Curable resin, cured product thereof, and resin composition

Abstract

To provide a curable resin and the like excellent in flame retardancy.SOLUTION: The present invention provides a curable resin and the like, the curable resin having a structural unit represented by the following formula (1), a dihydroxy structural unit, a structural unit represented by the following formula (2a), and a carbonate structural unit. [In the formula (1), R represents a divalent group having an ethylenic double bond and / or an acetylenic triple bond.] [In the formula (2a), each R independently represents a C1-6 alkyl group or an optionally substituted C6-14 aryl group; and n represents the number of repeating units.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin, a cured product thereof, a resin composition, and the like. [Background technology]

[0002] Polyester carbonates are used in a variety of applications due to their excellent mechanical strength, heat resistance, transparency, etc., and various polyester carbonates and methods for producing them have been reported.

[0003] For example, Patent Document 1 discloses a method for producing an aliphatic polyester carbonate having a weight average molecular weight of 100,000 or more, which comprises: reacting maleic anhydride with a glycol having 2 to 20 carbon atoms, a diluent, and hydrogen in the presence of a hydrogenation catalyst, polycondensing the resulting reaction product in the presence of an ester exchange catalyst to obtain an aliphatic polyester oligomer having a number average molecular weight of 200 to 5,000, and then reacting the aliphatic polyester oligomer with a carbonate diester.

[0004] Furthermore, Patent Document 2 discloses a polyester resin C including "a hard segment based on an ester bond-containing diol oligomer A1 having at least two ester bonds and hydroxyl groups at both ends, a soft segment based on a carbonate group-containing diol oligomer A2 having at least two carbonate groups and hydroxyl groups at both ends, and a residual carboxyl group-containing segment B based on an acid dianhydride." [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2003-2959 A [Patent Document 2] JP 2010-13527 A Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, various polyester carbonates are known, but the polyester carbonates have low compatibility with curable resins and are difficult to add to curable resins. In addition, there is still room for improvement in the properties of the conventional polyester carbonates described above. Therefore, the present invention aims to provide a curable resin having excellent flame retardancy. [Means for solving the problem]

[0007] As a result of intensive research, the present inventors have found that a curable resin having excellent flame retardancy can be obtained by reacting a dicarboxylic acid compound, a diol compound, and a carbonate compound having a predetermined structure.

[0008] The present invention includes the following embodiments. [1] A structural unit represented by the following formula (1), [ka] [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylenic triple bond] A structural unit represented by the following formula (2), [ka] [In the formula, R 2 is a divalent linking group. A structural unit represented by the following formula (2a): [ka] [In the formula, R is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms which may have a substituent, and n is the number of repeating units.] A structural unit represented by the following formula (3), [ka] A curable resin having the formula: [2] The curable resin according to [1], wherein the structural unit represented by the formula (3) is derived from at least one selected from the group consisting of dialkyl carbonate, diaryl carbonate, and alkylaryl carbonate. [3] The structural unit represented by the formula (1) is derived from at least one selected from the group consisting of fumaric acid, maleic acid, and maleic anhydride. The curable resin according to [1] or [2]. [4] The glass transition temperature is 50°C or less. The curable resin according to any one of [1] to [3]. [5] The molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 0.01 or more and less than 1. The curable resin according to any one of [1] to [4]. [6] The content of the structural unit represented by the formula (2a) relative to the total amount of the structural unit represented by the formula (2) and the structural unit represented by the formula (2a) is 0.02 to 50 mol %. The curable resin according to any one of [1] to [5]. [7] The molar ratio of the structural unit represented by the formula (1) to the total amount of the structural unit represented by the formula (2) and the structural unit represented by the formula (2a) is 0.010 or more and less than 1.0. The curable resin according to any one of [1] to [6]. [8] The molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (3) is 0.010 or more and less than 1.0. The curable resin according to any one of [1] to [7]. [9] the molar ratio of the sum of the contents of the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the structural unit represented by the formula (3) to all the structural units constituting the curable resin is 0.60 or more; The curable resin according to any one of [1] to [8].

[10] Further containing an alicyclic skeleton as a structural unit The curable resin according to any one of [1] to [9].

[11] Further containing a structural unit represented by the following formula (4): The curable resin according to any one of [1] to

[10] . [ka]

[12] A cured product of the curable resin according to any one of [1] to

[11] .

[13] A resin composition comprising the curable resin according to any one of [1] to

[11] .

[14] The resin composition according to

[13] , wherein the amount of the curable resin per 100 parts by mass of the resin component contained in the resin composition is 1.0 part by mass or more.

[15] The resin composition according to

[13] , which is for use as an electronic material.

[16] An electronic component comprising the resin composition according to

[13] .

[17] A fiber-reinforced composite material comprising the resin composition according to

[13] and reinforcing fibers.

[18] A fiber-reinforced molded product, which is a cured product of the fiber-reinforced composite material according to

[17] .

[19] A semiconductor encapsulation material comprising the resin composition according to

[13] and an inorganic filler.

[20] A semiconductor device comprising a cured product of the semiconductor encapsulation material according to

[19] . [twenty one] A prepreg comprising a substrate and the resin composition according to

[13] impregnated into or applied to the substrate. [twenty two] A laminate comprising the prepreg according to

[21] . [twenty three] A circuit board comprising the laminate according to

[22] and a metal foil disposed on one or both sides of the laminate. [twenty four] A build-up film comprising a cured product of the resin composition according to

[13] and a substrate film. Effect of the Invention

[0009] According to the present invention, it is possible to provide a curable resin having excellent flame retardancy. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the embodiments of the present invention will be described in detail, however, the present invention is not limited to these and various modifications are possible without departing from the gist of the present invention.

[0011] <Curing resin> One embodiment of the present invention relates to a structural unit represented by the following formula (1) (hereinafter also referred to as a "dicarboxylic acid unit"), [ka] [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylenic triple bond] A structural unit represented by the following formula (2) (hereinafter also referred to as a "dihydroxy unit") [ka] [In the formula, R 2 is a divalent linking group. A structural unit represented by the following formula (2a) (hereinafter also referred to as a "siloxane skeleton unit"), [ka] [In the formula, R is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms which may have a substituent, and n is the number of repeating units.] A structural unit represented by the following formula (3) (hereinafter also referred to as a "carbonate unit"), [ka] The present invention relates to a curable resin having the formula:

[0012] The curable resin of the present embodiment has an ethylenic double bond and / or an acetylenic triple bond in the dicarboxylic acid unit, and therefore can be crosslinked intramolecularly or intermolecularly, i.e., can be cured by an appropriate method. Conventional polyester carbonates do not have a point (functional group) that can be crosslinked with a curable resin, and therefore, when added to a curable resin with low compatibility, there are problems such as phase separation and peeling at the interface with the curable resin. In addition, since the curable resin of the present embodiment is a resin containing an ester bond, a carbonate bond, and a siloxane skeleton, it has an ethylenic double bond and / or an acetylenic triple bond, and therefore when mixed with another curable resin, it can react with the functional group of the other curable resin to crosslink. As a result, the curable resin of the present embodiment can be cured alone, and even when mixed with another curable resin, phase separation and interface peeling are unlikely to occur.

[0013] In addition, the curable resin of this embodiment is presumed to exhibit high flame retardancy (friction resistance) due to the presence of the siloxane skeleton represented by the above formula (2a). Furthermore, due to the presence of the siloxane skeleton represented by the above formula (2a), the curable resin of this embodiment is expected to have relatively excellent flexibility, high bending strength, low thermal expansion, and suppression of warping.

