Propylene-based resin, composition, cured product, printed wiring board, semiconductor sealing material, and build-up film

Abstract

[Problem] According to the present invention, according to the present invention, a propenyl resin having excellent molding fluidity (particularly spiral flow) when mixed with a curing agent, such as a curing agent having an unsaturated double bond, and having excellent curability (particularly gel time) and heat resistance (particularly glass transition temperature) when cured can be obtained; a composition containing the propenyl resin; and a cured product thereof. [Solution] The present disclosure is a propenyl resin represented by general formula (1), a composition containing a maleimide resin and the propenyl resin represented by general formula (1), a cured product of the composition, a printed wiring board obtained using the composition, and a semiconductor sealing material obtained using the composition. And a build-up film obtained using the composition.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a propenyl group-containing resin, a composition, a cured product, a printed wiring board, a semiconductor sealing material, and a build-up film. BACKGROUND

[0002] With the recent trend toward energy saving and reduction of CO2 emissions, the use of power semiconductors is expanding in the field of power conversion of new energy or in the field of EV. Therefore, in various electronic material applications, particularly, advanced material applications, such as semiconductor sealing materials or printed circuit boards, further improvement in performance, represented by heat resistance and dielectric properties, and materials and compositions that have both of them are required. In particular, in the field of power semiconductors, SiC devices are being increasingly used because of their high conversion efficiency and ability to achieve miniaturization and weight reduction. Such SiC devices can operate at high temperatures, and therefore, high heat resistance that ensures operating reliability at high temperatures is required for next-generation power semiconductor sealing materials. Conventional semiconductor sealing materials use epoxy resins that have excellent balance of various properties such as heat resistance and moisture resistance, but in order to achieve further high heat resistance, research has been conducted on the use or replacement of resins with higher heat resistance (Tg) such as maleimide resins, benzoxazine resins, or cyanate ester resins.

[0003] For example, Patent Literature 1 discloses a technology relating to a propenyl group-containing resin, and a composition containing a maleimide compound having two or more maleimide groups in one molecule and the aforementioned propenyl group-containing resin.

[0004] Prior Art Documents

[0005] Patent Literature

[0006] Patent Literature 1: Japanese Patent Application Publication No. 2019-019149 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, in the technology of Patent Literature 1, although heat resistance, gelation time, and water absorption were studied, molding fluidity (particularly, spiral flow) was not considered at all. In particular, in resin materials used in various electronic material applications such as semiconductor sealing materials or printed circuit boards, a new problem point was confirmed in terms of productivity and curability of the composition, that is, because of the coexistence of multiple functional groups with different reactivity, thickening or gelation at low temperatures can occur unexpectedly, or a high curing temperature is required for complete curing of the composition.

[0009] Thus, the present disclosure aims to provide a propylene-based resin that has excellent mold flowability (particularly, spiral flow) when mixed with a curing agent, such as a curing agent having an unsaturated double bond, and that has both excellent curability (particularly, gel time) and heat resistance (particularly, glass transition temperature) when cured, a composition containing the propylene-based resin, and a cured product thereof.

[0010] Means for solving the problem

[0011] The present inventors and others have conducted intensive research in order to solve the above problem, and as a result, have found that by using a propylene-based resin having a specific chemical structure, a propylene-based resin that has excellent mold flowability (particularly, spiral flow) when mixed with a curing agent, such as a curing agent having an unsaturated double bond, and that has both excellent curability (particularly, gel time) and heat resistance (particularly, glass transition temperature) when cured can be obtained, thereby completing the present invention of any one of [1] to [8] below.

[0012] In addition, the propylene-based resin of the present disclosure can also use a raw material derived from plants (biomass raw material) as a reaction raw material, and thus provides a propylene-based resin and a composition containing the propylene-based resin that have moldability that can be adapted to conventional manufacturing processes, and that have low environmental load derived from biomass raw materials.

[0013] [1] A propylene-based resin represented by the following general formula (1).

[0014] [Chemical Formula 1]

[0015]

[0016] (In the above general formula (1), Ar 11 and Ar 12 each independently represent an aromatic hydrocarbon group represented by the following general formula (2),

[0017] [Chemical Formula 2]

[0018]

[0019] (In the above general formula (2), R 21 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and n21 represents an integer of 0 to 4. “*” represents a bonding end that is bonded to an oxygen atom.)

[0020] Ar 13 represents an aryl group having 6 to 10 carbon atoms that can be substituted with a substituent R 30 represented by the following general formula (3),

[0021] [Chemical Formula 3]

[0022]

[0023] (In the above general formula (3), ring A represents the substitutable group R) 30 Substituted benzene ring or naphthalene ring, R 30 Each of these groups 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 a group containing an aromatic ring with 6 to 10 carbon atoms. n31 represents an integer from 0 to 5, and * indicates a bonding end bonded to an oxygen atom.

[0024] n1 is an integer from 0 to 10.

[0025] [2] According to the propylene resin of [1], wherein the double bond equivalent is more than 200 g / mol and less than 800 g / mol.

[0026] [3] A composition comprising the acrylic resin described in [1] or [2] and the maleimide resin.

[0027] [4] According to the composition described in [3], the aforementioned maleimide resin is represented by the following general formula (4):

[0028] [Chemistry 4]

[0029]

[0030] (In the above general formula (4), R) 41 and R 42 Each can be independently represented by a hydroxyl, alkyl, alkoxy, or aryl group, M 41 Indicates a divalent linker.

[0031] m41 represents an integer greater than 0 and less than 4.

[0032] m42 represents an integer greater than 0 and less than 3.

[0033] n41 is the number of repeating units, representing a natural number.

[0034] [5] The composition according to [3] or [4], wherein the content of the aforementioned acrylic resin is 20 to 70% by mass relative to the total composition.

[0035] [6] A cured product of any one of the compositions described in any one of [3] to [5].

[0036] [7] A printed wiring substrate, made using any one of the compositions described in [3] to [5].

[0037] [8] A semiconductor sealing material, made using any one of the compositions described in [3] to [5].

[0038] [9] A build-up film formed using the composition according to any one of [3] to [5].

[0039] Effects of Invention

[0040] According to the present disclosure, there is provided a propenyl resin, a composition containing the propenyl resin, and a cured product thereof, the aforementioned propenyl resin having excellent molding fluidity (particularly, spiral flow) when mixed with a curing agent, such as a curing agent having an unsaturated double bond, and having both excellent curability (particularly, gel time) and heat resistance (particularly, glass transition temperature) when cured.

[0041] According to the present disclosure, the aforementioned cured product is particularly useful in printed wiring boards, semiconductor sealing materials, build-up films, and the like. BRIEF DESCRIPTION OF DRAWINGS

[0042] [ Figure 1 ] Figure 1 FD-MS spectrum of the propenyl resin (1) synthesized in Example 1.

[0043] [ Figure 2 ] Figure 2 FD-MS spectrum of the propenyl resin (1) synthesized in Example 1. 1 H-NMR chart.

[0044] [ Figure 3 ] Figure 3 FD-MS spectrum of the propenyl resin (1) synthesized in Example 1. 13 C-NMR chart.

[0045] [ Figure 4 ] Figure 4 GPC chart of the propenyl resin (1) synthesized in Example 1. DETAILED DESCRIPTION

[0046] Hereinafter, an embodiment of the present disclosure (referred to as "the present embodiment") will be described in detail, but the present disclosure is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

[0047] [Terminology]

[0048] In the present specification, "reaction raw material" refers to a compound that partially constitutes the chemical structure of the target compound, used in order to obtain the target compound through a chemical reaction such as bonding or decomposition, and does not include substances such as solvents and catalysts that play a role as an aid in the chemical reaction. In the present specification, in particular, "reaction raw material" refers to a precursor for obtaining a propenyl resin represented by General Formula (1) through a chemical reaction.

[0049] In this specification, "organic group" refers to a group whose chemical structure is formed by an organic compound containing one or more carbon atoms in the form of a group with a valence of 1 to 4. In other words, "organic group" refers to an atomic group formed by removing one to four hydrogen atoms from an organic compound containing one or more carbon atoms. Therefore, in addition to carbon atoms, the aforementioned organic group may also contain one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms, oxygen atoms, halogen atoms, sulfur atoms, and phosphorus atoms.

[0050] As a specific example of the aforementioned organic group, it is preferred to be a group having a hydrocarbon group, more preferably a group having a straight-chain or branched aliphatic hydrocarbon group or a cyclic hydrocarbon group, and even more preferably a group having a straight-chain or branched saturated aliphatic hydrocarbon group, a group having a cyclic hydrocarbon group or an aromatic ring containing one or more unsaturated bonds.

[0051] In this specification, "linking group" refers to the bond or group of atoms used to connect structural units to each other, such as divalent organic groups, single bonds, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, or -N(R)2-. 0 )-.

[0052] It should be noted that the aforementioned R 0 It represents an alkyl group having 1 to 5 hydrogen atoms or carbon atoms.

[0053] In this specification, "aromatic hydrocarbon group" refers to any hydrocarbon group having an aromatic ring with an n-valent (e.g., 1 to 4 valents) charge. Examples include aryl or aralkyl groups, or groups obtained by removing n-1 arbitrary hydrogen atoms from the aryl or aralkyl group. Aromatic ring hydrocarbon groups with a 2-valent or higher charge are preferably groups obtained by removing 1 to 3 arbitrary hydrogen atoms from the aryl or aralkyl group. It should be noted that the aforementioned aromatic ring can be, for example, a monocyclic aromatic ring, a fused-ring aromatic ring, or a cyclic aromatic ring. Examples of monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. Examples of fused-ring aromatic rings include naphthalene, anthracene, phenatene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples of aromatic rings in the aforementioned ring set include biphenyl, binatidine, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and tetraphenyl.

[0054] The aforementioned n-valent value is preferably 1 to 4 valents.

[0055] In this specification, "aliphatic hydrocarbon group" refers to a group containing a hydrocarbon with one or more carbon atoms, including straight-chain or branched hydrocarbon groups such as alkyl, alkenyl, alkylene, alkenyl, and yndiyl, as well as monocyclic or polycyclic alicyclic hydrocarbon groups.

[0056] Furthermore, one or more of the aforementioned alkyl, alkenyl, and alkynyl groups (-CH2-) can be substituted with -O- or -C(=O)-. Therefore, "aliphatic hydrocarbon groups" include groups containing ester, ether, or ketone bonds.

