Propenyl group-containing compound, curable resin composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device

Abstract

To provide a propenyl group-containing compound which exhibits excellent handling properties with a high softening point while maintaining low melt viscosity.SOLUTION: The propenyl group-containing compound is represented by the general formula (I) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a propenyl group-containing compound, a curable resin composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device. [Background technology]

[0002] Conventionally, epoxy resins are formed into cured products by combining them with curing agents such as amine resins or phenolic resins. Because they exhibit high heat resistance and moisture absorption, they are widely used as electrical and electronic materials, such as semiconductor encapsulants and insulating materials for printed wiring boards.

[0003] In the field of semiconductor encapsulation, the development of power semiconductors is progressing due to the increasing demand for electric vehicles, and resistance to high heat generated by high currents and high voltages is required. However, it is difficult for existing cured products of epoxy resins and phenolic resins to meet the high-temperature resistance requirement. Therefore, various studies are being conducted to incorporate maleimide resins, which exhibit high heat resistance, into cured systems of epoxy resins and phenolic resins, etc., with the aim of improving heat resistance.

[0004] For example, Patent Document 1 discloses a propenyl group-containing composition having a specific structure in which a propenyl group is present on an aromatic ring, and Patent Documents 2 and 3 disclose curable resin compositions containing a propenyl group-containing compound having a specific structure in which a propenyl group is present on an aromatic ring and an epoxy compound.

[0005] Patent Document 4 discloses a propenyl group-containing resin having a specific structure, and Patent Document 5 discloses a resin composition containing a propenyl group-containing resin and a maleimide compound having two or more maleimide groups in one molecule.

[0006] Furthermore, Patent Document 6 discloses an alkenyl-group-containing resin in which 50% or more of the alkenyl groups in the molecule are propenyl groups. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent Publication No. 2021-116427 [Patent Document 2] Japanese Patent Publication No. 2023-3713 [Patent Document 3] Japanese Patent Publication No. 2023-3714 [Patent Document 4] Patent No. 6319703 [Patent Document 5] Patent No. 6942550 [Patent Document 6] Patent No. 6963565 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the propenyl group-containing compounds described in the above patent documents, etc., have the problem of poor handleability due to their low softening points when preparing resin compositions using conventional propenyl group-containing compounds. Furthermore, compounds with molecular weight distributions such as those disclosed in Patent Documents 4 and 5 tend to have high viscosity (melt viscosity, etc.), which undesirably reduces the fluidity and handleability when preparing a resin composition. Therefore, it is preferable to maintain a low melt viscosity.

[0009] Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a propenyl group-containing compound that has a high softening point and excellent handleability while maintaining a low melt viscosity. Another object of the present invention is to provide a curable resin composition containing the propenyl group-containing compound, a cured product thereof, a prepreg having a semi-cured product of the curable resin composition, a circuit board in which the prepreg and copper foil are laminated, a build-up film containing the curable resin composition, a semiconductor encapsulant, and a semiconductor device including a cured product of the semiconductor encapsulant. [Means for solving the problem]

[0010] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that the softening point can be increased by introducing an aromatic hydrocarbon group into the crosslinked portion of two aromatic rings in a propenyl group-containing compound, and that the crystallinity can be reduced by changing the two substituents at the crosslinked portion of the propenyl group-containing compound to different substituents, thereby reducing symmetry and thereby achieving the present invention. The gist and configuration of the present invention to solve the above problems is as follows.

[0011] [1] A propenyl group-containing compound represented by the following general formula (I): [ka] (In the above general formula (I), Ar I1 represents an aromatic hydrocarbon group having 6 or more carbon atoms, R I1 Ar I1 represents an alkyl group having a number of carbon atoms equal to or less than the number of carbon atoms of R I2 and R I3 each independently represents a hydrogen atom or a glycidyl group, R I4 and R I5 each independently represents a hydrogen atom or a propenyl group, R I6 and R I7 each independently represents a hydrogen atom or a propenyl group, provided that R I4 , R I5 , R I6 and R I7 at least one of which is a propenyl group; R Ia and R Ib each independently represents an alkyl group, an alkenyl group, or an alkoxy group, n I1 and n I2 each independently represents an integer of 0 to 1. However, in the above general formula (1), among the two carbon atoms adjacent to the carbon atom on the benzene ring to which the propenyl group is bonded, -OR I2 group or -OR I3 Any carbon atom that does not have a group attached has a hydrogen atom attached to it.)

[0012] [2] Ar in the general formula (I) I1 The propenyl group-containing compound according to [1], wherein the compound is represented by the following general formula (II) or (III): [ka] (In general formula (II), R IIc each independently represents an alkyl group, n II1 represents an integer of 0 to 5. In addition, * in general formula (II) represents a bond to another atom. [ka] (In general formula (III), R IIId each independently represents an alkyl group, n III1 represents an integer of 0 to 7. In addition, * in general formula (III) represents a bond to another atom.

[0013] [3] R in the general formula (I) I2 and R I3 The propenyl group-containing compound according to [1] or [2], wherein

[0014] [4] The propenyl group-containing compound according to [3], which has a softening point of 50°C or higher and 120°C or lower.

[0015] [5] The propenyl group-containing compound according to [3] or [4], having a hydroxyl group equivalent of 150 g / equivalent or more and 250 g / equivalent or less.

[0016] [6] R in the general formula (I) I2 and R I3is a glycidyl group.

[0017] [7] The propenyl group-containing compound according to [6], which has a softening point of more than 45°C and not more than 120°C.

[0018] [8] The propenyl group-containing compound according to [6] or [7], having an epoxy equivalent of 230 g / equivalent or more and 300 g / equivalent or less.

[0019] [9] A curable resin composition containing the propenyl group-containing compound according to any one of [1] to [8].

[0020]

[10] A curable resin composition comprising the propenyl group-containing compound according to any one of [3] to [5], an epoxy resin, and a maleimide resin.

[0021]

[11] A curable resin composition comprising the propenyl group-containing compound according to any one of [6] to [8], a phenolic resin, and a maleimide resin.

[0022]

[12] A cured product of the curable resin composition according to any one of [9] to

[11] .

[0023]

[13] A prepreg comprising a reinforcing substrate and a semi-cured product of the curable resin composition according to any one of [9] to

[11] impregnated into the reinforcing substrate.

[0024]

[14] A circuit board obtained by laminating the prepreg according to

[13] and copper foil and subjecting the laminate to thermocompression molding.

[0025]

[15] A build-up film containing the curable resin composition according to any one of [9] to

[11] .

[0026]

[16] A semiconductor encapsulant containing the curable resin composition according to any one of [9] to

[11] .

