Propenyl resin, composition, cured product, printed circuit board, semiconductor encapsulation material, and build-up film

Abstract

The present invention provides a propenyl resin that, when mixed with a curing agent, such as a curing agent having an unsaturated double bond, exhibits excellent moldability and, during curing, achieves both excellent curability and heat resistance; a composition containing the propenyl resin; and a cured product thereof. [Solution] A propenyl resin represented by general formula (1), a resin composition containing a maleimide resin and the propenyl resin, a cured product of the composition, a printed circuit board using the composition, a semiconductor encapsulation material using the composition, and a build-up film using the composition. TIFF2026046880000033.tif57166

Description

[Technical Field]

[0001] This disclosure relates to propenyl resins, compositions, cured products, printed circuit boards, semiconductor encapsulation materials, and build-up films. [Background technology]

[0002] In line with recent trends toward energy conservation and CO2 emission reduction, the adoption of power semiconductors is expanding in the fields of new energy power conversion and electric vehicles (EVs). Therefore, in various electrical material applications such as semiconductor encapsulation materials and printed circuit boards, particularly in advanced material applications, there is a demand for further improvements in performance, such as heat resistance and dielectric properties, as well as for materials and compositions possessing both. In the power semiconductor field in particular, the adoption of SiC-based devices is expanding due to their high conversion efficiency and the ability to achieve miniaturization and weight reduction. Since such SiC-based devices can operate at high temperatures, next-generation power semiconductor encapsulation materials require high heat resistance to ensure reliable operation at high temperatures. Conventional semiconductor encapsulation materials have used epoxy resins, which offer an excellent balance of various physical properties such as heat resistance and moisture resistance. However, to achieve even higher heat resistance, research is underway to use or replace these with resins that have higher heat resistance (Tg), such as maleimide resins, benzoxazine resins, or cyanate resins. For example, Patent Document 1 discloses technology relating to a propenyl group-containing resin, a maleimide compound having two or more maleimide groups in one molecule, and a composition containing the propenyl group-containing resin. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-019149 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, while the technology described in Patent Document 1 considers heat resistance, gelation time, and water absorption, it does not consider molding fluidity (especially spiral flow) at all. In particular, new problems have been identified regarding productivity and curability of compositions, such as the unexpected occurrence of thickening or gelation at low temperatures, or the requirement of high curing temperatures for complete curing of the composition, due to the coexistence of multiple functional groups with different reactivity in resin materials used for various electrical materials such as semiconductor encapsulation materials or printed circuit boards. Therefore, the technical problem that this disclosure aims to solve is to provide a propenyl resin that, when mixed with a curing agent, such as a curing agent having an unsaturated double bond, has excellent moldability (especially spiral flow), and achieves both excellent curability (especially gel time) and heat resistance (especially glass transition temperature) during curing, a composition containing the propenyl resin, and a cured product thereof. [Means for solving the problem]

[0005] As a result of diligent research to solve the above-mentioned problems, the inventors have found that by using a propenyl resin having a specific chemical structure, when mixed with a curing agent, for example a curing agent having an unsaturated double bond, it is possible to achieve excellent moldability (especially spiral flow) and excellent curability (especially gel time) and heat resistance (especially glass transition temperature) during curing, and have completed one of the present inventions described in [1] to [8] below. Furthermore, the present disclosure provides a propenyl resin that can also use plant-derived raw materials (biomass raw materials) as reaction raw materials, has moldability that is adaptable to conventional manufacturing processes, and has a low environmental impact derived from biomass raw materials, as well as a composition containing said propenyl resin.

[0006] [1] A propenyl resin represented by the following general formula (1). [ka] [In the above general formula (1), Ar 11 and Ar 12Each independently represents an aromatic hydrocarbon group represented by the following general formula (2): [Chemical formula] (In the above general formula (2), R 21 Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, n21 represents an integer of 0 to 4, and "*" represents a bond that binds to an oxygen atom.) Ar 13 represents an aryl group having 6 to 10 carbon atoms which may be substituted by a substituent R 30 (In the above general formula (3), [Chemical formula] (In the above general formula (3), Ring A represents a benzene ring or a naphthalene ring which may be substituted by a substituent R 30 (In the above general formula (3), R 30 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aromatic ring-containing group having 6 to 10 carbon atoms, n31 represents an integer of 0 to 5, and "*" represents a bond that binds to an oxygen atom.) n1 is an integer of 0 to 10.)

[0007] [2] The propenyl resin according to [1], wherein the double bond equivalent is 200 g / mol or more and 800 g / mol or less.

[0008] [3] A composition comprising the propenyl resin according to [1] or [2] and a maleimide resin.

[0009] [Chemical formula] (In the above general formula (4), R 41 and R 42 ​Each of these independently represents a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group, M 41 This represents a divalent linking group, m41 represents an integer between 0 and 4, m42 represents an integer between 0 and 3, n41 is the number of repeating units and represents a natural number. The composition described in [3] is represented as follows:

[0010] [5] The composition according to either [3] or [4], wherein the content of the propenyl resin is 20 to 70% by mass relative to the whole composition.

[0011] A cured product of any of the compositions described in [6], [3], to [5].

[0012] A printed circuit board comprising any of the compositions described in [7], [3], to [5].

[0013] A semiconductor encapsulation material comprising any of the compositions described in [8], [3], to [5].

[0014] A build-up film comprising any of the compositions described in [9], [3], to [5]. [Effects of the Invention]

[0015] The present disclosure provides a propenyl resin that, when mixed with a curing agent, such as a curing agent having an unsaturated double bond, has excellent moldability (especially spiral flow), and achieves both excellent curability (especially gel time) and heat resistance (especially glass transition temperature) during curing, a composition containing the propenyl resin, and a cured product thereof. According to this disclosure, the cured product is particularly useful in printed circuit boards, semiconductor encapsulation materials, and build-up films. [Brief explanation of the drawing]

[0016] [Figure 1] Figure 1 shows the FD-MS spectrum of the propenyl resin (1) synthesized in Example 1. [Figure 2] Figure 2 shows the 1H-NMR chart of the propenyl resin (1) synthesized in Example 1. [Figure 3] Figure 3 shows the 13C-NMR chart of the propenyl resin (1) synthesized in Example 1. [Figure 4] Figure 1 shows the GPC chart of the propenyl resin (1) synthesized in Example 1. [Modes for carrying out the invention]

[0017] The embodiments of the present invention (hereinafter referred to as "these embodiments") will be described in detail below, but this disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0018] [term] In this specification, "reaction material" refers to a compound used to obtain a target compound through a chemical reaction such as bonding or decomposition, and which partially constitutes the chemical structure of the target compound. Substances that act as aids to the chemical reaction, such as solvents and catalysts, are excluded. Specifically in this specification, "reaction material" refers to a precursor for obtaining the target propenyl resin represented by general formula (1) through a chemical reaction.

[0019] In this specification, "organic group" refers to a group whose chemical structure is formed by an organic compound containing one or more carbon atoms being transformed into a 1- to 4-valent group. In other words, an "organic group" is an atomic group obtained by removing one to four hydrogen atoms from an organic compound containing one or more carbon atoms. Therefore, the organic group may contain one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms, oxygen atoms, halogen atoms, sulfur atoms, and phosphorus atoms, in addition to carbon atoms. Specific examples of the aforementioned organic group are preferably groups having hydrocarbon groups, more preferably groups having linear or branched aliphatic hydrocarbon groups or cyclic hydrocarbon groups, and even more preferably groups having linear or branched saturated aliphatic hydrocarbon groups, cyclic hydrocarbon groups having one or more unsaturated bonds, or groups having aromatic rings. In this specification, "linking group" refers to a bond or atomic group that connects structural units, and includes divalent organic groups, single bonds, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, or -N(R) 0 )- are examples. Note that the above R 0 This represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In this specification, "aromatic hydrocarbon group" refers to any hydrocarbon group having an n-valent (e.g., monovalent to tetravalent) aromatic ring, such as an aryl group or an aralkyl group, or a group obtained by removing n-1 arbitrary hydrogen atoms from the aryl group or aralkyl group. Aromatic ring hydrocarbon groups with two or more valents are preferably groups obtained by removing 1 to 3 arbitrary hydrogen atoms from an aryl group or an aralkyl group. Examples of the aromatic ring include monocyclic aromatic rings, fused aromatic rings, or ring-aggregated aromatic rings. Examples of monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the fused aromatic rings include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the ring-aggregated aromatic rings include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. The n-valent value is preferably 1 to 4-valent. In this specification, "aliphatic hydrocarbon group" refers to a group containing a hydrocarbon having one or more carbon atoms, and includes linear or branched hydrocarbon groups and monocyclic or polycyclic alicyclic hydrocarbon groups such as alkyl groups, alkenyl groups, alkylene groups, alkendiyl groups, and alkinediyl groups. Furthermore, one or more -CH2- groups in the alkyl group, the alkenyl group, and the alkynediyl group may be substituted with -O- or -C(=O)-. Therefore, "aliphatic hydrocarbon group" includes groups containing ester bonds, ether bonds, or ketone bonds. In this specification, "alkyl group" may be linear, branched, or cyclic, and examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or cyclononyl group. The aforementioned "alkyl group" includes a "cycloalkyl group," and examples of such "cycloalkyl groups" 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. In this specification, "alkenyl group" refers to, for example, vinyl group (ethenyl group), 1-propenyl group (hereinafter also simply referred to as propenyl group), 2-propenyl group (hereinafter also simply referred to as allyl group), isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, propadienyl group, 1,3-butadienyl group, 2-methylpropenyl group (methallyl group), n-pentenyl group, 1-pentenyl group. Examples include the nyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methylbutenyl group, n-hexenyl group, 2-methylpentenyl group, n-heptenyl group, n-octenyl group, 2-ethylhexenyl group, n-nonel group, 2-ethylheptenyl group, n-decenyl group, n-dodecenyl group, cyclopentenyl-1- group and cyclohexenyl-1- group, cycloheptenyl-1- group, etc. In this specification, "alkoxy group" refers to, for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, or nonyloxy group. In this specification, "aryl group" refers to, for example, a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. In this specification, "aralkyl group" refers to a group in which one hydrogen atom of an alkyl group is replaced by a monovalent group that removes one hydrogen atom from the aromatic ring (e.g., benzene, naphthalene, or biphenyl). Examples include benzyl group, phenethyl group (1-phenylethyl group, 2-phenylethyl group), phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group, naphthylbutyl group, naphthylpentyl group, or naphthylhexyl group. In this specification, "alkylene group" refers to a group obtained by removing one arbitrary hydrogen atom from the exemplary groups of "alkyl group" or "cycloalkyl group" described above. Specific examples of "alkylene group" include, for example, linear alkylene groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group; and Examples of branched alkylene groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. In this specification, "halogen atom" refers to, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In this specification, "structural unit" refers to a (repeating) unit of chemical structure formed during a reaction or polymerization. In other words, in a compound formed by a reaction or polymerization, it refers to a substructure other than the chemical bond structure involved in the reaction or polymerization, and is commonly known as a residue.