[0057] In this specification, "alkyl" can be any of the following: linear, branched, or cyclic. Examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n)heptyl, (n)octyl, (n)nonyl, (n)decyl, (n)undecyl, (n)dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or cyclononyl.

[0058] The aforementioned "alkyl" includes "cycloalkyl", and examples of such "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, or adamantyl.

[0059] Examples of "alkenyl" in this specification include vinyl (ethene), 1-propenyl (hereinafter also referred to as propenyl), 2-propenyl (hereinafter also referred to as allyl), isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, propadienyl, 1,3-butadienyl, 2-methylpropenyl (methpropenyl), n-pentenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-yl and cyclohexenyl-1-yl, cycloheptenyl-1-yl, etc.

[0060] Examples of "alkoxy" in this specification include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, 2-ethylhexoxy, octoxy, or nonoxy.

[0061] Examples of "aryl" in this specification include phenyl, 1-naphthyl, or 2-naphthyl.

[0062] In this specification, "aralkyl" refers to a group in which one hydrogen atom of an alkyl group is replaced by a monovalent group obtained by removing one hydrogen atom of the aforementioned aromatic ring (e.g., benzyl, naphthalene, or biphenyl). Examples of such groups include benzyl, phenethyl (1-phenylethyl, 2-phenylethyl), phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, naphthylmethyl, naphthylethyl, naphthylpropyl, naphthylbutyl, naphthylpentyl, or naphthylhexyl.

[0063] In this specification, "alkylene" can be, for example, a group obtained by removing one arbitrary hydrogen atom from the exemplary groups of "alkyl" or "cycloalkyl" described above. Specific examples of "alkylene" include linear alkylene groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; and

[0064] Branched alkylene compounds such as ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl.

[0065] In this specification, "halogen atom" may include, for example, fluorine, chlorine, bromine, or iodine atoms.

[0066] In this specification, "structural unit" refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization. In other words, it refers to the part of the structure other than the chemical bonds involved in the reaction or polymerization in the resulting compound, and refers to the so-called residue.

[0067] [Acrylic resin]

[0068] This disclosure refers to a propylene-based resin represented by the following general formula (1).

[0069] [Chemistry 5]

[0070]

[0071] In the above general formula (1), Ar 11 and Ar 12 Each of the aromatic hydrocarbon groups represented by the following general formula (2) can be independently represented.

[0072] [Chemistry 6]

[0073]

[0074] (In the above general formula (2), R) 21 Each of these can be independently represented as an alkyl group or an alkoxy group with 1 to 10 carbon atoms, n21 represents an integer from 0 to 4, and "*" represents a bond end bonded to an oxygen atom.

[0075] Ar 13 The substituent R can be represented by the following general formula (3). 30Aryl groups with 6 to 10 carbon atoms that are substituted.

[0076] [Chemistry 7]

[0077]

[0078] (In the above general formula (3), ring A represents the substitutable group R) 30 Substituted benzene ring or naphthalene ring, R 30 Each of these groups 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 a group containing an aromatic ring with 6 to 10 carbon atoms. n31 represents an integer from 0 to 5, and * indicates a bonding end bonded to an oxygen atom.

[0079] n1 is an integer from 0 to 10.

[0080] Therefore, when mixed with a curing agent, such as a curing agent with unsaturated double bonds, it exhibits excellent molding flowability (especially spiral flow) and, during curing, it can achieve both excellent curability (especially gel time) and heat resistance (especially glass transition temperature).

[0081] It should be noted that in the above general formula (3), when n31 is an integer greater than or equal to 1, there are n31 substituents R. 30 It can be bonded to any of the carbon atoms at positions 1 to 6 of the benzene ring (which is ring A) or any of the carbon atoms at positions 1 to 8 of the naphthalene ring (which is ring A). The bonding end can also be any of the carbon atoms at positions 1 to 6 of the benzene ring (which is ring A) or any of the carbon atoms at positions 1 to 8 of the naphthalene ring (which is ring A).

[0082] The acrylic resin of this embodiment has the chemical structure represented by the above general formula (1), thereby achieving the following effects: when mixed with a curing agent, such as a curing agent having unsaturated double bonds, it has excellent molding flowability (especially spiral flow), and exhibits excellent curability (especially gel time) and heat resistance (especially glass transition temperature) during curing.

[0083] Furthermore, as described later, when using maleimide resin as a curing agent with unsaturated double bonds, in the composition of acrylic resin and maleimide resin represented by general formula (1), the gel time is short, and the curing reaction with maleimide resin can be completed at conventional curing temperatures (e.g., below 175°C).

[0084] The propylene-based resin represented by general formula (1) in this embodiment is preferably a substance having one or more 1-propylene groups and one or more unsaturated bonds in the molecule and having a conjugated diene structure with an s-cis conformation. Moreover, the aforementioned propylene-based resin is more preferably a compound capable of forming a conjugated diene structure with an s-cis conformation from the aforementioned 1-propylene groups and the aforementioned unsaturated bonds.

[0085] Specifically, it is preferred that the carbon-carbon double bond at the -CH=CH-CH3 site in the above general formula (2) forms a conjugated diene structure with one or more unsaturated bonds in the benzene ring in an s-cis conformation.

[0086] Thus, the acrylic resin represented by general formula (1) can be a substrate for the Diels-Alder reaction of groups with unsaturated double bonds, such as maleimide groups, which are diephiles (so-called diephiles).

[0087] The preferred embodiment of the propylene-based resin represented by the above general formula (1) will be described in detail below.

[0088] “Ar 11 "

[0089] Ar in the above general formula (1) 11 It is the aromatic hydrocarbon group represented by the following general formula (2).

[0090] [Chemistry 8]

[0091]

[0092] (In the above general formula (2), R) 21 Each of these can be independently represented as an alkyl group or an alkoxy group with 1 to 10 carbon atoms, n21 represents an integer from 0 to 4, and "*" represents a bond end bonded to an oxygen atom.

[0093] Ar in the above general formula (1) 11In a preferred embodiment, the carbon-carbon double bond at the -CH=CH-CH3 site of general formula (2) forms a conjugated diene structure in an s-cis conformation with one or more unsaturated bonds in the benzene ring of general formula (2). Thus, the group represented by general formula (2) can serve as a substrate for the Diels-Alder reaction of a dienophile (e.g., a group with an unsaturated double bond, such as a maleimide group, which is a dienophile). Therefore, the Diels-Alder reaction proceeds easily, resulting in superior curing properties (especially gel time). That is, because the Diels-Alder reaction proceeds easily, the curing temperature of the composition comprising the acrylic resin of this embodiment and a curing agent with an unsaturated double bond (e.g., a maleimide resin) can be set to a lower temperature (e.g., 200°C or less (preferably 175°C or less)), thereby achieving the effect of suppressing thickening or gelation and superior curing properties (especially gel time).

[0094] Ar in the above general formula (1) 11 In a preferred manner, the position of -CH=CH-CH3(1-propenyl) in general formula (2) can be the ortho (2 or 6), meta (3 or 5), or para (4) position of the benzene ring. From the viewpoint of reactivity with curing agents having unsaturated double bonds (e.g., maleimide resins), the meta (3 or 5) or para (4) position is preferred, and the para (4) position is more preferred.

[0095] Ar in the above general formula (1) 11 In the preferred manner, the substituent R in general formula (2) 21 Preferably, it is an alkyl group or an alkoxy group with 1 to 10 carbon atoms, more preferably an alkyl group or an alkoxy group with 1 to 4 carbon atoms, and even more preferably an alkyl group or an alkoxy group with 1 to 2 carbon atoms.

[0096] Ar in the above general formula (1) 11 The preferred method is if the substituent R 21 If it is an electron-donating group, then it has the substituent R bonded to it. 11 The HOMO of the diene of the benzene ring increases, thus enhancing its Diels-Alder reactivity with groups having unsaturated double bonds (such as maleimide groups). Consequently, the reaction is thought to proceed more readily at lower temperatures, thus improving curability (especially gel time). Therefore, the substituent R... 21 Preferably, it is an electron-donating group such as the alkyl or alkoxy group described above.

[0097] Furthermore, from the perspective of benzene ring activation, the substituent R 21More preferably, it is bonded to the ortho (2 or 6) or para (4) position of the benzene ring. From the viewpoint of the positional relationship with -CH=CH-CH3, it is even more preferred to bond to the ortho (2 or 6) position of the benzene ring.

[0098] The aforementioned 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 aforementioned [Terms] column.

[0099] Ar in the above general formula (1) 11 In the preferred embodiment, n21 in the above general formula (2) preferably represents an integer from 0 to 2, and more preferably represents an integer from 1 to 2.

[0100] It is believed that by having more than one substituent R 21 This increases the HOMO of the diene, thus enhancing its reactivity with Diels-Alder groups having unsaturated double bonds (such as maleimide groups). As a result, the reaction is more likely to occur at low temperatures, thus improving curability (especially gel time).

[0101] “Ar 12 "

[0102] Ar in the above general formula (1) 12 Each is an aromatic hydrocarbon group represented independently by the following general formula (2).

[0103] [Chemistry 9]

[0104]

[0105] (In the above general formula (2), R) 21 Each of these can be independently represented as an alkyl group or an alkoxy group with 1 to 10 carbon atoms, n21 represents an integer from 0 to 4, and "*" represents a bond end bonded to an oxygen atom.

[0106] Ar in the above general formula (1) 12In a preferred embodiment, the carbon-carbon double bond at the -CH=CH-CH3 site of general formula (2) forms a conjugated diene structure in an s-cis conformation with one or more unsaturated bonds in the benzene ring of general formula (2). Thus, the group represented by general formula (2) can serve as a substrate for the Diels-Alder reaction of a dienophile (e.g., a group with an unsaturated double bond, such as a maleimide group, which is a dienophile). Therefore, the Diels-Alder reaction proceeds easily, resulting in superior curing properties (especially gel time). That is, because the Diels-Alder reaction proceeds easily, the curing temperature of the composition comprising the acrylic resin of this embodiment and a curing agent with an unsaturated double bond (e.g., a maleimide resin) can be set to a lower temperature (e.g., 200°C or less (preferably 175°C or less)), thereby achieving the effect of suppressing thickening or gelation and superior curing properties (especially gel time).

