Curable resin, curable resin composition, and cured product

Abstract

Provided are a curable resin, a curable resin composition, and a cured product. A cured product having excellent heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties) is obtained by using a curable resin having a specific structure with excellent storage stability. Specifically, provided is a curable resin represented by the following general formula (1) and having a hydroxyl group concentration of 0.005 mmol / kg to 3800 mmol / kg.

Description

TECHNICAL FIELD

[0001] The present application relates to a curable resin having a specific structure, a curable resin composition containing the curable resin, and a cured product obtained from the curable resin composition. BACKGROUND

[0002] With the increase in information traffic in recent years, information communication in a high frequency band is actively performed, and for more excellent electrical properties, including reduction in transmission loss in a high frequency band, an electrical insulating material having a low dielectric constant and a low dielectric loss tangent is required.

[0003] Further, a printed board or an electronic component using these electrical insulating materials is exposed to a reflow soldering in which a high temperature is applied at the time of mounting, and thus a material exhibiting a high glass transition temperature, which is excellent in heat resistance, is required. In particular, in recent years, from the viewpoint of environmental problems, a solder having a high melting point, which is lead-free, is used, and thus the requirement for an electrical insulating material having higher heat resistance is increasing.

[0004] In response to these requirements, curable resins having various chemical structures containing a vinyl group have been proposed since before. As such a curable resin, for example, a bisphenol divinylbenzyl ether or a novolak polyvinylbenzyl ether, and the like, have been proposed (for example, refer to Patent Document 1 and Patent Document 2). However, these vinylbenzyl ethers cannot provide a cured product having sufficiently small dielectric properties, and the obtained cured product has a problem in terms of stable use in a high frequency band, and further, the bisphenol divinylbenzyl ether cannot be said to be sufficiently high in heat resistance.

[0005] For a vinylbenzyl ether for improving the properties, in order to achieve improvement in dielectric properties and the like, several polyvinylbenzyl ethers having specific structures have been proposed (for example, refer to Patent Documents 3 to 9). However, although attempts to suppress the dielectric loss tangent or to improve the heat resistance have been made, the improvement in these properties cannot be said to be sufficient, and further improvement in the properties is expected.

[0006] Thus, the curable resin containing a vinyl group, which contains the previous polyvinylbenzyl ether, cannot provide a cured product having both a low dielectric loss tangent, which is necessary for an electrical insulating material use, particularly an electrical insulating material use for coping with a high frequency, and heat resistance that can withstand a lead-free solder processing.

[0007] In addition, the curable resin containing a vinyl group also has a disadvantage that the vinyl group reacts during storage, and thus has poor storage stability, and improvement is expected.

[0008] PRIOR ART DOCUMENTS

[0009] PATENT DOCUMENTS

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 63-68537

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 64-65110

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. Hl-503238

[0013] Patent Document 4: Japanese Patent Application Laid-Open No. H5-43623

[0014] Patent Document 5: Japanese Patent Application Laid-Open No. 9-31006

[0015] Patent Document 6: Japanese Patent Application Laid-Open No. 2005-281618

[0016] Patent Document 7: Japanese Patent Application Laid-Open No. 2005-314556

[0017] Patent Document 8: Japanese Patent Application Laid-Open No. 2015-030776

[0018] Patent Document 9: Japanese Patent Application Laid-Open No. 2015-189925 SUMMARY

[0019] PROBLEMS TO BE SOLVED BY THE INVENTION

[0020] Therefore, an object of the present application is to provide a hardening resin which is excellent in storage stability and can contribute to heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties), and a hardened product which is excellent in heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties) by using the hardening resin.

[0021] MEANS OF SOLVING THE PROBLEM

[0022] Therefore, the present inventors and others have made earnest studies in order to solve the problem, and as a result, have found that a hardening resin which is excellent in storage stability and can contribute to heat resistance and low dielectric properties, and a hardened product which is excellent in heat resistance and low dielectric properties obtained from a hardening resin composition containing the hardening resin, and thus completed the present application.

[0023] That is, the present application relates to a hardening resin which is represented by the following general formula (1) and has a hydroxyl group concentration of 0.005 mmol / kg to 3800 mmol / kg.

[0024] [Chemical Formula 1]

[0025]

[0026] (In formula (1), Z is a hydrocarbon having a carbon number of 2 to 15, Y is a substituent represented by the following general formula (2), and n represents an integer of 3 to 5,

[0027] [Chemistry 2]

[0028]

[0029] In formula (2), Ra and Rb are independently represented by alkyl, aryl, aralkyl or cycloalkyl groups having 1 to 12 carbon atoms, m represents an integer from 0 to 3, and X represents hydroxyl, (meth)acryloyloxy, vinylbenzyl ether or allyl ether.

[0030] The curable resin of the present invention is preferably composed of hydroxyl groups with a concentration of 0.01 mmol / kg to 1500 mmol / kg.

[0031] The curable resin of the present invention is preferably X, which is methacryloyloxy.

[0032] The curable resin of the present invention is preferably an aliphatic hydrocarbon, wherein Z is a hydrocarbon.

[0033] This invention relates to a curable resin composition, wherein the curable resin is contained.

[0034] The present invention relates to a hardened material, wherein the hardening resin composition can be obtained by a hardening reaction.

[0035] The effects of the invention

[0036] The curing resin of the present invention has a specific structure, excellent storage stability, and can contribute to heat resistance and low dielectric properties. Therefore, the cured articles obtained from the curing resin composition containing the curing resin have excellent heat resistance and low dielectric properties and are useful. Attached Figure Description

[0037] Figure 1 This is the 1H nuclear magnetic resonance (NMR) spectrum of the curable resin obtained in Example 1.

[0038] Figure 2 This is the 1H-NMR spectrum of the curable resin obtained in Example 9.

[0039] Figure 3 This is the 1H-NMR spectrum of the curable resin obtained in Example 10. Detailed Implementation

[0040] The present invention will be described in detail below.

[0041] <Curing Resin>

[0042] The present invention relates to a curable resin, wherein it is represented by the following general formula (1) and the hydroxyl concentration is 0.005 mmol / kg to 3800 mmol / kg.

[0043] [Chemical Formula 3]

[0044]

[0045] In the general formula (1), Z is a hydrocarbon having a carbon number of 2 to 15, Y is a substituent represented by the following general formula (2), and n represents an integer of 3 to 5.