[0020] [Propenyl resin] This disclosure relates to a propenyl resin represented by the following general formula (1). [ka] [In the above general formula (1), Ar 11 and Ar 12 Each of these independently represents an aromatic hydrocarbon group represented by the following general formula (2): [ka] (In the above general formula (2), R 21 Each of the following independently represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, n21 represents an integer from 0 to 4, and "*" indicates a bond with an oxygen atom. Ar 13 This is the substituent R represented by the following general formula (3) 30 Represents an aryl group having 6 to 10 carbon atoms, which may be substituted by [ka] (In the above general formula (3), Ring A has substituent R 30 Represents a benzene ring or naphthalene ring that may be substituted by, R 30 Each of these independently represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, or an aromatic ring-containing group with 6 to 10 carbon atoms. n31 represents an integer from 0 to 5, and "*" indicates a bond with an oxygen atom. n1 is an integer between 0 and 10. As a result, when mixed with a curing agent, such as a curing agent having an unsaturated double bond, it exhibits excellent moldability (especially spiral flow), and during curing, it is possible to achieve both excellent curability (especially gel time) and heat resistance (especially glass transition temperature). Furthermore, in the above general formula (3), if n31 is an integer of 1 or more, there are n31 substituents R 30 The bonded element can be any carbon atom at positions 1-6 of the benzene ring (ring A), or any carbon atom at positions 1-8 of the naphthalene ring (ring A). Similarly, the bonded element can be any carbon atom at positions 1-6 of the benzene ring (ring A), or any carbon atom at positions 1-8 of the naphthalene ring (ring A). The propenyl resin of this embodiment, having the chemical structure represented by the general formula (1) above, exhibits excellent molding fluidity (especially spiral flow) when mixed with a curing agent, such as a curing agent having an unsaturated double bond, and also exhibits excellent curability (especially gel time) and heat resistance (especially glass transition temperature) during curing. Furthermore, as described later, when maleimide resin is used as a curing agent having an unsaturated double bond, in a composition containing both propenyl resin represented by general formula (1) and maleimide resin, the gel time is short, and the curing reaction with the maleimide resin can be completed at conventional curing temperatures (e.g., 175°C or lower). The propenyl resin represented by general formula (1) in this embodiment is preferably a substance having one or more 1-propenyl groups and one or more unsaturated bonds in its molecule, and having a conjugated diene structure in an s-cis conformation. More preferably, the propenyl resin is a compound capable of forming a conjugated diene structure in an s-cis conformation through the 1-propenyl groups and the unsaturated bonds. Specifically, it is preferable that the carbon-carbon double bond at the -CH=CH-CH3 site in the above general formula (2) and one or more unsaturated bonds in the benzene ring form a conjugated diene structure in an s-cis conformation. As a result, propenyl resins represented by general formula (1) can serve as substrates for the Diels-Alder reaction with dienephiles (so-called dienophiles) that have unsaturated double bonds, such as maleimide groups.

[0021] The preferred forms of the propenyl resin represented by the above general formula (1) will be described in detail below.

[0022] Ar 11 " In the above general formula (1), Ar 11 This is an aromatic hydrocarbon group represented by the following general formula (2). [ka] (In the above general formula (2), R 21 Each of the following independently represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, n21 represents an integer from 0 to 4, and "*" indicates a bond with an oxygen atom.

[0023] In the above general formula (1), Ar 11 In a preferred embodiment, it is preferable that the carbon-carbon double bond at the -CH=CH-CH3 site in general formula (2) and one or more unsaturated bonds in the benzene ring in general formula (2) form a conjugated diene structure in an s-cis conformation. This allows the group represented by general formula (2) to serve as a substrate for the Diels-Alder reaction with a dienephile (for example, a group having an unsaturated double bond, such as a maleimide group, which is a dienophile). As a result, the Diels-Alder reaction proceeds more easily, resulting in a more curable (especially gel time) effect. That is, because the Diels-Alder reaction proceeds easily, the curing temperature of the composition containing the propenyl resin of this embodiment and a curing agent having an unsaturated double bond (for example, a maleimide resin) can be set to a relatively low temperature (for example, 200°C or less (preferably 175°C or less)), which is thought to suppress thickening or gelation and result in a more curable (especially gel time) effect.

[0024] In the above general formula (1), Ar11 In preferred embodiments, the position of the -CH=CH-CH3 (1-propenyl group) in general formula (2) can be the ortho position (2nd or 6th), meta position (3rd or 5th), or para position (4th) of the benzene ring. However, from the viewpoint of reactivity with curing agents having unsaturated double bonds (e.g., maleimide resin), the meta position (3rd or 5th) or para position (4th) is preferred, and the para position (4th) is more preferred.

[0025] In the above general formula (1), Ar 11 A preferred embodiment is the substituent R in general formula (2). 21 It is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 2 carbon atoms or an alkoxy group having 1 to 2 carbon atoms. In the above general formula (1), Ar 11 A preferred embodiment is the substituent R 21 If it is an electron-donating group, then the substituent R 11 Since the HOMO of the diene compound having a benzene ring to which the substituent R is attached increases, the Diels-Alder reactivity with groups having unsaturated double bonds (e.g., maleimide groups) can be enhanced, and as a result, the reaction proceeds more easily at low temperatures, which is thought to improve curability (especially gel time). Therefore, substituent R 21 It is preferable that this is an electron-donating group such as the alkyl group or alkoxy group described above. Furthermore, from the viewpoint of activating the benzene ring, substituent R 21 It is more preferable that the compound is bonded to the ortho position (position 2 or 6) or para position (position 4) of the benzene ring, and even more preferable that it is bonded to the ortho position (position 2 or 6) of the benzene ring from the viewpoint of its positional relationship with -CH=CH-CH3. The substituent R 21 Examples of alkyl groups having 1 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms are as described in the [Terminology] section above.

[0026] In the above general formula (1), Ar11 In a preferred embodiment, n21 in the above general formula (2) is preferably an integer between 0 and 2, and more preferably an integer between 1 and 2. Substituent R 21 By having one or more of these elements, the HOMO of the diene increases, which enhances the Diels-Alder reactivity with groups having unsaturated double bonds (e.g., maleimide groups). As a result, the reaction proceeds more easily at low temperatures, which is thought to improve curability (especially gel time).

[0027] Ar 12 " In the above general formula (1), Ar 12 Each of these is an aromatic hydrocarbon group represented by the following general formula (2). [ka] (In the above general formula (2), R 21 Each of the following independently represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, n21 represents an integer from 0 to 4, and "*" indicates a bond with an oxygen atom.

[0028] In the above general formula (1), Ar 12In a preferred embodiment, it is preferable that the carbon-carbon double bond at the -CH=CH-CH3 site in general formula (2) and one or more unsaturated bonds in the benzene ring in general formula (2) form a conjugated diene structure in an s-cis conformation. This allows the group represented by general formula (2) to serve as a substrate for the Diels-Alder reaction with a dienephile (for example, a group having an unsaturated double bond, such as a maleimide group, which is a dienophile). As a result, the Diels-Alder reaction proceeds more easily, resulting in a more curable (especially gel time) effect. That is, because the Diels-Alder reaction proceeds easily, the curing temperature of the composition containing the propenyl resin of this embodiment and a curing agent having an unsaturated double bond (for example, a maleimide resin) can be set to a relatively low temperature (for example, 200°C or less (preferably 175°C or less)), which is thought to suppress thickening or gelation and result in a more curable (especially gel time) effect.

[0029] In the above general formula (1), Ar 12 In preferred embodiments, the position of the -CH=CH-CH3 (1-propenyl group) in general formula (2) can be the ortho position (2nd or 6th), meta position (3rd or 5th), or para position (4th) of the benzene ring. However, from the viewpoint of reactivity with curing agents having unsaturated double bonds (e.g., maleimide resin), the meta position (3rd or 5th) or para position (4th) is preferred, and the para position (4th) is more preferred.

