Resin compositions, curable resin compositions, cured products, and electrical and electronic components

Abstract

To provide a resin composition which is excellent in moldability and solvent solubility and gives a cured product excellent in heat resistance.SOLUTION: The resin composition contains a phenolic resin having a structure represented by the following formula (1). (R1 and R2 each represent a hydrogen atom, a linear aliphatic hydrocarbon group or the like; and R3-R10 each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or the like.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to resin compositions, curable resin compositions, cured products, and electrical and electronic components. [Background technology]

[0002] Thermosetting resin compositions are used in various fields as thermosetting molding materials and the like, taking advantage of their curing properties. Among them, phenolic resins are particularly suitable as curing agents for epoxy resins, and thermosetting resin compositions combining phenolic resins and epoxy resins are widely used in the semiconductor and electronic component fields as printed circuit board materials, interlayer insulating materials for built-up substrates, semiconductor encapsulating materials, conductive adhesive materials, etc., due to their excellent properties such as heat resistance and adhesion.

[0003] Various types of phenolic resins with different skeletons and structures are known. For example, Patent Documents 1 and 2 propose polyvalent phenolic compounds having a flavan skeleton, obtained by polycondensation of resorcinols and carbonyl compounds. Patent Document 3 discloses a phenolic resin having propenyl groups, and also discloses a heat-resistant resin composition containing this propenyl group-containing phenolic resin and a maleimide compound having two or more maleimide groups in one molecule. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 4-241353 [Patent Document 2] Japanese Patent Application Publication No. 8-169937 [Patent Document 3] Japanese Patent Publication No. 2019-019149 [Overview of the project] [Problems that the invention aims to solve]

[0005] Traditionally, semiconductors have been mostly used in applications involving relatively small currents and power, such as LSIs. However, in recent years, the development of power semiconductors and other semiconductors used for controlling motors and lighting, as well as for power conversion, has been rapidly progressing. Consequently, there is a growing demand for semiconductors and semiconductor encapsulants that can handle higher powers and currents than before, and semiconductor encapsulants require higher heat resistance than conventional materials. Furthermore, printed circuit boards used in electrical and electronic equipment are increasingly being applied in harsh environments such as high temperatures, requiring high heat resistance. Furthermore, among printed circuit boards, especially multilayer printed circuit boards, there is a demand for even higher layer counts, higher density, thinner designs, lighter weights, and improved reliability and moldability. Furthermore, as wiring becomes more miniaturized, the resin material used for the substrate requires even greater heat resistance and moldability. Furthermore, in printed circuit board applications, curable resin compositions are sometimes dissolved in solvents and used as varnishes, so the resins used require high solvent solubility.

[0006] In response to these requirements, the polyvalent phenol compounds having a flavan skeleton described in Patent Documents 1 and 2 were not satisfactory in terms of heat resistance. Furthermore, many phenolic resins containing a flavan skeleton have numerous OH groups directly substituted onto the flavan skeleton, leading to the formation of many hydrogen bonds. This results in high melting points and viscosities, potentially leading to insufficient moldability for printed circuit board applications, where further miniaturization and complexity are progressing.

[0007] On the other hand, the resin composition containing a propenyl group-containing phenol resin and a maleimide compound described in Patent Document 3 was not satisfactory in terms of heat resistance for use in the above-mentioned applications, or in terms of low viscosity and solvent solubility for molding.

[0008] The present invention aims to provide a resin composition that yields a cured product with excellent moldability and solvent solubility, as well as excellent heat resistance, a curable resin composition using the same, a cured product thereof, and electrical and electronic components. [Means for Solving the Problems]

[0009] As a result of intensive studies to solve the above problems, the present inventor has found that, based on the idea that there is a correlation between the structure of a phenolic resin having a flavan skeleton and the viscosity, Tg, and heat resistance of the resulting resin composition, a flavan skeleton-containing phenolic resin having a specific structure, specifically, one having at least one phenyl group having a propenyl group and having a structure in which the positions and numbers of OH groups substituted on the flavan skeleton are controlled, can solve the above problems, and thus the present invention has been completed. That is, the gist of the present invention resides in the following [1] to [7].

[0010] [1] A resin composition containing a phenolic resin having a structure represented by the following formula (1).

[0011] [Chemical Formula]

[0012] (In the above formula (1), R 1 , R 2 each independently represents a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, except when both R 1 , R 2 are hydrogen atoms. R 3 to R 10 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but at least one of R 3 to R 10 is a substituent represented by the following formula (2). Adjacent groups of R 3 to R 10 may be bonded to form a ring.)

[0013] [Chemical Formula]

[0014] (In formula (2) above, Y is a divalent linking group selected from direct bonds, -SO2-, -O-, -CO-, -C(CF3)2-, -S-, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms. 21 (These are hydrogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, or halogen atoms.)

[0015] [2] The resin composition according to [1], comprising 0.1 to 100,000 parts by mass of a compound represented by the following formula (3) per 100 parts by mass of a phenol resin having the structure represented by formula (1).

[0016] [ka]

[0017] (In formula (3) above, X is a divalent linking group selected from direct bonds, -SO2-, -O-, -CO-, -C(CF3)2-, -S-, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms. 11 and R 12 (These are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, or halogen atoms, and may be the same or different from each other.)

[0018] A curable resin composition comprising 0.01 to 10,000 parts by mass of at least one selected from the group consisting of epoxy resin, maleimide resin, phenol resin other than the phenol resin having the structure represented by formula (1), benzoxazine resin, cyanate ester resin, active ester resin, resin having a radically polymerizable functional group, isocyanate resin, acid anhydride resin, and carbodiimide resin, per 100 parts by mass of the resin composition described in [1] or [2].

[0019] [4] A cured product obtained by curing the curable resin composition described in [3].

[0020] [5] Electrical and electronic components comprising a cured product of the curable resin composition described in [4].

[0021] [6] A cured product containing a structure derived from the structure represented by the following formula (1).

[0022] [ka]

[0023] (In the above formula (1), R 1 , R 2 Each of these independently represents a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but R 1 , R 2 This excludes the case where both are hydrogen atoms. 3 ~R 10 Each of these independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but R 3 ~R 10 At least one of them is a substituent represented by the following formula (2). 3 ~R 10 (The adjacent groups may be bonded together to form a ring.)

[0024] [ka]

[0025] (In formula (2) above, Y is a divalent linking group selected from direct bonds, -SO2-, -O-, -CO-, -C(CF3)2-, -S-, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms. 21 (These are hydrogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, or halogen atoms.)

[0026] Electrical and electronic components containing the cured products described in [7] and [6]. [Effects of the Invention]

[0027] The resin composition of the present invention is a resin composition that yields a cured product with excellent moldability and solvent solubility, as well as excellent heat resistance. For this reason, the resin composition and curable resin composition of the present invention can be particularly effectively applied to electrical and electronic components such as semiconductor encapsulants and laminates. [Modes for carrying out the invention]

[0028] The embodiments of the present invention will be described in detail below, but the following description is merely one example of an embodiment of the present invention, and the present invention is not limited to the following description unless it exceeds the gist of the invention. In this specification, when the expression "~" is used, it is used to mean an expression that includes the numerical value or physical property value before and after it.

[0029] [Resin composition] The resin composition of the present invention is characterized by containing a phenol resin having the structure represented by the following formula (1) (hereinafter sometimes referred to as "phenol resin (1)"). The structure represented by the following formula (1) does not include a repeating structure, but is a single-molecule structure, however it is referred to as "phenol resin" in this industry and is sometimes sold as "phenol resin". Furthermore, in this industry, "phenol compounds (uncured)" are also called "phenol resin," so the compound represented by the following formula (1) is also called "phenol resin," and therefore phenol resin (1) is generally referred to as "phenol resin."

[0030] [ka]

[0031] (In the above formula (1), R 1 , R 2 Each of these independently represents a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but R 1 , R 2 This excludes the case where both are hydrogen atoms. 3 ~R 10Each of these independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but R 3 ~R 10 At least one of them is a substituent represented by the following formula (2). 3 ~R 10 (The adjacent groups may be bonded together to form a ring.)

