Alkenyl compound, resin composition, cured product, printed wiring board, semiconductor sealing material, and laminate film

Abstract

According to the present disclosure, it is possible to provide an alkenyl compound having excellent curability (gel time) and exhibiting excellent appearance and high heat resistance when cured, a resin composition containing the alkenyl compound, and a cured product thereof. The present disclosure relates to an alkenyl compound represented by general formula (1), a resin composition containing the alkenyl compound, a cured product of the resin composition, a printed wiring board using the resin composition, a semiconductor sealing material using the resin composition, and a laminate film using the resin composition. # imgabs0 #

Description

Technical Field

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

[0002] Prepregs obtained by impregnating glass cloth with thermosetting resins represented by epoxy resins or BT (bismaleimide-triazine) resins and heating and drying, laminates obtained by heating and curing the prepregs, and multilayer boards obtained by combining the laminates and the prepregs and heating and curing them are widely used as circuit substrate materials for electronic devices. Among them, as a type of printed wiring board that realizes the function of an interposer for mounting semiconductors, the thinning of the packaging substrate has become a problem, and thus, in order to suppress the warping of the packaging substrate during installation, a material showing high heat resistance is required.

[0003] In addition, recently, in various electrical material applications such as semiconductor sealing materials and printed circuit boards, especially in advanced material applications, heat resistance and further improvement of performance represented by dielectric properties are required, and materials and compositions that have both of these are required. In particular, in the field of power semiconductors, the adoption of SiC-based devices is expanding due to their high conversion efficiency and the ability to achieve miniaturization and lightweight. SiC-based devices can operate at high temperatures, so in the next generation of power semiconductor sealing materials, high heat resistance that can ensure operational reliability at high temperatures is required. In previous semiconductor sealing materials, epoxy resins with excellent balance of various physical properties such as heat resistance and moisture resistance were used, but in order to further achieve high heat resistance, research on the combined use or replacement of resins with higher heat resistance (Tg) such as maleimide resins, benzoxazine resins or cyanate resins is underway.

[0004] For example, Patent Document 1 describes an alkenyl group-containing compound and a curable resin composition, and a cured product thereof, which exhibit excellent heat resistance and low dielectric properties when cured, as a sealing material for a semiconductor element or the like.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2019-198606 Summary of the invention

[0008] Problems to be solved by the invention

[0009] However, in the technology of Patent Document 1, although heat resistance and low dielectric properties have been studied, curing time and appearance have not been considered at all. In addition, Patent Document 1 describes the content and experimental data of using a radical polymerization initiator for the (radical) reaction of the vinyl groups of the compound containing vinyl groups with each other and with maleimide groups. However, in Patent Document 1, the problem of the curability of the maleimide resin itself, for example, in a curable resin composition containing an epoxy resin and a maleimide resin, the fact that it cannot be cured at all under conventional curing conditions and the fact that cracks are generated during curing due to brittleness have not been studied at all.

[0010] Therefore, the technical problem to be solved by the present disclosure is to provide a vinyl compound, a resin composition containing the vinyl compound, and a cured product thereof, which have excellent curability, and in which voids or unevenness are reduced during curing, showing excellent appearance.

[0011] Method for Solving the Problem

[0012] The inventors of the present invention have repeatedly conducted in-depth studies to solve the above problems, and as a result, they have found that by having a chemical structure represented by the general formula (1), a vinyl compound, a resin composition containing the vinyl compound, and a cured product thereof can be obtained, which can achieve excellent curability, and in which voids or unevenness are reduced during curing, showing excellent appearance, thus completing the present invention.

[0013] In addition, the vinyl compound of the present disclosure can also use a plant-derived raw material (biomass raw material) as a reaction raw material, so it provides a vinyl compound and a resin composition that have moldability adaptable to conventional manufacturing processes and have a low environmental load from biomass raw material sources.

[0014] [1] A vinyl compound represented by the following general formula (1).

[0015]

[0016] (In the above general formula (1), M 1 represents an n1-valent organic group,

[0017] L 1 represents -O- or -S-,

[0018] L 2 represents an alkylene group having 2 to 10 carbon atoms, wherein one or more of the -CH2- in the above alkylene group can be replaced by -CH(-OH)-, -O- or -C(=O)-,

[0019] M 2 represents a cyclic group that can be substituted by a substituent R 3 substituted,

[0020] R 1 and R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

[0021] n1 represents a natural number of 2 or more and 4 or less.)

[0022] [2] The alkenyl compound according to [1] is represented by the following general formula (1-1).

[0023]

[0024] (In the above general formula (1-1), M 1 represents an n1-valent organic group,

[0025] L 1 represents -O- or -S-,

[0026] M 2 represents a cyclic group which may be substituted by a substituent R 3 substituted,

[0027] R 1 and R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

[0028] n1 represents a natural number of 2 or more and 4 or less.)

[0029] [3] The alkenyl compound according to [1] or [2], M in the above general formula (1) 1 is a group representing any one of the following formulas (i) to (vi).

[0030]

[0031] (In the above formulas (i) to (vi), "*" represents a bonding bond to other atoms.)

[0032] [4] The alkenyl compound according to any one of [1] to [3] uses an epoxy compound and an alkenylphenol compound as reaction raw materials.

[0033] [5] A resin composition comprising the alkenyl compound according to any one of [1] to [4] and a maleimide resin.

[0034] [6] A cured product of the resin composition according to [5].

[0035] [7] A printed wiring board using the resin composition according to [5].

[0036] [8] A semiconductor sealing material using the resin composition according to [5].

[0037] [9] A laminated film made of the resin composition described in [5].

[0038] Advantages of the Invention

[0039] According to the present disclosure, there is provided a vinyl compound having excellent curability and reducing voids or unevenness during curing, thereby exhibiting excellent appearance.

[0040] According to the present disclosure, in the coexistence of a vinyl compound and a compound or resin having a maleimide group, the gel time of the resin composition is short, and at a conventional curing temperature (e.g., 175 °C or lower), the curing reaction with the compound or resin having a maleimide group can be completed.

[0041] According to the present disclosure, for the maleimide group, a curing reaction can be carried out by a pericyclic reaction.

[0042] According to the present disclosure, there can be provided a resin composition containing a vinyl compound having excellent curability and reducing voids or unevenness during curing, thereby exhibiting excellent appearance, and a cured product thereof. Such a cured product is particularly useful in printed wiring boards, semiconductor encapsulants, laminated films, and the like.

[0043] According to the present disclosure, a compound derived from biomass can be used as a reaction raw material, thereby reducing the environmental load, and in the coexistence of a compound or resin having a maleimide group, the gel time of the composition is short, and at a conventional curing temperature, the curing reaction with the compound or resin having a maleimide group can be completed. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 Shows the FD-MS spectrum of the mixture (1) containing the vinyl compound synthesized in Example 1.

[0045] Figure 2A Shows the 1 H-NMR spectrum of the mixture (1) containing the vinyl compound synthesized in Example 1.

[0046] Figure 2B Shows the 13 C-NMR spectrum of the mixture (1) containing the vinyl compound synthesized in Example 1. DETAILED DESCRIPTION

[0047] Hereinafter, embodiments of the present invention (referred to as "the present embodiments") will be described in detail. The present disclosure is not limited to the following description and can be implemented with various modifications within the scope of its gist.

[0048] [Terms]

[0049] The "reaction raw material" in this specification refers to a compound that is used to obtain a target compound through a chemical reaction such as combination or decomposition and partially constitutes the chemical structure of the target compound, excluding substances that act as assistants for chemical reactions such as solvents and catalysts. In this specification, in particular, the "reaction raw material" refers to a precursor for obtaining a target alkenyl compound through a chemical reaction.

[0050] The "alkyl group" in this specification can be any of linear, branched, or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n)heptyl, (n)octyl, (n)nonyl, (n)decyl, (n)undecyl, (n)dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or cyclononyl.

[0051] The above "alkyl group" includes "cycloalkyl group", and examples of the "cycloalkyl group" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, or adamantyl.

[0052] Examples of the "alkylthio group" in this specification include methylthio, ethylthio, propylthio, butylthio, octylthio, or 2-ethylhexylthio.

[0053] Examples of the "alkenyl group" in this specification include vinyl, 1-propenyl (hereinafter, also simply referred to as propenyl), 2-propenyl (hereinafter, also simply referred to as allyl), isopropenyl, or 2-methylpropenyl (methallyl).

[0054] Examples of the "alkoxy group" in this specification include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, or nonyloxy.

[0055] Examples of the "aryl group" in this specification include phenyl, 1-naphthyl, or 2-naphthyl.

[0056] Examples of the "aryloxy group" in this specification include phenoxy, naphthyloxy, anthryloxy, phenanthryloxy, or pyrenyloxy.

[0057] Examples of the "arylthio group" in this specification include arylthio groups such as phenylthio, naphthylthio, anthrylthio, phenanthrylthio, or pyrenylthio.

[0058] Examples of the "halogen atom" in this specification include, for example, fluorine atom, chlorine atom, bromine atom, or iodine atom.

[0059] The "structural unit" in this specification refers to the (repeating) unit of the chemical structure formed during a reaction or polymerization. In other words, it refers to the part of the structure of the resulting compound formed by the reaction or polymerization other than the chemical bond structure involved in the reaction or polymerization, that is, the so-called residue.

[0060] [Vinyl compound]

[0061] The vinyl compound of this embodiment is represented by the following general formula (1).

[0062]

[0063] (In the above general formula (1), M 1 represents an n1-valent organic group,

[0064] L 1 represents -O- or -S-,

[0065] L 2 represents an alkylene group having 2 to 10 carbon atoms, wherein one or more of the -CH2- in the above alkylene group can be replaced by -CH(-OH)-, -O- or -C(=O)-,

[0066] M 2 represents a cyclic group that can be substituted by a substituent R 3 substituent,

[0067] R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

[0068] n1 represents a natural number of 2 or more and 4 or less.)

[0069] Thereby, an effect of excellent curability and excellent appearance with reduced voids or non-uniformity during curing is achieved.

[0070] In addition, in a composition in which the vinyl compound represented by the general formula (1) coexists with a compound or resin having a maleimide group, the gel time is short, and at a conventional curing temperature (for example, 175 °C or lower), the curing reaction with the compound or resin having a maleimide group can be completed.

[0071] In the above general formula (1), M 1 represents an n1-valent organic group. The value of n1 can be a natural number of 2 or more and 4 or less.

[0072] The above organic group refers to a group in the form of an organic compound having n1 valences (2 to 4 valences) as a compound containing one or more carbon atoms, which constitutes a chemical structure, and refers to an atomic group formed by removing n1 hydrogen atoms from an organic compound containing one or more carbon atoms.

