Anthracene resin, curable resin composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device

Abstract

To provide a material that has excellent compatibility and can achieve an excellent dielectric loss tangent (i.e., a low dielectric loss tangent) and uniformity in appearance upon curing.SOLUTION: The invention provides an anthracene resin represented by the general formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an anthracene resin, a curable resin composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device. [Background technology]

[0002] Prepregs obtained by impregnating glass cloth with a thermosetting resin and then drying it by heating are widely used as circuit board materials for electronic devices.

[0003] In recent years, with the advancement of faster and higher signal speeds and frequencies, there is a demand for thermosetting resin compositions that provide cured products that exhibit a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant under these conditions. Furthermore, improvements in rigidity and heat resistance are also required to accommodate the trend toward miniaturization of devices. Maleimide compounds and maleimide resins having a maleimide group as a curable substituent have attracted attention as materials that can meet these requirements.

[0004] There is also a demand for a thermosetting resin composition that produces a cured product with excellent uniformity in appearance upon curing.

[0005] In response to this, for example, Patent Document 1 discloses a curable resin composition containing a maleimide (A) having an indane skeleton and a diene polymer (B). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2020 / 217678 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the curable resin composition of Patent Document 1 has a problem with the compatibility between the maleimide (A) and the diene polymer (B), and there is room for further improvement in the dielectric loss tangent and uniformity of appearance of the cured product for high-frequency communication applications.

[0008] Therefore, an object of the present invention is to provide a material that can contribute to the development of heat resistance and a low dielectric loss tangent when cured.

[0009] Another object of the present invention is to provide a cured product having an excellent dielectric loss tangent (i.e., a low dielectric loss tangent) and uniform appearance. Still another object of the present invention is to provide a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that include such a curable resin composition or cured product. [Means for solving the problem]

[0010] The anthracene resin according to the present invention is an anthracene resin represented by general formula (1), [ka] In general formula (1), Each A independently has a structure represented by general formula (2) or (3), B each independently has a structure represented by general formula (4) or (5), L each independently has a structure selected from the group consisting of general formula (6), general formula (7), general formula (8), and general formula (9), p is an integer from 0 to 1000, However, at least one of A and B has a structure represented by general formula (2) or a structure represented by general formula (4), [ka] JPEG2025155408000003.jpg79170In general formula (2), R 1are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 is selected from the group consisting of R 4 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; n is an integer from 1 to 9, * represents the point of attachment to L; In general formula (3), R 2 are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 groups, with the proviso that at least one is an alkyl group; R 4 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; m is an integer from 1 to 5; * represents the point of attachment to L; In general formula (4), R 1 are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 is selected from the group consisting of R 4 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; n is an integer from 1 to 8, * represents the point of attachment to L; In general formula (5), R 2 are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 groups, with the proviso that at least one is an alkyl group; R 4 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; m is an integer from 1 to 4, * represents the point of attachment to L; In the general formula (6), the general formula (8) and the general formula (9), R 3 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; In the general formula (6), the general formula (7), the general formula (8) and the general formula (9), * indicates an anthracene resin, one of which represents the point of attachment to A and the other represents the point of attachment to B.

[0011] In one embodiment of the anthracene resin according to the present invention, the hydroxyl group equivalent weight is 1000 g / equivalent or more.

[0012] In one embodiment of the anthracene resin according to the present invention, A has at least a structure represented by general formula (3), in which m is 2 to 5 and at least two R 2 is an alkyl group; and B has at least a structure represented by general formula (5), in which m is 2 to 4, and at least two R 2 is an alkyl group.

[0013] In one embodiment of the anthracene resin according to the present invention, A has at least a structure represented by general formula (3), in which m is 2 to 5, and at least one R 2 is an alkyl group, and at least one R2 is a methacryloyloxy group, an acryloyloxy group, or an -OCH2 styryl group; and B has at least a structure represented by general formula (5), in which m is 2 to 4, and at least one R 2 is an alkyl group, and at least one R 2 is a methacryloyloxy group, an acryloyloxy group, or an -OCH2 styryl group.

