Alkenyl resin, resin composition, cured product, printed wiring board, semiconductor encapsulating material, and build-up film

Abstract

To provide an alkenyl resin capable of achieving high compatibility between low moisture absorption and high adhesion to a metal serving as a material of a lead frame during a curing process, a resin composition containing the alkenyl resin, a cured product formed by curing the resin composition, and a printed wiring board, a semiconductor encapsulating material, and a build-up film using the cured product.SOLUTION: The present invention provides an alkenyl resin represented by general formula (1).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to an alkenyl resin, a resin composition, a cured product, a printed wiring board, a semiconductor encapsulating material, and a build-up film.

Background Art

[0002] A prepreg obtained by impregnating a glass cloth with a thermosetting resin typified by an epoxy resin or a BT (bismaleimide-triazine) resin and heating and drying, a laminate obtained by thermally curing the prepreg, and a multilayer board obtained by thermally curing a combination of the laminate and the prepreg are widely used as circuit board materials for electronic devices. Among them, a package substrate, which is a type of printed wiring board that plays a role of an interposer for mounting a semiconductor, is becoming thinner, and warping of the package substrate during mounting has become a problem. Therefore, in order to suppress warping of the package substrate during mounting, a material that exhibits high heat resistance is required. Particularly recently, in the fields of various electrical materials such as semiconductor encapsulating materials or printed circuit boards, there are high demands for miniaturization and high integration of electronic devices, and a shift to surface mount packages such as ball grid arrays (BGAs) or chip scale packages (CSPs) or the adoption of copper wires using a metal with high bonding reliability at high temperatures, particularly copper, is progressing. However, copper wires are more likely to be corroded than conventional gold wires. In addition, when interfacial deterioration such as peeling occurs at the interface between the encapsulating resin and the lead frame, moisture concentrates in the peeled portion due to capillary action, corroding the chip or wire bonding joint. Furthermore, since moisture expands rapidly in the reflow process at high temperatures, causing cracks, it is required to reduce the moisture absorption rate of the encapsulating resin and improve the adhesive strength with the lead frame. Particularly in the field of power semiconductors, the adoption of SiC-based devices is spreading because of their high conversion efficiency and the possibility of miniaturization and weight reduction. Since SiC-based devices can operate at high temperatures, next-generation power semiconductor encapsulating materials are required to have high heat resistance that can ensure operational reliability at high temperatures. Conventional semiconductor encapsulation materials have used epoxy resins that are excellent in the balance of various physical properties such as heat resistance and moisture resistance. However, in order to achieve further higher heat resistance, studies are underway on the combined use or replacement of resins with higher heat resistance (Tg), such as maleimide resins, benzoxazine resins, or cyanate resins. For example, Patent Document 1 describes a propenyl group-containing resin and a resin composition having excellent curability that can form a cured product having excellent heat resistance and low water absorption while suppressing the occurrence of voids.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, although the resin composition of Patent Document 1 mentions that the curing rate is fast and the curability is excellent, the mechanism of its curing reaction has not been studied. Further, in the technology of Patent Document 1, the adhesion between the cured product of the propenyl group-containing resin and the metal which is the material of the lead frame has not been evaluated at all. Therefore, the technical problem to be solved by the present disclosure is to provide an alkenyl resin, a resin composition containing the alkenyl resin, and a cured product thereof that can achieve both high low moisture absorption and high adhesion to a metal which is the material of a lead frame at a high level during curing.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above-described problems, the present inventors have found that an alkenyl resin having a chemical structure represented by the general formula (1), a resin composition containing the alkenyl resin, and a cured product thereof exhibit excellent adhesion to a metal and low moisture absorption during curing, and have completed the present invention. In addition, since the alkenyl resin of the present disclosure can also use plant-derived raw materials (biomass raw materials) as reaction raw materials, it has moldability adaptable to conventional manufacturing processes, can reduce the environmental load derived from biomass raw materials, and at the time of curing, it is possible to achieve high-order compatibility of low hygroscopicity and high adhesion to a metal which is a material of a lead frame. An object of the present invention is to provide an alkenyl resin, a resin composition containing the alkenyl resin, and a cured product thereof.

[0006] [1] The following general formula (1):

Chemical formula

[0007] [2] The following general formula (1-1):

Chemical formula

[0008] [3] The alkenyl resin according to [1] or [2], using an epoxy resin and an alkenylphenol compound as reaction raw materials.

[0009] [4] The alkenyl resin according to any one of [1] to [3], wherein M in the general formula (1) 3 represents a group represented by any one of the following formulas (i-1) to (v-1).

Chemical formula

[0010] [5] A resin composition containing the alkenyl resin according to any one of [1] to [4] and a maleimide resin.

[0011] [6] A cured product of the resin composition according to [5].

[0012] [7] A printed wiring board using the resin composition according to [5].

[0013] A semiconductor encapsulating material using the resin composition described in [8][5].

[0014] A build-up film using the resin composition described in [9][5].

Advantages of the Invention

[0015] According to the present disclosure, at the time of curing, it is possible to achieve both low moisture absorption and high adhesion to a metal, which is a material of a lead frame, at a high level. According to the present disclosure, the curing reaction can proceed by a pericyclic reaction with respect to the maleimide group. According to the present disclosure, it is possible to provide a resin composition containing an alkenyl resin that can achieve both low moisture absorption and high adhesion to a metal, which is a material of a lead frame, at a high level at the time of curing, and a cured product thereof. Therefore, the cured product using the alkenyl resin of the present disclosure has excellent adhesion and low moisture absorption, and thus can exhibit heat shock adhesion characteristics, so-called reflow resistance. Such a cured product is particularly useful in printed wiring boards, semiconductor encapsulating materials, build-up films, and the like. According to the present disclosure, since a biomass-derived compound can be used as a reaction raw material, the environmental load can be reduced, and a composition in the coexistence with a compound or resin having a maleimide group can achieve both low moisture absorption and high adhesion to a metal, which is a material of a lead frame, at a high level.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0017] Hereinafter, embodiments of the present invention (referred to as "the present embodiments") will be described in detail. However, the present disclosure is not limited to the following description, and various modifications can be made and implemented within the scope of the gist thereof.

[0018] [Terms] As used herein, the "reaction raw material" refers to a compound used to obtain a target compound through a chemical reaction such as combination or decomposition, and constitutes a part of the chemical structure of the target compound. Substances that play the role of chemical reaction aids, such as solvents and catalysts, are excluded. In particular, in this specification, the "reaction raw material" refers to a precursor for obtaining a target alkenyl resin through a chemical reaction. The "alkyl group" in this specification may be linear, branched, or cyclic. For example, it includes methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or cyclononyl group. The above "alkyl group" includes "cycloalkyl group". Examples of the "cycloalkyl group" include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, or adamantyl group, etc. The "alkylthio group" in this specification includes methylthio group, ethylthio group, propylthio group, butylthio group, octylthio group, or 2-ethylhexylthio group. The "alkenyl group" in this specification includes a vinyl group, 1-propenyl group (hereinafter, also simply referred to as a propenyl group), 2-propenyl group (hereinafter, also simply referred to as an allyl group), isopropenyl group, or 2-methylpropenyl group (methallyl group), etc. The "alkoxy group" in this specification includes, for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, or nonyloxy group, etc. The "aryl group" in this specification includes a phenyl group, 1-naphthyl group, or 2-naphthyl group, etc. The "aryloxy group" in this specification includes a phenoxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, or pyrenyloxy group, etc. The "arylthio group" in this specification includes arylthio groups such as a phenylthio group, naphthylthio group, anthrylthio group, phenanthrylthio group, or pyrenylthio group. The "halogen atom" in this specification includes, for example, a fluorine atom, chlorine atom, bromine atom, or iodine atom, etc. The "structural unit" in this specification refers to the (repeating) unit of the chemical structure formed during a reaction or polymerization. In other words, in the resulting compound formed by a reaction or polymerization, it refers to the partial structure other than the structure of the chemical bond involved in the reaction or polymerization, that is, a so-called residue.