[0027]

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

[16] . [Effects of the Invention]

[0028] According to the present invention, it is possible to provide a propenyl group-containing compound that has a high softening point and excellent handleability while maintaining a low melt viscosity. According to the present invention, it is possible to provide a curable resin composition containing such a propenyl group-containing compound, a cured product thereof, a prepreg having a semi-cured product of the curable resin composition, a circuit board in which the prepreg and copper foil are laminated, a build-up film containing the curable resin composition, a semiconductor encapsulant, and a semiconductor device including a cured product of the semiconductor encapsulant. [Brief explanation of the drawings]

[0029] [Figure 1] 1 shows a GPC chart of the propenyl group-containing compound synthesized in Example 1. [Figure 2] 1 shows a 13C-NMR chart of the propenyl group-containing compound synthesized in Example 1. [Figure 3] 1 shows an FD-MS chart of the propenyl group-containing compound synthesized in Example 1. [Figure 4] 1 shows a GPC chart of the propenyl group-containing compound synthesized in Example 2. [Figure 5] 1 shows a 13C-NMR chart of the propenyl group-containing compound synthesized in Example 2. [Figure 6] 1 shows the FD-MS spectrum of the propenyl group-containing compound synthesized in Example 2. [Figure 7] 1 shows a GPC chart of the propenyl group-containing compound synthesized in Comparative Example 1. [Figure 8] 1 shows a GPC chart of the propenyl group-containing compound synthesized in Comparative Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0030] The propenyl group-containing compound, curable resin composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device of the present invention will be described in detail below with reference to their embodiments.

[0031] In this specification, the expression "a to b" in the description of a range of values means that the range is from a to b, unless otherwise specified.

[0032] <Terminology> Unless otherwise stated herein, the following terms apply.

[0033] The "aromatic hydrocarbon group" in this specification preferably has an aromatic ring having 3 to 30 carbon atoms, and more preferably has an aromatic ring having 4 to 26 carbon atoms. The "aromatic hydrocarbon group" in this specification may have a hydrogen atom of the aromatic ring substituted with a substituent, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. The "aromatic hydrocarbon group" also includes heteroaromatic groups, and may be substituted with -O-, -S-, or -N= so that -CH2- or -CH= in the "aromatic hydrocarbon group" are not adjacent to each other. Examples of the aromatic ring include a monocyclic aromatic ring, a fused aromatic ring, and an assembled aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the fused aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the assembled aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, and diphenylthiophene. Furthermore, a hydrogen atom on the aromatic ring in the aromatic hydrocarbon group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. The term "monovalent aromatic hydrocarbon group" refers to a group obtained by removing one hydrogen atom from an aromatic hydrocarbon group, a "divalent aromatic hydrocarbon group" refers to a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon group, and a "trivalent to hexavalent aromatic hydrocarbon group" refers to a group obtained by removing three to six hydrogen atoms from an aromatic hydrocarbon group.

[0034] In this specification, the "aromatic hydrocarbon group" is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, and even more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a diphenylmethyl group, a diphenylethyl group, a diphenylpropyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, and a propylphenyl group. The term "monovalent aromatic hydrocarbon group" refers to a group obtained by removing one hydrogen atom from an aromatic hydrocarbon group.

[0035] The term "aryl group" as used herein refers to a monovalent aromatic hydrocarbon group, which may be either monocyclic or polycyclic, and includes groups having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, or an indanyl group.

[0036] The "alkyl group" in this specification may be a linear, branched, or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, a (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. or a cyclononyl group. The "alkylene group" includes a divalent group obtained by removing any one hydrogen atom from the above-mentioned "alkyl group."

[0037] As used herein, the term "alkenyl group" includes an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, an isopropenyl group, and the like. The "alkenylene group" includes a divalent group obtained by removing any one hydrogen atom from the "alkenyl group".

[0038] As used herein, the term "alkoxy group" includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

[0039] As used herein, the term "halogen atom" includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0040] In this specification, the term "crosslinking site (binding site)" refers to a crosslinking site (binding site) of R I1 Ar I1 The moiety connecting the two aromatic rings in the following general formula (I), i.e., -C(R I1 )(Ar I1 )- refers to

[0041] <Propenyl group-containing compounds> The propenyl group-containing compound of this embodiment is characterized by being a propenyl group-containing compound represented by the following general formula (I). [ka] (In the above general formula (I), Ar I1 represents an aromatic hydrocarbon group having 6 or more carbon atoms, R I1 Ar I1 represents an alkyl group having a number of carbon atoms equal to or less than the number of carbon atoms of R I2 and R I3 each independently represents a hydrogen atom or a glycidyl group, R I4 and R I5 each independently represents a hydrogen atom or a propenyl group, R I6 and R I7 each independently represents a hydrogen atom or a propenyl group, provided that R I4 , R I5 , R I6 and R I7 at least one of which is a propenyl group; R Ia and R Ib each independently represents an alkyl group, an alkenyl group, or an alkoxy group, n I1 and n I2 each independently represents an integer of 0 to 1. However, in the above general formula (1), among the two carbon atoms adjacent to the carbon atom on the benzene ring to which the propenyl group is bonded, -OR I2 group or -ORI3 Any carbon atom that does not have a group attached has a hydrogen atom attached to it.) The propenyl group-containing compound represented by the general formula (I) has a low melt viscosity and is soft. It has a high melting point, making it easy to handle. The propenyl group-containing compound represented by the general formula (I) has an aromatic hydrocarbon group as a substituent at the crosslinking site (hereinafter sometimes referred to as the "bonding site") between two aromatic rings. The planar structure of the aromatic hydrocarbon group improves rigidity and increases intermolecular interactions, which is presumably why the softening point of the propenyl group-containing compound rises. Furthermore, in the propenyl group-containing compound represented by the general formula (I), one of the two substituents at the crosslinking site is an aromatic hydrocarbon group, which increases steric hindrance. In addition, because the two substituents at the crosslinking site are different, the symmetry within the molecule is reduced, which is presumably why the crystallinity is reduced. Therefore, as long as there is at least one propenyl group on the aromatic ring in the above general formula (I), and one of the two substituents at the crosslinking site is an aromatic hydrocarbon group and the other is a substituent different from the aromatic hydrocarbon group, the crystallinity can be reduced and the softening point can be improved, and therefore the optional other substituent is not particularly limited and can be a variety of substituents.

[0042] In the above general formula (I), Ar I1 represents an aromatic hydrocarbon group having 6 or more carbon atoms. The aromatic hydrocarbon group having 6 or more carbon atoms is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, and even more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 or more carbon atoms is preferably a monovalent aromatic hydrocarbon group, and examples thereof include those exemplified in the explanation section above regarding terms, and preferred examples include a phenyl group, a naphthyl group, an indanyl group, an indenyl group, a fluorenyl group, an anthracenyl group, etc. Among the above aromatic hydrocarbon groups, a phenyl group or a naphthyl group is more preferred. Furthermore, a hydrogen atom on the aromatic ring of these aromatic hydrocarbon groups may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. Examples of the alkyl group, alkoxy group, and halogen atom include those exemplified in the explanation section above.