[0014] The curable resin of the present embodiment is a resin that cures in response to an appropriate stimulus or spontaneously. In one aspect, the curable resin of the present embodiment is a thermosetting resin, in another aspect, a light curable resin, and in yet another aspect, a heat or light curable resin.

[0015] The order of bonding of the dicarboxylic acid unit, the dihydroxy unit, the siloxane skeleton unit and the carbonate unit in the curable resin is not particularly limited, but it is preferable that the dicarboxylic acid unit and the carbonate unit are adjacent to the dihydroxy unit. In this case, it is preferable that the siloxane skeleton unit is contained in the dihydroxy unit. By making the dihydroxy unit have a siloxane skeleton, the handling during preparation of the curable resin tends to be improved. In addition, the oxygen atoms at the ends of these units are shared with the oxygen atoms at the ends of the adjacent units. For example, when the dicarboxylic acid unit and the dihydroxy unit are adjacent to each other, the oxygen at the ends of both units are shared to form an ester bond. In addition, when the carbonate unit and the dihydroxy unit are adjacent to each other, the oxygen at the ends of both units are shared to form a carbonate bond.

[0016] The curable resin of the present embodiment may be a random copolymer of dicarboxylic acid units, dihydroxy units, siloxane skeleton units and carbonate units, may be a copolymer in which a copolymer of a carbonate unit and a dihydroxy unit having a siloxane skeleton is linked to a dicarboxylic acid unit, or may be a copolymer in which a copolymer of a dicarboxylic acid unit and a dihydroxy unit having a siloxane skeleton is linked to a carbonate unit.

[0017] The curable resin of the present embodiment can exhibit high strength by curing. The reason for this is assumed to be that the glass transition temperature of the curable resin is lowered by having the dihydroxy unit represented by formula (2) or the siloxane skeleton unit represented by formula (2a), and that the flexibility of the dihydroxy unit represented by formula (2) or the siloxane skeleton unit represented by formula (2a) itself is high, but the present invention is not limited by this assumed reason.

[0018] The curable resin of the present embodiment contains a dicarboxylic acid unit represented by the above formula (1). In the above formula (1), R is a divalent group having at least one of an ethylenic double bond and an acetylenic triple bond, preferably a divalent group having an ethylenic double bond, more preferably a divalent hydrocarbon group having an ethylenic double bond, still more preferably a divalent hydrocarbon group having 2 to 6 carbon atoms and an ethylenic double bond, particularly preferably a divalent hydrocarbon group having 2 to 4 carbon atoms and an ethylenic double bond, and most preferably a divalent hydrocarbon group having 2 carbon atoms and an ethylenic double bond. The dicarboxylic acid unit in which R is a divalent hydrocarbon group having 2 carbon atoms and an ethylenic double bond can be derived from at least one selected from the group consisting of fumaric acid, maleic acid, and maleic anhydride, for example.

[0019] In the present specification, the term "ethylenic double bond" refers to a carbon-carbon double bond that does not form an aromatic ring. In addition, in the present specification, the term "acetylenic triple bond" refers to a carbon-carbon triple bond that does not form an aromatic ring. Since the curable resin of the present embodiment has an ethylenic double bond and / or an acetylenic triple bond, it can be cured alone without using a crosslinking agent.

[0020] When the dicarboxylic acid unit has an ethylenic double bond, the isomeric structure is not particularly limited. That is, the dicarboxylic acid unit having an ethylenic double bond may be in a cis configuration or a trans configuration.

[0021] The dicarboxylic acid unit represented by the above formula (1) is preferably a structural unit represented by the following formula (1-1) or (1-2). [ka] [ka] In the above formulas (1-1) and (1-2), R 1A R is independently a hydrogen atom, a methyl group, or an ethyl group. 1Aare preferably each independently a hydrogen atom or a methyl group.

[0022] The dicarboxylic acid unit is particularly preferably a structural unit derived from fumaric acid, maleic acid, or maleic anhydride. In this case, R in the above formula (1) is a divalent hydrocarbon group having 2 carbon atoms and an ethylenic double bond. According to such an embodiment, the dielectric properties of the curable resin tend to be further improved.

[0023] The curable resin of the present embodiment may contain only one type of dicarboxylic acid unit, or may contain two or more types of dicarboxylic acid units. In addition, each dicarboxylic acid unit may be composed of only one type of stereoisomer, or may contain multiple stereoisomers. From the viewpoint of easy production and easy control of resin properties, it is preferable that the type of dicarboxylic acid unit contained in the curable resin is one type.

[0024] The curable resin of the present embodiment contains a dihydroxy unit represented by the above formula (2). 2 From the viewpoints of the flame retardancy of the resulting curable resin and the ease of handling during preparation of the curable resin, R in the dihydroxy unit may be 2 is preferably a divalent group having a siloxane skeleton unit. More specifically, R 2 It is preferable that the copolymer has a structural unit represented by the following formula (2a). [ka] [In the formula, R 2 is a divalent linking group. [ka] [In the formula, R is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms which may have a substituent, and n is the number of repeating units.]

[0025] Here, in the above formula (2a), the alkyl group having 1 to 6 carbon atoms is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably an alkyl group having 1 carbon atom. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a 3-hexyl group, a tert-hexyl group, and a cyclohexyl group. In addition, in the above formula (2a), the aryl group having 6 to 14 carbon atoms which may have a substituent is more preferably a phenyl group which may have a substituent or a naphthyl group which may have a substituent. These substituents are not particularly limited, but are more preferably the above-mentioned alkyl groups of 1 to 4, even more preferably the alkyl groups of 1 to 3, particularly preferably the alkyl groups of 1 to 2, and particularly preferably the alkyl groups having 1 carbon atom. Note that n in the above formula (2a) means the number of repeating units, and is not particularly limited, but is preferably 1 to 20, more preferably 2 to 17, even more preferably 3 to 15, and particularly preferably 3 to 12.

[0026] The curable resin of the present embodiment may contain only one type of dihydroxy unit, or may contain two or more types of dihydroxy units. In addition, each dihydroxy unit may be composed of only one type of stereoisomer, or may contain multiple stereoisomers. From the viewpoint of ease of production and ease of control of the resin properties, it is preferable that the curable resin contains only one type of dihydroxy unit, and in this case, the dihydroxy unit is R 2 Particularly preferred are those having a siloxane skeleton.

[0027] In addition, the curable resin of the present embodiment has a structural unit represented by the above formula (2), 2 may further contain an alicyclic dihydroxy unit, which is a divalent group having an alicyclic structure.2 It is presumed that the main chain of the curable resin of this embodiment becomes rigid and the molar volume becomes larger by further containing an alicyclic dihydroxy unit, which is a divalent group having an alicyclic structure. This restricts the movement of the molecular chain of the entire resin molecule, and improves the dielectric properties. However, the reason for this is not limited to this. 2 In the above, the alicyclic structure may be in the main chain, in the side chain, or in both the main chain and the side chain. 2 Preferably, R in the alicyclic dihydroxy unit has an alicyclic structure in the main chain. 2 has at least one alicyclic structure, but may have two or more alicyclic structures.