[0032] [ka]

[0033] (In formula (2) above, Y is a divalent linking group selected from direct bonds, -SO2-, -O-, -CO-, -C(CF3)2-, -S-, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms. 21 (These are hydrogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, or halogen atoms.)

[0034] <Phenolic resin (1)> R in equation (1) above 1 , R 2 Preferred examples of the linear aliphatic hydrocarbon group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, and alkynyl groups having 2 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups. Examples of alkenyl groups having 2 to 6 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group. Examples of alkynyl groups having 2 to 6 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, and 3-butynyl groups.

[0035] R 1 , R 2Examples of substituted or unsubstituted aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, ethinylphenyl, naphthyl, and vinylnaphthyl groups. Examples of substituents that the aryl group may have include alkyl groups, alkoxy groups, aryl groups, alkenyl groups, and alkynyl groups, and the molecular weight of the substituent is usually 500 or less.

[0036] R 1 , R 2 Examples of substituted or unsubstituted heteroaryl groups include furan rings, benzofuran rings, dibenzofuran rings, thiophene rings, benzothiophene rings, dibenzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, carbazole rings, thienothiophene rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinnoline rings, quinoxaline rings, and perimidine rings, all of which have a monovalent free valency. Examples of substituents that the heteroaryl group may have include alkyl groups, alkoxy groups, aryl groups, alkenyl groups, and alkynyl groups, and the molecular weight of the substituent is usually 500 or less.

[0037] Among these, R 1 , R 2 However, it is preferable that it be a hydrogen atom or a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, and from the viewpoint of being able to improve heat resistance, R 1 , R 2 Both are preferably linear aliphatic hydrocarbon groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 6 carbon atoms, and most preferably methyl groups. 1 , R 2 When both are hydrogen atoms, their solvent solubility is poor, R 1 , R 2 This excludes cases where both atoms are hydrogen atoms.

[0038] R in equation (1) above 3 ~R10 Each of these independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but R 3 ~R 10 At least one of these is a substituent represented by formula (2) above.

[0039] R 3 ~R 10 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0040] R 3 ~R 10 The aliphatic hydrocarbon group is not particularly limited, but examples include alkyl groups, alkenyl groups, alkynyl groups, and alkoxy groups. The substituents that the aliphatic hydrocarbon group may have include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, alkylthio groups, and arylthio groups. The molecular weight of the substituent is preferably 400 or less. Examples of substituted or unsubstituted alkyl groups include the following: for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n-decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, 2-phenylisopropyl group, etc. Examples of substituted or unsubstituted alkoxy groups include the following: for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, tert-pentoxy group, cyclopentoxy group, n-hexyloxy group, isohexyloxy group, cyclohexyloxy group, n-heptoxy group, cycloheptoxy group, methylcyclohexyloxy group, n-oc These include tyroxy group, cyclooctyroxy group, n-nonyloxy group, 3,3,5-trimethylcyclohexyloxy group, n-decyloxy group, cyclodecyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclododecyloxy group, benzyloxy group, methylbenzyroxy group, dimethylbenzyroxy group, trimethylbenzyroxy group, naphthylmethoxy group, phenethyloxy group, 2-phenylisopropoxy group, etc. Examples of substituted or unsubstituted alkenyl groups include the following: vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, cyclohexenyl group, cyclohexadienyl group, cinnamyl group, naphthylvinyl group, etc. Examples of substituted or unsubstituted alkynyl groups include the following: for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butanedienyl group, phenylethynyl group, naphthylethynyl group, etc.

[0041] R 3 ~R 10 Examples of substituted or unsubstituted aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, ethinylphenyl, naphthyl, and vinylnaphthyl groups. Examples of substituents that the aryl group may have include alkyl groups, alkoxy groups, alkenyl groups, and alkynyl groups, the molecular weight of which is usually 200 or less.

[0042] R 3 ~R 10 Examples of substituted or unsubstituted heteroaryl groups include furan rings, benzofuran rings, dibenzofuran rings, thiophene rings, benzothiophene rings, dibenzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, carbazole rings, thienothiophene rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinnoline rings, quinoxaline rings, and perimidine rings, all of which have a monovalent free valency. Examples of substituents that the heteroaryl group may have include alkyl groups, alkoxy groups, aryl groups, alkenyl groups, and alkynyl groups, and the molecular weight of the substituent is usually 500 or less.

[0043] Also, R 3 ~R 10 At least one of these is the substituent represented by formula (2) above (hereinafter sometimes referred to as "substituent (2)").

[0044] In formula (2) above, the aliphatic hydrocarbon group having 1 to 20 carbon atoms in Y is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 10 carbon atoms that may be branched. Y is preferably directly bonded or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably directly bonded, a methylene group, or an isopropylidene group, even more preferably directly bonded or an isopropylidene group, and most preferably Y is directly bonded.

[0045] R 21 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. 21 Examples of hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms. Preferably, R 21 This is a hydrogen atom or a methyl group, most preferably a hydrogen atom.

[0046] Since substituent (2) has a propenyl group, it has the effect of contributing to heat resistance, and the softening point or melting point does not become too high, and tends to have excellent fluidity and moldability. In formula (2) above, the propenyl group is preferably located at the meta position relative to the carbon atom to which Y is bonded, from the viewpoint of reactivity. Furthermore, the hydroxyl group is preferably located at the para or ortho position relative to the carbon atom to which Y is bonded, from the viewpoint of reactivity. 21 From a reactivity standpoint, it is preferable that Y is located at the meta position relative to the carbon atom to which it is bonded.

[0047] Note that if there are multiple substituents (2) in formula (1), each Y, R 21 They may be the same or they may be different.

[0048] R 3 ~R 10 Adjacent groups may bond to form a ring. In this case, the formed ring may be either an aromatic ring or a non-aromatic ring, but is preferably an aromatic ring. 3 ~R 10 When adjacent groups bond to form a ring, the molecular weight of that ring is usually 300 or less.

[0049] In the present invention, the preferred phenolic resin (1) is, in formula (1), R 3 ~R 6 One of them is substituent (2), and the remaining three are, independently, a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R 7 ~R 10 One of them is substituent (2), and the remaining three are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and a more preferred phenol resin (1) is in formula (1), R 5 ,R 9 is substituent (2), R 3 ,R 4 ,R 6,R 7 ,R 8 ,R 10 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, particularly preferably an unsaturated aliphatic hydrocarbon group having 2 to 3 carbon atoms.

[0050] From the viewpoints of heat resistance and moldability (low viscosity), the phenolic resin (1) is most preferably a phenolic resin having a structure represented by the following formula (1A).

[0051] [Chemical formula]

[0052] (In the above formula (1A), Y, R 21 is synonymous with Y, R in formula (2), and the preferred ones are the same. R 21 3 ,R 7 3 is synonymous with R in formula (1), and the preferred ones are the same. 7 ,R 3 7

[0053] Since the phenolic resin having the structure represented by formula (1A) has both a flavan skeleton and a phenyl group, it tends to exhibit higher heat resistance. Further, since it has a propenyl group, the curable resin composition prepared by mixing with a maleimide resin exhibits excellent thermosetting properties and can give a cured product having high heat resistance.

[0054] R in formula (1A) 21 ,R 11 ,R 12 is preferably, each independently, a hydrogen atom or a methyl group, and most preferably both are hydrogen atoms.

[0055] <Compound (3)> The resin composition of the present invention preferably contains 0.1 to 100,000 parts by mass of a compound represented by the following formula (3) (hereinafter, may be referred to as "compound (3)") with respect to 100 parts by mass of the phenolic resin (1). <000037​ [Chemical formula]

[0057] (In the above formula (3), X is a divalent linking group selected from a direct bond, -SO2-, -O-, -CO-, -C(CF3)2-, -S-, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms. R 11 and R 12 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and they may be the same or different from each other.)