[0043] In the above general formula (I), R I1 is an alkyl group, and R I1 The number of carbon atoms in Ar I1 The number of carbon atoms is less than or equal to R I1 The number of carbon atoms in Ar I1 There are no particular limitations on the alkyl group as long as it has no more than 10 carbon atoms. I1 The alkyl group having no more than this number of carbon atoms is, for example, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. R I1 The number of carbon atoms in Ar I1 It is presumed that when the number of carbon atoms is equal to or less than 1, the entire molecule is likely to have a planar structure, which improves rigidity and increases intermolecular interactions, thereby increasing the softening point of the propenyl group-containing compound. The alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an (n-)heptyl group, an (n-)octyl group, an (n-)nonyl group, an (n-)decyl group, an (n-)undecyl group, an (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group.

[0044] In the above general formula (I), R I2 and R I3R each independently represents a hydrogen atom or a glycidyl group. I2 and R I3 When R is a hydrogen atom, the propenyl group-containing compound is a phenol compound having a propenyl group (hereinafter, also referred to as a "propenyl group-containing phenol compound"). I2 and R I3 is a glycidyl group, propenyl The propenyl group-containing compound is an epoxy compound having a propenyl group (hereinafter, also referred to as a "propenyl group-containing epoxy compound"). Both the propenyl group-containing phenol compound and the propenyl group-containing epoxy compound can function as a curing agent for maleimide resins and the like.

[0045] In the above general formula (I), R I4 and R I5 each independently represents a hydrogen atom or a propenyl group; R I6 and R I7 each independently represents a hydrogen atom or a propenyl group, provided that R I4 , R I5 , R I6 and R I7 At least one of R is a propenyl group. I4 , R I5 , R I6 and R I7 When at least one of the R groups is a propenyl group (1-propenyl group or 2-propenyl group, the same applies below), the benzene ring in general formula (I) and the propenyl group (particularly the 1-propenyl group) can form a diene structure, which makes it easier to bond with a double bond such as a maleimide group through a Diels-Alder reaction. Therefore, for example, in a resin composition containing a propenyl group-containing compound represented by the general formula (I) above and a maleimide resin, the propenyl group-containing compound of this embodiment can bond with the maleimide resin. I4 , R I5 , R I6 and R I7 Two of the R groups may be propenyl groups, three may be propenyl groups, or four may be propenyl groups. I4 , R I5 , RI6 and R I7 When two of the groups are propenyl groups, R I4 and R I5 is a propenyl group, and R I6 and R I7 Preferably, one of the groups is a propenyl group. Furthermore, when the propenyl group is a 2-propenyl group, curing with the maleimide group proceeds via an Alder-ene reaction, which has a higher reaction temperature than a Diels-Alder reaction. Therefore, from the viewpoint of the curing initiation temperature with the maleimide resin, the propenyl group is preferably a 1-propenyl group, which reacts at a lower temperature.

[0046] R Ia and R Ib each independently represents an alkyl group, an alkenyl group, or an alkoxy group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, a (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, and an isopropenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

[0047] In addition, in the above general formula (I), among the two carbon atoms adjacent to the carbon atom on the benzene ring to which the propenyl group is bonded, -OR I2 group or -OR I3 A hydrogen atom is bonded to the carbon atom to which no group is bonded. I2 group or -OR I3 If atoms other than hydrogen atoms are bonded to carbon atoms not bonded to groups, the rate of curing with the maleimide resin will be slow due to steric hindrance, which is undesirable.

[0048] Ar in the above general formula (I) I1 is preferably a substituent represented by the following general formula (II) or (III). [ka] (In general formula (II), R IIc each independently represents an alkyl group, n II1 represents an integer of 0 to 5. In addition, * in general formula (II) represents a bond to another atom. [ka] (In general formula (III), R IIId each independently represents an alkyl group, n III1 represents an integer of 0 to 7. In addition, * in general formula (III) represents a bond to another atom. Ar I1 However, if the substituent is represented by the following general formula (II) or (III), the solubility and softening point are improved, and the synthesis of the propenyl group-containing compound of this embodiment is easy, which is preferable.

[0049] R in general formula (II) IIc is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include the groups described in the explanation of terms.

[0050] Similarly, R in general formula (III) IIId is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include the groups described in the explanation of terms.

[0051] The propenyl group-containing compound of this embodiment preferably has a melt viscosity at 150°C of 0.1 mPa·s or more and 2.0 mPa·s or less. If the melt viscosity at 150°C is outside this range, the compound will have poor flowability, making transfer molding difficult. From the viewpoint of handleability, the melt viscosity at 150°C is more preferably 1.0 mPa·s or less, and even more preferably 0.5 mPa·s or less. If the melt viscosity (150°C) of the propenyl group-containing compound of the present embodiment exceeds approximately 2.0 mPa·s, the fluidity tends to decrease, making transfer molding difficult. Therefore, it is believed that if the melt viscosity (150°C) of the propenyl group-containing compound of the present disclosure is approximately 2.0 mPa·s or less, the melt viscosity can be kept low. The melt viscosity of the propenyl group-containing compound at 150°C can be measured using an ICI viscometer in accordance with ASTM D4287. The preferred softening point of the propenyl group-containing compound represented by general formula (I) of this embodiment varies depending on the type of each group in general formula (I), but if it is generally 50°C or higher, the temperature difference from room temperature becomes clear and handling tends to be easy. Since the balance between softening point and melt viscosity is important for handling, it cannot be said that excellent handling is exhibited solely based on the softening point. However, in this specification, a softening point of 50°C or higher is defined as a high softening point, and a softening point of 50°C or higher and a melt viscosity at 150°C of 2.0 mPa s or less is defined as good handling. The softening point can be measured in accordance with JIS K7234.

[0052] [Propenyl group-containing phenolic compounds] In the above general formula (I), R I2 and R I3 is preferably a hydrogen atom. I2 and R I3 is a hydrogen atom, such a propenyl-containing compound is referred to herein as a propenyl-group-containing phenolic compound. The propenyl group-containing phenolic compound functions as a curing agent for the epoxy resin in a curable resin composition containing the propenyl group-containing phenolic compound. In a cured system of an epoxy resin and a phenolic compound, the curing reaction proceeds through the reaction of the glycidyl group of the epoxy resin with the hydroxyl group of the propenyl group-containing phenolic compound. Furthermore, because the propenyl group-containing phenolic compound contains a propenyl group, it can also react with resins other than epoxy resins (hereinafter sometimes referred to as "non-epoxy resins"), such as maleimide resins. Because the propenyl group-containing phenolic compound contains a propenyl group, the epoxy resin does not need to contain a propenyl group, which has the advantage of allowing the selection of a more appropriate epoxy resin depending on the application.

[0053] The softening point of the propenyl group-containing phenol compound is preferably 50°C or higher and 120°C or lower. When the softening point is in the above range, the compound is solid at room temperature and therefore easy to handle. From the viewpoint of improving the handleability, the softening point of the propenyl group-containing phenol compound is more preferably 60°C or higher, and even more preferably 70°C or higher. Alternatively, the softening point may be 100°C or lower. The softening point can be measured in accordance with JIS K7234.