[0028] The alicyclic dihydroxy unit is preferably a structural unit represented by the following formula (4). [ka]

[0029] In addition, the alicyclic dihydroxy compound as described above is not particularly limited, but examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,4-butenediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 2-ethyl-2-methylpropanediol, and the like. Examples of the hexanediol include 1,3-hexanediol, 2-butyl-2-ethylpropane-1,3-diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-dimethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

[0030] In addition, the curable resin of the present embodiment has a structure represented by the formula (2) R 2may further contain an aromatic dihydroxy unit, which is a divalent group having an aromatic ring structure. 2 It is presumed that the main chain of the curable resin of this embodiment becomes rigid and the molar volume becomes larger by further containing an aromatic dihydroxy unit in which R is a divalent group having an aromatic ring structure. This restricts the movement of the molecular chain of the entire resin molecule, and improves the dielectric properties. However, the reason for this is not limited to this. 2 In the above, the aromatic ring structure may be in the main chain, in the side chain, or in both the main chain and the side chain. 2 Preferably, R has an aromatic ring structure in the main chain. 2 has at least one aromatic structure, but may have two or more aromatic structures.

[0031] The aromatic dihydroxy compound as described above is not particularly limited, but examples thereof include hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, xylylene glycol, 4,4'-dihydroxydiphenylbenzophenone, bisphenols, etc. Examples of bisphenols include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-(4-hydroxy ... 1,1-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-diphenyl Examples of such hydroxydiphenyl sulfone include bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-(propane-2,2-diyl)bis(2-allylphenol), and 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane.

[0032] In addition, examples of aromatic dihydroxy compounds include dihydroxy compounds having an ether group bonded to an aromatic group, such as 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone; and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9 and dihydroxy compounds having a fluorene ring, such as 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene.

[0033] The curable resin of the present embodiment contains a carbonate unit represented by the above formula (3). The carbonate unit is preferably a structural unit derived from at least one selected from the group consisting of dialkyl carbonate, diaryl carbonate, and alkylaryl carbonate. Specific examples of dialkyl carbonate, diaryl carbonate, and alkylaryl carbonate will be described later.

[0034] The curable resin of the present embodiment may contain additional structural units in addition to the above-mentioned dicarboxylic acid unit, dihydroxy unit, and carbonate unit. The additional structural units are not particularly limited, but are preferably those that do not adversely affect the flame retardancy of the curable resin. Examples of the additional structural units include structural units derived from dicarboxylic acid compounds that do not fall under the dicarboxylic acid unit of formula (1), structural units derived from dihydroxy compounds that do not fall under the dihydroxy unit of formula (2), structural units derived from alkyl-substituted phenyl compounds that do not fall under the siloxane skeleton unit of formula (2a), and monohydroxy compounds having ethylenic double bonds.

[0035] Such dicarboxylic acid compounds are not particularly limited, but examples thereof include saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and acid anhydrides thereof. Examples of saturated aliphatic dicarboxylic acids include cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, adipic acid, succinic acid, sebacic acid, alkylsuccinic acids, cyclohexanediacetic acid, azelaic acid, malonic acid, dimethylmalonic acid, and oxalic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 2,5-furandicarboxylic acid, and 2,5-thiophenedicarboxylic acid.

[0036] Examples of monohydroxy compounds having an ethylenic double bond include hydroxy group-containing (meth)acrylic acid esters, specifically 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate.

[0037] By introducing the structural units and / or partial structures as described above into the curable resin of the present embodiment, it tends to be possible to improve or impart properties such as flexibility, mechanical strength, heat resistance, flame retardancy, color tone, and solvent solubility.

[0038] The terminal group in the curable resin of this embodiment is not particularly limited and may be, for example, a carboxy group and / or a hydroxy group, but is preferably a structure in which the carboxy group and / or the hydroxy group are blocked with a terminal blocking agent. According to an embodiment having a terminal blocking agent, the dielectric properties of the curable resin tend to be more excellent. The terminal carboxyl group capping agent is not particularly limited as long as it is a compound having a group that reacts with a carboxyl group, and examples thereof include carbodiimide compounds such as monocarbodiimide and polycarbodiimide compounds, oxazoline compounds, and one-terminal diols. Examples of the terminal hydroxyl group-capping agent include diphenyl carbonate and monocarboxylic acid.

[0039] In one aspect, the curable resin of the present embodiment includes a polyester portion that contains a dihydroxy unit, a siloxane skeleton unit, and a dicarboxylic acid unit and does not contain a carbonate unit. In this aspect, the curable resin is preferably a polyester carbonate in which a plurality of polyester portions each consisting of a dihydroxy unit, a siloxane skeleton unit, and a dicarboxylic acid unit are linked to a plurality of carbonate units. According to such an aspect, the dielectric properties of the curable resin tend to be further improved.

[0040] The content N of the dihydroxy unit represented by the formula (2) OH The content N of the dicarboxylic acid unit represented by the formula (1) COOH Molar ratio of N COOH / N OH The molar ratio N can be appropriately set depending on the desired performance, and is not particularly limited, but is preferably 0.01 or more and less than 1, more preferably 0.05 or more and 0.6 or less, and further preferably 0.05 or more and 0.3 or less. COOH / N OHWhen the molar ratio N is within the above range, the flexibility of the polycarbonate skeleton (cyclohexanedimethanol-diphenyl carbonate copolymer skeleton) can be utilized, and crosslinking with the thermosetting resin can be sufficiently performed, thereby improving the strength. COOH / N OH can be measured by a nuclear magnetic resonance (NMR) spectrometer.

[0041] The content ratio of the siloxane skeleton unit represented by the formula (2a) to the total amount of the dihydroxy unit represented by the formula (2) and the siloxane skeleton unit represented by the formula (2a) can be appropriately set according to the desired performance and is not particularly limited, but is preferably 0.02 to 50 mol%, more preferably 0.03 to 40 mol%, and further preferably 0.05 to 30 mol%. The above molar ratio can be measured by a nuclear magnetic resonance (NMR) apparatus.

[0042] The molar ratio of the dicarboxylic acid unit represented by the formula (1) to the total amount of the dihydroxy unit represented by the formula (2) and the siloxane skeleton unit represented by the formula (2a) can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 0.010 or more and less than 1.0, more preferably 0.05 or more and 0.6 or less, and even more preferably 0.05 or more and 0.3 or less. The above molar ratio can be measured by a nuclear magnetic resonance apparatus (NMR).

[0043] The content N of the dihydroxy unit represented by the formula (2) OH The content N of the carbonate unit represented by the formula (3) OCOO Molar ratio of N OCOO / N OH The molar ratio N can be appropriately set depending on the desired performance, and is not particularly limited, but is preferably 0.01 or more and less than 1, more preferably 0.4 or more and 0.95 or less, and further preferably 0.7 or more and 0.95 or less. OCOO / N OHWhen the molar ratio N is within the above range, the reaction proceeds smoothly and the flexibility of the polycarbonate skeleton (cyclohexanedimethanol-diphenyl carbonate copolymer skeleton) can be utilized. OCOO / N OH can be measured by a nuclear magnetic resonance (NMR) spectrometer.

[0044] The content N of the carbonate unit represented by the formula (3) OCOO The content N of the dicarboxylic acid unit represented by the formula (1) COOH Molar ratio of N COOH / N OCOO can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 0.010 or more and less than 1.0, more preferably 0.05 or more and 0.6 or less, and even more preferably 0.05 or more and 0.3 or less. When the molar ratio is within the above range, the flexibility of the polycarbonate skeleton (cyclohexanedimethanol-diphenyl carbonate copolymer skeleton) can be utilized, and crosslinking with the thermosetting resin can be sufficiently performed, thereby improving the strength. The above molar ratio can be measured by a nuclear magnetic resonance (NMR) device.