[0107] Ar in the above general formula (1) 12 In a preferred manner, the position of -CH=CH-CH3(1-propenyl) in general formula (2) can be the ortho (2 or 6), meta (3 or 5), or para (4) position of the benzene ring. From the viewpoint of reactivity with curing agents having unsaturated double bonds (e.g., maleimide resins), the meta (3 or 5) or para (4) position is preferred, and the para (4) position is more preferred.

[0108] Ar in the above general formula (1) 12 In the preferred manner, the substituent R in general formula (2) 21 Preferably, it is an alkyl group or an alkoxy group with 1 to 10 carbon atoms, more preferably an alkyl group or an alkoxy group with 1 to 4 carbon atoms, and even more preferably an alkyl group or an alkoxy group with 1 to 2 carbon atoms.

[0109] Ar in the above general formula (1) 12 The preferred method is if the substituent R 21 If it is an electron-donating group, then it has the substituent R bonded to it. 21 The HOMO of the diene of the benzene ring increases, thus enhancing its Diels-Alder reactivity with groups having unsaturated double bonds (such as maleimide groups). Consequently, the reaction is thought to proceed more readily at lower temperatures, thus improving curability (especially gel time). Therefore, the substituent R... 21 Preferably, it is an electron-donating group such as the alkyl or alkoxy group described above.

[0110] Furthermore, from the perspective of benzene ring activation, the substituent R 21More preferably, it is bonded to the ortho (2 or 6) or para (4) position of the benzene ring. From the viewpoint of the positional relationship with -CH=CH-CH3 (1-propenyl), it is even more preferred to bond to the ortho (2 or 6) position of the benzene ring.

[0111] The aforementioned 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 [Terms] column above.

[0112] Ar in the above general formula (1) 12 In the manner of Ar in general formula (1) 12 There are n1 Ar atoms, which can have the same chemical structure or different chemical structures. It is preferred that there are n1 Ar atoms. 12 They have the same chemical structure as each other.

[0113] Ar in the above general formula (1) 12 In the preferred embodiment, n21 in the above general formula (2) preferably represents an integer from 0 to 2, and more preferably represents an integer from 1 to 2.

[0114] It is believed that by having more than one substituent R 21 This increases the HOMO of the diene, thus enhancing its reactivity with Diels-Alder groups having unsaturated double bonds (such as maleimide groups). As a result, the reaction is more likely to occur at low temperatures, thus improving curability (especially gel time).

[0115] “Ar 13 "

[0116] Ar 13 The substituent R can be represented by the following general formula (3). 30 Aryl groups with 6 to 10 carbon atoms are substituted.

[0117] [Chemistry 10]

[0118]

[0119] (In the above general formula (3), ring A represents the substitutable group R) 30 Substituted benzene ring or naphthalene ring, R 30 Each of these groups 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 a group containing an aromatic ring with 6 to 10 carbon atoms. n31 represents an integer from 0 to 5, and * indicates a bonding end bonded to an oxygen atom.

[0120] In the above general formula (3), ring A (the figure with A marked in the center of the circle) represents an aromatic ring, specifically, it can be a substitutable group R.30 Substituted benzene rings or naphthalene rings.

[0121] It should be noted that in the above general formula (3), when n31 is an integer greater than or equal to 1, there are n31 substituents R. 30 It can be bonded to any of the carbon atoms at positions 1 to 6 of the benzene ring (which is ring A) or any of the carbon atoms at positions 1 to 6 of the naphthalene ring (which is ring A). The bonding end can also be any of the carbon atoms at positions 1 to 6 of the benzene ring (which is ring A) or any of the carbon atoms at positions 1 to 6 of the naphthalene ring (which is ring A).

[0122] It should be noted that in this specification, Ar 13 As shown in the general formula (3) above, since a benzene ring or a naphthalene ring is required, it is only represented as an aryl group, Ar. 13 This can be understood as a group containing the aryl group represented by the general formula (3) above. The aromatic ring-containing group having 6 to 10 carbon atoms is used as a substituent R. 30 In the case of Ar 13 The whole can also be a ring set, but the aryl group represented by general formula (3) is interpreted as a group of atoms containing aryl groups, and therefore also includes a ring set.

[0123] Ar in the above general formula (1) 13 In the preferred manner, the substituent R in general formula (3) 30 The number of carbon atoms is preferably 1 to 20, more preferably 3 to 14, and even more preferably 6 to 10.

[0124] It is assumed that if the 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 acrylic resin becomes lower, thus resulting in excellent molding flowability (especially spiral flow) of the composition.

[0125] Substituent R in general formula (3) 30 Each of the following 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 a group containing an aromatic ring having 6 to 10 carbon atoms, R 30 More preferably, it represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a group containing an aromatic ring having 6 to 10 carbon atoms; even more preferably, it represents a group containing an aromatic ring having 6 to 10 carbon atoms.

[0126] By Ar in the above general formula (1) 13 By introducing large groups into the resin, the propylene equivalent increases, and the amount of curing agents with unsaturated double bonds (such as maleimide resins) used decreases, thus exhibiting a tendency to increase brittleness or hygroscopicity.

[0127] The aforementioned 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 [Terms] column above.

[0128] Ar in the above general formula (1) 13 Preferably, it is an aromatic hydrocarbon group represented by any one of the following general formulas (3-1) to (3-3).

[0129] [Chemistry 11]

[0130]

[0131] (In the above general formula (3-1), R) 31 Each independently represents an alkenyl group with 3 carbon atoms, n 32 (This represents an integer from 0 to 7; * indicates a bond end bonded to an oxygen atom.)

[0132] [Chemistry 12]

[0133]

[0134] (In the above general formula (3-2), L) 31 Indicates a linking group, representing a single bond or an alkylene group having 1 to 4 carbon atoms, R 31 R represents alkyl groups having 1 to 4 carbon atoms, each independently. 32 Each alkyl group, having 1 to 4 carbon atoms, is represented independently; n 33 n represents an integer from 0 to 4. 34 n represents an integer from 0 to 5. 35 (This represents an integer from 1 to 5, with * indicating a bond end bonded to an oxygen atom.)

[0135] [Chemistry 13]

[0136]

[0137] (In the above general formula (3-3), R) 31 Each of these can independently represent 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 "*" represents a bonding end bonded to an oxygen atom.

[0138] In addition, in general formula (3-3), n31 is an integer greater than or equal to 1 and more than one R. 31 When the alkenyl group is used, it is preferred that the carbon-carbon double bond at the -CH=CH- site of the alkenyl group forms a conjugated diene structure with one or more unsaturated bonds in the benzene ring of general formula (3-3) in an s-cis conformation, or that the aforementioned aromatic ring itself has a conjugated diene structure with an s-cis conformation.

[0139] Ar in general formula (1) 13 When the aromatic hydrocarbon group is represented by any of the general formulas (3-1) to (3-3), it is preferred from the viewpoint of excellent molding flowability (especially spiral flow).

[0140] In (3-2) above, the alkylene group having 1 to 4 carbon atoms and the alkyl group having 1 to 4 carbon atoms refer to the terms described in the [Terminology] column above. Furthermore, 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 refer to the terms described in the [Terminology] column above.

[0141] In this embodiment, Ar 13 More preferably, it is an aromatic hydrocarbon group selected from the group consisting of the following general formulas (3.1) to (3.4).

[0142] [Chemistry 14]

[0143]

[0144] (In the above general formula (3.1), R) 31 Each group independently represents an alkenyl group with 3 carbon atoms, n32 represents an integer from 0 to 7, and "*" represents a bonding end bonded to an oxygen atom.

[0145] (In the above general formulas (3.2) to (3.3), R) 31 R represents alkyl groups having 1 to 4 carbon atoms, each independently. 32 R represents alkyl groups having 1 to 4 carbon atoms, each independently. 3a and R 3b Each of these groups independently represents a hydrogen atom and an alkyl group with 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 "*" represents a bond end bonded to an oxygen atom.

[0146] (In the above general formula (3.4), R) 31 Each of these can independently represent 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 "*" represents a bonding end bonded to an oxygen atom.

[0147] In the above general formula (3.1), the "*" representing the bonding end with the oxygen atom is preferably located at position 1, 2, 3, or 4 of the naphthalene ring. Additionally, the substituent R... 31 Preferably, it is present at position 1, position 2, position 3, or position 4. As this substituent R... 31 Preferably allyl or 1-propenyl.

[0148] In the above general formula (3.2), the "*" representing the bonding end with the oxygen atom is preferably located at the 2', 4', or 6' position of the benzene ring (1' to 6' positions), more preferably at the 4' position. Additionally, the substituent R... 31 Preferably, it is present at any one of the 2' to 6' positions, and more preferably at a position other than 4'. As this substituent R... 31 Methyl group is preferred. Additionally, substituent R... 32 Preferably, it is present at any one of the 2 to 6 positions of the benzene ring, more preferably at the 3, 4, or 5 position. As this substituent R... 32 Methyl group is preferred.

[0149] In the above general formula (3.3), the "*" representing the bonding end with the oxygen atom is preferably located at the 2', 4', or 6' position of the benzene ring (1' to 6' positions), more preferably at the 4' position. Additionally, the substituent R... 31 Preferably, it is present at any one of the 2' to 6' positions, and more preferably at a position other than 4'. As this substituent R... 31 Methyl group is preferred. Additionally, substituent R... 32 Preferably, it is present at any one of the 2 to 6 positions of the benzene ring, more preferably at the 3, 4, or 5 position. As this substituent R... 32 Methyl group is preferred.

[0150] In the above general formula (3.4), the "*" representing the bonding end with the oxygen atom is preferably located at position 1 (positions 1-6) of the benzene ring, and is free of substitutions or substituents R. 31 It exists at any position from 2 to 6. As this substituent R... 31 Preferably, methyl, ethyl, tert-butyl, methoxy, or 1-propenyl groups are used.

[0151] In this embodiment, from the viewpoint of excellent molding flowability (especially spiral flow) and flame retardancy, Ar in the above general formula (1) 13 Of the above general formulas (3.1) to (3.4), general formula (3.3) is preferred.

[0152] In the above general formula (3), the substituent R 30 When choosing an alkenyl group with 2 to 20 carbon atoms, the terminology described in the [Terminology] section above shall apply to the alkenyl group with 2 to 20 carbon atoms. Specifically, R, as the substituent in the aforementioned general formula (3), 30 1-Propylene is preferred.