[0046] [Chemical Formula 4]

[0047]

[0048] In the general formula (2), Raand Rbare each independently represented by an alkyl group having a carbon number of 1 to 12, an aryl group, an aralkyl group, or a cycloalkyl group, m represents an integer of 0 to 3, and X represents a hydroxyl group, a (meth)acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group.

[0049] The curable resin contains a plurality of X (crosslinking group (X)) which functions as a crosslinking group, and thus the curable resin is crosslinked, and the crosslinking density of the obtained hardened product is high, and the heat resistance is excellent. In addition, the crosslinking group is also a polar group, but due to the presence of a substituent (particularly, Ra) adjacent to the crosslinking group, the molecular mobility of the crosslinking group is inhibited to be low, and the obtained hardened product is preferably satisfied with low dielectric properties (particularly, low dielectric loss tangent).

[0050] X which functions as the crosslinking group refers to a functional group such as a (meth)acryloyloxy group, etc. which contains an unsaturated double bond, and a vinyl group, etc. which directly contributes to a crosslinking reaction (self-crosslinking) or a polymerization reaction. In addition, the hydroxyl group contained in the X functions as a polymerization inhibitor in the present application, but can also contribute to a reaction with an epoxy resin, etc., and thus the hydroxyl group is described as being contained in the crosslinking group here.

[0051] In the general formula (1), Z is a hydrocarbon having a carbon number of 2 to 15, preferably a hydrocarbon having a carbon number of 2 to 10, and more preferably a hydrocarbon having a carbon number of 2 to 6. By the carbon number being within the range, the curable resin becomes a low molecular weight body, and compared to the case of a high molecular weight body, the crosslinking density is high, the glass transition temperature of the obtained hardened product is high, the heat resistance is excellent, and thus it is a preferable form. In addition, when the carbon number is less than 2, there is a tendency that the obtained curable resin excessively becomes a low molecular weight body, the crosslinking density of the hardened product becomes excessively high, the hardened product itself becomes brittle and cannot form a film, etc., or there is a tendency that the handling property, flexibility, softness, and brittle resistance are poor, and in addition, when the carbon number exceeds 15, the obtained curable resin becomes a high molecular weight body, the proportion of the crosslinking group (X) in the curable resin is low, and along therewith, the crosslinking density decreases, and the heat resistance of the obtained hardened product is poor and is not preferable.

[0052] As the hydrocarbon, if it is a hydrocarbon having a carbon number of 2 to 15, there is no particular limitation, and for example, aliphatic hydrocarbons such as alkane, alkene, alkyne, etc. are preferred, and aromatic hydrocarbons containing an aromatic group, a combination of aliphatic and aromatic hydrocarbons, etc. can be exemplified.

[0053] As the aliphatic hydrocarbon, for example, ethane, propane, butane, pentane, hexane, cyclohexane, etc. can be exemplified.

[0054] As the alkene, for example, alkenes containing a vinyl group, 1-methylethenyl group, propenyl group, butenyl group, pentenyl group, etc. can be exemplified.

[0055] As the alkyne, for example, alkyne containing an ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, etc. can be exemplified.

[0056] As the aromatic hydrocarbon, for example, aromatic hydrocarbons containing a phenyl group, tolyl group, xylyl group, naphthyl group, etc. as an aromatic group can be exemplified.

[0057] As the compound of a combination of aliphatic and aromatic hydrocarbons, for example, compounds containing a benzyl group, phenylethyl group, phenylpropyl group, tolylmethyl group, tolylethyl group, tolylpropyl group, xylylmethyl group, xylylethyl group, xylylpropyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group, etc. can be exemplified.

[0058] Among the hydrocarbons, in terms of obtaining a hardened product having low polarity and low dielectric properties (low dielectric constant and low dielectric loss tangent), aliphatic hydrocarbons or aromatic hydrocarbons containing only carbon atoms and hydrogen atoms, alicyclic hydrocarbons are preferred, and among them, hydrocarbons of the following General Formula (3-1) to General Formula (3-6) having very little polarity and industrially usable are preferred, and the aliphatic hydrocarbons of the following General Formula (3-1) are more preferred because of their excellent low dielectric properties. In the following General Formula (3-1), k represents an integer of 0 to 5, preferably 0 to 3, and Rc in the following General Formula (3-1), General Formula (3-2), and General Formula (3-4) to General Formula (3-6) is preferably represented by a hydrogen atom or a methyl group.

[0059] [Chemical Formula 5]

[0060]

[0061] In the General Formula (1), the number average molecular weight of Z (central structure) is preferably 20 to 200. In the case where the number average molecular weight is less than 20, there is a tendency to be brittle due to a high crosslinking density, and in the case where it exceeds 200, there is a tendency to be weak in heat resistance due to a low crosslinking density.

[0062] In the general formula (2), Raand Rbindependently represent an alkyl group having 1 to 12 carbons, an aryl group, an aralkyl group, or a cycloalkyl group, and preferably an alkyl group having 1 to 4 carbons, an aryl group, or a cycloalkyl group. By having an alkyl group having 1 to 12 carbons or the like, the planarity around the benzene ring is reduced, the crystallinity is reduced, and thus the solvent solubility is improved, and the melting point is lowered, and thus this is preferable. In addition, it is presumed that by having Raand Rb(in particular, Raadjacent to X as a crosslinking group), steric hindrance is generated, the molecular mobility of the crosslinking group (X) is further reduced, and a hardened product having lower dielectric properties (in particular, a low dielectric loss tangent) can be obtained, and thus this is preferable. Among these, in the case of a t-butyl group, thermal decomposition occurs upon heating, and isobutene gas is easily generated, and thus this is not preferable.

[0063] In the general formula (2), m represents an integer of 0 to 3, and preferably m is 0 or 1, and more preferably 1. By having m in this range, Rb as a substituent becomes steric hindrance, the molecular mobility of the crosslinking group (X) is reduced, and low dielectric properties are excellent, and thus this is preferable. In addition, in the case where m is 0, Rb represents a hydrogen atom.

[0064] In the general formula (1), n is the number of substituents, and represents an integer of 3 to 5, and preferably 3 or 4, and more preferably 4. By having n in this range, the hardenable resin becomes a low molecular weight, and compared to the case of a high molecular weight, the crosslinking density is increased, the glass transition temperature of the obtained hardened product is increased, and heat resistance is excellent, and thus this is preferable. In addition, in the case where n is 2, the crosslinking group (X) is reduced, the crosslinking density of the obtained hardened product is low, and sufficient heat resistance cannot be obtained. On the other hand, in the case where n is 6 or more, there is a tendency that the crosslinking density of the hardened product becomes too high, the hardened product itself becomes brittle and cannot form a film or the like, or the handling properties, flexibility, softness, and brittleness resistance are poor, and thus this is not preferable.