[0045] All structural units N constituting the curable resin of this embodiment all The molar ratio of the sum of the contents of dihydroxy units, dicarboxylic acid units, and carbonate units to OH +N COOH +N OCOO ) / N all The molar ratio (N OH +N COOH +N OCOO ) / N all The upper limit of the molar ratio (N OH +N COOH +N OCOO ) / N allWhen the molar ratio (N OH +N COOH +N OCOO ) / N all can be measured by a nuclear magnetic resonance (NMR) spectrometer.

[0046] From the viewpoint of further improving the dielectric properties, solvent solubility, bleed-out resistance, etc. of the curable resin, the ratio of the structural unit represented by formula (1) among all the structural units derived from the dicarboxylic acid compound in the curable resin is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. The upper limit of the ratio is not particularly limited, and may be, for example, 1.0, 0.98, or 0.96. From the same viewpoint, the ratio of the structural unit represented by formula (2) among all the structural units derived from the dihydroxy compound in the curable resin is preferably 0.10 or more, more preferably 0.20 or more, even more preferably 0.30 or more, and even more preferably 0.50 or more. The upper limit of the ratio is not particularly limited, and may be, for example, 1.0, 0.98, or 0.96. The proportion of the structural unit represented by the above formula (1) and the proportion of the structural unit represented by the above formula (2) can be measured by a nuclear magnetic resonance (NMR) spectrometer.

[0047] The content of the structural units derived from each monomer can be controlled by adjusting the amount (used amount) of each monomer in the production of the curable resin. In this case, it is preferable to use a monomer that is easily evaporated and easily leaks out of the system in more amount than a monomer that is difficult to evaporate, taking into consideration the leakage out of the system.

[0048] The molar ratio of the alicyclic diol unit represented by the formula (4) to the dihydroxy unit represented by the formula (2) ([alicyclic diol unit] / [dihydroxy unit]) can be appropriately set depending on the desired performance, and is not particularly limited, but is preferably 0.01 or more and 0.99 or less, more preferably 0.05 or more and 0.8 or less, and even more preferably 0.1 or more and 0.6 or less.

[0049] The number average molecular weight of the curable resin of the present embodiment is not particularly limited, but is preferably 5.00×10 2 Above 3.00 x 10 4 More preferably, it is 1.00×10 or less. 3 Above 2.00 x 10 4 More preferably, it is 3.00×10 or less. 3 Above 1.00 x 10 4 and even more preferably 3.00×10 3 Above 1.00 x 10 4 The number average molecular weight is 3.00×10 or less. 4 When the number average molecular weight is 3.00×10 or less, the solubility of the curable resin in the solvent tends to be improved. 4 The following embodiment can be suitably used for applications such as impregnating a filler (e.g., glass cloth) in a copper-clad laminate, or for applications such as dissolving in a solvent like unsaturated polyester. 4 If the content is equal to or less than this, there is a tendency that bleed-out (a phenomenon in which the resin does not react uniformly and the same composition gathers at a visible level) can be more reliably prevented from occurring when the resin is mixed with other curable resins such as maleimide resins and cured. On the other hand, the number average molecular weight of the curable resin is 5.00 × 10 2 When the molecular weight is equal to or greater than this, the polycarbonate skeleton tends to be sufficiently incorporated into the resin, and strength tends to be further improved. The number average molecular weight can be measured by gel permeation chromatography (GPC).

[0050] The glass transition temperature (Tg) of the curable resin is preferably 60° C. or less, more preferably 50° C. or less, and even more preferably 45° C. or less. When Tg is within the above range, the curable resin can provide even higher strength. Tg can be measured by the method described in the examples.

[0051] <Method of manufacturing hardening resin> One embodiment of the present invention relates to a method for producing a curable resin. The method for producing a curable resin according to the present embodiment includes the steps of: [ka] [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylenic triple bond, R 1 and R 2 are each independently a hydrogen atom or an alkyl group. A compound represented by the following formula (5) (hereinafter also referred to as a "dihydroxy compound having a siloxane skeleton"), [ka] [In the formula, R 2 is a divalent linking group containing a structural unit represented by the following formula (2a), R 5 and R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms.] [ka] [In the formula, R is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms which may have a substituent, and n is the number of repeating units.] A carbonate compound represented by the following formula (3A): [ka] [In the formula, R 5 and R 6 are each independently an alkyl group or an aryl group. The present invention relates to a method for producing a curable resin, comprising the step of reacting (hereinafter referred to as the "reaction step")

[0052] The dicarboxylic acid unit represented by the above formula (1) is derived from the dicarboxylic acid compound represented by the above formula (1A) or an acid anhydride thereof. The dihydroxy unit represented by the above formula (2) is derived from a dihydroxy compound having a siloxane skeleton represented by the above formula (2A). The siloxane skeleton unit represented by the above formula (2a) is derived from a dihydroxy compound having a siloxane skeleton represented by the above formula (2A). The carbonate unit represented by the above formula (3) is derived from the carbonate compound represented by the above formula (3A).

[0053] In the method for producing the curable resin of this embodiment, the dicarboxylic acid compound or the dicarboxylic anhydride reacts and is incorporated into the resin, thereby generating the dicarboxylic acid unit of the curable resin of this embodiment. Similarly, the dihydroxy compound and the carbonate compound having a siloxane skeleton react and are incorporated into the resin, thereby generating the siloxane skeleton unit, the dihydroxy unit, and the carbonate unit of the curable resin of this embodiment. That is, the dicarboxylic acid unit, the dihydroxy unit, the siloxane skeleton unit, and the carbonate unit of the curable resin of this embodiment are structural units derived from the above-mentioned dicarboxylic acid compound or the dicarboxylic anhydride, the dihydroxy compound having a siloxane skeleton, and the carbonate compound, respectively. The siloxane skeleton unit can also be incorporated into the resin by blending a siloxane skeleton compound.

[0054] In formula (1A), a preferred embodiment of R is as explained in relation to R in formula (1) described in the section <Curable resin> above. Although not particularly limited, the dicarboxylic acid compound is preferably fumaric acid or maleic acid, and the acid anhydride of the dicarboxylic acid compound is preferably maleic anhydride.

[0055] In formula (1A), R 1 and R2 are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom.

[0056] In the above-mentioned method for producing a curable resin, a dihydroxy compound represented by the following formula (2A) may be reacted. [ka] [In the formula, R 3 and R 4 are each independently a hydrogen atom or an alkyl group.

[0057] In formula (2A), R 3 and R 4 are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom.

[0058] In formula (5), R 5 , and R 6 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a phenyl group, or a benzyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0059] R in Equation (5) 2 is a divalent group containing at least one of the structural units represented by the above formula (2a), and R and n in the above formula (2a) are as described above, and preferred embodiments are also as described above.