[0073] As the above-mentioned organic group, a group having a hydrocarbon group is preferred, a group having a cyclic hydrocarbon group is more preferred, and a group having an aromatic ring is further preferred.

[0074] If the organic group is a group having a cyclic hydrocarbon group, effects such as low dielectric properties and low hygroscopicity can be easily achieved. Further, if it is a group having an aromatic ring, effects such as high heat resistance and high flame retardancy can be easily achieved.

[0075] The number of carbon atoms of the above-mentioned organic group is preferably 1 to 50, more preferably 6 to 40, further preferably 10 to 30, and still more preferably 10 to 20.

[0076] If the number of carbon atoms of the organic group is 10 or more, the distance between crosslinking points becomes longer, so that cracks generated during curing can be easily suppressed. If the number of carbon atoms of the organic group is 20 or less, the viscosity becomes low, so that high filling of the filler can be easily achieved.

[0077] As the preferred M in the general formula (1) 1 , it preferably has a chemical structure having a rigid part (so-called mesomorphic structure, such as a cyclic group) and a linear or branched linking group, preferably has a cyclic group having 6 to 30 carbon atoms, and a linear or branched alkylene group having 1 to 8 carbon atoms bonded to the carbon atoms in the cyclic group (one or more -CH2- in the alkylene group can be replaced by -CH(-OH)-, -O- or -C(=O)-).

[0078] It is considered that by M in the general formula (1) 1 having a linking group of a predetermined length, an appropriate distance from M 2 which is a cyclic group can be obtained, and M 1 and M 2 can ensure a relatively soft positional relationship with each other, thereby reducing steric hindrance and facilitating the pericyclic reaction with the large-volume maleimide group.

[0079] As an example of M 1 in the general formula (1), groups represented by the following formulas (I) to (VI) are preferred.

[0080]

[0081] (In the above formulas (I) to (VI), "*" represents a bonding bond to other atoms, R f , R e , R g , R h , R j , R k and R lEach independently represents a hydroxyl group, an amino group, a cyano group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

[0082] n f 、n e 、n g and n h each independently represents an integer of 0 or more and 4 or less,

[0083] n j represents an integer of 0 or more and 6 or less,

[0084] n k and n l each independently represents an integer of 0 or more and 5 or less.)

[0085] Among the groups represented by the above formulas (I) to (IV), the linking group -O-* preferably binds to the carbon atom at the para position (4-position) of each benzene ring.

[0086] Among the groups represented by the above formula (V), the linking group -O-* preferably binds to one of the carbon atoms at the 1-4 positions and one of the carbon atoms at the 5-8 positions of the naphthalene ring, respectively.

[0087] Among the groups represented by the above formula (VI), the linking group -O-* preferably binds to one of the carbon atoms at the 1-4 positions and one of the carbon atoms at the 5-8 positions of each naphthalene ring, respectively.

[0088] In the chemical structure of the alkenyl compound of this embodiment, in M in the general formula (1) 1 , a rigid mesomorphic structure can be formed in the molecule through a cyclic group, particularly having an aromatic ring, and thus an effect such as high heat resistance is exhibited.

[0089] M in the above general formula (1) 1 is particularly preferably one or more selected from the groups represented by the following formulas (i) to (vi).

[0090]

[0091] (In the above formulas (i) to (vi), "*" represents a bonding site for bonding to other atoms.)

[0092] Among the groups represented by the above formulas (i) to (iv), the linking group -O-* preferably binds to the carbon atom at the para position (4-position) of each benzene ring.

[0093] In the group represented by the above formula (v), as the linking group, -O-* preferably binds to one of the carbon atoms at the 1-4 positions and one of the carbon atoms at the 5-8 positions of the naphthalene ring, respectively.

[0094] In the group represented by the above formula (vi), as the linking group, -O-* preferably binds to one of the carbon atoms at the 1-4 positions and one of the carbon atoms at the 5-8 positions of each naphthalene ring, respectively.

[0095] Among the groups represented by the above formulas (i)-(vi), from the viewpoint of low viscosity, the above formulas (i), (ii), (iv), and (v) are preferred.

[0096] In addition, M in the general formula (1) 1 is a group (so-called residue) contained in the epoxy compound source described later.

[0097] In the above general formula (1), L 1 represents -O- or -S-, and from the viewpoint of suppressing the corrosion deterioration of the Cu wire, -O- is preferred.

[0098] In addition, L in the general formula (1) 1 is a group (so-called residue) contained in the alkenylphenol compound source described later.

[0099] In the above general formula (1), L 2 represents an alkylene group having 2 to 10 carbon atoms, and one or more -CH2- in the above alkylene group may be replaced by -CH(-OH)-, -O-, or -C(=O)-.

[0100] It is considered that in the general formula (1), L 2 has a molecular chain of a predetermined length, so that multiple Ms as cyclic groups 2 can obtain an appropriate distance from each other, and M 1 and multiple Ms 2 can respectively ensure a relatively soft positional relationship with each other, thereby reducing steric hindrance and facilitating the pericyclic reaction with the large-sized maleimide group. In addition, by having a flexible alkylene group, the melting point (softening point of the resin) of the compound can be reduced, and thus it is compatible with the maleimide resin under the conventional kneading conditions, and a uniform composition and cured product can be produced. On the other hand, it is considered that if the number of carbon atoms of L 1 is 1, the rigidity is high and the melting point becomes high, and thus it is not easily compatible with the maleimide resin under the conventional kneading conditions. As a result, L 2 by having a molecular chain of a predetermined length, can provide an alkenyl compound that shows excellent appearance with reduced voids or non-uniformity during curing.

[0101] L of the above general formula (1)2 The number of carbon atoms is preferably 2 to 9, more preferably 2 to 8, and still more preferably 3 to 6. In addition, L in the above general formula (1) 2 is preferably linear or branched.

[0102] By L 2 having a molecular chain of a predetermined length, an alkenyl compound capable of providing an excellent appearance with reduced voids or non-uniformity during curing can be provided.

[0103] L in the above general formula (1) 2 is preferably an alkylene group having 2 to 10 carbon atoms, an alkyleneoxy group having 2 to 9 carbon atoms (-[(CH2) n (CH2O) m p -), -[(CH2) n (CH(OH)) m -(CH2) k p - or -[(CH2) n (CH(OH)) m -(CH2) k p -O-C(=O)-. Among them, n is an integer of 0 or more and 8 or less, m is an integer of 1 or more and 9 or less, k is an integer of 0 or more and 8 or less, p is an integer of 1 or more and 3 or less, and n + m + k = an integer of 2 or more and 9 or less.

[0104] Therefore, it is considered that the pericyclic reaction with the large maleimide group is easy, and it is easy to be compatible with the maleimide resin. As a result, a uniform composition and cured product can be produced, and it is considered that voids or non-uniformity are reduced during curing, showing an excellent appearance.

[0105] In addition, L in the general formula (1) 2 includes a group (so-called residue) derived from an epoxy compound described later and a group (so-called residue) derived from a compound containing an aromatic hydrocarbon having an alkenyl group and a second reactive functional group (in particular, an alkenylphenol compound).

[0106] In the above general formula (1), M 2 represents a cyclic group that can be substituted by a substituent R 3 and is preferably a divalent cyclic group that can be substituted by a substituent R 3 .

[0107] The number of carbon atoms of the cyclic group is preferably 5 to 14, more preferably 6 to 12, still more preferably 6 to 10, and still more preferably 6.

[0108] ​​​The cyclic group refers to a group of atoms in which the constituent atoms are cyclically bonded, including carbocyclic, heterocyclic, saturated or unsaturated cyclic structures, monocyclic, ring assemblies, polycyclic structures (e.g., bicyclic structures), aromatic, non-aromatic, etc., and can be a group combining them. In addition, the cyclic group may contain at least one heteroatom. Further, any at least one hydrogen atom in the cyclic group may be substituted by at least one substituent R 3 (e.g., an electron-donating group).

[0109] As the above cyclic group, it preferably has an aromatic ring (including multiple aromatic rings). For example, a monocyclic aromatic ring, a condensed aromatic ring, or a ring assembly aromatic ring, etc. can be cited. As the above monocyclic aromatic ring, for example, benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. can be cited. As the above condensed aromatic ring, for example, naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. can be cited. As the above ring assembly aromatic ring, for example, biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. can be cited.

[0110] Therefore, in M in the above general formula (1) 2 When having an aromatic ring as a divalent cyclic group, the preferred divalent cyclic group can be a group obtained by removing any two hydrogen atoms from each of the above-exemplified aromatic rings.

[0111] If having an aromatic ring as a cyclic group, a diene structure can be formed, thereby facilitating the Diels-Alder reaction with a maleimide group and achieving a more excellent effect of curability.

[0112] In addition, the Diels-Alder reaction has high reactivity, so it can carry out low-temperature curing with a compound having an unsaturated group such as a maleimide group.

[0113] In addition, in M in the above general formula (1) 2 When having an aromatic ring as a divalent cyclic group, one or more hydrogen atoms of the aromatic ring can be substituted by one or more substituents R 3 substituted. As the substituent R 3 , it is preferably an electron-donating group. The substituent R 3 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.

[0114] The above cyclic group is more preferably any one of the following groups (a) to (e), still more preferably any one of (b) to (e), still more preferably the group of (b) or (c), and still more preferably a group that can be substituted by one or more substituents R 3 substituted 1,4-phenylene group.

[0115] (a) 1,4-cyclohexylene group that can be substituted by substituent R 3 (in this group, one -CH2- or two or more non-adjacent -CH2- present can be substituted by -O-, or one or more -CH2-CH2- present in this 1,4-cyclohexylene group can be substituted by vinylene (-CH=CH-).),

[0116] (b) 1,4-phenylene group that can be substituted by substituent R 3 (in this group, one -CH= or two or more non-adjacent -CH= present can be substituted by -N=.).

[0117] (c) 1,3-phenylene group that can be substituted by substituent R 3 (in this group, one -CH= or two or more non-adjacent -CH= present can be substituted by -N=.).

[0118] (d) 1,2-phenylene group that can be substituted by substituent R 3 (in this group, one -CH= or two or more non-adjacent -CH= present can be substituted by -N=.), and

[0119] (e) naphthylene group that can be substituted by substituent R 3 (in naphthylene, one -CH= or two or more non-adjacent -CH= present can be substituted by -N=.).

[0120] Among the groups of (a), (b), (c), (d) and (e) above, the substituent R 3 is preferably an electron-donating group. 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.

