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

Abstract

To provide an alkenyl compound that offers superior curability (gel time) and demonstrates superior appearance and high heat resistance during a curing process, a resin composition containing the alkenyl compound, and a cured product thereof.SOLUTION: 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 formed using the resin composition, a semiconductor encapsulating material formed using the resin composition, and a build-up film formed using the resin composition.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Prepregs obtained by impregnating a thermosetting resin, such as epoxy resin or BT (bismaleimide-triazine) resin, into a glass cloth and drying it by heating, laminates obtained by heating and curing the prepregs, and multilayers obtained by combining the laminates and the prepregs and curing them by heating are widely used as circuit board materials for electronic devices. In particular, package substrates, which are a type of printed wiring board that serves as an interposer for mounting semiconductors, are becoming thinner and warping of the package substrate during mounting is becoming a problem, so that materials that exhibit high heat resistance are required to suppress warping of the package substrate during mounting. Recently, in various electrical material applications such as semiconductor encapsulation materials and printed circuit boards, especially in advanced material applications, there is a demand for materials and compositions that have improved performance, such as heat resistance and dielectric properties, and that combine these. In particular, in the power semiconductor field, the use of SiC-based devices is becoming more widespread due to their high conversion efficiency and the possibility of achieving miniaturization and weight reduction. Since SiC-based devices can operate at high temperatures, next-generation power semiconductor encapsulation materials are required to have high heat resistance to ensure operational reliability at high temperatures. Conventional semiconductor encapsulation materials have used epoxy resins, which have an excellent balance of physical properties such as heat resistance and moisture resistance, but in order to achieve even higher heat resistance, studies are underway to use them in combination with or replace them with resins with higher heat resistance (Tg), such as maleimide resins, benzoxazine resins, or cyanate resins. For example, Patent Document 1 describes an alkenyl group-containing compound and a curable resin composition that exhibit excellent heat resistance and low dielectric properties when cured as a sealing material for semiconductor elements, and a cured product thereof. [Prior art documents] [Patent documents]

[0003] Patent Document 1 International Publication No. 2019-198606 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0004] However, in the technology of Patent Document 1, although heat resistance and low dielectric characteristics are considered, the curing time and appearance are not considered at all. Further, Patent Document 1 describes that a radical polymerization initiator is used and experimental data are provided for the purpose of (radical) reacting alkenyl groups of an alkenyl group-containing compound with each other or an alkenyl group and a maleimide group. However, Patent Document 1 does not consider at all the problems of the curability of the maleimide resin itself, for example, in a curable resin composition containing an epoxy resin and a maleimide resin, the point that it cannot be completely cured under conventional curing conditions, and the point that cracks occur during curing because it is hard and brittle. Therefore, the technical problem to be solved by the present disclosure is to provide an alkenyl compound having excellent curability and showing an excellent appearance with reduced voids or unevenness during curing, a resin composition containing the alkenyl compound, and a cured product thereof. MEANS FOR SOLVING THE PROBLEMS

[0005] As a result of intensive studies to solve the above-described problems, the present inventors have found that an alkenyl compound, a resin composition containing the alkenyl compound, and a cured product thereof having an excellent chemical structure represented by the general formula (1) can have excellent curability and show an excellent appearance with reduced voids or unevenness during curing, and have completed the present invention. In addition, since the alkenyl compound of the present disclosure can also use a plant-derived raw material (biomass raw material) as a reaction raw material, it has moldability adaptable to a conventional manufacturing process, and provides an alkenyl compound and a resin composition with a low environmental load derived from a biomass raw material.

[0006] [1] An alkenyl compound represented by the following general formula (1). [Chemical formula] (In the above general formula (1), M 1 represents an n1-valent organic group, L 1 represents -O- or -S-, L 2 represents an alkylene group having 2 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O- or -C(=O)-, M 2 represents a cyclic group which may be substituted by a substituent R 3 , R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n1 represents a natural number of 2 or more and 4 or less.)

[0007] [2] The alkenyl compound according to [1], represented by the following general formula (1-1). [Chemical formula] (In the above general formula (1-1), M 1 represents an n1-valent organic group, L 1 represents -O- or -S-, M 2 represents a cyclic group which may be substituted by a substituent R 3 , R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n1 represents a natural number of 2 or more and 4 or less.)

[0008] [3] The alkenyl compound according to [1] or [2], wherein M 1 in the general formula (1) represents a group represented by any one of the following formulas (i) to (vi). [Chemical formula] (In the above formulas (i) to (vi), “*” represents a bond that binds to other atoms.)

[0009] [4] The alkenyl compound according to any one of [1] to [3], which uses an epoxy compound and an alkenylphenol compound as reaction raw materials.

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

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

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

[0013] [8] A semiconductor encapsulating material using the resin composition according to [5].

[0014] [9] A build-up film using the resin composition according to [5]. [Advantages of the Invention]

[0015] According to the present disclosure, there is provided an alkenyl compound having excellent curability and showing an excellent appearance with reduced voids or unevenness during curing. According to the present disclosure, a resin composition in the coexistence of an alkenyl compound and a compound or resin having a maleimide group has a short gel time and can complete a curing reaction with the compound or resin having the maleimide group at a conventional curing temperature (for example, 175° C. or lower). According to the present disclosure, a curing reaction can proceed with respect to the maleimide group by a pericyclic reaction. According to the present disclosure, it is possible to provide a resin composition containing an alkenyl compound having excellent curability and showing an excellent appearance with reduced voids or unevenness during curing, and a cured product thereof. Such a cured product is particularly useful in printed wiring boards, semiconductor encapsulating materials, build-up films, and the like. According to the present disclosure, since compounds derived from biomass can be used as reaction raw materials, the environmental load can be reduced, and the composition in the coexistence with a compound or resin having a maleimide group has a short gel time and can complete the curing reaction with the compound or resin having a maleimide group at a conventional curing temperature.

Brief Description of Drawings

[0016]

Figure 1

Figure 2A

Figure 2B

Embodiments for Carrying Out the Invention

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

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

[0019] [Alkenyl compound] The alkenyl compound of this embodiment is represented by the following general formula (1). [Chemical formula] (In the above general formula (1), M 1 represents an n1-valent organic group, L 1 represents -O- or -S-, L 2 represents an alkylene group having 2 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O- or -C(=O)-, M 2 represents a cyclic group which may be substituted by a substituent R 3 , R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number of 2 or more and 4 or less.) Thereby, it has excellent curability and exhibits an excellent appearance with reduced voids or unevenness during curing. Further, in a composition in which the alkenyl compound represented by the general formula (1) and a compound or resin having a maleimide group coexist, the gel time is short, and the curing reaction with the compound or resin having a maleimide group can be completed at a conventional curing temperature (for example, 175 ° C or lower).

[0020] In the general formula (1) above, 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. The organic group is a group whose chemical structure is formed by an organic compound containing one or more carbon atoms being in the form of an n1-valent (divalent to tetravalent) group, and refers to an atomic group obtained by removing n1 hydrogen atoms from an organic compound containing one or more carbon atoms. As the organic group, a group having a hydrocarbon group is preferable, a group having a cyclic hydrocarbon group is more preferable, and a group having an aromatic ring is even more preferable. When the organic group is a group having a cyclic hydrocarbon group, it is easy to exhibit the effects of low dielectric characteristics and low moisture absorption. Furthermore, when it is a group having an aromatic ring, it is easy to exhibit the effects of high heat resistance and high flame retardancy. The number of carbon atoms of the organic group is preferably 1 to 50, more preferably 6 to 40, even more preferably 10 to 30, and still more preferably 10 to 20. When the number of carbon atoms of the organic group is 10 or more, the distance between crosslinking points becomes long, so it is easy to suppress cracks generated during curing. When the number of carbon atoms of the organic group is 20 or less, the viscosity becomes low, so it is easy to highly fill the filler. Preferred M in the general formula (1) 1 is preferably a chemical structure having a rigid part (so-called mesogenic structure, for example, a cyclic group) and a linear or branched linking group, a cyclic group having 6 to 30 carbon atoms, and a carbon atom number of 1 to 8 bonded to the carbon atoms in the cyclic group. It preferably has a linear or branched alkylene group (one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O- or -C(=O)-). M in the general formula (1) 1 By having a linking group of a predetermined length, M which is a cyclic group 2 can take an appropriate distance, and M 1 and M 2 can ensure a flexible relative positional relationship with each other, so it is considered that steric hindrance is reduced and the pericyclic reaction with the bulky maleimide group proceeds easily. M in the general formula (1) 1 As an example, it is preferably a group represented by the following formulas (I) to (VI).