[0065] In the general formula (2), X is a hydroxyl group, a (meth)acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group as a crosslinking group, and preferably a (meth)acryloyloxy group, and more preferably a methacryloyloxy group. By having the crosslinking group in the hardenable resin, a hardened product having a low dielectric loss tangent can be obtained, and thus this is preferable.

[0066] In addition, it is presumed that the methacryloyloxy group, compared to other crosslinking groups (for example, a vinylbenzyl ether group or an allyl ether group, or the like, an ether group as a polar group) includes a methyl group in the structure of the hardenable resin, and thus the steric hindrance is increased, the molecular mobility is further reduced, and a hardened product having a lower dielectric loss tangent can be obtained, and thus this is preferable. In addition, in the case where the crosslinking group is plural, the crosslinking density is increased, and the heat resistance is increased, and thus this is preferable.

[0067] X as the crosslinking group is also a polar group, but by being adjacent to Raor Rb, especially Ra, as a substituent group, steric hindrance is caused, the molecular mobility of X is inhibited, the dielectric loss tangent of the obtained hardened product is lowered, and a preferable form is obtained.

[0068] In addition, in the case where X is a hydroxyl group, during storage of the hardening resin, radicals generated by light or heat, air, or the like are stabilized by abstracting the phenolic hydrogen of the hydroxyl group, and function as a polymerization inhibitor by preventing radical polymerization, and thus the storage stability of the hardening resin is improved, and is useful.

[0069] The hardening resin of the present application is a mixture of hardening resins having a crosslinking group or a substituent group, etc. in the structure thereof, which is formed by various combinations, and for example, refers to a hardening resin including a hardening resin having a hydroxyl group as a crosslinking group (X), or a hardening resin having a functional group such as a (meth)acryloyl group, which facilitates a direct crosslinking reaction, or a hardening resin having both a hydroxyl group and a (meth)acryloyl group.

[0070] Further, the hardening resin of the present application has a hydroxyl group concentration within a specific range, and thus at least a hardening resin having a hydroxyl group as a crosslinking group (X) is included in the hardening resin as the mixture. Further, the hydroxyl group functions as a polymerization inhibitor in the present application, but in the case where an epoxy resin, etc. is formulated at the time of hardening using the hardening resin, the hydroxyl group value can function as a crosslinking group.

[0071] In addition, the hardening resin of the present application is preferably represented by the following general formula (1A) from the general formula (1). By specifying the structure of the general formula (1) to the following general formula (1A), in which the position of Z is fixed (limited) with respect to Raand X, compared to the structural formula described in the general formula (1), the reactivity of the crosslinking group is increased in the hardening resin having the structure represented by the general formula (1A), a dense crosslinked body is formed, and is more excellent in terms of heat decomposition resistance, and is a preferable form.

[0072] [Chemical Formula 6]

[0073]

[0074] The hardening resin of the present application is preferably the case where n is 4. By n being 4 in the general formula (1A), the crosslinking density of the hardening resin is increased, and in addition, the crosslinking group does not become excessive, and thus sufficient heat resistance is obtained, and at the same time, handling properties, flexibility, softness, and brittleness resistance are excellent, and is a more preferable form.

[0075] The curable resin of the present application is preferably one in which X is a methacryloyloxy group. By X being a methacryloyloxy group in the general formula (1A), a crosslinking group is present in the curable resin, whereby a cured product having a low tangent of dielectric loss can be obtained, and is thus a preferred form. Furthermore, it is presumed that the methacryloyloxy group, compared to other crosslinking groups such as a vinylbenzyl ether group or an allyl ether group, etc., as a polar group, the structure of the curable resin contains a methyl group, and thus the steric hindrance becomes large, the molecular mobility further becomes low, a cured product having a lower tangent of dielectric loss can be obtained, and is thus more preferred. In addition, in the case where the crosslinking group is plural, the crosslinking density increases, the heat resistance increases, and is thus more preferred. Furthermore, the curable resin of the present application has a hydroxyl group concentration within a specific range, and thus, as with the formula (2), one containing a curable resin having a hydroxyl group as the crosslinking group (X) is included.

[0076] The curable resin of the present application is preferably one in which Z is an aliphatic hydrocarbon. By Z being an aliphatic hydrocarbon in the general formula (1A), the polarity becomes low, and a low dielectric property (low dielectric constant, low tangent of dielectric loss) is obtained, and is thus a more preferred form.

[0077] In addition, in the general formula (1A), Z is preferably an aliphatic hydrocarbon having a carbon number of 2 to 15, and more preferably an aliphatic hydrocarbon having a carbon number of 2 to 10. In the case where the carbon number is less than 2, the crosslinking density becomes too high and becomes brittle, the brittle resistance is poor, and in the case where the carbon number exceeds 15, the crosslinking density becomes low, the heat resistance is poor, and is thus not preferred. Furthermore, as the aliphatic hydrocarbon, the same as the aliphatic hydrocarbon in the exemplification of the hydrocarbon in the general formula (1) is common.

[0078] In the general formula (1A), Ra, Rb, m, and n are common to Ra, Rb, m, and n in the general formula (1) and general formula (2).

[0079] Furthermore, in the general formula (1), not only the general formula (1A), but also the following general formula (1B) is included, and the general formula (1A) is in a position where X as a crosslinking group easily reacts, and thus the hardening reaction easily proceeds and is preferred. On the other hand, there is a risk that the curable resin represented by the following general formula (1B) easily remains in an unhardened form at the time of the hardening reaction and the thermal decomposition temperature becomes low.

[0080] [Chem. 7]

[0081]

[0082] The hydroxyl group concentration of the curable resin of the present application is 0.005 mmol / kg to 3800 mmol / kg, preferably 0.008 mmol / kg to 3500 mmol / kg, more preferably 0.01 mmol / kg to 3000 mmol / kg, and particularly preferably 0.01 mmol / kg to 1500 mmol / kg. By the hydroxyl group concentration being within the range, during storage of the curable resin or a curable resin composition containing the curable resin, the generated radicals react with phenolic hydrogen, thereby becoming stable radicals, and the reaction of crosslinking groups other than the hydroxyl group is inhibited, the storage stability of the curable resin itself or the curable resin composition is excellent, and a preferred mode is obtained. Further, when the hydroxyl group concentration is less than 0.005 mmol / kg, the storage stability becomes insufficient, and when the hydroxyl group concentration exceeds 3800 mmol / kg, the crosslinking density based on the crosslinking groups other than the hydroxyl group becomes insufficient, or the polarity based on the hydroxyl group becomes high, thereby the dielectric loss tangent or the dielectric constant becomes poor (increases) and is not preferred. Further, the hydroxyl group concentration is a value calculated based on a hydroxyl group value measurement (a method according to Japanese Industrial Standards (JIS) K 1557-1).