[0058] In the above formula (3), as the aliphatic hydrocarbon group having 1 to 20 carbon atoms for X, preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably an alkylene group which may have a branch having 1 to 10 carbon atoms can be mentioned. X is preferably a direct bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a direct bond, a methylene group, or an isopropylidene group, still more preferably a direct bond or an isopropylidene group, and most preferably, X is a direct bond.)

[0059] R 11 , R 12 Examples of the halogen atom of are a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, examples of the hydrocarbon group having 1 to 10 carbon atoms of R 11 , R 12 include an alkyl group having 1 to 10 carbon atoms. Preferably, R 11 , R 12 are each independently a hydrogen atom or a methyl group, and most preferably both are hydrogen atoms.)

[0060] In the resin composition of the present invention, the higher the content of the above compound (3) with respect to the phenol resin (1), the lower the melt viscosity tends to be, and the lower the content, the higher the solvent solubility tends to be. From such a viewpoint, in the resin composition of the present invention, it is more preferable to contain 1 to 1000 parts by mass of the compound (3) with respect to 100 parts by mass of the phenol resin (1), and still more preferably 2 to 800 parts by mass.)

[0061] <Melting viscosity> The resin composition of the present invention preferably has a melt viscosity of 0.01 to 100.0 P at 150°C, more preferably 0.05 to 90 P, and even more preferably 0.1 to 80 P. If the melt viscosity is below the above upper limit, it is easy to mix with maleimide resins, epoxy resins, etc., as described later, due to its low viscosity. If the melt viscosity is above the above lower limit, bleed-out is less likely to occur when molding in a mold or the like. The melt viscosity of the resin composition is measured by the method described in the Examples section below.

[0062] <Softening point or melting point> The softening point or melting point of the resin composition of the present invention is preferably 40 to 150°C, more preferably 50 to 140°C, and even more preferably 55 to 120°C. If the softening point or melting point is above the lower limit, blocking is less likely to occur, and if it is below the upper limit, it flows quickly when heated. The softening point or melting point of the resin composition is measured by the method described in the Examples section below.

[0063] <Manufacturing of phenolic resin (1)> The method for producing the phenol resin (1) is not particularly limited, but for example, one method is to heat and flavanize a phenol compound having an allyl group represented by the following formulas (4) and / or (5) (hereinafter referred to as "phenol compound (4)" and "phenol compound (5)" respectively, and sometimes collectively referred to as "phenol compound (4), (5)"). Phenol compounds (4) and (5) may be used individually or in combination. When heating, phenol compounds (4) and (5) may be dissolved in a solvent, or a catalyst may be added.

[0064] [ka]

[0065] (In equations (4) and (5) above, R 1 ~R 10R in equation (1) above is 1 ~R 10 This is equivalent to the above. Preferably, in formula (4), R 5 is substituent (2), R 3 ,R 4 ,R 6 R is a hydrogen atom, and in equation (5), 9 is substituent (2), R 7 ,R 8 ,R 10 (This is a hydrogen atom.)

[0066] Any solvent that can dissolve the phenol compounds (4) and (5) can be used in the flavanization reaction. Examples include toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methanol, ethanol, butanol, ethylene glycol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and tetrahydrofuran. The solvent may be used alone or in combination of two or more.

[0067] When using a solvent, it is preferable to use 10 to 1000 parts by mass, particularly 50 to 500 parts by mass, of phenol compounds (4) and (5) per 100 parts by mass.

[0068] When a catalyst is added to the flavanization reaction, examples of catalysts include acidic catalysts such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and acetic acid. One type of catalyst may be used alone, or two or more types may be used in combination.

[0069] When a catalyst is used, the amount used is preferably 0.001 to 5.0 times the total molar amount of hydroxyl groups of phenol compounds (4) and (5), and more preferably 0.002 to 2.0 times the molar amount.

[0070] The reaction temperature for the flavanization reaction is preferably 50 to 200°C, and more preferably 80 to 160°C. If the reaction temperature is above the lower limit, the flavanization reaction proceeds easily. If the reaction temperature is below the upper limit, side reactions are less likely to occur.

[0071] After the flavanization reaction, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation, concentration, and purification (washing, column chromatography, etc.), if necessary.

[0072] <Production of compound (3)> The method for producing compound (3) is not particularly limited, but for example, one method is to allylate a divalent phenol compound represented by the following formula (6) (hereinafter sometimes abbreviated as "divalent phenol compound (6)") to obtain an allyloxy group-containing compound represented by the following formula (7) (hereinafter sometimes abbreviated as "allyloxy group-containing compound (7)"), then transfer the allyl group of the allyloxy group-containing compound (7) to obtain a 2-propenyl group-containing phenol compound (8) represented by the following formula (8), and then change the 2-propenyl group of this 2-propenyl group-containing phenol compound (8) to a 1-propenyl group to obtain compound (3).

[0073] [ka]

[0074] (In the above equations (6), (7), and (8), X, R 11 , R 12 This is equivalent to the expression in equation (3) above.

[0075] One method for allylating the divalent phenol compound (6) is to react the divalent phenol compound (6) with an allyl halide to convert at least some of the hydroxyl groups into an allyl ether, thereby converting them to -O-CH2-CH=CH2.

[0076] In this reaction, it is preferable to use 2.0 to 8.0 moles, particularly 3.0 to 6.0 moles, of allyl halide relative to the divalent phenol compound (6), from the viewpoint of efficiently carrying out the reaction while keeping production costs down.

[0077] The allyl etherification reaction between the divalent phenol compound (6) and the allyl halogen is preferably carried out in the presence of a catalyst.

[0078] Examples of catalysts for the allyl etherification reaction include alkali metals such as sodium hydroxide, potassium hydroxide, and potassium carbonate; amines such as diazabicyclononene, diazabicycloundecene, and triethylamine; sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, silicon-based amines, and lithium tetramethylpiperidine. Among these, alkali metals, diazabicyclononene, and diazabicycloundecene are preferred because they are relatively inexpensive and less prone to side reactions. The catalyst may be used alone or in combination of two or more.

[0079] The amount of catalyst used in the allyl etherification reaction is preferably 0.7 to 2.0 times the molar amount of allyl halide used, and more preferably 0.8 to 1.5 times. If too little catalyst is used, the reaction rate will be slow, and if too much is used, excess alkali will have to be removed, reducing productivity.

[0080] Furthermore, the allyl etherification reaction is preferably carried out in the presence of a solvent. Examples of solvents for the allyl etherification reaction include polar solvents used in the propenylation reaction described later.

[0081] The reaction temperature for the allyl etherification reaction is not particularly limited as long as it is the temperature at which the hydroxyl group of the divalent phenol compound (6) reacts with the allyl halide, and is preferably 10 to 150°C, and more preferably 40 to 130°C.

[0082] After the allyl etherification reaction, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation, concentration, and purification (washing, column chromatography, etc.), if necessary.

[0083] The allyl group in the allyloxy group-containing compound (7) obtained by the allylation of the divalent phenol compound (6) can be rearranged, for example, by a Claisen rearrangement reaction, which is performed by heating the allyloxy group-containing compound (7) after the allylation reaction. In the Claisen rearrangement reaction, the allyl group of the allyloxy group (-O-CH2-CH=CH2) bonded to the benzene ring of the allyloxy group-containing compound (7) rearranges to the ortho position where the allyloxy group was present.

[0084] The Claisen rearrangement reaction can be carried out according to a conventional method, for example, by heating the allyloxy group-containing compound (7) in the presence of a high-boiling point solvent such as carbitol, paraffin oil, N,N'-dimethylaniline, or N,N'-diethylaniline, or without a solvent. The solvent is used as needed, in amounts of 10 to 200 parts by mass per 100 parts by mass of the allyloxy group-containing compound (7). After the reaction is complete, the solvent used can be removed as needed to obtain the 2-propenyl group-containing phenol compound (8). After the reaction, the 2-propenyl group-containing phenol compound (8) can be recovered by adding the reaction solution dropwise to an aqueous sodium hydroxide solution and stirring the separated aqueous layer dropwise into an acid solution.