Chemical formula

[0021] M in the general formula (1) above 1 is particularly preferably one or more selected from the groups represented by the following formulas (i) to (vi). [Chemical formula] (In the above formulas (i) to (vi), "*" indicates a bond that binds to other atoms.) In the groups represented by the above formulas (i) to (iv), the linking group -O-* is preferably bonded to the carbon atom at the para-position (4-position) of each benzene ring. In the group represented by the above formula (v), the linking group -O-* is preferably bonded to one of the carbon atoms at the 1st to 4th positions and one of the carbon atoms at the 5th to 8th positions of the naphthalene ring, respectively. In the group represented by the above formula (vi), the linking group -O-* is preferably bonded to one of the carbon atoms at the 1st to 4th positions and one of the carbon atoms at the 5th to 8th positions of each naphthalene ring, respectively. Among the groups represented by the above formulas (i) to (vi), from the viewpoint of low viscosity, the above formulas (i), (ii), (iv), and (v) are preferable. Incidentally, M in the general formula (1) 1 is included in the group (so-called residue) derived from the epoxy compound described later.

[0022] In the general formula (1) above, L 1 represents -O- or -S-, and -O- is preferable from the viewpoint of suppressing the corrosion deterioration of the Cu wire. Incidentally, L in the general formula (1) 1 is included in the group (so-called residue) derived from the alkenylphenol compound described later. In the general formula (1) above, L 2 represents an alkylene group having 2 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O-, or -C(=O)-. In the general formula (1), L 2 has a molecular chain of a predetermined length, so that a plurality of M which are cyclic groups 2They can maintain an appropriate distance from each other, and M 1 and a plurality of M 2 can respectively ensure a flexible relative positional relationship with each other, so it is considered that the three-dimensional obstacle is reduced and the pericyclic reaction with the bulky maleimide group proceeds easily. In addition, by having a flexible alkylene group, the melting point (softening point of the resin) of the compound can be lowered, so that it is compatible with the maleimide resin under conventional kneading conditions and a uniform composition and cured product can be produced. On the other hand, when the number of carbon atoms of L 1 is 1, the rigidity is high and the melting point is high, so it is considered that it becomes difficult to be compatible with the maleimide resin under conventional kneading conditions. As a result, by having a molecular chain of a predetermined length for L 2 , an alkenyl compound can be provided that exhibits an excellent appearance with reduced voids or unevenness during curing. For L 2 in the general formula (1) above, the number of carbon atoms may preferably be 2 to 9, more preferably 2 to 8, and still more preferably 3 to 6. Also, L 2 in the general formula (1) above is preferably linear or branched. L 2 By having a molecular chain of a predetermined length, an alkenyl compound can be provided that exhibits an excellent appearance with reduced voids or unevenness during curing. For L 2 in the general formula (1) above, 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)- is preferred. However, 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 is an integer of 2 or more and 9 or less.​​​ As a result, the peri-cyclic reaction with the bulky maleimide group proceeds easily, and it is considered to be easily compatible with the maleimide resin. As a result, a uniform composition and cured product can be produced, and it is considered that, at the time of curing, an excellent appearance with reduced voids or unevenness is exhibited. In the general formula (1), L 2 is included in a group (so-called residue) derived from an epoxy compound described later, an alkenyl group, and a group (so-called residue) derived from an aromatic hydrocarbon-containing compound having a second reactive functional group (particularly, an alkenylphenol compound).

[0023] In the general formula (1) above, M 2 represents a cyclic group which may be substituted by a substituent R 3 , and is preferably a divalent cyclic group which may be substituted by a substituent R 3 . The cyclic group preferably has 5 to 14 carbon atoms, more preferably 6 to 12, still more preferably 6 to 10, and still more preferably 6. The cyclic group refers to an atomic group in which the constituent atoms are cyclically bonded, and includes a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic ring, a ring assembly, a polycyclic structure (for example, a bicyclic structure), an aromatic group, a non-aromatic group, etc., and may be a group combining these. Further, the cyclic group may contain at least one hetero atom, and furthermore, any at least one hydrogen atom in the cyclic group may be substituted by at least one substituent R 3 (for example, an electron-donating group).

[0024] As the cyclic group, it preferably has an aromatic ring (including a heteroaromatic ring), and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, or a ring assembly aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. Examples of the condensed aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples of the ring assembly aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. Therefore, M in the general formula (1) above 2 When it has an aromatic ring as a divalent cyclic group, a preferable divalent cyclic group can be a group obtained by removing any two hydrogen atoms from each of the above-exemplified aromatic rings. When the cyclic group has an aromatic ring, it can form a diene structure, so the Diels-Alder reaction with the maleimide group proceeds easily, and it has the effect of being more excellent in curability. In addition, since the Diels-Alder reaction has high reactivity, low-temperature curing is possible with a compound having an unsaturated group such as a maleimide group. Also, M in the general formula (1) above 2 When it has an aromatic ring as a divalent cyclic group, one or more hydrogen atoms of the aromatic ring may be substituted by one or more substituents R 3 The substituent R 3 is preferably an electron-donating group, and 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.

[0025] The cyclic group is more preferably any one of the following groups (a) to (e), still more preferably any one of the groups (b) to (e), still more preferably the group (b) or (c), and has one or more substituents R 3 and is more preferably a 1,4-phenylene group which may be substituted by the substituent R (a) A 1,4-cyclohexylene group which may be substituted by the substituent R 3 (in this group, one -CH2- or two or more non-adjacent -CH2- present therein may be replaced by -O-, or one or more -CH2-CH2- present in the 1,4-cyclohexylene group may be replaced by an ethenylene group (-CH=CH-).) (b) A 1,4-phenylene group which may be substituted by the substituent R 3 (in this group, one -CH= or two or more non-adjacent -CH= present therein may be replaced by -N=).) (c) A 1,3-phenylene group which may be substituted by the substituent R 3 (in this group, one -CH= or two or more non-adjacent -CH= present therein may be replaced by -N=). (d) A 1,2-phenylene group which may be substituted by the substituent R 3 (in this group, one -CH= or two or more non-adjacent -CH= present therein may be replaced by -N=), and (e) A naphthalenediyl group which may be substituted by the substituent R 3 (in the naphthalenediyl group, one -CH= or two or more non-adjacent -CH= present therein may be replaced by -N=). In the groups (a), (b), (c), (d) and (e) above, the substituent R 3 is preferably an electron-donating group, specifically, 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. When the cyclic group is any one of the groups (a) to (e), the alkenyl group adopts a planar conformation, reducing steric hindrance and facilitating the pericyclic reaction with the bulky maleimide group, resulting in a more excellent curability effect. Further, when the cyclic group is any one of the groups (b) to (e), an electron-rich diene structure is formed, facilitating the Diels-Alder reaction with the maleimide group and resulting in a more excellent curability effect. Furthermore, when the cyclic group is the group (b) or (c), the two ortho positions of the alkenyl group can be reaction sites, facilitating the Diels-Alder reaction with the maleimide group and resulting in a more excellent curability effect. Also, due to the high reactivity of the Diels-Alder reaction, low-temperature curing is possible with a compound having an unsaturated group such as a maleimide group.

[0026] In the above general formula (1), M 2 The cyclic group which is is preferably a group having one or more unsaturated bonds. 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 preferably have a diene structure (= conjugated diene), or more preferably, the cyclic group itself has a diene structure (= conjugated diene). Thereby, in addition to the Alder-ene reaction, a faster Diels-Alder reaction is likely to proceed, resulting in a more excellent curability effect. Also, since the alkenyl compound represented by the general formula (1) requires the -CR 1 =CR 2 -CH3 moiety, the relative positional relationship between the one or more unsaturated bonds in the cyclic group where M 2 is and the double bond in the -CR 1 =CR 2 -CH3 moiety is likely to form a so-called 1,3-butadiene skeleton. In the general formula (1), the divalent cyclic group preferably has a ring structure having a diene structure, and more preferably has a diene structure fixed in the s-cis conformation. As a result, the cyclic group can be a substrate for the Diels-Alder reaction with a maleimide group which is a dienophile (so-called dieneophile). 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 made relatively low (for example, 200°C or lower (preferably 175°C or lower)).