[0030] In the above general formula (1), Ar 12 A preferred embodiment is the substituent R in general formula (2). 21 It is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 2 carbon atoms or an alkoxy group having 1 to 2 carbon atoms. In the above general formula (1), Ar 12 A preferred embodiment is the substituent R 21 If it is an electron-donating group, then the substituent R 21Since the HOMO of the diene compound having a benzene ring to which the substituent R is attached increases, the Diels-Alder reactivity with groups having unsaturated double bonds (e.g., maleimide groups) can be enhanced, and as a result, the reaction proceeds more easily at low temperatures, which is thought to improve curability (especially gel time). Therefore, substituent R 21 It is preferable that this is an electron-donating group such as the alkyl group or alkoxy group described above. Furthermore, from the viewpoint of activating the benzene ring, substituent R 21 It is more preferable that the compound is bonded to the ortho position (position 2 or 6) or para position (position 4) of the benzene ring, and even more preferable that it is bonded to the ortho position (position 2 or 6) of the benzene ring from the viewpoint of its positional relationship with -CH=CH-CH3 (1-propenyl group). The substituent R 21 Examples of alkyl groups having 1 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms are as described in the [Terminology] section above.

[0031] In the above general formula (1), Ar 12 As an example, Ar in general formula (1) 12 There are n1 of them, and they may have the same chemical structure or different chemical structures, preferably there are n1 Ar 12 They have the same chemical structure as each other. In the above general formula (1), Ar 12 In a preferred embodiment, n21 in the above general formula (2) is preferably an integer between 0 and 2, and more preferably an integer between 1 and 2. Substituent R 21 By having one or more of these elements, the HOMO of the diene increases, which enhances the Diels-Alder reactivity with groups having unsaturated double bonds (e.g., maleimide groups). As a result, the reaction proceeds more easily at low temperatures, which is thought to improve curability (especially gel time).

[0032] Ar 13 " Ar 13 This is the substituent R represented by the following general formula (3) 30This represents an aryl group having 6 to 10 carbon atoms, which may be substituted by [another element]. [ka] (In the above general formula (3), Ring A has substituent R 30 Represents a benzene ring or naphthalene ring that may be substituted by, R 30 Each of these independently represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, or an aromatic ring-containing group with 6 to 10 carbon atoms. n31 represents an integer from 0 to 5, and "*" indicates a bond with an oxygen atom. In the general formula (3) above, ring A (indicated by the letter A in the center of the circle) represents an aromatic ring, specifically, substituent R 30 It may be a benzene ring or naphthalene ring that may be substituted by... Furthermore, in the above general formula (3), if n31 is an integer of 1 or more, there are n31 substituents R 30 The bonded element can be any of the carbon atoms at positions 1 through 6 of the benzene ring (ring A), or any of the carbon atoms at positions 1 through 6 of the naphthalene ring (ring A). Similarly, the bonded element can be any of the carbon atoms at positions 1 through 6 of the benzene ring (ring A), or any of the carbon atoms at positions 1 through 6 of the naphthalene ring (ring A). In this specification, Ar 13 As shown in the general formula (3) above, it requires a benzene ring or a naphthalene ring, and is therefore simply referred to as an aryl group. 13 This may be interpreted as an atomic group containing an aryl group represented by the general formula (3) above. Substituent R 30 When it has an aromatic ring-containing group with 6 to 10 carbon atoms, Ar 13 While the whole can be a ring set, the aryl group represented by general formula (3) is understood as an atomic group containing an aryl group, and therefore also includes a ring set.

[0033] In the above general formula (1), Ar 13 A preferred embodiment is the substituent R in general formula (3). 30The number of carbon atoms is preferably 1 to 20, more preferably 3 to 14, and even more preferably 6 to 10. Substituent R in general formula (3) 30 When the number of carbon atoms is in the range of 1 to 20, the viscosity of the propenyl resin decreases, which is thought to result in excellent molding fluidity (especially spiral flow) of the composition. Substituent R in general formula (3) 30 Each of these is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aromatic ring-containing group having 6 to 10 carbon atoms. 30 It is more preferable that this represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aromatic ring-containing group having 6 to 10 carbon atoms, and even more preferable that it represents an aromatic ring-containing group having 6 to 10 carbon atoms. In the above general formula (1), Ar 13 By introducing bulky groups, the propenyl equivalent increases, and the amount of curing agent containing unsaturated double bonds (e.g., maleimide resin) used is reduced, which tends to improve brittleness or hygroscopicity. The substituent R 30 Examples of alkyl groups having 1 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms are as described in the [Terminology] section above.

[0034] In the above general formula (1), Ar 13 It is preferable that the group is an aromatic hydrocarbon group represented by any of the following general formulas (3-1) to (3-3). [ka] (In the above general formula (3-1), R 31 Each of these independently represents an alkenyl group with 3 carbon atoms, and n 32 The integers 0 through 7 are represented, and the asterisk (*) indicates a bond with the oxygen atom. [ka] (In the above general formula (3-2), L 31R represents a linking group, a single bond or an alkylene group with 1 to 4 carbon atoms. 31 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and R 32 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and n 33 represents an integer from 0 to 4, and n 34 represents an integer from 0 to 5, and n 35 The integers 1 through 5 represent integers, and the asterisk (*) indicates a bond that connects to an oxygen atom. [ka] (In the above general formula (3-3), R 31 Each of these independently represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 20 carbon atoms. n31 represents an integer from 0 to 5, and "*" indicates a bond with an oxygen atom. Furthermore, in general formula (3-3), n31 is an integer greater than or equal to 1, and R is greater than or equal to 1. 31 When is an alkenyl group, it is preferable that the carbon-carbon double bond at the -CH=CH- site in the alkenyl group and one or more unsaturated bonds in the benzene ring in general formula (3-3) form an s-cis conformational conjugated diene structure, or that the aromatic ring itself has an s-cis conformational conjugated diene structure. Ar in general formula (1) 13 It is preferable from the viewpoint of excellent molding fluidity (especially spiral flow) if the compound is an aromatic hydrocarbon group represented by any of the general formulas (3-1) to (3-3). In (3-2) above, the alkylene group having 1 to 4 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the [Terminology] section above. Also, in the general formula (3-3) above, the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, or the alkenyl group having 2 to 20 carbon atoms are as described in the [Terminology] section above.

[0035] In this embodiment, Ar 13 More preferably, one aromatic hydrocarbon group selected from the group consisting of the following general formulas (3.1) to (3.4) is used. [Chemical formula] (In the above general formula (3.1), each R 31 independently represents an alkenyl group having 3 carbon atoms, n32 represents an integer from 0 to 7, and "*" indicates a bond that binds to an oxygen atom.) (In the above general formulas (3.2) to (3.3), each R 31 independently represents an alkyl group having 1 to 4 carbon atoms, each R 32 independently represents an alkyl group having 1 to 4 carbon atoms, each R 3a and R 3b independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n32 represents an integer from 0 to 4, n33 represents an integer from 0 to 4, n34 represents an integer from 0 to 5, and "*" indicates a bond that binds to an oxygen atom.) (In the above general formula (3.4), each R 31 independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, n31 represents an integer from 0 to 5, and "*" indicates a bond that binds to an oxygen atom.)

[0036] The position of "*", which is the bond that binds to the oxygen atom in the above general formula (3.1), preferably exists at the 1st, 2nd, 3rd, or 4th position of the naphthalene ring. Further, the substituent R 31 preferably exists at the 1st, 2nd, 3rd, or 4th position. As the substituent R 31 , an allyl group or a 1-propenyl group is preferable.) The position of "*", which is the bond that binds to the oxygen atom in the above general formula (3.2), preferably exists at the 2nd, 4th, or 6th position of the benzene ring (1' to 6' positions), and more preferably exists at the 4th position. Further, the substituent R 31 preferably exists at any of the 2' to 6' positions, and more preferably exists at positions other than the 4th position. As the substituent R 31 , a methyl group is preferable. Further, the substituent R 32Preferably, it is present at any one of the 2nd to 6th positions of the benzene ring, more preferably at the 3rd, 4th or 5th position. The substituent R 32 is preferably a methyl group. The position of "*", which is a bond connecting to the oxygen atom in the general formula (3.3), is preferably at the 2nd, 4th or 6th position of the benzene ring (1' to 6' positions), more preferably at the 4th position. Further, the substituent R 31 is preferably present at any one of the 2' to 6' positions, more preferably present at positions other than the 4' position. The substituent R 31 is preferably a methyl group. Further, the substituent R 32 Preferably, it is present at any one of the 2nd to 6th positions of the benzene ring, more preferably at the 3rd, 4th or 5th position. The substituent R 32 is preferably a methyl group. The position of "*", which is a bond connecting to the oxygen atom in the general formula (3.4), is at the 1st position of the benzene ring (1 to 6 positions), and the substituent R 31 is preferably present at any one of the 2nd to 6th positions. The substituent R 31 is preferably a methyl group, an ethyl group, a tert-butyl group, a methoxy group, or a 1-propenyl group.

[0037] In the present embodiment, Ar in the general formula (1) 13 is preferably the general formula (3.3) from the viewpoints of excellent molding fluidity (especially spiral flow) and flame retardancy among the general formulas (3.1) to (3.4).

[0038] In the general formula (3), when the substituent R 30 selects an alkenyl group having 2 to 20 carbon atoms, the description in the column of [terms] above is incorporated. Among them, the substituent R 30 in the general formula (3) is preferably a 1-propenyl group. Further, as a preferred embodiment of Ar in the general formula (1) 13 this Ar 13This may be an aromatic hydrocarbon group represented by the above general formula (2). In other words, the aromatic hydrocarbon group represented by the above general formula (3) includes the aromatic hydrocarbon group represented by the above general formula (2). And Ar 13 The Ar in the above general formula (1) may be an aromatic hydrocarbon group represented by the general formula (2). 13 This is Ar in the general formula (1) above. 11 and / or Ar 12 It may have the same chemical structure.

