Curable resin, cured product thereof, and resin composition

Abstract

The present disclosure provides, inter alia: a curable resin having excellent heat resistance; a resin composition containing an unsaturated polyester carbonate resin and having an excellent performance balance between copper foil peeling strength and dielectric properties; a cured product of the resin composition. The curable resin according to the present disclosure has a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3), and has a weight average molecular weight (Mw) of 9000 or more and a functional group equivalent of 1000-5000. [In formula (1), R is a divalent group having an ethylenic double bond and / or an acetylenic triple bond.] [In formula (2), R2 is a C4-15 linear chain alkylene group.]

Description

Curable resins and their cured products, and resin compositions

[0001] This invention relates to curable resins and their cured products, as well as resin compositions, etc.

[0002] Polyester carbonate is used in a variety of applications due to its excellent mechanical strength, heat resistance, transparency, and other properties, and various types of polyester carbonate and their manufacturing methods have been reported.

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

[0004] Furthermore, Patent Document 2 discloses an unsaturated polyester resin composition characterized by comprising an unsaturated polyester (A), a polymerizable unsaturated monomer (B), a curing agent (C), and a reactive oligomer (D) obtained by reacting a polycarbonate diol with an unsaturated dibasic acid as essential components.

[0005] Japanese Patent Publication No. 2003-002959 Japanese Patent Publication No. 2010-013527

[0006] However, it has been found that conventional unsaturated polyester carbonates have room for improvement in terms of heat resistance, and furthermore, that the resin compositions and cured products obtained using them have room for improvement in terms of the balance between copper foil peel strength and dielectric properties.

[0007] The present invention has been made in view of the above problems. Specifically, the present invention aims to provide a curable resin (unsaturated polyester carbonate resin) with excellent heat resistance, and a resin composition and its cured product, etc., that contain the unsaturated polyester carbonate resin and have an excellent balance of copper foil peel strength and dielectric properties.

[0008] The inventors of the present invention, after diligently studying to solve the above problems, have newly developed a curable resin containing a predetermined structural unit, and have found that the above problems can be solved by using this curable resin, thus completing the present invention. That is, the present invention provides various specific embodiments as shown below.

[0009] [1] A structural unit represented by the following formula (1), [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylene triple bond] A structural unit represented by the following formula (2), [In the formula, R ２ This is a linear alkylene group having 4 to 15 carbon atoms. The structural unit is represented by the following formula (3), A curable resin having a weight-average molecular weight (Mw) of 9,000 or more and a functional group equivalent of 1,000 or more and 5,000 or less. [2] The curable resin according to [1], wherein the structural unit represented by formula (1) is derived from at least one selected from the group consisting of fumaric acid, maleic acid, and maleic anhydride. [3] The curable resin according to [1] or [2], wherein the structural unit represented by formula (2) is derived from at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, and 1,15-pentadecanediol. [4] A curable resin according to any one of [1] to [3], wherein the glass transition temperature is 30°C or lower. [5] A curable resin according to any one of [1] to [4], wherein the molar ratio of structural units represented by formula (1) to structural units represented by formula (2) is 0.02 or more and less than 0.5. [6] A curable resin according to any one of [1] to [5], wherein the molar ratio of structural units represented by formula (3) to structural units represented by formula (2) is 0.5 or more and less than 1. [7] A curable resin according to any one of [1] to [6], wherein the molar ratio of the sum of structural units represented by formula (1), structural units represented by formula (2), and structural units represented by formula (3) to all structural units constituting the curable resin is 0.6 or more. [8] A cured product of a curable resin according to any one of [1] to [7]. [9] A resin composition containing a curable resin according to any one of [1] to [7].

[10] The resin composition according to [9], 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.

[0010] According to the present invention, it is possible to provide a curable resin (unsaturated polyester carbonate resin) with excellent heat resistance, and also to provide a resin composition and its cured product, etc., containing the unsaturated polyester carbonate resin, which has an excellent balance between copper foil peel strength and dielectric properties.

[0011] The embodiments of the present invention will be described in detail below, but the present invention is not limited thereto, and various modifications are possible without departing from its essence. In this specification, for example, the notation of a numerical range such as "1 to 100" includes both the lower limit "1" and the upper limit "100". The same applies to the notation of other numerical ranges.

[0012] <Curable Resin> The curable resin according to this embodiment comprises a structural unit represented by the following formula (1) (hereinafter also referred to as a "dicarboxylic acid unit"), [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylene triple bond] The structural unit represented by the following formula (2) (hereinafter also referred to as the "linear alkylenedihydroxy unit"), [In the formula, R ２ This is a linear alkylene group having 4 to 15 carbon atoms. The structural unit represented by the following formula (3) (hereinafter also called the "carbonate unit") is, This invention relates to a curable resin having a weight-average molecular weight (Mw) of 9,000 or more, and a functional group equivalent of 1,000 to 5,000.

[0013] The order in which dicarboxylic acid units, linear alkylenedihydroxy units, and carbonate units are bonded in the curable resin is not particularly limited, but it is preferable that the dicarboxylic acid units and carbonate units are adjacent to the linear alkylenedihydroxy units.

[0014] Furthermore, the terminal oxygen atoms of these units are shared with the terminal oxygen atoms of adjacent units. For example, when a dicarboxylic acid unit and a linear alkylenedihydroxy unit are adjacent, the terminal oxygen atoms of both units are shared, forming the ester bond shown below.

[0015] Furthermore, when a carbonate unit and a linear alkylenedihydroxy unit are adjacent, the oxygen atoms at the ends of both units are shared, forming the carbonate bond described below.

[0016] The curable resin of this embodiment may be a random copolymer of dicarboxylic acid units, linear alkylenedihydroxy units, and carbonate units, wherein the copolymer of carbonate units and linear alkylenedihydroxy units may be a copolymer in which dicarboxylic acid units are linked, and the copolymer of dicarboxylic acid units and linear alkylenedihydroxy units may be a copolymer in which carbonate units are linked.

[0017] The curable resin according to this embodiment exhibits excellent heat resistance, and the resin composition and cured products obtained using it have an excellent balance between copper foil peel strength and dielectric properties. The reason for the improved heat resistance of the curable resin is assumed to be that setting an appropriate molecular weight strengthens the entanglement of the molecular chains and suppresses thermal decomposition from the ends. Furthermore, the reason for the increased copper foil peel strength of the resin composition and cured products obtained using it is assumed to be that the presence of a linear alkylenedihydroxy unit represented by formula (2) lowers the glass transition temperature of the curable resin, the linear alkylenedihydroxy unit represented by formula (2) itself has high flexibility, in addition to maintaining a relatively large balance of functional group equivalents to weight-average molecular weight, and the introduction of ethylenic double bonds and / or acetylene triple unsaturated bonds in the dicarboxylic acid unit represented by formula (1). Moreover, the reason for the good dielectric properties of the resin composition and cured products obtained using it is assumed to be that the overall structure is maintained as a small polarity skeleton of carbonate units and hydrocarbon units. However, the present invention is not limited in any way by these assumed reasons.

[0018] The curable resin according to this embodiment has dicarboxylic acid units, linear alkylenedihydroxy units, and carbonate units. The curable resin may be a thermosetting resin or a photocurable resin.

[0019] In formula (1), R is a divalent group having an ethylenic double bond and / or an acetylene triple bond, preferably a divalent group having an ethylenic double bond, more preferably a divalent hydrocarbon group having an ethylenic double bond, even more preferably a C2-C6 divalent hydrocarbon group having an ethylenic double bond, particularly preferably a C2-C4 divalent hydrocarbon group having an ethylenic double bond, and most preferably a C2 divalent hydrocarbon group having an ethylenic double bond. The dicarboxylic acid unit in which R is a C2 divalent hydrocarbon group having an ethylenic double bond is preferably derived from at least one selected from the group consisting of fumaric acid, maleic acid, and maleic anhydride.

[0020] When R in formula (1) has an ethylenically unsaturated double bond, the isomer structure of R is not particularly limited. That is, the dicarboxylic acid unit represented by formula (1) may be in a cis configuration or a trans configuration.

[0021] When R in formula (1) has an aromatic ring, the isomer structure of R is not particularly limited. That is, the dicarboxylic acid unit represented by formula (1) may be in an ortho configuration, a meta configuration, or a para configuration.