[0027] In general formula (1), preferred M 2 is a divalent cyclic group having one or more unsaturated bonds which may be substituted by substituent R 3 , and the carbon-carbon double bond at the -CR 1 =CR 2 -CH3 moiety in general formula (1) and the one or more unsaturated bonds in the divalent cyclic group have a diene structure (= conjugated diene), or the divalent cyclic group itself has a diene structure (= conjugated diene). Furthermore, it is more preferable that the diene structure (= conjugated diene) is a diene structure fixed in the s-cis conformation, and it is even more preferable that the substituent R 3 is an electron-donating group. Due to the carbon-carbon double bond at the -CR 2 =CR 1 -CH3 moiety bonded to M 2 in general formula (1) and the one or more unsaturated bonds in the divalent cyclic group which is M 2 satisfying the relationship of a diene structure (= conjugated diene), the Diels-Alder reaction by heat between the maleimide group and the diene structure can proceed, so that the curability is improved. Furthermore, by the diene structure (= conjugated diene) satisfying the relationship of the s-cis conformation, it becomes easier to be a substrate for the Diels-Alder reaction with the maleimide group. As defined by the Woodward-Hoffmann rules, in the cycloaddition of two molecules, in thermal reactions, the reaction is regulated by the HOMO of the diene (the diene structure in the general formula (1), for example, a cyclic group and a propenyl group) and the LUMO of the dienophile (maleimide group), and in photochemical reactions, the reaction is regulated by both LUMOs. Therefore, an electron-rich diene having a strong electron-donating group has a smaller energy difference between the HOMO of the diene and the LUMO of the maleimide group, so the reaction proceeds more easily at a lower temperature. In other words, if the substituent R 3 is an electron-donating group, the HOMO of the diene to which the substituent R 3 is attached increases, so the Diels-Alder reactivity with the maleimide group can be enhanced. As a result, the reaction proceeds more easily at a lower temperature, and it is considered that the curability is improved. Therefore, in the alkenyl compound having a 1-propenylbenzene (β-methylstyrene) skeleton shown in the examples (for example, Example 1) which is an example of the present embodiment, by introducing a methoxy group as the electron-donating substituent R 3 to the aromatic ring, it was confirmed that the Diels-Alder reactivity with the maleimide group can be enhanced. Further, since two alkoxy groups are substituted in the alkenyl compound described in the examples, it has been found that the reactivity with the maleimide group is higher than that of the unsubstituted or monosubstituted 1-propenylbenzene skeleton. In addition, since the alkenyl compound of the present embodiment has a flexible and polar specific chemical structure (particularly, a 2-hydroxypropylene ether skeleton), the softening point is lowered, and it is compatible with a maleimide resin or the like at a relatively low kneading temperature (for example, 110 ° C (preferably 100 ° C)), and a uniform composition can be prepared. In the above general formula (1), specific examples of M 2 include a phenylene group having an alkoxy group having 1 to 12 carbon atoms as the electron-donating substituent R 3 , and a phenylene group having an alkyl group having 1 to 12 carbon atoms as the electron-donating substituent R 3 are preferred. In addition, M in the general formula (1) 2It is contained in a group (so-called residue) derived from an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group described later (particularly, an alkenylphenol compound).

[0028] In the general formula (1) 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. Substituent R 3 From the viewpoint of raising the HOMO of the cyclic group to which it is bonded, substituent R 3 is more preferably a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0029] In the general formula (1) above, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 1 and R 2 are each more preferably independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. R 1 and R 2 When they are hydrogen atoms, a pericyclic reaction with a double bond such as a maleimide group easily proceeds. In addition, R 1 and R 2 in the general formula (1) are contained in a group (so-called residue) derived from an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group described later (particularly, an alkenylphenol compound). In the general formula (1) above, n1 represents a natural number of 2 or more and 4 or less, preferably 2 or 3, and more preferably 2.

[0030] The alkenyl compound of this embodiment is more preferably represented by the following general formula (1-1).

Chemical formula

[0031] The alkenyl compound of this embodiment is preferably one or more compounds selected from the group consisting of the following general formulas (1.1) to (1.9).

Chemical formula

Chemical formula

Chemical formula

[0032] (Physical properties of alkenyl compound) <Double bond equivalent of alkenyl compound (g / mol)> The double bond equivalent (g / mol) of the alkenyl compound of this embodiment is preferably 100 g / mol or more and 1000 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less, and even more preferably 300 g / mol or more and 600 g / mol or less. The "double bond equivalent (g / mol)" in this specification is an amount that serves as an index for the amount of double bonds contained in a molecule. For compounds with the same molecular weight, the smaller the numerical value of the double bond equivalent, the greater the tendency for the introduced amount of double bonds to be larger. The said "double bond equivalent (g / mol)" is a calculated value obtained from the methods described in the following method and examples columns. Regarding the preferable range of the above double bond equivalent (g / mol), the respective upper limits and lower limits can be appropriately combined and changed. - Method for calculating the double bond equivalent of an alkenyl compound - The double bond equivalent, which is the content of carbon-carbon double bonds in the alkenyl compound of this embodiment, is calculated using the iodine value method in accordance with JIS K0070:1992.

[0033] <Molecular weight of the alkenyl compound> The molecular weight of the alkenyl compound of this embodiment is preferably in the range of 300 to 2000, more preferably in the range of 400 to 1500, and even more preferably in the range of 500 to 1000. The measurement of the molecular weight of the alkenyl compound of this embodiment is as described in the examples below, and is performed by FD-MS measurement.

[0034] (Another aspect of the alkenyl compound) The alkenyl compound of this embodiment preferably uses, as reaction raw materials, an aliphatic or aromatic hydrocarbon-containing compound having a first reactive functional group and an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group. Examples of the first reactive functional group in the aliphatic or aromatic hydrocarbon-containing compound having the first reactive functional group include a glycidyl group, a halogenated alkyl group, a hydroxyl group, a carboxylic acid group, and -C(=O)-X (where X is a halogen atom). Examples of the second reactive functional group in the aromatic hydrocarbon-containing compound having the alkenyl group and the second reactive functional group include a halogen atom, a hydroxyl group, a mercapto group, and a glycidyl group.

[0035] As the aliphatic or aromatic hydrocarbon-containing compound having the first reactive functional group, for example, a compound having a structure represented by the following general formula (4) is preferable. [Chemical Formula] (In the above general formula (4), M 6 represents an aliphatic or aromatic hydrocarbon group, preferably represents a tetravalent aromatic ring, L 3 each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -O- or -C(=O)-, Y 1 represents the first reactive functional group, and each independently is one selected from the group consisting of a halogen atom, a hydroxyl group, a glycidyl group, a carboxylic acid group, and -C(=O)-X (X is a halogen atom), and n4 represents an integer of 2 or more and 4 or less.)

[0036] M in the above general formula (4) 6 represents a divalent to tetravalent aliphatic hydrocarbon group or a divalent to tetravalent aromatic hydrocarbon group. The aliphatic hydrocarbon group is an acyclic divalent to tetravalent aliphatic hydrocarbon group, which may be linear or branched. Further, the aliphatic hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon group, and more preferably a linear saturated hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 13 carbon atoms. For example, examples of the divalent acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms which may have a substituent include alkanediyl groups such as methanediyl group, ethanediyl group, n-propanediyl group, i-propanediyl group, n-butanediyl group, n-pentanediyl group, n-hexanediyl group, n-heptanediyl group, n-octanediyl group, n-nonanediyl group, and n-decanediyl group. Similarly, the trivalent acyclic aliphatic hydrocarbon group which may have a substituent refers to a group obtained by removing any one hydrogen atom from the above divalent acyclic aliphatic hydrocarbon group. Further, the trivalent acyclic aliphatic hydrocarbon group which may have a substituent refers to a group obtained by removing any two hydrogen atoms from the above divalent acyclic aliphatic hydrocarbon group.