[0019] [Alkenyl resin] The alkenyl resin of this embodiment is represented by the following general formula (1). [Chemical formula] (In the above general formula (1), Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon group, L 11 and L 21each independently represents an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH- in the alkylene group may be replaced by -CH(-OH)-, -O- or -C(=O)-; L 12 and L 22 each independently represents -O- or -S-; M 11 and M 21 each independently represents a substituent R 13 represents a cyclic group which may be substituted by M 3 each independently represents an organic group having 6 to 20 carbon atoms, R 11 , R 12 , R 21 and R 22 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number.) This allows the adhesive to have both low moisture absorption and high adhesion to the metal of the lead frame during curing. As a result, the adhesive exhibits both excellent adhesion and low moisture absorption, and is therefore able to exhibit heat shock resistant adhesive properties, or so-called reflow resistance. Furthermore, in a composition in which the alkenyl resin represented by the general formula (1) and a compound or resin having a maleimide group coexist, a cured product having excellent adhesion and moisture absorption properties can be obtained.

[0020] In the above general formula (1), Ar 1 preferably represents a divalent aromatic hydrocarbon group. This makes it easier to achieve the effects of low dielectric properties, low moisture absorption, high heat resistance, or high flame retardancy. The divalent aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, even more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. If the divalent aromatic hydrocarbon group has 21 or more carbon atoms, the reactivity of the alkenyl group decreases due to steric hindrance, resulting in poor curability. In the above general formula (1), Ar 1The divalent aromatic hydrocarbon group represented as [description] includes divalent groups having an aromatic ring. And as said aromatic ring, a monocyclic aromatic ring, a condensed aromatic ring, or an aromatic ring of a ring assembly is included. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. Examples of the condensed aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples of the aromatic ring of the ring assembly include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. Preferable embodiments of the divalent aromatic hydrocarbon group include groups obtained by removing any two hydrogen atoms from the above aromatic rings, and a phenylene group, a naphthylene group, an anthracenediyl group, a biphenylene group, or a phenanthrylene group is more preferable. These divalent aromatic hydrocarbon groups may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms); an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group; a halogen atom; a hydroxy group, etc.

[0021] In the above general formula (1), Ar 2 preferably represents a trivalent aromatic hydrocarbon group. Thereby, it becomes easy to exhibit effects such as low dielectric characteristics, low hygroscopicity, high heat resistance, or high flame retardancy. The number of carbon atoms of the trivalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 12, and even more preferably 6 to 10. When the number of carbon atoms of the trivalent aromatic hydrocarbon group is 21 or more, the reactivity of the alkenyl group decreases due to steric hindrance, and thus the curability deteriorates. Ar in the above general formula (1)2 The trivalent aromatic hydrocarbon group represented as such includes trivalent groups having an aromatic ring. Preferable embodiments of the trivalent aromatic hydrocarbon group include groups obtained by removing any three hydrogen atoms from an aromatic ring. Also, as the aromatic ring, the same aromatic rings as those of the above-mentioned divalent aromatic hydrocarbon group are adopted. Among these, benzene triyl group, naphthalene triyl group, anthracene triyl group, biphenylene triyl group or phenanthrene triyl group is more preferable. These trivalent aromatic hydrocarbon groups may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms); an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group; a halogen atom; a hydroxy group and the like.

[0022] In the above general formula (1), M 3 represents an organic group having 6 or more and 20 or less carbon atoms, and M 3 preferably has 6 or more and 20 or less carbon atoms and represents a divalent organic group. Also, the n1 M's 3 may be the same as or different from each other. The organic group is a group whose chemical structure is constituted by an organic compound containing at least one carbon atom in the form of an m-valent group, and refers to an atomic group obtained by removing m hydrogen atoms from an organic compound containing at least one carbon atom (where m is, for example, a natural number of 1 or more and 5 or less). Therefore, the divalent organic group refers to an atomic group obtained by removing two hydrogen atoms from an organic compound containing at least one carbon atom. Specifically, the organic group is a group having a hydrocarbon group, preferably a group having a cyclic hydrocarbon group, and more preferably an alicyclic hydrocarbon group or a group having an aromatic ring. Examples of the alicyclic hydrocarbon group include divalent monocyclic alicyclic hydrocarbon groups such as cyclohexanediyl group, cyclooctanediyl group, cyclononanediyl group, cyclodecanediyl group; bicyclo[1.1.0]butanediyl group, tricyclo[2.2.1.0]heptanediyl group, bicyclo[3.2.1]octanediyl group, bicyclo[2.2.2.]octanediyl group, adamantanediyl group, bicyclo[4.3.2]undecanediyl group, tricyclo[5.3.1.1]dodecanediyl group, tricyclo[5.2.1.0 2,6 decandiy group, adamantanediyl group, norbornane group or isobornane group, etc. are preferable. And, as a substituent, the alicyclic hydrocarbon group may be bonded with an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as phenyl group, naphthyl group: a halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; a hydroxy group; etc. On the other hand, when M 3 is a group having an aromatic ring with 6 or more and 20 or less carbon atoms, the aromatic ring is the same as the aromatic ring listed in the divalent aromatic hydrocarbon group which is a preferable form of the above Ar 1 . Therefore, M 3 is preferably a group having an aromatic ring with 6 or more and 20 or less carbon atoms.

[0023] In the general formula (1), when the organic group where M 3 is a group having an alicyclic hydrocarbon group, it is easy to exhibit the effects of low dielectric characteristics and low moisture absorption. Furthermore, when the organic group is a group having an aromatic ring, it is easy to exhibit the effects of high heat resistance and high flame retardancy. The number of carbon atoms of the organic group is preferably 6 to 20, more preferably 6 to 17, still more preferably 7 to 16, even more preferably 8 to 15, and particularly preferably 8 to 14.

[0024] M in the general formula (1) 3As an example, it is preferably a group represented by the following formulas (I) to (III), more preferably a group represented by the formulas (i) to (v), and even more preferably a group represented by the formulas (i-1) to (v-1) from the viewpoint of low dielectric characteristics.

Chemical formula

Chemical formula

Chemical formula

[0025] In the above general formula (1), L 12 and L 22 each independently represents -O- or -S-, and -O- is preferred from the viewpoint of suppressing the corrosion deterioration of the Cu wire. In the general formula (1), L 12 and L 22 are included in the group (so-called residue) derived from the alkenylphenol compound described later.

[0026] In the above general formula (1), L 11 and L 21 each independently represents an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O- or -C(=O)-. In the general formula (1), L 11 and L 21 By having a molecular chain of a predetermined length, the softening point of the resin can be lowered, so that it can be compatible with the maleimide resin under conventional kneading conditions and a uniform composition and cured product can be produced.

[0027] L in the above general formula (1) 11 and L 21 The number of carbon atoms of each can independently be preferably 1 to 9, more preferably 2 to 8, and even more preferably 3 to 6. Also, the molecular chains of L 11 and L 21 in the above general formula (1) are each independently preferably linear or branched. L in the above general formula (1)11 and L 21 is an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms (-[(CH2) n -(CH2O) m p -(CH2) k -), -[(CH2) n -(CH(OH)) m -(CH2) k p - or -[(CH2) n -(CH(OH)) m -(CH2) k p -O-C(=O)-(CH2) l -C(=O)- is preferred. However, the said n is an integer of 0 or more and 8 or less, the said m is an integer of 1 or more and 9 or less, the said k is an integer of 0 or more and 8 or less, the said l is an integer of 2 or more and 4 or less, the said p is an integer of 1 or more and 3 or less, and n + m + k + l = an integer of 1 or more and 10 or less. Thereby, it can be made compatible with the maleimide resin under conventional kneading conditions, and a uniform composition and cured product can be produced. Among them, L in the general formula (1) above 11 and L 21 being -[(CH2) n -(CH(OH)) m -(CH2) k p - means that since it has a 2-hydroxypropylene ether skeleton similar to the cured product of the epoxy resin, an interaction by hydrogen bonding acts between the OH group and the metal surface, and higher adhesiveness is exhibited during curing. In addition, L in the general formula (1) 11 and L 21 are included in the groups (so-called residues) derived from the epoxy resin described later.

[0028] In the above general formula (1), M 11 and M 21 each independently represent a cyclic group which may be substituted by a substituent R 13 , and it is preferably a divalent cyclic group which may be substituted by a substituent R 13 . ​​​​The number of carbon atoms in the cyclic group is preferably 5 to 14, more preferably 6 to 12, still more preferably 6 to 10, and even more preferably 6. The cyclic group refers to an atomic group in which the constituent atoms are cyclically bonded, and includes a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic ring, a ring assembly, a polycyclic structure (for example, a bicyclic structure), an aromatic group, a non-aromatic group, etc., and may be a group combining these. Further, the cyclic group may contain at least one heteroatom, and furthermore, any at least one hydrogen atom in the cyclic group may be substituted by at least one substituent R 13 (for example, an electron-donating group).