[0039] For example, in the general formula (3) above, n is the substituent R of which there are 31. 31 one of the substituents R 31 However, a 1-propenyl group may also be used. Furthermore, in the general formula (3) above, n31 substituents R 31 If one of them is a 1-propenyl group (-CH=CH-CH3 moiety), then the substituent R 31 It is preferable that the carbon-carbon double bond of the 1-propenyl group and one or more unsaturated bonds in the benzene ring in general formula (3) form a conjugated diene structure in s-cis conformation. This allows the group represented by general formula (3) to also be a substrate for the Diels-Alder reaction with groups having unsaturated double bonds, such as the maleimide group, which is a dienephil. Therefore, it is thought that the heat resistance (especially the glass transition temperature) is improved because the number of sites that can be substrates for the Diels-Alder reaction with the aforementioned groups having unsaturated double bonds (e.g., the maleimide group) increases.

[0040] Furthermore, in the above general formula (3), there are n31 substituents R 31 If one of them is a 1-propenyl group, then the other (n31-1) substituents R 31 If it has an electron-donating group inside, the substituent R 31Since the HOMO of the diene compound having a benzene ring to which is bonded increases, the Diels-Alder reactivity with groups having unsaturated double bonds (e.g., maleimide groups) can be enhanced, and as a result, the reaction proceeds more easily at low temperatures, which is thought to improve curability (especially gel time). Therefore, the substituent R, which is present in n31, 31 If one of them is a 1-propenyl group, then n31 is preferably an integer of 2 or greater. Furthermore, when prioritizing curability (especially gel time), from the viewpoint of activating the benzene ring in general formula (3), substituents other than the 1-propenyl group R 31 It is more preferable that the substituent R is bonded to the ortho position (position 2 or 6) or para position (position 4) of the benzene ring, and from the viewpoint of the positional relationship with the 1-propenyl group, the substituent R other than the 1-propenyl group is bonded to the ortho position (position 2 or 6) of the benzene ring. 31 It is even more preferable that the 1-propenyl group is bonded to the para position (position 4).

[0041] In the above general formula (1), Ar 13 In a preferred embodiment, n31 in the above general formula (3) is preferably an integer between 0 and 4, more preferably an integer between 0 and 3, and even more preferably an integer between 0 and 2. Substituent R 30 By having two or more of these groups, and selecting one of them to be a 1-propenyl group, the HOMO of the diene compound containing a benzene ring to which an electron-donating group is attached increases. This enhances the Diels-Alder reactivity with groups having unsaturated double bonds (e.g., maleimide groups), making the reaction proceed more easily at low temperatures, and thus improving curability (especially gel time).

[0042] "n 1 " In the above general formula (1), n 1 n represents an integer between 0 and 10, preferably between 0 and 5, and more preferably between 0 and 3. 1 When the value is an integer between 0 and 10, it is preferable from the viewpoint of having excellent molding fluidity (especially spiral flow).

[0043] "Physical properties of propenyl resin represented by general formula (1)" <Amount of double bonds (g / mol) in propenyl resin represented by general formula (1)> The double bond equivalent (g / mol) of the propenyl resin represented by general formula (1) in this embodiment is preferably 150 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. In this specification, "double bond equivalent (g / mol)" is an indicator of the amount of double bonds contained in a molecule. For compounds of the same molecular weight, a smaller double bond equivalent value tends to indicate a greater amount of double bonds. The "double bond equivalent (g / mol)" is a calculated value obtained from the method described below and the method described in the Examples section. The preferred range for the double bond equivalent (g / mol) can be adjusted by appropriately rearranging the above upper and lower limits. -Method for calculating the double bond equivalent of propenyl resin represented by general formula (1)- The double bond equivalent, which is the content of carbon-carbon double bonds in the propenyl resin represented by general formula (1) of this embodiment, is calculated using the iodine value method in accordance with JIS K0070:1992.

[0044] <Molecular weight of propenyl resin represented by general formula (1)> The molecular weight (number average molecular weight) of the propenyl resin represented by general formula (1) in this embodiment is preferably in the range of 300 to 2000, more preferably in the range of 300 to 1500, and even more preferably in the range of 300 to 1000. The molecular weight (weight-average molecular weight) of the propenyl resin represented by general formula (1) in this embodiment is preferably in the range of 300 to 4000, more preferably in the range of 300 to 3000, and even more preferably in the range of 300 to 2000. The molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the propenyl resin represented by general formula (1) in this embodiment is preferably in the range of 1.0 to 2.0, and more preferably in the range of 1.0 to 1.3. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the propenyl resin represented by general formula (1) in this embodiment were measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the examples below.

[0045] (Another embodiment of propenyl resin represented by general formula (1)) The preferred propenyl resin represented by general formula (1) in this embodiment is preferably reacted using an epihalohydrin and an alkenylphenol compound as reaction raw materials, and more preferably using the epihalohydrin, the alkenylphenol compound, and a phenol compound as reaction raw materials.

[0046] The propenyl resin represented by the general formula (1) may contain an epihalohydrin represented by the general formula (A) as a reaction raw material. Preferably, the epihalohydrin is a compound represented by the following general formula (A). [ka] (In the above general formula (A), X is a halogen atom, and a chlorine atom is preferred.)

[0047] The aforementioned alkenylphenol compound is preferably a compound represented by general formula (B) or (C). [ka] (In the above general formulas (B) and (C), R 31 Each of these independently represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, and n31 represents an integer between 0 and 4 (inclusive). The chemical structures in the above general formulas (B) and (C) are the same as those in the above general formula (1) with Ar 11 and Ar 12 It corresponds to. Examples of the aforementioned alkenylphenol compounds include 2-allylphenol, 4-allylphenol, 2-(1-propenyl)phenol, 4-(1-propenyl)phenol, 4-allyl-2,6-xylenol, 4-(1-propenyl)-2,6-xylenol, eugenol, isoeugenol, hydroxycavicol, and propenylguaetol. Of these alkenylphenol compounds, eugenol and isoeugenol are more preferred, and isoeugenol is even more preferred.

[0048] If the alkenylphenol compound of this embodiment is eugenol, that is, in the above general formula (B), R 31 When the methoxy group is substituted at position 2 and n31 is 1, plant-derived eugenol can be incorporated into the chemical structure of the propenyl resin represented by general formula (1), thus providing a compound that reduces environmental impact. If the alkenylphenol compound of this embodiment is isoeugenol, that is, in the above general formula (C), R 31 When the methoxy group is substituted at position 2 and n31 is 1, plant-derived isoeugenol can be incorporated into the chemical structure of the propenyl resin represented by general formula (1), thus providing a compound that reduces environmental impact.

[0049] As the phenol compound, a compound represented by the following general formula (D) is preferred. [ka] (In the above general formula (D), M 11 ( is one of the bases in the general formulas (3.1) to (3.4) above.) The chemical structure in the above general formula (D) is the same as the Ar in the above general formula (1). 13 It corresponds to. Examples of the phenol compounds include alkylphenols such as phenol, cresol, xylenol, tert-butylphenol, tert-octylphenol, di-tert-butylcresol, octylphenol, and nonylphenol; alkoxyphenols such as methoxyphenol, ethoxyphenol, butoxyphenol, and octyloxyphenol; alkenylphenols such as 2-allylphenol, 4-allylphenol, 2-(1-propenyl)phenol, 4-(1-propenyl)phenol, 4-allyl-2,6-xylenol, 4-(1-propenyl)-2,6-xylenol, eugenol, isoeugenol, hydroxycavicol, propenylguaetol, and cardanol; aralkylphenols such as benzylphenol, cumylphenol, and dicumylphenol; phenylphenols such as phenylphenol and diphenylphenol; and naphthols such as 1-naphthol and 2-naphthol. Of these phenol compounds, alkenylphenols, aralkylphenols, phenylphenols, and naphthols are preferred, alkenylphenols and aralkylphenols are more preferred, and aralkylphenols are even more preferred.

[0050] (Method for producing propenyl resin represented by general formula (1)) The following describes a method for producing the propenyl resin represented by general formula (1) of this disclosure. The method for producing the propenyl resin represented by general formula (1) in this embodiment is not particularly limited as long as it is a method that can produce the chemical structure represented by general formula (1). For example, the raw materials used in the method for producing the propenyl resin represented by general formula (1) of this disclosure may be an epihalohydrin represented by general formula (A), an alkenylphenol compound represented by general formula (B) or (C), and a phenol compound represented by general formula (D) which may be added as needed. Furthermore, the method for producing the propenyl resin may take known synthesis conditions and methods into consideration.

[0051] An example of a method for producing the propenyl resin represented by the general formula (1) of this disclosure is a manufacturing method that includes, for example, the following steps (i-1) and (i-2), and one or more steps selected from the group consisting of steps (i-3) to (i-4) which may be provided as needed. Step (i-1): A step of reacting the epihalohydrin with the alkenylphenol compound as reaction raw materials; Step (i-2): A step in which a phenol compound represented by the general formula (D) is further added to the reaction product of the epihalohydrin and the alkenylphenol compound as a reaction raw material and the reaction is carried out; Step (i-3): A step of purifying the reaction product from the mixture containing the reaction product; Step (i-4): When a compound having the structure represented by general formula (B) is used as the reaction raw material as the alkenylphenol compound, this step involves carrying out an isomerization reaction of the carbon-carbon double bond of the allyl group in general formula (B).

[0052] Specifically, the method for producing the propenyl resin represented by general formula (1) of this embodiment preferably comprises the steps of: (i-1) reacting an epihalohydrin represented by general formula (A) with an alkenylphenol compound represented by general formula (B) or (C) in the presence of a basic compound; (i-2) further mixing a basic compound and a phenol compound represented by general formula (D) with the reaction product obtained in step (i-1) and reacting them in the presence of the basic compound; (i-3) purifying the reaction product produced in step (i-2) using an acidic aqueous solution and an organic solvent; and (i-4) performing a carbon-carbon double bond isomerization reaction as necessary. The following describes each step of the method for producing the propenyl resin represented by the general formula (1) of this disclosure.