[0014] The curable resin composition according to the present invention is a curable resin composition containing any one of the anthracene resins and maleimide resins described above.

[0015] In one embodiment of the curable resin composition according to the present invention, the curable resin composition contains a Diels-Alder adduct of an anthracene ring of any of the above anthracene resins and a maleimide ring of the maleimide resin.

[0016] In one embodiment of the curable resin composition according to the present invention, the Diels-Alder adduct has one or more structural units selected from the group consisting of general formula (10), general formula (11), and general formula (12), [ka] JPEG2025155408000005.jpg90170 In general formulas (10) to (12), R 1 and n is as defined in general formula (4), R 5 are independently an organic substituent having an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a maleimide group, L and p are as defined in general formula (1), The * on the right side represents the point of attachment to A, and the * on the left side represents the point of attachment to L on the left side of general formula (1).

[0017] The cured product according to the present invention is a cured product of any of the above curable resin compositions.

[0018] One embodiment of the cured product according to the present invention contains a Diels-Alder adduct of an anthracene ring of the anthracene resin and a maleimide ring of the maleimide resin.

[0019] The prepreg according to the present invention is A reinforcing substrate; a semi-cured product of any one of the curable resin compositions impregnated into the reinforcing substrate; It is a prepreg having the following structure.

[0020] The circuit board according to the present invention is a circuit board comprising the above-mentioned cured product.

[0021] The buildup film according to the present invention is a buildup film containing any one of the curable resin compositions described above.

[0022] The semiconductor encapsulant according to the present invention is a semiconductor encapsulant containing any one of the curable resin compositions described above.

[0023] The semiconductor device according to the present invention is a semiconductor device including a cured product of the semiconductor encapsulant. [Effects of the Invention]

[0024] According to the present invention, it is possible to provide an anthracene resin that can contribute to the development of heat resistance and a low dielectric dissipation factor when cured. It is also possible to provide a curable resin composition that can achieve an excellent dielectric dissipation factor (i.e., a low dielectric dissipation factor) and uniformity in appearance. Furthermore, according to the present invention, it is possible to provide a cured product having an excellent dielectric dissipation factor and uniformity in appearance. Furthermore, according to the present invention, it is possible to provide a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that include such a curable resin composition or cured product. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a GPC chart of anthracene resin 1 of Example 1. [Figure 2]FIG. 2 is a GPC chart of anthracene resin 2 in Example 2. [Figure 3] FIG. 3 is a GPC chart of anthracene resin 3 of Example 3. [Figure 4] FIG. 4 is a GPC chart of anthracene resin 4 of Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0026] Hereinafter, embodiments of the present invention will be described. These descriptions are for the purpose of illustrating the present invention and are not intended to limit the present invention in any way.

[0027] In the present invention, two or more embodiments can be combined in any manner.

[0028] Unless otherwise specified, the materials, components, compounds, resins, structural units, catalysts and solvents described herein may be used alone or in combination of two or more.

[0029] In the present invention, an acryloyl group represents H2C=CH-C(=O)-, and a methacryloyl group represents H2C=C(CH3)-C(=O)-.

[0030] In the present invention, the -OCH2 styryl group represents -OCH2-C6H4CH=CH2.

[0031] In the present invention, the hydroxyl group equivalent of the anthracene resin is a value determined by the measurement method described in the Examples.

[0032] In this specification, the symbols "first," "second," (1), (2), (3), (4), etc. are merely symbols for distinguishing one element from another, and are not symbols for limiting the quantity or order.