[0029] The cyclic group preferably has an aromatic ring (including a heteroaromatic ring) or an alicyclic hydrocarbon, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, an aromatic ring of a ring assembly, or an alicyclic hydrocarbon. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. Examples of the condensed aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples of the aromatic ring of the ring assembly include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. Examples of the alicyclic hydrocarbon include saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane, or unsaturated alicyclic hydrocarbons such as cyclopentene, cyclohexene, adamantene, norbornene, isobornene (2,2,3-trimethylbicyclo[2.2.1]heptene), tricyclodecene, tetracyclododecene, etc. Therefore, M in the above general formula (1) 11 and M21 When each independently has an aromatic ring or an alicyclic hydrocarbon as a divalent cyclic group, a preferred divalent cyclic group can be a group obtained by removing any two hydrogen atoms from each of the above-exemplified aromatic rings or each alicyclic hydrocarbon. When having an aromatic ring or an unsaturated alicyclic hydrocarbon as a cyclic group, a diene structure can be formed, so that the Diels-Alder reaction with a maleimide group easily proceeds, and an effect of excellent curability is exhibited. Also, M in the general formula (1) 11 and M 21 When having an aromatic ring as a divalent cyclic group, one or more hydrogen atoms of the aromatic ring may be substituted by one or more substituents R 13 . The substituent R 13 is preferably an electron-donating group, and the substituent R 13 is preferably, for example, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an amino group, or an imino group having an alkyl group having 1 to 5 carbon atoms.

[0030] The cyclic group is more preferably any one of the following groups (a) to (e), even more preferably any one of the groups (b) to (e), even more preferably the group (b) or (c), and even more preferably a 1,4-phenylene group which may be substituted by one or more substituents R 13 . (a) A 1,4-cyclohexylene group which may be substituted by a substituent R 13 (one -CH2- present in this group or two or more non-adjacent -CH2- may be replaced by -O-, or one or more -CH2-CH2- present in the 1,4-cyclohexylene group may be replaced by an ethenylene group (-CH=CH-).) (b) A 1,4-phenylene group which may be substituted by a substituent R 13 (one -CH= present in this group or two or more non-adjacent -CH= may be replaced by -N=).) (c) A substituent R 13A 1,3-phenylene group which may be substituted by (one -CH= or two or more non - adjacent -CH= present in this group may be replaced by -N=), (d) A substituent R 13 A 1,2-phenylene group which may be substituted by (one -CH= or two or more non - adjacent -CH= present in this group may be replaced by -N=), and (e) A substituent R 13 A naphthalenediyl group which may be substituted by (one -CH= or two or more non - adjacent -CH= present in the naphthalenediyl group may be replaced by -N=). In the groups of the above (a), (b), (c), (d) and (e), the substituent R 13 is preferably an electron - donating group, specifically, one or more selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an amino group and an imino group having an alkyl group having 1 to 5 carbon atoms. When the cyclic group is any of the above (a) - (e) groups, due to the alkenyl group taking a planar conformation, steric hindrance is reduced, and the pericyclic reaction with the bulky maleimide group proceeds easily, showing an effect of more excellent curability. Further, when the cyclic group is any of the above (b) - (e) groups, since an electron - rich diene structure is formed, the Diels - Alder reaction with the maleimide group proceeds easily, showing an effect of more excellent curability. Further, when the cyclic group is the group of the above (b) or (c), since two ortho - positions of the alkenyl group can be reaction points, the Diels - Alder reaction with the maleimide group proceeds easily, showing an effect of more excellent curability.

[0031] In the above general formula (1), the cyclic group which is M 11 and / or M 21 preferably has one or more unsaturated bonds. The alkenyl group (-CHR 11 =CR 12 -CH3 moiety, or -CHR 21 =CR22 It is more preferable that the double bond at the position of -CH3) and the one or more unsaturated bonds in the cyclic group have a diene structure (=conjugated diene), or the cyclic group itself has a diene structure (=conjugated diene). As a result, in addition to the Alder-ene reaction, a faster Diels-Alder reaction tends to proceed, achieving an effect of more excellent curability. Further, the alkenyl resin represented by the general formula (1) has an alkenyl group (-CHR 11 =CR 12 at the position of -CH3, and -CHR 21 =CR 22 at the position of -CH3). Therefore, one or more unsaturated bonds in the cyclic group that is M 11 and / or M 21 and the double bond in the position of -CHR 11 =CR 12 at the position of -CH3, and / or -CHR 21 =CR 22 at the position of -CH3 are likely to form a so-called 1,3-butadiene skeleton in their relative positional relationship. In the general formula (1), the divalent cyclic group preferably has a ring structure having a diene structure, and preferably has a diene structure fixed in the s-cis conformation. As a result, the cyclic group can be a substrate for the Diels-Alder reaction with a maleimide group that is a dienophile (so-called dieneophile).

[0032] In the general formula (1), preferable M 11 and / or M 21 is a divalent cyclic group having one or more unsaturated bonds, which may be substituted by the substituent R 13 , and -CHR 11 =CR 12 at the position of -CH3 in the general formula (1), and / or -CHR 21 =CR 22The carbon-carbon double bond at the -CH3 site and the one or more unsaturated bonds in the divalent cyclic group have a diene structure (=conjugated diene), or the divalent cyclic group itself has a diene structure (=conjugated diene). Further, it is more preferable that the diene structure (=conjugated diene) is a diene structure fixed in the s-cis conformation, and the substituent R 13 is even more preferably an electron-donating group. M in the general formula (1) 21 The carbon-carbon double bond at the -CHR 21 =CR 22 -CH3 site and the one or more unsaturated bonds in the divalent cyclic group which is M 21 satisfy the relationship of a diene structure (=conjugated diene), so that the Diels-Alder reaction by heat between the maleimide group and the diene structure can proceed, and the curability is improved. Similarly, M in the general formula (1) 11 The carbon-carbon double bond at the -CHR 11 =CR 12 -CH3 site and the one or more unsaturated bonds in the divalent cyclic group which is M 11 satisfy the relationship of a diene structure (=conjugated diene), so that the Diels-Alder reaction by heat between the maleimide group and the diene structure can proceed, and the curability is improved. Furthermore, by satisfying the relationship of the s-cis conformation for these diene structures (=conjugated dienes), it becomes easier to be a substrate for the Diels-Alder reaction with respect to the maleimide group. As defined in the Woodward-Hoffmann rules, in the cyclic addition of two molecules, in the thermal reaction, the reaction is regulated by the HOMO of the diene (the diene structure in the general formula (1), for example, the cyclic group and the propenyl group) and the LUMO of the dienophile (maleimide group), and in the photochemical reaction, the reaction is regulated by both LUMOs. Therefore, an electron-rich diene having a strong electron-donating group has a smaller energy difference between the HOMO of the diene and the LUMO of the maleimide group, so that the reaction proceeds more easily at a lower temperature. In other words, if the substituent R 13 is an electron-donating group, the substituent R 13Since the HOMO of the conjugated diene increases, the Diels-Alder reactivity with the maleimide group can be enhanced. As a result, the reaction proceeds more easily at low temperatures, and thus the curability is considered to be improved. For example, in an alkenyl resin having a 1-propenylbenzene (β-methylstyrene) skeleton shown in an example (e.g., Example 1) which is an example of the present embodiment, an electron-donating substituent R 13 is introduced as a methoxy group into the aromatic ring, and it was confirmed that the Diels-Alder reactivity with the maleimide group can be enhanced. Further, since two alkoxy groups are substituted in the alkenyl resin described in the examples, it has been found that the reactivity with the maleimide group is higher compared to unsubstituted or monosubstituted 1-propenylbenzene. In the above general formula (1), M 11 and M 21 As specific examples of, a phenylene group having an alkoxy group as an electron-donating substituent R 13 is preferable. In addition, M in the general formula (1) 11 and M 21 are included in the groups (so-called residues) derived from the alkenylphenol compounds described later.