[0083] In addition, from the viewpoint of the storage stability of the curable resin itself or the curable resin composition, it is considered that a polymerization inhibitor is additionally used, but the curable resin of the present application has a large number of crosslinking groups (n is 3 to 5) and is polyfunctional, and therefore even if a polymerization inhibitor is used, it is difficult to sufficiently obtain the effect of the storage stability, and in addition, when the blending amount of the polymerization inhibitor is increased, the storage stability is improved, but the dielectric constant or the dielectric loss tangent increases, and therefore is not preferred.

[0084] <Method for producing intermediate phenol compound>

[0085] As a method for producing the curable resin, first, a method for producing an intermediate phenol compound which is a raw material (precursor) of the curable resin will be described below.

[0086] As the method for producing the intermediate phenol compound, the intermediate phenol compound can be obtained by mixing an aldehyde compound or a ketone compound represented by the following General Formula (4) to General Formula (9) with a phenol or a derivative thereof represented by the following General Formula (10) to General Formula (16), and reacting them in the presence of an acid catalyst. Further, k, Ra, and Rb in General Formula (4) to General Formula (16) are common to k, Ra, and Rb in General Formula (2) and General Formula (3-1).

[0087] [Chemical Formula 8]

[0088]

[0089] [Chemical Formula 9]

[0090]

[0091] As specific examples of the aldehyde compound or ketone compound (hereinafter, sometimes referred to as "compound (a)", the aldehyde compound can be exemplified by: formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, cyclohexanone, diphenylacetaldehyde, ethyl butyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxaldehyde, malondialdehyde, succindialdehyde, salicylaldehyde, naphthaldehyde, glyoxal, glutaraldehyde, crotonaldehyde, phthalaldehyde, p-xylylaldehyde, and the like. Among the aldehyde compounds, from the aspect of being easily available industrially, glyoxal, glutaraldehyde, crotonaldehyde, phthalaldehyde, p-xylylaldehyde, and the like are preferable. Also, as the ketone compound, cyclohexanone and benzil are preferable, and among these, from the aspect of being easily available industrially, cyclohexanone is more preferable. The compound (a) is not limited to only one, but two or more kinds can be used in combination.

[0092] In addition, the phenol or derivative thereof (hereinafter, sometimes referred to as "compound (b)") is not particularly limited, and specifically, for example, the following can be mentioned: o-cresol, m-cresol, p-cresol, and the like; phenol; 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol (2,6-dimethylphenol), 3,4-dimethylphenol, 3,5-dimethylphenol, 3,6-dimethylphenol, and the like; o-ethylphenol (2-ethylphenol), m-ethylphenol, p-ethylphenol, and the like; isopropylphenol, butylphenol, p-t-butylphenol, and the like; p-pentylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, and the like; o-phenylphenol (2-phenylphenol), p-phenylphenol, 2-cyclohexylphenol, 2-benzylphenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, 2-cyclohexyl-5-methylphenol, 2-t-butyl-5-methylphenol, 2-isopropyl-5-methylphenol, 2-methyl-5-isopropylphenol, 2,6-t-butylphenol, 2,6-diphenylphenol, 2,6-dicyclohexylphenol, 2,6-diisopropylphenol, 3-benzyl biphenyl-2-ol, 2,4-di-t-butylphenol, 2,4-diphenylphenol, 2-t-butyl-4-methylphenol, and the like. These phenols or derivatives thereof can be used alone or in combination of two or more. Among them, it is more preferable to use a compound in which the phenolic hydroxyl group is substituted with an alkyl group at the ortho position and the para position, such as 2,6-dimethylphenol or 2,4-dimethylphenol. Among them, if the steric hindrance is too large, there is a concern that the reactivity during the synthesis of the intermediate phenol compound will be inhibited, and thus it is preferable to use a compound (b) having a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, or a benzyl group.

[0093] In the production method of the intermediate phenol compound used in the present application, the intermediate phenol compound can be obtained by reacting the compound (a) with the compound (b) at a molar ratio (compound (b) / compound (a)) of the compound (b) to the compound (a) of preferably 0.1 to 10, more preferably 0.2 to 8, in the presence of an acid catalyst.

[0094] As the acid catalyst used in the reaction, for example, inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, solid acids such as activated clay, acid clay, silica alumina, zeolite, strongly acidic ion exchange resin, and heteropoly acid can be mentioned, but it is preferable to use an inorganic acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, which is a homogeneous catalyst that can be easily removed by neutralization with a base and washing with water after the reaction.

[0095] As for the amount of the acid catalyst to be used, the acid catalyst is used in an amount of 0.001 part by mass to 40 parts by mass, relative to 100 parts by mass of the total amount of the compound (a) and the compound (b) as raw materials, but from the viewpoints of handling and economy, it is preferably used in an amount of 0.001 part by mass to 25 parts by mass.

[0096] The reaction temperature is usually in the range of 30°C to 150°C, but from the viewpoints of suppressing the generation of isomer structures, avoiding side reactions such as thermal decomposition, and obtaining an intermediate phenol compound with high purity, it is preferably in the range of 60°C to 120°C.

[0097] The reaction time is usually in the range of 0.5 hours to 24 hours in total, and preferably in the range of 0.5 hours to 15 hours in total, under the reaction temperature conditions, because the reaction cannot be completed in a short time, and if it is set to be long, side reactions such as thermal decomposition of the product occur.

[0098] In the method for producing the intermediate phenol compound, since phenol or a derivative thereof serves as a solvent, another solvent can not necessarily be used, but a solvent can be used.

[0099] As the organic solvent to be used for the synthesis of the intermediate phenol compound, there can be mentioned ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and phenylacetone; alcohols such as 2-ethoxyethanol, methanol, and isopropyl alcohol; N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, aprotic solvents such as sulfolane and tetrahydrofuran; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, and xylene; and the like, and these can be used alone or in combination.

[0100] As the hydroxyl equivalent (phenol equivalent) of the intermediate phenol compound, it is preferably in the range of 80 g / eq to 500 g / eq, and more preferably in the range of 100 g / eq to 300 g / eq, from the viewpoint of heat resistance. Note that the hydroxyl equivalent (phenol equivalent) of the intermediate phenol compound is calculated by titration, and is determined in accordance with the neutralization titration method of JIS K0070.