[0153] In addition, Ar in the above general formula (1) 13 The preferred method, the Ar 13It can 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). Moreover, Ar 13 It can be an aromatic hydrocarbon group represented by the aforementioned general formula (2). Therefore, Ar in the aforementioned general formula (1) 13 It can be Ar in the above general formula (1) 11 and / or Ar 12 They have the same chemical structure.

[0154] For example, in the above general formula (3), there are n31 substituents R. 31 One substituent R in 31 It can be 1-propenyl.

[0155] Moreover, in the above general formula (3), there are n31 substituents R. 31 When one of them is a 1-propenyl group (-CH=CH-CH3 site), it is preferably used as the aforementioned substituent R. 31 The carbon-carbon double bond of the 1-propenyl group forms a conjugated diene structure in an s-cis conformation with one or more unsaturated bonds in the benzene ring of general formula (3). Therefore, the group represented by general formula (3) can also serve as a substrate for Diels-Alder reactions with groups having unsaturated double bonds, such as maleimide, which are dienophiles (so-called dienophiles). It is therefore believed that the increased number of sites that can serve as substrates for Diels-Alder reactions with the aforementioned groups having unsaturated double bonds (e.g., maleimide) further enhances the heat resistance (especially the glass transition temperature).

[0156] In addition, in the above general formula (3), there are n31 substituents R. 31 When one of them is a 1-propenyl group, if the other (n31-1) substituents R 31 If a substance contains an electron-donating group, then it has a substituent R bonded to it. 31 The HOMO of the diene of the benzene ring increases, thus enhancing its Diels-Alder reactivity with groups having unsaturated double bonds (such as maleimide groups). As a result, it is believed to become easier to react at low temperatures, thus improving curability (especially gel time). Therefore, there are n31 substituents R 31 When one of them is a 1-propenyl group, n31 is preferably an integer of 2 or more.

[0157] Furthermore, considering the importance of curing properties (especially gel time), from the perspective of the activation of the benzene ring in general formula (3), substituents other than the 1-propenyl group R 31More preferably, the substituent R is bonded to the ortho (2 or 6) or para (4) position of the benzene ring. From the viewpoint of its positional relationship with the 1-propenyl group, substituents other than the 1-propenyl group are even more preferred. 31 It is bonded to the ortho position (2 or 6 position) of the benzene ring, and the 1-propenyl group is bonded to the para position (4 position).

[0158] Ar in the above general formula (1) 13 In the preferred embodiment, n31 in the above general formula (3) preferably represents an integer from 0 to 4, more preferably an integer from 0 to 3, and even more preferably an integer from 0 to 2.

[0159] It is believed that by having more than two substituents R 30 Furthermore, one of the choices is 1-propenyl, which increases the HOMO of the diene containing a benzene ring bonded with an electron-donating group. This enhances the Diels-Alder reactivity with groups having unsaturated double bonds (such as maleimide groups), making it easier to react at low temperatures, thus improving curability (especially gel time).

[0160] “n 1 "

[0161] In the above general formula (1), n 1 It represents an integer from 0 to 10, preferably an integer from 0 to 5, and more preferably an integer from 0 to 3. 1 When the integer is 0 to 10, it is preferred from the viewpoint of having excellent molding flowability (especially spiral flow).

[0162] Properties of acrylic resins represented by general formula (1)

[0163] <The amount of double bonds in the acrylic resin represented by general formula (1) (g / mol)>

[0164] The double bond equivalent (g / mol) of the propylene 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.

[0165] The term "double bond equivalent (g / mol)" in this specification 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 tends to indicate a greater amount of double bonds. This "double bond equivalent (g / mol)" is a calculated value obtained using the methods described in the "Methods and Examples" section below.

[0166] The preferred range of the aforementioned double bond equivalent (g / molar) can be appropriately combined with the above upper and lower limits.

[0167] - Calculation method for double bond equivalent of propylene resin represented by general formula (1) -

[0168] The content of carbon-carbon double bonds in the acrylic resin represented by general formula (1) in this embodiment, i.e., the double bond equivalent, is calculated using the iodine value method according to JIS K0070:1992.

[0169] <Molecular weight of acrylic resin represented by general formula (1)>

[0170] The molecular weight (number average molecular weight) of the acrylic 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.

[0171] The molecular weight (weight-average molecular weight) of the acrylic 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.

[0172] The molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the propylene-based resin represented by general formula (1) in this embodiment is preferably in the range of 1.0 to 2.0, and more preferably 1.0 to 1.3.

[0173] 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 propylene resin represented by general formula (1) in this embodiment were determined using gel permeation chromatography (hereinafter referred to as "GPC") under the determination conditions described in the examples described later.

[0174] (Other ways of representing acrylic resins as in general formula (1))

[0175] The preferred acrylic resin represented by general formula (1) of this embodiment preferably uses epihaloalcohol and alkenylphenol compound as reaction raw materials, and more preferably uses the aforementioned epihaloalcohol, the aforementioned alkenylphenol compound and phenol compound as reaction raw materials.

[0176] As a reaction raw material for the propylene-based resin represented by the aforementioned general formula (1), it may contain a surface haloalcohol represented by general formula (A). Moreover, the aforementioned surface haloalcohol is preferably a compound represented by the following general formula (A).

[0177] [Chemistry 15]

[0178]

[0179] (In the above general formula (A), X is a halogen atom, preferably a chlorine atom.)

[0180] The aforementioned alkenylphenol compounds are preferably those represented by general formula (B) or (C).

[0181] [Chemistry 16]

[0182]

[0183] (In the above general formulas (B) and (C), R) 31 Each of the following groups independently represents an alkyl group or an alkoxy group with 1 to 10 carbon atoms, and n31 represents an integer greater than 0 and less than 4.

[0184] Furthermore, the chemical structures in general formulas (B) and (C) above correspond to Ar in general formula (1) above. 11 and Ar 12 .

[0185] Examples of the aforementioned alkenylphenol compounds include: 2-allylphenol, 4-allylphenol, 2-(1-propenyl)phenol, 4-(1-propenyl)phenol, 4-allyl-2,6-dimethylphenol, 4-(1-propenyl)-2,6-dimethylphenol, eugenol, isoeugenol, hydroxypiperol, and propenylethylguaiacol.

[0186] Among these alkenylphenol compounds, eugenol and isoeugenol are further preferred, and isoeugenol is even more preferred.

[0187] When the alkenylphenol compound in this embodiment is eugenol, that is, R in the above general formula (B) 31 When the methoxy group at the 2-position is substituted and n31 is 1, plant-derived eugenol can be introduced into the chemical structure of the propylene resin represented by the general formula (1) as the target, thus providing a compound that reduces environmental impact.

[0188] When the alkenylphenol compound in this embodiment is isoeugenol, i.e., R in the above general formula (C) 31 When the methoxy group at the 2-position is substituted and n31 is 1, plant-derived isoeugenol can be introduced into the chemical structure of the propylene resin represented by general formula (1) as the target, thus providing a compound that reduces environmental impact.

[0189] As the aforementioned phenolic compound, the compound represented by the following general formula (D) is preferred.

[0190] [Chemistry 17]

[0191] M 11 ——OH (D)

[0192] (In the above general formula (D), M) 11 It can be any group from the general formulas (3.1) to (3.4) above.

[0193] The chemical structure in the above general formula (D) corresponds to Ar in the above general formula (1). 13 .

[0194] Examples of the aforementioned phenolic 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 octylphenol; 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, hydroxypiperol, propenylethylguaiacol, and cashew phenol; aralkylphenols such as benzylphenol, cumylphenol, and dicumylphenol; phenylphenols such as phenylphenol and diphenylphenol; and naphthols such as 1-naphthol and 2-naphthol.

[0195] Among these phenolic compounds, alkenylphenols, aralkylphenols, phenylphenols, and naphthols are preferred, alkenylphenols and aralkylphenols are further preferred, and aralkylphenols are even more preferred.

[0196] (The method for manufacturing acrylic resin represented by general formula (1))

[0197] Hereinafter, a method for manufacturing the propylene-based resin represented by general formula (1) of this disclosure will be described. The method for manufacturing the propylene-based resin represented by general formula (1) of this embodiment is not particularly limited as long as it is a manufacturing method capable of manufacturing the chemical structure represented by general formula (1).

[0198] For example, the raw materials used in the method for manufacturing the propylene-based resin represented by general formula (1) of this disclosure can be epihaloalcohols represented by general formula (A), alkenylphenol compounds represented by general formula (B) or (C), and phenolic compounds represented by general formula (D) as needed. Furthermore, the aforementioned method for manufacturing the propylene-based resin can refer to known synthesis conditions and methods.

[0199] As an example of a method for manufacturing a propylene-based resin represented by general formula (1) of this disclosure, a manufacturing method may be provided that includes 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) as needed.

[0200] Step (i-1): The step of reacting the aforementioned epihaloalcohol, which is a reactant, with the aforementioned alkenylphenol compound;

[0201] Step (i-2): A step in which the phenolic compound represented by the aforementioned general formula (D), which is used as a reaction raw material, is further combined with the reaction product of the aforementioned epihaloalcohol and the aforementioned alkenylphenol compound to carry out the reaction.

[0202] Step (i-3): Step of purifying the aforementioned reaction products from the mixture containing the aforementioned reaction products;

[0203] Step (i-4): When a compound having the structure represented by general formula (B) is used as the aforementioned alkenylphenol compound as a reaction raw material, a step is performed to perform an isomerization reaction of the carbon-carbon double bond of the allyl group in the aforementioned general formula (B).

[0204] Specifically, the method for manufacturing the propylene-based resin represented by general formula (1) of this embodiment preferably includes: step (i-1), reacting the epihaloalcohol represented by general formula (A) with the alkenylphenol compound represented by general formula (B) or (C) in the presence of an alkaline compound; step (i-2), further combining the reaction product obtained in step (i-1) with an alkaline compound and a phenol compound represented by general formula (D), and reacting it in the presence of the aforementioned alkaline compound; step (i-3), purifying the reaction product generated in step (i-2) using an acidic aqueous solution and an organic solvent; and step (i-4), performing an isomerization reaction of carbon-carbon double bonds as required.

[0205] The following describes each step of the method for manufacturing the acrylic resin represented by general formula (1) of this disclosure.