[0053] <Process (i-1)> The mixing ratio of the epihalohydrin represented by the general formula (A) and the alkenylphenol compound represented by the general formula (B) or (C) is preferably 0.01 to 1.0 moles, more preferably 0.1 to 0.8 moles, and more preferably 0.2 to 0.3 moles, of the hydroxyl group of the alkenylphenol compound represented by the general formula (B) or (C) per mole of the epihalohydrin. Furthermore, the specific methods for carrying out the above reaction generally involve either charging all the raw materials together and reacting them at a predetermined temperature, or charging the alkenylphenol compound, the epihalohydrin, and the organic solvent, and reacting them while maintaining a predetermined temperature and adding the basic compound dropwise. In this case, the dropwise addition time is usually 0.5 to 10 hours, with 1 to 6 hours being preferable.

[0054] The basic compound that can be used in step (i-1) of this embodiment can be an inorganic basic compound, etc. Examples of inorganic basic compounds include hydroxides of alkali metals such as potassium and sodium. From the viewpoint of ease of purification by washing with water, alkali metal hydroxides (e.g., potassium hydroxide, sodium hydroxide, lithium hydroxide, etc.) are preferred as the basic compound in this embodiment, and potassium hydroxide and sodium hydroxide are more preferred. The basic compound is preferably in a molar ratio of 1.0 to 2.0 moles, more preferably 1.0 to 1.5 moles, and more preferably 1.0 to 1.2 moles, per mole of the alkenylphenol compound represented by the general formula (B) or (C).

[0055] In step (i-1) of this embodiment, a phase-transfer catalyst may be used. The phase transfer catalysts that can be used in step (i-1) of this embodiment include, specifically, quaternary ammonium salts, quaternary phosphonium salts, or crown ethers. Quaternary ammonium salts and quaternary phosphonium salts are particularly preferred due to their excellent catalytic activity, and specifically include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, and tetrabutylphosphonium bromide. When used, these correlation transfer catalysts may be used in the form of an aqueous solution of about 10% to 55% by mass, or in solid form. The amount of the phase transfer catalyst is typically 0.01 to 1.00 parts by mass per 100 parts by mass of the total amount of raw materials to be charged (for example, the total amount of reaction raw materials such as epihalohydrin represented by general formula (A) and alkenylphenol compounds represented by general formula (B) or (C)), but 0.05 to 0.20 parts by mass is preferred from the viewpoint of handling and economic efficiency. In step (i-1) of this embodiment, an organic solvent may be used. Examples of such organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, n-butanol, and t-butanol; 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; and aromatic solvents such as benzene, toluene, and xylene. These may be used individually or in combination.

[0056] In step (i-1) of this embodiment, the reaction temperature between the epihalohydrin represented by general formula (A) and the alkenylphenol compound represented by general formula (B) or (C) can usually be in the range of 30 to 80°C, but 40 to 70°C is preferred in order to avoid side reactions such as the formation of polymers and hydrolysis of the glycidyl group. In step (i-1) of this embodiment, the reaction time between the epihalohydrin represented by general formula (A) and the alkenylphenol compound represented by general formula (B) or (C) is usually in the range of 0.5 to 10 hours, but preferably in the range of 1 to 6 hours, because if the reaction is too short, the reaction will not proceed completely, and if it is too long, side reactions such as thermal decomposition of the product will occur. Therefore, in step (i-1) of this embodiment, it is more preferable to carry out the reaction while stirring at a temperature of 40 to 70°C for 1 to 6 hours. Furthermore, it is preferable to carry out the reaction in step (i-1) under an inert gas atmosphere such as nitrogen, helium, or argon.

[0057] <Process (i-2)> The blending ratio of the phenol compound represented by general formula (D) to the reaction product obtained in step (i-1) is preferably 0.1 to 2.0 moles, preferably 0.2 to 1.5 moles, and more preferably 0.3 to 1.2 moles, of the hydroxyl group of the phenol compound represented by general formula (D) per mole of the alkenylphenol compound represented by general formula (B) or (C) blended in step (i-1). Furthermore, as a specific method for carrying out the above reaction, it is common to either charge all the raw materials together and react them at a predetermined temperature, or to charge them with a basic compound and react them dropwise while maintaining the predetermined temperature with the phenol compound represented by the general formula (D). In this case, the dropwise addition time is usually 0.5 to 24 hours, and preferably 0.5 to 4 hours. The basic compound and phase transfer catalyst that can be used in step (i-2) of this embodiment are the same as those described in step (i-1). In step (i-2) of this embodiment, an organic solvent may be used. Examples of such organic solvents 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; and aromatic solvents such as benzene, toluene, and xylene. These may be used individually or in combination. The reaction temperature in step (i-2) of this embodiment can normally be in the range of 50 to 170°C, but 100 to 140°C is preferred in order to avoid side reactions such as polymer formation and hydrolysis of the glycidyl group. In step (i-2) of this embodiment, the reaction time is typically in the range of 0.5 to 24 hours, but preferably in the range of 1 to 6 hours, because a short reaction time will not allow the reaction to proceed completely, and a long reaction time will cause side reactions such as thermal decomposition of the product. Therefore, in step (i-2) of this embodiment, it is more preferable to carry out the reaction while stirring at a temperature range of 100 to 140°C for a period of 1 to 6 hours. Furthermore, it is preferable to carry out the reaction in step (i-2) under an inert gas atmosphere such as nitrogen, helium, or argon.

[0058] <Process (i-3)> Step (i-3) in this embodiment is performed as needed and is a step to recover the reaction product obtained in step (i-2) (= the target product, which is a propenyl resin or allyl group-containing resin represented by general formula (1)). An acidic aqueous solution is added to the solution obtained in step (i-2) containing the reaction product and an organic solvent, and after removing the salt of the basic compound and impurities by neutralization, washing with water, etc. using the acidic aqueous solution, dehydration is performed by azeotropy, and after microfiltration, the organic solvent and unreacted compounds are removed by distillation under reduced pressure to obtain the reaction product. In addition, a dehydrating agent may be used during the reaction if necessary.

[0059] The stability of the resulting resin can be improved by washing the reaction product with an acidic aqueous solution. Specific examples of acids that can be 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, as well as their salts (e.g., alkali metal or alkaline earth metal salts). These acids may be used individually or in mixtures of two or more types. Examples of dehydrating agents used in step (i-2) of this embodiment include inorganic acids such as sulfuric acid and porous ceramics such as molecular sieves.

[0060] <Process (i-4)> After step (i-2) or step (i-3) of this embodiment, a step (i-4) of performing a carbon-carbon double bond isomerization reaction may be provided as necessary. Specifically, when an alkenylphenol compound represented by general formula (B) is used as a reaction raw material, a step (i-4) may be further provided in which the obtained reaction product isomerized to isomerize the allyl group in the alkenylphenol compound represented by general formula (B) to a 1-propenyl group, thereby synthesizing a propenyl resin represented by general formula (1). As a method for isomerizing the allyl group to a 1-propenyl group, known methods can be employed, such as carbon-carbon bond isomerization reactions using palladium acetate as a catalyst (see J.Am.Chem.Soc., 91, pp. 6707-6714 (1969)), or carbon-carbon bond isomerization reactions using alkali metal hydroxides (potassium hydroxide) as a base catalyst (see J.Am.Chem.Soc., 78, pp. 1709-1715 (1956)). This makes it possible to easily synthesize the propenyl resin represented by the above general formula (1).

[0061] [Composition] This embodiment may be a composition containing a propenyl resin represented by general formula (1) and a maleimide resin. This makes it possible to provide a composition that has superior molding fluidity (especially spiral flow) and, during curing, achieves both superior curability (especially gel time) and heat resistance (especially glass transition temperature). Generally, the curing reaction between alkenyl compounds and maleimide compounds is known to exhibit different reaction mechanisms depending on the type of alkenyl group, the catalyst system, and the temperature conditions. In uncatalyzed curing reactions, at low temperatures, Diels-Alder reactions between conjugated dienes and maleimide groups, or alternating polymerization between electron-rich vinyl or 1-propenyl groups and maleimide groups tend to occur. On the other hand, at relatively high temperatures, Alder-ene reactions with allyl groups tend to proceed, and at even higher temperatures, homopolymerization of maleimide groups tends to occur. Furthermore, in radical-catalyzed curing reactions, the aforementioned alternating polymerization and homopolymerization tend to be promoted. Conversely, in anionic-catalyzed curing reactions, it has been reported that trimerization reactions between maleimide groups occur at low temperatures, inhibiting the progress of the Diels-Alder and Alder-ene reactions. Therefore, when multiple alkenyl groups with different reactivity coexist in a composition, problems with curability (especially gel time) and productivity are likely to occur, such as unexpected thickening or gelation at low temperatures, or requiring high curing temperatures for complete curing. However, the composition of this disclosure uses a propenyl resin represented by general formula (1) having a conjugated diene structure with high Diels-Alder reactivity, and it has been confirmed that it exhibits excellent curability (especially gel time).

[0062] The composition of this embodiment preferably contains a propenyl resin represented by general formula (1) and a maleimide resin. The composition may optionally contain one or more selected from the group consisting of fillers (inorganic fillers) and additives described later.

[0063] "Composition ratio" In the composition of this embodiment, the content of maleimide resin, for example, maleimide resin represented by general formula (4), is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, even more preferably 30% to 70% by mass, even more preferably 35% to 65% by mass, and particularly preferably 40% to 60% by mass, based on the total amount of the composition (100% by mass).

[0064] In the composition of this embodiment, the content of the propenyl resin represented by general formula (1) is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, even more preferably 30% to 70% by mass, even more preferably 35% to 65% by mass, and particularly preferably 40% to 60% by mass, based on the total amount of the composition (100% by mass).