[0033] In the above general formula (1), the substituent R 13 is preferably an electron-donating group, and specifically, it is preferably one or more selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an amino group, and an imino group having an alkyl group having 1 to 5 carbon atoms. From the viewpoint of increasing the HOMO of the cyclic group to which the substituent R 13 is bonded, the substituent R 13 is more preferably a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0034] In the above general formula (1), R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R11 and R 12 is more preferably, each independently, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. R 11 and R 12 being a hydrogen atom facilitates the pericyclic reaction with a double bond such as a maleimide group. Similarly, in the general formula (1), R 21 and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 21 and R 22 is more preferably, each independently, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. R 21 and R 22 being a hydrogen atom facilitates the pericyclic reaction with a double bond such as a maleimide group. Incidentally, R 11 , R 12 , R 21 and R 22 are included in the group (so-called residue) derived from the alkenylphenol compound described later. In the general formula (1), n1 represents a natural number of 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

[0035] The alkenyl resin of this embodiment is more preferably represented by the following general formula (1-1).

Chemical formula

[0036] The alkenyl resin of this embodiment is preferably one or more compounds selected from the group consisting of the following general formulas (1.1) to (1.3). [Chemical formula] [Chemical formula] (In the above general formulas (1.1) to (1.3), M 3 represents a group selected from the group consisting of the above formulas (i) to (v), and R 13 each independently represents an electron-donating group, and R 14 represents an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms); an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group, na represents an integer of 0 or more and 4 or less, and nb represents an integer of 0 or more and 3 or less.) Since the above general formulas (1.1) to (1.3) all have a diene structure formed by a terminal propenyl group and an unsaturated bond in the cyclic group in the molecule, the Diels-Alder reaction with a maleimide group can proceed. In addition, since the HOMO of the diene to which the substituent R 13 which is an electron-donating group, is increased, the Diels-Alder reactivity with a maleimide group can be enhanced.

[0037] (Physical properties of the alkenyl resin) <Double bond equivalent of the alkenyl resin> The double bond equivalent (g / mol) of the alkenyl resin of this embodiment is preferably 100 g / mol or more and 1000 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less, and even more preferably 300 g / mol or more and 600 g / mol or less. The "double bond equivalent (g / mol)" in this specification is an amount that serves as an index for the amount of double bonds contained in a molecule. For compounds with the same molecular weight, the smaller the numerical value of the double bond equivalent, the greater the tendency for the introduced amount of double bonds to be larger. The "double bond equivalent (g / mol)" is a calculated value obtained from the methods described in the following methods and examples sections. The preferable range of the above double bond equivalent (g / mol) can be appropriately recombined with each of the above upper limits and lower limits. - Method for calculating the double bond equivalent of an alkenyl resin - The double bond equivalent, which is the content of carbon-carbon double bonds in the alkenyl resin of this embodiment, is calculated using the iodine value method in accordance with JIS K0070:1992.

[0038] <Molecular weight of alkenyl resin> The number average molecular weight (Mn) of the alkenyl resin of this embodiment is preferably in the range of 600 to 3000, more preferably in the range of 800 to 2500, and even more preferably in the range of 1000 to 2000. Also, the weight average molecular weight (Mw) of the alkenyl resin is preferably in the range of 600 to 5000, more preferably in the range of 800 to 4000, and even more preferably in the range of 1000 to 3000. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkenyl resin of this embodiment is preferably in the range of 1.0 to 2.0, more preferably 1.0 to 1.3. Note that the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkenyl resin of this embodiment were measured under the measurement conditions described in the examples below using gel permeation chromatography (hereinafter abbreviated as "GPC").

[0039] (Another preferable aspect of the alkenyl resin) An example of a preferable aspect of the alkenyl resin of this embodiment is preferably using an epoxy resin and an alkenylphenol compound as reaction raw materials. Furthermore, as the alkenylphenol compound, it is more preferable to use eugenol or isoeugenol as a reaction raw material. Generally, eugenol is a component contained in spices such as cloves and laurel, and is a biomass compound derived from natural products classified as so-called monophenol propanoids. Therefore, by using eugenol or isoeugenol obtained by the isomerization reaction of eugenol as a reaction raw material, the environmental load can be reduced.

[0040] <Epoxy resin> The epoxy resin of the present embodiment is not particularly limited as long as it is an epoxy resin having a partial structure represented by the following general formula (2). The epoxy resin having a partial structure represented by the general formula (2) is simply referred to as epoxy resin (A). [Chemical formula] (In the above general formula (2), Ar 2 represents a trivalent aromatic hydrocarbon group similar to Ar in the above general formula (1), 2 M represents an organic group having 6 to 20 carbon atoms independently of each other, 3 and n represents an integer of 1 or more and 10 or less.)

[0041] Specific examples of the epoxy resin (A) include those obtained by condensation of epichlorohydrin and polyhydric phenols such as bisphenols, and glycidyl ether type epoxy resins of polyhydric phenols such as phenylaralkyl type, biphenylaralkyl type, cycloalkylene type, alkylene type, cycloalkylidene type, benzylidene type, and fluorenylidene type can be exemplified. In addition, although epoxy resins modified by various methods can be mentioned, it is not limited to these. ​The epoxy resin (A) is not particularly limited, but for example, it is preferably a curable resin that contains two or more glycidyl groups in the molecule and can be cured by forming a crosslinked network with the glycidyl groups.

[0042] The epoxy resin (A) of the present embodiment is preferably a resin having two or more glycidyl groups in the molecule. For example, aralkyl type epoxy resins such as phenol phenylaralkyl type epoxy resin, cresol phenylaralkyl type epoxy resin, naphthol phenylaralkyl type epoxy resin, and phenol biphenylaralkyl type epoxy resin; cycloalkylene type epoxy resins such as dicyclopentadiene phenol type epoxy resin; alkylene type epoxy resins such as 1,3-dimethylbutylene bisphenol type epoxy resin; cycloalkylidene type epoxy resins such as cyclohexylidene bisphenol type epoxy resin, 3,3,5-trimethylcyclohexylidene bisphenol type epoxy resin, and cyclododecylidene bisphenol type epoxy resin; benzylidene type epoxy resins such as benzylidene bisphenol type epoxy resin and α-methylbenzylidene bisphenol type epoxy resin; fluorenylidene type epoxy resins such as 9-fluorenylidene bisphenol type epoxy resin; may be mentioned. Among these epoxy resins (A), aralkyl type epoxy resins, cycloalkylene type epoxy resins, and cycloalkylidene type epoxy resins are more preferable from the viewpoints of hygroscopicity and heat resistance. In addition, the above-mentioned epoxy resin (A) may be used alone or in combination of two or more.

[0043] In this embodiment, the epoxy equivalent of the epoxy resin (A) is preferably 180 g / mol or more, more preferably 220 g / mol or more and 400 g / mol or less. When the epoxy equivalent of the polyfunctional epoxy resin (A) is 180 g / mol or more, the resulting cured product is preferably excellent in adhesion and low moisture absorption. On the other hand, when the epoxy equivalent of the epoxy resin (A) is 400 g / mol or less, the resulting cured product is preferably excellent in heat resistance.

[0044] The functional group equivalent ratio (hydroxyl group or mercapto group of the alkenylphenol compound / glycidyl group of the epoxy resin (A)) of the amount of the alkenylphenol compound used with respect to the amount of the epoxy resin (A) used is preferably 0.5 to 1.5, more preferably 0.8 to 1.3. When the functional group equivalent ratio is 0.5 or more, the resulting alkenyl resin is preferably excellent in lower viscosity and curability.

[0045] The number average molecular weight (Mn) of the epoxy resin (A) is preferably 300 to 3000, more preferably 350 to 2000. When the number average molecular weight of the epoxy resin (A) is 300 or more, the resulting cured product is preferably a cured product showing more excellent mechanical strength. On the other hand, when the weight average molecular weight of the epoxy resin (A) is 3000 or less, the resulting alkenyl resin is preferably low in viscosity. In this specification, the value of the "number average molecular weight" shall be the value measured by the following method. That is, the value obtained by measuring gel permeation chromatography (GPC) under the following conditions is adopted.

