least one phenolic hydroxyl group in its molecule include those represented by the following general formulas (8.1) to (8.5).

[0096] [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...

[0097] Furthermore, examples of compounds having phenolic hydroxyl groups include reaction products that require a compound having at least one phenolic hydroxyl group in its molecule, a compound represented by any of the following general formulas (9.1) to (9.5), and / or formaldehyde as essential reaction raw materials. In addition, novolac-type phenolic resins that use one or more compounds having at least one phenolic hydroxyl group in their molecule as reaction raw materials can also be used.

[0098] [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.]

[0099] Specific examples of compounds having the aforementioned phenolic hydroxyl group include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resins having a cyclocyclic structure. The aforementioned compounds having phenolic hydroxyl groups may be used individually or in combination of two or more.

[0100] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. The alkylene oxide may be used alone or in combination of two or more types. Among these, ethylene oxide or propylene oxide is preferred as the alkylene oxide.

[0101] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. The alkylene carbonate may be used alone or in combination of two or more types. Among these, ethylene carbonate or propylene carbonate is preferred as the alkylene carbonate.

[0102] Examples of the N-alkoxyalkyl(meth)acrylamide compounds 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. The N-alkoxyalkyl(meth)acrylamide compounds may be used individually or in combination of two or more.

[0103] The polybasic anhydrides and unsaturated monobasic acids are the same as those previously described for resins (B1), etc.

[0104] The method for producing the polymerizable unsaturated acrylamide resin (B5) is not particularly limited and can be any method. In producing the polymerizable unsaturated acrylamide resin (B5), the process may be carried out in an organic solvent as needed, and a basic catalyst and an acidic catalyst may also be used as needed. In that case, the organic solvent and basic catalyst are the same as those described above for resin (B1), etc.

[0105] 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 may be used individually or in combination of two or more types.

[0106] --Ester resin (B6) having polymerizable unsaturated groups-- Examples of the polymerizable unsaturated ester resin (B6) include those obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride. Although polybasic acid anhydrides can be used as reaction raw materials for resin (B6) as described above, it is preferable not to use them. The resin (B6) preferably has polymerizable unsaturated groups but does not have acid groups.

[0107] The compounds having phenolic hydroxyl groups, alkylene oxides, alkylene carbonates, unsaturated monobasic acids, and polybasic acid anhydrides are the same as those previously described with respect to resins (B1) and resins (B5), etc.

[0108] The method for producing the polymerizable unsaturated ester resin (B6) is not particularly limited and can be any method. The production of the polymerizable unsaturated ester resin (B6) may be carried out in an organic solvent as needed, and a basic catalyst and an acidic catalyst may also be used as needed. In that case, the organic solvent, basic catalyst and acidic catalyst are the same as those described above for resin (B1) and resin (B5), etc.

[0109] --Content-- The content of the polymerizable unsaturated resin (B) 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 60% by mass or more, and even more preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of improving adhesion and dielectric properties in a balanced manner while increasing the elastic modulus.

[0110] 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 polymerizable unsaturated resin (B) [(A) / (B)] is preferably 5 / 95 to 50 / 50, and more preferably 10 / 90 to 30 / 70, from the viewpoint of improving heat resistance and dielectric properties in a balanced manner while increasing the elastic modulus.

[0111] The curable resin composition of this embodiment may consist only of the active ester resin (A) and the resin having polymerizable unsaturated groups (B), but may further contain photopolymerization initiators and the like, as described later. The total content of the active ester resin (A) and the polymerizable unsaturated resin (B) in the total amount (100% by mass) of the curable resin composition of this embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 95% by mass or less, and more preferably 90% by mass or less, from the viewpoint of improving heat resistance and dielectric properties in a balanced manner while increasing the elastic modulus.

[0112] (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.

[0113] 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.

[0114] 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).

[0115] 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 polymerizable unsaturated group resin (B).

[0116] (Optional addition ingredient) The curable resin composition of this embodiment may further contain optional additives, as long as they do not deviate from the purpose. Examples of optional additives include compounds having polymerizable unsaturated groups, curing agents, curing accelerators, other resins, organic solvents, polymerization inhibitors, antioxidants, flame retardants, fillers, pigments, defoamers, viscosity modifiers, leveling agents, UV stabilizers, and storage stabilizers.

[0117] --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.

[0118] --Hardening 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. When the curing agent is an epoxy resin, the epoxy groups of the epoxy resin react with the active ester groups of the active ester resin (A), and the effects of the present invention become more pronounced.

[0119] 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.

[0120] 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 dielectric properties and adhesion in a balanced manner.

[0121] 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.

[0122] 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 amount of solids (non-volatile content) of the active ester resin (A) and the polymerizable unsaturated resin (B). If the amount 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.

[0123] --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.

[0124] 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 accelerators 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).

[0125] 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 polymerizable unsaturated resin (B). 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 polymerizable unsaturated resin (B).