[0121] When the cyclic group is any one of the groups (a) to (e), the alkenyl group takes a planar configuration, thereby reducing steric hindrance and facilitating the pericyclic reaction with a bulky maleimide group, achieving a more excellent curability effect. Further, when the cyclic group is any one of the groups (b) to (e), an electron-rich diene-diene structure is formed, thereby facilitating the Diels-Alder reaction with the maleimide group and achieving a more excellent curability effect. Further, when the cyclic group is the group (b) or (c), two ortho positions of the alkenyl group can become reaction sites, thereby facilitating the Diels-Alder reaction with the maleimide group and achieving a more excellent curability effect. In addition, since the Diels-Alder reaction has high reactivity, it can perform low-temperature curing with a compound having an unsaturated group such as a maleimide group.

[0122] In the above general formula (1), as M 2 the cyclic group preferably has one or more unsaturated bonds, and the double bond of the alkenyl group (=-CR 1 =CR 2 -CH3 moiety) in the general formula (1) and the one or more unsaturated bonds in the cyclic group have a diene structure (= conjugated diene), or the cyclic group itself more preferably has a diene structure (= conjugated diene).

[0123] Thus, in addition to the Alder-ene reaction, a faster Diels-Alder reaction is also facilitated, achieving a more excellent curability effect. In addition, the alkenyl compound represented by the general formula (1) must have a -CR 1 =CR 2 -CH3 moiety. Therefore, the relative positional relationship between one or more unsaturated bonds in the cyclic group as M 2 and the double bond in the -CR 1 =CR 2 -CH3 moiety is liable to form a so-called 1,3-butadiene skeleton.

[0124] In the general formula (1), the divalent cyclic group is preferably a ring structure having a diene structure, and preferably has a diene structure fixed in the s-cis configuration.

[0125] Thus, the cyclic group can be a substrate for the Diels-Alder reaction with respect to the maleimide group as a dienophile. As a result, the curing temperature of a composition containing the alkenyl compound of the present embodiment and a compound or resin having an unsaturated group such as a maleimide group can be a relatively low temperature (for example, 200 °C or lower (preferably 175 °C or lower)).

[0126] In the general formula (1), the preferred M 2 is one that can be substituted by the substituent R 3A substituted divalent cyclic group having one or more unsaturated bonds, and -CR in the general formula (1) 1 =CR 2 The carbon-carbon double bond at the -CH3 moiety and the one or more unsaturated bonds in the above divalent cyclic group have a diene structure (= conjugated diene), or the above divalent cyclic group itself has a diene structure (= conjugated diene). Further, the above diene structure (= conjugated diene) is more preferably a diene structure fixed in the s-cis configuration, and the above substituent R 3 Is even more preferably an electron-donating group.

[0127] M in the general formula (1) 2 The -CR to which it is bonded 1 =CR 2 The carbon-carbon double bond at the -CH3 moiety and the one or more unsaturated bonds in the divalent cyclic group as M 2 Satisfy the relationship of a diene structure (= conjugated diene), so that the maleimide group and the above diene structure can undergo a Diels-Alder reaction using heat, thereby improving the curability. Further, the diene structure (= conjugated diene) satisfies the relationship of the s-cis configuration, so that it is easily a substrate for the Diels-Alder reaction with respect to the maleimide group.

[0128] As stipulated in the Woodward–Hoffmann rules, in the cycloaddition of two molecules, in a thermal reaction, the reaction is regulated by the HOMO of the diene (the diene structure in the general formula (1), such as a cyclic group and an allyl group) and the LUMO of the dienophile (maleimide group), and in a photochemical reaction, both are regulated by the LUMO. Therefore, for an electron-rich diene with a strong electron-donating group, since the energy difference between the HOMO of the diene and the LUMO of the maleimide group becomes smaller, the reaction is more easily carried out at a lower temperature. In other words, it can be considered that if the substituent R 3 Is an electron-donating group, the HOMO of the diene to which the substituent R 3 Is bonded rises, so that the Diels-Alder reactivity with the maleimide group can be improved, and as a result, the reaction is easily carried out at a low temperature, thereby improving the curability.

[0129] Therefore, in the alkenyl compound having a 1-propenylbenzene (β-methylstyrene) skeleton shown in an example (for example, Example 1) as an example of the present embodiment, by introducing a methoxy group as an electron-donating substituent R into the aromatic ring 3, thus confirming that the Diels-Alder reactivity with maleimide groups can be enhanced. In addition, the following insight is obtained: among the alkenyl compounds described in the examples, two alkoxy groups are substituted, and thus the reactivity with maleimide groups is higher than that of the 1-propenylbenzene skeleton with no substitution or one substitution. Further, the alkenyl compound of the present embodiment has a specific chemical structure that is soft and polar (in particular, 2-hydroxypropyl ether skeleton), and thus the softening point becomes low, and it is compatible with maleimide resins and the like at a relatively low kneading temperature (for example, 110 °C (preferably 100 °C)), and a uniform composition can be produced.

[0130] In the above general formula (1), as M 2 Specific examples of 3 are preferably a phenylene group having an alkoxy group with 1 to 12 carbon atoms as the electron-donating substituent R 3 and a phenylene group having an alkyl group with 1 to 12 carbon atoms as the electron-donating substituent R.

[0131] In addition, M in the general formula (1) 2 is a group (so-called residue) derived from a compound containing an aromatic hydrocarbon having an alkenyl group and a second reactive functional group (in particular, an alkenylphenol compound) described later.

[0132] In the above general formula (1), the substituent R 3 is preferably an electron-donating group, specifically, preferably one or more selected from the group consisting of an alkyl group with 1 to 12 carbon atoms, an aryl group with 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group with 1 to 12 carbon atoms, an amino group, and an imino group having an alkyl group with 1 to 5 carbon atoms.

[0133] From the viewpoint of raising the HOMO of the cyclic group to which the substituent R 3 is bonded, the substituent R 3 is more preferably a hydroxyl group, an alkyl group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.

[0134] In the above general formula (1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R 1 and R 2 are each independently more preferably a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and particularly preferably a hydrogen atom.

[0135] If R 1 and R 2 are hydrogen atoms, it is easy to perform a pericyclic reaction with a double bond such as a maleimide group.

[0136] In addition, R in the general formula (1) 1 and R2 A group (so-called residue) derived from a compound containing an aromatic hydrocarbon having an alkenyl group and a second reactive functional group (in particular, an alkenylphenol compound) described below.

[0137] In the above general formula (1), n1 represents a natural number of 2 or more and 4 or less, preferably 2 or 3, and more preferably 2.

[0138] The alkenyl compound of the present embodiment is more preferably represented by the following general formula (1-1).

[0139]

[0140] (In the above general formula (1-1), M 1 represents an n1-valent organic group,

[0141] L 1 represents -O- or -S-,

[0142] M 2 represents a cyclic group which may be substituted by a substituent R 3 substituent,

[0143] R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

[0144] n1 represents a natural number of 2 or more and 4 or less.)

[0145] Accordingly, it has a soft and polar 2-hydroxypropyl group, so that the melting point (or softening point) is lowered, and the compatibility with a maleimide resin or the like is further improved. Therefore, it is easy to prepare a uniform composition, and an excellent appearance effect in which voids or unevenness are further reduced during curing is exhibited.

[0146] "M 1 , n1, L 1 , M 2 , substituent R 3 , R 1 and R 2 " in the above general formula (1-1) is the same as "M 1 , n1, L 1 , M 2 , substituent R 3 , R 1 and R 2 " in the above general formula (1). Therefore, the description of "M 1 , n1, L 1 , M 2 , substituent R 3 , R 1 and R 2” content.

[0147] The alkenyl compound of the present embodiment is preferably one or more compounds selected from the group consisting of the following general formulas (1.1) to (1.9).

[0148]

[0149] (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), (IV), and (V), R 3 represents an electron-donating group, ni represents an integer of 0 or more and 4 or less, and nx represents an integer of 0 or more and 6 or less.)

[0150]

[0151] (In the above general formulas (1.4) to (1.6), M 4 represents the above formula (II), R 3 represents an electron-donating group, ni represents an integer of 0 or more and 4 or less, and nx represents an integer of 0 or more and 6 or less.)

[0152]

[0153] (In the above general formulas (1.7) to (1.9), M 5 represents a group selected from the group consisting of the above formulas (III) and (VI), R 3 represents an electron-donating group, ni represents an integer of 0 or more and 4 or less, and nx represents an integer of 0 or more and 6 or less.)

[0154] The above general formulas (1.1) to (1.9) all have a diene structure formed by the unsaturated bond in the terminal propenyl group and the cyclic group in the molecule, so they can undergo a Diels-Alder reaction with the maleimide group. In addition, the HOMO of the diene combined with the substituent R 3 as an electron-donating group rises, so the Diels-Alder reactivity with the maleimide group can be improved. As a result, the reaction is easy to carry out at low temperature, so the moldability such as curability and appearance can be improved.

[0155] (Physical properties of alkenyl compound)

[0156] <Double bond equivalent (g / mol) of alkenyl compound>

[0157] The double bond equivalent (g / mol) of the alkenyl compound of the present 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 further preferably 300 g / mol or more and 600 g / mol or less.

[0158] The "double bond equivalent (g / mol)" in this specification is the amount that serves as an index for the amount of double bonds contained in a molecule. For compounds of the same molecular weight, the smaller the value representing the double bond equivalent, the greater the tendency for the introduced amount of double bonds. This "double bond equivalent (g / mol)" is a calculated value obtained by the methods described in the following methods and examples columns.

[0159] The preferred range of the above double bond equivalent (g / mol) can be changed by appropriately combining the above upper limits and lower limits.

[0160] - Method for calculating the double bond equivalent of alkenyl compounds -

[0161] The double bond equivalent, which is the content of carbon-carbon double bonds in the alkenyl compounds of this embodiment, is calculated using the iodine value method in accordance with JIS K0070:1992.

[0162] <Molecular weight of alkenyl compounds>

[0163] The molecular weight of the alkenyl compounds of this embodiment is preferably in the range of 300 to 2000, more preferably in the range of 400 to 1500, and further preferably in the range of 500 to 1000.

[0164] The molecular weight of the alkenyl compounds of this embodiment is measured by FD-MS as described in the examples below.

[0165] (Other forms of alkenyl compounds)

[0166] The alkenyl compounds of this embodiment preferably use a compound containing an aliphatic or aromatic hydrocarbon having a first reactive functional group and a compound containing an aromatic hydrocarbon having an alkenyl and a second reactive functional group as reaction raw materials.

[0167] Examples of the first reactive functional group in the compound containing an aliphatic or aromatic hydrocarbon having the first reactive functional group include a glycidyl group, a haloalkyl group, a hydroxyl group, a carboxylic acid group, and -C(=O)-X (X is a halogen atom).