[0046] Measurement conditions of GPC "Measuring device" "HLC-8320 GPC" manufactured by Tosoh Corporation "Measurement conditions" Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: “GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation Column temperature: 40°C Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual of the “GPC-8320 GPC”. Polystyrene used “A-500” manufactured by Tosoh Corporation “A-1000” manufactured by Tosoh Corporation “A-2500” manufactured by Tosoh Corporation “A-5000” manufactured by Tosoh Corporation “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 “F-128” manufactured by Tosoh Corporation Sample: A 1.0 mass% tetrahydrofuran solution converted to resin solids, filtered through a microfilter (50 μl).

[0047] <Alkenylphenol compound> The alkenylphenol compound of the present embodiment is a general term for a compound having an optionally substituted alkenyl group (e.g., allyl group or propenyl group), a hydroxyl group or a mercapto group, and a cyclic group to which the alkenyl group (e.g., allyl group or propenyl group) and the hydroxyl group or the mercapto group are bonded and which has an unsaturated bond, and there is no particular limitation as long as it is an alkenylphenol compound represented by the following general formula (3A) or (3B). Hereinafter, the alkenylphenol compound represented by the following general formula (3A) or (3B) is simply referred to as alkenylphenol compound (B). As the alkenylphenol compound (B) of the present embodiment, it is more preferably represented by the general formula (3A-1) or (3B-1), and examples thereof include 2-allylphenol, 4-allylphenol, 2-(2-propenyl)phenol, 4-(2-propenyl)phenol, 2-methallylphenol, eugenol, isoeugenol, hydroxycavicol, and propenylguaethol. Among these alkenylphenol compounds (B), eugenol and isoeugenol are more preferable, and isoeugenol is even more preferable.

Chemical formula

Chemical formula

[0048] In the above general formulas (3A) and (3B), M 2’ corresponds to M in the above general formula (1). 21 In the above general formulas (3A), (3B), (3A-1) and (3B-1), R 11 and R 12 are the same as R, R, R, and R in the above general formula (1), 11 R, 12 R, 21 and R 22 and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom is preferable from the viewpoint of curability. In the above general formulas (3A), (3B), (3A-1) and (3B-1), Z 1 represents a hydroxyl group or a mercapto group, and is preferably a hydroxyl group from the viewpoint of suppressing corrosion deterioration of the Cu wire.

[0049] When the alkenylphenol compound (B) of the present embodiment is eugenol, that is, in the above general formula (3A-1), R 11 and R 12 are hydrogen atoms, R 13 is a methoxy group substituted at the 2-position, Z 1 is a hydroxyl group at the 1-position, and n3 is 1, plant-derived eugenol can be incorporated into the chemical structure of the target alkenyl resin, so that a compound with reduced environmental load can be provided. When the alkenylphenol compound (B) of the present embodiment is isoeugenol, that is, in the above general formula (3B-1), R 11 and R 12 are hydrogen atoms, R 13 is a methoxy group substituted at the 2-position, Z 1 is a hydroxyl group at the 1-position, and n3 is 1, plant-derived isoeugenol can be incorporated into the chemical structure of the target alkenyl resin, so that a compound with reduced environmental load can be provided.

[0050] (Method for producing alkenyl resin) Hereinafter, the method for producing the alkenyl resin of the present disclosure will be described. The production method of the alkenyl resin of the present embodiment is not particularly limited as long as it can produce the compound represented by the general formula (1).

[0051] Hereinafter, for convenience of explanation, as an example of the method for producing the alkenyl resin of the present disclosure, the case where an epoxy resin (A), which is an example of an aromatic hydrocarbon-containing compound having a reactive functional group, and an alkenylphenol compound (B) are used as reaction raw materials will be described as an example. As an example of the method for producing the alkenyl resin of the present disclosure, for example, a production method including the following step (1) and step (2) provided as necessary can be mentioned. Step (1): A step of reacting an epoxy resin (A) and an alkenylphenol compound (B) as reaction raw materials; Step (2): A step of purifying the reaction product from a mixture containing the reaction product of the epoxy resin (A) and the alkenylphenol compound (B). Specifically, the method for producing the alkenyl resin of the present embodiment includes a step (1-1) of reacting an epoxy resin (A) and an alkenylphenol compound (B) in the presence of a basic compound, and a step of purifying the reaction product using an aqueous solvent and an organic solvent in the reaction product generated in the step (1-1) (2-1) preferably has. Hereinafter, each step of the method for producing the alkenyl resin of the present disclosure will be described in order.

[0052] <Step (1)> The blending ratio of the epoxy resin (A) and the alkenylphenol compound (B) is appropriately selected in consideration of the moldability and curability physical property balance of the resulting alkenyl resin, the raw materials used, and the like. For example, when using an epoxy resin (A) as the aromatic hydrocarbon-containing compound having a reactive functional group and an alkenylphenol compound (B) as the alkenyl group-containing compound, the molar ratio of the hydroxyl group or mercapto group of the alkenylphenol compound (B) to 1 mol of the glycidyl group of the epoxy resin (A) is preferably 0.1 to 2.0 mol, more preferably 0.5 to 1.5 mol, and still more preferably 0.8 to 1.3 mol. Also, as a specific method for carrying out the above reaction, all raw materials may be charged at once and reacted at a predetermined temperature as it is, or an alkenylphenol compound (B) and a basic compound may be charged, and while maintaining the temperature at a predetermined level, the epoxy resin (A) is added dropwise and reacted. In this case, the dropping time is usually 0.5 to 24 hours, preferably 0.5 to 4 hours.

[0053] As the basic compound used in step (1) of this embodiment, an inorganic basic compound, an organic basic compound, etc. can be used. Examples of the inorganic basic compound include hydroxides of alkali metals such as potassium and sodium; carbonates of alkali metals such as potassium and sodium; hydroxides of alkaline earth metals such as calcium and barium; carbonates of calcium and barium, etc. On the other hand, examples of the organic basic compound include phosphines such as triphenylphosphine. From the viewpoint of ease of purification by washing with water, the basic compound of this embodiment is preferably an alkali metal hydroxide (for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, etc.), and more preferably potassium hydroxide and sodium hydroxide. It is preferable to use the basic compound in an amount in the range of 0.01 to 10 parts by mass, and more preferably in the range of 1 to 5% by mass, based on 100 parts by mass in total of the epoxy resin (A) and the alkenylphenol compound (B).

[0054] In step (1) of this embodiment, a phase transfer catalyst may be used. Specific examples of usable phase transfer catalysts include quaternary ammonium salts, quaternary phosphonium salts, or crown ethers. Quaternary ammonium salts and quaternary phosphonium salts are preferred from the viewpoint of particularly excellent catalytic activity, and specific examples include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and the like. When used, these basic catalysts may be used in the form of an aqueous solution of about 10% to 55% by mass, or may be used in a solid form. The blending amount of the phase transfer catalyst is in the range of 0.01 to 1.00 parts by mass with respect to 100 parts by mass of the total amount of the raw materials to be charged (= for example, the total amount of reaction raw materials such as epoxy resin (A) and alkenylphenol compound (B)). From the viewpoints of handleability and economy, 0.05 to 0.20 parts by mass is preferred. In step (1) of this embodiment, an organic solvent may be used. Examples of the organic solvent include ketones such as methyl isobutyl ketone, acetone, methyl ethyl ketone (MEK), cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; aromatic solvents such as benzene, toluene, and xylene. These may be used alone or in combination.

[0055] In step (1) of this embodiment, the reaction temperature between the epoxy resin (A) and the alkenylphenol compound (B) may usually be in the range of 50 to 170°C. However, in order to avoid side reactions such as the formation of multimers or the hydrolysis of the glycidyl group, 100 to 140°C is preferred. In step (1) of the present embodiment, the reaction time between the epoxy resin (A) and the alkenylphenol compound (B) is such that if the time is short, the reaction does not proceed completely, and if the time is long, side reactions such as the thermal decomposition reaction of the product occur. Therefore, under the reaction temperature conditions, usually, it is in the range of about 0.5 to 24 hours, preferably in the range of about 1 to 6 hours. Therefore, in step (1) of the present embodiment, it is more preferable to carry out the reaction with stirring in the range of 100 to 140 °C and in the range of 1 to 6 hours. Also, the atmosphere in step (1) is preferably a reaction carried out under an inert gas atmosphere such as nitrogen, helium, or argon.