[0085] The heating temperature for this Claisen rearrangement reaction is preferably 150 to 220°C, more preferably 170 to 200°C, and even more preferably in the presence of an inert gas such as nitrogen. If the heating temperature is above the lower limit, the rearrangement reaction of the allyl group is likely to occur. If the heating temperature is below the upper limit, polymerization of the allyl group is unlikely to occur.

[0086] After the reaction, the reaction product may be subjected to treatment such as washing with water, if necessary.

[0087] The dropwise addition time to the sodium hydroxide aqueous solution after the reaction is preferably 10 to 30 minutes. If the dropwise addition time is greater than or equal to the lower limit, heat generation due to mixing is suppressed and the product can be manufactured safely. If the dropwise addition time is less than or equal to the upper limit, productivity is improved. The stirring time after dropwise addition to the acid solution is preferably 15 to 60 minutes. If the stirring time is greater than or equal to the lower limit, the neutralization reaction proceeds and the yield in the subsequent separation step is improved. If the stirring time is less than or equal to the upper limit, productivity is improved.

[0088] A method for converting the 2-propenyl group of a 2-propenyl group-containing phenol compound (8) to a 1-propenyl group is to dissolve the 2-propenyl group-containing phenol compound (8) in a solvent and heat it under a propenylation catalyst.

[0089] Any solvent that can dissolve the 2-propenyl group-containing phenol compound (8) can be used in the propenylation reaction, and typically polar solvents are used. Examples of polar solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methanol, ethanol, butanol, ethylene glycol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and tetrahydrofuran. A single solvent may be used, or two or more may be used in combination.

[0090] The solvent is preferably used in amounts of 20 to 900 parts by mass, particularly 50 to 600 parts by mass, per 100 parts by mass of the 2-propenyl group-containing phenol compound (8).

[0091] Examples of catalysts for the propenylation reaction include alkali metals such as sodium hydroxide and potassium hydroxide, amines such as diazabicyclononene, diazabicycloundecene, and triethylamine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, silicon-based amines, and lithium tetramethylpiperidine. Among these, potassium hydroxide and sodium hydroxide are preferred because they are relatively inexpensive and less likely to cause side reactions. The catalyst may be used alone or in combination of two or more types.

[0092] The amount of catalyst used in the propenylation reaction is preferably 0.4 to 6.0 times the total molar amount of hydroxyl groups in the 2-propenyl group-containing phenol compound (8), and more preferably 1.0 to 4.0 times the molar amount. If too little catalyst is used, the propenylation reaction will not proceed easily, and if too much is used, the excess alkali will have to be removed, reducing productivity.

[0093] The reaction temperature for the propenylation reaction is preferably 40 to 140°C, and more preferably 70 to 120°C. If the reaction temperature is above the lower limit, the propenylation reaction proceeds easily. If the reaction temperature is below the upper limit, polymerization of the propenyl group is less likely to occur.

[0094] After the propenylation reaction, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation, concentration, and purification (washing, column chromatography, etc.), if necessary.

[0095] <Method for producing resin compositions> One method for producing the resin composition of the present invention is to prepare a phenol resin (1) obtained by heating and flavanizing phenol compounds (4) and (5), and compound (3), and then mix them to produce the resin composition of the present invention. However, as described above, it is also possible to obtain the resin composition of the present invention by allylating the divalent phenol compound (6) to obtain an allyloxy group-containing compound (7), then transferring the allyl group of the allyloxy group-containing compound (7) to obtain a 2-propenyl group-containing phenol compound (8), changing the 2-propenyl group of this 2-propenyl group-containing phenol compound (8) to a 1-propenyl group to obtain compound (3), and then subjecting it to a flavanization reaction to produce a phenol resin (1) while leaving compound (3) in the mixture.

[0096] The resin composition of the present invention comprises a phenolic resin (1), preferably a phenolic resin (1) and a compound (3). The content of phenolic resin (1) or the total content of phenolic resin (1) and compound (3) in 100% by mass of the resin composition of the present invention is not particularly limited, but is preferably 30% by mass or more, particularly 40% by mass or more, and especially preferably 50 to 100% by mass.

[0097] When the resin composition of the present invention is produced by allylation of a divalent phenol compound (6) to obtain an allyloxy group-containing compound (7), then transferring the allyl group of the allyloxy group-containing compound (7) to obtain a 2-propenyl group-containing phenol compound (8), and changing the 2-propenyl group of this 2-propenyl group-containing phenol compound (8) to a 1-propenyl group to obtain compound (3), and then subjecting it to a flavanization reaction to produce a phenol resin (1) while leaving compound (3) in the background, the content of phenol resin (1) and compound (3) in the resulting resin composition will vary depending on the flavanization reaction temperature and time, the addition of a catalyst, etc., but typically the content of phenol resin (1) is 1 to 99% by mass, the content of compound (3) is 1 to 99% by mass, and the resin composition obtained will contain approximately 1 to 60% by mass of by-products such as high molecular weight substances produced in the series of reactions. Such resin compositions may be used as is in the production of the curable resin composition of the present invention or in the production of the cured product (1) of the present invention as described later, or they may be used for these purposes after removing other reaction by-products other than the phenolic resin (1) and compound (3) by chromatographic separation or crystallization.

[0098] [Curable resin composition] The curable resin composition of the present invention comprises the resin composition of the present invention described above and one or more resins selected from the group consisting of epoxy resins, maleimide resins, phenol resins other than phenol resin (1) (hereinafter sometimes referred to as "other phenol resins"), benzoxazine resins, cyanate ester resins, active ester resins, resins having radically polymerizable functional groups, isocyanate resins, acid anhydride resins, and carbodiimide resins (hereinafter sometimes referred to as "curing components"). The curing components are preferably one or more resins selected from the group consisting of epoxy resins, maleimide resins, and other phenol resins.

[0099] In the curable resin composition of the present invention, curing proceeds when the propenyl group in the phenol resin (1) of the resin composition of the present invention reacts with the maleimide group of the maleimide resin under predetermined conditions. Thus, the resin composition of the present invention functions as a curing agent for maleimide resin. In the case of epoxy resins, the curing reaction proceeds through the reaction between the hydroxyl groups in the phenolic resin (1) of the resin composition of the present invention and the epoxy groups of the epoxy resin. In this case as well, the resin composition of the present invention functions as a curing agent for epoxy resins. Furthermore, other phenolic resins can be used in combination with epoxy resins. The curable resin composition of the present invention is preferable, particularly for semiconductor encapsulant applications, to contain an epoxy resin as a curing component, due to its excellent adhesion to the cured product and the ease with which the curing reaction proceeds, resulting in a higher molecular weight of the cured product.

[0100] In the curable resin composition of the present invention, the content ratio of the curing component is 0.01 to 10,000 parts by mass per 100 parts by mass of the resin composition of the present invention, preferably 0.1 to 1,000 parts by mass, and more preferably 1.0 to 500 parts by mass. If the content ratio of the curing component is above the lower limit, a cured product with excellent heat resistance and good adhesion can be obtained. If the content ratio of the curing component is below the upper limit, a uniform cured product with excellent curability can be produced.

[0101] <Curing component> The curing components included in the curable resin composition of the present invention are described below.

[0102] <Maleimide resin> Maleimide resins are maleimide compounds that have an average of one or more maleimide groups per molecule. Examples of maleimide resins include bismaleimides, which have two maleimide groups per molecule, and polyphenylmethanemaleimides.

[0103] Examples of bismaleimides include alkylbismaleimides, diphenylmethanebismaleimides, phenylenebismaleimides, bisphenol A diphenyl ether bismaleimides, 4,4'-diphenylmethanebismaleimides such as 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimides, 4-methyl-1,3-phenylenebismaleimides, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimides, 4,4'-diphenylsulfone bismaleimides, 1,3-bis(3-maleimoidphenoxy)benzene, and 1,3-bis(4-maleimoidphenoxy)benzene. Polyphenylmethanemaleimide is a polymer in which three or more benzene rings, each substituted with a maleimide group, are linked together via methylene groups.