[0022] In this specification, "ethylenic double bond" means a carbon-carbon double bond that does not form an aromatic ring. In this specification, "acetylene triple bond" means a carbon-carbon triple bond that does not form an aromatic ring.

[0023] The curable resin according to this embodiment has an ethylenic double bond and / or an acetylene triple bond, and therefore can be cured on its own without the use of a crosslinking agent.

[0024] Conventional polyester carbonates lack crosslinking points (functional groups) with curable resins, and when added to curable resins with low compatibility, problems such as phase separation or delamination at the interface with the curable resin occur. The curable resin according to this embodiment, while containing ester and carbonate bonds, has at least one ethylenic double bond and one acetylene triple bond. Therefore, when mixed with another curable resin, it can react with the functional groups of the other curable resin and crosslink. As a result, the curable resin of this embodiment can be cured on its own, and even when mixed with another curable resin, phase separation and interfacial delamination are less likely to occur.

[0025] The curable resin according to this embodiment may have further structural units in addition to dicarboxylic acid units, linear alkylenedihydroxy units, and carbonate units. The further structural units are not particularly limited, but it is preferable that they do not adversely affect the heat resistance, dielectric properties, skeletal flexibility, and glass transition temperature of the curable resin. Examples of further structural units include structural units derived from compounds having a siloxane bond and two hydroxyl groups. Other examples of further structural units include structural units derived from dicarboxylic acid compounds that do not fall under formula (1), structural units derived from dihydroxy compounds that do not fall under formula (2), and monohydroxy compounds having an ethylenic double bond.

[0026] Such dicarboxylic acid compounds are not particularly limited, and 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 acid, 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, 2,5-thiophenedicarboxylic acid, glutaric acid, heptanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, and pentadecanedioic acid.

[0027] Furthermore, as the dicarboxylic acid compound, alkyl dicarboxylates such as methyl dicarboxylate and ethyl dicarboxylate can also be used for polymerization.

[0028] Furthermore, the dihydroxy compounds as mentioned above are not particularly limited, and examples thereof include aliphatic dihydroxy compounds having no structural unit represented by the above formula (1), alicyclic dihydroxy compounds, and aromatic dihydroxy compounds.

[0029] Examples of the aliphatic dihydroxy compounds having no structural unit represented by the above formula (1) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butenediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-2-methylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-dimethyl-1,5-pentanediol, and 2,2,4-trimethyl-1,3-pentanediol.

[0030] Alicyclic dihydroxy compounds are dihydroxy compounds having an alicyclic structure. The alicyclic structure may be a monocyclo ring, bicyclo ring, tricyclo ring, or polycyclo ring, which may have alkyl groups. The alkyl groups that the alicyclic structure may have are not particularly limited, but are preferably methyl or ethyl groups. The alicyclic structure may be a divalent alicyclic structure without alkyl groups. The alicyclic structure may have 0 to 6 alkyl groups, 0 to 4 alkyl groups, 0 to 3 alkyl groups, 0 to 2 alkyl groups, or 0 to 1 alkyl group. The alicyclic structure preferably contains a cycloalkane skeleton or a norbornane skeleton, more preferably a cyclohexane skeleton or a norbornane skeleton, even more preferably a cyclohexane ring or a norbornane skeleton, and particularly preferably a cyclohexane ring or a decahydro-1,4:5,8-dimethanonaphthalene skeleton. When the alicyclic structure includes a cycloalkane skeleton, a cyclohexane skeleton, a cyclohexane ring, a norbornane skeleton, a norbornane skeleton, and / or a decahydro-1,4:5,8-dimethanonaphthalene skeleton, the groups bonded to the alicyclic structure may be bonded to any part of the skeleton or ring, or to another cyclo ring further bonded to the skeleton. According to this embodiment, the dielectric properties of the curable resin tend to be further improved. In this specification, "cycloalkane skeleton" means a skeleton selected from the group consisting of a skeleton containing a cycloalkane and a skeleton in which the single bonds in the skeleton are replaced with unsaturated bonds. A cycloalkane skeleton includes, for example, a cycloalkane skeleton and a cycloalkene skeleton. A "cyclohexane skeleton" means a skeleton selected from the group consisting of a skeleton containing cyclohexane and a skeleton in which the single bonds in the skeleton are replaced with unsaturated bonds. Therefore, a cyclohexane skeleton includes, for example, a cyclohexane skeleton and a cyclohexene skeleton. Furthermore, in this specification, "norbornane-based skeleton" means a skeleton selected from the group consisting of skeletons containing norbornane (bicyclo[2.2.1]heptane) and skeletons in which the single bonds in said skeleton are replaced with unsaturated bonds.Therefore, norbornane skeletons include, for example, norbornane skeletons and norbornene skeletons.

[0031] Examples of aromatic dihydroxy compounds include hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, xylylene glycol, 4,4'-dihydroxydiphenylbenzophenone, and bisphenols. 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-dibromophenyl)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, and 1,1-bis(4-hydroxyphenyl)-2-ethylhexane Examples include 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 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'-dihydroxydiphenylsulfone, 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, and 4,4'-(propane-2,2-diyl)bis(2-allylphenol).

[0032] Furthermore, as aromatic dihydroxy compounds, dihydroxy compounds having an ether group bonded to an aromatic group such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 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-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene Fluorene (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-( Examples of dihydroxy compounds having a fluorene ring include 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] In equation (2), R ２ R is a linear alkylene group having 4 to 15 carbon atoms. ２The linear alkylene group is preferably a linear alkylene group having 4 to 12 carbon atoms, more preferably a linear alkylene group having 5 to 12 carbon atoms, and even more preferably a linear alkylene group having 6 to 12 carbon atoms. The linear alkylenedihydroxy unit represented by formula (2) is preferably derived from at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, and 1,15-pentadecanediol.

[0034] Examples of monohydroxy compounds having an ethylenic double bond include hydroxyl group-containing (meth)acrylic acid esters, specifically 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropanedi (meth)acrylate, pentaerythritol tri(meth)acrylate, and the like.

[0035] The structural unit represented by formula (3) is preferably derived from at least one selected from the group consisting of dialkyl carbonates, diaryl carbonates, and alkylaryl carbonates. Specific examples include, for example, 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-substituted diphenyl carbonate, but is not particularly limited to these.

[0036] Furthermore, the curable resin may include, as a partial structure, a structure derived from a silicone oil having a hydroxyl group in its molecular structure, and a structure derived from a silicone oil having a carboxyl group in its molecular structure.

[0037] As silicone oils having hydroxyl groups in their molecular structure, commercially available products can be used, for example, "KF-6001" (functional group equivalent 900) and "KF-6002" (functional group equivalent 1600), which have hydroxyl groups at both ends; "X-22-1821" (functional group equivalent 1470), which has phenolic hydroxyl groups at both ends (all manufactured by Shin-Etsu Chemical Co., Ltd.); "BY-16-752A" (functional group equivalent 1500) (both manufactured by Toray Dow Corning Co., Ltd.); and "X-22-170BX" (functional group equivalent 2800), "X-22-170DX" (functional group equivalent 4670), and "X-22-176DX" (functional group equivalent 1600), which have a hydroxyl group at one end. Examples include "X-22-176F" (functional group equivalent 6300) (both manufactured by Shin-Etsu Chemical Co., Ltd.), "X-22-4039" (functional group equivalent 970) and "X-22-4015" (functional group equivalent 1870) (both manufactured by Shin-Etsu Chemical Co., Ltd.) which have hydroxyl groups in the side chain, "SF8427" (functional group equivalent 930, manufactured by Toray Dow Corning Co., Ltd.) and "X-22-4952" (functional group equivalent 1100, manufactured by Shin-Etsu Chemical Co., Ltd.) which have hydroxyl groups in the polyether at both ends; and "FZ-2162" (functional group equivalent 750) and "SH3773M" (functional group equivalent 800) (both manufactured by Toray Dow Corning Co., Ltd.) which have hydroxyl groups in the side chain polyether.

[0038] Furthermore, commercially available silicone oils having carboxyl groups in their molecular structure can be used, for example, "X-22-162C" (functional group equivalent 2300) which has carboxyl groups at both ends, "X-22-3710" (functional group equivalent 1450) which has a carboxyl group at one end, and "X-22-3701E" (functional group equivalent 4000) which has a carboxyl group in its side chain (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0039] By introducing the above-described structural units and / or substructures into the curable resin of this embodiment, it is possible to improve or impart properties such as flexibility, strength, heat resistance, flame retardancy, color tone, solvent solubility, low curing shrinkage, low thermal expansion, good moldability, metal adhesion, glass adhesion, substrate adhesion, low-temperature curability, good processability, chemical resistance, and compatibility.