[0060] As the dihydroxy compound having the siloxane skeleton of formula (5), for example, carbinol-modified silicone can also be used. As the carbinol-modified silicone, any of those in which a hydroxyl group is introduced to the side chain of the siloxane structure, those in which a hydroxyl group is introduced to the terminal of the siloxane structure, and mixtures thereof may be used. Among these, carbinol-modified silicone in which a hydroxyl group is introduced to both terminals of the siloxane structure is more preferable. In addition, diol-modified silicone can also be used. As the diol-modified silicone, any of those in which a diol group is introduced to the side chain of the siloxane structure, those in which a diol group is introduced to the terminal of the siloxane structure, and mixtures thereof may be used. In addition, carboxy-modified silicone having a carboxy group in the molecular structure can be used. As the carboxy-modified silicone, any of those in which a carboxy group is introduced to the side chain of the siloxane structure, those in which a carboxy group is introduced to the terminal of the siloxane structure, and mixtures thereof may be used. Furthermore, phenol-modified silicone can also be used. The phenol-modified silicone may be one in which a phenolic hydroxyl group is introduced into the side chain of the siloxane structure, one in which a phenolic hydroxyl group is introduced into the terminal of the siloxane structure, or a mixture of these. The dihydroxy compound having the siloxane skeleton of formula (5) may be a commercially available product. For example, BY-16-201 (Dow Corning Toray Co., Ltd.) having hydroxyl groups at both ends, SF8427 (Dow Corning Toray Co., Ltd.) and SF8428 (Dow Corning Toray Co., Ltd.) having hydroxyl groups in the polyether at both ends, KF-6000 (Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups at both ends, KF-6001 (Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups at both ends, KF-6002 (Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups at both ends, and KF-6003 (Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups at both ends may be mentioned, but is not particularly limited thereto.

[0061] In formula (3A), R 5 and R 6are each independently an alkyl group or an aryl group, preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 carbon atoms (phenyl group), and even more preferably a phenyl group.

[0062] The carbonate compound is not particularly limited, but examples thereof include diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, and dicyclohexyl carbonate. The carbonate compound is preferably diphenyl carbonate and / or alkyl group-substituted diphenyl carbonate.

[0063] The above dicarboxylic acid compounds, dicarboxylic anhydrides, dihydroxy compounds having a siloxane skeleton, and carbonate compounds may be used alone or in combination of two or more.

[0064] In the method for producing the curable resin of this embodiment, a dicarboxylic acid compound represented by formula (1A) or its acid anhydride, a dihydroxy compound having a siloxane skeleton represented by formula (5), and a monomer, oligomer, or polymer other than the carbonate compound represented by formula (3A) may be added to the reaction system and incorporated into the curable resin. Examples of such compounds include dicarboxylic acid compounds other than the dicarboxylic acid compound represented by formula (1A) and their anhydrides, dihydroxy compounds other than the dihydroxy compound having a siloxane skeleton represented by formula (2A), monohydroxy compounds having an ethylenic double bond, and silicone oils having a carboxy group in the molecular structure. Examples of these compounds include those described in detail in the description of the curable resin of this embodiment, and may be used alone or in combination of two or more.

[0065] In the reaction step, the amounts (molar ratios) of the dicarboxylic acid compound or its acid anhydride, the dihydroxy compound having a siloxane skeleton, the carbonate compound, and the alicyclic diol compound are as described in the <Curable resin> section in relation to [dicarboxylic acid unit] / [dihydroxy unit], [carbonate unit] / [dihydroxy unit], [carbonate unit] / [dicarboxylic acid unit], and [alicyclic diol unit] / [dihydroxy unit]. The amount of each compound used may be increased by using the ease of evaporation of each compound (for example, the saturated vapor pressure at the reaction temperature) as an index.

[0066] In the total amount of compounds used in the method for producing a curable resin of this embodiment, the sum of the amounts of dicarboxylic acid compounds, dicarboxylic anhydrides, dihydroxy compounds having a siloxane skeleton, and carbonate compounds used is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more, in terms of molar ratio. The upper limit of the ratio is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96. By setting the ratio to 0.60 or more, it tends to be possible to produce a curable resin that is more excellent in solvent solubility, bleed-out resistance, etc.

[0067] From the viewpoint of obtaining a curable resin having even more excellent solvent solubility, bleed-out resistance, etc., the ratio of the amount of the dicarboxylic acid compound represented by formula (1A) and its anhydride among all the compounds having two carboxy groups and their anhydrides used in the production method of this embodiment is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. The upper limit of this ratio is not particularly limited, and may be, for example, 1.0, 0.98, or 0.96. From the same viewpoint, the ratio of the amount of the dihydroxy compound having a siloxane skeleton represented by formula (5) used in the production method of this embodiment to all the compounds having two hydroxy groups is preferably 0.10 or more, more preferably 0.20 or more, even more preferably 0.30 or more, and even more preferably 0.50 or more. The upper limit of this ratio is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96.

[0068] In the reaction step, it is preferable to react a dihydroxy compound having a siloxane skeleton with a carbonate compound (hereinafter referred to as the "first reaction"), and then react a dicarboxylic acid compound or its acid anhydride (hereinafter referred to as the "second reaction").

[0069] The temperature of the first reaction is preferably 100 to 290°C, more preferably 130 to 280°C, and further preferably 160 to 260°C.

[0070] The pressure in the first reaction is preferably 50 kPa or less, more preferably 10 kPa or less, and further preferably 1 kPa or less.

[0071] The first reaction is preferably carried out in the presence of an inert gas, such as nitrogen gas or argon gas.

[0072] The first reaction is preferably carried out in the presence of a catalyst. Examples of the catalyst include catalysts generally used in the synthesis of polycarbonates or polyesters. Specific examples include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and salts of titanium, tin, zinc, zirconium, and / or lead. It is also possible to use a basic compound such as a basic boron compound or a basic phosphorus compound in combination with the alkali metal compound and / or the alkaline earth metal compound as an auxiliary.

[0073] Examples of the alkali metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenyl borohydride, boron phenylide, and boron phenylide. Examples of such compounds include potassium, lithium phenylborate, cesium phenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, sodium, potassium, lithium, and cesium alcoholates and phenolates, and the disodium, dipotassium, dilithium, and dicesium salts of bisphenol A.

[0074] Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds.Specific examples include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

[0075] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and their salts, amines, etc. Specific examples include quaternary ammonium hydroxides having an alkyl group and / or an aryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines, such as diethylamine and dibutylamine; primary amines, such as propylamine and butylamine; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; and bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0076] Titanium salts include, for example, tetramethyl titanate, tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraisobutyl titanate, and tetraphenyl titanate.

[0077] Examples of tin salts include tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin oxide, dibutyltin dilaurate, dibutyltin dimethoxide, and dibutyltin diacetate.

[0078] Zinc salts include, for example, zinc acetate, zinc benzoate, and zinc 2-ethylhexanoate.

[0079] Examples of zirconium salts include zirconium acetylacetonate, zirconium oxyacetate, and zirconium tetrabutoxide.

[0080] Lead salts include, for example, lead(II) acetate and lead(IV) acetate.

[0081] In addition, examples of basic boron compounds that can be used in combination with the alkali metal compound and / or alkaline earth metal compound include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, and butyltriphenyl boron, etc.

[0082] Examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0083] Other catalysts commonly used in the synthesis of polycarbonates and polyesters include antimony compounds such as diantimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; manganese compounds, and the like, as well as the catalysts disclosed in U.S. Pat. Nos. 4,025,492, 4,136,089, 4,176,224, 4,238,593, and 4,208,527, and RE Wilfong, Journal of Polymer Science, 54, 385, (1961), and the like.

[0084] The temperature of the second reaction is preferably 80 to 290°C, more preferably 120 to 270°C, and further preferably 150 to 250°C.

[0085] The pressure in the second reaction is preferably 100 kPa or less, more preferably 50 kPa or less, and further preferably 30 kPa or less.