[0104] Among the maleimide resins mentioned above, 4,4'-diphenylmethanebismaleimide and polyphenylmethanemaleimide are preferred due to their excellent compatibility with the propenyl group-containing composition of the present invention and their relatively low cost.

[0105] Commercially available maleimide resins may be used. Examples of commercially available maleimide resins include "BMI-1100" (4,4'-diphenylmethanebismaleimide) and "BMI-2300" (polyphenylmethanemaleimide) manufactured by Yamato Chemical Industries, Ltd.

[0106] Maleimide resin may be used alone or in combination of two or more types.

[0107] <Epoxy resin> The epoxy resin is not particularly limited, and examples include phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthol type epoxy resin, xylylene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, phosphorus atom-containing epoxy resin, and the like.

[0108] As the epoxy resin, an epoxy resin in which at least some of the hydroxyl groups of the propenyl group-containing composition are epoxidized may be used. The epoxidation of the hydroxyl groups can be carried out by known methods. For example, by reacting the propenyl group-containing composition with epichlorohydrin, an epoxy resin having a structure in which some or all of the hydroxyl groups of the propenyl group-containing composition are -OZ (where Z is a glycidyl group) can be obtained.

[0109] Epoxy resins may be used individually or in combination of two or more types.

[0110] <Other phenolic resins> Other phenolic resins besides the phenolic resin (1) contained in the resin composition of the present invention include, for example, novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, benzaldehyde, salicylaldehyde, etc., under an acidic catalyst; and phenol-A synthesized from phenols and / or naphthols and dimethoxyp-xylene or bis(methoxymethyl)biphenyl. Examples include alkyl resins; aralkyl-type phenolic resins such as biphenylene-type phenol-aralkyl resins and naphthol-aralkyl resins; dicyclopentadiene-type phenolic resins such as dicyclopentadiene-type phenol novolac resins and dicyclopentadiene-type naphthol novolac resins synthesized by copolymerization of phenols and / or naphthols with dicyclopentadiene; triphenylmethane-type phenolic resins; terpene-modified phenolic resins; paraxylylene and / or metaxylylene-modified phenolic resins; melamine-modified phenolic resins; cyclopentadiene-modified phenolic resins; and phenolic resins obtained by copolymerizing two or more of these.

[0111] These other phenolic resins may be used individually or in combination of two or more.

[0112] <Benzoxazine resin> Examples of benzoxazine resins include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine). The benzoxazine resin may also contain a structure in which the oxazine ring is formed by ring-open polymerization. Benzooxazine resins may be used individually or in combination of two or more types.

[0113] <Cyanate ester resin> Examples of cyanate ester resins include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) thioether, and bis(4-cyanatephenyl) ether; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs; and prepolymers in which these cyanate resins are partially triazined.

[0114] Cyanate ester resins may be used individually or in combination of two or more types.

[0115] <Activated ester resin> There are no particular restrictions on the active ester resin, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and the like. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0116] Specifically, active ester resins containing a dicyclopentadiene-type diphenol structure, active ester resins containing a naphthalene structure, active ester resins containing an acetylated phenol novolac, and active ester resins containing a benzoylated phenol novolac are preferred, with active ester resins containing a naphthalene structure and active ester resins containing a dicyclopentadiene-type diphenol structure being more preferred. Here, "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

[0117] The activated ester resin may be used alone or in combination of two or more types.

[0118] <Resin having radically polymerizable functional groups> Resins having radically polymerizable functional groups include resins having one or more ethylenically unsaturated groups with carbon-carbon double bonds in their molecules. The ethylenically unsaturated group is preferably one or more groups selected from the group consisting of acrylic groups, methacrylic groups, styryl groups, olefin groups, and maleimide groups. Preferred examples of olefin groups include allyl groups, vinyl groups, and propenyl groups. Therefore, in one preferred embodiment, the radically polymerizable functional group is one or more selected from the group consisting of acrylic groups, methacrylic groups, styryl groups, allyl groups, vinyl groups, propenyl groups, and maleimide groups. A resin having a radically polymerizable functional group may have one or more radically polymerizable functional groups.

[0119] Resins having radical polymerizable functional groups may be used individually or in combination of two or more types.

[0120] <Isocyanate resin> Examples of isocyanate resins include resins having one or more isocyanate groups in their molecules. Preferably, the isocyanate resin has two or more isocyanate groups in its molecule. Examples of isocyanate resins include 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate.

[0121] Isocyanate resins may be used individually or in combination of two or more types.

[0122] <Acid anhydride resin> Examples of acid anhydride resins include resins having one or more acid anhydride groups in their molecules. Examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, and bensophenone tetracarboxylic acid anhydride. Examples include aqueous solutions, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid.

[0123] Acid anhydride resins may be used individually or in combination of two or more types.

[0124] <Carbodiimide resin> Examples of carbodiimide resins include those having one or more carbodiimide groups (-N=C=N-) in their molecules. Preferably, carbodiimide resins have two or more carbodiimide groups in their molecules. Specific examples of carbodiimide resins include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0125] Carbodiimide resins may be used individually or in combination of two or more types.

[0126] <Other ingredients> The curable resin composition of the present invention may contain one or more other components in addition to the resin composition of the present invention and the curing component described above. Examples of other components include curing accelerators, inorganic fillers, solvents, mold release agents, surface treatment agents, colorants, thermoplastic polymers, organic fillers, and flame retardants.

[0127] There are no particular limitations on the curing accelerator, but specific examples include imidazoles, organic peroxides, phosphorus compounds, tertiary amines, organic acid metal salts, Lewis acids, and amine complex salts.

[0128] Examples of imidazoles include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole.

[0129] Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.

[0130] Examples of phosphorus-based compounds include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, and triphenyl phosphite. Examples of tertiary amines include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, and 1,8-diazabicyclo[5.4.0]undecene-7.

[0131] As a curing accelerator, it is preferable to use one that is relatively stable at high temperatures, has good solvent solubility, and is easy to handle. Preferred candidates include 2-ethyl-4-methylimidazole from the imidazole group, dicumyl peroxide from the dialkyl peroxide group of organic peroxides, and triphenylphosphine from the phosphorus group.

[0132] These curing accelerators may be used individually or in combination of two or more types.

[0133] If the curable resin composition of the present invention contains a curing accelerator, its content is preferably 0.1 to 5.0% by mass relative to the curing component such as maleimide resin.

[0134] Examples of inorganic fillers include crystalline silica powder, fused silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder. Of these, crystalline silica powder and fused silica powder are preferred. One type of inorganic filler may be used alone, or two or more types may be used in combination.

[0135] If the curable resin composition of the present invention contains an inorganic filler, its content is preferably 30 to 90% by mass relative to the entire curable resin composition.

[0136] When the curable resin composition of the present invention is used as a thermosetting molding material for forming a encapsulant, it is preferable that the curable resin composition of the present invention contains a curing accelerator and an inorganic filler.

[0137] The curable resin composition of the present invention can be made into a resin varnish by adding a solvent and dissolving curing components such as maleimide resin and epoxy resin in the solvent. The solvent is not particularly limited as long as it dissolves the phenol resin composition, curing components, etc., and the same solvents as those mentioned in the explanation of the flavanization reaction can be used. One solvent may be used alone, or two or more solvents may be used in combination.

[0138] The resin varnish comprises the resin composition of the present invention, a curing component such as maleimide resin or epoxy resin, and a solvent as essential components. Using this resin varnish, laminates such as copper-clad laminates can be manufactured, as described later.

[0139] The solvent content in the resin varnish is appropriately set according to the solid content concentration of the resin varnish. The solid content concentration of the resin varnish varies depending on the application, but is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. The solid content concentration of a resin varnish is the ratio of the mass of the resin varnish excluding the solvent to the total mass of the resin varnish.