[0040] The terminal groups in the curable resin of the present embodiment are not particularly limited, and may be, for example, carboxy groups and / or hydroxy groups. According to the embodiment having a terminal blocking agent, the dielectric properties of the curable resin tend to be more excellent, and compatibility tends to be improved when the glass transition temperature is low or the polarity is high. In addition, when there are many carboxy groups and / or hydroxy groups, compatibility with metallic materials (Al, Ni, Ag, Au, Sn, Ti, Mo, SUS, etc.), semiconductor / inorganic materials (Si, GaAs, GaN, ITO, SiO ２ , Si ３ N ４ etc.), resin / polymer materials (PI, PC, PP, PE, epoxy, fluororesin, etc.), ceramic materials (Al ２ O ３ , AlN, Si ３ N ４ , BaTiO ３ , ZrO ２ etc.), carbon-based materials (carbon fiber reinforced plastic CFRP, etc.) and the like tends to be improved. Adjustment can be made depending on the purpose. The terminal carboxy group blocking agent is not particularly limited as long as it is a compound having a group that reacts with a carboxy group, and examples thereof include carbodiimide compounds such as monocarbodiimide and polycarbodiimide compounds, oxazoline compounds, and one-terminal diols. Examples of the terminal hydroxy group blocking agent include diphenyl carbonate and monocarboxylic acids. Furthermore, when a copolymer in which a copolymer of carbonate units and linear alkylene dihydroxy units is linked to dicarboxylic acid units is polymerized and then an ethylenic double bond / triple bond is introduced, a large number of carboxy groups and / or hydroxy groups are present at terminals, resulting in good reactivity. On the other hand, when a copolymer of dicarboxylic acid units and linear alkylene dihydroxy units is polymerized and then carbonate units are introduced, the terminals become groups other than carboxy groups and / or hydroxy groups, which tends to result in good dielectric properties.

[0041] The molar ratio of dicarboxylic acid units represented by formula (1) to linear alkylenedihydroxy units represented by formula (2) ([dicarboxylic acid units] / [linear alkylenedihydroxy units]) can be appropriately set according to the desired performance and is not particularly limited, but is preferably 0.02 or more and less than 0.5, more preferably 0.05 or more and 0.4 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 can be utilized and crosslinking with thermosetting resins can be sufficiently performed, thereby improving compatibility and heat resistance. The molar ratio can be measured by nuclear magnetic resonance (NMR) spectrometer.

[0042] The molar ratio of carbonate units represented by formula (3) to linear alkylenedihydroxy units represented by formula (2) ([carbonate units] / [linear alkylenedihydroxy units]) can be appropriately set according to the desired performance and is not particularly limited, but is preferably 0.5 or more and less than 1, more preferably 0.5 or more and 0.95 or less, and even more preferably 0.8 or more and 0.95 or less. When the molar ratio is within the above range, the reaction proceeds suitably and the flexibility of the polycarbonate skeleton can be utilized. The molar ratio can be measured by nuclear magnetic resonance (NMR) spectrometer.

[0043] The molar ratio of carbonate units represented by formula (3) to dicarboxylic acid units represented by formula (1) ([carbonate units] / [dicarboxylic acid units]) can be appropriately set according to the desired performance and is not particularly limited, but is preferably 1 to 100, more preferably 2 to 50, and even more preferably 4 to 20. When the molar ratio is within the above range, the flexibility of the polycarbonate skeleton can be utilized and crosslinking with thermosetting resins can be sufficiently performed, thereby improving compatibility and heat resistance. The molar ratio can be measured by nuclear magnetic resonance (NMR) spectrometer.

[0044] The molar ratio of the total dicarboxylic acid units, linear alkylenedihydroxy units, and carbonate units to all structural units constituting the curable resin ([dicarboxylic acid units + linear alkylenedihydroxy units + carbonate units] / [total structural units]) can be appropriately set according to the desired performance and is not particularly limited, but is preferably 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.8 or higher, and preferably 0.9 or higher. The upper limit of the molar ratio is not particularly limited, but may be, for example, 1, 0.98, or 0.96. The molar ratio can be measured by nuclear magnetic resonance (NMR) spectrometer.

[0045] From the viewpoint of further improving the solvent solubility, bleed-out resistance, etc., of the curable resin, the proportion of structural units represented by formula (1) among all structural units derived from dicarboxylic acid compounds 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 this proportion is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96. From a similar viewpoint, the proportion of structural units represented by formula (2) among all structural units derived from dihydroxy compounds 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 this proportion is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96. The proportions of structural units represented by formula (1) and formula (2) can be measured by nuclear magnetic resonance (NMR).

[0046] Furthermore, the content of structural units derived from each monomer can be controlled by adjusting the amount of each monomer added (used) during the production of the curable resin. In this case, it is preferable to use more monomers that evaporate easily and tend to leak out of the system than monomers that do not evaporate easily, taking into account the leakage out of the system.

[0047] The weight-average molecular weight (Mw) of the curable resin in this embodiment is not particularly limited, but is preferably 9,000 or more, with an upper limit of less than 100,000 and 50,000 or less. In one embodiment, the weight-average molecular weight of the curable resin is 9,000 or more and 50,000 or less, preferably 9,000 or more and 30,000 or less, more preferably 9,000 or more and 25,000 or less, and even more preferably 9,000 or more and 20,000 or less. When the weight-average molecular weight (Mw) is below the above preferred upper limit, the solubility of the curable resin in solvents and its compatibility with thermosetting resins used for reinforcement are further improved. When mixed with other curable resins such as maleimide resin and cured, it tends to more reliably prevent bleed-out (a phenomenon in which the resin does not react uniformly and the same composition accumulates at a visually observable level). Therefore, embodiments in which the weight-average molecular weight (Mw) is below the above preferred upper limit can be suitably used in applications such as impregnation into fillers (e.g., glass cloth) such as copper-clad laminates, coating onto films, dissolving in another crosslinking agent, dissolving in a solvent like unsaturated polyester, and curing together with other thermosetting resins. Furthermore, if the weight-average molecular weight (Mw) of the curable resin is above the above preferred lower limit, the heat resistance (weight loss temperature) of the resin alone improves, which tends to reduce outgassing during curing and improve heat resistance. On the other hand, if the weight-average molecular weight (Mw) of the curable resin is 9,000 or more, the heat resistance tends to improve. The above weight-average molecular weight (Mw) can be measured by gel filtration chromatography (GPC).

[0048] The functional group equivalent of the curable resin in this embodiment is not particularly limited, but is preferably 1,000 to 5,000, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,000. If the functional group equivalent is greater than this range, compatibility and reactivity with other thermosetting resins such as maleimide decrease, bleed-out occurs when curing, and copper foil peel strength, chemical resistance, and electrical reliability tend to deteriorate. On the other hand, adhesion to metals other than copper foil, adhesion to glass, and adhesion to substrates tend to be improved.

[0049] In this specification, the functional group equivalent (g / eq) of the curable resin means the total amount (g) of the curable resin per equivalent (eq) of carbon-carbon unsaturated bonds possessed by R, a structural unit represented by formula (1). That is, the functional group equivalent (g / eq) of the curable resin = total amount of curable resin (g) / value expressed as 1 equivalent (eq) of carbon-carbon unsaturated bonds possessed by R, a structural unit represented by formula (1). To give a specific example, when synthesizing a reaction product of 404.2 g of curable resin (containing 4.81 g of by-product water (= 0.267 * 18.015)) by reacting 26.2 g (0.267 mol) of maleic anhydride, a starting compound having a dicarboxylic acid unit containing one equivalent (eq) of carbon-carbon unsaturated bond, with 378 g of diol, a starting compound containing a carbonate unit and a linear alkylenedihydroxy unit, the functional group equivalent of the curable resin is (378 g + 26.2 g - 4.81 g) / 0.267 eq = 1496 (g / eq). Furthermore, when maleic anhydride is used as the raw material compound for the structural unit represented by formula (1), the only carbon-carbon unsaturated bond in question is the ethylene group (-CH=CH-), and the functional group equivalent is calculated by considering only the ethylene group (-CH=CH-) as 1 molar equivalent (mol eq).