[0033] (anthracene resin) The anthracene resin according to the present invention is an anthracene resin represented by general formula (1), [ka] In general formula (1), Each A independently has a structure represented by general formula (2) or (3), B each independently has a structure represented by general formula (4) or (5), L each independently has a structure selected from the group consisting of general formula (6), general formula (7), general formula (8), and general formula (9), p is an integer from 0 to 1000, However, at least one of A and B has a structure represented by general formula (2) or a structure represented by general formula (4), [ka] JPEG2025155408000008.jpg78170In general formula (2), R 1 are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 is selected from the group consisting of R 4 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; n is an integer from 1 to 9, * represents the point of attachment to L; In general formula (3), R 2 are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 groups, with the proviso that at least one is an alkyl group; R 4are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; m is an integer from 1 to 5; * represents the point of attachment to L; In general formula (4), R 1 are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 is selected from the group consisting of R 4 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; n is an integer from 1 to 8, * represents the point of attachment to L; In general formula (5), R 2 are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R 4 O group, R 4 2N groups, COR 4 Groups and COOR 4 groups, with the proviso that at least one is an alkyl group; R 4 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; m is an integer from 1 to 4, * represents the point of attachment to L; In the general formula (6), the general formula (8) and the general formula (9), R 3 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; In the general formula (6), the general formula (7), the general formula (8) and the general formula (9), * indicates an anthracene resin, one of which represents the point of attachment to A and the other represents the point of attachment to B.

[0034] Although the reason why the present invention has an effect is not clear, it is presumed that the anthracene ring is composed of a hydrocarbon, and the proportion of hydrocarbon is high, so that the dielectric tangent can be reduced when the composition is cured.

[0035] Furthermore, the anthracene resin of the present invention has excellent compatibility with maleimide compounds and maleimide resins. Therefore, when the anthracene resin of the present invention is mixed with a maleimide compound and a maleimide resin to form a cured product, the cured product also has excellent transparency. In circuit board materials, nonuniformity greater than the size of the copper wiring / insulation (line and space, L / S) is unacceptable. Since the L / S is on the order of μm, if the cured product lacks transparency upon visual observation of its appearance, it can be determined that the resin blended with the maleimide resin has phase-separated from the maleimide resin. Therefore, the visual transparency of the cured product is at least essential for circuit board materials.

[0036] In general formula (1), at least one of A and B has a structure represented by general formula (2) or general formula (4). That is, of all As and Bs in general formula (1), at least one A or B has an anthracene ring.

[0037] p represents the number of repeating units and is an integer from 0 to 1000. In one embodiment, p is 1 to 1000. In another embodiment, p is 0 or more, 1 or more, 10 or more, 50 or more, 100 or more, or 500 or more. In yet another embodiment, p is 1000 or less, 500 or less, 100 or less, 50 or less, or 10 or less.

[0038] R in general formula (2) 1 Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0039] R in general formula (2) 1 The aryl group may, for example, be an aryl group having 6 to 10 carbon atoms.

[0040] R in general formula (2) 4 The alkyl and aryl groups in R 1 The alkyl and aryl groups are the same as those in the above.

[0041] In the general formula (2), n is 1, 2, 3, 4, 5, 6, 7 or 8.

[0042] In one embodiment, general formula (2) is 1 are all hydrogen.

[0043] In one embodiment, the bond * in general formula (2) is located at the 1st, 2nd, 3rd, 4th, 5th, 6th, 7th, 8th, 9th or 10th position of the anthracene ring.

[0044] R in general formula (3) 2 The alkyl group and aryl group in the general formula (2) are 1 The alkyl and aryl groups are the same as those in the above.

[0045] R in general formula (3) 4 The alkyl group and aryl group in the general formula (2) are 4 The alkyl and aryl groups are the same as those in the above.

[0046] In the general formula (3), m is 1, 2, 3, 4 or 5.

[0047] In one embodiment, general formula (3) is 2 are all methyl groups.

[0048] R in general formula (4) 1 and R 4 is R in general formula (2) 1 and R 4 is the same as:

[0049] In the general formula (4), n is 1, 2, 3, 4, 5, 6, 7 or 8.