[0140] The resin varnish can be manufactured by mixing a curing component such as maleimide resin or epoxy resin with the resin composition of the present invention and other components and solvents as needed. The mixing of each component can be carried out by the method described above.

[0141] In the production of resin varnish, a curing component such as maleimide resin may be mixed with the resin composition of the present invention and a solvent, and then the maleimide resin and the resin composition of the present invention may be pre-reacted. Performing the pre-reaction in the varnish state can suppress the precipitation of highly crystalline maleimide resin from the resin varnish.

[0142] The reaction temperature during the preliminary reaction is preferably 50-150°C, more preferably 70-130°C, and even more preferably 80-120°C. If the reaction temperature is too low, the reaction will not proceed easily. If the reaction temperature is too high, it will be difficult to control the reaction, making it difficult to obtain a stable resin varnish.

[0143] Examples of release agents include various waxes such as carnauba wax. Examples of surface treatment agents include well-known silane coupling agents. Examples of coloring agents include carbon black.

[0144] Examples of thermoplastic polymers include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamide-imide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyetheretherketone resin, polyetherimide resin, silicone resin, and tetrafluoroethylene resin.

[0145] Examples of organic fillers include resin fillers with a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., and resin fillers with a core-shell structure having a rubbery core layer made of acrylic ester resin, methacrylic ester resin, conjugated diene resin, etc., and a glassy shell layer made of acrylic ester resin, methacrylic ester resin, aromatic vinyl resin, vinyl cyanide resin, etc.

[0146] Examples of flame retardants include halogenated flame retardants containing bromine or chlorine; phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, and red phosphorus; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene; and inorganic flame retardants such as antimony trioxide.

[0147] The curable resin composition of the present invention is preferably cured by controlling the curing temperature to 150 to 250°C. An example of a curing operation is to first cure it at the above-mentioned preferred curing temperature for 30 seconds to 3 hours, and then perform a post-curing at the above-mentioned preferred curing temperature for 1 to 20 hours.

[0148] The applications of the curable resin composition of the present invention will be described further below, but examples include encapsulants for electronic components such as semiconductors, electrical insulating materials, resins for copper-clad laminates, resists, resins for liquid crystal color filters, various coating agents, adhesives, build-up laminate materials, fiber-reinforced plastics (FRP), and the like.

[0149] The curable resin composition of the present invention may be used after curing for these applications, or it may be cured in the manufacturing process applicable to these applications.

[0150] [Cured product] <Cured product made from the curable resin composition of the present invention> A cured product of the present invention can be obtained by curing the curable resin composition of the present invention. The cured product of the present invention, obtained by curing the curable resin composition of the present invention, has excellent properties in terms of heat resistance and adhesion.

[0151] The method for curing the curable resin composition of the present invention is not particularly limited, but a cured product can usually be obtained by a thermosetting reaction by heating. During the thermosetting reaction, it is preferable to appropriately select the curing temperature depending on the type of curing component used. For example, when maleimide resin is used, the curing temperature is usually 80 to 250°C, and when epoxy resin is used, it is usually 100 to 200°C. It is also possible to lower the curing temperature by adding a curing accelerator to these curing components. The curing reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and even more preferably 3 to 15 hours. A reaction time above the lower limit is preferable because it tends to allow the curing reaction to proceed sufficiently. On the other hand, a reaction time below the upper limit is preferable because it is easier to reduce degradation due to heating and energy loss during heating.

[0152] <Cured product (1)> A cured product according to another aspect of the present invention is a cured product containing a structure derived from the structure represented by the following formula (1) (hereinafter sometimes referred to as "cured product (1)"), which can be obtained by curing the resin composition of the present invention or the curable resin composition of the present invention described above.

[0153] [ka]

[0154] (In the above formula (1), R 1 , R 2 Each of these independently represents a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but R 1 , R 2 This excludes the case where both are hydrogen atoms. 3 ~R 10 Each of these independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but R 3 ~R 10 At least one of them is a substituent represented by the following formula (2). 3 ~R 10 (The adjacent groups may be bonded together to form a ring.)

[0155] [ka]

[0156] (In formula (2) above, Y is a divalent linking group selected from direct bonds, -SO2-, -O-, -CO-, -C(CF3)2-, -S-, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms. 21 (These are hydrogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, or halogen atoms.)

[0157] The explanations for formulas (1) and (2) in the phenolic resin (1) described above apply to formulas (1) and (2) above.

[0158] The cured product (1) also has excellent heat resistance and adhesive properties due to having a structure derived from the structure represented by formula (1).

[0159] [Application] The curable resin composition of the present invention exhibits excellent solvent solubility, moldability, and heat resistance, and the cured product and cured product (1) using the curable resin composition of the present invention exhibit excellent heat resistance and adhesion.

[0160] Therefore, the resin composition, curable resin composition and cured product thereof, and cured product (1) of the present invention can be effectively used in any application where these physical properties are required. For example, they can be suitably used in the fields of paints such as optical materials, automotive paints such as electrodeposition paints for automobiles, heavy-duty anticorrosive paints for ships and bridges, and paints for coating the inside of beverage cans; in the fields of electrical and electronics such as composite materials, laminates, semiconductor encapsulants, liquid insulating encapsulants, insulating powder coatings, and coil impregnation; and in the fields of civil engineering, construction, and adhesives such as seismic reinforcement of bridges, concrete reinforcement, flooring materials for buildings, lining for water supply facilities, drainage and permeable pavement, and adhesives for structures, vehicles, and aircraft. Among these, they are particularly useful for electrical and electronic components.

[0161] [Laminated board] A method for manufacturing a laminate using the curable resin composition of the present invention includes a method of producing a laminate by heating and pressurizing a laminate containing a prepreg in which a fibrous substrate is impregnated with the aforementioned resin varnish made of the curable resin composition of the present invention, and curing it.

[0162] More specifically, a resin varnish is impregnated into a fibrous substrate, dried, and the solvent is removed to form a prepreg. This prepreg is then laminated with other substrates as needed to form a laminate, and the laminate is heated and pressurized to cure it and obtain a laminated board.

[0163] The number of prepreg layers in the laminate may be one or two or more. Other substrates besides prepregs may also be laminated in the laminate. Examples of other substrates include metal foils such as copper foil.

[0164] Examples of fibers constituting the fibrous base material include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, and stainless steel fibers; natural fibers such as cotton, hemp, and paper; and synthetic organic fibers such as polyester resin and polyamide resin. These fibers may be used individually or in combination of two or more types.

[0165] The shape of the fibrous base material is not particularly limited and includes, for example, short fibers, yarn, mats, sheets, etc.

[0166] The amount of resin varnish to impregnate the fibrous substrate is not particularly limited; for example, the amount of solid content of the resin varnish to be impregnated should be approximately 30-50% by mass relative to the fibrous substrate (100% by mass). The heating temperature when heating and pressurizing the laminate is preferably the curing temperature mentioned above. The pressurizing conditions are 2 to 20 kN / m 2 It is preferable.

[0167] The laminate manufactured in this manner comprises a fiber-reinforced resin layer containing a fibrous substrate and a cured resin varnish. The number of fiber-reinforced resin layers in the laminate may be one or two or more. As mentioned above, the laminate may also have a metal foil layer such as copper foil.

[0168] [Sealing material] When the curable resin composition of the present invention is used as a encapsulant, the shape of the encapsulant to which the curable resin composition of the present invention is applied is not particularly limited, and for example, a shape similar to that used in known semiconductors can be adopted. Methods for forming a encapsulant using the curable resin composition of the present invention include, for example, methods for encapsulating semiconductors using transfer molding, compression molding, and the like. [Examples]

[0169] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples unless it exceeds its gist. The various manufacturing conditions and evaluation result values ​​in the following examples have meaning as preferred upper or lower limits in embodiments of the present invention, and the preferred range may be defined by a combination of the aforementioned upper or lower limits and the values ​​of the following examples or the values ​​of the examples themselves.