[0050] The glass transition temperature (Tg) of the curable resin is preferably 30°C or lower, more preferably 20°C or lower, and even more preferably 10°C or lower. When Tg is within the above range, the curable resin can have even greater flexibility. Tg can be measured by the method described in the examples.

[0051] <Method for producing curable resin> One embodiment of the present invention involves a dicarboxylic acid compound represented by the following formula (1A) or its acid anhydride, [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylene triple bond, R １ and R ２ Each is independently a hydrogen atom or an alkyl group. A linear alkylenedihydroxy compound represented by the following formula (2A) [In the formula, R ２ R is a linear alkylene group having 4 to 15 carbon atoms. ３ and R ４ Each is independently a hydrogen atom or an alkyl group. A carbonate compound represented by the following formula (3A) [In the formula, R ５ and R ６ The present invention relates to a method for producing a curable resin, which includes a step of reacting an alkyl group or an aryl group (hereinafter referred to as the "reaction step"), each of which is independently.

[0052] The dicarboxylic acid unit represented by formula (1) is derived from the dicarboxylic acid compound represented by formula (1A) or its acid anhydride. The linear alkylenedihydroxy unit represented by formula (2) is derived from the linear alkylenedihydroxy compound represented by formula (2A). The carbonate unit represented by formula (3) is derived from the carbonate compound represented by formula (3A).

[0053] In formula (1A), the preferred embodiment of R is as described in relation to R in formula (1) in the section on <curable resins> 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.

[0054] In equation (1A), R １ and R ２ Each of these is 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.

[0055] In equation (2A), R ２ A preferred embodiment is R of formula (2) described in the <Curable Resin> section above. ２ As explained in relation to, In equation (2A), R ３ and R ４ Each of these is 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] The linear alkylenedihydroxy compound represented by formula (2A) is not particularly limited, but is preferably at least one selected from the group consisting of, for example, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, and 1,15-pentadecanediol.

[0057] In equation (3A), R ５ and R ６ Each of these is 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 (phenyl group) having 6 carbon atoms, and even more preferably a phenyl group.

[0058] The carbonate compound represented by formula (3A) is not particularly limited, but examples 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-substituted diphenyl carbonate.

[0059] The above-mentioned dicarboxylic acid compounds, dicarboxylic acid anhydrides, linear alkylenedihydroxy compounds, and carbonate compounds may be used individually or in combination of two or more.

[0060] In the method for producing the curable resin of this embodiment, monomers, oligomers, or polymers other than the dicarboxylic acid compound represented by formula (1A) or its acid anhydride, the linear alkylenedihydroxy compound represented by formula (2A), and 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 linear alkylenedihydroxy compound represented by formula (2A), monohydroxy compounds having an ethylenic double bond, silicone oils having a hydroxyl group in their molecular structure, and silicone oils having a carboxyl group in their molecular structure. Examples of these compounds are those described in detail in the description of the curable resin of this embodiment, and they may be used individually or in combination of two or more.

[0061] The amounts (molar ratios) of dicarboxylic acid compounds or their acid anhydrides, linear alkylenedihydroxy compounds, and carbonate compounds used in the reaction process are as described in the <Curable Resin> section above, in relation to [dicarboxylic acid units] / [linear alkylenedihydroxy units], [carbonate units] / [linear alkylenedihydroxy units], and [carbonate units] / [dicarboxylic acid units]. Furthermore, the amount of each compound used may be increased based on its ease of evaporation (e.g., saturated vapor pressure at the reaction temperature), with the amount of the more easily evaporable compound being used being the indicator.

[0062] In the method for producing the curable resin of this embodiment, the sum of the amounts of dicarboxylic acid compounds, dicarboxylic acid anhydrides, linear alkylenedihydroxy compounds, and carbonate compounds used in the total amount of 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 molar ratio. The upper limit of the above ratio is not particularly limited, but for example, it may be 1.0, 0.98, or 0.96. By setting the above ratio to 0.60 or more, it tends to be possible to produce a curable resin with even better solvent solubility, bleed-out resistance, etc.

[0063] From the viewpoint of obtaining a curable resin with even better solvent solubility, bleed-out resistance, etc., the proportion of the dicarboxylic acid compound represented by formula (1A) and its anhydride used among all the compounds having two carboxyl groups and their anhydrides used in the manufacturing 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 proportion is not particularly limited, but for example it may be 1.0, 0.98, or 0.96. From a similar viewpoint, the proportion of the linear alkylenedihydroxy compound represented by formula (2A) used among all the compounds having two hydroxyl groups used in the manufacturing method of this embodiment 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 proportion is not particularly limited, but for example it may be 1.0, 0.98, or 0.96.

[0064] In the reaction process, it is preferable to react a linear alkylenedihydroxy compound 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"). This tends to prevent gelation and other issues.

[0065] The temperature of the first reaction is preferably 100 to 290°C, more preferably 150 to 280°C, and even more preferably 190 to 230°C. This allows for faster phenol leaching and an increased reaction rate, while also tending to minimize resin decomposition and raw material leakage.

[0066] The pressure of the first reaction is preferably 50 kPa or less, more preferably 10 kPa or less, and even more preferably 1 kPa or less. This allows for rapid phenol leaching and an increased reaction rate, while minimizing the leaching of raw materials.

[0067] The first reaction is preferably carried out in the presence of an inert gas. Examples of inert gases include nitrogen gas and argon gas.

[0068] The first reaction is preferably carried out in the presence of a catalyst. Examples of catalysts include those commonly used in the synthesis of polycarbonates or polyesters. Specifically, examples include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and salts of titanium, tin, zinc, zirconium, and / or lead. In addition, basic compounds such as basic boron compounds and basic phosphorus compounds can be used in combination with alkali metal compounds and / or alkaline earth metal compounds as auxiliary agents.

[0069] Examples of the alkali metal compounds mentioned above include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specifically, these include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, 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 phenylboron, and phenylboron. Examples include potassium, lithium borophenylamide, cesium borophenylamide, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate, sodium, potassium, lithium, cesium alcoholates and phenolates, and disodium, dipotassium, dilithium, and dicesium salts of bisphenol A.

[0070] Examples of the above-mentioned alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. Specifically, examples include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, 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.

[0071] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides and their salts, amines, etc. Specifically, these include quaternary ammonium hydroxides having alkyl and / or aryl groups 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; or ammonia, bases or basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0072] Examples of titanium salts include tetramethyl titanate, tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraisobutyl titanate, and tetraphenyl titanate.

[0073] 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.

[0074] Examples of zinc salts include zinc acetate, zinc benzoate, and zinc 2-ethylhexanoate.

[0075] Examples of zirconium salts include zirconium acetylacetonate, zirconium oxyacetate, and zirconium tetrabutoxide.

[0076] Examples of lead salts include lead(II) acetate and lead(IV) acetate.

[0077] Examples of basic boron compounds that can be used in combination with alkali metal compounds and / or alkaline earth metal compounds include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts of tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.

[0078] Examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0079] Other catalysts commonly used in the synthesis of polycarbonates and polyesters include antimony compounds such as antimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; manganese compounds; and catalysts disclosed in U.S. Patents No. 4,025,492, 4,136,089, 4,176,224, 4,238,593, and 4,208,527, as well as RE Wilfong, Journal of Polymer Science, 54, 385, (1961), etc.

[0080] The temperature of the second reaction is preferably 80 to 290°C, more preferably 120 to 230°C, and even more preferably 150 to 220°C. This allows for improved reaction rate while suppressing the leakage of raw materials and inhibiting resin decomposition and gelation.

[0081] The pressure of the second reaction is preferably 100 kPa or less, more preferably 50 kPa or less, and even more preferably 30 kPa or less. This can improve the reaction rate.

[0082] The second reaction is preferably carried out in the presence of an inert gas. Examples of inert gases include nitrogen gas and argon gas.

[0083] The second reaction is preferably carried out in the presence of a catalyst. Examples of catalysts include those exemplified as catalysts for the first reaction. It is preferable to use the same catalyst used in the first reaction in the second reaction. However, the catalyst may be added again.

[0084] The manufacturing method according to this embodiment may be appropriately referenced from the "Polyester Resin Handbook" (authored by Eiichiro Takiyama, published by Nikkan Kogyo Shimbun).