[0065] In the composition of this embodiment, the content of additives added as needed is preferably 0% to 5.0% by mass, more preferably 0.001% to 3.0% by mass, even more preferably 0.01% to 2.0% by mass, even more preferably 0.03% to 1.5% by mass, and particularly preferably 0.05% to 1.0% by mass, based on the total amount of the composition (100% by mass).

[0066] In the composition of this embodiment, the total content of the propenyl resin represented by general formula (1), the maleimide resin, and the additive is preferably 10% to 100% by mass, more preferably 20% to 100% by mass, even more preferably 30% to 100% by mass, even more preferably 40% to 100% by mass, and particularly preferably 50% to 100% by mass, based on the total amount of the composition (100% by mass).

[0067] When the composition of this embodiment contains a propenyl resin represented by general formula (1), a maleimide resin, a filler (inorganic filler), and additives other than the filler (inorganic filler), the total content of the propenyl resin represented by general formula (1), the maleimide resin, the filler (inorganic filler), and additives other than the filler (inorganic filler) is preferably 10% to 100% by mass, more preferably 20% to 100% by mass, even more preferably 30% to 100% by mass, even more preferably 40% to 100% by mass, and particularly preferably 50% to 100% by mass, based on the total amount (100% by mass) of the composition. On the other hand, if the composition of this embodiment contains a propenyl resin represented by general formula (1) and a maleimide resin, and does not contain a filler (inorganic filler), the total content of the propenyl resin, the maleimide resin, and additives other than the filler is preferably 10% to 100% by mass, more preferably 20% to 100% by mass, even more preferably 30% to 100% by mass, even more preferably 40% to 100% by mass, and particularly preferably 50% to 100% by mass, based on the total amount of the composition (100% by mass).

[0068] The following describes in detail the maleimide resin, which is a component of the composition of this embodiment, and the fillers and additives that may be added as needed.

[0069] (Maleimide resin) The composition of this embodiment preferably contains a maleimide resin as an example of a curing agent. Furthermore, the maleimide resin is preferably a compound having two or more maleimide groups in its molecule. Examples of the maleimide resin include 4,4'-diphenylmethanebismaleimide, polyphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, or other maleimide resins. Other maleimide resins include the maleimide described in International Publication No. 2020 / 217679, the maleimide resin described in Japanese Patent No. 7140307, ​​the maleimide resin (A) described in Japanese Patent Application Publication No. 2023-146886, the acid-modified maleimide resin (A) described in International Publication No. 2020 / 166212, the first maleimide compound (A1) and / or the second maleimide compound (A2) described in Japanese Patent Application Publication No. 2023-152757, the polymaleimide compound (A) described in Japanese Patent Application Publication No. 2023-152755, and the like. These maleimide resins may be used alone or as a mixture of two or more. In this embodiment, among the maleimide resins exemplified above, aromatic maleimide resins having two or more maleimide groups in the molecule are more preferable. This makes it easier to obtain a cured product with high heat resistance (especially glass transition temperature).

[0070] Furthermore, the maleimide resin of this embodiment may be a polymerization adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in its molecule with an aromatic polyamine. In other words, the maleimide resin of this embodiment may be an aromatic maleimide resin having two or more maleimide groups in its molecule, or a compound using an aromatic maleimide resin having two or more maleimide groups in its molecule and an aromatic polyamine as reaction raw materials.

[0071] When forming a polymerization adduct by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule with an aromatic polyamine, the aromatic polyamine can be, for example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3-methyldiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, or bis(4-aminophenyl)phenyl Examples include amines, m-xylenediamine, p-xylenediamine, 1,3-bis[4-aminophenoxy]benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2',5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl-4-aminophenyl)propane, 2,2-bis(2,3-dichloro-4-aminophenyl)propane, bis(2,3-dimethyl-4-aminophenyl)phenylethane, ethylenediamine, and hexamethylenediamine.

[0072] The maleimide resin of this embodiment is preferably represented by the following general formula (4). [ka] (In the above general formula (4), R 41 and R 42 Each of these independently represents a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group, M 41 This represents a divalent linking group, m41 represents an integer between 0 and 4, m42 represents an integer between 0 and 3, n41 is the number of repeating units and represents a natural number. As a result, because the maleimide resin has an aromatic ring, it becomes easier to obtain a cured product with even higher heat resistance (especially in terms of glass transition temperature) during curing.

[0073] In the above general formula (1), R 41 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. In the above general formula (1), R 42 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.

[0074] In the above general formula (1), M 41 In a preferred embodiment, the divalent linking group is preferably an alkylene group having 1 to 10 carbon atoms, or a divalent aromatic ring hydrocarbon group having 7 to 16 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms. The aforementioned divalent aromatic ring hydrocarbon group may be any hydrocarbon group having an aromatic ring, and examples include a group obtained by removing one arbitrary hydrogen atom from an aryl group or an aralkyl group. Preferably, the aforementioned divalent aromatic ring hydrocarbon group may be a group obtained by removing one arbitrary hydrogen atom from an aralkyl group.

[0075] In general formula (4), m41 is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0. In general formula (4), m42 is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0. In general formula (1), n41 is preferably a natural number from 1 to 20, more preferably a natural number from 1 to 10, and even more preferably a natural number from 1 to 5.

[0076] The preferred maleimide resin in this embodiment may be one or more compounds selected from the group consisting of 4,4'-diphenylmethanebismaleimide, polyphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane. In the composition of this embodiment, the content of the maleimide resin represented by general formula (4) is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, even more preferably 30% to 70% by mass, even more preferably 35% to 65% by mass, and particularly preferably 40% to 60% by mass, based on the total amount of the composition (100% by mass). When the maleimide resin content is within the above range, it achieves a high level of compatibility between curability (especially gel time), heat resistance (especially glass transition temperature), and molding fluidity (especially spiral flow). The upper and lower limits of the maleimide resin content can be adjusted as appropriate.

[0077] The number-average molecular weight (Mn) of the maleimide resin in this embodiment is preferably in the range of 300 to 2000, and more preferably in the range of 300 to 1000.

[0078] (Optional additives) The composition of this embodiment may contain known curing agents other than the propenyl resin and maleimide resin represented by general formula (1) (especially curing agents having unsaturated double bonds), and may further contain various compounding agents such as curing accelerators, silane coupling agents, mold release agents, pigments, emulsifiers, non-halogenated flame retardants, fillers (also referred to as inorganic fillers), flame retardants (e.g., inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, halogen-based flame retardants), and solvents as needed. Furthermore, the composition of this embodiment may contain known resin components in addition to the propenyl resin and the maleimide resin, as long as it does not impair the purpose of this disclosure. Suitable known resin components may include epoxy resins, phenolic resins, activated 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, and the like. Furthermore, examples of such fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. The shape of the filler is not particularly limited, but the average particle size of the filler is preferably 1 μm to 50 μm. The average particle size of the filler refers to the peak value when the composition of this embodiment is measured with a laser diffraction particle size analyzer (LA500) manufactured by Horiba, Ltd. Furthermore, the presence of multiple peaks indicates the existence of fillers with different average particle sizes. Therefore, if there are multiple peaks, at least one of the top values ​​of each peak should fall within the range of 1 μm to 50 μm.

[0079] (Preferred properties of the composition) When manufacturing semiconductor encapsulating materials using the propenyl resin composition of this embodiment, transfer molding is commonly used. This transfer molding method involves heating and softening the material composition in a plunger, then allowing the heated and softened composition to flow through internal mold channels such as gates, sprues, and runners, and finally pushing it into a heated mold cavity to harden. Therefore, the fluidity of the material composition is crucial in transfer molding. If the fluidity is not appropriately adjusted for the desired shape of the semiconductor encapsulant, problems such as unfilled areas in the mold cavity or molding defects such as voids and cracks in the molded product are likely to occur. As described above, the composition containing propenyl resin of this embodiment can be cured at low temperatures, and therefore transfer molding can be performed at relatively low temperatures (for example, 175°C or below). Furthermore, as described above, the propenyl resin of this embodiment can undergo a synergistic reaction with a curing agent having an unsaturated double bond (for example, maleimide resin) via a highly reactive Diels-Alder reaction, and therefore the composition of this embodiment can be cured in a relatively short time (for example, within 180 seconds, more preferably within 150 seconds, even more preferably within 120 seconds, and particularly preferably within 90 seconds). In the composition of this embodiment, if the composition contains propenyl resin and maleimide resin, and the maleimide resin content is 10 to 90% by mass and the propenyl resin content is 90 to 10% by mass relative to the total amount (100% by mass) of the composition, the gel time of the composition is preferably 120 seconds or less, and more preferably 90 seconds or less. The gel time is measured under the conditions described in the Examples section below.

[0080] [Method for producing the composition] The method for manufacturing the composition of this embodiment is not particularly limited. For example, melt kneading is preferred as a method for producing the composition. Examples of equipment used in melt kneading include extruders, Banbury mixers, rollers, kneaders, etc., which are operated batch or continuously. Generally, when manufacturing a composition, it is preferable to thoroughly melt and mix it until it becomes uniform using an extruder, kneader, roll, etc., at a temperature above the melting point of the composition.

[0081] [Cured product] The cured product of this disclosure is preferably obtained from a composition containing the propenyl resin of this embodiment. The cured product can be obtained by curing the composition. Therefore, since the cured product of this disclosure reflects the properties of the composition, it is possible to achieve a high degree of both excellent curability (especially gel time) and heat resistance (especially glass transition temperature). The composition can be obtained by uniformly mixing the above-mentioned components (e.g., curing agent, compounding agent) and can be easily cured in the same manner as conventionally known methods. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films.