[0170] [Materials used] The compounds and resins used in the following examples and comparative examples are as follows.

[0171] • Maleimide resin: Polyphenylmethanemaleimide represented by the following structural formula ("BMI-2300" manufactured by Yamato Chemical Industries, Ltd.)

[0172] [ka]

[0173] • Other phenolic resins: Phenolic novolacs represented by the following structural formula (PSM4261, manufactured by Gun-ei Chemical Industry Co., Ltd.)

[0174] [ka]

[0175] Other flavan structure-containing phenolic resins: 4',7-isoflavandiol (manufactured by Tokyo Chemical Industry Co., Ltd.), represented by the following structural formula.

[0176] [ka]

[0177] • Other propenyl resins: Propenyl derivatives of phenol biphenylene resin represented by the following structural formula (BPN-01S, manufactured by Gun-ei Chemical Industry Co., Ltd.)

[0178] [ka]

[0179] • Epoxy resin: Tetramethylbiphenyl type epoxy resin represented by the following structural formula (Mitsubishi Chemical Corporation's "YX4000")

[0180] [ka]

[0181] • Curing accelerator: Triphenylphosphine

[0182] [Example 1: Production of resin composition A containing phenolic resin (1)] <allylation> 840 mL of N,N-dimethylformamide, 575 g (7.51 mol) of allyl chloride, 1245 g (9.01 mol) of potassium carbonate, and 280 g (1.50 mol) of biphenol were added to a 10 L autoclave, which was then sealed and heated to 40 °C, followed by a 1-hour heating to 65 °C. After aging at 65 °C for 5 hours, the mixture was cooled to room temperature and the autoclave was opened. 1678 g of water and 1600 g of methyl isobutyl ketone were added to dissolve the inorganic salt and crystals, and the aqueous layer was removed by liquid-liquid separation. 1678 g of water was added to the remaining methyl isobutyl ketone layer, and the washing process at 60 °C was repeated three times. The methyl isobutyl ketone was then removed by distillation to obtain the compound represented by the following formula (7-1) (hereinafter referred to as "compound (7-1)").

[0183] [ka]

[0184] <Claisen rearrangement reaction> 165 g (620 mmol) of compound (7-1) and 825 mL of N,N-diethylaniline were placed in a 2 L four-necked flask and heated at 200 °C for 6 hours, then cooled to room temperature. Next, 495 mL of water and 149 mL (1.86 mol) of 50% by mass sodium hydroxide aqueous solution were placed in a 2 L separable flask and cooled to 10 °C. The N,N-diethylaniline solution was then added dropwise, stirred for 30 minutes, and allowed to stand. The upper and lower layers were then separated. Next, 495 mL of water and 93.1 g (1.86 mol) of concentrated sulfuric acid were placed in a 2 L separable flask and cooled to 10 °C. The lower layer separated in the previous step was then added dropwise, and the mixture was stirred for 1 hour. The precipitated solid was recovered by filtration, washed with water, and then dried under reduced pressure to obtain 148 g (1.19 mol, 2-step yield 80.4%) of a gray solid, which is a 2-propenyl group-containing phenol compound (8) represented by the following formula (8-1) (hereinafter referred to as "compound (8-1)").

[0185] [ka]

[0186] <Propenylation> 100 parts by mass of compound (8-1) and 100 parts by mass of methanol were charged into a reaction vessel, stirred, and dissolved. Then, 79 parts by mass of granular potassium hydroxide (purity 85%) was added. After the addition, methanol was removed by distillation while heating, and the reaction was carried out for 4 hours while maintaining the internal temperature at 100°C. Next, 203 parts by mass of methyl isobutyl ketone was added, neutralized with sulfuric acid, and then washed with water repeatedly. Then, methyl isobutyl ketone was removed from the oil layer by distillation under reduced pressure at 120°C, to obtain 95 parts by mass of a resin composition containing a propenyl group-containing phenol compound (3) represented by the following formula (3-1) (hereinafter referred to as "compound (3-1)").

[0187] [ka]

[0188] <Flavanization> The resin composition containing the compound (3-1) obtained by the above propenylation was charged into a reaction vessel, and the reaction was carried out for 2.5 hours while maintaining the internal temperature at 120 °C with stirring and heating, whereby 100 parts by mass of a resin composition A containing a phenol resin (1) having a structure represented by the following formula (1-1) (hereinafter referred to as "compound (1-1)") was obtained.

[0189]

Chemical formula

[0190] As is clear from the following compositional analysis, this resin composition A contains the compound (1-1) and the compound (3-1).

[0191] <Identification of the resin composition containing phenol resin (1) by NMR analysis> The obtained resin composition A was dissolved in deuterated chloroform, and using a BRUKER AVANCE NEO spectrometer, 1 1H-NMR, DOSY, COSY, 1 1H- 13 13C HSQC, 1 1H- 13 1H-13C HMBC analysis was performed to identify the molecular structure. The resin composition A was analyzed, and as a result of the assignment, the structure of the compound (1-1) could be confirmed.

[0192] The obtained resin composition A was subjected to compositional analysis by the following method. Also, a solvent solubility test was conducted by the following method. The results are shown in Table 1.

[0193] <� <Compositional analysis of the resin composition> [[]]The resin composition A was dissolved in tetrahydrofuran to a concentration of 0.1% by mass, and using "HLC-8320GPCEcoSEC (registered trademark)" manufactured by Tosoh Corporation, analysis was performed under the following conditions. Apparatus: Agilent 1100 series Column: "TSKGEL SuperHM-H + H5000 + H4000 + H3000 + H2000" manufactured by Tosoh Corporation Eluent: Tetrahydrofuran Flow rate: 0.5 mL / min Detection: RI Temperature: 40 °C Injection: 10 μL

[0194] <Solvent solubility test> Using toluene as the test solvent, the resin composition A was added to toluene so that the concentration of the resin composition A was 75% by mass, and a test solution was prepared and weighed into a 50 mL vial. Then, after heating to completely dissolve the resin composition A, it was stored at 23 °C and no crystals were precipitated within 1 day. Then, those in which no crystals were precipitated within 1 week when stored at -5 °C were evaluated as having excellent solvent solubility "○", those in which no crystals were precipitated within 1 day when stored at 23 °C and crystals were precipitated within 1 day when stored at -5 °C were evaluated as having good solvent solubility "△", and those in which crystals were precipitated 1 day after storage at 23 °C were evaluated as having poor solvent solubility "×".

[0195] [Example 2: Production of Resin Composition B Containing Phenolic Resin (1)] In Example 1, the same procedure was carried out except that the reaction time in <Flavanation> was changed from 2.5 hours to 10 minutes to obtain a resin composition B containing phenolic resin (1), and the same composition analysis and solvent solubility test as in Example 1 were carried out. The results are shown in Table 1.

[0196] [Example 3: Production of Resin Composition C Containing Phenolic Resin (1)] In Example 1, the same procedure was carried out except that the reaction time in <Flavanation> was changed from 2.5 hours to 10 hours to obtain a resin composition C containing phenolic resin (1), and the same composition analysis and solvent solubility test were carried out. The results are shown in Table 1.

[0197] [Example 4: Production of Resin Composition D Containing Phenolic Resin (1)] <Propenylation> Except for using a 2-propenyl group-containing phenol compound represented by the following formula (8-2) (DABPA, manufactured by Yamato Kasei Co., Ltd.) instead of compound (8-1), propenylation was carried out in the same manner as in Example 1 to obtain a resin composition containing a propenyl group-containing phenol compound (3), which is represented by the following formula (3-2) (hereinafter referred to as "compound (3-2)").

[0198] [ka]

[0199] <Flavanization> A resin composition containing compound (3-2) obtained by the above propenylation was charged into a reaction vessel, and flavanization was carried out in the same manner as in Example 1 to obtain a resin composition D containing a phenol resin (1) having a structure represented by the following formula (1-2) (hereinafter referred to as "compound (1-2)"). The same compositional analysis and solvent solubility tests as in Example 1 were performed on resin composition D. The results are shown in Table 1.