[0037] The number of carbon atoms of the divalent to tetravalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 12, and even more preferably 6 to 10. Further, examples of the divalent to tetravalent aromatic hydrocarbon group include a divalent to tetravalent group having an aromatic ring. As the aromatic ring, the content of the aromatic ring exemplified in M in the above general formula (1) 2 is incorporated. Preferred embodiments of the divalent aromatic hydrocarbon group include a group obtained by removing any two hydrogen atoms from the above aromatic ring, and a phenylene group, a naphthylene group, an anthracenediyl group, a biphenylene group, or a phenanthrylene group is more preferred. Preferred embodiments of the trivalent aromatic hydrocarbon group include a group obtained by removing any three hydrogen atoms from the above aromatic ring. Further, as the aromatic ring, the same aromatic ring as the above divalent aromatic hydrocarbon group is incorporated. Among the trivalent aromatic hydrocarbon groups, a benzenetriyl group, a naphthalenetriyl group, an anthracenetriyl group, a biphenylenetriyl group, or a phenanthrenetriyl group is more preferred. As a preferred embodiment of the tetravalent aromatic hydrocarbon group, a group obtained by removing any four hydrogen atoms from the above aromatic ring can be mentioned. Further, as the aromatic ring, the same aromatic ring as the divalent aromatic hydrocarbon group described above is adopted. Among the tetravalent aromatic hydrocarbon groups, a benzene tetrayl group, a naphthalene tetrayl group, an anthracene tetrayl group, a biphenylene tetrayl group, or a phenanthrene tetrayl group is more preferable. The above divalent to tetravalent aliphatic hydrocarbon group or divalent to tetravalent aromatic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms); an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group; a halogen atom; a hydroxyl group and the like.

[0038] In addition, as a preferred embodiment of the aliphatic or aromatic hydrocarbon-containing compound having the first reactive functional group, an epoxy compound (for example, an epoxy compound having an aromatic ring), a divalent to tetravalent alkyl halide compound (for example, an aromatic compound having 2 to 4 halogenated alkyl 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.

[0039] As the aromatic hydrocarbon-containing compound having the alkenyl group and the second reactive functional group, for example, a compound having a structure represented by the following general formula (5) is preferable.

Chemical formula

[0040] The alkenyl compound of this embodiment is preferably used as any one of the following reaction raw materials (Z1) to (Z4), more preferably used as any one of the reaction raw materials (Z1) or (Z4), and even more preferably used as the reaction raw material (Z1). (Z1) The alkenyl compound of this embodiment uses an epoxy compound (preferably a divalent to tetravalent epoxy compound) and an alkenylphenol compound, an alkenylthiophenol compound, or an alkenylnaphthol compound having one alkenyl group as reaction raw materials. (Z2) The alkenyl compound of this embodiment uses a divalent to tetravalent alkyl halide compound and an alkenylphenol compound, an alkenylthiophenol compound, or an alkenylnaphthol compound having one alkenyl group as reaction raw materials. (Z3) The alkenyl compound of this embodiment uses a carboxylic acid halide having a valence of 2 to 4 and an alkenylphenol compound, an alkenylthiophenol compound, or an alkenylnaphthol compound having one alkenyl group as reaction raw materials. (Z4) The alkenyl compound of this embodiment uses a phenol compound or an alcohol compound having a valence of 2 to 4 and an alkenylphenyl glycidyl ether compound having one alkenyl group as reaction raw materials. Among these, it is more preferable that the alkenyl compound of this embodiment uses an epoxy compound and an alkenylphenol compound having one alkenyl group as reaction raw materials, and it is particularly preferable to use an epoxy compound and eugenol or isoeugenol as reaction raw materials. Generally, eugenol is a component contained in spices such as cloves and laurel, and is a biomass compound derived from a natural product classified as a so-called monophenol propanoid. Therefore, by using eugenol or isoeugenol obtained by the isomerization reaction of the eugenol as a reaction raw material, the environmental load can be reduced.

[0041] <Epoxy compound> It is preferable that the alkenyl compound of this embodiment uses an epoxy compound as a reaction raw material. The epoxy compound of this 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 is simply referred to as an epoxy compound. Although various epoxy compounds can be used, a polyvalent epoxy compound having 2 or more and 4 or less epoxy groups in one molecule is preferable. Further, the epoxy compound is a compound having a structure represented by the general formula (4), and Y in the general formula (4) 1 is preferably a compound when it is a glycidyl group.

[0042] Specific examples of the polyvalent epoxy compound include those obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenols, polyhydric alcohols, glycidyl ether type epoxy resins such as 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, novolak type, phenol novolak type, orthocresol novolak type, tris(hydroxyphenyl)methane type, tetraphenylolethane type, phenyl aralkyl type, biphenyl aralkyl type, dicyclopentadiene phenol type, etc. can be exemplified. In addition, glycidyl ester type epoxy resins obtained by condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives and fatty acids, glycidyl amine type epoxy resins obtained by reaction of epichlorohydrin with amines, cyanuric acids, hydantoins, and further epoxy resins modified by various methods can be mentioned, but are not limited thereto. 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, and preferably 250 or more and 350 or less. Thereby, excellent curability and excellent appearance effects are achieved. Note that the molecular weight of the epoxy compound is calculated by FD-MS measurement as described in the examples described later.

[0043] The epoxy compound of the present embodiment is preferably represented by the following general formula (2).

Chemical formula

[0044] <Alkenylphenol compound> The alkenyl compound of the present embodiment preferably uses an alkenylphenol compound as a reaction raw material. Further, the alkenylphenol compound of the present embodiment is preferably 4-propenyl-2,6-xylenol, eugenol, and isoeugenol, more preferably eugenol and isoeugenol, and even more preferably isoeugenol. The alkenylphenol compound refers to an aromatic compound in which an optionally substituted alkenyl group, a phenolic hydroxyl group, and the alkenyl group and the hydroxyl group are bonded, and the alkenylphenol compound has a structure represented by the general formula (5), and Y in the general formula (5) 2 is preferably a compound when it is a hydroxyl group. When the alkenylphenol compound of the present embodiment is isoeugenol, that is, in the above general formula (5), Ar 1 is a benzene ring, R 51 is a propenyl group (1-propenyl group), R 52 is a methoxy group, L 5 is a single bond, Y 2 is a hydroxyl group, and when n51 and n52 are each 1, plant-derived isoeugenol can be incorporated into the chemical structure of the target alkenyl compound, so that a compound with reduced environmental impact can be provided.

[0045] (Alkenyl compound-containing mixture) The present disclosure may be an alkenyl compound-containing mixture containing an alkenyl compound represented by the general formula (1). The content of the alkenyl compound represented by the general formula (1) of the present embodiment can be calculated by area% of GPC by the method described later, and is preferably 20 area% or more, more preferably 40 area% or more and 100 area% or less, and even more preferably 60 area% or more and 100 area% or less with respect to the total amount (100 area%) of the alkenyl compound-containing mixture. When the content of the alkenyl compound represented by the general formula (1) in the mixture is 20 area% or more, its effects can be exhibited. Components other than the alkenyl compound represented by the general formula (1) contained in the alkenyl compound-containing mixture can be by-products and multimers generated in the production process of the reaction raw material and the epoxidation process.

[0046] (Method for producing alkenyl compound) Hereinafter, the method for producing the alkenyl compound of the present disclosure will be described. The production method of the alkenyl compound of the present embodiment is not particularly limited as long as it can produce the compound represented by the general formula (1). For example, as the method for producing the alkenyl compound of the present disclosure, an aliphatic or aromatic hydrocarbon-containing compound having a first reactive functional group represented by the general formula (4) and an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group represented by the general formula (5) can be used as reaction raw materials. In addition, known synthesis conditions and synthesis methods can be considered for the method for producing the alkenyl compound. Hereinafter, for the sake of convenience of explanation, as an example, the case where an epoxy compound and an alkenylphenol compound are used as reaction raw materials in the method for producing the alkenyl compound of the present disclosure will be described. As an example of the method for producing the alkenyl compound of the present disclosure, for example, a production method including the following step (1) and step (2) and step (3) provided as necessary can be mentioned. Step (1): A step of reacting an epoxy compound and an alkenylphenol compound as reaction raw materials; Step (2): A step of purifying the reaction product from a mixture containing the reaction product of the epoxy compound and the alkenylphenol compound; Step (3): The case where a compound having a structure represented by the general formula (5) is used as the alkenylphenol compound as a reaction raw material, and R in the general formula (5) 51 When is an allyl group, a step of performing an isomerization reaction of the carbon-carbon double bond. Specifically, the method for producing an alkenyl compound according to this embodiment includes a step (1-1) of reacting an epoxy compound with an alkenylphenol compound in the presence of a basic compound, a step (2-1) of purifying the reaction product obtained in the step (1-1) using an acidic aqueous solution and an organic solvent, and preferably a step (3-1) of performing an isomerization reaction of a carbon-carbon double bond provided as needed. Hereinafter, each step of the method for producing the alkenyl compound of the present disclosure will be described in order.