[0056] <Step (2)> Step (2) in the present embodiment is an optional step and is a step of recovering the reaction product (= the target alkenyl resin) obtained in the above step (1). To a solution containing the reaction product (= the target alkenyl resin) and the organic solvent obtained in step (1), a known acidic aqueous solvent is added, and after removing the salt of the basic compound and impurities by neutralization, washing with water, etc. using the acidic aqueous solvent, a dehydration operation by azeotropy is performed, and after precision filtration, the solvent and the unreacted compound are distilled off under reduced pressure conditions to obtain the target alkenyl resin. Also, a dehydrating agent may be used during the reaction if necessary.

[0057] Examples of the dehydrating agent used in step (2) of the present embodiment include inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves.

[0058] After step (1) or (2) of the present embodiment, if necessary, a step (3) of synthesizing an alkenyl resin represented by the general formula (1) by isomerizing the reaction product obtained by reacting the epoxy resin (A) with an alkenylphenol compound (B) having an allyl group (the compound represented by the above general formula (3A)) so that the allyl group is isomerized to a propenyl group may be provided. As a method for isomerizing the allyl group into a propenyl group, known methods can be adopted. For example, an isomerization reaction of a carbon-carbon bond using a palladium acetate catalyst or the like (see [J. Am. Chem. Soc., 91, p6707 - 6714 (1969)]), or an isomerization reaction of a carbon-carbon bond using an alkali metal hydroxide or the like (potassium hydroxide) as a base catalyst (see [J. Am. Chem. Soc., 78, p1709 - 1715 (1956)]) can be mentioned.

[0059] [Resin composition] The alkenyl resin of the present disclosure can be used for preparing a resin composition. That is, the resin composition of the present disclosure preferably contains the above-mentioned alkenyl resin and a maleimide resin. Since the alkenyl resin of the present embodiment is excellent in solvent solubility, fluidity during heat melting, and handleability, and can further contribute to dimensional stability, low moisture absorption, brittleness resistance, heat resistance, and low dielectric constant and low dielectric tangent, the cured product obtained from the resin composition containing the alkenyl resin is excellent in moldability (especially curing time and appearance), heat resistance, and dielectric properties.

[0060] (Maleimide resin) The maleimide resin of this embodiment is not particularly limited as long as it has a maleimide group. Examples of the maleimide resin include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane. Other maleimide resins include the maleimide described in International Publication No. 2020 / 217679, the maleimide resin described in Japanese Patent No. 7140307, the maleimide resin (A) described in JP-A-2023-146886, the acid-modified maleimide resin (A) described in International Publication No. 2020 / 166212, the first maleimide compound (A1) and / or the second maleimide compound (A2) described in JP-A-2023-152757, the polymaleimide compound (A) described in JP-A-2023-152755, and the like. In the resin composition of this embodiment, the content of the maleimide resin is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, still more preferably 20 to 70% by mass, and particularly preferably 25 to 65% by mass with respect to the total amount (100% by mass) of the resin composition. When the content of the maleimide resin is within the above range, excellent moldability, heat resistance, and mechanical strength effects are achieved. Each upper limit and each lower limit of the content of the maleimide resin can be appropriately changed.

[0061] (Optional additive component) The resin composition of the present disclosure may contain optional additive components, in addition to the alkenyl resin or maleimide resin, if necessary. Examples of such optional additive components include various compounding agents such as curing agents, curing accelerators, silane coupling agents, mold release agents, pigments, emulsifiers, non-halogen flame retardants, inorganic fillers, flame retardants (e.g., inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants), solvents, and resin components. The resin composition of the present disclosure may contain a curing agent, in addition to the alkenyl resin or maleimide resin, and further, various compounding agents such as a curing accelerator, a silane coupling agent, a mold release agent, a pigment, an emulsifier, a non-halogen flame retardant, an inorganic filler, a flame retardant (e.g., inorganic phosphorus-based flame retardant, organic phosphorus-based flame retardant, halogen-based flame retardant), and a solvent can be added as needed. Also, within a range that does not impair the object of the present disclosure, known resin components may be contained in addition to the alkenyl resin and the maleimide resin. Examples of such known resin components include epoxy resins, phenolic resins, active ester resins, cyanate resins, polyphenylene ether resins, benzoxazine resins, styrene maleic anhydride copolymers, polybutadiene and its modified products, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluororesins, polystyrene, polyethylene, polyimide resins, silicone gels, silicone oils, etc., which can be appropriately blended.

[0062] [Cured product] The cured product of the present disclosure is preferably obtained from the resin composition. The cured product can be obtained by subjecting the resin composition to a curing reaction. The resin composition can be obtained by uniformly mixing the above-described respective components (e.g., curing agent, compounding agent), and can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, castings, adhesive layers, coating films, and films.

[0063] [Semiconductor encapsulation material] The present disclosure relates to a semiconductor encapsulating material containing the resin composition or cured product of the present embodiment. The semiconductor encapsulating material obtained by using the resin composition of the present embodiment has improved curability, heat resistance, or appearance by using the alkenyl resin of the present disclosure, and thus is excellent in processability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0064] The resin composition of the present embodiment used in the semiconductor encapsulating material can contain an inorganic filler. The filling rate of the inorganic filler can be, for example, in the range of 0.5 to 1200 parts by mass of the inorganic filler with respect to 100 parts by mass of the total amount of the alkenyl resin and maleimide resin of the present embodiment. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, nobel clay, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and the like.

[0065] As a method for obtaining the semiconductor encapsulating material, a method of sufficiently melt-mixing the resin composition of the present embodiment with an additive, which is an optional component, as needed using an extruder, kneader, roll, etc. until it becomes uniform can be mentioned.

[0066] [Semiconductor device] The present disclosure relates to a semiconductor device including a cured product of the semiconductor encapsulating material. The semiconductor device obtained by using the semiconductor encapsulating material obtained by using the resin composition of the present embodiment has low viscosity and excellent fluidity because it uses the alkenyl resin of the present disclosure. Furthermore, since its hygroscopicity, elastic modulus at high temperature, or adhesiveness to a metal material is improved, it is excellent in processability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0067] As a method for obtaining the semiconductor device, a method of casting the semiconductor encapsulating material or molding it using a transfer molding machine, injection molding machine, etc., and then heat-curing it in a temperature range of room temperature (20°C) to 250°C can be mentioned.

[0068] [Prepreg] The present disclosure relates to a prepreg having a reinforcing base material and a semi-cured product of the resin composition of the present embodiment impregnated in the reinforcing base material. As a method for obtaining a prepreg from the above resin composition, an organic solvent described later is blended to varnish the resin composition, and then the impregnated resin composition is impregnated into a reinforcing base material (such as paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass rovings cloth, etc.). Thereafter, by heating at a heating temperature corresponding to the type of solvent used, preferably at 50 to 170°C, the resin composition is semi-cured (or uncured) to obtain a prepreg. The mass ratio of the resin composition to the reinforcing base material used at this time is not particularly limited, but usually, it is preferably prepared so that the resin content in the prepreg is 20 to 60% by mass. In the present embodiment, the semi-cured product of the 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 can have a degree of curing of, for example, 85% or less and 5% or more. On the other hand, the cured product in the present embodiment can have a higher degree of curing than the semi-cured product. Note that the degree of curing of the semi-cured product can be calculated from the following formula by measuring the heat of curing during heating of the resin composition and the heat of curing of the semi-cured product using DSC. Degree of curing (%) = [1 - (Heat of curing of semi-cured product / Heat of curing of curable composition)] × 100

[0069] Examples of the organic solvent used for the production of the prepreg include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The selection and appropriate usage amount thereof can be appropriately selected according to the application. For example, when further manufacturing a printed circuit board from the prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it is also preferable to use it at a ratio such that the non-volatile content is 40 to 80% by mass.

[0070] [Circuit Board] The present disclosure relates to a circuit board which is a laminate of the prepreg and a copper foil. As a method for obtaining a printed circuit board from the resin composition of the present embodiment, the above prepreg is laminated by a conventional method, a copper foil is appropriately stacked, and heat pressure bonding is performed at 170 to 300 °C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[0071] [Build-up film] The present disclosure relates to a build-up film containing the resin composition of the present embodiment. As a method for manufacturing the build-up film of the present embodiment, a method of applying the above resin composition on a support film to form a resin composition layer to obtain an adhesive film for a multilayer printed wiring board can be mentioned.