[0126] --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.

[0127] --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.

[0128] --Polymerization inhibitor-- The polymerization inhibitor is not particularly limited, but may 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; 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(dimethyldithiocarbamato-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.

[0129] --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.

[0130] 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.

[0131] --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.

[0132] 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.

[0133] 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 active ester resin (A) and the polymerizable unsaturated resin (B). 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 active ester resin (A) and the polymerizable unsaturated resin (B).

[0134] --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.

[0135] 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.

[0136] 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.

[0137] When using the filler described above, 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 active ester resin (A) and the polymerizable unsaturated resin (B). 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 active ester resin (A) and the polymerizable unsaturated resin (B).

[0138] 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.

[0139] <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 high 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] <Goods> The article of this embodiment is characterized by having a coating film made of the cured material described above. In the article of this embodiment, the coating film can function as an insulating material with high heat resistance, high elastic modulus, and excellent dielectric properties.

[0146] The article of this embodiment is typically a printed circuit board or a substrate for a semiconductor package, wherein a solder resist film (the coating film) is formed in appropriate locations on the surface. [Examples]

[0147] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples. Unless otherwise specified, "parts" and "%" in the examples refer to mass. The GPC measurement conditions in these examples are as follows.

[0148] [GPC measurement conditions] 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.

[0149] (Synthesis Example 1) Synthesis of the active ester (A-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer was charged with 220 parts by mass (2.0 moles) of catechol, 144 parts by mass (1.0 mole) of α-naphthol, and 2061 parts by mass of toluene. The system was then purged with reduced pressure nitrogen and dissolved. Next, 505 parts by mass (2.5 moles) of isophthalic acid chloride was charged and the system was purged with reduced pressure nitrogen and dissolved. Subsequently, 1.0 part by mass of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the system temperature was controlled to below 60°C, and 1030 parts by mass of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was complete, the mixture was allowed to stand and separated, and the aqueous layer was removed. Water was then added to the toluene phase containing the dissolved reactants and stirred for about 15 minutes, and the mixture was allowed to stand and separated, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Subsequently, the mixture was dried under reduced pressure and heated to obtain 652 parts by mass of the active ester (A-1) shown in the following structural formula. The ester group equivalent of this active ester (A-1) was 137 g / equivalent, the softening point was 118°C, and the theoretical average number of repeating units n from the raw material charging ratio was 4. The number of repeating units n is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5. Having the number of repeating units n within this range is desirable because it results in high heat resistance, low dielectric constant, and low dielectric loss tangent.

[0150] [ka]

[0151] (Synthesis Example 2) Synthesis of the active ester (A-2) 759 parts by mass of the active ester (A-2) was obtained in the same manner as in Example 1, except that 220 parts by mass (2.0 mol) of catechol in Example 1 was replaced with 332 parts by mass (2.0 mol) of tert-butylcatechol. The ester group equivalent of this active ester (A-2) was 160 g / equivalent, the softening point was 128°C, and the theoretical average number of repeating units n from the raw material charging ratio was 4.

[0152] [ka]

[0153] (Synthesis Example 3) Synthesis of activated ester (A-3) 765 parts by mass of the active ester (A-3) was obtained in the same manner as in Example 1, except that 220 parts by mass (2.0 mol) of catechol in Example 1 was replaced with 332 parts by mass (2.0 mol) of tert-butylcatechol and 144 parts by mass (1.0 mol) of α-naphthol was replaced with 150 parts by mass (1.0 mol) of para-tert-butylphenol. The ester group equivalent of this active ester (A-3) was 161 g / equivalent, the softening point was 124°C, and the theoretical average number of repeating units n from the raw material charging ratio was 4.

[0154] [ka]

[0155] (Synthesis Example 4) Synthesis of activated ester (C-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer was charged with 165 parts by mass of dicyclopentadiene and phenol weight addition reaction resin (hydroxyl group equivalent: 165 g / equivalent, softening point 85°C), 72 parts by mass (0.5 mol) of α-naphthol, and 630 parts by mass of toluene. The system was then purged with reduced pressure nitrogen and dissolved. Next, 152 parts by mass (0.75 mol) of isophthalic acid chloride was charged and the system was purged with reduced pressure nitrogen and dissolved. Subsequently, 0.6 parts by mass of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the system temperature was controlled to below 60°C, and 315 parts by mass of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was complete, the mixture was allowed to stand and separated, and the aqueous layer was removed. Water was then added to the toluene layer containing the dissolved reactants and stirred for about 15 minutes, and the mixture was allowed to stand and separated, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Afterward, the mixture was dried under reduced heat to synthesize the active ester (C-1). The ester group equivalent of this active ester (C-1) was 223 g / equivalent, and its softening point was 150°C.