[0047] <Step (1)> Regarding the blending ratio of the epoxy compound and the alkenylphenol compound, considering the balance of physical properties such as moldability and curability of the resulting alkenyl compound, the molar ratio of the hydroxyl group of the alkenylphenol compound to 1 mol of the glycidyl group of the epoxy compound is preferably 0.1 to 2.0 mol, preferably 0.5 to 1.5 mol, and more preferably 0.8 to 1.3 mol. Also, as a specific method for carrying out the above reaction, all the raw materials are charged at once and reacted at a predetermined temperature as it is, or an alkenylphenol compound and a basic compound are charged, and while maintaining the temperature at a predetermined temperature, the epoxy compound is added dropwise and reacted. Generally, the dropping time is usually 0.5 to 24 hours, preferably 0.5 to 4 hours.

[0048] As the basic compound used in the step (1) of this embodiment, an inorganic basic compound, an organic basic compound, etc. can be used. Examples of the inorganic basic compound include hydroxides of alkali metals such as potassium and sodium; carbonates of alkali metals such as potassium and sodium; hydroxides of alkaline earth metals such as calcium and barium; carbonates such as calcium and barium. On the other hand, examples of the organic basic compound include phosphines such as triphenylphosphine. From the viewpoint of ease of purification by washing with water, the basic compound of this embodiment is preferably an alkali metal hydroxide (for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, etc.), and more preferably potassium hydroxide and sodium hydroxide. It is preferable to use the basic compound in an amount in the range of 0.01 to 10 parts by mass, and more preferably in the range of 1 to 5% by mass, based on 100 parts by mass in total of the epoxy compound and the propenylphenol compound.

[0049] 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. Quaternary ammonium salts and quaternary phosphonium salts are preferable from the viewpoint of particularly excellent catalytic activity. Specific examples include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and the like. When used, these basic catalysts may be used in the form of an aqueous solution of about 10% to 55% by mass, or may be used in a solid form. The blending amount of the phase transfer catalyst is in the range of 0 to 15 parts by mass of the phase transfer catalyst with respect to 100 parts by mass of the total amount of the raw materials to be charged (= the total amount of the epoxy compound and the alkenylphenol compound). In step (1) of the present embodiment, it is preferable to react the epoxy compound with the alkenylphenol compound using an organic solvent. Examples of the organic solvent include ketones such as methyl isobutyl ketone, acetone, methyl ethyl ketone (MEK), cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; aromatic solvents such as benzene, toluene, and xylene. These may be used alone or in combination.

[0050] In step (1) of the present embodiment, the reaction temperature between the epoxy compound and the alkenylphenol compound is usually preferably in the range of 50 to 170°C, and more preferably 100 to 140°C in order to avoid side reactions such as formation of multimers and hydrolysis of glycidyl groups. In step (1) of this embodiment, regarding the reaction time between the epoxy compound and the alkenylphenol compound, if the time is too short, the reaction will not proceed completely, and if it is too long, side reactions such as thermal decomposition reaction of the product will occur. Therefore, under the said reaction temperature conditions, usually, it is in the range of about 0.5 to 24 hours, preferably in the range of about 1 to 6 hours. Therefore, for step (1) of this embodiment, it is more preferable to carry out the reaction with stirring in the range of 100 to 140 °C for 1 to 6 hours. Also, for the atmosphere in step (1), it is preferable to carry out the reaction under an inert gas atmosphere such as nitrogen, helium, or argon.

[0051] <Step (2)> Step (2) in this embodiment is an optional step for recovering the reaction product (= the target alkenyl compound) obtained in the above step (1). To the solution containing the reaction product (= the target alkenyl compound obtained by the general formula (1)) and the organic solvent obtained in step (1), an acidic aqueous solution is added. After removing the salt of the basic compound and impurities by neutralization and washing with the acidic aqueous solution, a dehydration operation by azeotropy is carried out. After precision filtration, the solvent and unreacted compounds are distilled off under reduced pressure to obtain the target alkenyl compound. Also, a dehydrating agent may be used during the reaction if necessary.

[0052] By washing the reaction product with an acidic aqueous solution, the stability of the obtained compound can be improved. Specific examples of the acid used in the 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). Also, these acids may be used alone or in combination of two or more. Examples of the dehydrating agent used in step (2) of this embodiment include inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves.

[0053] <Step (3)> After the step (1) or (2) of the present embodiment, a step (3) of performing an isomerization reaction of a carbon-carbon double bond may be provided if necessary. Specifically, in the alkenylphenol compound represented by the above general formula (5), R 51 When is an allyl group (that is, when an alkenylphenol compound having an allyl group is used as a reaction raw material), by subjecting the reaction product obtained by reacting an epoxy compound with the alkenylphenol compound having the allyl group to an isomerization reaction, the allyl group is isomerized to a 1-propenyl group, and a step (3) of synthesizing an alkenyl compound represented by the general formula (1) may be further provided. As a method for isomerizing the allyl group to 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 or the like (see [J. Am. Chem. Soc., 91, p6707~6714 (1969)]), or an isomerization reaction of a carbon-carbon bond using an alkali metal hydroxide or the like (potassium hydroxide) as a base catalyst (see [J. Am. Chem. Soc., 78, p1709~1715 (1956)]). Thereby, the alkenyl compound represented by the above general formula (1) can be easily synthesized.

[0054] [Resin composition] 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-described alkenyl compound and a maleimide resin. Since the alkenyl compound of the present embodiment is excellent in solvent solubility, fluidity during heat melting, and handleability, and can further contribute to dimensional stability, low hygroscopicity, brittleness resistance, heat resistance, and low dielectric constant and low dielectric tangent, the cured product obtained from the resin composition containing the alkenyl compound is excellent in moldability (particularly curing time and appearance), heat resistance, and dielectric properties. The manufacturing method of the resin composition of this embodiment is not particularly limited. For example, melt-kneading is preferable as a method for making the resin composition. Examples of the apparatus used for melt-kneading include an extruder, Banbury mixer, roller, kneader, etc., and these are operated batchwise or continuously. Generally, when manufacturing a resin composition, it is heated to a temperature equal to or higher than the melting point temperature of the resin composition and sufficiently melt-mixed using an extruder, kneader, roller, etc. until it becomes uniform. On the other hand, since the alkenyl compound of this embodiment has a low softening point (or melting point), it is compatible with a maleimide resin, etc. at a conventional kneading temperature (for example, 110 ° C (preferably 100 ° C)), and a uniform composition can be produced. Thereby, by curing the resin composition of this embodiment, a cured product excellent in appearance and heat resistance can be produced.

[0055] (Maleimide resin) The maleimide resin of this embodiment is not particularly limited as long as it has a maleimide group. Examples of the maleimide resin include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane. Further, 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 JP-A-2023-146886, the acid-modified maleimide resin (A) described in International Publication No. 2020 / 166212, the first maleimide compound (A1) and / or the second maleimide compound (A2) described in JP-A-2023-152757, the polymaleimide compound (A) described in JP-A-2023-152755, etc. may be mentioned. In the resin composition of this embodiment, the content of the maleimide resin is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, still more preferably 20 to 70% by mass, and particularly preferably 25 to 65% by mass with respect to the total amount (100% by mass) of the resin composition. When the content of the maleimide resin is within the above range, excellent moldability, heat resistance, and mechanical strength effects are achieved. Each upper limit and each lower limit of the content of the maleimide resin can be appropriately changed.

[0056] (Optional additive component) The resin composition of the present disclosure may contain a curing agent in addition to the alkenyl compound or maleimide resin, and further, if necessary, various compounding agents such as a curing accelerator, a silane coupling agent, a release agent, a pigment, an emulsifier, a non-halogen flame retardant, an inorganic filler, a flame retardant (for example, an inorganic phosphorus-based flame retardant, an organic phosphorus-based flame retardant, a halogen-based flame retardant), and a solvent can be added. Also, within a range that does not impair the object of the present disclosure, in addition to the alkenyl compound and the maleimide resin, known resin components may be contained. Examples of the known resin components include epoxy resins, phenol resins, active ester resins, cyanate resins, polyphenylene ether resins, benzoxazine resins, styrene maleic anhydride copolymers, polybutadiene and its modified products, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluororesins, polystyrene, polyethylene, polyimide resins, silicone gels, silicone oils, etc., which can be appropriately blended.

[0057] When emphasis is placed on suppressing voids in this embodiment, the resin composition may not substantially contain a polymerization initiator. It has been confirmed that voids tend to occur when a polymerization initiator such as DCPO (dicumyl peroxide) is used. The reason is thought to be that at high temperatures such as melt kneading and heat curing, the polymerization initiator in the resin composition decomposes, and the generated radicals cause oxidative decomposition of the maleimide resin or alkenyl compound, and the low molecular weight components generated thereby volatilize, resulting in voids in the cured product.