[0168] Examples of the second reactive functional group in the compound containing an aromatic hydrocarbon having an alkenyl and a second reactive functional group include a halogen atom, a hydroxyl group, a mercapto group, and a glycidyl group.

[0169] As the compound containing an aliphatic or aromatic hydrocarbon having the first reactive functional group, for example, a compound having the structure represented by the following general formula (4) is preferably used.

[0170]

[0171] (In the above general formula (4),

[0172] M 6 represents an aliphatic or aromatic hydrocarbon group, preferably represents an n-valent aromatic ring,

[0173] L 3 each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, wherein one or more of the -CH2- in the alkylene group may be replaced by -O- or -C(=O)-,

[0174] Y 1 represents a first reactive functional group, each independently being one selected from the group consisting of a halogen atom, a hydroxyl group, a glycidyl group, a carboxyl group, and -C(=O)-X (X is a halogen atom), and n4 represents an integer of 2 or more and 4 or less.)

[0175] M in the above general formula (4) 6 represents a divalent to tetravalent aliphatic hydrocarbon group or a divalent to tetravalent aromatic hydrocarbon group.

[0176] The aliphatic hydrocarbon group is an acyclic divalent to tetravalent aliphatic hydrocarbon group, which may be either linear or branched. In addition, the aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, preferably a saturated hydrocarbon group, more preferably a linear saturated hydrocarbon group. As the above aliphatic hydrocarbon group, preferably having 1 to 13 carbon atoms.

[0177] For example, as a divalent acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms that may have substituents, there may be mentioned methanediyl, ethanediyl, n-propanediyl, isopropanediyl, n-butanediyl, n-pentanediyl, n-hexanediyl, n-heptanediyl, n-octanediyl, n-nonanediyl, and n-decanediyl, etc. alkanediyls. Similarly, as a trivalent acyclic aliphatic hydrocarbon group that may have substituents, it refers to the group after removing one arbitrary hydrogen atom from the above divalent acyclic aliphatic hydrocarbon group. In addition, as a tetravalent acyclic aliphatic hydrocarbon group that may have substituents, it refers to the group after removing two arbitrary hydrogen atoms from the above divalent acyclic aliphatic hydrocarbon group.

[0178] The number of carbon atoms of the above divalent to tetravalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, further preferably 6 to 12, and even more preferably 6 to 10.

[0179] In addition, the above divalent to tetravalent aromatic hydrocarbon group may include a divalent to tetravalent group having an aromatic ring. As the aromatic ring, the content of the exemplified aromatic ring in M in the above general formula (1) 2 is cited.

[0180] As a preferred form of the divalent aromatic hydrocarbon group, there may be mentioned the group after removing two arbitrary hydrogen atoms from the above aromatic ring, more preferably phenylene, naphthylene, anthracenediyl, biphenylene, or phenanthrylene.

[0181] As a preferred embodiment of the trivalent aromatic hydrocarbon group, a group after removing three arbitrary hydrogen atoms from the above aromatic ring can be mentioned. In addition, as this aromatic ring, the same aromatic ring as the above divalent aromatic hydrocarbon group is cited. The above trivalent aromatic hydrocarbon group is more preferably a benzene triyl, naphthalene triyl, anthracene triyl, biphenylene triyl or phenanthrene triyl.

[0182] As a preferred embodiment of the tetravalent aromatic hydrocarbon group, a group after removing four arbitrary hydrogen atoms from the above aromatic ring can be mentioned. In addition, as this aromatic ring, the same aromatic ring as the above divalent aromatic hydrocarbon group is cited. The above tetravalent aromatic hydrocarbon group is more preferably a benzene tetrayl, naphthalene tetrayl, anthracene tetrayl, biphenylene tetrayl or phenanthrene tetrayl.

[0183] The above divalent to tetravalent aliphatic hydrocarbon group or divalent to tetravalent aromatic hydrocarbon group may have a substituent. As the above substituent, for example, 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 hydroxyl group and the like can be mentioned.

[0184] In addition, as a preferred embodiment of the compound containing an aliphatic or aromatic hydrocarbon having the first reactive functional group, an epoxy compound (for example, an epoxy compound having an aromatic ring), a divalent to tetravalent haloalkyl compound (for example, an aromatic compound having 2 to 4 haloalkyl groups), a divalent to tetravalent carboxylic acid halide (for example, an aromatic compound having 2 to 4 -C(=O)-X (X is a halogen atom)), and a divalent to tetravalent phenol compound or alcohol compound (for example, an aromatic compound having 2 to 4 hydroxyl groups) can be mentioned.

[0185] As the compound containing an aromatic hydrocarbon having an alkenyl group and a second reactive functional group, for example, a compound having a structure represented by the following general formula (5) is preferred.

[0186]

[0187] (In the above general formula (5),

[0188] Ar 1 represents an (n51 + n52 + 1)-valent aromatic ring,

[0189] R 51 is an alkenyl group, preferably represents an allyl group or a propenyl group,

[0190] R 52 each independently is an electron-donating group, preferably represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms,

[0191] L 5 each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, wherein one or more —CH2— in the above alkylene group may be substituted with —O— or —C(═O)—

[0192] Y 2 represents a second reactive functional group, and each independently is one selected from the group consisting of a halogen atom, a hydroxyl group, a mercapto group, and a glycidyl group

[0193] n51 represents an integer of 1 or more and 4 or less

[0194] n52 represents an integer of 0 or more and 4 or less

[0195] n51 + n52 represents an integer of 1 or more and 5 or less.)

[0196] In addition, as a preferred mode of the above compound containing an aromatic hydrocarbon having an alkenyl group and a second reactive functional group, an alkenylphenol compound having 1 alkenyl group, an alkenylbenzenethiol compound, an alkenylnaphthol compound, and an alkenylphenyl glycidyl ether compound having 1 alkenyl group can be mentioned

[0197] The alkenyl compound of the present embodiment is preferably a reaction raw material of any one of the following (Z1) to (Z4), more preferably a reaction raw material of any one of (Z1) or (Z4), and still more preferably a reaction raw material of (Z1).

[0198] (Z1) The alkenyl compound of the present embodiment uses an epoxide (preferably a 2- to 4-valent epoxide) and an alkenylphenol compound, an alkenylbenzenethiol compound, or an alkenylnaphthol compound having 1 alkenyl group as reaction raw materials

[0199] (Z2) The alkenyl compound of the present embodiment uses a 2- to 4-valent haloalkyl compound and an alkenylphenol compound, an alkenylbenzenethiol compound, or an alkenylnaphthol compound having 1 alkenyl group as reaction raw materials

[0200] (Z3) The alkenyl compound of the present embodiment uses a 2- to 4-valent acyl halide and an alkenylphenol compound, an alkenylbenzenethiol compound, or an alkenylnaphthol compound having 1 alkenyl group as reaction raw materials

[0201] (Z4) The alkenyl compound of the present embodiment uses a 2- to 4-valent phenol compound or an alcohol compound and an alkenylphenyl glycidyl ether compound having 1 alkenyl group as reaction raw materials

[0202] Among them, the alkenyl compound of the present embodiment is further more preferably a reaction raw material of an epoxide and an alkenylphenol compound having 1 alkenyl group, and particularly preferably a reaction raw material of an epoxide and eugenol or isoeugenol

[0203] Generally speaking, eugenol is a component contained in spices such as cloves and laurel, and is a biomass compound of natural origin classified as a monophenol propanol. Therefore, by using eugenol or isoeugenol obtained by the isomerization reaction of this eugenol as a reaction raw material, the environmental load can be reduced.

[0204] <Epoxy compound>

[0205] The alkenyl compound of the present embodiment preferably uses an epoxy compound as a reaction raw material. The epoxy compound of the present embodiment is not particularly limited as long as it is a compound having 2 to 4 glycidyl groups in one molecule. Hereinafter, a compound having 2 to 4 epoxy groups in one molecule will be simply referred to as an epoxy compound. Various epoxy compounds can be used, but a polyepoxy compound having 2 or more and 4 or less epoxy groups in one molecule is preferred. In addition, the epoxy compound is preferably a compound having the structure shown by the general formula (4), and Y in the general formula (4) 1 is a compound in the case of a glycidyl group.

[0206] Specific examples of the polyepoxy compound are substances obtained by the condensation of epichlorohydrin with polyphenols such as bisphenols, polyols, and the like, and examples thereof include bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, novolac type, phenol novolac type, o-cresol novolac type, tris(hydroxyphenyl)methane type, tetraphenylolethane type, phenyl aralkyl type, biphenyl aralkyl type, dicyclopentadiene phenol type and other glycidyl ether type epoxy resins. In addition, glycidyl ester type epoxy resins obtained by the condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives and fatty acids can be cited; glycidyl amine type epoxy resins obtained by the reaction of epichlorohydrin with amines, cyanuric acids, hydantoins; and epoxy resins modified by various methods, but are not limited thereto.

[0207] In the present embodiment, the molecular weight of the epoxy compound is preferably 100 or more and 600 or less, preferably 200 or more and 500 or less, preferably 250 or more and 350 or less. Thereby, the effects of excellent curability and excellent appearance are exhibited.

[0208] In addition, the molecular weight of the epoxy compound is calculated by FD-MS measurement as described in the examples described later.

[0209] The epoxy compound of the present embodiment is preferably represented by the following general formula (2).

[0210]

[0211] (In the above general formula (2),

[0212] M 7 represents a group selected from the group consisting of the above formulas (I) to (VI),

[0213] and n1 represents an integer of 2 or more and 4 or less.)

[0214] <Alkenyl phenol compound>

[0215] The alkenyl compound of this embodiment preferably uses an alkenyl phenol compound as a reaction raw material. In addition, the alkenyl phenol compound of this embodiment is preferably 4 - allyl - 2,6 - xylenol, eugenol, and isoeugenol, more preferably eugenol and isoeugenol, and further preferably isoeugenol.

[0216] The above alkenyl phenol compound refers to an aromatic compound having an alkenyl group that can be substituted, a phenolic hydroxyl group, and the above alkenyl group and the above hydroxyl group. The alkenyl phenol compound is preferably a compound having the structure shown in general formula (5), and Y in general formula (5) 2 is a compound in the case of a hydroxyl group.

[0217] When the alkenyl phenol compound of this embodiment is isoeugenol, that is, in the above general formula (5), Ar 1 is a benzene ring, R 51 is an allyl group (1 - propenyl), R 52 is a methoxy group, L 5 is a single bond, Y 2 is a hydroxyl group, and n51 and n52 are both 1, the isoeugenol of plant origin can be introduced into the chemical structure of the target alkenyl compound, thereby providing a compound with reduced environmental load.