[0054] The propenyl group-containing phenolic compound preferably has a hydroxyl group equivalent of 100 g / equivalent or more and 300 g / equivalent or less. A hydroxyl group equivalent within the above range is preferred because it provides a good balance between heat resistance and viscosity. The hydroxyl group equivalent of the propenyl group-containing phenolic compound is more preferably 120 g / equivalent or more, even more preferably 150 g / equivalent or more, and more preferably 280 g / equivalent or less, even more preferably 250 g / equivalent or less. The hydroxyl group equivalent can be measured in accordance with JIS K 0070.

[0055] (Production of Propenyl Group-Containing Phenol Compounds) The method for producing a propenyl group-containing phenol compound is not limited, but for example, an allyl ether represented by the following general formula (1) can be obtained using a predetermined raw material, and then the allyl group of the allyl ether can be subjected to Claisen rearrangement to obtain a propenyl group-containing phenol compound represented by the following general formula (2). Furthermore, after obtaining the propenyl group-containing phenol compound represented by the following general formula (2) by the above method, if necessary, a known A reaction to change the position of the double bond in the propenyl group may be further carried out by isomerizing a 2-propenyl group to a 1-propenyl group using a method such as a carbon-carbon bond isomerization reaction using a palladium acetate catalyst or the like, or a carbon-carbon bond isomerization reaction using an alkali metal hydroxide or the like as a base catalyst (see [J. Am. Chem. Soc., 78, pp. 1709-1715 (1956)]). [ka] [ka] (The symbols in the above general formulas (1) and (2) have the same meanings as the symbols in the above general formula (I). In the above general formula (1), R I4 or R I6 is a hydrogen atom, and R I5 or R I7 Either of the groups may be a hydrogen atom.)

[0056] [Propenyl group-containing epoxy compounds] In the above general formula (I), R I2 and R I3 is preferably a glycidyl group. I2 and R I3 is a glycidyl group, such a propenyl group-containing compound is referred to herein as a propenyl group-containing epoxy compound. A propenyl group-containing epoxy compound can be used as an epoxy resin in a curable resin composition containing the propenyl group-containing epoxy compound. In a cured system of an epoxy compound and a phenolic resin, the curing reaction proceeds through the reaction of the glycidyl group of the propenyl group-containing epoxy compound with the hydroxyl group of the phenolic resin. Furthermore, if the propenyl group-containing epoxy compound contains a propenyl group (1-propenyl group or 2-propenyl group), the benzene ring in general formula (I) and the propenyl group (particularly the 1-propenyl group) can form a diene structure, which facilitates bonding with groups having double bonds such as maleimide groups via a Diels-Alder reaction. Therefore, it can also react with resins other than epoxy resins (hereinafter sometimes referred to as "non-epoxy resins"). Because the propenyl group-containing epoxy compound contains both a propenyl group and a glycidyl group, resins other than epoxy resins, such as phenolic resins, do not need to contain propenyl groups, which has the advantage of allowing for the selection of a more appropriate resin depending on the application.

[0057] The propenyl group-containing epoxy compound preferably has a softening point of more than 45°C and not more than 120°C. When the softening point is within the above range, the epoxy compound is solid at room temperature and therefore easy to handle. From the viewpoint of improving the handleability, the softening point of the propenyl group-containing epoxy compound is more preferably 50°C or higher, even more preferably 60°C or higher, and particularly preferably 70°C or higher. Alternatively, the softening point may be 100°C or lower. The softening point can be measured in accordance with JIS K7234.

[0058] The epoxy equivalent of the propenyl group-containing epoxy compound is preferably 180 g / equivalent or more and 350 g / equivalent or less. The epoxy equivalent within this range is preferred because it provides a good balance between heat resistance and viscosity. The epoxy equivalent of the propenyl group-containing epoxy compound is more preferably 200 g / equivalent or more, and even more preferably 230 g / equivalent or more. The epoxy equivalent of the propenyl group-containing epoxy compound is more preferably 320 g / equivalent or less, and even more preferably 300 g / equivalent or less. The hydroxyl group equivalent can be measured in accordance with JIS K 7236.

[0059] (Method of producing a propenyl group-containing epoxy compound) The method for producing the propenyl group-containing epoxy compound is not limited, but for example, the propenyl group-containing epoxy compound can be obtained by reacting the propenyl group-containing phenol compound represented by the above general formula (2) with epichlorohydrin.

[0060] <Curable resin composition> The curable resin composition of the present embodiment preferably contains the propenyl group-containing compound of the present embodiment. The curable resin composition of the present embodiment has excellent heat resistance.

[0061] In the curable resin composition of the present embodiment, the content of the propenyl group-containing compound of the present embodiment is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 60% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less, based on the total amount of the curable resin composition.

[0062] The curable resin composition of this embodiment preferably has a gel time of 0 to 120 seconds at 175°C. A gel time in the above range at 175°C is preferable because it provides good handleability during transfer molding. The gel time at 175°C is more preferably 20 to 100 seconds, and even more preferably 30 to 60 seconds. The gel time can be measured by the method described in the Examples below.

[0063] The curable resin composition of the present embodiment preferably has a glass transition temperature (Tg) of 180°C or higher. A glass transition temperature (Tg) in the above range is preferred because the composition has high thermal stability at high temperatures. The glass transition temperature (Tg) is more preferably 200°C or higher, and even more preferably 250°C or higher. The glass transition temperature can be measured by dynamic viscoelasticity measurement (DMA) using a dynamic viscoelasticity device (manufactured by Rheometrics).

[0064] The curable resin composition of this embodiment preferably has a 5% weight loss temperature of 350°C or higher. The 5% weight loss temperature refers to the temperature at which the weight is reduced by 5%. A 5% weight loss temperature within the above range is preferable because the composition has high thermal stability under high heat. The 5% weight loss temperature is more preferably 380°C or higher, and even more preferably 400°C or higher. The 5% weight loss temperature can be measured using a thermogravimetric analyzer (manufactured by SII Nano Technology Co., Ltd.) at a temperature rise rate of 5°C / min in a nitrogen atmosphere.

[0065] In addition to the propenyl group-containing compound, the curable resin composition of this embodiment preferably contains one or more resins selected from the group consisting of epoxy resins (hereinafter also referred to as "epoxy compounds"), phenolic resins (hereinafter also referred to as "phenolic compounds"), maleimide resins, benzoxazine resins, cyanate ester resins, active ester resins, resins having a radically polymerizable functional group, isocyanate resins, acid anhydride resins, and carbodiimide resins. Among these, the resin contained in the curable resin composition is more preferably one or more resins selected from the group consisting of epoxy resins, phenolic resins, and maleimide resins. In the curable resin composition of the present embodiment, the content of components other than the propenyl group-containing compound can be 10% by mass or more and 90% by mass or less with respect to the entire curable resin composition (100% by mass). In the curable resin composition of the present embodiment, the total content of the propenyl group-containing compound and components other than the propenyl group-containing compound can be 10% by mass or more and 90% by mass or less with respect to the entire curable resin composition (100% by mass).