[0082] [Semiconductor encapsulation material] This disclosure relates to a semiconductor encapsulation material containing a composition containing the propenyl resin of this embodiment or a cured product thereof. The semiconductor encapsulation material obtained using the composition of this embodiment has improved moldability and curability (particularly gel time), thus suppressing molding defects such as short molds and cracks in the manufacturing process, resulting in a preferred embodiment.

[0083] The composition containing the propenyl resin of this embodiment used in the semiconductor encapsulating material may contain a filler (also referred to as an inorganic filler). The filler content can be, for example, 0.5 to 1200 parts by mass of filler per 100 parts by mass of the total amount of propenyl resin and maleimide resin represented by general formula (1) of this embodiment. Examples of fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. The filler is preferably fused silica or spherical silica, which suppresses curing shrinkage of the cured product of the composition, resulting in a lower CTE, and can also improve properties such as adhesion and hardness.

[0084] A method for obtaining the aforementioned semiconductor encapsulating material includes, as necessary, a method of thoroughly melting and mixing the composition of this embodiment with an optional additive until uniform, using an extruder, needle, roll, or the like.

[0085] [Semiconductor device] This disclosure relates to a semiconductor device comprising a cured product of the semiconductor encapsulation material. A semiconductor device obtained using the semiconductor encapsulation material obtained using the composition containing the propenyl resin of this embodiment exhibits improved curability (especially gel time) and heat resistance (especially glass transition temperature), resulting in excellent release properties and reflow resistance during the manufacturing process, which is a desirable embodiment.

[0086] Methods for obtaining the semiconductor device include casting the semiconductor encapsulating material, molding it using a transfer molding machine, injection molding machine, etc., and then heat-curing it in a temperature range of room temperature (20°C) to 250°C.

[0087] [Prepreg] This disclosure relates to a prepreg having a reinforcing substrate and a semi-cured product of a composition containing the propenyl resin of this embodiment impregnated into the reinforcing substrate. The resulting semi-cured product exhibits excellent curability (particularly gel time) and heat resistance (particularly glass transition temperature). One method for obtaining a prepreg from the above composition is to impregnate a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) with a varnished composition containing an organic solvent, as described later. The varnished composition is then heated at a temperature appropriate to the solvent used, preferably 50 to 170°C, to partially cure (or leave uncured) the composition and obtain a prepreg. The mass ratio of the composition to the reinforcing substrate used at this time is not particularly limited, but it is generally preferable to prepare the prepreg so that the resin content is 20 to 60% by mass. In this embodiment, a semi-cured product of a composition containing propenyl resin is obtained by adjusting the heating temperature and heating time to stop the curing reaction before it is completed. For example, the semi-cured product may have a degree of curing of 85% or less and 5% or more. On the other hand, the cured product in this embodiment may have a higher degree of curing than the semi-cured product. The degree of hardening of the semi-cured product can be calculated using the following formula by measuring the heat generated during the heating of the composition and the heat generated during the curing of the semi-cured product using DSC. Degree of curing (%) = [1 - (heat generated during curing of the semi-cured material / heat generated during curing of the composition)] × 100

[0088] Examples of organic solvents used in the production of prepregs include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of these solvents can be appropriately chosen depending on the application. For example, when further manufacturing printed circuit boards from prepregs as described below, it is preferable to use polar solvents with a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, and dimethylformamide, and it is also preferable to use them in a proportion that results in a non-volatile content of 40 to 80% by mass.

[0089] [Circuit board] This disclosure relates to a circuit board which is a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the propenyl resin-containing composition of this embodiment is to laminate the prepreg by a conventional method, add copper foil as appropriate, and heat-press it at 170 to 300°C for 10 minutes to 3 hours under pressure of 1 to 10 MPa.

[0090] [Build-up film] This disclosure relates to a build-up film comprising a composition containing the propenyl resin of this embodiment. A method for manufacturing the build-up film of this embodiment is to apply the composition onto a support film to form a layer of the composition, thereby producing an adhesive film for multilayer printed circuit boards. The resulting build-up film exhibits excellent curability (especially gel time) and heat resistance (especially glass transition temperature).

[0091] When manufacturing a build-up film from a composition, it is essential that the film softens under the lamination temperature conditions (usually 70-140°C) in the vacuum lamination method and exhibits moldability (resin flow) that allows for simultaneous lamination of the circuit board and resin filling of via holes or through holes present in the circuit board. It is preferable to formulate the above-mentioned components in such a way as to exhibit these characteristics.

[0092] Here, the diameter of the through-holes in a multilayer printed circuit board is typically 0.1 to 0.5 mm, and the depth is typically 0.1 to 1.2 mm. It is generally preferable to be able to fill the holes with resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0093] The adhesive film described above can be manufactured by first preparing the varnish-like composition, then applying the varnish-like composition to the surface of a support film (Y), and finally drying the organic solvent by heating or blowing hot air to form a composition layer (X) made of the composition.

[0094] The thickness of the formed composition layer (X) is usually preferably greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the composition layer is preferably 10 to 100 μm.

[0095] In this embodiment, the composition layer (X) may be protected by a protective film, which will be described later. Protecting it with a protective film can prevent dust and other debris from adhering to the surface of the composition layer and prevent scratches.

[0096] The support film (Y) and protective film mentioned above can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and also release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be treated with a mat treatment, corona treatment, or release treatment.

[0097] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0098] The support film (Y) described above is peeled off after lamination to the circuit board or after an insulating layer is formed by heat curing. Peeling off the support film (Y) after heat curing the adhesive film prevents the adhesion of dust and other debris during the curing process. When peeling off after curing, the support film is usually treated with a release agent beforehand.

[0099] [Heat-resistant materials and electronic materials] The cured products obtained from compositions containing the propenyl resin of this disclosure exhibit excellent curability (especially gel time) and heat resistance (especially glass transition temperature), making them suitable for use in heat-resistant members or electronic components. In particular, they are suitable for use in prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up substrates, adhesives and resist materials using conductive pastes, and the like. They are also suitable for use as matrix resins in fiber-reinforced resins, and are especially suitable as prepregs with excellent heat resistance (especially glass transition temperature) or curability (especially gel time). Furthermore, the propenyl resin contained in the composition exhibits excellent solubility in various solvents, making it possible to manufacture paints. The heat-resistant members and electronic components thus obtained are suitable for use in a variety of applications, including, but are not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, wind power generation housing components, and the like. [Examples]

[0100] The present invention will be specifically described by examples and comparative examples, but unless otherwise specified, "parts" and "%" below refer to mass. The physical properties of the synthesized propenyl resin were measured as follows.

[0101] (1) Measurement of double bond equivalent (iodine value) The double bond equivalent of the propenyl resin obtained in the examples was calculated in accordance with JIS K 0070.

[0102] (2) GPC measurement The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the propenyl resins obtained in the examples were calculated using the following measuring equipment and conditions. "Measuring device" Tosoh Corporation's "HLC-8320 GPC" "Measurement conditions" Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 1.0ml / min Sample: A tetrahydrofuran solution containing 1.0% by mass of the propenyl resin obtained in the examples, filtered through a microfilter (50 μl).

[0103] (3) FD-MS measurement The FD-MS spectra of the propenyl resins obtained in the examples were measured using the following measuring equipment and conditions. "Measuring device" JEOL Ltd.'s "JMS-T100GC AccuTOF" "Measurement conditions" Measurement range: m / z = 4.00~2000.00 Rate of change: 51.2 mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 sec

[0104] (4)NMR measurement The propenyl resin obtained in the example 1 H-NMR spectrum and 13 The 1C-NMR spectrum was measured using the following measuring instrument and conditions. "Measuring device" JEOL RESONANCE "JNM-ECA500" "Measurement conditions" 1 H-NMR spectrum Resonance frequency: 500MHz Total number of times: 16 Solvent: Chloroform-d Sample concentration: 4% by mass 13 C-NMR spectrum Resonance frequency: 125MHz Total number of times: 2000 Solvent: Chloroform-d Sample concentration: 30% by mass

[0105] (Example 1) In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 328 g (2.0 mol) of isoeugenol, 925 g (10.0 mol) of epichlorohydrin, 476 g of n-butanol, and 80 g of water were charged and dissolved while purging with nitrogen gas. After raising the temperature to 60°C, 179 g (2.2 mol) of 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. After stirring continued under the same conditions for 30 minutes, the mixture was washed three times with 140 g of water. Unreacted epichlorohydrin was then removed by vacuum distillation. Next, 33 g (0.4 mol) of 49% sodium hydroxide, 187 g (0.9 mol) of p-cumylphenol, and 1000 g of methyl isobutyl ketone were added, the temperature of the system was raised to 120°C, and stirring was continued for 3 hours. After the reaction was complete, the system was cooled to 80°C, 200g of 12% monosodium phosphate aqueous solution was added, and the mixture was stirred for 15 minutes. The aqueous layer was then separated by standing liquid-liquid extraction and removed. Further, water was added to the methyl isobutyl ketone layer containing the dissolved reactants, and the mixture was stirred for 15 minutes. The aqueous layer was then separated by standing liquid-liquid extraction and removed. Dehydration was performed by azeotropy, and the solvent was removed under reduced pressure to obtain propenyl resin (1) represented by the following chemical formula (1-1). The propenyl resin (1) was semi-solid at room temperature. The double bond equivalent of the propenyl resin (1) was 310 g / mol. The Mn of the propenyl resin (1) was 683, the Mw was 766, and the Mw / Mn ratio was 1.12. Furthermore, the FD-MS spectrum of the propenyl resin (1) is shown in Figure 1. 1 H-NMR spectrum and 13 The 1C-NMR spectra are shown in Figures 2 and 3, and the GPC data is shown in Figure 4. [ka]

[0106] (Example 2) Except for replacing the "187 g (0.9 mol) of p-cumylphenol" used in Example 1 with "467 g (2.2 mol) of p-cumylphenol," the same procedure as in Example 1 was performed to obtain a propenyl resin (2) represented by the following chemical formula (1-2). The propenyl resin (2) was liquid at room temperature. The double bond equivalent of the propenyl resin (2) was 404 g / mol. The Mn of the propenyl resin (2) was 536, the Mw was 556, and the Mw / Mn ratio was 1.04. [ka] Furthermore, the chemical structure of the propenyl resin (2) was determined by FD-MS spectroscopy, similar to the example in Example 1 above. 1 H-NMR spectrum and 13 Confirmed by 13C-NMR spectroscopy.