[0218] (Mixture containing alkenyl compound)

[0219] This disclosure can be a mixture containing an alkenyl compound represented by general formula (1). The content of the alkenyl compound represented by general formula (1) of this embodiment can be calculated as the area% of GPC by the method described below. Relative to the total amount (100 area%) of the mixture containing the alkenyl compound, it is preferably 20 area% or more, more preferably 40 area% or more and 100 area% or less, and further preferably 60 area% or more and 100 area% or less.

[0220] In this mixture, if the content of the alkenyl compound represented by the general formula (1) is 20 area% or more, its effects can be exerted. Components other than the alkenyl compound represented by the general formula (1) contained in the mixture containing the alkenyl compound may be by-products and polymers generated in the manufacturing process of the reaction raw materials and the epoxidation process.

[0221] (Manufacturing method of alkenyl compound)

[0222] Hereinafter, the manufacturing method of the alkenyl compound of the present disclosure will be described. The manufacturing method of the alkenyl compound of the present embodiment is not particularly limited as long as it is a manufacturing method capable of manufacturing the compound represented by the general formula (1). For example, as the manufacturing method of the alkenyl compound of the present disclosure, a compound containing an aliphatic or aromatic hydrocarbon having a first reactive functional group represented by the above general formula (4) and a compound containing an aromatic hydrocarbon having an alkenyl and a second reactive functional group represented by the above general formula (5) can be used as reaction raw materials. In addition, the manufacturing method of the above alkenyl compound can refer to known synthesis conditions and synthesis methods.

[0223] Hereinafter, for convenience of explanation, as an example of the manufacturing method of the alkenyl compound of the present disclosure, the case where an epoxy compound and an alkenylphenol compound are used as reaction raw materials will be described.

[0224] As an example of the manufacturing method of the alkenyl compound of the present disclosure, for example, a manufacturing method including the following step (1) and steps (2) and (3) provided as needed can be cited.

[0225] Step (1): A step of reacting an epoxy compound and an alkenylphenol compound as reaction raw materials;

[0226] Step (2): A step of refining the reaction product from a mixture containing the reaction product of the epoxy compound and the alkenylphenol compound;

[0227] Step (3): In the case where a compound having the structure represented by the general formula (5) as the alkenylphenol compound is used as a reaction raw material, and R 51 is allyl, a step of performing an isomerization reaction of the carbon-carbon double bond.

[0228] Specifically, the manufacturing method of the alkenyl compound of the present embodiment preferably has: a step (1-1) of reacting an epoxy compound and an alkenylphenol compound in the presence of a basic compound; a step (2-1) of refining the reaction product using an acidic aqueous solution and an organic solvent for the reaction product generated by the above step (1-1); and a step (3-1) of performing an isomerization reaction of the carbon-carbon double bond provided as needed.

[0229] Hereinafter, each step of the method for producing the alkenyl compound of the present disclosure will be described in turn.

[0230] <Step (1)>

[0231] Regarding the mixing ratio of the above epoxy compound and the above alkenyl phenol compound, considering the physical property balance of the moldability and curability of the resulting alkenyl compound, the molar ratio of the hydroxyl group of the above alkenyl phenol compound to 1 mole of the glycidyl group of the above epoxy compound is preferably 0.1 to 2.0 moles, more preferably 0.5 to 1.5 moles, and still more preferably 0.8 to 1.3 moles.

[0232] In addition, as a specific method for carrying out the above reaction, usually all the raw materials are charged together and directly reacted at a predetermined temperature, or the alkenyl phenol compound and the basic compound are charged and reacted while maintaining at a predetermined temperature and dropping the epoxy compound. At this time, the dropping time is usually 0.5 to 24 hours, preferably 0.5 to 4 hours.

[0233] The basic compound used in step (1) of the present embodiment can be an inorganic basic compound, an organic basic compound, etc. 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 the ease of purification by water washing, the basic compound of the present embodiment is preferably an alkali metal hydroxide (for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, etc.), and more preferably potassium hydroxide and sodium hydroxide.

[0234] The above basic compound is preferably used 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 above epoxy compound and the above allyl phenol compound.

[0235] Specific examples of the phase transfer catalyst used in step (1) of the present embodiment include quaternary ammonium salts, quaternary phosphonium salts or crown ethers. In particular, from the aspect of excellent catalytic activity, quaternary ammonium salts and quaternary phosphonium salts are preferred. Specifically, examples include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, etc. When used, these basic catalysts can be used in the form of an aqueous solution of about 10% to 55% by mass, or in a solid form.

[0236] Regarding the compounding amount of the above-mentioned phase transfer catalyst, the phase transfer catalyst is compounded in the range of 0 parts by mass to 15 parts by mass with respect to 100 parts by mass of the total amount of the raw materials added (the total amount of the epoxide and the alkenylphenol compound).

[0237] In the step (1) of the present embodiment, it is preferable to use an organic solvent to react the epoxide with the above-mentioned alkenylphenol compound. 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. In addition, they can be used alone or in combination.

[0238] In the step (1) of the present embodiment, the reaction temperature of the epoxide and the alkenylphenol compound is usually in the range of 50 to 170 °C, but in order to avoid side reactions such as the formation of polymers and the hydrolysis of glycidyl groups, it is preferably 100 to 140 °C.

[0239] In the step (1) of the present embodiment, as the reaction time of the epoxide and the alkenylphenol compound, since the reaction does not proceed at all in a short time and side reactions such as thermal decomposition of the product occur when the time is set to be long, under the above reaction temperature conditions, it is usually in the range of 0.5 to 24 hours in total, and preferably in the range of 1 to 6 hours in total.

[0240] Therefore, in the step (1) of the present embodiment, it is more preferable to carry out the reaction while stirring in the range of 100 to 140 °C and in the range of 1 to 6 hours.

[0241] In addition, the atmosphere of step (1) is preferably to carry out the reaction in an inert gas atmosphere such as nitrogen, helium, or argon.

[0242] <Step (2)>

[0243] The step (2) in the present embodiment is carried out as needed, and it is a step of recovering the reaction product obtained from the above step (1) (the alkenyl compound of the target substance). An acidic aqueous solution is added to the solution containing the reaction product obtained from step (1) (the alkenyl compound obtained from the general formula (1) as the target substance) and the organic solvent, and using this acidic aqueous solution, after removing the salts and impurities of the basic compound by neutralization, washing, etc., an azeotropic dehydration operation is carried out, and after precision filtration, the solvent and the unreacted compound are distilled off under reduced pressure to obtain the alkenyl compound as the target substance. In addition, a dehydrating agent can be used during the reaction as needed.

[0244] The above reaction product is washed with an acidic aqueous solution, thereby enabling the improvement of the stability of the resulting compound. Specific examples of the acid used as the above acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, and maleic acid, and their salts (for example, alkali metal or alkaline earth metal salts). In addition, these acids can be used alone or in combination of two or more.

[0245] 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.

[0246] <Process (3)>

[0247] After step (1) or (2) of the present embodiment, a step (3) for carrying out an isomerization reaction of a carbon-carbon double bond can be provided as needed. Specifically, the following step (3) can be further provided: in the alkenylphenol compound represented by the above general formula (5), when R 51 is an allyl group (that is, when an alkenylphenol compound having an allyl group is used as a reaction raw material), an isomerization reaction is carried out on the reaction product obtained by reacting an epoxide with the alkenylphenol compound having the above allyl group, thereby isomerizing the allyl group into a 1-propenyl group to synthesize the alkenyl compound represented by the general formula (1).

[0248] As a method for isomerizing the allyl group into a 1-propenyl group, a known method can be adopted. For example, an isomerization reaction of a carbon-carbon bond using a palladium acetate catalyst (refer to [J. Am. Chem. Soc., 91, p6707-6714 (1969)]), or an isomerization reaction of a carbon-carbon bond using an alkali metal hydroxide such as potassium hydroxide as a base catalyst (refer to [J. Am. Chem. Soc., 78, p1709-1715 (1956)]) can be cited.

[0249] Thereby, the alkenyl compound represented by the above general formula (1) can be easily synthesized.

[0250] [Resin composition]

[0251] The alkenyl compound 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 alkenyl compound and a maleimide resin. The solvent solubility, fluidity, and operability of the alkenyl compound of the present embodiment during heating and melting are excellent. Further, it can contribute to dimensional stability, low moisture absorption, brittleness resistance, heat resistance, and low dielectric constant and low dielectric loss tangent. Therefore, the moldability (especially curing time and appearance), heat resistance, and dielectric properties of the cured product obtained from the resin composition containing the above alkenyl compound are excellent.

[0252] The manufacturing method of the resin composition of the present embodiment is not particularly limited. For example, as a method for producing the resin composition, melt-kneading is preferred. As examples of the apparatus used in melt-kneading, in particular, an extruder, a Banbury mixer, a roll, a kneader, etc. can be cited, and they are operated intermittently or continuously.

[0253] Generally, in the case of manufacturing a resin composition, it is set to be above the melting point temperature of the resin composition, and an extruder, a kneader, a roll, etc. are used to sufficiently melt and mix until it becomes uniform. On the other hand, the softening point (or melting point) of the vinyl compound of the present embodiment is low, so it is compatible with a maleimide resin, etc. at the conventional kneading temperature (for example, 110 °C (preferably 100 °C)), and a uniform composition can be produced. Thus, by curing the resin composition of the present embodiment, a cured product excellent in appearance and heat resistance can be produced.

[0254] (Maleimide resin)

[0255] The maleimide resin of the present embodiment is not particularly limited as long as it has a maleimide group. As the above maleimide resin, for example, 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 can be cited. In addition, as other maleimide resins, the maleimide described in International Publication No. 2020 / 217679, the maleimide resin described in Japanese Patent No. 7140307, the maleimide resin (A) described in Japanese Patent Application Laid-Open No. 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 Japanese Patent Application Laid-Open No. 2023-152757, the polymaleimide compound (A) described in Japanese Patent Application Laid-Open No. 2023-152755, etc. can be cited.

[0256] In the resin composition of the present 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, based on the total amount (100% by mass) of the resin composition.

[0257] When the content of the above-mentioned maleimide resin is within the above range, excellent moldability, heat resistance, and mechanical strength can be achieved. The upper and lower limits of the content of the above-mentioned maleimide resin can be appropriately combined and changed.