[0086] The second reaction is preferably carried out in the presence of an inert gas, such as nitrogen gas or argon gas.

[0087] The second reaction is preferably carried out in the presence of a catalyst. Examples of the catalyst include those exemplified as the catalyst for the first reaction. It is preferable to use the catalyst used in the first reaction as it is in the second reaction. The catalyst may be added again.

[0088] The manufacturing method of this embodiment may be appropriately referred to "Polyester Resin Handbook" (by Eiichiro Takiyama, published by Nikkan Kogyo Shimbun Ltd.).

[0089] In addition to the above-mentioned manufacturing method, the curable resin of this embodiment may be manufactured by a method of reacting at least one of a dicarboxylic acid compound and a dicarboxylic anhydride with a polycarbonate diol. The polycarbonate diol used is not particularly limited as long as it contains a carbonate bond and has hydroxyl groups at both ends, and may be a conventionally known commercially available polycarbonate diol. The reaction conditions and the catalyst that may be used may be the same as those of the above-mentioned second reaction.

[0090] <Resin composition> One embodiment of the present invention relates to a resin composition comprising the above-mentioned curable resin. The resin composition of the present embodiment may further comprise another component.

[0091] Other components that may be contained in the resin composition of the present embodiment include, for example, epoxy resins, cyanate ester compounds, maleimide compounds, BT resins, compounds having a polymerizable unsaturated group, compounds having an ester structure derived from a phenol group and an aromatic carboxylic acid group, modified silicone oils, heat stabilizers, antioxidants, curing agents, and curing accelerators. The above-mentioned components may be used alone or in combination of two or more.

[0092] Examples of epoxy resins include phenol phenyl aralkyl novolac type epoxy resins, phenol biphenyl aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, anthraquinone type epoxy resins, polyoxynaphthylene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, trifunctional phenol type epoxy resins, tetrafunctional phenol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, aralkyl novolac type epoxy resins, alicyclic epoxy resins, polyol type epoxy resins, glycidyl amine, glycidyl ester, or butadiene double bond epoxidized compounds, compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin, and halides thereof. These may be used alone or in combination of two or more.

[0093] Examples of the cyanate ester compound include naphthol aralkyl type cyanate ester compounds, novolak type cyanate esters, phenol biphenyl aralkyl type cyanate ester compounds, bis(3,5-dimethyl 4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis( 4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, 2,2-bis(4-cyanatophenyl) propane, polymethylene polyphenyl polyisocyanate, m-tetramethylxylene diisocyanate, hydrogenated xylylene diisocyanate (1,3-bis(isocyanatomethyl) cyclohexane), isophorone diisocyanate, norbornene diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated methylene bisphenylene diisocyanate, 1,4-cyclohexane diisocyanate 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, trifunctional isocyanate having an isocyanurate ring obtained by trimerizing a bifunctional isocyanate compound, etc. These may be used alone or in combination of two or more.

[0094] Examples of the maleimide compound include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These may be used alone or in combination of two or more.

[0095] The BT resin is a prepolymer obtained by dissolving a cyanate ester compound and a maleimide compound in an organic solvent such as methyl ethyl ketone, N-methylpyrrolidin, dimethylformamide, dimethylacetamide, toluene, or xylene, heating and mixing the compounds. The cyanate ester compound and the maleimide compound may be the same as those described above. These may be used alone or in combination of two or more.

[0096] The compound having a polymerizable unsaturated group is not particularly limited, and examples thereof include vinyl compounds such as ethylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, tricyclodecanol (meth)acrylate, tricyclodecanol di(meth)acrylate, tricyclodecanol tri(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. Examples of the compounds having a polymerizable unsaturated group include (meth)acrylates of monohydric or polyhydric alcohols such as tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; allyl compounds such as allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, and diallyl maleate; benzocyclobutene resins; and (bis)maleimide resins. These compounds having a polymerizable unsaturated group can be used alone or in combination of two or more.

[0097] Examples of compounds having an ester structure derived from a phenol group and an aromatic carboxylic acid group include an active ester resin (I) using a compound selected from a compound (a1) having one phenolic hydroxyl group, a compound (a2) having two or more phenolic hydroxyl groups, and an aromatic polycarboxylic acid or its acid halide (a3) ​​as a reaction raw material, and an active ester resin (II) using a compound selected from a compound (b1) having two or more phenolic hydroxyl groups, an aromatic monocarboxylic acid or its acid halide (b2), and an aromatic polycarboxylic acid or its acid halide (b3) as a reaction raw material. Specific examples of these compounds can be found in International Publication No. WO 2020 / 003824. These may be used alone or in combination of two or more.

[0098] The modified silicone oil may have a chain-like siloxane skeleton and a group other than hydrogen or a hydrocarbon group in the molecular structure. The modified group may be, for example, an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, an alkoxy group, or a silanol group. These may be used alone or in combination of two or more.

[0099] Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, and the like. Examples of the phosphate include bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), benzene phosphonic acid dimethyl, benzene phosphonic acid diethyl, benzene phosphonic acid dipropyl, etc. These may be used alone or in combination of two or more.

[0100] Examples of the antioxidant include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Examples of such compounds include methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, etc. These compounds may be used alone or in combination of two or more.

[0101] Examples of the curing agent include polyfunctional phenol compounds such as phenol novolac, cresol novolac, and aminotriazine novolac resins; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; and acid anhydrides such as phthalic anhydride, pyromellitic anhydride, and maleic anhydride.

[0102] Examples of the curing accelerator include organometallic salts and organometallic complexes such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt bisacetylacetonate (II), cobalt trisacetylacetonate (III), zinc (II) acetylacetonate, and iron (III) acetylacetonate; imidazoles and derivatives thereof; organophosphorus compounds; secondary amines; tertiary amines; and quaternary ammonium salts. These may be used alone or in combination of two or more.

[0103] Of the above components, the resin composition of the present embodiment preferably contains a component that reacts with the curable resin of the present embodiment and cures together with it, such as (meth)acrylate, isocyanurate, maleimide compound, compound having a vinyl group, compound having an allyl group, etc.

[0104] The resin composition may further contain an initiator for initiating curing. Examples of the initiator include organic peroxide initiators that initiate curing by heating, and ultraviolet initiators that initiate curing by irradiation with light.

[0105] Examples of the organic peroxide initiator include ketone peroxides such as methyl ethyl ketone peroxide and acetyl acetone peroxide; diacyl peroxides such as benzoyl peroxide; peroxy esters such as t-butyl peroxybenzoate; hydroperoxides such as cumene hydroperoxide; and dialkyl peroxides such as dicumyl peroxide.

[0106] Examples of ultraviolet initiators include benzophenones such as benzophenone, benzil, and methyl orthobenzoyl benzoate; benzoin ethers such as benzoin alkyl ethers; acetophenones such as benzil dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and 1,1-dichloroacetophenone; and thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.

[0107] The resin composition may further contain a crosslinking agent other than the above. However, the curable resin of the present embodiment can be cured alone without using a crosslinking agent due to the presence of an ethylenic double bond and / or an acetylenic triple bond. Therefore, the resin composition of the present embodiment may not contain a crosslinking agent.

[0108] The content of the curable resin of this embodiment contained in the resin composition may be, for example, 1.0 part by mass or more with respect to 100 parts by mass of the resin component (resin and a component that cures together with the resin; synonymous with the solid component). For example, when the curable resin of this embodiment is added to a resin composition as a compatibilizer, the content of the curable resin of this embodiment may be, for example, 1.0 parts by mass or more and 10 parts by mass or less, or 3.0 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the resin component.