[0050] In one embodiment, general formula (4) is a group in which n is 8 and R 1 are all hydrogen.

[0051] In one embodiment, the two bonds * in general formula (4) are located at the 2- and 3-positions; the 1- and 4-positions; the 9- and 10-positions; the 5- and 8-positions; or the 6- and 7-positions of the anthracene ring.

[0052] R in general formula (5) 2 and R 4 is R in general formula (3). 2 and R 4 is the same as:

[0053] In the general formula (5), m is 1, 2, 3 or 4.

[0054] In one embodiment, general formula (5) is 2 are all methyl groups.

[0055] R in general formulas (6), (8) and (9) 3 The alkyl and aryl groups in R 1 The alkyl and aryl groups are the same as those in the above.

[0056] In one embodiment, general formula (6) has two substituents attached to the para position of the benzene ring, and two R 3 is hydrogen.

[0057] In one embodiment, general formula (8) has two substituents attached to the tetrahydrodicyclopentadiene ring and R3 is hydrogen.

[0058] In one embodiment, general formula (9) has two substituents attached to the methylene group and R3 is hydrogen.

[0059] In one embodiment, L has a structure selected from the group consisting of general formulas (6) and (7), where general formula (6) has two substituents attached to the para position of the benzene ring and two R 3 is hydrogen.

[0060] In one embodiment, the anthracene resin of general formula (1) has one or more structures selected from the group consisting of general formulas (13), (14), and (15). [ka]

[0061] In one embodiment, the anthracene resin has a hydroxyl equivalent of 1000 g / equivalent or more, and in another embodiment, the anthracene resin has a hydroxyl equivalent of 1000 to 20000 g / equivalent.

[0062] (Method for synthesizing anthracene resin) The method for synthesizing the anthracene resin of the present invention is not particularly limited, and the anthracene resin can be obtained by reacting a compound that forms A in general formula (1), a compound that forms B, and a crosslinking agent that forms L as reaction raw materials.

[0063] Among A in general formula (1), examples of the compound that forms the structure of general formula (2) include substituted or unsubstituted anthracene.

[0064] Among A in general formula (1), examples of compounds that form the structure of general formula (3) include substituted or unsubstituted benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene.

[0065] Other compounds that form the structure of general formula (3) include aromatic compounds having multiple substituents, including two or more alkyl groups or one or more radically polymerizable functional groups. Examples of the radically polymerizable functional groups include known radically polymerizable functional groups, such as vinyl, allyl, isopropenyl, 1-propenyl, acryloyl, methacryloyl, styryl, and styrylmethyl groups.

[0066] Examples of aromatic compounds having multiple substituents containing two or more alkyl groups or one or more radically polymerizable functional groups include mesitylene, 2,6-dimethylmethacryloyloxybenzene, and 2,6-dimethylacryloyloxybenzene.

[0067] Among B in general formula (1), compounds that form the structure of general formula (4) include, for example, substituted or unsubstituted anthracene.

[0068] Among B in general formula (1), examples of the compound that forms the structure of general formula (5) include substituted or unsubstituted benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene.

[0069] Among L in general formula (1), examples of the crosslinking agent that forms the structure of general formula (6) include 1,4-bis(hydroxymethyl)benzene, 1,4-bis(methoxymethyl)benzene, and divinylbenzene.

[0070] Among L in general formula (1), examples of the crosslinking agent that forms the structure of general formula (7) include 4,4'-bis(methoxymethyl)biphenyl.

[0071] Among L in the general formula (1), examples of the crosslinking agent that forms the structure of the general formula (8) include dicyclopentadiene.

[0072] Among L in general formula (1), examples of the crosslinking agent that forms the structure of general formula (9) include formaldehyde.

[0073] The compound that forms A in general formula (1) is blended in an amount of, for example, 10 to 90% by mass relative to the total mass of the raw materials.