[0206] <Process (i-1)>

[0207] As for the proportion of the epihaloalcohol represented by the aforementioned general formula (A) to the alkenylphenol compound represented by the aforementioned general formula (B) or (C), the molar ratio of the hydroxyl group of the alkenylphenol compound represented by the aforementioned general formula (B) or (C) to 1 mole of the aforementioned epihaloalcohol is preferably 0.01 to 1.0 moles, preferably 0.1 to 0.8 moles, and more preferably 0.2 to 0.3 moles.

[0208] In addition, a common method for carrying out the above reaction is as follows: all raw materials are loaded at once and the reaction is carried out directly at a predetermined temperature; or, the aforementioned alkenylphenol compound, the aforementioned epihalool, and the organic solvent are loaded, and the reaction is carried out while a basic compound is added dropwise while maintaining the predetermined temperature. In this case, the dropwise addition time is usually 0.5 to 10 hours, preferably 1 to 6 hours.

[0209] In step (i-1) of this embodiment, an inorganic basic compound or the like can be used as the basic compound. Examples of inorganic basic compounds include hydroxides of alkali metals such as potassium and sodium. From the viewpoint of ease of purification based on water washing, 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.

[0210] Relative to 1 mole of the alkenylphenol compound represented by the aforementioned general formula (B) or general formula (C), the aforementioned basic compound is preferably 1.0 to 2.0 moles, more preferably 1.0 to 1.5 moles, and more preferably 1.0 to 1.2 moles in molar proportion.

[0211] In step (i-1) of this embodiment, a phase transfer catalyst may be used.

[0212] The phase transfer catalysts that can be used in step (i-1) of this embodiment include quaternary ammonium salts, quaternary phosphonium salts, or crown ethers. In particular, quaternary ammonium salts and quaternary phosphonium salts are preferred from the perspective of excellent catalytic activity; specifically, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, and tetrabutylphosphonium bromide are examples. These phase transfer catalysts can be used in the form of an aqueous solution of approximately 10% to 55% by mass, or in solid form.

[0213] Regarding the amount of the aforementioned phase transfer catalyst, relative to 100 parts by mass of the total amount of raw materials input (e.g., the total amount of epihaloalcohols represented by general formula (A) and alkenylphenol compounds represented by general formula (B) or (C), the amount of the phase transfer catalyst is in the range of 0.01 to 1.00 parts by mass, and preferably 0.05 to 0.20 parts by mass from the perspective of operability and economy.

[0214] In step (i-1) of this embodiment, an organic solvent can be used. Examples of such organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, n-butanol, and tert-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 solvents can be used individually or in combination.

[0215] In step (i-1) of this embodiment, the reaction temperature of the epihaloalcohol represented by general formula (A) with the alkenylphenol compound represented by general formula (B) or general formula (C) is usually in the range of 30 to 80°C, but in order to avoid side reactions such as polymer formation and hydrolysis of glycidyl groups, it is preferred to be 40 to 70°C.

[0216] In step (i-1) of this embodiment, the reaction time of the epihaloalcohol represented by general formula (A) and the alkenylphenol compound represented by general formula (B) or (C) is such that the reaction will not be completed in a short time. In addition, if it is set to a long time, side reactions such as thermal decomposition of the product will occur. Therefore, under the aforementioned reaction temperature conditions, the total reaction time is usually in the range of 0.5 to 10 hours, preferably in the range of 1 to 6 hours.

[0217] Therefore, in this embodiment, step (i-1) is more preferably carried out while stirring within a temperature range of 40 to 70°C and a time range of 1 to 6 hours.

[0218] In addition, regarding the atmosphere of process (i-1), it is preferable to carry out the reaction in an inert gas atmosphere such as nitrogen, helium, or argon.

[0219] <Process (i-2)>

[0220] As for the proportion of the phenolic compound represented by the aforementioned general formula (D) relative to the reaction product obtained in step (i-1), considering the balance of the physical properties of the acrylic resin represented by the obtained general formula (1) in terms of its moldability and curing properties (especially gel time), the molar ratio of the hydroxyl groups of the phenolic compound represented by the aforementioned general formula (D) relative to 1 mole of the alkenylphenol compound represented by general formula (B) or (C) 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.

[0221] Furthermore, a typical method for carrying out the above reaction is as follows: all raw materials are loaded at once, and the reaction is carried out directly at a predetermined temperature; or a basic compound is loaded, and the phenolic compound represented by the aforementioned general formula (D) is added dropwise while maintaining the predetermined temperature. In this case, the dropwise addition time is typically 0.5 to 24 hours, preferably 0.5 to 4 hours.

[0222] The alkaline compound and phase transfer catalyst that can be used in step (i-2) of this embodiment refer to the contents of step (i-1).

[0223] In step (i-2) of this embodiment, an organic solvent can 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 solvents can be used individually or in combination.

[0224] In this embodiment, the reaction temperature in step (i-2) is usually in the range of 50 to 170°C, but in order to avoid side reactions such as the formation of polymers and hydrolysis of glycidyl groups, it is preferred to be 100 to 140°C.

[0225] As for the reaction time in step (i-2) of this embodiment, the reaction is not fully carried out in a short time. In addition, if it is set to a long time, side reactions such as thermal decomposition of the product will occur. Therefore, under the aforementioned reaction temperature conditions, it is usually in the range of 0.5 to 24 hours in total, and preferably in the range of 1 to 6 hours in total.

[0226] Therefore, in this embodiment, step (i-2) is more preferably carried out while stirring within a temperature range of 100 to 140°C and a time range of 1 to 6 hours.

[0227] In addition, regarding the atmosphere of process (i-2), it is preferable to carry out the reaction in an inert gas atmosphere such as nitrogen, helium, or argon.

[0228] <Process (i-3)>

[0229] In this embodiment, step (i-3) is performed as needed and is a step to recover the reaction product (= the propylene resin or allyl-containing resin represented by the general formula (1) as the target) obtained in the aforementioned step (i-2). An acidic aqueous solution is added to the solution containing the reaction product and organic solvent obtained in step (i-2). After removing the salts and impurities of the alkaline compound by neutralization and washing with water using this acidic aqueous solution, an azeotropic dehydration operation is performed. After precise filtration, the organic solvent and unreacted compounds are removed by distillation under reduced pressure to obtain the reaction product. Alternatively, a dehydrating agent may be used during the reaction as needed.

[0230] The stability of the resulting resin can be improved by washing the aforementioned reaction products with an acidic aqueous solution. Specific examples of acids that can be used in the aforementioned acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrogen cyanide, 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). Furthermore, these acids can be used alone or in combination of two or more.

[0231] 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.

[0232] <Process (i-4)>

[0233] After step (i-2) or step (i-3) in this embodiment, a step (i-4) for performing a carbon-carbon double bond isomerization reaction can be provided as needed. Specifically, when using an alkenylphenol compound represented by general formula (B) as a reaction raw material, step (i-4) can be further provided: by performing an isomerization reaction on the obtained reaction product, the allyl group in the alkenylphenol compound represented by general formula (B) isomerized to 1-propenyl, and the propenyl resin represented by general formula (1) is synthesized.

[0234] As a method for isomerizing the allyl group to 1-propenyl, known methods can be used, such as carbon-carbon isomerization reactions using palladium acetate catalysts (see [J. Am. Chem. Soc., 91, pp. 6707-6714 (1969)]), or carbon-carbon isomerization reactions using alkali metal hydroxides (potassium hydroxide) as alkali catalysts (see [J. Am. Chem. Soc., 78, pp. 1709-1715 (1956)]).

[0235] Therefore, the propylene-based resin represented by the above general formula (1) can be easily synthesized.

[0236] [Composition]

[0237] This embodiment may be a composition containing a propylene resin and a maleimide resin represented by general formula (1).

[0238] Therefore, it is possible to provide compositions with superior molding flowability (especially spiral flow) and superior curability (especially gel time) and heat resistance (especially glass transition temperature) during curing.

[0239] Generally, the curing mechanisms of alkenyl compounds and maleimide compounds vary depending on the type of alkenyl group, the catalyst system, and the temperature conditions. In curing reactions without a catalyst, there is a tendency for Diels-Alder reactions of conjugated dienes and maleimide groups to occur at low temperatures, as well as alternating polymerization of electron-dense vinyl or 1-propenyl groups with maleimide groups. On the other hand, there is a tendency for Alder-ene reactions (alkene reactions) with allyl groups to occur at higher temperatures, followed by homopolymerization of maleimide groups at high temperatures. Furthermore, in curing reactions using free radical catalyst systems, there is a tendency to promote the aforementioned alternating polymerization and homopolymerization. However, there are reports that in curing reactions using anionic catalyst systems, trimerization of maleimide groups occurs at low temperatures, hindering the aforementioned Diels-Alder and Alder-ene reactions.

[0240] Therefore, when multiple alkenyl groups with different reactivity coexist in a composition, problems with curability (especially gel time) and productivity can easily arise, such as unexpected thickening or gelation at low temperatures, or the need for high curing temperatures for complete curing. However, in the compositions disclosed herein, it has been confirmed that excellent curability (especially gel time) is achieved due to the use of a propylene-based resin represented by general formula (1) having a highly reactive conjugated diene structure.

[0241] The composition of this embodiment preferably contains a propylene resin represented by general formula (1) and a maleimide resin. Moreover, the aforementioned composition may, as needed, contain one or more of the fillers (inorganic fillers) and additives selected from the group consisting of those described later.

[0242] "Composition ratio"

[0243] In the composition of this embodiment, the content of maleimide resin, such as maleimide resin represented by general formula (4), relative to the total amount of the composition (100% by mass) is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, further preferably 30% to 70% by mass, even more preferably 35% to 65% by mass, and particularly preferably 40% to 60% by mass.

[0244] In the composition of this embodiment, the content of propylene resin represented by general formula (1) is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, further preferably 30% to 70% by mass, even more preferably 35% to 65% by mass, and particularly preferably 40% to 60% by mass, relative to the total amount of the composition (100% by mass).

[0245] In the composition of this embodiment, the content of the additives to be added as needed relative to the total amount of the composition (100% by mass) 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.

[0246] In the composition of this embodiment, the total content of the acrylic resin, maleimide resin and additives represented by general formula (1) is preferably 10% to 100% by mass relative to the total amount of the composition (100% by mass), more preferably 20% to 100% by mass, further preferably 30% to 100% by mass, even more preferably 40% to 100% by mass, and particularly preferably 50% to 100% by mass.