[0066] Furthermore, when the propenyl group-containing compound of this embodiment is the above-mentioned propenyl group-containing phenolic compound, the curable resin composition of this embodiment preferably contains the propenyl group-containing phenolic compound of this embodiment, an epoxy resin, and a maleimide resin. Furthermore, when the propenyl group-containing compound of this embodiment is the above-mentioned propenyl group-containing epoxy compound, the curable resin composition of this embodiment preferably contains the propenyl group-containing epoxy compound of this embodiment, a phenolic resin, and a maleimide resin.

[0067] [Epoxy resin] The epoxy resin is not particularly limited, and examples thereof include phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, naphthol type epoxy resins, xylylene type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene type epoxy resins, stilbene type epoxy resins, sulfur atom-containing epoxy resins, and phosphorus atom-containing epoxy resins.

[0068] When the propenyl group-containing compound of the present embodiment is a propenyl group-containing epoxy compound, the propenyl group-containing epoxy compound may be contained as an epoxy resin. In addition to the propenyl group-containing epoxy compound, the epoxy resin may also be contained.

[0069] The epoxy resins may be used alone or in combination of two or more.

[0070] In the curable resin composition of the present embodiment, the content of the epoxy resin is preferably 5% by mass or more and 70% by mass or less, more preferably 7% by mass or more and 60% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less, based on the entire curable resin composition.

[0071] [Phenol resin] Examples of phenolic resins include novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and / or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, benzaldehyde, and salicylaldehyde, under an acidic catalyst; phenol-aralkyl resins synthesized from phenols and / or naphthols and dimethoxy-paraxylene or bis(methoxymethyl)biphenyl; biphenylene-type phenol-aralkyl resins, naphthol-aralkyl resins, etc. dicyclopentadiene-type phenolic resins such as dicyclopentadiene-type phenol novolac resins and dicyclopentadiene-type naphthol novolac resins, which are synthesized by copolymerizing 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.

[0072] When the propenyl group-containing compound of the present embodiment is a propenyl group-containing phenolic compound, the propenyl group-containing phenolic compound may be contained as a phenolic resin. In addition to the propenyl group-containing phenolic compound, the above-mentioned phenolic resin may be contained.

[0073] The phenolic resin may be used alone or in combination of two or more kinds.

[0074] In the curable resin composition of the present embodiment, the content of the phenol resin is preferably 5% by mass or more and 70% by mass or less, more preferably 7% by mass or more and 60% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less, based on the entire curable resin composition.

[0075] [Maleimide resin] Maleimide resin refers to a maleimide compound having an average of one or more maleimide groups per molecule. Examples of maleimide resins include bismaleimides having two maleimide groups per molecule and polyphenylmethane maleimide.

[0076] Examples of bismaleimides include alkyl bismaleimide, diphenylmethane bismaleimide, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 4,4'-diphenylmethane bismaleimide such as 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and 1,3-bis(4-maleimidophenoxy)benzene. Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with maleimide groups are linked via methylene groups.

[0077] Of the above-mentioned maleimide resins, 4,4'-diphenylmethane bismaleimide and polyphenylmethane maleimide are preferred as the maleimide resin because they have excellent compatibility with the propenyl group-containing compound of this embodiment and are relatively inexpensive.

[0078] Commercially available maleimide resins may be used, such as those manufactured by Daiwa Chemical Industry Co., Ltd. under the product names "BMI-1100" (4,4'-diphenylmethane bismaleimide) and "BMI-2300" (polyphenylmethane maleimide).

[0079] The maleimide resin may be used alone or in combination of two or more kinds.

[0080] In the curable resin composition of the present embodiment, the content of the maleimide resin is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and even more preferably 20% by mass or more and 60% by mass or less, based on the entire curable resin composition.

[0081] [Benzoxazine resin] Examples of benzoxazine resins include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc. The benzoxazine resin may contain a structure in which the oxazine ring is ring-opening polymerized. The benzoxazine resin may be used alone or in combination of two or more kinds.

[0082] [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; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. The cyanate ester resins may be used alone or in combination of two or more.

[0083] [Activated ester resin] The active ester resin is not particularly limited, but compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester resin is preferably one 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. From the viewpoint of improving heat resistance in particular, 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 a phenol 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 compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, 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, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0084] Specifically, active ester resins containing a dicyclopentadiene-type diphenol structure, active ester resins containing a naphthalene structure, active ester resins containing an acetylated product of phenol novolac, and active ester resins containing a benzoylated product of phenol novolac are preferred, and among these, active ester resins containing a naphthalene structure and active ester resins containing a dicyclopentadiene-type diphenol structure are more preferred. Here, the "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

[0085] The active ester resin may be used alone or in combination of two or more kinds.

[0086] [Resin with radically polymerizable functional groups] Resins having radically polymerizable functional groups include resins having one or more ethylenically unsaturated groups with a carbon-carbon double bond in the molecule. The ethylenically unsaturated groups are preferably one or more groups selected from the group consisting of an acrylic group, a methacrylic group, a styryl group, an olefin group, and a maleimide group. Preferred examples of the olefin group include an allyl group, a vinyl group, and a propenyl group. Therefore, in a preferred embodiment, the radically polymerizable functional group is one or more groups selected from the group consisting of an acrylic group, a methacrylic group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a maleimide group. The resin having a radically polymerizable functional group may have one or more types of radically polymerizable functional groups.

[0087] The resin having a radically polymerizable functional group may be used alone or in combination of two or more kinds.

[0088] [Isocyanate resin] The isocyanate resin may be a resin having one or more isocyanate groups in the molecule. Preferably, the isocyanate resin has two or more isocyanate groups in the molecule. Examples of the isocyanate resin include 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate. The isocyanate resin may be used alone or in combination of two or more kinds.

[0089] [Acid anhydride resin] Examples of acid anhydride resins include resins having one or more acid anhydride groups in the molecule. 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-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride. Examples of suitable anhydrides include hydrates, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic 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 polymeric anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. The acid anhydride resins may be used alone or in combination of two or more.

[0090] [Carbodiimide resin] The carbodiimide resin may be a resin having one or more carbodiimide groups (-N=C=N-) in the molecule. The carbodiimide resin preferably has two or more carbodiimide groups in the molecule. Specific examples of the carbodiimide resin include "V-03" and "V-07" manufactured by Nisshinbo Chemical Inc. The carbodiimide resin may be used alone or in combination of two or more kinds.

[0091] [Other ingredients] The curable resin composition of the present embodiment is a curable resin composition containing the propenyl group-containing compound of the present invention and the above-mentioned resins. In addition, the composition may contain one or more other components, such as a curing accelerator, inorganic filler, solvent, mold release agent, surface treatment agent, colorant, thermoplastic polymer, organic filler, and flame retardant. In the curable resin composition of the present embodiment, the content of other components can be set to 0.01% by mass or more and 95% by mass or less.

[0092] Examples of the curing accelerator include imidazoles, organic peroxides, phosphorus compounds, tertiary amines, organic acid metal salts, Lewis acids, amine complex salts, etc. These may be used alone or in combination of two or more. 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. Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. Examples 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. Among these curing accelerators, phosphorus compounds, particularly triphenylphosphine, are preferred because they are superior in curability, heat resistance, and electrical properties, and moisture resistance reliability is less likely to decrease. In the curable resin composition of the present embodiment, the content of the curing accelerator can be set to 0.01% by mass or more and 5% by mass or less.