[0101] <Method for producing a curable resin>

[0102] The method for producing a curable resin (introducing a (meth)acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group into an intermediate phenol compound) will be described below.

[0103] The curable resin can be obtained by a known method such as reacting (meth)acrylic anhydride, (meth)acryloyl chloride, chloromethylstyrene, chlorostyrene, chlorinated allyl, brominated allyl, or the like (hereinafter, sometimes referred to as "(meth)acrylic anhydride, etc.") with the intermediate phenol compound in the presence of a basic or acidic catalyst. By reacting them, a crosslinking group (X) can be introduced into the intermediate phenol compound, and in addition, a thermally cured resin having a low dielectric constant and a low dielectric loss tangent is obtained, and a preferable form is obtained.

[0104] As the (meth)acrylic anhydride, for example, acrylic anhydride and methacrylic anhydride can be exemplified. As the (meth)acryloyl chloride, for example, methacryloyl chloride and acryloyl chloride can be exemplified. In addition, as the chloromethylstyrene, for example, p-chloromethylstyrene, m-chloromethylstyrene can be exemplified, as the chlorostyrene, for example, p-chlorostyrene, m-chlorostyrene can be exemplified, as the chlorinated allyl, for example, 3-chloro-l-propene can be exemplified, and as the brominated allyl, for example, 3-bromo-l-propene can be exemplified. These can be used individually or in combination. Among them, it is preferable to use methacrylic anhydride or methacryloyl chloride which can obtain a hardened product having a lower dielectric loss tangent.

[0105] As the basic catalyst, specifically, dimethylaminopyridine, alkaline earth metal hydroxide, alkali metal carbonate, alkali metal hydroxide, and the like can be exemplified. As the acidic catalyst, specifically, sulfuric acid, methanesulfonic acid, and the like can be exemplified. In particular, dimethylaminopyridine is excellent in terms of catalyst activity.

[0106] As the reaction of the intermediate phenol compound with the (meth)acrylic anhydride, etc., the following method can be exemplified: 1 mole to 10 moles of the (meth)acrylic anhydride, etc. is added with respect to 1 mole of the hydroxyl group contained in the intermediate phenol compound, and 0.01 mole to 0.2 mole of the basic catalyst is added at once or slowly, and it is reacted at a temperature of 30°C to 150°C for 1 hour to 40 hours.

[0107] In addition, when reacting with the (meth)acrylic anhydride, etc. (introduction of the crosslinking group), an organic solvent is also used, and thereby the reaction speed at the time of synthesizing the curable resin can be increased. As such an organic solvent, there is no particular limitation, and for example, ketones such as acetone, methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol, tert-butanol, cellusolves such as methyl cellusolve, ethyl cellusolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethoxyethane, aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, and toluene can be exemplified. These organic solvents can be used individually, and in addition, two or more kinds can be used in combination as appropriate in order to adjust the polarity.

[0108] After the reaction with the (meth)acrylic anhydride or the like (introduction of crosslinking group) is completed, the reaction product is reprecipitated in a poor solvent, and the precipitate is stirred in the poor solvent at a temperature of 20°C to 100°C for 0.1 hour to 5 hours, filtered under reduced pressure, and dried at a temperature of 40°C to 80°C for 1 hour to 10 hours, whereby the hardening resin of interest can be obtained. As the poor solvent, hexane or the like can be used.

[0109] The softening point of the hardening resin is preferably 150°C or lower, and more preferably 20°C to 140°C. When the softening point of the hardening resin is within the range, the processability is excellent, and thus is preferred.

[0110] <Hardening resin composition>

[0111] The present application relates to a hardening resin composition containing the hardening resin. The hardening resin can contribute to heat resistance and low dielectric properties (particularly, low dielectric loss tangent), and thus a hardening product obtained by using the hardening resin composition containing the hardening resin is excellent in heat resistance and low dielectric properties, and is a preferred form.

[0112] [Other resin or the like]

[0113] In the hardening resin composition of the present application, other resins, hardening agents, hardening accelerators, or the like can be used without particular limitation within a range not impairing the object of the present application, in addition to the hardening resin. The hardening resin, as described later, can obtain a hardening product by heating or the like without blending a hardening agent, and for example, when other resins or the like are blended together, a hardening agent or a hardening accelerator or the like can be blended and used.

[0114] Further, the hardening resin composition of the present application contains the hardening resin, and in the hardening resin, when X is an allyl ether group, X is different from a (meth)acryloyloxy group, a vinylbenzyl ether group, and cannot be polymerized (crosslinked) alone (a hardening product cannot be obtained alone), and thus in the case where X is an allyl ether group, a hardening agent or a hardening accelerator or the like must be used.

[0115] [Other resin]

[0116] As the other resin, for example, an olefin group-containing compound such as a bismaleimide, an allyl ether compound, an allyl amine compound, a triallyl cyanurate, an allyl phenol compound, a vinyl group-containing polyolefin compound, or the like can be added. In addition, other thermally hardening resins such as a thermally hardening polyimide resin, an epoxy resin, a phenol resin, an active ester resin, a benzoxazine resin, a cyanate ester resin, or the like can be appropriately blended according to the purpose.

[0117] [Hardening agent]

[0118] As the hardening agent, for example, an amine-based compound, an amide-based compound, an acid anhydride-based compound, a phenol-based compound, a cyanate-based compound, and the like can be exemplified. These hardening agents can be used alone or in combination of two or more.

[0119] [Hardening accelerator]

[0120] As the hardening accelerator, various substances can be used, and for example, a phosphorus-based compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, an amine complex salt, and the like can be exemplified. In particular, in the case of use as a semiconductor sealing material, a phosphorus-based compound such as triphenylphosphine or an imidazole is preferable in terms of excellent aspects of hardening property, heat resistance, electric characteristics, moisture resistance reliability, and the like. These hardening accelerators can be used alone or in combination of two or more.

[0121] [Flame retardant]

[0122] In the hardening resin composition of the present application, in order to exhibit flame retardancy, a flame retardant can be compounded as necessary, and a non-halogen-based flame retardant which does not substantially contain a halogen atom is preferable. As the non-halogen-based flame retardant, for example, a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicone-based flame retardant, an inorganic-based flame retardant, an organic metal salt-based flame retardant, and the like can be exemplified, and these flame retardants can be used alone or in combination of two or more.