[0109] Alternatively, the content of the curable resin of the present embodiment contained in the resin composition may be, for example, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more, relative to 100 parts by mass of the resin component. When the content of the curable resin of the present embodiment is within the above range, a resin composition having even better flame retardancy tends to be obtained. In addition, the cured product of such a resin composition tends to have excellent flexibility as well as high strength (for example, bending strength, tensile strength, or impact strength) and low warpage performance. The upper limit of the content of the curable resin of this embodiment contained in the resin composition is not particularly limited, and may be 100 parts by mass, 99 parts by mass, 95 parts by mass, 90 parts by mass, or 80 parts by mass per 100 parts by mass of the resin component. The content of components other than the curable resin of this embodiment contained in the resin composition may be appropriately adjusted so long as the content of the curable resin of this embodiment in the resin composition falls within the above-mentioned range.

[0110] The resin composition may further contain a reinforcing base material or a filler such as an inorganic filler.

[0111] The inorganic filler is not particularly limited as long as it is one that is commonly used in the art.Specific examples of the inorganic filler include silicas such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide is heat-treated to remove a part of the crystal water), magnesium hydroxide, and metal hydroxides such as boehmite; nitride compounds such as aluminum nitride and boron nitride; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, glass short fibers (glass fine powders such as E glass and D glass), hollow glass, spherical glass, titanium oxide, silicone rubber, and silicone composite powder.

[0112] Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven cloth, aramid paper, aramid cloth, glass mat, and glass roving cloth.

[0113] The fillers may be used alone or in combination of two or more.

[0114] The content of the filler in the resin composition is not particularly limited and is, for example, 1 to 2000 parts by mass relative to 100 parts by mass of the resin component. The content of the filler can be appropriately changed depending on the application of the resin composition.

[0115] The resin composition may contain a silane coupling agent or a wetting and dispersing agent in addition to the filler. By containing these components, the dispersibility of the filler, particularly the inorganic filler, is improved, and the adhesive strength between the resin and the filler tends to be improved.

[0116] Silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic matter.Specific examples thereof include aminosilane-based silane coupling agents such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.; epoxysilane-based silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, etc.; vinylsilane-based silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, etc.; cationic silane-based silane coupling agents such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.; phenylsilane-based silane coupling agents; p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styrylmethyldimethoxysilane, p-styrylmethyldiethoxysilane, styrylsilane-based coupling agents such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc.

[0117] The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints.Specific examples of the wetting and dispersing agent include Disperbyk-110, 111, 180, 161, BYK-W996, W9010, W903, etc., manufactured by BYK-Chemie Japan Co., Ltd.

[0118] These silane coupling agents and wetting and dispersing agents may be used alone or in combination of two or more.

[0119] Furthermore, the resin composition of the present embodiment may contain a solvent as necessary. When the resin composition contains an organic solvent, the viscosity during preparation of the resin composition tends to decrease, and the handleability tends to improve. The solvent is not particularly limited as long as it can dissolve at least one component in the resin composition. Specifically, for example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol methyl ether and its acetate, etc. may be mentioned. The solvent may be used alone or in combination of two or more.

[0120] <Cured product> One embodiment of the present invention relates to a cured product of the above-mentioned curable resin or a cured product of the above-mentioned resin composition. The cured product of this embodiment is a cured product containing the curable resin of this embodiment, and therefore has excellent flame retardancy. In addition, the cured product of this embodiment tends to have excellent flexibility, high strength (e.g., bending strength, tensile strength, or impact strength) and low warpage performance.

[0121] The method for curing the curable resin or resin composition of the present embodiment is not particularly limited and may be appropriately selected depending on the type of resin. Examples of the curing method include heat curing and photocuring. When the resin composition is cured, it is preferable that the resin composition is first dissolved in a solvent, mixed, and dried so that each component is uniformly mixed, and then cured.

[0122] <Application> The curable resin, resin composition, and their cured products of the present embodiment can be used, for example, in electronic materials.Specific examples include electronic components, semiconductor sealing materials, molded resins, rigid substrates, prepregs, laminates, resin-coated copper foils, circuit boards, underfill materials, and build-up films.Other uses include fiber-reinforced composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, either alone or together with additives such as unsaturated polyesters and epoxy resins.

[0123] The fiber-reinforced composite material contains the resin composition of the present embodiment and reinforcing fibers, and can be cured to produce a fiber-reinforced molded product. The reinforcing fibers are not particularly limited, and examples thereof include glass fibers, carbon fibers, boron fibers, and aramid fibers. The semiconductor encapsulation material contains the resin composition of the present embodiment and an inorganic filler, and is used in the manufacture of semiconductor devices. As the inorganic filler, the above-mentioned materials can be used.

[0124] The prepreg includes a substrate and a resin composition impregnated or applied to the substrate. The method for producing the prepreg can be performed according to a conventional method and is not particularly limited. For example, the prepreg can be produced by impregnating or applying the resin composition to the substrate, and then semi-curing (B-stage) the substrate by heating in a dryer at 100 to 200°C for 1 to 30 minutes. The substrate is not particularly limited, and known materials used in various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Specific examples of fibers constituting the substrate are not particularly limited, and include glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; inorganic fibers other than glass such as quartz; wholly aromatic polyamides such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.) and copolyparaphenylene-3,4'-oxydiphenylene-terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products Co., Ltd.); polyesters such as 2,6-hydroxynaphthoic acid-parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.) and Zexion (registered trademark, manufactured by KB Seiren); organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide. These base materials may be used alone or in combination of two or more kinds.

[0125] The laminate is a laminate containing at least a prepreg. The laminate can be obtained, for example, by combining the prepreg and another layer and laminating and molding it. The other layer is not particularly limited, but may be, for example, a wiring board for an inner layer prepared separately.

[0126] The circuit board includes a laminate and a metal foil disposed on one or both sides of the laminate. The circuit board is, for example, a copper foil-clad laminate obtained by laminating the above prepreg and copper foil and curing the laminate. The copper foil used is not particularly limited as long as it is used for circuit boards, but known copper foils such as rolled copper foil and electrolytic copper foil are preferred.

[0127] The build-up film includes a cured product of a resin composition and a substrate film. "Build-up" refers to the production of a multi-layer printed wiring board by laminating prepregs or resin sheets and repeating processes such as drilling holes and forming wiring for each layer.

[0128] Further effects of this embodiment are expected to include, for example, low thermal expansion, crack prevention, good color tone, solvent solubility, and suppression of separation of resins during curing. EXAMPLES

[0129] The present invention will be described in more detail below using examples and comparative examples, but the technical scope of the present invention is not limited to these.

[0130] <Measurement method> [Glass transition temperature] Using a DSC 7000X (Hitachi High-Tech Science Corporation), approximately 10 mg of the sample was placed in an aluminum sealed container and measurements were performed in a nitrogen gas (30 ml / min) flow at a heating rate of 20°C / min. The temperature at the midpoint of the region where discontinuities appeared in the baseline (where the specific heat was halved) was taken as the glass transition temperature (Tg).