[0156] (Synthesis Example 5: Production of resin (B-1) having polymerizable unsaturated groups) In a flask equipped with a thermometer, stirrer, and reflux condenser, 188 parts by mass of bisphenol A type epoxy resin (DIC Corporation's "EPICLON 850-S", epoxy equivalent 188 g / equivalent) was charged. After adding 0.3 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 8 hours while blowing in air to obtain a polymerizable unsaturated resin (B-1).

[0157] (Synthesis Example 6: Production of epoxy resin (B-2) having polymerizable unsaturated groups) In a flask equipped with a thermometer, stirrer, and reflux condenser, 346 parts by mass of bisphenol A type epoxy resin (DIC Corporation's "EPICLON 850CRP", epoxy equivalent 173 g / eq) was charged. 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of methoquinone as a thermal polymerization inhibitor were added. Then, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 100°C for 10 hours while blowing in air. After confirming that the acid value was 1 mg KOH / g or less, 0.21 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain epoxy resin (B-2) having polymerizable unsaturated groups. The epoxy equivalent of this resin (B-2) was 450 g / eq.

[0158] (Examples 1-6, Comparative Example 1) The components were mixed in the proportions shown in Table 1 below to obtain curable resin compositions (1) to (3) and (C1). The following tests were performed on the obtained curable resin compositions.

[0159] [Method for evaluating heat resistance] The curable resin compositions obtained in each example and comparative example were applied to copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS", 18 μm) using an applicator to a thickness of 50 μm, and dried at 80°C for 30 minutes. Then, a metal halide lamp was used to measure 10 kJ / m³. 2 After irradiation with ultraviolet light, the mixture was heated at 160°C for 1 hour to obtain a cured coating. Next, the cured coating was peeled off the copper foil to obtain a cured material (test piece 1). A 6 mm × 35 mm test piece was cut from the cured material, and the temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometric's RSAII solid viscoelasticity measuring device, tensile method: frequency 1 Hz, heating rate 3°C / min). A higher glass transition temperature indicates better heat resistance.

[0160] [Method for evaluating elasticity] The elasticity was evaluated by measuring the modulus of elasticity through tensile testing.

[0161] <Tensile Test> The aforementioned test specimen 1 was cut to a size of 10 mm x 80 mm, and a tensile test was performed on the specimen using the Shimadzu Corporation's Autograph "AG-IS" precision universal testing machine under the following measurement conditions. The elastic modulus (MPa) until the specimen fractured was measured and evaluated according to the following criteria.

[0162] Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm / min

[0163] [Method for measuring dielectric constant] 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 dried at 80°C for 30 minutes. Then, a metal halide lamp was used to measure 10 kJ / m³. 2After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour to obtain a cured coating. Next, the cured coating was peeled off the glass substrate to obtain a cured product. Then, the product was stored in a room at 23°C and 50% humidity for 24 hours to obtain a test specimen, and the dielectric constant of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies Network Analyzer E8362C.

[0164] [Method for measuring dielectric loss tangent] 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 dried at 80°C for 30 minutes. Then, a metal halide lamp was used to measure 10 kJ / m³. 2 After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour to obtain a cured coating. Next, the cured coating was peeled off the glass substrate to obtain a cured product. Then, a test specimen was stored in a room at 23°C and 50% humidity for 24 hours, and the dielectric loss tangent of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies, Inc. Network Analyzer E8362C.

[0165] [Table 1]

[0166] The following were used in Tables 1 and 2. Acrylate monomer: EO-modified diacrylate of bisphenol A (Miramaer M240, manufactured by Miwon Specialty Chemical) Photopolymerization initiator: IGM Resins, brand name "Omnirad 907"

[0167] Table 1 shows that the cured products obtained by curing the curable resin compositions of Examples 1 to 4 according to the present invention have higher heat resistance, higher elastic modulus, and superior dielectric properties (lower dielectric constant and dielectric loss tangent) compared to the cured product of Comparative Example 1, which uses an active ester resin that does not use an aromatic compound (a) having two hydroxyl groups at adjacent positions on the aromatic ring as a reaction raw material. [Industrial applicability]

[0168] The curable resin composition and cured product of the present invention can be used in various articles such as printed circuit boards and semiconductor package substrates.

Claims

1. It contains an active ester resin (A) and a resin (B) having polymerizable unsaturated groups, The activated ester resin (A) uses as essential reaction raw materials an aromatic compound (a) having two hydroxyl groups in adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound and / or its acid halide or esterified product (c) having two or more carboxyl groups. A curable resin composition characterized in that the aromatic compound (a) is at least one compound selected from the group consisting of the following general formulas (1) to (3). 【Chemistry 1】 (In the above formula, R independently represents a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer from 0 to 4, and m represents an integer from 0 to 2.)

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

3. A cured product characterized by being obtained by curing the curable resin composition described in claim 1 or 2.

4. An article characterized by having a coating film made of the cured product described in claim 3.

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