[0123] [Filler]

[0124] In the hardening resin composition of the present application, an inorganic filler can be compounded as necessary. As the inorganic filler, for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like can be exemplified. In the case of particularly increasing the compounding amount of the inorganic filler, it is preferable to use fused silica. The fused silica can use any one of a crushed shape and a spherical shape, but in order to increase the compounding amount of the fused silica and suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical silica. In order to further increase the compounding amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. In addition, in the case of using the hardening resin composition for the use of a conductive paste and the like which will be described below in detail, a conductive filler such as silver powder or copper powder can be used.

[0125] [Other compounding agent]

[0126] In the hardening resin composition of the present application, various compounding agents such as a silane coupling agent, a release agent, a pigment, an emulsifier, and the like can be added as necessary.

[0127] <Hardened product>

[0128] The present application relates to a hardened product, wherein the hardened product is obtained by allowing the hardenable resin composition to undergo a hardening reaction. The hardenable resin composition can be obtained by the hardenable resin alone, or by uniformly mixing each component other than the hardenable resin, and the hardened product can be easily produced by the same method as the previously known method. As the hardened product, there can be cited a molded hardened product such as a laminate, a cast, an adhesive layer, a coating film, a film, and the like.

[0129] As the hardening reaction, there can be cited a thermal hardening reaction or an ultraviolet hardening reaction, and the like, wherein the thermal hardening reaction is easily performed even in the absence of a catalyst, but in the case where the reaction is to be performed more rapidly, it is effective to add a polymerization initiator such as an organic peroxide, an azo compound, or the like, or a basic catalyst such as a phosphine-based compound, a tertiary amine, or the like. For example, there can be cited benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, and the like.

[0130] <Usage>

[0131] The hardened product obtained from the hardenable resin composition of the present application is excellent in heat resistance and dielectric properties, and thus can be preferably used for a heat-resistant member or an electronic member. In particular, it can be preferably used for a prepreg, a circuit substrate, a semiconductor sealing material, a semiconductor device, a build-up film, a build-up substrate, an adhesive, or a resist material, and the like. In addition, it can be preferably used for a matrix resin of a fiber-reinforced resin, and is particularly suitable as a prepreg having high heat resistance. In addition, the hardenable resin contained in the hardenable resin composition exhibits excellent solubility with respect to various solvents, and thus can be paintable. The heat-resistant member or the electronic member thus obtained can be preferably used for various uses, and for example, there can be cited industrial machine parts, general machine parts, automobile / railway / vehicle parts, space / aerospace-related parts, electronic / electrical parts, building materials, container / packaging members, household goods, sports / recreation goods, wind power generation frame members, and the like, but is not limited thereto.

[0132] Examples

[0133] Hereinafter, the present application will be specifically described by way of examples and comparative examples, and "parts" and "%" are on a mass basis unless otherwise specified. In addition, the hardenable resin and the hardened product obtained using the hardenable resin composition containing the hardenable resin were synthesized under the conditions shown below, and the further obtained hardened product was measured and evaluated under the conditions below.

[0134] <Examples> 1 H-NMR Measurement

[0135] 1 H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE

[0136] Magnetic field strength: 600MHz

[0137] Total number of times: 32

[0138] Solvent: CDCl3

[0139] Sample concentration: 1% by mass

[0140] Through the above 1 The synthesis of the curable resin obtained by the following manufacturing method was confirmed by the disappearance of the aldehyde peak during 1H-NMR determination (refer to Example 1). Figure 1 Example 9 Figure 2 Example 10 Figure 3 In addition, besides Examples 1, 9, and 10, the same applies through the methods described above. 1 H-NMR measurements were used to confirm the synthesis of the curable resin (not shown).

[0141] <Determination of Hydroxyl Concentration>

[0142] The hydroxyl value was determined according to the method of JIS K 1557-1, and the hydroxyl concentration (mmol / kg) was calculated based on the formula 1000 × hydroxyl value / 56.11.

[0143] (Example 1)

[0144] In a 200 mL three-necked flask equipped with a cooling tube, 67.19 g (0.55 mol) of 2,6-xylenol and 56.19 g of 96% sulfuric acid were added and dissolved in 30 mL of methanol while nitrogen was flowing through them. The mixture was heated in an oil bath at 70 °C, and after 6 hours of stirring, 25.03 g (0.125 mol) of a 50% glutaraldehyde aqueous solution was added, followed by stirring for another 12 hours. After the reaction was complete, the resulting reaction mixture was cooled to room temperature, and 200 mL of toluene was added to the reaction solution, followed by washing with 200 mL of water. The organic layer was then injected into 500 mL of hexane, and the precipitated solid was filtered and dried under vacuum to obtain 21.56 g (0.039 mol) of the intermediate phenolic compound.

[0145] In a 200 mL flask equipped with a thermometer, a cooling tube, and a stirrer, 20 g of toluene and 32.17 g (0.039 mol) of the intermediate phenol compound were mixed, and heated to 110°C. 1.95 g (0.016 mol) of dimethylaminopyridine was added. At the point when the solid was completely dissolved, 24.02 g (0.1558 mol) of methacrylic anhydride was added slowly. While continuously mixing the obtained solution, it was maintained at 110°C for 20 hours. Next, the solution was cooled to room temperature, and was added dropwise over 30 minutes to 360 g of hexane, which was vigorously stirred using a magnetic stirrer in a 1 L beaker. The obtained precipitate was filtered under reduced pressure, and dried, to obtain 32.18 g (0.039 mol) of a curable resin.

[0146] According to 1 H-NMR measurement (refer to Figure 1 ) and hydroxyl value measurement, it was judged that the following structural formula was the main component (also including the case where a part of the methacryloyl groups in the following structural formula do not react with methacrylic anhydride and remain as hydroxyl groups).

[0147] [Chemical Formula 10]

[0148]

[0149] (Example 2)

[0150] Except that the methacrylic anhydride in Example 1 was changed to 23.98 g (0.1555 mol), synthesis was performed using the same method as in Example 1, to obtain a curable resin having a hydroxyl concentration of 0.1 mmol / kg, with the same structure as in Example 1 as the main component.

[0151] (Example 3)

[0152] Except that the methacrylic anhydride in Example 1 was changed to 23.93 g (0.1552 mol), synthesis was performed using the same method as in Example 1, to obtain a curable resin having a hydroxyl concentration of 1 mmol / kg, with the same structure as in Example 1 as the main component.