[0093] Examples of inorganic fillers include crystalline silica powder, fusible silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder. Of these, crystalline silica powder and fusible silica powder are preferred. One type of inorganic filler may be used alone, or two or more types may be used in combination. In the curable resin composition of the present embodiment, the content of the inorganic filler can be set to 0.5% by mass or more and 95% by mass or less.

[0094] The solvent is not particularly limited as long as it dissolves the propenyl group-containing composition, the curing component, etc., and typically, a polar solvent is used.

[0095] Examples of the release agent include various waxes such as carnauba wax. In the curable resin composition of the present embodiment, the content of the release agent can be set to 0.1% by mass or more and 5% by mass or less.

[0096] Examples of the surface treatment agent include known silane coupling agents. In the curable resin composition of the present embodiment, the content of the surface treatment agent can be set to 0.1% by mass or more and 5% by mass or less.

[0097] Examples of colorants include carbon black. In the curable resin composition of the present embodiment, the content of the colorant can be set to 0.1% by mass or more and 10% by mass or less.

[0098] Examples of thermoplastic polymers include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyetheretherketone resin, polyetherimide resin, silicone resin, and tetrafluoroethylene resin. In the curable resin composition of the present embodiment, the content of the thermoplastic polymer can be set to 0.1% by mass or more and 10% by mass or less.

[0099] 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 an acrylic acid ester resin, a methacrylic acid ester resin, a conjugated diene resin, etc., and a glassy shell layer made of an acrylic acid ester resin, a methacrylic acid ester resin, an aromatic vinyl resin, a vinyl cyanide resin, etc. In the curable resin composition of the present embodiment, the content of the organic filler can be set to 0.5% by mass or more and 95% by mass or less.

[0100] Examples of the flame retardant include halogen-containing 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. In the curable resin composition of the present embodiment, the content of the flame retardant can be set to 0.1% by mass or more and 50% by mass or less.

[0101] <Cured product> The cured product of this embodiment is preferably a cured product of the curable resin composition of this embodiment. The cured product can be obtained by subjecting the curable resin composition to a curing reaction. The curable resin composition can be easily cured by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

[0102] <Prepreg> The prepreg of this embodiment is preferably a prepreg having a reinforcing substrate and a semi-cured product of the curable resin composition of this embodiment impregnated into the reinforcing substrate. A method for obtaining a prepreg from the curable resin composition includes blending an organic solvent (described below) to form a varnish of the curable resin composition, impregnating a reinforcing substrate (such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, or glass roving cloth) with the varnished curable resin composition, and then heating the cured resin composition at a temperature appropriate for the solvent used, preferably 50 to 170°C, to semi-cure (or uncur) the curable resin composition to obtain a prepreg. The mass ratio of the curable resin composition to the reinforcing substrate used in this method is not particularly limited, but it is generally preferable to prepare the prepreg so that the resin content in the prepreg is 20 to 60% by mass. In this embodiment, the semi-cured product of the curable resin composition is obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without completing it. Also, for example, the semi-cured product may have a degree of cure of, for example, 5% to 85%. The cured product may have a higher degree of cure than the semi-cured product. The degree of cure of the semi-cured product can be calculated from the following formula by measuring the amount of heat generated during curing when the curable resin composition is heated and the amount of heat generated during curing of the semi-cured product by DSC. Degree of cure (%) = [1 - (cure heat generation amount of semi-cured product / cure heat generation amount of curable resin composition)] x 100

[0103] Examples of organic solvents used in producing the prepreg include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of the organic solvent can be determined appropriately depending on the application. For example, when a printed circuit board is further produced from the prepreg as described below, it is preferable to use a polar solvent with a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, or dimethylformamide, and it is also preferable to use it in a proportion such that the non-volatile content is 40 to 80% by mass.

[0104] <Circuit board> The circuit board of this embodiment is a circuit board that is a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the curable resin composition of this embodiment includes laminating the prepreg by a conventional method, overlaying copper foil as appropriate, and subjecting them to heat-pressure bonding at 170 to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0105] <Build-up film> The buildup film of the present embodiment is preferably a buildup film containing the curable resin composition of the present embodiment. A method for producing the buildup film of the present embodiment includes applying the curable resin composition to a support film to form a curable resin composition layer, thereby forming an adhesive film for a multilayer printed wiring board.

[0106] When producing a build-up film from a curable resin composition, it is essential that the film softens under the lamination temperature conditions (usually 70 to 140°C) in a vacuum lamination method and exhibits fluidity (resin flow) that allows resin to fill via holes or through holes present in the circuit board at the same time as lamination onto the circuit board, and it is preferable to blend the above-mentioned components so as to exhibit such properties.

[0107] Here, the diameter of the through-holes in the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling within these ranges. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes with resin.

[0108] Specifically, the adhesive film can be produced by preparing the curable resin composition in a varnish form, applying the varnish-like composition to the surface of the support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a composition layer (X) made of the curable resin composition.

[0109] The thickness of the composition layer (X) to be formed is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0110] The composition layer (X) in this embodiment may be protected with a protective film, which will be described later. By protecting with a protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be prevented. This can be prevented.

[0111] Examples of the support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a mud treatment, a corona treatment, or a release treatment.

[0112] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm, and the thickness of the protective film is preferably 1 to 40 μm.

[0113] The support film (Y) is peeled off after laminating it onto the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0114] <Semiconductor encapsulation material> The semiconductor encapsulation material of the present embodiment is preferably a semiconductor encapsulation material containing the curable resin composition of the present embodiment. The semiconductor encapsulation material containing the curable resin composition of the present embodiment is excellent in heat resistance because it uses the curable resin composition of the present embodiment, and is a preferred embodiment. The curable resin composition of this embodiment used in the semiconductor encapsulation material may contain an inorganic filler. The inorganic filler may be used in an amount of, for example, 0.5 to 1,200 parts by mass per 100 parts by mass of the curable resin composition of this embodiment. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0115] Examples of a method for obtaining the semiconductor encapsulating material include a method in which the curable resin composition of the present embodiment and optional additives are further melt-mixed, as needed, using an extruder, kneader, rolls, or the like until the mixture becomes homogeneous.

[0116] <Semiconductor device> The semiconductor device of the present embodiment is a semiconductor device including a cured product of the semiconductor encapsulation material. The semiconductor device obtained using the semiconductor encapsulation material obtained using the curable resin composition of the present embodiment has excellent heat resistance, which is a preferred embodiment, since the curable resin composition of the present embodiment is used.

[0117] The semiconductor device can be obtained by molding the semiconductor encapsulating material using a casting machine, a transfer molding machine, an injection molding machine, or the like, and then heat-curing the material at a temperature ranging from room temperature (20°C) to 250°C. [Example]

[0118] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0119] <Measurement method> In the examples, various measurements were carried out by the following methods.

[0120] [Softening point measurement] The softening points of the propenyl group-containing compounds of Examples 1 and 2 and Comparative Examples 1 and 2 were measured in accordance with JIS K7234.