[0074] The compounding amount of the compound forming B in general formula (1) is, for example, 10 to 90 mass % relative to the total mass of the raw materials.

[0075] When there is one type of compound forming A and B in general formula (1), the amount blended is, for example, 10 to 90 mass % relative to the total mass of the raw materials.

[0076] The amount of the crosslinking agent to be added is, for example, 10 to 90% by mass relative to the total mass of the raw materials.

[0077] The reaction temperature can be set to, for example, 120°C to 140°C.

[0078] The reaction time can be, for example, 9 hours or more.

[0079] In one embodiment, the compound forming A in general formula (1) is one or more selected from the group consisting of unsubstituted anthracene and mesitylene; the compound forming B in general formula (1) is one or more selected from the group consisting of unsubstituted anthracene and mesitylene; and the crosslinker forming L in general formula (1) is one or more selected from the group consisting of 1,4-bis(hydroxymethyl)benzene and 4,4'-bis(methoxymethyl)biphenyl.

[0080] The anthracene resin of the present invention may have one or both ends modified with a functional group such as a methacryloyl group. For example, the ends of the anthracene resin can be methacrylic-modified by reacting an anthracene resin having a terminal phenolic hydroxyl group with methacrylic acid.

[0081] (Curable resin composition) The curable resin composition according to the present invention is a curable resin composition containing an anthracene resin represented by general formula (1) and a maleimide resin.

[0082] The maleimide resin is not particularly limited, and any known maleimide resin can be used. The maleimide resin may be, for example, a synthesized maleimide resin or a commercially available maleimide resin.

[0083] Examples of the synthesized maleimide resin include the maleimide resins and maleimide compounds described in Patent Document 1, International Publication No. 2020 / 217679, and Japanese Patent Application Laid-Open No. 2023-152756.

[0084] Examples of commercially available maleimide resins include 4,4'-diphenylmethane bismaleimide (trade name: BMI-1000), phenylmethane maleimide (trade name: BMI-2000), m-phenylene bismaleimide (trade name: BMI-3000), bisphenol A diphenyl ether bismaleimide (trade name: BMI-4000), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (trade name: BMI-5100), 4-methyl-1,3-phenylene bismaleimide (trade name: BMI-7000), and 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (trade name: BMI-TMH), all of which are manufactured by Daiwa Chemical Industry Co., Ltd.

[0085] In one embodiment of the curable resin composition according to the present invention, the curable resin composition contains a Diels-Alder adduct of an anthracene ring of any of the anthracene resins and a maleimide ring of the maleimide resin. For example, a Diels-Alder adduct may be obtained in advance and then blended into the curable resin composition.

[0086] In one embodiment of the curable resin composition according to the present invention, the Diels-Alder adduct has one or more structural units selected from the group consisting of general formula (10), general formula (11), and general formula (12), [ka] JPEG2025155408000011.jpg84170 In general formulas (10) to (12), R 1 and n is as defined in general formula (4), R 5 are independently an organic substituent having an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a maleimide group, L and p are as defined in general formula (1), The * on the right side represents the point of attachment to A, and the * on the left side represents the point of attachment to L on the left side of general formula (1).

[0087] R 5 Examples of the aromatic hydrocarbon group include a structure represented by general formula (16): [ka] In general formula (16), R 6 are each independently an alkyl group, an aryl group, or R 4 selected from the group consisting of an O group, an alkylthio group, an arylthio group, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, and a mercapto group; each r is independently 1, 2, or 3; R 7 are each independently an alkyl group, an aryl group, or R 4 selected from the group consisting of an O group, an alkylthio group, an arylthio group, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, and a mercapto group; s is 0, 1, 2 or 3; q represents the number of repeating units and is an integer of 1 to 20; * denotes the point of attachment to the succinimide ring in general formulae (10) to (12).

[0088] R 6 Examples of the alkyloxy group include a methoxy group and an ethoxy group.

[0089] R 6 Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, and a pyrenyloxy group.