[0058] (Preferred Properties and Composition of Resin Composition) When manufacturing a semiconductor encapsulant using the resin composition of this embodiment, transfer molding is generally used. In this transfer molding, the resin composition as the material is first heated and softened in a plunger, and then the heated and softened resin composition is made to flow through an in-mold runner such as a gate, sprue, and runner, and is pushed into a heated mold cavity and cured. Therefore, in transfer molding, the fluidity of the resin composition as the material is important. If the fluidity is not appropriately adjusted with respect to the shape of the desired semiconductor encapsulant, molding defects such as unfilled portions in the mold cavity or voids and cracks in the molded product are likely to occur. As described above, the resin composition of this embodiment can be cured at a low temperature and contains an alkenyl compound having a relatively low softening point (or melting point). Therefore, when performing transfer molding, it can be carried out at a relatively low temperature (for example, 175°C or lower). Also, as described above, since the alkenyl compound of this embodiment can undergo a concerted reaction with the maleimide resin by the highly reactive Diels-Alder reaction, the resin composition of this embodiment can be cured in a relatively short time (for example, within 180 seconds (more preferably within 120 seconds, still more preferably within 100 seconds, and particularly preferably within 50 seconds)). In the resin composition of this embodiment, when the resin composition contains an alkenyl compound and a maleimide resin, and the content of the maleimide resin is 10 to 80% by mass and the content of the alkenyl compound is 90 to 20% by mass with respect to 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. The gel time is measured under the conditions described in the Examples section below. 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 maleimide resin is 10 to 80% by mass and the content of the alkenyl compound is 90 to 20% by mass with respect to 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. In the resin composition of the present embodiment, 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 with respect to the total amount (100% by mass) of the resin composition. In the resin composition of the present embodiment, 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 with respect to the total amount (100% by mass) of the resin composition.

[0059] [Cured product] The cured product of the present disclosure is preferably obtained from the resin composition. The cured product can be obtained by subjecting the resin composition to a curing reaction. The resin composition can be obtained by uniformly mixing the above-described respective components (for example, a curing agent, a compounding agent), and can be easily made into a cured product by the same method as a conventionally known method. Examples of the cured product include molded cured products such as laminates, castings, adhesive layers, coating films, and films.

[0060] [Semiconductor encapsulant] The present disclosure is a semiconductor encapsulant containing the resin composition or the cured product of the present embodiment. The semiconductor encapsulant obtained by using the resin composition of the present embodiment has improved curability, heat resistance, or appearance by using the alkenyl compound of the present disclosure, and thus is excellent in processability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0061] The resin composition of the present embodiment used for the semiconductor encapsulating material can contain an inorganic filler. As the filling rate of the inorganic filler, for example, the inorganic filler can be used in the range of 0.5 to 1200 parts by mass with respect to 100 parts by mass of the total amount of the alkenyl compound and the maleimide resin of the present embodiment. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, noble silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and the like.

[0062] As a method for obtaining the semiconductor encapsulating material, a method of sufficiently melt-mixing the resin composition of the present embodiment with an additive, which is an optional component, as necessary, using an extruder, kneader, roll, etc. until it becomes uniform, can be mentioned.

[0063] [Semiconductor device] The present disclosure is a semiconductor device including a cured product of the semiconductor encapsulating material. The semiconductor device obtained by using the semiconductor encapsulating material obtained by using the resin composition of the present embodiment uses the alkenyl compound of the present disclosure, so it has a low viscosity and excellent fluidity. Furthermore, since its hygroscopicity, elastic modulus at high temperature, or adhesiveness to a metal material is improved, it is excellent in processability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0064] As a method for obtaining the semiconductor device, a method of casting the semiconductor encapsulating material or molding it using a transfer molding machine, injection molding machine, etc., and then heat-curing it in the temperature range of room temperature (20°C) to 250°C can be mentioned.

[0065] [Prepreg] The present disclosure relates to a prepreg having a reinforcing base material and a semi-cured product of the resin composition of the present embodiment impregnated in the reinforcing base material. As a method for obtaining a prepreg from the above resin composition, an organic solvent described later is blended to form a varnished resin composition, which is impregnated into a reinforcing base material (such as paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass rovings cloth, etc.), and then heated at a heating temperature corresponding to the type of solvent used, preferably 50 to 170 °C, to semi-cure (or uncure) the resin composition to obtain a prepreg. The mass ratio of the resin composition to the reinforcing base material used at this time is not particularly limited, but usually, it is preferably prepared so that the resin content in the prepreg is 20 to 60% by mass. In the present embodiment, the semi-cured product of the resin composition is obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without completing it. Also, for example, the semi-cured product can have a degree of cure of, for example, 85% or less and 5% or more. On the other hand, the cured product in the present embodiment can have a higher degree of cure than the semi-cured product. Note that the degree of cure of the semi-cured product can be calculated from the following formula by measuring the heat of curing during heating of the resin composition and the heat of curing of the semi-cured product using DSC. Degree of cure (%) = [1 - (Heat of curing of semi-cured product / Heat of curing of resin composition)] × 100

[0066] Examples of the organic solvent used in the production of the prepreg include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The selection and appropriate usage amount thereof can be appropriately selected according to the application. For example, when further manufacturing a printed circuit board from the prepreg as follows, 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., and it is also preferable to use it at a ratio such that the non-volatile content is 40 to 80% by mass.

[0067] [Circuit board] The present disclosure relates to a circuit board which is a laminate of the prepreg and a copper foil. As a method for obtaining a printed circuit board from the resin composition of the present embodiment, a method of laminating the prepreg by a conventional method, appropriately stacking copper foils, and thermocompression bonding at 170 to 300 ° C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours can be mentioned.

[0068] [Build-up film] The present disclosure relates to a build-up film containing the resin composition of the present embodiment. As a method for manufacturing the build-up film of the present embodiment, a method of applying the resin composition on a support film to form a resin composition layer to obtain an adhesive film for a multilayer printed wiring board can be mentioned.

[0069] When manufacturing a build-up film from a resin composition, it is important that the film softens under the temperature conditions of lamination in the vacuum lamination method (usually 70 to 140 ° C) and exhibits fluidity (resin flow) that enables resin filling in the via holes or through holes present in the circuit board at the same time as lamination of the circuit board. It is preferable to blend the above components so as to exhibit such characteristics.

[0070] Here, the diameter of the through holes of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable to enable resin filling within this range. When laminating both sides of the circuit board, it is desirable that the through holes are filled about half.

[0071] Specifically, the method for manufacturing the above adhesive film can be carried out by preparing the resin composition in a varnish form, applying this varnish-like composition on the surface of the support film (Y), and further drying the organic solvent by heating or hot air blowing to form a composition layer (X) made of the resin composition.

[0072] The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.

[0073] In addition, the composition layer (X) in the present embodiment may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the adhesion of dust or the like to the surface of the resin composition layer and scratches.

[0074] Examples of the above-mentioned support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and further release paper, metal foils such as copper foil and aluminum foil. Note that the support film and the protective film may be subjected to a matting treatment, a corona treatment, or a release treatment.

[0075] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0076] The above-mentioned support film (Y) is peeled off after being laminated on the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, it is possible to prevent the adhesion of dust or the like during the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment.

[0077] [Heat-resistant materials and electronic materials] Since the cured product obtained from the resin composition containing the alkenyl compound of the present disclosure exhibits curability and is excellent in appearance and heat resistance, it can be suitably used for heat-resistant members or electronic members. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, resist materials, etc. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg having high heat resistance or excellent appearance. Further, since the alkenyl compound contained in the resin composition exhibits excellent solubility in various solvents, it can be made into a paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, and examples include industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

Examples

[0078] The present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The physical properties of the synthesized alkenyl compound were measured as follows.

[0079] (1) Measurement of double bond equivalent (iodine value) The double bond equivalent of the alkenyl compound-containing mixture obtained in the examples was calculated in accordance with JIS K 0070.

[0080] (2) GPC measurement The content ratio (area %) of the alkenyl compound in the alkenyl compound-containing mixture obtained in the examples was calculated using the following measuring apparatus and measuring conditions. "Measuring apparatus" "HLC-8320 GPC" manufactured by Tosoh Corporation "Measuring conditions" Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Column temperature: 40 °C Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Sample: A 1.0 mass% tetrahydrofuran solution of the alkenyl compound-containing mixture obtained in the examples, filtered through a microfilter (50 μl).