[0121] [Melt viscosity at 150°C] The melt viscosity at 150°C was evaluated as an index of the handleability of the propenyl group-containing compound. The melt viscosities at 150°C of the propenyl group-containing compounds of Examples 1 and 2 and Comparative Examples 1 and 2 were measured using an ICI viscometer in accordance with ASTM D4287.

[0122] [Gel time measurement] The gel time corresponds to the time required for curing, and was therefore evaluated as an index of the handleability that represents the ease of handling of a curable composition containing a propenyl group-containing compound. The prepared curable resin composition was placed on an iron plate heated to 175°C, and the time until the resin composition gelled (gel time) was measured. The time until gelling was defined as the time until the curable resin composition lost its fluidity. The gel time corresponds to the curing time, and a shorter gel time indicates a shorter time until curing.

[0123] [Measurement of glass transition temperature (Tg)] The curable resin composition was cured, and the resulting cured product was subjected to dynamic viscoelasticity measurement (DMA) using a dynamic viscoelasticity analyzer (manufactured by Rheometrics) to measure the glass transition temperature (Tg). A higher value indicates better heat resistance.

[0124] [Thermal decomposition (5% weight loss temperature)] The curable resin composition was cured, and the resulting cured product was measured using a thermogravimetric analyzer (manufactured by SII Nano Technology Inc.) at a heating rate of 5°C / min in a nitrogen atmosphere to determine the temperature at which the weight of the cured product decreased by 5% (5% weight loss temperature (Td5)). A higher value indicates better heat resistance.

[0125] [Measurement of hydroxyl equivalent] The hydroxyl equivalent was measured by a method based on the neutralization titration method specified in JIS K0070 (1992).

[0126] [Measurement of epoxy equivalent weight] The epoxy equivalent was measured in accordance with JIS K 7236.

[0127] [GPC measurement] Measurements were performed using the following measuring equipment and conditions to obtain the GPC charts of the propenyl group-containing compounds of the following Examples and Comparative Examples. From the results of the GPC charts, it was confirmed that the target product (propenyl group-containing compound) was produced, based on the decrease and disappearance of the raw material peaks. Measurement equipment: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation Tosoh Corporation "F-128" Sample: A tetrahydrofuran solution (50 μl) of 1.0 mass % in terms of solid content of the polyindene compound obtained in the following synthesis examples and working examples was filtered through a microfilter and used.

[0128] [ 13 C-NMR measurement] The propenyl group-containing compounds obtained in the examples 13 The C-NMR spectrum was measured using the following measuring device and conditions. 13 C-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 150MHz Accumulation count: 320 times Solvent: DMSO-d6 Sample concentration: 30% by mass The aforementioned 13 From the results of the C-NMR chart, peaks derived from the target products were confirmed, confirming that the target products were obtained in each reaction.

[0129] [FD-MS measurement] The FD-MS spectra of the propenyl group-containing compounds obtained in the examples were measured using the following measuring device and under the following measuring conditions. Measurement equipment: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z = 4.00 to 2000.00 Rate of change: 51.2mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 sec

[0130] <Synthesis and Evaluation of Propenyl Group-Containing Compounds> Example 1: Synthesis of propenyl group-containing compound (A-1) (propenyl group-containing phenol compound (A-1)) In a flask equipped with a thermometer, a condenser, and a stirrer, 290 g (1 mol) of 4,4'-(1-phenylethylidene)bisphenol and 580 g of methanol were charged and dissolved while purging with nitrogen gas. 96 g (2.4 mol) of sodium hydroxide was added, and the temperature was raised to 60°C. The sodium hydroxide was completely dissolved. The mixture was then cooled to 40°C, and 183 g (2.4 mol) of allyl chloride was added dropwise over 3 hours. After the dropwise addition, the mixture was heated to 60°C over 2 hours and allowed to react for an additional 4 hours. After the reaction was complete, 580 g of methyl isobutyl ketone was added, and the temperature was raised to 80°C, and the methanol was distilled off. The mixture was then neutralized and washed with 290 g of water three times until the pH of the washings became neutral. The system was then dehydrated and desolvated to synthesize an allyl ether. The resulting allyl ether was then heated to 190°C and heated and stirred for 5 hours, causing a Claisen rearrangement. After the reaction was complete, the mixture was cooled to 60°C, and 134.7 g (2.4 mol) of potassium hydroxide and 43 g of isopropanol were added to completely dissolve the potassium hydroxide. The mixture was then heated to 115°C while distilling off the isopropanol, and allowed to react for 6 hours. After the reaction was completed, 580 g of methyl isobutyl ketone was added, the mixture was cooled to 80°C, and the mixture was neutralized and washed with water. This was repeated three times with 290 g of water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain a propenyl group-containing compound (A-1) represented by the following formula (i) (hereinafter sometimes referred to as "propenyl group-containing phenolic compound (A-1)" or "A-1"). The hydroxyl group equivalent of the obtained propenyl group-containing phenolic compound (A-1) was 195 g / eq. The GPC chart of the obtained propenyl group-containing phenolic compound (A-1) is shown in Figure 1. 13 The C-NMR chart is shown in Figure 2, and the FD-MS spectrum is shown in Figure 3. [ka]

[0131] Example 2: Synthesis of propenyl group-containing compound (B-1) (propenyl group-containing epoxy compound (B-1)) A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas and charged with 150 g of the propenyl group-containing phenol compound (A-1) obtained in Example 1, 375 g (4 mol) of epichlorohydrin, 101 g of n-butanol, and 19 g of water, and dissolved. After heating to 50°C, 73 g (0.89 mol) of 49 wt% aqueous sodium hydroxide solution was added over 3 hours, and the reaction was continued for another hour at 50°C. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 120°C. Next, 276 g of methyl isobutyl ketone was added to the resulting crude epoxy resin and dissolved. 82 g of 5 wt% aqueous sodium hydroxide solution was added to the solution, and the reaction was continued for 2 hours at 80°C. The solution was then washed twice with 92 g of water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain a propenyl group-containing compound (B-1) (hereinafter also referred to as "propenyl group-containing epoxy compound (B-1)" or "B-1") represented by the following (ii). The epoxy equivalent of the obtained epoxy resin was 254 g / eq. The GPC chart of the obtained propenyl group-containing epoxy compound (B-1) is shown in Figure 4. 13 The C-NMR spectrum is shown in Figure 5, and the FD-MS spectrum is shown in Figure 6. [ka]

[0132] Comparative Example 1: Synthesis of Propenyl Group-Containing Compound (A-2) (Propenyl Group-Containing Phenol Compound (A-2)) The same synthesis method as in Example 1 was carried out, except that 4,4'-isopropylidenediphenol was used instead of 4,4'-(1-phenylethylidene)bisphenol used in Example 1, to obtain a propenyl group-containing compound (A-2) represented by the following (iii) (hereinafter also referred to as "propenyl group-containing phenol compound (A-2)" or "A-2"). The GPC chart of the obtained propenyl group-containing phenol compound (A-2) is shown in Figure 7. [ka]

[0133] Comparative Example 2: Synthesis of Propenyl Group-Containing Compound (B-2) (Propenyl Group-Containing Epoxy Compound (B-2)) The same synthesis as in Example 2 was carried out, except that the propenyl group-containing compound (A-2) obtained in Comparative Example 1 was used instead of the propenyl group-containing phenol compound (A-1), to obtain a propenyl group-containing compound (B-2) (hereinafter also referred to as "propenyl group-containing epoxy compound (B-2)" or "B-2") represented by the following formula (iv). The GPC chart of the obtained propenyl group-containing epoxy compound (B-2) is shown in Figure 8. [ka]

[0134] The measurement results of the propenyl group-containing compounds synthesized in the above Examples and Comparative Examples are shown in Table 1 below.