[0085] In addition to the manufacturing method described above, the curable resin of this embodiment may also be manufactured by reacting a polycarbonate diol with at least one of a dicarboxylic acid compound and a dicarboxylic acid anhydride. The polycarbonate diol used is not particularly limited as long as it is a compound containing a carbonate bond and a linear alkylenedihydroxy unit, with hydroxyl groups at both ends, and examples include conventionally known commercially available polycarbonate diols. The reaction conditions and the catalyst that may be used may be the same as those for the second reaction described above. Furthermore, in the manufacturing method including the first and second reactions described above, a polycarbonate diol may be used in addition to the linear alkylenedihydroxy compound represented by formula (2A). The polycarbonate diol used is not particularly limited as long as it is a compound containing a carbonate bond, with hydroxyl groups at both ends, and examples include conventionally known commercially available polycarbonate diols. With such an embodiment, there is a tendency to obtain a curable resin containing a large amount of carbonate units.

[0086] <Resin Composition> One embodiment of the present invention relates to a resin composition comprising the curable resin described above. The resin composition according to this embodiment may further contain other components.

[0087] Other components that the resin composition of this embodiment may contain include, for example, epoxy resins, cyanate ester compounds, maleimide compounds and their resins, allyl resins, vinyl resins, (meth)acrylic resins, phenyl resins, compounds having polymerizable unsaturated groups, polyphenylene ether compounds, compounds having ester structures derived from phenol groups and aromatic carboxylic acid groups, modified silicone oils, heat stabilizers, antioxidants, curing agents, and curing accelerators. The above components may be used individually or in combination of two or more.

[0088] Examples of epoxy resins include phenolphenylaralkyl novolac type epoxy resins, phenol biphenylaralkyl 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, compounds in which double bonds of glycidylamine, glycidyl esters, or butadiene are epoxidized, compounds obtained by the reaction of hydroxyl group-containing silicone resins with epichlorohydrin, and halides thereof. These may be used individually or in combination of two or more.

[0089] Examples of cyanate ester compounds include naphthol aralkyl type cyanate ester compounds, novolac 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( Examples include 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 bisphenyl diisocyanate, 1,4-cyclohexane diisocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, and trifunctional isocyanates having a triply modified isocyanurate ring of a bifunctional isocyanate compound. These may be used individually or in combination of two or more.

[0090] Suitable maleimide compounds include those used in technical fields such as FCCL (flexible substrates), semiconductor encapsulants, 2.5D / 3D packages, and insulating layers. Examples include bismaleimide, N-phenylmaleimide, and prepolymers of these maleimide compounds with amine compounds, but are not particularly limited to these. Suitable maleimide resins include so-called maleimide resins, specifically bismaleimide-triazine resins (BT resins), but are not particularly limited to these. These may be used individually or in combination of two or more. BT resin is obtained by dissolving a cyanate ester compound and a maleimide compound in a solvent-free solution or in an organic solvent such as methyl ethyl ketone, N-methylpyrrodrin, dimethylformamide, dimethylacetamide, toluene, or xylene, heating and mixing, and then prepolymerizing them. The cyanate ester compound and maleimide compound described above can be used. These may be used individually or in combination of two or more.

[0091] Suitable allyl resins include those used in technical fields such as printed circuit boards, semiconductor encapsulants, heat-resistant adhesives, sealants, and UV-curable resins. Examples include allyl ester resins, diallyl phthalate (DAP), triallyl isocyanurate (TAIC), and triallyl cyanurate (TAC), but the material is not particularly limited to these. These may be used individually or in combination of two or more.

[0092] Suitable vinyl resins include those used in technical fields such as resists, heat-resistant resist materials, substrate materials, semiconductor packaging, encapsulants, semiconductor encapsulants, and high-performance adhesives. Examples include vinyl ester resins, vinyl silane resins, and vinyl sulfone resins, but the material is not particularly limited to these. These may be used individually or in combination of two or more.

[0093] As the (meth)acrylic resin, those used in technical fields such as resists, adhesives, encapsulants, circuit boards, and flexible substrate materials can be suitably used, and examples include acrylic resin, methacrylic resin, and acrylic urethane resin, but are not particularly limited to these. These may be used individually or in combination of two or more.

[0094] Suitable norbornene resins can be those used in technical fields such as ABF substrates (build-up substrates) and FCCL (flexible substrates). For example, polynorbornene resin can be used, but the invention is not particularly limited to these. These can be used individually or in combination of two or more types.

[0095] Suitable phenyl resins include those used in technical fields such as semiconductor packaging materials, heat-resistant adhesives, circuit boards, semiconductor encapsulants, and high-temperature resistant adhesives. Examples include phenylsilane resins and phenyl epoxy resins, but the invention is not particularly limited to these. These may be used individually or in combination of two or more types.

[0096] Compounds having polymerizable unsaturated groups are not particularly limited, but include, for example, 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 include monohydric or polyhydric alcohol (meth)acrylates such as 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 resin; and (bis)maleimide resin. These polymerizable compounds having unsaturated groups can be used individually or in combination of two or more.

[0097] The polyphenylene ether compounds are not particularly limited, but examples include polyphenylene ether oligomers, styrene derivatives of polyphenylene ether oligomers, hydroxyl-terminated polyphenylene ether oligomers, methacrylate-terminated polyphenylene ether oligomers, and glycidyl ether-terminated polyphenylene ether oligomers. Examples of styrene derivatives of polyphenylene ether oligomers include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of hydroxyl-terminated polyphenylene ether oligomers include SA-90 and SA-120 manufactured by SABIC Corporation. Examples of methacrylate-terminated polyphenylene ether oligomers include SA-9000 manufactured by SABIC Corporation.

[0098] Examples of compounds having ester structures derived from phenolic groups and aromatic carboxylic acid groups include activated ester resins (I) using compounds selected from compounds having one phenolic hydroxyl group (a1), compounds having two or more phenolic hydroxyl groups (a2), and aromatic polycarboxylic acids or their acid halides (a3) ​​as reaction raw materials, and activated ester resins (II) using compounds selected from compounds having two or more phenolic hydroxyl groups (b1), aromatic monocarboxylic acids or their acid halides (b2), and aromatic polycarboxylic acids or their acid halides (b3) as reaction raw materials. Specific examples of these compounds can be found in International Publication No. 2020 / 003824. These may be used individually or in combination of two or more.

[0099] Modified silicone oils include those having a chain-like siloxane skeleton and containing groups other than hydrogen or hydrocarbon groups in their molecular structure. Examples of modifying groups include epoxy groups, amino groups, hydroxyl groups, methacrylic groups, mercapto groups, carboxyl groups, alkoxy groups, and silanol groups. These may be used individually or in combination of two or more.

[0100] Examples of heat stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and their esters. Specifically, 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. Examples include sphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, tetrakis(2,4-di-tert-butylphenyl) biphenylenediphosphinate, dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. These may be used individually or in combination of two or more.

[0101] Examples of antioxidants 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, and 1,3,5-tri Examples include methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tetrakis(2,4-di-tert-butylphenyl)biphenylenediphosphinate, and 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. These may be used individually or in combination of two or more.

[0102] Examples of curing agents 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.

[0103] Examples of curing accelerators include organometallic salts and organometallic complexes such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bisacetylacetonate cobalt(II), trisacetylacetonate cobalt(III), zinc(II) acetylacetonate, and iron(III) acetylacetonate, as well as imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used individually or in combination of two or more.

[0104] The resin composition of this embodiment preferably contains a component that reacts with the curable resin of this embodiment and hardens together. Examples of such components include (meth)acrylate, isocyanurate, maleimide compounds, compounds having a vinyl group, and compounds having an allyl group.

[0105] The resin composition may further contain an initiator for initiating curing. Examples of initiators include organic peroxide-based initiators that initiate curing upon heating, and ultraviolet initiators that initiate curing upon light irradiation. The initiation temperature can be adjusted by selecting the initiator. For example, selecting an initiator that cures at a low temperature can reduce damage to surrounding devices at the curing temperature. Adjusting the curing temperature to a high temperature allows sufficient time to fill in irregularities in the substrate to be bonded, improving moldability. Furthermore, using an initiator with good dielectric properties can further reduce the dielectric strength.

[0106] Examples of organic peroxide initiators include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; peroxyesters such as t-butyl peroxybenzoate; hydroperoxides such as cumene hydroperoxide; and dialkyl peroxides such as dicumyl peroxide.

[0107] Examples of UV initiators include benzophenones such as benzophenone, benzyl, and methyl orthobenzoyl benzoate; benzoin ethers such as benzoin alkyl ethers; acetophenones such as benzyl 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.