[0153] (Example 4)

[0154] Except that the methacrylic anhydride in Example 1 was changed to 23.81 g (0.1544 mol), synthesis was performed using the same method as in Example 1, to obtain a curable resin having a hydroxyl concentration of 10 mmol / kg, with the same structure as in Example 1 as the main component.

[0155] (Example 5)

[0156] A synthesis was conducted in the same manner as in Example 1, except that the methacrylic anhydride in the example 1 was changed to 23.57 g (0.1529 mol), to obtain a curable resin having a hydroxyl concentration of 110 mmol / kg, with the same structure as in Example 1 as a main component.

[0157] (Example 6)

[0158] A synthesis was conducted in the same manner as in Example 1, except that the methacrylic anhydride in the example 1 was changed to 19.24 g (0.1248 mol), to obtain a curable resin having a hydroxyl concentration of 1000 mmol / kg, with the same structure as in Example 1 as a main component.

[0159] (Example 7)

[0160] A synthesis was conducted in the same manner as in Example 1, except that the methacrylic anhydride in the example 1 was changed to 17.07 g (0.1108 mol), to obtain a curable resin having a hydroxyl concentration of 1510 mmol / kg, with the same structure as in Example 1 as a main component.

[0161] (Example 8)

[0162] A synthesis was conducted in the same manner as in Example 1, except that the methacrylic anhydride in the example 1 was changed to 12.02 g (0.0780 mol), to obtain a curable resin having a hydroxyl concentration of 2950 mmol / kg, with the same structure as in Example 1 as a main component.

[0163] (Example 9)

[0164] In a 200 ml three-necked flask equipped with a cooling tube, 2,6-dimethylphenol 67.19 g (0.55 mol) and 96% sulfuric acid 56.19 g were charged, and dissolved in methanol 30 ml while passing nitrogen. The temperature was raised in an oil bath at 70°C, and after 50% glutaraldehyde aqueous solution 25.03 g (0.125 mol) was added while stirring for 6 hours, the reaction was carried out for 12 hours while stirring. After the reaction was completed, the obtained reaction mixture was cooled to room temperature, and toluene 200 ml was added to the reaction solution, followed by washing with water 200 ml. Then, the organic layer was poured into hexane 500 ml, the precipitated solid was separated by filtration, and vacuum dried to obtain intermediate phenol compound 21.56 g (0.039 mol).

[0165] In a 300 mL flask equipped with a thermometer, a cooling tube, and a stirrer, the obtained intermediate phenol compound 21.56 g (0.039 mol), 2,4-dinitrophenol (DNP) 0.046 g (0.00025 mol), tetrabutylammonium bromide (TBAB) 5.9 g (0.018 mol), chloromethylstyrene 23.56 g (0.1544 mol), and methyl ethyl ketone 100 g were added, and the temperature was raised to 75°C while stirring.

[0166] Next, 48% NaOH aq. was added dropwise to the reaction vessel maintained at 75°C over 20 minutes. After the addition was completed, stirring was further continued at 75°C for 20 hours. After 20 hours, the temperature was cooled to room temperature, toluene 100 g was added, and then neutralization was performed using 10% HC1. Then, the separation was performed by phase separation of the aqueous phase, and further, 3 times of washing was performed using water 300 ml. The obtained organic phase was concentrated by distillation, methanol was added, and the product was reprecipitated. The precipitate was filtered and dried to obtain a curable resin 39.68 g (0.039 mol).

[0167] According to 1 H-NMR measurement (refer to Figure 2 ) and hydroxyl value measurement, it was judged that the structure having a hydroxyl concentration of 9 mmol / kg was the main component (including the case where a part of the vinylbenzyl ether group in the following structural formula does not react with chloromethylstyrene and remains as a hydroxyl group).

[0168] [Chemical 11]

[0169]

[0170] (Example 10)

[0171] In a 200 ml three-necked flask equipped with a cooling tube, 2-cyclohexyl-5-methylphenol 104.66 g (0.55 mol), 96% sulfuric acid 56.19 g were charged, and dissolved in methanol 30 ml while passing nitrogen. The temperature was raised in an oil bath at 70°C, and after 50% glutaraldehyde aqueous solution 25.03 g (0.125 mol) was added while stirring for 6 hours, the reaction was performed for 12 hours while stirring. After the reaction was completed, the obtained reaction mixture was cooled to room temperature, toluene 200 ml was added to the reaction solution, and then washed using water 200 ml. Then, the organic layer was poured into hexane 500 ml, the precipitated solid was separated by filtration, and vacuum dried to obtain an intermediate phenol compound 32.18 g (0.039 mol).

[0172] In a 200 mL flask equipped with a thermometer, a cooling tube, and a stirrer, 20 g of toluene and 32.18 g (0.039 mol) of the obtained intermediate phenol compound were mixed, and heated to 110°C.

[0173] Next, 1.95 g (0.016 mol) of dimethylaminopyridine was added. At the point when the solid was completely dissolved, 23.81 g (0.1544 mol) of methacrylic anhydride was slowly added. While continuously mixing the obtained solution, it was maintained at 110°C for 20 hours.

[0174] Next, the obtained solution was cooled to room temperature, and added dropwise over 30 minutes to 360 g of hexane, which was vigorously stirred using a magnetic stirrer in a 1 L beaker, to obtain a precipitate. The obtained precipitate was dried after being filtered under reduced pressure, to obtain a curable resin 42.80 g (0.039 mol).

[0175] According to 1 H-NMR measurement (refer to Figure 3 ) and hydroxyl value measurement, it was judged that the following structure was the main component (also including the case where a part of the methacryloyl group in the following structure does not react with methacrylic anhydride and remains as a hydroxyl group).

[0176] [Chemical Formula 12]

[0177]

[0178] (Comparative Example 1)

[0179] Except that the methacrylic anhydride in Example 1 was changed to 30.6 g (0.25 mol), synthesis was performed using the same method as in the above Example 1, to obtain a curable resin having a hydroxyl concentration of 0 mmol / kg, with the same structure as in Example 1 as the main component.

[0180] (Comparative Example 2)

[0181] Except that the methacrylic anhydride in Example 1 was changed to 8.42 g (0.0546 mol), synthesis was performed using the same method as in the above Example 1, to obtain a curable resin having a hydroxyl concentration of 4040 mmol / kg, with the same structure as in Example 1 as the main component.

[0182] (Comparative Example 3)

[0183] By mixing 10 parts by mass of the curable resin obtained in Comparative Example 1 and 0.0013 parts by mass of 4-methoxyphenol, a curable resin (mixture) having a hydroxyl concentration of 10 mmol / kg was obtained.