[0247] When the composition of this embodiment contains the acrylic resin represented by general formula (1), the maleimide resin, the filler (inorganic filler material), and the additives other than the aforementioned filler (inorganic filler material), the total content of the acrylic resin represented by general formula (1), the aforementioned maleimide resin, the aforementioned filler (inorganic filler material), and the additives other than the aforementioned filler (inorganic filler material) relative to the total amount of the composition (100% by mass) is preferably 10% to 100% by mass, more preferably 20% to 100% by mass, further preferably 30% to 100% by mass, even more preferably 40% to 100% by mass, and particularly preferably 50% to 100% by mass.

[0248] On the other hand, when the composition of this embodiment contains propylene resin and maleimide resin represented by general formula (1) and does not contain filler (inorganic filler material), the total content of the aforementioned propylene resin, the aforementioned maleimide resin and additives other than the aforementioned filler, relative to the total amount of the composition (100% by mass), 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.

[0249] Hereinafter, the maleimide resin, which is a component of the composition constituting this embodiment, and the fillers and additives added as needed will be described in detail.

[0250] (Maleimide resin)

[0251] The composition of this embodiment preferably contains a maleimide resin as a curing agent. Furthermore, the aforementioned maleimide resin is preferably a compound having two or more maleimide groups within its molecule.

[0252] Examples of the aforementioned maleimide resins include: 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, or other maleimide resins.

[0253] Furthermore, other maleimide resins mentioned above 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 Unexamined 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 Unexamined Patent Application Publication No. 2023-152757, and the polymaleimide compound (A) described in Japanese Unexamined Patent Application Publication No. 2023-152755. These maleimide resins can be used alone or in combination of two or more.

[0254] The maleimide resin of this embodiment is more preferably an aromatic maleimide resin having two or more maleimide groups within the molecule, as exemplified above. This readily yields a cured product with high heat resistance (especially glass transition temperature).

[0255] Furthermore, the maleimide resin in this embodiment can be an addition polymer formed by polymerizing an aromatic maleimide resin having two or more maleimide groups within its molecule with an aromatic polyamine. In other words, the maleimide resin in this embodiment can be an aromatic maleimide resin having two or more maleimide groups within its molecule, or a compound using an aromatic maleimide resin having two or more maleimide groups within its molecule and an aromatic polyamine as reactants.

[0256] When an aromatic maleimide resin having two or more maleimide groups within its molecule is polymerized with an aromatic polyamine to form an addition polymer, examples of the aforementioned aromatic polyamine include 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, and bis(4-aminophenyl)benzene. The following substances are listed: methylamine, 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.

[0257] The maleimide resin of this embodiment is preferably represented by the following general formula (4).

[0258] [Chemistry 18]

[0259]

[0260] (In the above general formula (4), R) 41 and R 42 Each can be independently represented by a hydroxyl, alkyl, alkoxy, or aryl group, M 41 Indicates a divalent linker.

[0261] m41 represents an integer greater than 0 and less than 4.

[0262] m42 represents an integer greater than 0 and less than 3.

[0263] n41 is the number of repeating units, representing a natural number.

[0264] Therefore, maleimide resins have aromatic rings, which makes it easier to obtain cured products with higher heat resistance (especially glass transition temperature) during curing.

[0265] In the above general formula (1), R 41 Alkyl groups with 1 to 4 carbon atoms are preferred, and alkyl groups with 1 to 2 carbon atoms are more preferred.

[0266] In the above general formula (1), R 42Alkyl groups with 1 to 4 carbon atoms are preferred, and alkyl groups with 1 to 2 carbon atoms are more preferred.

[0267] In the above general formula (1), M 41 In a preferred embodiment, the divalent linking group is preferably an alkylene group with 1 to 10 carbon atoms or a divalent aromatic cyclic hydrocarbon group with 7 to 16 carbon atoms, and more preferably an alkylene group with 1 to 10 carbon atoms.

[0268] As for the aforementioned divalent aromatic ring hydrocarbon group, any hydrocarbon group having an aromatic ring is acceptable; examples include groups obtained by removing any one hydrogen atom from an aryl or aralkyl group. Preferably, the aforementioned divalent aromatic ring hydrocarbon group is a group obtained by removing any one hydrogen atom from an aralkyl group.

[0269] In general formula (4), m41 is preferably an integer greater than or equal to 0 and less than or equal to 2, more preferably 0 or 1, and even more preferably 0.

[0270] In general formula (4), m42 is preferably an integer greater than or equal to 0 and less than or equal to 2, more preferably 0 or 1, and even more preferably 0.

[0271] 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.

[0272] The preferred maleimide resin of this embodiment may be one or more compounds selected from the group consisting of 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane and 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane.

[0273] In the composition of this embodiment, the content of maleimide resin represented by general formula (4) relative to the total amount of the composition (100% by mass) is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, further preferably 30% to 70% by mass, even more preferably 35% to 65% by mass, and particularly preferably 40% to 60% by mass.

[0274] If the content of the maleimide resin is within the above range, it achieves a high level of balance between curability (especially gel time), heat resistance (especially glass transition temperature), and molding flowability (especially spiral flow). The upper and lower limits of the maleimide resin content can be appropriately combined.

[0275] 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.

[0276] (Any added ingredients)

[0277] The composition of this embodiment may contain known curing agents (especially curing agents with unsaturated double bonds) other than the acrylic resin and maleimide resin represented by general formula (1), and may further contain various compounding agents such as curing accelerators, silane coupling agents, release agents, pigments, emulsifiers, non-halogen flame retardants, fillers (also known as inorganic filler materials), flame retardants (e.g., inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants), solvents, etc., as needed.

[0278] Furthermore, without prejudice to the purpose of this disclosure, the composition of this embodiment may contain known resin components in addition to the aforementioned acrylic resin and maleimide resin. These known resin components may also include epoxy resin, phenolic resin, reactive ester resin, cyanate ester resin, polyphenylene ether resin, benzoxazine resin, styrene-maleic anhydride copolymer, polybutadiene and its modified forms, polyacetal resin, polyvinyl alcohol resin, liquid crystal polymer, fluoropolymer, polystyrene, polyethylene, polyimide resin, silicone gel, silicone oil, etc.

[0279] Furthermore, examples of fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Noiburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0280] The shape of the aforementioned 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 aforementioned filler refers to the value of the peak when the composition of this embodiment is measured using a laser diffraction particle size analyzer (LA500) manufactured by Horiba Corporation.

[0281] Furthermore, the presence of multiple peaks indicates the presence of fillers with varying average particle sizes. Therefore, in the case of multiple peaks, at least one of the values ​​at the peak tip should fall within the aforementioned range of 1 μm to 50 μm.

[0282] (Preferred characteristics of the composition)

[0283] When manufacturing semiconductor sealing materials using a composition containing the acrylic resin of this embodiment, transfer molding is typically used. Transfer molding is a molding method in which the composition, as a material, is temporarily heated and softened within a plunger, then flows through flow paths within a mold such as a gate, runner, and channel, and is pressed into a heated mold cavity to solidify. Therefore, in transfer molding, the flowability of the composition becomes important. If the flowability is not properly adjusted relative to the desired shape of the semiconductor seal, problems such as unfilled portions in the mold cavity or voids and cracks in the molded product can occur.

[0284] As described above, the composition containing acrylic resin of this embodiment can be cured at low temperatures, and therefore transfer molding can be performed at lower temperatures (e.g., below 175°C). Furthermore, as described above, the acrylic resin of this embodiment can undergo a synergistic reaction with a curing agent having unsaturated double bonds (e.g., maleimide resin) via a highly reactive Diels-Alder reaction, thus the composition of this embodiment can be cured in a shorter time (e.g., within 180 seconds, more preferably within 150 seconds, further preferably within 120 seconds, and particularly preferably within 90 seconds).

[0285] In the composition of this embodiment, when the composition contains acrylic resin and maleimide resin, and the content of the aforementioned maleimide resin is 10 to 90% by mass and the content of the aforementioned acrylic resin is 90 to 10% by mass relative to the total amount (100% by mass) of the aforementioned composition, the gel time of the aforementioned composition is preferably within 120 seconds, more preferably within 90 seconds.

[0286] The gel time was determined under the conditions described in the Examples section below.

[0287] [Method for manufacturing the composition]

[0288] There are no particular limitations on the method of manufacturing the composition of this embodiment. For example, melt mixing is preferred as a method of manufacturing the composition. As an example of the apparatus used in melt mixing, extruders, Banbury mixers, rollers, kneaders, etc. can be specifically mentioned, and they are operated in batches or continuously.

[0289] In general, when manufacturing a composition, it is preferable to set the temperature above the melting point of the composition and use an extruder, kneader, roller, etc. to fully melt and mix it until homogeneous.

[0290] [cured material]

[0291] The cured product disclosed herein is preferably obtained from a composition containing the acrylic resin of this embodiment. The aforementioned cured product can be obtained by subjecting the aforementioned composition to a curing reaction. Therefore, the cured product of this disclosure reflects the characteristics of the composition, thus achieving a high degree of balance between excellent curability (especially gel time) and heat resistance (especially glass transition temperature). The aforementioned composition can be obtained by uniformly mixing the aforementioned components (e.g., curing agent, compounding agent), and the cured product can be easily prepared using the same methods as those known in the past. Examples of the aforementioned cured products include laminates, castings, adhesive layers, coatings, films, and other molded cured products.

[0292] [Semiconductor sealing materials]

[0293] This disclosure pertains to semiconductor sealing materials comprising a composition containing an acrylic resin or a cured form thereof according to the present embodiment. Semiconductor sealing materials obtained using the composition of this embodiment exhibit improved molding flowability and curability (especially gel time), thus suppressing molding defects such as short molds and cracks during the manufacturing process, making it a preferred method.

[0294] The acrylic resin-containing composition of this embodiment used in the aforementioned semiconductor sealing material may contain filler (also called inorganic filler material). It should be noted that, as the filling ratio of the aforementioned filler, relative to 100 parts by mass of the total amount of acrylic resin and maleimide resin represented by general formula (1) of this embodiment, the filler may be used in the range of 0.5 to 1200 parts by mass. Furthermore, examples of such fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Noiburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0295] The aforementioned fillers are preferably molten silica or spherical silica, which can suppress the curing shrinkage of the cured composition, resulting in a lower CTE. In addition, they can improve properties such as adhesion and hardness.

[0296] As a method for obtaining the aforementioned semiconductor sealing material, examples include further using an extruder, kneader, roller, or the like to fully melt and mix the additives, which are any components, to a uniform consistency in the composition of this embodiment, as needed.