[0090] R 5 Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups having 1 to 10 carbon atoms.

[0091] R 5 Examples of the organic substituent having a maleimide group include a 4-maleimidophenyl group and a 4-(4-maleimidobenzyl)phenyl group.

[0092] Synthesis of Diels-Alder adducts Diels-Alder adducts can be synthesized by mixing anthracene resin and maleimide resin and heating the mixture in toluene. Diels-Alder adducts can also be synthesized during the curing of a curable resin composition.

[0093] When a Diels-Alder adduct is synthesized by heating an anthracene resin and a maleimide resin in toluene, the blending amounts of the anthracene resin and the maleimide resin are, for example, 10 to 5,000 parts by mass of maleimide resin per 100 parts by mass of anthracene resin. When a Diels-Alder adduct is synthesized by heating an anthracene resin and a maleimide resin in toluene, the blending amounts of the anthracene resin and the maleimide resin are, from the viewpoint of low dielectric properties, preferably in the range of 10 to 500 parts by mass of maleimide resin per 100 parts by mass of anthracene resin, and from the viewpoint of curability, preferably in the range of 500 to 5,000 parts by mass of maleimide resin per 100 parts by mass of anthracene resin.

[0094] The temperature for heating in toluene can be, for example, 80 to 120° C. The time for heating in toluene can be 1 to 3 hours.

[0095] The amount of anthracene resin in the curable resin composition is not particularly limited and can be adjusted appropriately. The amount of anthracene resin in the curable resin composition is, for example, 50 to 100 parts by mass relative to 100 parts by mass of the resin components of the curable resin composition. In one embodiment, the amount of anthracene resin relative to 100 parts by mass of the resin components of the curable resin composition is 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more. In another embodiment, the amount of anthracene resin relative to 100 parts by mass of the resin components of the curable resin composition is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less.

[0096] In addition to the anthracene resin and the maleimide resin, the curable resin composition may contain known components that are blended into curable resin compositions, such as other resins, curing agents, curing accelerators, flame retardants, fillers, silane coupling agents, release agents, pigments, emulsifiers, and solvents.

[0097] Other resins The other resin is not particularly limited, and known resins can be used, such as thermosetting polyimide resin, epoxy resin, phenol resin, active ester resin, and cyanate resin.

[0098] Examples of components such as the curing agent described above include those described in Patent Document 1, International Publication No. 2020 / 217679, and Japanese Patent Application Laid-Open No. 2023-152756.

[0099] Method for preparing a curable resin composition The method for preparing the curable resin composition is not particularly limited, and the composition can be obtained by mixing an anthracene resin, a maleimide resin, and optional components.

[0100] ·Applications of curable resin compositions Examples of uses of the curable resin composition include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, insulating materials for circuit boards such as build-up adhesive films, resin casting materials, adhesives, semiconductor encapsulating materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up boards, fiber-reinforced composite materials, molded articles obtained by curing the composite materials, etc. Further examples of uses include those described in Patent Document 1, International Publication No. 2020 / 217679, and JP-A No. 2023-152756.

[0101] (cured product) The cured product of the present invention is a cured product of the above-mentioned curable resin composition. The cured product of the present invention can be obtained by curing the curable resin composition by, for example, the methods described in Patent Document 1, International Publication No. 2020 / 217679, and Japanese Patent Application Laid-Open No. 2023-152756.

[0102] A cured product can be obtained, for example, by heat-curing the curable resin composition at a temperature of, for example, 100 to 300° C. The heating time is, for example, 1 to 24 hours.

[0103] One embodiment of the cured product according to the present invention contains a Diels-Alder adduct of an anthracene ring of the anthracene resin and a maleimide ring of the maleimide resin of the present invention.

[0104] The uses of the cured product are the same as those of the curable resin composition described above.

[0105] (prepreg) The prepreg of the present invention comprises a reinforcing substrate and a semi-cured product of the curable resin composition of the present invention impregnated into the reinforcing substrate.