[0108] The resin composition may further contain a crosslinking agent. However, the curable resin of this embodiment can be cured on its own without the use of a crosslinking agent, due to the presence of an ethylenic double bond and / or an acetylene triple bond. Therefore, the resin composition of this embodiment may not contain a crosslinking agent.

[0109] The content of the curable resin of this embodiment in the resin composition can be adjusted as appropriate according to the desired performance and is not particularly limited, but may be, for example, 1.0 part by mass or more, and more likely to be 3.0 parts by mass or more, or 5.0 parts by mass or more, per 100 parts by mass of the resin component (resin and component that hardens together with the resin; synonymous with solid component). For example, when the curable resin of this embodiment is added to the resin composition as a compatibilizer, the content of the curable resin of this embodiment may be, for example, 1.0 part by mass or more and 10 parts by mass or 3.0 parts by mass or more and 5.0 parts by mass, per 100 parts by mass of the resin component.

[0110] Alternatively, the content of the curable resin of this embodiment 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, per 100 parts by mass of the resin component. When the content of the curable resin of this embodiment is within the above range, it tends to be possible to obtain a resin composition with even better dielectric properties. Furthermore, the cured product of such a resin composition tends to have a low degree of yellowness, i.e., a good color tone. In addition, metal adhesion also tends to improve. The upper limit of the content of the curable resin of this embodiment 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. If it is between 5 parts by mass and 50 parts by mass, it is easy to utilize the properties of the curable resin of this embodiment while utilizing the properties of other thermosetting resins. The content of components other than the curable resin of this embodiment in the resin composition may be appropriately adjusted within the range in which the content of the curable resin of this embodiment in the resin composition is within the above range.

[0111] In this specification, "excellent dielectric properties" means that both the dielectric constant and the dielectric loss tangent are low. The specific values ​​of the dielectric constant and dielectric loss tangent are not particularly limited, but for example, if the dielectric constant (relative dielectric constant) of the cured product of a curable resin or resin composition produced as in the example is 2.75 or less and the dielectric loss tangent is 0.0125 or less, it can be said that it has excellent dielectric properties. The curable resin and resin composition of this embodiment have low dielectric constant and dielectric loss tangent even when cured.

[0112] The resin composition may further contain fillers such as reinforcing substrates and inorganic fillers.

[0113] The inorganic filler is not particularly limited as long as it is commonly used in this industry. Specifically, examples include silicas such as natural silica, fused silica, amorphous silica, and hollow silica; metal hydroxides such as aluminum hydroxide, heat-treated aluminum hydroxide (aluminum hydroxide that has been heat-treated to reduce some of its crystal water), magnesium hydroxide, and 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 powders such as E glass and D glass), hollow glass, spherical glass, titanium dioxide, silicone rubber, silicone composite powder, organic nanofibers, and inorganic nanofibers.

[0114] Examples of reinforcing materials include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, and carbon fiber.

[0115] The filler material may be used alone or in combination of two or more types.

[0116] The amount of filler contained in the resin composition is not particularly limited, but is, for example, 1 to 2000 parts by mass per 100 parts by mass of the resin component. The amount of filler can be appropriately changed depending on the application of the resin composition.

[0117] The resin composition may also contain silane coupling agents and wetting dispersants in addition to the filler. The inclusion of these components tends to improve the dispersibility of the filler, especially inorganic fillers, and further improve the adhesive strength between the resin and the filler.

[0118] The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic materials. Specifically, examples include aminosilane-based silane coupling agents such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; epoxysilane-based silane coupling agents such as γ-glycidoxypropyltrimethoxysilane; vinylsilane-based silane coupling agents such as γ-methacryloxypropyltrimethoxysilane; cationic silane-based silane coupling agents such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane-based silane coupling agents; and styrylsilane-based coupling agents such as p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styrylmethyldimethoxysilane, p-styrylmethyldiethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride.

[0119] The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specifically, examples include wetting and dispersing agents such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010, and W903 manufactured by Big Chemie Japan Co., Ltd.

[0120] These silane coupling agents and wetting / dispersing agents may be used individually or in combination of two or more.

[0121] Furthermore, the resin composition of this embodiment may contain a solvent as needed. The inclusion of an organic solvent in the resin composition tends to reduce its viscosity during preparation and improve its handling properties. The solvent is not particularly limited, as long as it can dissolve at least one component of the resin composition. Specifically, examples include ketones such as acetone, methyl ethyl ketone, and methyl cellsolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; and propylene glycol methyl ether and its acetate. The solvent may be used alone or in combination of two or more.

[0122] <Cured Product> One embodiment of the present invention relates to a cured product of the curable resin described above, or a cured product of the resin composition described above. The cured product has an excellent balance between copper foil peel strength and dielectric properties. In one embodiment, the cured product preferably has high strength (e.g., flexural strength, tensile strength, or impact strength). The cured product also preferably has excellent adhesion to metals other than copper foil, to glass, and to substrates. Furthermore, the cured product preferably has a low coefficient of thermal expansion.

[0123] The method for curing a curable resin or resin composition is not particularly limited and can be appropriately selected depending on the type of resin. Examples of curing methods include thermosetting and photocuring.

[0124] <Applications> Applications of this embodiment include, for example, electronic materials, and specific examples include electronic components, semiconductor encapsulation materials, semiconductor devices containing semiconductor encapsulation materials, molding resins, rigid substrates, prepregs, laminates, resin-coated copper foil, circuit boards, underfill materials, and build-up films. In addition, it can be used as a fiber-reinforced composite material such as carbon fiber reinforced plastics and glass fiber reinforced plastics, either together with additives such as unsaturated polyesters and epoxy resins, or alone.

[0125] The fiber-reinforced composite material comprises the resin composition of this embodiment and reinforcing fibers, and a fiber-reinforced molded product can be manufactured by curing it. The reinforcing fibers are not particularly limited and include glass fibers, carbon fibers, boron fibers, and aramid fibers. The semiconductor encapsulation material comprises the resin composition of this embodiment and an inorganic filler, and is used in the manufacture of semiconductor devices. The semiconductor encapsulation material referred to here is intended for encapsulating or connecting electronic components, and includes, for example, mold materials, underfills, conformal coatings, etc. The inorganic filler can be one of those described above.

[0126] A prepreg comprises a substrate and a resin composition impregnated or coated onto the substrate. The method for manufacturing a prepreg can be carried out according to conventional methods and is not particularly limited. For example, it can be manufactured by impregnating or coating the substrate with a resin composition, and then partially curing it (B-stage formation) by heating it 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 circuit boards can be appropriately selected and used depending on the intended application and performance. Specific examples of fibers constituting the base material are not particularly limited, but include, for example, 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; fully aromatic polyamides such as poly(p-phenylene terephthalamide) (Kevlar®, manufactured by DuPont Ltd.) and copoly(p-phenylene 3,4'-oxydiphenylene terephthalamide) (Technora®, manufactured by Teijin Techno Products Ltd.); polyesters such as 2,6-hydroxynaphthoic acid / p-hydroxybenzoic acid (Vectran®, manufactured by Kuraray Co., Ltd.) and Zexion® (registered trademark, manufactured by KB Seiren); and organic fibers such as poly(p-phenylene benzoxazole) (Zylon®, manufactured by Toyobo Co., Ltd.) and polyimide. These base materials may be used individually or in combination of two or more types.

[0127] A laminate is a laminate containing at least a prepreg. A laminate can be obtained, for example, by laminating a prepreg with other layers. The other layers are not particularly limited, but examples include a separately manufactured wiring board for the inner layer.

[0128] A circuit board includes a laminate and metal foil arranged on one or both sides of the laminate. For example, a circuit board is a copper-clad laminate obtained by laminating and curing the above-mentioned prepreg and copper foil. The copper foil used is not particularly limited as long as it is suitable for use in circuit boards, but known copper foils such as rolled copper foil and electrolytic copper foil are preferred.

[0129] A build-up film comprises a cured resin composition and a base film. "Build-up" refers to the process of laminating prepregs or resin sheets and repeatedly performing processes such as drilling holes and forming wires with each layer to produce a multilayer printed circuit board.

[0130] Further advantages of this embodiment include, for example, low thermal expansion, crack prevention, good color tone, solvent solubility, and suppression of resin separation during curing.