[0072] When manufacturing a build-up film from a resin composition, the film softens under the temperature conditions of lamination in the vacuum lamination method (usually 70 to 140 °C), and at the same time as laminating the circuit board, it is important that the resin has fluidity (resin flow) that can fill vias or through-holes existing in the circuit board. It is preferable to blend the above components so as to exhibit such characteristics.

[0073] Here, the diameter of the through-hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable to enable resin filling within this range. When laminating both sides of the circuit board, it is desirable that the through-hole be filled about half.

[0074] Specifically, the method for manufacturing the above adhesive film can be carried out by preparing the resin composition in a varnish form, then applying this varnish composition on the surface of the support film (Y), and further drying the organic solvent by heating or hot air blowing to form a composition layer (X) made of the resin composition.

[0075] The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.

[0076] In addition, the composition layer (X) in this embodiment may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the adhesion of dust and the like and scratches on the surface of the resin composition layer.

[0077] Examples of the above-mentioned 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"), polyethylene naphthalate, polycarbonate, polyimide, and further release paper, metal foils such as copper foil and aluminum foil. Note that the support film and the protective film may be subjected to a matting treatment, a corona treatment, or a release treatment.

[0078] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0079] The above-mentioned support film (Y) is peeled off after being laminated on 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, it is possible to prevent the adhesion of dust and the like in the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment.

[0080] [Heat-resistant Materials and Electronic Materials] Since the cured product obtained from the resin composition containing the alkenyl resin of the present disclosure exhibits excellent curability and is excellent in appearance and heat resistance, it can be suitably used for heat-resistant members or electronic members. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, resist materials, etc. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg having high heat resistance or excellent appearance. Further, since the alkenyl resin contained in the resin composition exhibits excellent solubility in various solvents, it can be made into a paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, and examples thereof include industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

Examples

[0081] The present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The physical properties of the synthesized alkenyl resin were measured as follows and are shown in Table 1.

[0082] (1) Double bond equivalent (%) The double bond equivalent, which is the content of carbon-carbon double bonds in the alkenyl resin obtained in each Example and each Comparative Example, was calculated using the iodine value method in accordance with JIS K0070:1992.

[0083] (2) GPC measurement The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the alkenyl resin obtained in each Example and each Comparative Example were measured using the following measuring apparatus and measuring conditions. "Measuring apparatus" "HLC-8320 GPC" manufactured by Tosoh Corporation "Measuring conditions" Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Column temperature: 40 °C Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation". (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "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 "F-128" manufactured by Tosoh Corporation Sample: A 1.0 mass% tetrahydrofuran solution of the alkenyl resin obtained in each example, filtered through a microfilter (50 μl), in terms of resin solid content.

[0084] (3) FD-MS measurement The FD-MS spectra of the alkenyl resins obtained in each example were measured using the following measuring apparatus and measurement conditions. "Measuring apparatus" JMS-T100GC AccuTOF "Measurement Conditions" Measurement range: m / z = 4.00 - 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0085] For the alkenyl resins obtained in each example 1 1H-NMR spectrum and 13 13C-NMR spectrum were measured using the following measuring apparatus and measurement conditions. "Measuring Apparatus" "JNM-ECA500" manufactured by JEOL RESONANCE "Measurement Conditions" < 1 1H-NMR spectrum Resonance frequency: 500 MHz Number of integrations: 16 times Solvent: chloroform-d Sample concentration: 4 mass% < 13 13C-NMR spectrum Resonance frequency: 125 MHz Number of integrations: 2000 times Solvent: chloroform-d Sample concentration: 30 mass%

[0086] (5) Evaluation of Adhesion The adhesion evaluation method for each example and each comparative example uses the die shear test. Specifically, it is as follows. Using a transfer molding machine (manufactured by Kotaki Seiki Co., Ltd., KTS-15-1.5C), with a mold temperature of 150 °C, a molding pressure of 9.8 MPa, and a curing time of 600 seconds, a copper foil ("EFTEC-64T" manufactured by Furukawa Electric Co., Ltd.) was sandwiched between the molds, and the resin compositions of Examples 7 - 8 and Comparative Examples 4 - 6 prepared with the compositions in Table 1 were each injection molded to produce Test Piece 1 with a length of 6 mm, a width of 6 mm, and a thickness of 2 mm on the copper foil. Thereafter, the test piece 1 was post-cured at 175°C for 5 hours. The adhesion was measured at a measurement temperature of 40°C using a bonding tester ("PTR-1102" manufactured by RHESCA). The height from the base material was 0.1 mm, the shear rate was 0.1 mm / second, and N = 5 was used for one test. The average value (gf) of the peel strength from the copper foil was calculated. The relative strength of each resin composition was calculated with the molded product of Comparative Example 1 taken as 100.

[0087] (6) Evaluation of glass transition temperature and moisture absorption (6-1) <Preparation of evaluation samples> The resin compositions of each example and each comparative example prepared according to the compositions shown in Table 1 were poured into a mold of 11 cm × 9 cm × 2.4 mm, molded at a temperature of 175°C for 10 minutes with a press, then the molded product was taken out of the mold, and then post-cured at a temperature of 175°C for 5 hours to obtain evaluation samples.

[0088] (6-2) Measurement of glass transition temperature A test piece 2 with a thickness of 2.4 mm of the cured product prepared in the column of (6-1) <Preparation of evaluation samples> above was cut out to be 5 mm in width and 54 mm in length, and the temperature at which the change in elastic modulus was maximum (the change rate of tanδ was the largest) was measured as the glass transition temperature using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric Scientific, rectangular tension method: frequency 1 Hz, heating rate 3°C / min).

[0089] (6-3) Evaluation of moisture absorption A test piece 3 with a thickness of 2.4 mm of the cured product prepared in the column of (6-1) <Preparation of evaluation samples> above was cut out to be 75 mm × 25 mm, left in an environment of temperature / humidity: 85°C / 85%RH for 300 hours, and then the moisture absorption rate (%) was calculated by the following formula to evaluate the moisture absorption. Moisture absorption rate (%) = {(weight of test piece 3 after the test) - (weight of test piece 3 before the test)} ÷ (weight of test piece 3 before the test) × 100

[0090] (7) Measurement of softening point The softening points of the resins obtained in each example and each comparative example were measured in accordance with JIS K7234.

[0091] (8) Measurement of epoxy equivalent The epoxy equivalent of the present disclosure was measured in accordance with JIS K 7236.

[0092] (Example 1) Into a flask equipped with a thermometer, a fractionating column, and a stirrer, 300 g (1.83 mol) of isoeugenol, 15 g (0.18 mol) of 49% sodium hydroxide, 410 g of HP-7200L (dicyclopentadiene-type epoxy resin (manufactured by DIC Corporation), epoxy equivalent: 249 g / mol, Mn = 430, Mw = 566, Mw / Mn = 1.315, number of moles of glycidyl group: 1.65 mol, see the following formula (S1)) as an epoxy resin, 0.50 g of tetrabutylammonium bromide, and 600 g of methyl isobutyl ketone were charged. While purging with nitrogen gas, the temperature inside the system was raised to 120 °C and stirring was continued for 3 hours. [Chemical formula] After completion of the reaction, the temperature inside the system was lowered to 80 °C, 300 g of a 12% aqueous sodium phosphate monobasic solution was added, stirred and mixed for 15 minutes, allowed to stand for liquid separation, and the aqueous layer was removed. Further, water was added to the methyl isobutyl ketone layer in which the reactants were dissolved, stirred and mixed for 15 minutes, allowed to stand for liquid separation, and the aqueous layer was removed. A dehydration operation by azeotropy was performed, and after precision filtration, the solvent and excess isoeugenol were distilled off under reduced pressure to obtain an alkenyl resin (1) represented by the following chemical formula (1-1.1). The softening point of the alkenyl resin (1) was 83 °C. The double bond equivalent of the alkenyl resin (1) was 385 g / mol. The Mn of the alkenyl resin (1) was 1113, the Mw was 1331, and the Mw / Mn was 1.196. Chemical formula (1-1.1): [Chemical formula] The FD-MS spectrum of the obtained alkenyl resin (1) is shown in Fig. 1A, the GPC chart is shown in Fig. 1B, 1 the 1H-NMR spectrum is shown in Fig. 2A,13 The 13C-NMR spectrum is shown in Fig. 2B.