[0081] (3) FD-MS measurement The FD-MS spectrum of the alkenyl compound-containing mixture obtained in the examples was measured using the following measuring apparatus and measurement conditions. "Measuring apparatus" "JMS-T100GC AccuTOF" manufactured by JEOL Ltd. "Measurement conditions" Measurement range: m / z = 4.00~2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0082] (4) NMR measurement The 1 1H-NMR spectrum and 13 13C-NMR spectrum of the alkenyl compound-containing mixture obtained in the examples were measured under the following measuring apparatus and measurement conditions. "Measuring apparatus" "JNM-ECA500" manufactured by JEOL RESONANCE "Measurement conditions" 1 1H-NMR spectrum Resonance frequency: 500 MHz Number of integrations: 16 times Solvent: chloroform-d Sample concentration: 4 mass% 13 C-NMR spectrum Resonance frequency: 125 MHz Number of integrations: 2000 times Solvent: chloroform-d Sample concentration: 30 mass%

[0083] (Example 1) Into a flask equipped with a thermometer, a fractionating column, and a stirrer, 300 g (1.83 mol) of isoeugenol as an alkenylphenol compound, 15 g (0.18 mol) of 49% sodium hydroxide, an epoxy resin mainly composed of an epoxy compound represented by the chemical formula (X-1) (molecular weight: 340) (EXA-850CRP 285 g (number of moles of glycidyl group: 1.65 mol, see the following formula (X-1)), 0.50 g of tetrabutylammonium bromide, and 600 g of methyl isobutyl ketone were charged. While purging with nitrogen gas, the temperature inside the system was raised to 120 °C and stirring was continued for 3 hours. After completion of the reaction, the temperature inside the system was lowered to 80 °C, 300 g of a 12% aqueous sodium phosphate monobasic solution was added, and the mixture was stirred and mixed for 15 minutes. Then, it was allowed to stand for liquid separation 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 and mixed for 15 minutes. Then, it was allowed to stand for liquid separation to remove the aqueous layer. A dehydration operation by azeotropy was performed. After precision filtration, the solvent was distilled off under reduced pressure conditions to obtain an alkenyl compound-containing mixture (1) containing 89 area% of the alkenyl compound represented by the following chemical formula (1-1.1). The softening point of the alkenyl compound-containing mixture (1) was 60 °C. The double bond equivalent of the alkenyl compound-containing mixture (1) was 341 g / mol. Also, the FD-MS spectrum of the alkenyl compound-containing mixture (1) is shown in Figure 1, and the 1 H-NMR spectrum and 13 C-NMR spectrum of the alkenyl compound-containing mixture (1) are shown in Figures 2A and 2B.

Chemical formula

[0084] (Example 2) The same operations as in Example 1 were carried out except that the type of epoxy compound was changed to an epoxy resin (EXA-830CRP (number of moles of glycidyl group: 1.65 moles)) mainly composed of an epoxy compound represented by chemical formula (X-2) (molecular weight: 312), and an alkenyl compound-containing mixture (2) containing 85 area% of an alkenyl compound (2) represented by the following chemical formula (1-1.2) was obtained. The softening point of the alkenyl compound-containing mixture (2) was 58 °C. The double bond equivalent of the alkenyl compound-containing mixture (2) was 328 g / mol. [Chemical formula] Chemical formula (1-1.2): [Chemical formula] In addition, the chemical structure, molecular weight, etc. of the obtained alkenyl compound (2) represented by chemical formula (1-1.2) were confirmed by FD-MS spectrum, 1 H-NMR spectrum and 13 C-NMR spectrum in the same manner as in Example 1.

[0085] (Example 3) The same operations as in Example 1 were carried out except that the type of epoxy compound was changed to an epoxy resin (HP-4032D (number of moles of glycidyl group: 1.65 moles)) mainly composed of an epoxy compound represented by chemical formula (X-3) (molecular weight: 272), and an alkenyl compound-containing mixture (3) containing 88 area% of an alkenyl compound (3) represented by the following chemical formula (1-1.3) was obtained. The softening point of the alkenyl compound-containing mixture (3) was 71 °C. The double bond equivalent of the alkenyl compound-containing mixture (3) was 310 g / mol. [Chemical formula] Chemical formula (1-1.3): [Chemistry] In addition, the chemical structure, molecular weight, etc. of the alkenyl compound (3) represented by the obtained chemical formula (1-1.3) were confirmed by FD-MS spectrum, 1 1H-NMR spectrum and 13 13C-NMR spectrum in the same manner as in Example 1.

[0086] (Example 4) The same operations as in Example 1 were carried out except that the type of the epoxy compound was changed to an epoxy resin (EXA-7250 (the number of moles of glycidyl groups: 1.65 moles)) mainly composed of the epoxy compound represented by the chemical formula (X-4) (molecular weight: 493), and an alkenyl compound-containing mixture (4) containing 68 area% of the alkenyl compound (4) represented by the following chemical formula (1-1.4) was obtained. The softening point of the alkenyl compound-containing mixture (4) was 83°C. The double bond equivalent of the alkenyl compound-containing mixture (4) was 318 g / mol. [Chemistry] Chemical formula (1-1.4): [Chemistry] In addition, the chemical structure, molecular weight, etc. of the alkenyl compound (4) represented by the obtained chemical formula (1-1.4) were confirmed by FD-MS spectrum, 1 1H-NMR spectrum and 13 13C-NMR spectrum in the same manner as in Example 1.

[0087] (Example 5) The type of the epoxy compound was changed to an epoxy resin (HP-4700RC (the number of moles of glycidyl groups: 1.65 moles)) mainly composed of an epoxy compound represented by the chemical formula (X-5) (molecular weight: 557), and the same operations as in Example 1 were performed, except that an alkenyl compound-containing mixture (5) containing 68 area% of an alkenyl compound (5) represented by the following chemical formula (1-1.5) was obtained. The softening point of the alkenyl compound-containing mixture (5) was 98 °C. The double bond equivalent of the alkenyl compound-containing mixture (5) was 304 g / mol.

Chemical formula

Chemical formula

[0088] (Example 6) The type of the epoxy compound was changed to an epoxy resin (YX-4000 (the number of moles of glycidyl groups: 1.65 moles)) mainly composed of an epoxy compound represented by the chemical formula (X-6) (molecular weight: 354), and the same operations as in Example 1 were performed, except that an alkenyl compound-containing mixture (6) containing 69 area% of an alkenyl compound (6) represented by the following chemical formula (1-1.6) was obtained. The softening point of the alkenyl compound-containing mixture (6) was 76 °C. The double bond equivalent of the alkenyl compound-containing mixture (5) was 334 g / mol.

Chemical formula

Chemical formula

[0089] (Comparative Example 1) The same operation as in Example 1 was carried out except that isoeugenol was changed to eugenol (1.83 mol), and an allyl compound-containing mixture (1) containing 92 area% of the allyl compound (1) represented by the following chemical formula (C1) was obtained. The allyl compound-containing mixture (1) was semi-solid at room temperature. The double bond equivalent of the allyl compound-containing mixture (1) was 339 g / mol. Chemical formula (C1): [Chemical formula] The chemical structure, molecular weight, etc. of the obtained allyl compound (1) represented by the chemical formula (C1) were confirmed by FD-MS spectrum, 1 1H-NMR spectrum and 13 13C-NMR spectrum in the same manner as in Example 1.

[0090] (Example 7) A flask equipped with a thermometer, a fractionating column, and a stirrer was charged with 170 g (allyl group mole number 0.5 mol) of the allyl compound-containing mixture (1) obtained in Comparative Example 1, 5.6 g (0.1 mol) of potassium hydroxide, and 85 g of toluene. While purging with nitrogen gas, the temperature inside the system was raised to 145 °C and stirring was continued for 6 hours. After completion of the reaction, the temperature in the system was lowered to 80°C, 400 g of methyl isobutyl ketone and 180 g of a 12% aqueous solution of sodium primary phosphate were added, and the mixture was stirred and mixed for 15 minutes, followed by standing and liquid separation to remove the aqueous layer. Further, water was added to the methyl isobutyl ketone layer in which the reactants were dissolved, and the mixture was stirred and mixed for 15 minutes, followed by standing and liquid separation to remove the aqueous layer. A dehydration operation by azeotropy was carried out, and after precision filtration, the solvent was distilled off under reduced pressure conditions to obtain an alkenyl compound-containing 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 alkenyl compound-containing mixture (7) was 345 g / mol. In addition, the chemical structure, molecular weight, etc. of the alkenyl compound (1) represented by the chemical formula (1-1.1) obtained above were determined by FD-MS spectrum, 1 H-NMR spectrum and 13 C-NMR spectrum in the same manner as in Example 1.