[0131] Other applications of this embodiment include, for example, bonding materials (bonding materials for metal bonding, bonding materials for inorganic film bonding, bonding materials for device bonding, etc.), bonding structures, temporary adhesives, temporary adhesives for device manufacturing processes, etc. Specific examples include bonding materials for metal bonding (Cu / Cu hybrid bonding, microbump bonding, Au / Au bonding, etc.) aimed at high-density heterogeneous integration, and device bonding materials for chips. Furthermore, after thermal curing, SiO ２ Because it can bond to inorganic films such as SiN, SiCN, and glass, it can also be used to form bonding structures for various devices. Furthermore, to suppress chip misalignment and achieve accurate positioning, it can also be used as a temporary adhesive in the manufacturing process of integrated circuits and MEMS devices.

[0132] Other applications of this embodiment include, for example, electronic devices having a wiring structure between a semiconductor chip and a substrate, electronic structures having a connection to a conductive path, materials applied to the formation of high-density wiring layers (including wafer-level packages (WLP), rigid-flex substrates, etc.), semiconductor devices as components of electronic circuits, semiconductor package materials (including FCBGA, SiP, and FOWLP for CPU / GPU / memory), package structures for highly integrating semiconductor chips (including 2.5D / 3D packages, SiP, and FOWLP), electrical insulating layers for electronic components (including insulating materials for substrates, interposers, and power devices), and underfill materials applied between semiconductor devices and mounting substrates.

[0133] The resin composition of this embodiment contributes to the high integration and high reliability of semiconductor devices, and its applications are diverse. In particular, this resin composition can be applied to various advanced electronic devices, including high-performance processors (AI chips, server CPUs / GPUs, smartphone processors, etc.), image processing chips, high-bandwidth memory (HBM), power devices, image sensors, communication chips, and even integrated structures of heterogeneous devices, contributing to improved overall system performance and the realization of high-density packaging.

[0134] These devices are supported by packaging technologies that have advanced rapidly in recent years, and this resin composition is used as an insulating layer, encapsulant, adhesive layer, filler, and smoothing layer in high-density mounting structures such as 2.5D / 3D packages, SiP (System in Package), and FOWLP (Fan-Out Wafer Level Package). In particular, in laminated structures using through-silicon vias (TSVs), package structures utilizing interposer substrates, and high-density connection technologies using hybrid bonding, this resin composition improves reliability and contributes to shorter wiring and higher density.

[0135] Furthermore, this resin composition can be applied as a component material for semiconductor packages, including molding materials, encapsulating materials, and die-attach materials. It exhibits stable reliability even in high-temperature environments, making it suitable for device mounting requiring high reliability. It is also useful as an insulating or dielectric layer in the formation of high-density wiring layers, including redistribution layers (RDLs), build-up substrates, and silicon interposers, thereby supporting the performance enhancement of electronic circuits.

[0136] The resin composition of this embodiment can also be applied to components of electronic circuits such as transistors, diodes, integrated circuits (ICs), and large-scale integrated circuits (LSIs), and can improve the durability and reliability of these devices when used as a encapsulant or protective film.

[0137] Furthermore, this resin composition is also effective as an electrical insulating layer or protective layer in electronic components such as printed circuit boards (PCBs), insulating films for IC packages, flexible printed circuits (FPCs), and solder resists. This makes it possible to prevent unwanted electrical interference and improve signal transmission quality.

[0138] Furthermore, this resin composition is used as an underfill material in flip-chip connections and hybrid bonding. Specifically, it is applicable to various methods such as capillary underfill (CUF), molded underfill (MUF), non-conductive paste (NCP), and non-conductive film (NCF), contributing to improved connection reliability and stress relief between semiconductor chips and substrates. It can also be used as a layer for embedding and planarizing devices and wiring.

[0139] In addition, the resin composition of this embodiment can also be used for temporary fixing applications in semiconductor manufacturing processes. Specifically, it ensures stable holding of workpieces and maintains processing accuracy in processes such as wafer thinning, through-silicon via (TSV) formation, die stacking, and reflow bonding. Furthermore, this temporary fixing material has properties of thermal decomposition, ultraviolet (UV) decomposition, or solvent solubility, making it easy to remove after processing and allowing for separation without stressing subsequent processes, thus contributing to improved yields in three-dimensional mounting and wafer-level packaging.

[0140] Thus, the resin composition of this embodiment is a material that can be applied for a variety of purposes at every level of semiconductor technology, from the final electronic device to the package structure, wiring layer, components, and even the manufacturing process that constitute it. It is extremely useful as a core material that will support the future improvement of performance, density, and reliability of electronic devices.

[0141] 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 thereto.

[0142] <Measurement Method> [Hydroxyl Value] Hydroxyl value (mgKOH / g) = Mass of KOH (mg) / Mass of sample (g) Number of hydroxyl groups (mol) = Mass of sample (g) × Hydroxyl value (mg / g) / Molecular weight of KOH (mg / mol)

[0143] [Molecular Weight] The curable resin was dissolved in tetrahydrofuran to a resin concentration of 0.2% by mass, and measured by gel filtration chromatography (GPC). The weight-average molecular weight of each curable resin was calculated using a calibration curve prepared with standard polystyrene (PStQuick C). The measurement was performed using a Tosoh HLC-840 instrument with three Tosoh TSKgel SuperHM-M columns, at a column temperature of 40°C, a system temperature of 40°C, and tetrahydrofuran as the eluent. An injection volume of 10 μL was used, and tetrahydrofuran was flowed at a flow rate of 0.6 ml / min. The refractive index was measured using a refractive index detector (RI). The strongest peak detected initially was calculated.

[0144] [Weight Loss Temperature] For resins A to F, the temperature was increased from 40°C to 400°C at a rate of 10°C / min, and the 5% weight loss temperature was measured.

[0145] [Glass Transition Temperature] Using a Shimadzu DSC / TA-50WS, approximately 10 mg of the sample was placed in a sealed aluminum container and measured under a nitrogen gas (30 ml / min) flow at a heating rate of 20°C / min. The temperature at the midpoint of the region where a discontinuity appears in the baseline (where the specific heat changes by half) was defined as the glass transition temperature (Tg).

[0146] [Functional Group Equivalents] The functional group equivalents were calculated according to the following formula based on the mass (g) of each raw material compound at the time of preparation during synthesis, the mass (g) of the target curable resin (excluding the by-products water and phenol), and the molar equivalent of the ethylene group (-CH=CH-) of maleic anhydride. In this case, the functional group equivalent in the curable resin was defined as 1 molar equivalent of the ethylene group (-CH=CH-) derived from maleic anhydride. Functional group equivalents (g / eq) = {Mass of each raw material compound (g) - Mass of by-products (g)} / 1 equivalent of the ethylene group (-CH=CH-) of maleic anhydride (eq)

[0147] [Copper foil peel strength] Cuts were made in the copper foil at a width of 10 mm, and the copper foil was peeled off. The maximum tensile strength when the peeled copper foil was continuously pulled for a length of approximately 10 cm from a 90° direction was defined as the copper foil peel strength. The strength was measured using a Strograph EII-L (manufactured by Toyo Seiki) at a speed of 5 cm / min.

[0148] [Method for measuring dielectric constant] After slow cooling, the cured resin composition was removed from the mold. The removed cured material was cut into 0.8 mm wide strips to prepare rod-shaped samples. The cut samples were dried for one day in a vacuum dryer at 70°C, and then the dielectric constant and dielectric loss tangent at 10 GHz were measured using the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies).

[0149] [Measurement of Thermal Expansion Coefficient] The sample was cut to a length of 10 mm x 6 mm. The flow direction of the glass cloth was set to 10 mm. The thermal expansion coefficient of the sample dried at 120°C for 1 hour was measured using a horizontal dilatometer. The temperature was increased by 2 degrees from 60°C to 260°C, and the thermal expansion coefficient was measured a second time. The procedure was carried out with a load of 50 mN and a heating rate of 10°C / min.

[0150] The abbreviations for the compounds used below are as follows: BD: 1,4-butanediol HD: 1,6-hexanediol DD: 1,12-dodecanediol DPC: diphenyl carbonate TBT: tetra-n-butyl titanate

[0151] <Production of Curable Resin> (Synthesis Example 1) 316 g of HD, 516 g of diphenyl carbonate, and 0.027 g of titanium(IV) tetrabutoxide were placed in a 1 L separable flask (molar ratio of HD:DPC = 10:9), and while stirring, the temperature was gradually increased and the pressure reduced under a nitrogen flow until polymerization was carried out at 230°C and below 0.1 kPa. After that, the resin was air-cooled until the resin temperature dropped to room temperature. After air-cooling, 26.2 g of maleic anhydride was added, and the temperature was increased to 200°C under a nitrogen flow. After waiting for the distillation of water to stop, the pressure was gradually reduced to 13 kPa and maintained for about 30 minutes, after which resin A was extracted. The Tg of resin A before curing was 8°C.