[0258] (Optional additive components)

[0259] In the resin composition of the present disclosure, in addition to the vinyl compound or maleimide resin, a curing agent can be contained, and further, a curing accelerator, a silane coupling agent, a mold release agent, a pigment, an emulsifier, a non-halogen-based flame retardant, an inorganic filler, a flame retardant (e.g., an inorganic phosphorus-based flame retardant, an organic phosphorus-based flame retardant, a halogen-based flame retardant), a solvent, and various other compounding agents can be added as needed.

[0260] In addition, within the scope not impairing the object of the present disclosure, in addition to the above-mentioned vinyl compound and the above-mentioned maleimide resin, known resin components can be contained. As such known resin components, epoxy resins, phenolic resins, reactive ester resins, cyanate ester 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. can also be appropriately compounded.

[0261] When suppressing voids is emphasized in the present embodiment, the resin composition may substantially not contain a polymerization initiator. When a polymerization initiator such as DCPO (dicumyl peroxide) is used, a tendency for voids to occur is confirmed. As a reason therefor, it is considered that at high temperatures such as in melt kneading and thermal curing, the polymerization initiator in the resin composition decomposes to generate free radicals, and due to these free radicals, the maleimide resin or vinyl compound undergoes oxidative decomposition, and the resulting low molecular weight components volatilize, causing voids in the cured product.

[0262] (Preferred properties and composition of the resin composition)

[0263] When using the resin composition of the present embodiment to manufacture a semiconductor encapsulant, transfer molding is generally used. This transfer molding is a molding method in which the resin composition as a material is first heated and softened in a plunger, and then the heated and softened resin composition is made to flow through the flow paths in a mold such as a gate, a sprue, and a runner, and is pressed into a heated mold cavity to be cured. Therefore, in transfer molding, the fluidity of the resin composition as a material becomes important. When the fluidity is not appropriately adjusted with respect to the shape of the desired semiconductor encapsulant, problems such as the generation of unfilled portions in the mold cavity or the occurrence of molding defects such as voids and cracks in the molded product are likely to occur.

[0264] As described above, the resin composition of the present embodiment contains an alkenyl compound that can be cured at a low temperature and has a relatively low softening point (or melting point). Therefore, when transfer molding is performed, it can be carried out at a relatively low temperature (for example, 175 °C or lower). In addition, as described above, the alkenyl compound of the present embodiment can undergo a synergistic reaction with the maleimide resin through the highly reactive Diels-Alder reaction. Therefore, the resin composition of the present embodiment can be cured in a relatively short time (for example, within 180 seconds (more preferably within 120 seconds, further preferably within 100 seconds, and particularly preferably within 50 seconds)).

[0265] In the resin composition of the present embodiment, the resin composition contains an alkenyl compound and a maleimide resin. When the content of the above maleimide resin is 10 to 80% by mass and the content of the alkenyl compound is 90 to 20% by mass based on the total amount (100% by mass) of the resin composition, the gel time of the resin composition is preferably within 100 seconds, more preferably within 50 seconds.

[0266] The gel time is measured under the conditions described in the column of the following examples.

[0267] In the resin composition of the present embodiment, when the resin composition contains an alkenyl compound and a maleimide resin, and the content of the above maleimide resin is 10 to 80% by mass and the content of the alkenyl compound is 90 to 20% by mass based on the total amount (100% by mass) of the resin composition, the DSC exothermic peak of the resin composition is preferably 175 °C or lower, more preferably 165 °C or lower.

[0268] In the resin composition of the present embodiment, based on the total amount (100% by mass) of the resin composition, the total content of the alkenyl compound and the maleimide resin is preferably 20 to 100% by mass, more preferably 50 to 100% by mass.

[0269] In the resin composition of the present embodiment, based on the total amount (100% by mass) of the resin composition, the total content of the alkenyl compound, the maleimide resin, and any additive components is preferably 20 to 100% by mass, more preferably 50 to 100% by mass.

[0270] [Cured product]

[0271] The cured product of the present disclosure is preferably obtained from the above resin composition. The above cured product can be obtained by subjecting the above resin composition to a curing reaction. The above resin composition is obtained by uniformly mixing the above respective components (for example, a curing agent, a compounding agent), and can be easily made into a cured product by the same method as the conventionally known methods. Examples of the above cured product include molded cured products such as laminates, castings, adhesive layers, coating films, and films.

[0272] [Semiconductor encapsulating material]

[0273] 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 uses the vinyl compound of the present disclosure, thereby improving curability, heat resistance or appearance. Therefore, it has excellent processability, moldability and reflow resistance in the manufacturing process, and becomes a preferred mode.

[0274] In the resin composition of the present embodiment used in the above semiconductor encapsulating material, an inorganic filler may be contained. In addition, as the filling rate of the above inorganic filler, based on 100 parts by mass of the total amount of the vinyl compound and maleimide resin of the present embodiment, the inorganic filler can be used, for example, in the range of 0.5 to 1200 parts by mass. In addition, examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Noritake silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, aluminum nitride, etc.

[0275] As a method for obtaining the above semiconductor encapsulating material, the following methods can be cited: for the resin composition of the present embodiment, if necessary, an additive as an optional component is further used with an extruder, kneader, roller, etc. until it becomes uniform and is sufficiently melt-mixed.

[0276] [Semiconductor device]

[0277] The present disclosure relates to a semiconductor device including a cured product of the above semiconductor encapsulating material. The semiconductor device obtained by using the semiconductor encapsulating material obtained by using the resin composition of the present embodiment uses the vinyl compound of the present disclosure. Therefore, it has low viscosity and excellent fluidity. Further, its hygroscopicity, thermoelastic modulus or adhesiveness to a metal material is improved. Therefore, it has excellent processability, moldability and reflow resistance in the manufacturing process, and becomes a preferred mode.

[0278] As a method for obtaining the above semiconductor device, the above semiconductor encapsulating material can be cast, or molded using a transfer molding machine, injection molding machine, etc., and further heat-cured in the temperature range of room temperature (20°C) to 250°C.

[0279] [Prepreg]

[0280] The present disclosure is a prepreg having a reinforced substrate and a semi-cured product of the resin composition of the present embodiment impregnated in the above-mentioned reinforced substrate. As a method for obtaining a prepreg from the above-mentioned resin composition, the following method can be cited: After impregnating a varnished resin composition into a reinforced substrate (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass fiber mat, glass roving cloth, etc.) in combination with an organic solvent described later, heating is performed at a heating temperature corresponding to the type of solvent used, preferably at 50 to 170 °C, so as to semi-cure (or uncure) the above-mentioned resin composition to obtain a prepreg. As the mass ratio of the resin composition to the reinforced substrate used at this time, there is no particular limitation, and it is generally preferably adjusted so that the resin component in the prepreg becomes 20 to 60% by mass.

[0281] 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 allowing it to end. In addition, for example, the semi-cured product can have a degree of cure of, for example, 5% or more and 85% or less. On the other hand, the cured product in the present embodiment can have a higher degree of cure than the semi-cured product.

[0282] In addition, the degree of cure of the semi-cured product can be measured by DSC for the heat of cure during heating of the resin composition and the heat of cure of its semi-cured product, and calculated by the following formula.

[0283] Degree of cure (%) = [1 - (heat of cure of semi-cured product / heat of cure of resin composition)] × 100

[0284] As the organic solvent used in the manufacture of the prepreg, for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyldiglycol acetate, propylene glycol monomethyl ether acetate, etc. can be cited. Its selection and appropriate usage amount can be appropriately selected according to the use. For example, in the case of 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 less such as methyl ethyl ketone, acetone, dimethylformamide, etc. In addition, it is preferably used in a proportion such that the non-volatile component becomes 40 to 80% by mass.

[0285] [Circuit board]

[0286] The present disclosure is a circuit board as a laminate of the above-mentioned prepreg and copper foil. As a method for obtaining a printed circuit board from the resin composition of the present embodiment, the following method can be cited: laminating the above-mentioned prepreg by a conventional method, appropriately laminating copper foil, and heating and pressing at 170 to 300 °C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0287] [Laminated Film]

[0288] The present disclosure relates to a laminated film containing the resin composition of the present embodiment. As a method for manufacturing the laminated film of the present embodiment, a method can be cited in which the above resin composition is coated on a support film to form a resin composition layer, thereby manufacturing an adhesive film for a multilayer printed wiring board.

[0289] When manufacturing a laminated film from a resin composition, it is important that the film softens under the temperature conditions (usually 70 to 140 °C) of lamination in the vacuum lamination method, and at the same time as laminating with a circuit board, it shows fluidity (resin flow) capable of filling the resin into the vias or through holes present in the circuit board. It is preferable to blend the above components in such a way as to exhibit such characteristics.

[0290] Here, the diameter of the through hole of a multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is generally preferable to be able to fill the resin within this range. In addition, when laminating both sides of a circuit board, it is desirable to fill about 1 / 2 of the through hole.

[0291] Regarding the method for manufacturing the above adhesive film, specifically, after preparing the resin composition in a varnish form, the varnish-like composition can be coated on the surface of the support film (Y), and further dried by heating or hot air blowing, etc., to form a composition layer (X) containing the resin composition for manufacturing.

[0292] The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, and thus the thickness of the resin composition layer preferably has a thickness of 10 to 100 μm.

[0293] In addition, the composition layer (X) in the present embodiment can be protected by a protective film described later. By being protected by the protective film, it is possible to prevent the attachment and damage of garbage, etc. to the surface of the resin composition layer.

[0294] Examples of the above support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and metal foils such as release paper, copper foil, and aluminum foil. In addition, the support film and the protective film can be subjected to a release treatment in addition to MAD treatment and corona treatment.

[0295] The thickness of the support film is not particularly limited, usually 10 to 150 μm, and it is preferably used in the range of 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

[0296] After the above-mentioned support film (Y) is laminated on the circuit board, or after heating and curing to form an insulating layer, it is peeled off. If the adhesive film is heated and cured and then the support film (Y) is peeled off, it is possible to prevent the adhesion of garbage and the like in the curing process. In the case of peeling after curing, generally, a release treatment is performed on the support film in advance.

[0297] [Heat-resistant materials and electronic materials]

[0298] The cured product obtained from the resin composition containing an alkenyl compound of the present disclosure exhibits curability, and has excellent appearance and heat resistance, and thus 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, laminated films, laminated substrates, adhesives using conductive pastes, resist materials, and the like. In addition, 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, the alkenyl compound contained in the above resin composition exhibits excellent solubility in various solvents, and thus can be made into a coating. The heat-resistant members and electronic members obtained by such operations can be suitably used for various applications. For example, industrial machine parts, general machine parts, parts of automobiles / railways / vehicles, space / aerospace-related parts, electronic / electrical parts, building materials, container / packaging members, daily necessities, sports / leisure goods, housing members for wind power generation, etc. are exemplified, but are not limited thereto.