[0297] [Semiconductor Devices]

[0298] This disclosure pertains to a semiconductor device comprising a cured product of the aforementioned semiconductor sealing material. Semiconductor devices obtained using the semiconductor sealing material derived from the composition containing an acrylic resin according to this embodiment exhibit improved curability (particularly gel time) and heat resistance (particularly glass transition temperature), thus providing excellent demolding properties and reflow resistance during the manufacturing process, making it a preferred method.

[0299] As a method for obtaining the aforementioned semiconductor device, one can include casting the aforementioned semiconductor sealing material, molding it using a transfer molding machine, an injection molding machine, etc., and then heating and curing it in a temperature range of room temperature (20°C) to 250°C.

[0300] [Prepreg]

[0301] This disclosure relates to a prepreg having a reinforcing substrate and a semi-cured product of a composition containing a acrylic resin of this embodiment impregnated in the aforementioned reinforcing substrate. The resulting semi-cured product exhibits excellent curing properties (particularly gel time) and heat resistance (particularly glass transition temperature).

[0302] One method for obtaining a prepreg from the above composition is as follows: The composition, which is mixed with the organic solvent described later and then varnished, is impregnated into a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass fiber mat, glass fiber cloth, etc.). The substrate is then heated at a temperature appropriate to the type of solvent used, preferably 50–170°C, thereby partially curing (or partially curing) the composition to obtain the prepreg. The mass ratio of the composition to the reinforcing substrate used in this process is not particularly limited, but it is generally preferred to prepare the prepreg with a resin content of 20–60% by mass.

[0303] In this embodiment, the semi-cured product of the composition containing acrylic resin is obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without allowing it to complete. Furthermore, the semi-cured product may have a degree of cure of, for example, 85% or less and 5% or more. On the other hand, the cured product in this embodiment may have a higher degree of cure than the semi-cured product.

[0304] It should be noted that the degree of curing of the semi-cured material can be determined by DSC using the heat of curing when heating the composition and the heat of curing of the semi-cured material, and calculated by the following formula.

[0305] Degree of Curing (%) = [1 - (Heat generation of semi-cured product / Heat generation of composition)] × 100

[0306] Organic solvents used in the manufacture of prepregs include, for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of these solvents can be chosen according to 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 less, such as methyl ethyl ketone, acetone, and dimethylformamide. In addition, it is preferable to use them at a ratio of 40 to 80% by mass of non-volatile components.

[0307] [Circuit board]

[0308] This disclosure pertains to a circuit board, which is a laminate of the aforementioned prepreg and copper foil. As a method for obtaining a printed circuit board from the acrylic resin-containing composition of this embodiment, an example is a method of laminating the aforementioned prepreg using conventional methods, appropriately overlapping the copper foil, and then heating and pressing it at 170-300°C for 10 minutes to 3 hours under a pressure of 1-10 MPa.

[0309] [Lamination film]

[0310] This disclosure pertains to a laminated film comprising the acrylic resin-containing composition of this embodiment. As a method for manufacturing the laminated film of this embodiment, an example is a method of coating the above-described composition onto a support film to form a layer of the composition and then fabricating an adhesive film for a multilayer printed wiring board. The resulting laminated film exhibits excellent curing properties (especially gel time) and heat resistance (especially glass transition temperature).

[0311] When the build-up film is manufactured from the composition, it is important that the film exhibits the ability to soften at the lamination temperature conditions (typically 70–140°C) in a vacuum lamination process and to achieve molding flowability (resin flow) for filling the resin present in the vias or through holes of the circuit board during the lamination of the circuit board. It is preferable to combine the above-mentioned components to exhibit such characteristics.

[0312] Here, the diameter of the through-holes in the multilayer printed wiring board is typically 0.1–0.5 mm, and the depth is typically 0.1–1.2 mm, preferably within this range to allow for resin filling. It should be noted that, in the case of both sides of the laminated circuit board, it is preferable to fill approximately half of the through-hole.

[0313] Specifically, the method for manufacturing the above-mentioned adhesive film can be as follows: after preparing the above-mentioned composition in the form of a varnish, the varnish-like composition is coated on the surface of the support film (Y), and the organic solvent is dried by heating or blowing hot air to form a composition layer (X) containing the composition.

[0314] The thickness of the formed composition layer (X) is preferably greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer in the circuit board is typically in the range of 5 to 70 μm, therefore the thickness of the composition layer is preferably 10 to 100 μm.

[0315] It should be noted that the composition layer (X) in this embodiment can be protected by the protective film described later. By protecting it with the protective film, it is possible to prevent dust and other contaminants from adhering to the surface of the composition layer or causing damage to the surface of the composition layer.

[0316] Examples of the aforementioned support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate; polyimide; and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that the support film and protective film can also undergo matte treatment, corona treatment, and release treatment.

[0317] The thickness of the support film is not particularly limited, and is typically 10–150 μm, preferably in the range of 25–50 μm. Furthermore, the thickness of the protective film is preferably 1–40 μm.

[0318] The aforementioned support film (Y) is peeled off after being laminated onto the circuit board or after forming an insulating layer through heat curing. Peeling off the support film (Y) after the adhesive film has been heat-cured prevents the adhesion of dust and other contaminants during the curing process. When peeling off after curing, the support film is typically pre-treated with a demolding process.

[0319] [Heat-resistant materials and electronic materials]

[0320] The cured products obtained from the acrylic resin-containing compositions of this disclosure exhibit excellent curing properties (especially gel time) and heat resistance (especially glass transition temperature), making them suitable for use in heat-resistant components or electronic components. In particular, they are suitable for use in prepregs, circuit boards, semiconductor sealing materials, semiconductor devices, extension films, extension substrates, adhesives using conductive pastes, and photoresist materials. They are also suitable as matrix resins for fiber-reinforced resins, and are particularly suitable as prepregs with excellent heat resistance (especially glass transition temperature) or curing properties (especially gel time). Furthermore, the acrylic resin contained in the aforementioned compositions exhibits excellent solubility in various solvents, thus enabling coating. The heat-resistant components and electronic components thus obtained can be suitably used for a variety of applications, such as industrial machinery parts, general machinery parts, automotive / railway / vehicle parts, aerospace-related parts, electronic / electrical parts, building materials, container / packaging components, consumer goods, sports / leisure products, and wind power generation housing components, but are not limited to these.

[0321] Example

[0322] The present invention will be specifically described through examples and comparative examples. Unless otherwise specified, "parts" and "%" refer to mass. It should be noted that the physical properties of the synthesized acrylic resin were determined as follows.

[0323] (1) Determination of double bond equivalent (iodine value)

[0324] The double bond equivalent of the propylene-based resin obtained in the examples was calculated according to JIS K 0070.

[0325] (2) GPC determination

[0326] 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 propylene-based resin obtained in the examples were calculated using the following measuring apparatus and measuring conditions.

[0327] "Measuring device"

[0328] "HLC-8320GPC" manufactured by Tosoh Corporation

[0329] "Measurement conditions"

[0330] Column: Protective column "HXL-L" manufactured by Tosoh Corporation

[0331] + "TSK-GEL G4000 HXL" manufactured by Tosoh Corporation

[0332] + "TSK-GEL G3000 HXL" manufactured by Tosoh Corporation

[0333] + "TSK-GEL G2000 HXL" manufactured by Tosoh Corporation

[0334] + "TSK-GEL G2000 HXL" manufactured by Tosoh Corporation

[0335] Detector: RI (Differential Refractometer)

[0336] Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation"

[0337] Column temperature: 40℃

[0338] Developing solvent: Tetrahydrofuran

[0339] Flow rate: 1.0 ml / min

[0340] Sample: 50 μl of a tetrahydrofuran solution of the acrylic resin obtained in the examples, which was calculated as 1.0% by mass of solids, was filtered through a microfilter.

[0341] (3) FD-MS determination

[0342] The FD-MS spectrum of the acrylic resin obtained in the examples was measured using the following measuring apparatus and measuring conditions.

[0343] "Measuring device"

[0344] JMS-T100GC AccuTOF manufactured by Nippon Electronics Co., Ltd.

[0345] "Measurement conditions"

[0346] Measurement range: m / z = 4.00~2000.00

[0347] Rate of change: 51.2 mA / min

[0348] Final current value: 45mA

[0349] Cathode voltage: -10kV

[0350] Recording interval: 0.07 sec

[0351] (4) NMR measurement

[0352] The acrylic resin obtained in the examples 1 H-NMR spectra and 13 C-NMR spectra were measured using the following apparatus and under the following conditions.

[0353] "Measuring device"

[0354] JEOL RESONANCE manufactures "JNM-ECA500".

[0355] "Measurement conditions"

[0356] 1 H-NMR spectrum

[0357] Resonant frequency: 500MHz

[0358] Total number of times: 16

[0359] Solvent: Chloroform-d

[0360] Sample concentration: 4% by mass

[0361] 13 C-NMR spectrum

[0362] Resonant frequency: 125MHz

[0363] Total number of times: 2000

[0364] Solvent: Chloroform-d

[0365] Sample concentration: 30% by mass

[0366] (Example 1)

[0367] In a flask equipped with a thermometer, dropping funnel, cooling tube, 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 added and dissolved while purging with nitrogen. The mixture was heated to 60°C, and 179 g (2.2 mol) of 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. Then, under the same conditions, stirring was continued for 30 minutes, followed by washing 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, and the system was heated to 120°C and stirred for 3 hours.

[0368] After the reaction was completed, the system was cooled to 80°C, and 200g of a 12% sodium hydrogen phosphate aqueous solution was added. The mixture was stirred and mixed for 15 minutes, then allowed to stand and separate the layers, removing the aqueous layer. Water was then added to the methyl isobutyl ketone layer containing the reactants, and the mixture was stirred and mixed for 15 minutes. The mixture was allowed to stand and separate the layers, removing the aqueous layer. Dehydration was performed by azeotropic distillation, and the solvent was removed by distillation under reduced pressure to obtain the propylene resin (1) represented by the following chemical formula (1-1). This propylene resin (1) is a semi-solid at room temperature. The double bond equivalent of this propylene resin (1) is 310 g / mol. The Mn of this propylene resin (1) is 683, the Mw is 766, and the Mw / Mn ratio is 1.12.