[0152] (Synthesis Example 2) 230 g of BD, 500 g of diphenyl carbonate, and 0.027 g of titanium(IV) tetrabutoxide were placed in a 1 L separable flask (BD:DPC molar ratio = 10:9), and while stirring, the temperature was gradually increased and the pressure reduced under nitrogen flow until polymerization was carried out at 230°C and below 0.1 kPa. After that, the mixture was air-cooled until the resin temperature dropped to room temperature. After air-cooling, 20.8 g of maleic anhydride was added, and the temperature was increased to 200°C under nitrogen flow. After waiting for the distillation of water to stop, the pressure was gradually reduced to 13 kPa and maintained for about 30 minutes, after which resin B was extracted. The Tg of resin B before curing was 10°C.

[0153] (Synthesis Example 3) 380 g of DD, 336 g of diphenyl carbonate, and 0.027 g of titanium(IV) tetrabutoxide were placed in a 1 L separable flask (molar ratio of DD:DPC = 10:9), and while stirring, the temperature was gradually increased and the pressure reduced under a nitrogen flow until polymerization was carried out at 230°C and below 0.1 kPa. After that, the mixture was air-cooled until the resin temperature dropped to room temperature. After air-cooling, 30.8 g of maleic anhydride was added, and the temperature was increased to 200°C under a nitrogen flow. After waiting for the distillation of water to stop, the pressure was gradually reduced to 13 kPa and maintained for about 30 minutes before resin C was extracted. The Tg of resin C before curing was 5°C.

[0154] (Comparative Synthesis Example 1) 2029 g of poly-1,6-hexanecarbonatediol (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value 55.6 KOH mg / g, HD:DPC molar ratio = 10:9.3) was placed in a 1 L separable flask equipped with a stirrer, thermometer, and nitrogen inlet tube. The mixture was heated to 150°C while stirring under a nitrogen flow, and once the poly-1,6-hexanecarbonatediol had dissolved, 196 g of maleic anhydride was added. The mixture was reacted at 150°C under a nitrogen flow for 5 hours, after which resin D was extracted. The pre-curing Tg of resin D was 8°C.

[0155] (Comparative Synthesis Example 2) 2027 g of poly-1,6-hexanecarbonatediol (Nipporan 981: manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value 111.3 KOH mg / g, HD:DPC molar ratio = 10:8.6) was placed in a 1 L separable flask equipped with a stirrer, thermometer, and nitrogen inlet tube. The mixture was heated to 150°C while stirring under a nitrogen flow, and once the poly-1,6-hexanecarbonatediol had dissolved, 392 g of maleic anhydride was added. The mixture was reacted at 150°C under a nitrogen flow for 5 hours, after which resin E was extracted. The pre-curing Tg of resin E was 8°C.

[0156] (Comparative Synthesis Example 3) 2027 g of poly-1,6-hexanecarbonatediol (Nipporan 981: manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value 111.3 KOH mg / g, HD:DPC molar ratio = 10:8.6) was placed in a 1 L separable flask equipped with a stirrer, thermometer, and nitrogen inlet tube. The mixture was heated to 150°C while stirring under a nitrogen flow until the poly-1,6-hexanecarbonatediol dissolved. Then 294 g of maleic anhydride was added, and the mixture was reacted at 150°C under a nitrogen flow for 3 hours, followed by 210°C for 3 hours, after which resin F was extracted. The Tg of resin F before curing was 8°C.

[0157] (Example 1) 3 g of resin A, 7 g of BMI-2300 (manufactured by Yamato Chemical Industries, Ltd.), 0.1 g of perbutyl P (NOF Corporation), and 14.3 g of SC2500-MB (Admatex Corporation) were weighed out and dissolved with methyl ethyl ketone. The dissolved resin was applied to a 10 cm square piece of glass cloth E2118 (Nitto Boseki Co., Ltd.), with the solid content adjusted so that the resin weight was the same as that of the glass cloth. After air drying, the solution was dried at 150°C for 3 minutes to obtain a prepreg. The prepreg was sandwiched between copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., 3EC-M2S-VLP 12 μm) and gradually subjected to a pressure of 0.6 MPa using a vacuum press. Molding was then carried out at 230°C for 150 minutes. After molding, the material was allowed to cool, and the molded piece was removed from the SUS mold to obtain a sample for measuring the copper foil peel strength in Example 1. The copper foil was laminated so that the roughened surface was in contact with the resin. The resin solution A was dried and dried at 150°C for 3 minutes, placed in a 1 mm thick SUS mold, sandwiched between Aflex film (manufactured by AGC Inc.) and a SUS plate, and pressure was gradually applied at 0.6 MPa using a vacuum press. Molding was then carried out at 200°C for 150 minutes in this state to obtain a sample for measuring the dielectric properties in Example 1.

[0158] (Examples 2-3, Comparative Examples 1-3) Resin solutions B-F were prepared in the same manner as in Example 1, except that resins B-F were used instead of resin A. Then, samples for measuring the copper foil peel strength of Examples 2-3 and Comparative Examples 1-3, and samples for measuring the dielectric properties of Examples 2-3 and Comparative Examples 1-3 were obtained in the same manner as in Example 1, except that resin solutions B-F were used instead of resin solution A.

[0159] (Reference Example 1) 10 g of resin BMI-2300 (manufactured by Yamato Chemical Industries, Ltd.), 0.1 g of perbutyl P (NOF Co., Ltd.), and 14.3 g of SC2500-MB (Admatex Co., Ltd.) were weighed out and dissolved with methyl ethyl ketone. The dissolved resin was applied to a 10 cm square piece of glass cloth E2118 (Nitto Boseki Co., Ltd.), taking into account the solid content so that the resin weight was the same as that of the glass cloth. After air drying, the resin was dried at 150°C for 3 minutes to obtain a prepreg. The prepreg was sandwiched between copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., 3EC-M2S-VLP 12 μm) and gradually subjected to pressure of 0.6 MPa using a vacuum press. Molding was carried out at 230°C for 150 minutes under these conditions. After molding, it was allowed to cool, and the molded piece was removed from the SUS mold to obtain a sample for measuring the copper foil peel strength as in Reference Example 1. The copper foil was laminated so that its roughened surface was in contact with the resin. The resin solution was dried and then dried at 150°C for 3 minutes. It was placed in a 1 mm thick stainless steel mold, sandwiched between Aflex film (manufactured by AGC Inc.) and a stainless steel plate, and pressure was gradually applied at 0.6 MPa using a vacuum press. Molding was then carried out at 200°C for 150 minutes under these conditions to obtain a sample for dielectric property measurement as shown in Reference Example 1.

[0160]

Claims

1. A structural unit represented by the following formula (1), [In the formula, R is a divalent group having an ethylenic double bond and / or an acetylene triple bond] A structural unit represented by the following formula (2), [In the formula, R ２ This is a linear alkylene group having 4 to 15 carbon atoms. The structural unit is represented by the following formula (3), A curable resin having a weight-average molecular weight (Mw) of 9,000 or more, and a functional group equivalent of 1,000 to 5,000.

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

3. The curable resin according to claim 1, wherein the structural unit represented by formula (2) is derived from at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, and 1,15-pentadecanediol.

4. The curable resin according to claim 1, wherein the glass transition temperature is 30°C or lower.

5. The curable resin according to claim 1, wherein the molar ratio of structural units represented by formula (1) to structural units represented by formula (2) is 0.02 or more and less than 0.

5.

6. The curable resin according to claim 1, wherein the molar ratio of structural units represented by formula (3) to structural units represented by formula (2) is 0.5 or more and less than 1.

7. The curable resin according to claim 1, wherein the molar ratio of the total structural units represented by formula (1), formula (2), and formula (3) to all structural units constituting the curable resin is 0.6 or more.

8. A cured product of a curable resin according to any one of claims 1 to 7.

9. A resin composition comprising the curable resin according to any one of claims 1 to 7.

10. The resin composition according to claim 9, 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.

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