[0299] Examples

[0300] The present invention will be specifically described by way of Examples and Comparative Examples. Hereinafter, "parts" and "%" refer to mass basis unless otherwise specified. In addition, the physical properties of the synthesized alkenyl compound were measured as follows.

[0301] (1) Measurement of double bond equivalent (iodine value)

[0302] The double bond equivalent of the mixture containing an alkenyl compound obtained in the Examples was calculated according to JIS K 0070.

[0303] (2) GPC measurement

[0304] For the content ratio (area %) of the alkenyl compound in the mixture containing an alkenyl compound obtained in the Examples, it was calculated using the following measuring device and measuring conditions.

[0305] "Measuring device"

[0306] "HLC-8320GPC" manufactured by Tosoh Corporation

[0307] "Measuring conditions"

[0308] Column: Guard column "HXL-L" manufactured by Tosoh Corporation

[0309] + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0310] + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

[0311] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0312] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0313] Detector: RI (Differential Refractometer)

[0314] Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

[0315] Column temperature: 40 °C

[0316] Developing solvent: Tetrahydrofuran

[0317] Flow rate: 1.0 ml / min

[0318] Sample: A substance (50 μl) obtained by filtering a tetrahydrofuran solution in which the solid content of the mixture containing the alkenyl compound obtained in the examples is converted to 1.0 mass% using a microfilter

[0319] (3) FD-MS measurement

[0320] For the FD-MS spectrum of the mixture containing the alkenyl compound obtained in the examples, the following measuring apparatus and measuring conditions were used for measurement

[0321] "Measuring apparatus"

[0322] "JMS-T100GC AccuTOF" manufactured by JEOL Ltd

[0323] "Measuring conditions"

[0324] Measurement range: m / z = 4.00 - 2000.00

[0325] Rate of change: 51.2 mA / min

[0326] Final current value: 45 mA

[0327] Cathode voltage: -10 kV

[0328] Recording interval: 0.07 sec

[0329] (4) NMR measurement

[0330] Of the mixture containing an alkenyl compound obtained from the examples 1 1H-NMR spectrum and 13 13C-NMR spectrum were measured using the following measuring apparatus and measuring conditions.

[0331] "Measuring apparatus"

[0332] "JNM-ECA500" manufactured by JEOL RESONANCE

[0333] "Measuring conditions"

[0334] 1 1H-NMR spectrum

[0335] Resonance frequency: 500 MHz

[0336] Number of accumulations: 16 times

[0337] Solvent: chloroform-d

[0338] Sample concentration: 4 mass%

[0339] 13 13C-NMR spectrum

[0340] Resonance frequency: 125 MHz

[0341] Number of accumulations: 2000 times

[0342] Solvent: chloroform-d

[0343] Sample concentration: 30 mass%

[0344] (Example 1)

[0345] In a flask equipped with a thermometer, a fractionating tube, and a stirrer, 300 g (1.83 moles) of isoeugenol as an alkenylphenol compound, 15 g (0.18 moles) of 49% sodium hydroxide, 285 g of an epoxy resin (EXA-850CRP) having an epoxide compound represented by the chemical formula (X-1) (molecular weight: 340) as a main component (number of moles of glycidyl groups: 1.65 moles, refer to the following formula (X-1)), 0.50 g of tetrabutylammonium bromide, and 600 g of methyl isobutyl ketone were added. While purging with nitrogen, the temperature inside the system was raised to 120°C and stirring was continued for 3 hours.

[0346] After the reaction was completed, the temperature of the system was lowered to 80 °C, 300 g of a 12% aqueous solution of sodium dihydrogen phosphate was added, and the mixture was stirred for 15 minutes. The layers were allowed to stand and separated to remove the aqueous layer. Further, water was added to the methyl isobutyl ketone layer in which the reaction product was dissolved, and the mixture was stirred for 15 minutes. The layers were allowed to stand and separated to remove the aqueous layer. Azeotropic dehydration was carried out, and after precision filtration, the solvent was removed by distillation under reduced pressure to obtain a mixture (1) containing 89 area% of the alkenyl compound (1) represented by the following chemical formula (1-1.1). The softening point of the mixture (1) containing the alkenyl compound was 60 °C. The double bond equivalent of the mixture (1) containing the alkenyl compound was 341 g / mol. In addition, the FD-MS spectrum of the mixture (1) containing the alkenyl compound is shown in Figure 1 , and the 1 1H-NMR spectrum and 13 13C-NMR spectrum of the mixture (1) containing the alkenyl compound are shown in Figure 2A and Figure 2B .

[0347]

[0348] Chemical formula (1-1.1):

[0349]

[0350] (Example 2)

[0351] The type of the epoxy compound was changed to an epoxy resin (EXA-830CRP (number of moles of glycidyl group: 1.65 moles)) having the epoxy compound represented by the chemical formula (X-2) (molecular weight: 312) as a main component. Otherwise, the same operations as in Example 1 were carried out to obtain a mixture (2) containing 85 area% of the alkenyl compound (2) represented by the following chemical formula (1-1.2). The softening point of the mixture (2) containing the alkenyl compound was 58 °C. The double bond equivalent of the mixture (2) containing the alkenyl compound was 328 g / mol.

[0352]

[0353] Chemical formula (1-1.2):

[0354]

[0355] In addition, regarding the chemical structure, molecular weight, etc. of the alkenyl compound (2) represented by the obtained chemical formula (1-1.2), in the same manner as in Example 1, they were confirmed by FD-MS spectrum, 1 1H-NMR spectrum and 13 13C-NMR spectrum.

[0356] (Example 3)

[0357] The type of epoxy compound was changed to an epoxy resin (HP-4032D (number of moles of glycidyl group: 1.65 moles)) having an epoxy compound represented by the chemical formula (X-3) (molecular weight: 272) as the main component. Except for this, the same operations as in Example 1 were carried out, and a mixture (3) containing an alkenyl compound (3) represented by the following chemical formula (1-1.3) in an area of 88% was obtained. The softening point of the mixture (3) containing the alkenyl compound was 71 °C. The double bond equivalent of the mixture (3) containing the alkenyl compound was 310 g / mol.

[0358]

[0359] Chemical formula (1-1.3):

[0360]

[0361] In addition, for the chemical structure, molecular weight, etc. of the obtained alkenyl compound (3) represented by the chemical formula (1-1.3), in the same manner as in Example 1, through FD-MS spectrum, 1 H-NMR spectrum and 13 C-NMR spectrum were confirmed.

[0362] (Example 4)

[0363] The type of epoxy compound was changed to an epoxy resin (EXA-7250 (number of moles of glycidyl group: 1.65 moles)) having an epoxy compound represented by the chemical formula (X-4) (molecular weight: 493) as the main component. Except for this, the same operations as in Example 1 were carried out, and a mixture (4) containing an alkenyl compound (4) represented by the following chemical formula (1-1.4) in an area of 68% was obtained. The softening point of the mixture (4) containing the alkenyl compound was 83 °C. The double bond equivalent of the mixture (4) containing the alkenyl compound was 318 g / mol.

[0364]

[0365] Chemical formula (1-1.4):

[0366]

[0367] In addition, for the chemical structure, molecular weight, etc. of the obtained alkenyl compound (4) represented by the chemical formula (1-1.4), in the same manner as in Example 1, through FD-MS spectrum, 1 H-NMR spectrum and 13 C-NMR spectrum were confirmed.

[0368] (Example 5)

[0369] The type of epoxy compound was changed to an epoxy resin (HP-4700RC (number of moles of glycidyl group: 1.65 moles)) having an epoxy compound represented by the chemical formula (X-5) (molecular weight: 557) as the main component. Except for this, the same operations as in Example 1 were carried out, and a mixture (5) containing an alkenyl compound containing 68 area% of the alkenyl compound (5) represented by the following chemical formula (1-1.5) was obtained. The softening point of the mixture (5) containing the alkenyl compound was 98 °C. The double bond equivalent of the mixture (5) containing the alkenyl compound was 304 g / mol.

[0370]

[0371] Chemical formula (1-1.5):

[0372]

[0373] In addition, for the chemical structure, molecular weight, etc. of the obtained alkenyl compound (5) represented by the chemical formula (1-1.5), in the same manner as in Example 1, through FD-MS spectrum, 1 1H-NMR spectrum and 13 13C-NMR spectrum were confirmed.

[0374] (Example 6)

[0375] The type of epoxy compound was changed to an epoxy resin (YX-4000 (number of moles of glycidyl group: 1.65 moles)) having an epoxy compound represented by the chemical formula (X-6) (molecular weight: 354) as the main component. Except for this, the same operations as in Example 1 were carried out, and a mixture (6) containing an alkenyl compound containing 69 area% of the alkenyl compound (6) represented by the following chemical formula (1-1.6) was obtained. The softening point of the mixture (6) containing the alkenyl compound was 76 °C. The double bond equivalent of the mixture (5) containing the alkenyl compound was 334 g / mol.

[0376]

[0377] Chemical formula (1-1.6):

[0378]

[0379] In addition, for the chemical structure, molecular weight, etc. of the obtained alkenyl compound (6) represented by the chemical formula (1-1.6), in the same manner as in Example 1, through FD-MS spectrum, 1 1H-NMR spectrum and 13 13C-NMR spectrum were confirmed.

[0380] (Comparative Example 1)

[0381] Eugenol was changed to isoeugenol (1.83 moles), and otherwise, the same operation as in Example 1 was carried out to obtain a mixture (1) containing allyl compound (1) represented by the following chemical formula (C1) in an area of 92%. The mixture (1) containing allyl compound was semi-solid at room temperature. The double bond equivalent of the mixture (1) containing allyl compound was 339 g / mol.

[0382] Chemical formula (C1):

[0383]

[0384] In addition, for the chemical structure, molecular weight, etc. of the allyl compound (1) represented by the obtained chemical formula (C1), in the same manner as in Example 1, through FD-MS spectrum, 1 H-NMR spectrum and 13 C-NMR spectrum were confirmed.

[0385] (Example 7)

[0386] In a flask equipped with a thermometer, fractionating tube, and stirrer, 170 g (allyl mole number 0.5 mole) of the mixture (1) containing allyl compound obtained from Comparative Example 1, 5.6 g (0.1 mole) of potassium hydroxide, and 85 g of toluene were added. While performing nitrogen purge, the temperature inside the system was raised to 145 °C and stirring was continued for 6 hours.