[0091] (Synthesis Example 1) 244 g (2.0 mol) of 2,6-xylenol and 300 g of methanol were charged and dissolved in a flask equipped with a thermometer, a fractionating column, and a stirrer while purging with nitrogen gas. 96 g (2.4 mol) of sodium hydroxide was added, and the temperature was raised to 60°C to completely dissolve the sodium hydroxide. Then, the mixture was cooled to 40°C, and 184 g (2.4 mol) of allyl chloride was added dropwise over 3 hours. After the dropwise addition, the temperature was raised to 60°C over 2 hours, and the reaction was further carried out for 4 hours. After completion of the reaction, 46 g (0.47 mol) 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 and washing were carried out, and washing with 244 g of water was repeated 3 times until the pH of the washing liquid became neutral, and then the system was dehydrated and desolvated to synthesize an allyl ether compound. Subsequently, the obtained allyl ether compound was heated to 190°C and stirred for 5 hours to effect Claisen rearrangement. After the reaction was completed, the reaction mixture was cooled to 60 °C, 134 g (2.4 mol) of potassium hydroxide and 86 g of isopropanol were added, and the potassium hydroxide was completely dissolved. Then, while distilling off the isopropanol, the mixture was heated to 115 °C and reacted for 6 hours. After the reaction was completed, 238 g (2.4 mol) of phosphoric acid and 488 g of methyl isobutyl ketone were added, and the mixture was cooled to 80 °C. Then, it was neutralized with water and washed with water. The washing was repeated three times with 244 g of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy. After passing through a fine 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-propenyl-2,6-xylenol with a purity of 95%.

[0092] (Example 8) The same operations as in Example 1 were carried out except that the type of the alkenylphenol compound was changed to 4-propenyl-2,6-xylenol (1.83 mol) obtained in Synthesis Example 1, and an alkenyl compound-containing mixture (9) containing 64 area% of the alkenyl compound (9) represented by the following chemical formula (1-1.9) was obtained. The softening point of the alkenyl compound-containing mixture (9) was 47 °C. The double bond equivalent of the alkenyl compound-containing mixture (9) was 377 g / mol. Chemical formula (1-1.9): [Chemical formula] The chemical structure, molecular weight, etc. of the alkenyl compound (9) represented by the chemical formula (1-1.9) obtained above were confirmed by FD-MS spectrum, 1 H-NMR spectrum and 13 C-NMR spectrum in the same manner as in Example 1.

[0093] In addition, each raw material used in the above examples was obtained and prepared from the following. EXA-850CRP: Bisphenol A type epoxy resin (manufactured by DIC Corporation) EXA-830CRP: Bisphenol F type epoxy resin (manufactured by DIC Corporation) HP-4032D: Naphthalene type epoxy resin (manufactured by DIC Corporation) EXA-7250: Triphenylmethane type epoxy resin (manufactured by DIC Corporation) HP-4700RC: Methylenebisnaphthalene type epoxy resin (manufactured by DIC Corporation) YX-4000: Tetramethylbiphenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation) Isoeugenol: Manufactured by Tokyo Chemical Industry Co., Ltd. Eugenol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0094] <Examples 9 to 15 and Comparative Examples 2 to 4> <<Preparation of Resin Composition and Production of Cured Product>> The alkenyl compound-containing mixtures (1) to (6), (9) obtained in Examples 1 to 6, 8 above, the allyl compound-containing mixture (1) obtained in Comparative Example 1, and the following formula (8):

Chemical formula

[0095] Subsequently, according to the procedure described in the column of "-Production of Cured Product-" below, 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. Then, physical property evaluations of gel time, appearance of the cured product, and glass transition temperature were performed by the following methods. The results are shown in Table 1.

[0096] <<Measurement of Gel Time (Curability)>> 0.15 g of each resin composition prepared as shown in the composition of Table 1 below was placed on a hot plate heated to 175 °C, and the time until it became gel-like (until the fluidity disappeared and it became agar-like) was measured while stirring with a spatula. The same operation was repeated three times, and the average value was used for evaluation.

[0097] <<Measurement of Glass Transition Temperature (°C)>> - Preparation of Cured Products - Each resin composition prepared as shown in Table 1 below was poured into a mold of 11 cm × 9 cm × 2.4 mm, molded at a temperature of 175 °C for 10 minutes with a press, then the molded product was taken out of the mold, and then post-cured at a temperature of 175 °C for 5 hours to obtain each cured product (thickness 2.4 mm) from the resin compositions of Examples 9 to 15 and Comparative Examples 2 to 4. - Measurement of Glass Transition Temperature (°C) of Cured Products - Next, each cured product with a thickness of 2.4 mm prepared above was cut out into sizes of 5 mm in width and 54 mm in length, and this was designated as Test Specimen 1. Then, using a viscoelasticity measuring device (DMA: Solid Viscoelasticity Measuring Device "RSAII" manufactured by Rheometric, Rectangular Tension Method: frequency 1 Hz, heating rate 3 °C / min), the temperature at which the change in elastic modulus was maximum (the change rate of tanδ was the largest) was measured as the glass transition temperature (°C). The higher the glass transition temperature (°C), the better the heat resistance.

[0098] <<Appearance of Cured Products>> For each cured product obtained in the column of "- Preparation of Cured Products -" above, unevenness, cracks, voids, etc. were visually confirmed and evaluated according to the following criteria. Appearance Evaluation Criteria: S: A transparent plate-shaped molded product without unevenness, cracks, or voids was obtained. A: There were unevenness and voids, but a plate-shaped molded product was obtained. C: There were curing defects, cracks, etc., and a plate-shaped molded product could not be obtained.

[0099]

Table 1

[0100] From the results shown in Table 1 above, when comparing Examples 9 to 15 with Comparative Examples 2 to 4, it can be confirmed that by using the alkenyl compounds of Examples 1 to 6 and 8, excellent curability (gel time) was achieved, and at the time of curing, excellent appearance and high heat resistance were achieved. When the resin compositions of Examples 9 to 15 were prepared by dry blending using a mortar, slight unevenness was confirmed in the obtained plate-shaped molded articles (the evaluation results changed from S to A). Therefore, it was confirmed that the conventional manufacturing process (melt kneading (for example, melt kneading at 110°C or lower)) is important for the obtained cured product to exhibit excellent appearance (suppressing voids or unevenness). Therefore, it is considered that the combination of the alkenyl compound of the present embodiment and the conventional manufacturing process conditions (melt kneading (for example, melt kneading at 110°C or lower)) exerts a synergistic effect and the obtained cured product exhibits excellent appearance. For the following reasons, in the resin compositions of Examples 9 to 15, the alkenyl compound-containing mixtures (1) to (6), (9) were blended into the resin compositions as described above. Since no significant difference was confirmed in 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 except that the alkenyl compound (1) was used instead of the alkenyl compound-containing mixture (1), the alkenyl compound-containing mixture is used in this example.

Industrial Applicability

[0101] According to the present disclosure, it is possible to provide an alkenyl compound excellent in curability (gel time), and exhibiting 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): 【Chemistry 1】 (In the above general formula (1), M １ represents an n1-valent organic group, L １ represents -O- or -S-; L ２ represents an alkylene group having 2 to 10 carbon atoms, provided that the alkylene group has one or more -CH ２ - may be replaced by -CH(-OH)-, -O- or -C(=O)-; M ２ is a substituent R ３ represents a cyclic group which may be substituted by R １ and R ２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number between 2 and 4.)

2. The alkenyl compound according to claim 1, represented by the following general formula (1-1): 【Chemistry 2】 In the above general formula (1-1), M １ represents an n1-valent organic group, L １ represents -O- or -S-; M ２ is a substituent R ３ represents a cyclic group which may be substituted by R １ and R ２ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n1 represents a natural number between 2 and 4.)

3. M in the general formula (1) １ is a group represented by any one of the following formulas (i) to (vi): 【Chemistry 3】 In the above formulas (i) to (vi), "*" indicates a bond that bonds to another atom.

4. The alkenyl compound according to claim 2, which is produced by reacting an epoxy compound and an alkenylphenol compound as reaction raw materials.

5. A resin composition comprising the alkenyl compound according to any one of claims 1 to 4 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 encapsulation material comprising the resin composition according to claim 5.

9. A build-up film obtained by using the resin composition according to claim 5.

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