[0131] [Flame retardant] To evaluate flame retardancy, the oxygen index was measured in accordance with the oxygen index of Fire and Disaster Prevention No. 50. The converted combustion rate (%) was calculated according to the following conditions. The smaller this value, the better the flame retardancy. The converted combustion rate (%) was measured according to the following conditions. Fire Service Act Oxygen Index Test method: Compliant with Fire Prevention No. 50 oxygen index The Fire Service Act oxygen index is calculated by calculating the combustion rate at each oxygen concentration and determining when the combustion rate reaches equilibrium. The roller is the maximum combustion rate (%), and the point where the conversion combustion rate is 50% is the oxygen of the material. The index was used. Measurement items: Maximum burning rate, converted burning rate Burn rate (%) = 100 x (sample amount [M1] - remaining amount [M2]) / sample amount [M1] *Initial sample mass: M1 (g) *Remaining amount after burning: M2(g) Converted burn rate (%) = 100 x (burn rate (%) / maximum burn rate (%)) Sample shape: Sheet Sample cell: outer diameter 20 mm, depth 2 mm, thickness 1 mm (cup-shaped) Total flow rate: 11.4L / min Flame application method: 20mm flame for up to 120 seconds (check for ignition every 15 seconds) OI increase / decrease: 0.5%~1% Conditioning: (20±2)℃ and (65±5)%RH for more than 24 hours Test environment: 20~22℃, 45~54%RH, 1015~1018hPa Measuring device: Candle combustion tester DC type (manufactured by Toyo Seiki Seisakusho Co., Ltd.)

[0132] <Production of Curable Resin> [Example 1] 105g of carbinol-modified silicone (KF-6000, Shin-Etsu Chemical Co., Ltd.), 146g of 1,4-cyclohexanedimethanol, 216g of diphenyl carbonate, and 0.014g of titanium (IV) tetrabutoxide were placed in a 500ml separable flask, and while stirring, the temperature was gradually increased and the pressure was gradually reduced under nitrogen flow, and polymerization was finally performed at 230°C and 0.1kPa or less. Then, the mixture was air-cooled until the resin temperature decreased to room temperature. After air-cooling, 11g of maleic anhydride was added, and the mixture was heated to 200°C under nitrogen flow. After waiting for water to stop distilling, the pressure was gradually reduced to 13kPa, and the pressure was maintained for about 30 minutes, and resin A was extracted. The number average molecular weight of resin A was 5000, and the Tg of resin A before curing was -5°C.

[0133] [Comparative Example 1] 137g of 1,4-cyclohexanedimethanol, 183g of diphenyl carbonate, and 0.0097g of titanium (IV) tetrabutoxide were placed in a 500ml separable flask, and while stirring, the temperature was gradually increased and the pressure was gradually reduced under a nitrogen flow, and polymerization was finally carried out at 230°C and 0.1kPa or less. After that, the mixture was air-cooled until the resin temperature decreased to room temperature. After air-cooling, 9.3g of maleic anhydride was added, and the mixture was heated to 200°C under a nitrogen flow. After waiting for water to stop distilling, the pressure was gradually reduced to 13kPa, and this was maintained for about 30 minutes, and resin B was extracted. The number average molecular weight of resin B was 5000, and the Tg of resin B before curing was 45°C.

[0134] [Table 1]

[0135] [Comparative Example 2] 31.5g of carbinol-modified silicone (KF-6000, Shin-Etsu Chemical Co., Ltd.), 6.6g of maleic anhydride, and 4.2g of ethylene glycol were placed in a 500ml separable flask, and 0.06g of titanium (IV) tetrabutoxide and 0.08g of germanium oxide were further added, and the temperature was raised to 180°C while stirring under a nitrogen flow. After confirming that no water was distilled off, 118.8g of maleic anhydride and 75.4g of ethylene glycol were gradually added in 10 portions. After the entire amount was added, it was confirmed again that no water was distilled off, and the pressure was gradually reduced to 0.1kPa or less over 180 minutes. The temperature was then raised to 230°C over 30 minutes, and then resin C was extracted.

[0136] <Confirmation of resin phase separation> Resin A and resin C prepared as described above were each added to methyl ethyl ketone (MEK) so that the resin content was 50% by mass, and each was left at room temperature for one month. After that, the appearance of each resin in methyl ethyl ketone was confirmed, and phase separation was confirmed in resin C. This suggests that the carbinol-modified silicone has poor reactivity and compatibility with carboxylic acids and is unevenly distributed in the resin. On the other hand, no separation was observed in resin A even after being left for one month, and a uniform phase was maintained. This suggests that the inclusion of carbonates improves the reactivity and compatibility of the carbinol-modified silicone with carboxylic acids, and that it is relatively uniformly incorporated into the molecular chain.

Claims

1. A structural unit represented by the following formula (1): 【Chemistry 1】 [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylenic triple bond] A structural unit represented by the following formula (2): 【Chemistry 2】 [In the formula, R 2 is a divalent linking group. A structural unit represented by the following formula (2a): 【Chemistry 3】 [In the formula, each R is independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms which may have a substituent, and n is the number of repeating units.] A structural unit represented by the following formula (3): 【Chemistry 4】 A curable resin having the formula:

2. The curable resin according to claim 1, wherein the structural unit represented by the formula (3) is derived from at least one selected from the group consisting of a dialkyl carbonate, a diaryl carbonate, and an alkylaryl carbonate.

3. The structural unit represented by the formula (1) is derived from at least one selected from the group consisting of fumaric acid, maleic acid, and maleic anhydride. The curable resin according to claim 1 .

4. The glass transition temperature is 50° C. or less. The curable resin according to claim 1 .

5. The molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 0.01 or more and less than 1. The curable resin according to claim 1 .

6. The content ratio of the structural unit represented by the formula (2a) to the total amount of the structural unit represented by the formula (2) and the structural unit represented by the formula (2a) is 0.02 to 50 mol %. The curable resin according to claim 1 .

7. The molar ratio of the structural unit represented by the formula (1) to the total amount of the structural unit represented by the formula (2) and the structural unit represented by the formula (2a) is 0.010 or more and less than 1.

0. The curable resin according to claim 1 .

8. The molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (3) is 0.010 or more and less than 1.

0. The curable resin according to claim 1 .

9. the molar ratio of the sum of the contents of the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the structural unit represented by the formula (3) to all the structural units constituting the curable resin is 0.60 or more; The curable resin according to claim 1 .

10. Further containing an alicyclic skeleton as a structural unit The curable resin according to claim 1 .

11. Further containing a structural unit represented by the following formula (4): The curable resin according to claim 1 . 【Chemistry 5】

12. A cured product of the curable resin according to any one of claims 1 to 11.

13. A resin composition comprising the curable resin according to any one of claims 1 to 11.

14. The resin composition according to claim 13, wherein the amount of the curable resin per 100 parts by mass of the resin component contained in the resin composition is 1.0 part by mass or more.

15. The resin composition according to claim 13, which is for use as an electronic material.

16. An electronic component comprising the resin composition according to claim 13.

17. A fiber-reinforced composite material comprising the resin composition according to claim 13 and reinforcing fibers.

18. A fiber-reinforced molded product which is a cured product of the fiber-reinforced composite material according to claim 17.

19. A semiconductor encapsulating material comprising the resin composition according to claim 13 and an inorganic filler.

20. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 19.

21. A prepreg comprising a substrate and the resin composition according to claim 13 impregnated into or applied to the substrate.

22. A laminate comprising the prepreg of claim 21.

23. 23. A circuit board comprising the laminate of claim 22 and a metal foil disposed on one or both sides of the laminate.

24. A build-up film comprising a cured product of the resin composition according to claim 13 and a substrate film.

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