[0387] After the reaction was completed, the temperature inside the system was lowered to 80 °C, 400 g of methyl isobutyl ketone and 180 g of 12% aqueous sodium dihydrogen phosphate solution were added, stirred and mixed for 15 minutes, and the aqueous layer was removed by standing and separating. Further, water was added to the methyl isobutyl ketone layer in which the reactants were dissolved, stirred and mixed for 15 minutes, and the aqueous layer was removed by standing and separating. Azeotropic dehydration operation was carried out, and after precision filtration, the solvent was distilled off under reduced pressure to obtain a mixture (7) containing 85% of the alkenyl compound (1) represented by the above chemical formula (1-1.1). The softening point of the resin was 59 °C. The double bond equivalent of the mixture (7) containing alkenyl compound was 345 g / mol.

[0388] In addition, for the chemical structure, molecular weight, etc. of the alkenyl compound (1) represented by the obtained chemical formula (1-1.1), in the same manner as in Example 1, through FD-MS spectrum, 1 H-NMR spectrum and 13 C-NMR spectrum were confirmed.

[0389] (Synthesis Example 1)

[0390] In a flask equipped with a thermometer, a fractionating tube, and a stirrer, while performing nitrogen purging, 244 g (2.0 moles) of 2,6-xylenol and 300 g of methanol were added and dissolved. 96 g (2.4 moles) of sodium hydroxide was added, and the temperature was raised to 60 °C to completely dissolve the sodium hydroxide. Then, it was cooled to 40 °C, and 184 g (2.4 moles) of allyl chloride was added dropwise over 3 hours. After the dropwise addition, the temperature was raised to 60 °C over 2 hours and further reacted for 4 hours.

[0391] After the reaction was completed, 46 g (0.47 mole) of phosphoric acid and 489 g of methyl isobutyl ketone were added, and the temperature was raised to 80 °C to distill off methanol. Then, neutralization washing was performed until the pH of the washing liquid became neutral. After repeating the washing 3 times with 244 g of water, the system was dehydrated and desolvated to synthesize an allyl ether compound.

[0392] Next, the obtained allyl ether compound was heated to 190 °C and stirred for 5 hours to effect Claisen rearrangement.

[0393] After the reaction was completed, it was cooled to 60 °C, 134 g (2.4 moles) of potassium hydroxide and 86 g of isopropyl alcohol were added to completely dissolve the potassium hydroxide. Then, while distilling off isopropyl alcohol, it was heated to 115 °C and reacted for 6 hours. After the reaction was completed, 238 g (2.4 moles) of phosphoric acid and 488 g of methyl isobutyl ketone were added, cooled to 80 °C, and neutralization washing was performed until the pH of the washing liquid became neutral. The washing was repeated 3 times with 244 g of water. Then, the system was dehydrated by azeotropy, and after precision filtration, the solvent was distilled off under reduced pressure. Then, the temperature was raised to 170 °C and distilled under reduced pressure to obtain 240 g of 4-allyl-2,6-xylenol with a purity of 95%.

[0394] (Example 8)

[0395] The type of the alkenylphenol compound was changed to 4-allyl-2,6-xylenol (1.83 moles) obtained from Synthesis Example 1. Otherwise, the same operations as in Example 1 were performed to obtain a mixture (9) containing an alkenyl compound (9) with an alkenyl compound content of 64 area% represented by the following chemical formula (1-1.9). The softening point of the mixture (9) containing the alkenyl compound was 47 °C. The double bond equivalent of the mixture (9) containing the alkenyl compound was 377 g / mole. Chemical formula (1-1.9):

[0396]

[0397] In addition, with respect to the chemical structure, molecular weight, etc. of the alkenyl compound (9) represented by the chemical formula (1-1.9) obtained above, in the same manner as in Example 1, through FD-MS spectrum, 1 1H-NMR spectrum and 13 13C-NMR spectrum were confirmed.

[0398] In addition, each raw material used in the above examples was obtained and prepared as follows.

[0399] EXA-850CRP: Bisphenol A type epoxy resin (manufactured by DIC Corporation)

[0400] EXA-830CRP: Bisphenol F type epoxy resin (manufactured by DIC Corporation)

[0401] HP-4032D: Naphthalene type epoxy resin (manufactured by DIC Corporation)

[0402] EXA-7250: Triphenylmethane type epoxy resin (manufactured by DIC Corporation)

[0403] HP-4700RC: Methylene bisnaphthalene type epoxy resin (manufactured by DIC Corporation)

[0404] YX-4000: Tetramethylbiphenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation)

[0405] Isoeugenol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0406] Eugenol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0407] <Examples 9 to 15 and Comparative Examples 2 to 4>

[0408] <<Preparation of Resin Composition and Production of Cured Product>>

[0409] The mixtures (1) to (6), (9) containing the alkenyl compound obtained in Examples 1 to 6, 8 above, the mixture (1) containing the allyl compound obtained in Comparative Example 1, the maleimide resin (8) represented by the following formula (8) (“BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd.), and a curing accelerator (DCPO (“PERCUMYL D”, manufactured by NOF Corporation, dicumyl peroxide) were compounded in the proportions shown in Table 1 below, and using two rolls, melt-kneaded at a temperature of 100 °C for 5 minutes to prepare the resin compositions of Examples 9 to 15 and Comparative Examples 2 to 4.

[0410]

[0411] Next, according to the steps described in the column of "-Production of cured product-", the resin compositions of Examples 9 to 15 and Comparative Examples 2 to 4 were cured to produce the cured products corresponding to the resin compositions of Examples 9 to 15 and Comparative Examples 2 to 4, respectively. Moreover, the physical property evaluations of gel time, appearance of the cured product, and glass transition temperature were carried out according to the following method. The results are shown in Table 1.

[0412] <<Measurement of gel time (curability)>>

[0413] 0.15 g of each resin composition prepared as shown in Table 1 below was placed on a hot plate heated to 175°C, and the time until it became gel-like (the fluidity did not become agar-like) was measured while stirring with a spatula. This operation was repeated three times, and the average value was used for evaluation.

[0414] <<Measurement of glass transition temperature (°C)>>

[0415] -Production of cured product-

[0416] Each resin composition prepared as shown in Table 1 below was poured into a mold frame of 11 cm × 9 cm × 2.4 mm, and using a press, after molding at a temperature of 175°C for 10 minutes, the molded product was taken out from the mold frame. Then, it was post-cured at a temperature of 175°C for 5 hours, and each cured product (thickness 2.4 mm) was obtained from the resin compositions of Examples 9 to 15 and Comparative Examples 2 to 4.

[0417] -Measurement of glass transition temperature (°C) of cured product-

[0418] Next, each cured product with a thickness of 2.4 mm prepared as above was cut into a size of 5 mm in width and 54 mm in length, and this was designated as test piece 1. Moreover, for this test piece 1, using a viscoelasticity measuring device (DMA: Solid viscoelasticity measuring device "RSAII" manufactured by Rheometrics, Rectangular Tension Method: frequency 1 Hz, heating rate 3°C / minute), the temperature at which the elastic modulus changed to the maximum (the change rate of tanδ was the largest) was set as the glass transition temperature (°C) and measured. The higher the glass transition temperature (°C), the more excellent the heat resistance.

[0419] <<Appearance of cured product>>

[0420] For each cured product obtained from the column of "-Production of cured product-" above, unevenness, cracks, voids, etc. were visually confirmed and evaluated according to the following criteria.

[0421] Evaluation criteria for appearance:

[0422] S: A transparent plate-shaped molded article without unevenness, cracks, or voids was obtained. A: A plate-shaped molded article with unevenness and voids was obtained.

[0423] C: Poor curing, cracks, etc. were present, and a plate-shaped molded article was not obtained.

[0424] [Table 1]

[0425]

[0426] From the results shown in Table 1 above, it was confirmed that by comparing Examples 9 to 15 with Comparative Examples 2 to 4, the curability (gel time) was excellent by using the alkenyl compounds of Examples 1 to 6 and 8, and excellent appearance and high heat resistance were achieved during curing.

[0427] Moreover, when the resin compositions of Examples 9 to 15 were prepared by dry blending using a mortar, some unevenness was observed in the obtained plate-shaped molded articles (evaluation results were S to A). Therefore, it was confirmed that in terms of the obtained cured product showing excellent appearance (suppressing voids or unevenness), the conventional manufacturing process (melt blending (e.g., melt blending at 110°C or lower)) was important. Therefore, it is considered that by combining the alkenyl compound of the present embodiment with the conventional manufacturing process conditions (melt blending (e.g., melt blending at 110°C or lower)), a synergistic effect is exerted, and the obtained cured product shows excellent appearance.

[0428] In addition, for the following reasons, in the resin compositions of Examples 9 to 15, the mixtures (1) to (6) and (9) containing the alkenyl compound were blended into the resin composition as described above. Except for using alkenyl compound (1) instead of the mixture (1) containing the alkenyl compound, no significant difference was confirmed between the evaluation results (gel time, appearance of the cured product, and glass transition temperature (°C)) of the resin composition prepared under the same composition and the same conditions as in Example 9 and the values of the evaluation results of Example 9. Therefore, in this example, the mixture containing the alkenyl compound was used.

[0429] Industrial Applicability

[0430] According to the present disclosure, it is possible to provide an alkenyl compound having excellent curability (gel time), and showing excellent appearance and high heat resistance during curing, a resin composition containing the alkenyl compound, and a cured product thereof.

Claims

1. An alkenyl compound represented by the following general formula (1): In the general formula (1), M 1 represents an n1-valent organic group, L 1 Indicates -O- or -S-, L 2 represents an alkylene group having 2 to 10 carbon atoms, wherein One or more -CH2- in the alkylene group may be substituted by -CH(-OH)-, -O- or -C(=O)-. M 2 Indicates that it can be substituted by R 3 Substituted cyclic groups, R 1 and R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number greater than or equal to 2 and less than or equal to 4.

2. The alkenyl compound according to claim 1, which is represented by the following general formula (1-1): In the general formula (1-1), M 1 represents an n1-valent organic group, L 1 Indicates -O- or -S-, M 2 Indicates that it can be substituted by R 3 Substituted cyclic groups, R 1 and R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number greater than or equal to 2 and less than or equal to 4.

3. The alkenyl compound according to claim 1, wherein M1 in the general formula (1) is a group representing any one of the following formulas (i) to (vi), In the above formulae (i) to (vi), "*" represents a bond with other atoms. The alkenyl compound according to claim 2 , wherein the epoxy compound and the alkenyl phenol compound are used as reaction raw materials. 5 . A resin composition comprising the alkenyl compound 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, comprising the resin composition according to claim 5 . 8 . A semiconductor sealing material, comprising the resin composition according to claim 5 . 9 . A laminated film formed using the resin composition according to claim 5 .

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