[0106] The prepreg can be manufactured using a known prepreg manufacturing method, for example, the methods described in Patent Document 1, International Publication No. 2020 / 217679, and Japanese Patent Laid-Open No. 2023-152756.

[0107] Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth.

[0108] A semi-cured product of the curable resin composition can be obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without completing it.

[0109] The degree of cure of the semi-cured product may be, for example, 5 to 85%. The degree of cure of the semi-cured product can be calculated from the following formula by measuring the amount of heat generated when the curable composition is heated and the amount of heat generated when the semi-cured product is heated by DSC. Degree of cure (%) = {1 - (heat generated from curing of semi-cured product / heat generated from curing of curable resin composition)} x 100

[0110] (circuit board) The circuit board of the present invention includes the cured product of the present invention. In one embodiment, the circuit board includes a laminate of the prepreg and copper foil.

[0111] The circuit board can be manufactured by a known method for manufacturing a circuit board, such as the methods described in Patent Document 1 and JP-A-2023-152756.

[0112] (build-up film) The build-up film according to the present invention contains the above-mentioned curable resin composition.

[0113] The build-up film can be produced by a known build-up film production method, such as the methods described in Patent Document 1 and JP-A No. 2023-152756.

[0114] (Semiconductor encapsulation material) The semiconductor encapsulant according to the present invention contains the above-described curable resin composition.

[0115] The semiconductor encapsulation material can be produced by a known method for producing a semiconductor encapsulation material, such as the methods described in Patent Document 1 and JP-A No. 2023-152756.

[0116] (Semiconductor Devices) The semiconductor device according to the present invention includes a cured product of the semiconductor encapsulant.

[0117] The semiconductor device can be manufactured by a known method for manufacturing a semiconductor device, such as the methods described in Patent Document 1 and Japanese Patent Application Laid-Open No. 2023-152756. [Example]

[0118] The present invention will be described in more detail below by way of examples, but these examples are intended to illustrate the present invention and are not intended to limit the present invention in any way.

[0119] The materials used in the examples are as follows: Maleimide resin 1: Synthesized in the same manner as in Synthesis Example 10 (maleimide compound A-11) of WO 2020 / 217679. Maleimide resin 2: Synthesized in the same manner as in Example 1 (polymaleimide compound (1)) of JP-A No. 2023-007239. Maleimide resin 3: Daiwa Chemical Industry Co., Ltd., product name "BMI-5100", 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide Polybutadiene: Cray Valley Corporation, product name "Ricon (registered trademark) 157" Curing accelerator: cumene hydroperoxide, product name "Percumyl (registered trademark) H-80" manufactured by NOF Corporation

[0120] The apparatus and conditions used in the examples are as follows. Viscoelasticity measuring device (DMA): Hitachi High-Tech Science Corporation, solid viscoelasticity measuring device "DMS6100", deformation mode: double-sided bending, measurement mode: sine wave vibration, frequency 1 Hz, heating rate 3°C / min)

[0121] Evaluation of GPC measurements As a sample, a 1.0 mass% tetrahydrofuran solution (50 μl) of the resin obtained in the following synthesis example was filtered through a microfilter. GPC measurement was performed in the same manner as in the GPC measurement described in the examples of JP-A-2023-127139, and a GPC chart was obtained. Based on the number average molecular weight (Mn) of the GPC chart, the average number of repeating units p was calculated.