[0093] (Example 2) The same operations as in Example 1 were carried out except that the type of epoxy resin was changed to the epoxy resin described in Example 5 of JP-A-2023-65175 (epoxy equivalent: 234 g / mol, Mn = 712, Mw = 1228, Mw / Mn = 1.725; see the following formula (S2)), and an alkenyl resin (2) represented by the following chemical formula (1-1.2) was obtained. The softening point of the alkenyl resin (2) was 83°C. The double bond equivalent of the alkenyl resin (2) was 364 g / mol. The Mn of the alkenyl resin (2) was 1645, the Mw was 3142, and the Mw / Mn was 1.910. The chemical structure, molecular weight, etc. of the obtained alkenyl resin (2) were confirmed by FD-MS spectrum, GPC chart, 1 1H-NMR spectrum and 13 13C-NMR spectrum in the same manner as in Example 1. [Chemical formula] Chemical formula (1-1.2): [Chemical formula]

[0094] (Example 3) The same operations as in Example 1 were carried out except that the type of epoxy resin was changed to the epoxy resin described in Synthesis Example 1 of JP-A-2023-7254 (epoxy equivalent: 301 g / mol, Mn = 592, Mw = 944, Mw / Mn = 1.595; see the following formula (S3)), and an alkenyl resin (3) represented by the following chemical formula (1-1.3) was obtained. The softening point of the alkenyl resin (3) was 71°C. The double bond equivalent of the alkenyl resin (3) was 417 g / mol. The Mn of the alkenyl resin (3) was 1321, the Mw was 2259, and the Mw / Mn was 1.710. The chemical structure, molecular weight, etc. of the obtained alkenyl resin (3) were confirmed by FD-MS spectrum, GPC chart, 1Confirmed by 1H-NMR spectrum and 13 13C-NMR spectrum. [Chemical formula] Chemical formula (1-1.3): [Chemical formula]

[0095] (Example 4) (Synthesis Example 1: Synthesis of Epoxy Resin (1)) Into a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, while purging with nitrogen gas, 310 g (1.0 mol) of BisP-HTG, 926 g (5.0 equivalents) of epichlorohydrin, 476 g of n-butanol, and 80 g of water were charged and dissolved. After heating to 60 °C, 179 g (1.1 equivalents) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Then, after continuing stirring for 0.5 hour under the same conditions, washing with 140 g of water was repeated 3 times. And unreacted epichlorohydrin was distilled off by distillation under reduced pressure to obtain an epoxy resin (1) with an epoxy equivalent of 232 g / mol (see the following formula (S4)). The Mn of the epoxy resin was 511, the Mw was 563, and the Mw / Mn was 1.102. The chemical structure, molecular weight, etc. of the obtained epoxy resin (1) were confirmed by FD-MS spectrum, GPC chart, 1 1H-NMR spectrum and 13 13C-NMR spectrum in the same manner as in Example 1. [Chemical formula] (Synthesis of Alkenyl Resin (4) Using Epoxy Resin (1)) Next, the same operations as in Example 1 were carried out except that the type of epoxy resin was changed to the epoxy resin (1) obtained in Synthesis Example 1 above, and an alkenyl resin (4) represented by the following chemical formula (1-1.4) was obtained. The softening point of the alkenyl resin (4) was 89 °C. The double bond equivalent of the alkenyl resin (4) was 380 g / mol. The Mn of the alkenyl resin (4) was 1107, the Mw was 1288, and the Mw / Mn was 1.164. Chemical formula (1-1.4):

Chemical formula

[0096] (Example 5) (Synthesis Example 2: Synthesis of epoxy resin (2)) The same operations as in Synthesis Example 1 above were carried out except that BisP-HTG was changed to bisphenol-M, and an epoxy resin (2) with an epoxy equivalent of 247 g / mol (see the following formula (S5)) was obtained. The Mn of the epoxy resin was 527, the Mw was 589, and the Mw / Mn was 1.119. The chemical structure, molecular weight, etc. of the obtained epoxy resin (2) were confirmed by FD-MS spectrum, GPC chart, 1 1H-NMR spectrum and 13 13C-NMR spectrum in the same manner as in Example 1.

Chemical formula

[0097] (Comparative Example 1) The same procedures as in Example 1 were carried out except that the type of epoxy resin was changed to EXA-830CRP (bisphenol F type epoxy resin, manufactured by DIC Corporation, epoxy equivalent: 160 g / mol, Mn = 303, Mw = 320, Mw / Mn = 1.056, see the following formula (C0)) to obtain a propenyl resin (C1) represented by the following chemical formula (C1). The softening point of the propenyl resin (C1) was 58°C. The alkenyl equivalent of the propenyl resin (C1) was 328 g / mol. The Mn of the propenyl resin (C1) was 879, the Mw was 1173, and the Mw / Mn was 1.335. The chemical structure, molecular weight, etc. of the obtained propenyl resin (C1) were confirmed by FD-MS spectrum, GPC chart, 1 H-NMR spectrum, and 13 C-NMR spectrum in the same manner as in Example 1. [Chemical formula] Chemical formula (C1): [Chemical formula]

[0098] (Examples 6 to 10 and Comparative Example 2) (Preparation of Resin Composition and Production of Cured Product) The alkenyl resins (1) to (5) obtained in Examples 1 to 5 above, the propenyl resin (C1) obtained in Comparative Example 1, and the following formula (6): [Chemical formula] The maleimide resin represented by (manufactured by Daiwa Kasei Kogyo Co., Ltd., "BMI-2300") were blended at the ratios shown in Table 1 below, and melt-kneaded at a temperature of 100°C for 5 minutes using a two-roll mill to prepare the resin compositions of Examples 6 to 10 and Comparative Example 2. Next, physical property evaluations of adhesion, glass transition temperature, and hygroscopicity were performed by the method described above. The results are shown in Table 1.

[0099] [Table 1]

[0100] From the results shown in Table 1 above, comparing Examples 6 to 10 with Comparative Example 2, it can be confirmed that by using the alkenyl resins of Examples 1 to 5, both excellent adhesion and low hygroscopicity were achieved during curing. [Industrial Applicability]

[0101] According to the present invention, it is possible to provide an alkenyl resin that exhibits both excellent adhesion and low hygroscopicity during curing, a resin composition containing the alkenyl resin, and a cured product thereof.

Claims

1. The following general formula (1): 【Chemical 1】 (In the above general formula (1), Ar １ and Ar ２ each independently represents an aromatic hydrocarbon group, L １１ and L ２１ each independently represents an alkylene group having 1 to 10 carbon atoms, provided that one or more —CH ２ — in the alkylene group may be substituted with —CH(—OH)—, —O— or —C(═O)— L １２ and L ２２ each independently represents -O- or -S- M １１ and M ２１ each independently represents a cyclic group which may be substituted by a substituent R ３ and M ３ each independently represents an organic group having 6 to 20 carbon atoms, R １１ , R １２ , R ２１ and R ２２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number.) An alkenyl resin represented by the formula.

2. The following general formula (1-1): [Chemical 2] (In the above general formula (1), Ar １ and Ar ２ each independently represents an aromatic hydrocarbon group, L １２ and L ２２ each independently represents -O- or -S- M １１ and M ２１ each independently represents a cyclic group which may be substituted by a substituent R １３ and represents a cyclic group which may be substituted by M ３ each independently represents an organic group having 6 to 20 carbon atoms, R １１ 、 R １２ 、 R ２１ and R ２２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number.) The alkenyl resin according to Claim 1, represented by the formula.

3. The alkenyl resin according to Claim 1, which uses an epoxy resin and an alkenylphenol compound as reaction raw materials.

4. M in the general formula (1) ３ The alkenyl resin according to claim 1, wherein M is a group represented by any one of the following formulas (i-1) to (v-1). 【Chemical Formula 3】 (In the above formulas (i) to (v), “*” indicates a bond that binds to another atom.)

5. A resin composition containing the alkenyl resin according to Claim 1 and a maleimide resin.

6. A cured product of the resin composition according to Claim 5.

7. A printed wiring board using the resin composition according to Claim 5.

8. A semiconductor encapsulating material using the resin composition according to Claim 5.

9. A build-up film using the resin composition according to Claim 5.

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