[0184] Evaluation of storage stability

[0185] A resin solution having a solid content concentration of 80% was prepared using toluene to dissolve the curable resin. The initial viscosity was measured at 25°C and the viscosity after storage at 60°C for one month was measured using a RE100L viscometer manufactured by Tokimec, Inc. The storage stability was evaluated using the viscosity change rate (%) (100 x (viscosity after storage at 60°C for one month - viscosity before storage) / viscosity before storage). In addition, if the storage stability was O or Δ (viscosity change rate was not more than 20%), it was determined that there was no problem in practical use.

[0186] (Evaluation criteria)

[0187] O: viscosity change rate was not more than 10%

[0188] Δ: viscosity change rate was 10% to less than 20%

[0189] X: viscosity change rate was 20% or more

[0190] <Production of resin film (cured product)>

[0191] The curable resin obtained in the examples and comparative examples and a curable resin composition in which 5 parts by mass of α,α'-bis(tert-butylperoxy)diisopropylbenzene as a radical polymerization initiator was mixed with 100 parts by mass of the curable resin were put into a 5 cm square square-shaped mold frame, clamped with a stainless steel plate, and set in a vacuum press machine. The pressure was increased to 1.5 MPa at normal pressure and room temperature. Next, after the pressure was reduced to 10 torr, the temperature was increased to 100°C over 30 minutes and left to stand for 1 hour. Then, the temperature was increased to 220°C over 30 minutes and left to stand for 2 hours. Then, it was slowly cooled to room temperature. A uniform resin film (cured product) having an average film thickness of 100 μm was produced.

[0192] <Evaluation of heat resistance (glass transition temperature)>

[0193] After the observation of the heat generation peak temperature (heat curing temperature) that can be observed when the obtained resin film (hardened product) is measured using a Differential Scanning Calorimeter (DSC) apparatus (Pyris Diamond) manufactured by PerkinElmer at a temperature rise condition of 20°C / minute from room temperature, the temperature is held for 30 minutes at a temperature that is 50°C higher than the heat generation peak temperature. Next, the sample is cooled to room temperature at a temperature decrease condition of 20°C / minute, and then is warmed again at a temperature rise condition of 20°C / minute, and the glass transition temperature (Tg) (°C) of the resin film (hardened product) is measured. Further, as the glass transition temperature (Tg), if it is 100°C or higher, there is no problem in practice, and it is preferably 150°C or higher.

[0194] Evaluation of dielectric properties

[0195] As for the dielectric properties in the in-plane direction of the obtained resin film (hardened product), a network analyzer N5247A manufactured by Keysight Technology was used, and the dielectric constant and the dielectric loss tangent at a frequency of 10 GHz were measured by a split dielectric resonator method. Further, as the dielectric loss tangent, if it is 10.0 x 10 -3 -3.0 x 10 -3 -2.5 x 10 -3 -2.0 x 10. Further, as the dielectric constant, if it is 3.0 or lower, there is no problem in practice, and it is preferably 2.7 or lower, more preferably 2.5 or lower.

[0196] [Table 1]

[0197]

[0198] According to the evaluation results of the Table 1, it was confirmed that in the examples, the storage stability of the solution of the hardening resin was excellent, and the hardened product obtained by using the hardening resin could realize the coexistence of heat resistance and low dielectric properties, and was at a level that was not problematic in practice.

[0199] On the other hand, according to the evaluation results of the above Table 1, it was confirmed that in Comparative Example 1, the hydroxyl group concentration of the used curable resin was lower than the desired range, and thus the reactivity of the curable resin itself was increased, and the storage stability of the resin solution in which the curable resin was dissolved in toluene was poor. It was confirmed that in Comparative Example 2, the hydroxyl group concentration of the used curable resin exceeded the desired range, and thus the proportion of the crosslinking group other than the hydroxyl group in the curable resin was lowered, the crosslinking density of the cured product obtained using the curable resin was lowered, the glass transition temperature was low, the heat resistance was poor, and in addition, the dielectric properties were higher than those of the Examples. In addition, it was confirmed that in Comparative Example 3, the mixture of the curable resin in which 4-methoxyphenol was mixed with the curable resin having a hydroxyl group concentration lower than the desired range was a mixture in which the hydroxyl group concentration of the entire mixture was within the desired range, and the mixture solution was evaluated, and as a result, the reactivity of the curable resin itself was increased by the curable resin having a hydroxyl group concentration lower than the desired range, the storage stability of the entire mixture solution was poor, and it was important to adjust the hydroxyl group concentration of the curable resin within the desired range.

[0200] Industrial Applicability

[0201] The curable resin of the present application is excellent in storage stability, and the cured product obtained using the curable resin is excellent in heat resistance and dielectric properties, and thus can be preferably used for heat-resistant members or electronic members, and in particular, can be preferably used for prepregs, semiconductor sealing materials, circuit substrates, build-up films, build-up substrates, and the like, or adhesives or resist materials. In addition, it can also be preferably used for the matrix resin of fiber-reinforced resins, and is suitable as a prepreg having high heat resistance.

Claims

1. A curable resin, characterized in that, It is represented by the following general formula (1), and the hydroxyl concentration is 0.005 mmol / kg to 3800 mmol / kg; In formula (1), Z is a hydrocarbon represented by general formulas (3-1) to (3-6) below, or a compound composed of aliphatic and aromatic hydrocarbons containing one of naphthylmethyl, naphthylethyl, and naphthylpropyl; Y is a substituent represented by general formula (2) below; and n represents an integer from 3 to 5. In general formula (3-1), k represents an integer from 0 to 5, and Rc in general formulas (3-1), (3-2), and (3-4) to (3-6) represents a hydrogen atom or a methyl group. In formula (2), Ra and Rb are independently represented by alkyl, aryl, aralkyl or cycloalkyl groups having 1 to 12 carbon atoms, m represents an integer from 0 to 3, and X independently represents hydroxyl, (meth)acryloyloxy, vinyl benzyl ether or allyl ether, wherein at least one X is (meth)acryloyloxy, vinyl benzyl ether or allyl ether.

2. The curable resin according to claim 1, characterized in that, The concentration of the hydroxyl group is 0.01 mmol / kg to 1500 mmol / kg.

3. The curable resin according to claim 1 or 2, characterized in that, X is methacryloyloxy.

4. A curable resin composition, characterized in that, It contains a curable resin as described in any one of claims 1 to 3.

5. A hardened material, characterized in that, It can be obtained by subjecting the curing resin composition as described in claim 4 to a curing reaction.

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