[0369] In addition, the FD-MS spectrum of the acrylic resin (1) is shown in Figure 1 , the acrylic resin (1) 1 H-NMR spectra and 13 C-NMR spectra are shown in Figure 2 and Figure 3 Display GPC data Figure 4 .

[0370] [Chemistry 19]

[0371] Chemical formula (1-1):

[0372]

[0373] (Example 2)

[0374] Except for replacing "187g (0.9 mol) of p-cumylphenol" used in Example 1 above with "467g (2.2 mol) of p-cumylphenol", the same operation as in Example 1 above was performed to obtain the acrylic resin (2) represented by the following chemical formula (1-2). The acrylic resin (2) is liquid at room temperature. The double bond equivalent of the acrylic resin (2) is 404 g / mol. The Mn of the acrylic resin (2) is 536, the Mw is 556, and the Mw / Mn ratio is 1.04.

[0375] [Chemistry 20]

[0376] Chemical formula (1-2):

[0377]

[0378] It should be noted that the chemical structure of this acrylic resin (2) is the same as that of Example 1 described above, as determined by FD-MS spectroscopy. 1 H-NMR spectra and 13 This was confirmed by C-NMR spectroscopy.

[0379] (Example 3)

[0380] Except for replacing "187g (0.9 mol) of p-cumylphenol" used in Example 1 above with "213g (1.3 mol) of isoeugenol", the same operation as in Example 1 above was performed to obtain the propylene resin (3) represented by the following chemical formula (1-3). The propylene resin (3) is liquid at room temperature. The double bond equivalent of the propylene resin (3) is 200 g / mol. The Mn of the propylene resin (3) is 596, the Mw is 635, and the Mw / Mn ratio is 1.07.

[0381] [Chemistry 21]

[0382] Chemical formulas (1-3):

[0383]

[0384] It should be noted that the chemical structure of this acrylic resin (3) is the same as that of Example 1 described above, as determined by FD-MS spectroscopy. 1 H-NMR spectra and 13 This was confirmed by C-NMR spectroscopy.

[0385] (Example 4)

[0386] Except for replacing "187g (0.9 mol) of p-cumylphenol" used in Example 1 above with "83g (0.9 mol) of phenol", the same operation as in Example 1 above was performed to obtain the propylene resin (4) represented by the following chemical formula (1-4). The propylene resin (4) is liquid at room temperature. The double bond equivalent of the propylene resin (4) is 259 g / mol. The Mn of the propylene resin (4) is 608, the Mw is 677, and the Mw / Mn ratio is 1.11.

[0387] [Chemistry 22]

[0388] Chemical formulas (1-4):

[0389]

[0390] It should be noted that the chemical structure of this acrylic resin (4) is the same as that of Example 1 described above, as determined by FD-MS spectroscopy. 1 H-NMR spectra and 13 This was confirmed by C-NMR spectroscopy.

[0391] (Refer to Example 1 for synthesis)

[0392] In a flask equipped with a thermometer, a fractionating tube, and a stirrer, add 300g (1.83 mol) of isoeugenol, 15g (0.18 mol) of 49% sodium hydroxide, 285g of epoxy resin (EXA-850CRP2, with glycidyl groups of 1.65 mol, as shown in formula (X-1) below) mainly composed of an epoxy compound (molecular weight: 340) represented by chemical formula (X-1), 0.50g of tetrabutylammonium bromide, and 600g of methyl isobutyl ketone. While purging with nitrogen, heat the system to 120°C and continue stirring for 3 hours.

[0393] After the reaction was completed, the system was cooled to 80°C, and 300g of a 12% sodium hydrogen phosphate aqueous solution was added. The mixture was stirred and mixed for 15 minutes, allowed to stand, and the aqueous layer was removed. Water was then added to the methyl isobutyl ketone layer containing the reaction product, and the mixture was stirred and mixed for 15 minutes. The mixture was allowed to stand, and the aqueous layer was removed. An azeotropic dehydration process was performed, followed by precise filtration and distillation under reduced pressure to remove the solvent, yielding a comparative resin (5) containing 89% by area of ​​the propylene-based compound represented by the following chemical formula (C1). The softening point of this comparative resin (5) is 60°C. The double bond equivalent of this comparative resin (5) is 341 g / mol. The Mn of this comparative resin (5) is 1068, the Mw is 1138, and the Mw / Mn ratio is 1.07.

[0394] [Chemistry 23]

[0395]

[0396] [Chemistry 24]

[0397] Chemical formula (C1):

[0398]

[0399] <Examples 5-14 and Comparative Examples 1-2>

[0400] <<Preparation of the Composition>>

[0401] The compositions of Examples 5-14 and Comparative Examples 1-2 were prepared by combining the components with the compositions shown in Tables 1 and 2 below and using a two-roller to melt-mix at 90°C for 5 minutes. In addition, the details of the components other than the acrylic resins (1) to (4) used in Examples 5-14 and the comparative resin (5) used in Comparative Examples 1-2 are described below.

[0402] • Allyl compound (1): 2,2'-diallylbisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.) with the following formula (1.1):

[0403] [Chemistry 25]

[0404]

[0405] • Maleimide resin (1): Polyphenylmethane type maleimide resin (manufactured by Daiwa Chemical Industry Co., Ltd., "BMI-2300") The maleimide resin represented by the following formula (1.2)

[0406] [Chemistry 26]

[0407]

[0408] • Filler: Fused silica (Denka Corporation, “FB-9454”, average particle size (median particle size, D50) 19.9 μm)

[0409] Next, the compositions of Examples 5-14 and Comparative Examples 1-2, prepared according to the steps described in the <<Preparation of Compositions>> section above, were evaluated for glass transition temperature, gel time, and helical flow (fluidity) by the following methods. The results are shown in Tables 1 and 2.

[0410] <<Determination of Glass Transition Temperature (°C)>>

[0411] -Production of solidified materials-

[0412] Each composition prepared as shown in Table 1 below was poured into a mold frame of 11cm×9cm×2.4mm. After molding at 175°C for 10 minutes by pressing, the molded article was removed from the mold frame and then post-cured at 175°C for 5 hours. Each cured article (thickness 2.4mm) was obtained from the compositions of Examples 5 to 9 and Comparative Example 1.

[0413] -Determination of the glass transition temperature (°C) of the cured product-

[0414] Next, each cured material with a thickness of 2.4 mm was cut into pieces 5 mm wide and 54 mm long, which were then used as test pieces 1. For test piece 1, a viscoelasticity measuring device (DMA: Rheometrics RSAII solid viscoelasticity measuring device, rectangular tensile method: frequency 1 Hz, heating rate 3 °C / min) was used to determine the temperature at which the change in elastic modulus reached its maximum (the maximum rate of change of tanδ), which was then taken as the glass transition temperature (°C). A higher glass transition temperature (°C) indicates better heat resistance (especially in terms of glass transition temperature).

[0415] <<Determination of gelation time>>

[0416] The components were combined according to the composition shown in Table 1. After the composition was prepared, 0.15 g of the above composition was immediately placed on a hot plate heated to 175°C. The time (in seconds) until it became gel-like (until it lost its fluidity and became agar-like) was measured while stirring with a spatula. This operation was repeated three times and the average value was used for evaluation.

[0417] <<Determination of Helical Flow>>

[0418] The composition prepared according to the composition in Table 2 below was injected into a test mold at a temperature of 150°C and an injection pressure of 70 kg / cm². 2 The spiral flow value was measured under the condition of 120 seconds. The spiral flow values ​​of Examples 10 to 14 when Comparative Example 2 was set to 100 are shown in Table 2.

[0419] [Table 1]

[0420]

[0421] [Table 2]

[0422]

[0423] Based on the results shown in Table 1 above, when the cured products obtained from the compositions of Examples 5 to 9 are compared with the cured products obtained from the composition of Comparative Example 1, it can be confirmed that by using the compositions containing the acrylic resins of Examples 1 to 5, excellent curing properties (especially gel time) and heat resistance (especially glass transition temperature) are simultaneously achieved during curing.

[0424] Furthermore, based on the results shown in Table 2 above, when comparing the compositions of Examples 10-14 with the composition of Comparative Example 2, it can be confirmed that the compositions containing the acrylic resins of Examples 1-5 exhibit excellent molding flowability (especially spiral flow).

[0425] Based on the above, it was confirmed that the acrylic resins of Examples 1 to 5, when mixed with a curing agent having unsaturated double bonds, exhibit excellent molding flowability (especially spiral flow) and excellent curability (especially gel time) and heat resistance (especially glass transition temperature) during curing.

[0426] [Potential for Industrial Applications]

[0427] According to this disclosure, it is possible to obtain a propylene-based resin, a composition containing the propylene-based resin, and the cured product thereof that have excellent molding flowability (especially spiral flow) when mixed with a curing agent, such as a curing agent having unsaturated double bonds, and excellent curability (especially gel time) and heat resistance (especially glass transition temperature) during curing.

Claims

1. A propylene-based resin represented by the following general formula (1), [Chemical Formula 1] In the above general formula (1), Ar 11 and Ar 12 each independently represents an aromatic hydrocarbon group represented by the following general formula (2), [Chemical Formula 2] In General Formula (2) above, 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 bonding end to a nitrogen atom. Ar 13 represents a substituent R which can be represented by the following general formula (3) 30 a substituted aryl group having 6 to 10 carbon atoms, [Chemical Formula 3] In General Formula (3) above, ring A represents a substituted or unsubstituted 30 a substituted or unsubstituted phenyl ring or naphthyl ring, 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 bonding end to an oxygen atom, n1 is an integer of 0 to 10.

2. The propylene-based resin of claim 1, wherein, The double bond equivalent is 200 g / mole or more and 800 g / mole or less.

3. A composition comprising the propylene-based resin according to claim 1, and a maleimide resin.

4. The composition of claim 3, wherein, The maleimide resin is represented by the following general formula (4): [Chemical Formula 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, M 41 represents a divalent linking group, m41 represents an integer of 0 or more and 4 or less, m42 represents an integer of 0 or more and 3 or less, n41 is the number of repeating units and represents a natural number.

5. The composition of claim 3, wherein, The content of the propylene-based resin is 30 to 70 mass% with respect to the entire composition.

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

7. A printed wiring board produced using the composition according to any one of claims 3 to 5.

8. A semiconductor sealing material produced using the composition according to any one of claims 3 to 5.

9. A build-up film produced using the composition according to any one of claims 3 to 5.

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