[0107] (Example 3) Except for replacing the "187 g (0.9 mol) p-cumylphenol" used in Example 1 with "213 g (1.3 mol) isoeugenol," the same procedure as in Example 1 was performed to obtain a propenyl resin (3) represented by the following chemical formula (1-3). The propenyl resin (3) was liquid at room temperature. The double bond equivalent of the propenyl resin (3) was 200 g / mol. The Mn of the propenyl resin (3) was 596, the Mw was 635, and the Mw / Mn ratio was 1.07. [ka] Furthermore, the chemical structure of the propenyl resin (3) was determined by FD-MS spectroscopy, similar to the example in Example 1 above. 1 H-NMR spectrum and 13 Confirmed by 13C-NMR spectroscopy.

[0108] (Example 4) Except for replacing the "187 g (0.9 mol) of p-cumylphenol" used in Example 1 with "83 g (0.9 mol) of phenol," the same procedure as in Example 1 was performed to obtain a propenyl resin (4) represented by the following chemical formula (1-4). The propenyl resin (4) was liquid at room temperature. The double bond equivalent of the propenyl resin (4) was 259 g / mol. The Mn of the propenyl resin (4) was 608, the Mw was 677, and the Mw / Mn ratio was 1.11. [ka] Furthermore, the chemical structure of the propenyl resin (4) was determined by FD-MS spectroscopy, similar to the example in Example 1 above. 1 H-NMR spectrum and 13 Confirmed by 13C-NMR spectroscopy.

[0109] (Reference synthesis example 1) In a flask equipped with a thermometer, fractionation column, and stirrer, 300 g (1.83 mol) of isoeugenol, 15 g (0.18 mol) of 49% sodium hydroxide, 285 g of epoxy resin (EXA-850CRP) mainly composed of an epoxy compound represented by chemical formula (X-1) (molecular weight: 340) (number of moles of glycidyl groups: 1.65 mol, see formula (X-1) below), 0.50 g of tetrabutylammonium bromide, and 600 g of methyl isobutyl ketone were charged. The system was heated to 120°C while purging with nitrogen gas, and stirring was continued for 3 hours. After the reaction was complete, the system was cooled to 80°C, 300g of 12% sodium monophosphate aqueous solution was added, and the mixture was stirred for 15 minutes. The aqueous layer was then separated by standing liquid-liquid extraction and removed. Further, water was added to the methyl isobutyl ketone layer in which the reaction product was dissolved, and the mixture was stirred for 15 minutes. The aqueous layer was then separated by standing liquid-liquid extraction and removed. Dehydration was performed by azeotropic distillation, and after fine filtration, the solvent was removed under reduced pressure to obtain a comparative resin (5) containing 89 area% of the propenyl compound represented by the following chemical formula (C1). The softening point of the propenyl resin (5) was 60°C. The double bond equivalent of the comparative resin (5) was 341 g / mol. The Mn of the comparative resin (5) was 1068, the Mw was 1138, and the Mw / Mn ratio was 1.07. [ka] [ka]

[0110] <Examples 5-14 and Comparative Examples 1-2> <<Preparation of Composition>> The compositions of Examples 5-14 and Comparative Examples 1-2 were prepared by blending each component according to the compositions shown in Tables 1 and 2 below, and then melt-kneading them at 90°C for 5 minutes using two rolls. The details of each component other than the propenyl resins (1)-(4) used in Examples 5-14 and the comparative resin (5) used in Comparative Examples 1-2 are as follows. • Allyl compound (1): 2,2'-diallylbisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.) Formula (1.1): [ka] • Maleimide resin (1): Polyphenylmethane type maleimide resin (manufactured by Yamato Chemical Industries, Ltd., "BMI-2300") The following formula (1.2): [ka] Maleimide resin represented by • Filler: Fused silica (manufactured by Denka Co., Ltd., "FB-9454", average particle size (median diameter, D50) 19.9 μm)

[0111] Next, the compositions of Examples 5-14 and Comparative Examples 1-2, prepared according to the procedure described in the "Preparation of Compositions" section above, were evaluated for glass transition temperature, gel time, and spiral flow (fluidity) using the following method. The results are shown in Tables 1 and 2.

[0112] <<Measurement of glass transition temperature (°C)>> - Preparation of hardened material - Each composition prepared as shown in Table 1 below was poured into an 11cm × 9cm × 2.4mm mold, molded by pressing at 175°C for 10 minutes, then the molded product was removed from the mold, and then cured at 175°C for 5 hours to obtain cured products (2.4mm thick) from the compositions of Examples 5-9 and Comparative Example 1. -Measurement of the glass transition temperature (°C) of the cured product- Next, each of the 2.4 mm thick cured materials prepared above was cut into pieces measuring 5 mm in width and 54 mm in length, and these were designated as test specimen 1. Then, using a viscoelasticity measuring device (DMA: Rheometric's RSAII solid viscoelasticity measuring device, rectangular tension method: frequency 1 Hz, heating rate 3 °C / min), the temperature at which the change in elastic modulus was maximum (the rate of change in tanδ was largest) was measured as the glass transition temperature (°C). A higher glass transition temperature (°C) indicates superior heat resistance (especially the glass transition temperature).

[0113] <<Gel Time Measurement>> Each component was blended according to the composition shown in Table 1. Immediately after forming the composition, 0.15 g of the composition was placed on a hot plate heated to 175°C, and the time (in seconds) until it became gel-like (lost its fluidity and became agar-like) was measured while stirring with a spatula. This procedure was repeated three times, and the average value was used for evaluation.

[0114] <<Measurement of spiral flow>> The composition prepared according to the composition shown in Table 2 below was injected into a test mold at a mold temperature of 150°C and an injection pressure of 70 kg / cm². 2 The spiral flow value was measured under a 120-second condition. Table 2 shows the spiral flow values ​​for Examples 10 to 14, with Comparative Example 2 set to 100.

[0115] [Table 1]

[0116] [Table 2]

[0117] From the results shown in Table 1 above, when comparing the cured products obtained from the compositions of Examples 5 to 9 with the cured product obtained from the composition of Comparative Example 1, it was confirmed that by using the compositions containing the propenyl resins of Examples 1 to 5, excellent curability (especially gel time) and heat resistance (especially glass transition temperature) were achieved simultaneously during curing. Also, from the results shown in Table 2 above, when comparing the compositions of Examples 10 to 14 with the composition of Comparative Example 2, it was confirmed that by using the compositions containing the propenyl resins of Examples 1 to 5, excellent molding fluidity (especially spiral flow) was exhibited. From the above, it was confirmed that by using the propenyl resins of Examples 1 to 5, when mixed with a curing agent having an unsaturated double bond, it has excellent molding fluidity (especially spiral flow), and at the time of curing, excellent curability (especially gel time) and heat resistance (especially glass transition temperature) are achieved simultaneously.

Industrial Applicability

[0118] According to the present disclosure, a propenyl resin, a composition containing the propenyl resin, and a cured product thereof that have excellent molding fluidity (especially spiral flow) and, at the time of curing, excellent curability (especially gel time) and heat resistance (especially glass transition temperature) can be obtained when mixed with a curing agent, for example, a curing agent having an unsaturated double bond.

Claims

1. A propenyl resin represented by the following general formula (1). 【Chemistry 1】 [In the above general formula (1), Ar １１ and Ar １２ Each of these independently represents an aromatic hydrocarbon group represented by the following general formula (2): 【Chemistry 2】 (In the above general formula (2), R ２１ Each of these independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, n21 represents an integer from 0 to 4, and "*" indicates a bond that connects to an oxygen atom. Ar １３ This is the substituent R represented by the following general formula (3). ３０ Represents an aryl group having 6 to 10 carbon atoms, which may be substituted by 【Transformation 3】 (In the above general formula (3), Ring A has substituent R ３０ Represents a benzene ring or naphthalene ring that may be substituted by, R ３０ Each of these independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aromatic ring-containing group having 6 to 10 carbon atoms. n31 represents an integer from 0 to 5, and "*" indicates a bond that connects to an oxygen atom. n1 is an integer between 0 and 10.

2. The propenyl resin according to claim 1, wherein the double bond equivalent is 200 g / mol or more and 800 g / mol or less.

3. A resin composition comprising the propenyl resin described in claim 1 and a maleimide resin.

4. The maleimide resin is of the following general formula (4): 【Chemistry 4】 (In the above general formula (4), R ４１ and R ４２ each independently represents a hydroxyl group, an alkyl group, an alkoxy group or an aryl group, and M ４１ represents a divalent linking group, m41 represents an integer between 0 and 4, m42 represents an integer between 0 and 3, The composition according to claim 3, wherein n41 is the number of repeating units and represents a natural number.

5. The resin composition according to claim 3, wherein the content of the propenyl resin is 30 to 70% by mass relative to the entire resin composition.

6. A cured product of the composition according to any one of claims 3 to 5.

7. A printed circuit board comprising the composition described in any one of claims 3 to 5.

8. A semiconductor encapsulation material comprising the composition described in any one of claims 3 to 5.

9. A build-up film comprising the composition described in any one of claims 3 to 5.

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