[0135] [Table 1]

[0136] In Comparative Example 2, the propenyl group-containing compound (B-2) was in a liquid state, which indicates that the softening point was below room temperature or close to room temperature. Therefore, the compound (B-2) of Comparative Example 2 had a low melt viscosity but was very difficult to handle. In Comparative Example 1, the melt viscosity was low, but the softening point was not high enough, and the handleability was insufficient. On the other hand, Table 1 shows that the propenyl group-containing compound of the present invention, which has an aromatic hydrocarbon group at the crosslinking site, has a higher softening point than a propenyl group-containing compound that does not have an aromatic hydrocarbon group at the crosslinking site. In addition, it is also shown that the melt viscosity of the propenyl group-containing compound of the present invention is maintained low without increasing. Therefore, as can be seen from Table 1, the propenyl group-containing compound of the present invention has a high softening point and maintains a low melt viscosity, which means that it is easy to handle.

[0137] <Preparation and Evaluation of Curable Resin Composition and Cured Product> [Raw materials] In addition to the propenyl group-containing compounds synthesized in Examples 1 and 2 and Comparative Examples 1 and 2, the following substances were used. Phenolic compound (A-3): Phenol novolac resin "TD-2131" (DIC Corporation, hydroxyl equivalent: 104 g / eq) Epoxy compound (B-3): Cresol novolac epoxy resin "N-655-EXP-S" (DIC Corporation, epoxy equivalent: 201g / eq) Maleimide resin: BMI-2300 (manufactured by Daiwa Chemical Industry Co., Ltd.) Triphenylphosphine (TPP)

[0138] [Example 3] A curable resin composition was prepared by blending the phenol compound (A-3), 13 g of the propenyl group-containing epoxy compound (B-1), 18 g of maleimide resin, and 0.36 phr of triphenylphosphine (TPP) and melt-kneading the mixture at 110°C for 45 minutes. The mixture was then press-molded at 175°C for 30 minutes and heated at 200°C for 5 hours to produce a cured product.

[0139] [Example 4, Comparative Examples 3 and 4] Curable resin compositions and cured products were prepared in the same manner as in Example 3, except that the blending compositions were changed as shown in Table 2 below.

[0140] [Table 2]

[0141] From Table 2, it can be seen that the cured product of the curable resin composition containing the propenyl group-containing compound of the present invention has a high glass transition temperature and excellent heat resistance. Furthermore, it can be seen from Table 2 that by epoxidizing a propenyl group-containing phenol compound to form a propenyl group-containing epoxy compound, the gel time is shortened and the resin composition has excellent handleability. Furthermore, the 5% weight loss temperature increases by epoxidation, indicating better thermal stability. [Industrial Applicability]

[0142] According to the present invention, it is possible to provide a propenyl group-containing compound that has a high softening point and excellent handleability while maintaining a low melt viscosity.

Claims

1. A propenyl group-containing compound represented by the following general formula (I): 【Chemical 1】 (In the above general formula (I), Ar Ｉ１ represents an aromatic hydrocarbon group having 6 or more carbon atoms, R Ｉ１ is Ar Ｉ１ represents an alkyl group having a number of carbon atoms equal to or less than the number of carbon atoms of R Ｉ２ and R Ｉ３ each independently represents a hydrogen atom or a glycidyl group, R Ｉ４ and R Ｉ５ each independently represents a hydrogen atom or a propenyl group, R Ｉ６ and R Ｉ７ each independently represents a hydrogen atom or a propenyl group, provided that R Ｉ４ , R Ｉ５ , R Ｉ６ and R Ｉ７ at least one of is a propenyl group; R Ｉａ and R Ｉｂ each independently represents an alkyl group, an alkenyl group, or an alkoxy group, n I１ and n I２ each independently represents an integer of 0 to 1. However, in the above general formula (1), of the two carbon atoms adjacent to the carbon atom on the benzene ring to which the propenyl group is bonded, -O-R Ｉ２ group or -O-R Ｉ３ Carbon atoms that do not have groups attached have hydrogen atoms attached.)

2. Ar in the general formula (I) Ｉ１ The propenyl group-containing compound according to claim 1, wherein the compound is represented by the following general formula (II) or (III): 【Chemistry 2】 (In general formula (II), R ＩＩｃ each independently represents an alkyl group, n ＩＩ１ represents an integer of 0 to 5. In addition, * in general formula (II) represents a bond to another atom. 【Chemistry 3】 (In general formula (III), R ＩＩＩｄ each independently represents an alkyl group, n ＩＩＩ１ represents an integer of 0 to 7. In addition, * in general formula (III) represents a bond to another atom.

3. R in the general formula (I) Ｉ２ and R Ｉ３ The propenyl group-containing compound according to claim 1 , wherein is a hydrogen atom.

4. The propenyl group-containing compound according to claim 3, which has a softening point of 50°C or higher and 120°C or lower.

5. 4. The propenyl group-containing compound according to claim 3, wherein the hydroxyl group equivalent is 100 g / equivalent or more and 300 g / equivalent or less.

6. R in the general formula (I) Ｉ２ and R Ｉ３ The propenyl group-containing compound according to claim 1 , wherein is a glycidyl group.

7. The propenyl group-containing compound according to claim 6, which has a softening point of more than 45°C and not more than 120°C.

8. 7. The propenyl group-containing compound according to claim 6, having an epoxy equivalent of 180 g / equivalent or more and 350 g / equivalent or less.

9. A curable resin composition comprising the propenyl group-containing compound according to any one of claims 1 to 8.

10. A curable resin composition comprising the propenyl group-containing compound according to any one of claims 3 to 5, an epoxy resin, and a maleimide resin.

11. A curable resin composition comprising the propenyl group-containing compound according to any one of claims 6 to 8, a phenolic resin, and a maleimide resin.

12. A cured product of the curable resin composition according to claim 9.

13. A prepreg comprising a reinforcing substrate and a semi-cured product of the curable resin composition according to claim 9 impregnated into the reinforcing substrate.

14. A circuit board obtained by laminating the prepreg according to claim 13 and copper foil and subjecting the laminate to thermocompression molding.

15. A build-up film comprising the curable resin composition according to claim 9.

16. A semiconductor encapsulant comprising the curable resin composition according to claim 9.

17. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 16.

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