[0200] [ka]

[0201] [Table 1]

[0202] [Comparative Example 1: Other Phenolic Resins] We use phenol novolac resin (PSM4261, manufactured by Gun-ei Chemical Industry Co., Ltd.).

[0203] [Comparative Example 2: Other Flavan Structure-Containing Phenolic Resins] 4',7-Isoflavanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) is used.

[0204] The following evaluations were performed on the resin compositions A, B, and D of Examples 1, 2, and 4, and the phenolic resins of Comparative Examples 1 and 2, and the results are shown in Table 2.

[0205] <Measurement of Softening Point of Resin Composition> The softening point of the resin composition was measured in accordance with JIS K7234.

[0206] <Measurement of Melting Point of Resin Composition> Using a differential scanning calorimeter (DSC: EXSTAR 7020 manufactured by Seiko Instruments Inc.), the melting point of the resin composition was measured by increasing the temperature from 30°C to 250°C at a rate of 1°C / min.

[0207] <Measurement of Melt Viscosity of Resin Composition> The resin composition was melted on a hot plate of a cone plate viscometer (manufactured by Tokai Yasaka Co., Ltd.) adjusted to 150°C, and the melt viscosity was measured at a rotational speed of 750 rpm.

[0208] <Measurement of 5% Weight Loss Temperature of Resin Composition> Thermal analysis was performed using a thermal analyzer (TG / DTA: EXSTAR 7200 manufactured by Seiko Instruments Inc.) (heating rate: 10°C / min, measurement temperature range: 30°C to 600°C, air: flow rate 200 mL / min). The temperature at which the weight of the resin composition decreased by 5% was measured and defined as the 5% weight loss temperature.

[0209]

Table 2

[0210] [Examples 5 to 7, Comparative Example 3] The resin compositions A, B, D or other propenyl resins (BPN-01S), maleimide resin (BMI-2300), and a curing accelerator were mixed at the ratios shown in Table 3 to obtain a curable resin composition. Then, a curing reaction was carried out at 120°C for 2 hours and then at 200°C for 6 hours to produce a cured product. For the obtained cured product, Tg (tan δ) was measured by the following method. Also, using the produced curable resin composition, the shear adhesive strength to metal (Cu) was measured by the following method. The results are shown in Table 3.

[0211] <Cured product: Tg(tanδ) and storage modulus E'(40℃), E'(250℃)> Using test specimens obtained by cutting the hardened material to a length of 5 cm, width of 1 cm, and thickness of 4 mm, dynamic viscoelasticity measurements (DMA: Dynamic Mechanical Analysis) were performed under the following conditions to measure Tg (tanδ) and storage modulus (E') at 40°C and 250°C. Analytical instrument: Seiko Instruments EXSTAR6100 Measurement mode: 3-point bending mode Measurement temperature range: 30°C to 300°C Heating rate: 5°C / min Cooling rate: 5℃ / min *The temperature at the peak top of tanδ is defined as Tg(tanδ).

[0212] <Shear bonding strength to metals> The test was conducted in accordance with JIS-K6850. Specifically, a curable resin composition was applied between two metal pieces (copper plates (double-sided mirror-finish type manufactured by Yutaka Panel Service Co., Ltd.)) measuring 25 mm wide x 100 mm long x 1.6 mm thick, to create a strip measuring 25 mm wide x 12.5 mm long. After application, the strips were placed in a constant temperature bath and cured at 120°C for 2 hours and then at 200°C for 6 hours to prepare a peel test specimen. The prepared peel test specimens were subjected to tensile shear tests using an Instron 5582 tensile testing machine (manufactured by Instron Corporation) at a speed of 5 mm / min for a total of n=3 tests. The tensile shear strength was measured, and the average value was calculated.

[0213] [Table 3]

[0214] [Example 8, Comparative Example 4] A curable resin composition was obtained by mixing resin composition A or compound (8-1), maleimide resin (BMI-2300), and a curing accelerator in the proportions shown in Table 4. Then, a curing reaction was carried out at 120°C for 2 hours, followed by 200°C for 6 hours to produce a cured product. The storage modulus E'(40°C), E'(250°C), and Tg(tanδ) were measured for the obtained cured material using the method described above. The coefficient of linear expansion was also determined using the method described below. The results are shown in Table 4. In Comparative Example 4, the cured material was brittle in the tests for storage modulus E'(40°C) and storage modulus E'(250°C) and Tg(tanδ), making it impossible to prepare test specimens and perform evaluations.

[0215] <Coefficient of linear expansion> The hardened material was cut into cylindrical test pieces with a diameter of approximately 7 mm and a thickness of 4 mm, and thermomechanical analysis was performed using a thermomechanical analyzer (TMA: EXSTAR6000, manufactured by Seiko Instruments Corporation) in compression mode under the following conditions. Measurement weight: 30mN Heating rate: 5°C / min twice Measurement temperature range: 30°C to 300°C From the results of the second measurement, the coefficient of linear expansion in the temperature range shown in Table 4 was determined.

[0216] [Table 4]

[0217] [Evaluation of results] Table 1 shows that the resin compositions of the present invention (Examples 1-4) exhibit excellent solvent solubility. Table 2 shows that the resin compositions of the present invention (Examples 1, 2, and 4) have low melt viscosity, and furthermore, their softening point or melting point is lower than that of other flavan structure-containing phenolic resins (4',7-isoflavandiol, Comparative Example 2), indicating excellent moldability. In addition, regarding heat resistance, they have a 5% weight loss temperature higher than that of phenol novolac resin (PSM4261, Comparative Example 1) and other flavan structure-containing phenolic resins (4',7-isoflavandiol, Comparative Example 2), indicating excellent heat resistance. Table 3 shows that cured products using the resin composition of the present invention (Examples 5-7) exhibit superior heat resistance and high adhesion to metals compared to cured products using other propenyl resins (Comparative Example 3). Table 4 shows that the cured product using the resin composition of the present invention (Example 8) has higher strength and a lower coefficient of thermal expansion compared to the cured product using compound (8-1) (Comparative Example 4).

Claims

1. A resin composition comprising a phenolic resin having a structure represented by the following formula (1). 【Chemistry 1】 (In the above formula (1), R ３ , ３ , １０ , １０ , R ２ each independently represents a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, except when both R １ , R ２ are hydrogen atoms. R ３ to R １０ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, but at least one of R ３ to R １０ is a substituent represented by the following formula (2). Adjacent groups of R ３ to R １０ may be bonded to form a ring.) 【Chemistry 2】 (In the above formula (2), Y is a direct bond, -SO ２ -, -O-, -CO-, -C(CF ３ ) ２ It is a divalent linking group selected from -, -S-, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms. ２１ (These are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, or halogen atoms.)

2. The resin composition according to claim 1, comprising 0.1 to 100,000 parts by mass of a compound represented by the following formula (3) per 100 parts by mass of a phenol resin having the structure represented by formula (1). 【Transformation 3】 (In the above equation (3), X is a direct bond, -SO ２ -, -O-, -CO-, -C(CF ３ ) ２ It is a divalent linking group selected from -, -S-, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms. １１ and R １２ (These are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, or halogen atoms, and may be the same or different from each other.)

3. A curable resin composition comprising 0.01 to 100,000 parts by mass of at least one selected from the group consisting of epoxy resin, maleimide resin, phenol resin other than the phenol resin having the structure represented by formula (1), benzoxazine resin, cyanate ester resin, active ester resin, resin having a radical polymerization functional group, isocyanate resin, acid anhydride resin, and carbodiimide resin, per 100 parts by mass of the resin composition according to claim 1 or 2.

4. A cured product obtained by curing the curable resin composition described in claim 3.

5. An electrical or electronic component comprising a cured product of the curable resin composition described in claim 4.

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