[0122] Hydroxyl equivalent The hydroxyl group equivalent of the anthracene resin obtained in the examples was measured by the following method. Approximately 2.5 g of anthracene resin, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were weighed into a 500 mL Erlenmeyer flask with a stopper. A condenser was then attached to the Erlenmeyer flask, and the flask was heated to reflux in an oil bath set to 120°C for 150 minutes. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added to the flask. The resulting solution was titrated potentiometrically with a 0.5 mol / L potassium hydroxide-ethanol solution. A blank test was performed in the same manner to correct for the value. Hydroxyl group equivalent (g / equivalent)=(S×2,000) / (Blank-A) S: Amount of sample (g) A: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed (mL) Blank: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed in the blank test (mL)

[0123] Example 1: Synthesis of anthracene resin 1 A 2-L round-bottom flask was charged with 124.8 g of anthracene, 169.3 g of 1,4-bis(hydroxymethyl)benzene, 294.5 g of mesitylene, and 14.7 g of toluenesulfonic acid monohydrate. The mixture was heated at 140 °C for 9 hours. After the mixture was cooled to room temperature, 15.9 g of 20% aqueous sodium hydroxide, 15.9 g of 30% aqueous sodium phosphate dibasic, and 588 g of toluene were added. The resulting solution was washed five times with 588 g of water. Unreacted mesitylene was then distilled off under reduced pressure. Unreacted anthracene was then removed by steam distillation under vacuum to obtain Anthracene Resin 1. The Mn of Anthracene Resin 1 was 566, and the Mw was 1267. The hydroxyl equivalent weight of Anthracene Resin 1 was 4410 g / eq. A GPC chart of Anthracene Resin 1 is shown in Figure 1. The anthracene resin 1 is a compound represented by the general formula (1), in which A is "R 2 = methyl group, m = 3, general formula (3)" and B is "R 1 = hydrogen, n=8, general formula (4)" and L is "R 3 = hydrogen, and p is 0 to 70.

[0124] Example 2: Synthesis of anthracene resin 2 A 2-L round-bottom flask was charged with 53.5 g of anthracene, 127.2 g of 4,4'-bis(methoxymethyl)biphenyl, 126.2 g of mesitylene, and 9.0 g of toluenesulfonic acid monohydrate. The mixture was heated at 180 °C for 6 hours. After cooling to room temperature, 9.8 g of 20% aqueous sodium hydroxide, 9.8 g of 30% aqueous sodium phosphate dibasic, and 360 g of toluene were added. The resulting solution was washed five times with 360 g of water. Unreacted mesitylene was then distilled off under reduced pressure. Unreacted anthracene was then removed by steam distillation under vacuum to obtain anthracene resin 2. The Mn of anthracene resin 2 was 772, and the Mw was 2041. The hydroxyl equivalent weight of anthracene resin 2 was greater than 10,000 g / eq. A GPC chart of anthracene resin 2 is shown in Figure 2. The anthracene resin 2 is a compound represented by the general formula (1), in which A is "R 2 = methyl group, m = 3, general formula (3)" and B is "R1 = hydrogen, n=8, L is general formula (7), and p is 0 to 100.

[0125] Example 3: Synthesis of anthracene resin 4 having methacryloyl groups 1. Synthesis of anthracene resin 3 A 1-L round-bottom flask was charged with 71.3 g of anthracene, 133.0 g of 1,4-bis(methoxymethyl)benzene, 146.6 g of 2,6-xylenol, and 10.5 g of toluenesulfonic acid monohydrate. The mixture was heated at 160 °C for 6 hours. After cooling to room temperature, 11.4 g of 20% aqueous sodium hydroxide, 11.4 g of 30% aqueous sodium phosphate dibasic, and 500 g of toluene were added. The solution was washed five times with 500 g of water. The solvent was then distilled off under reduced pressure. Unreacted anthracene and 2,6-xylenol were then removed by steam distillation under vacuum to obtain anthracene resin 3. The Mn of anthracene resin 3 was 988, and the Mw was 1979. The hydroxyl equivalent weight of anthracene resin 3 was 333 g / eq. A GPC chart of anthracene resin 3 is shown in Figure 3. The anthracene resin 3 is a compound represented by the general formula (1), in which A is "two R 2 = methyl group, one R 2 =OH group, m=3, and general formula (3) 1 = hydrogen, n=8, general formula (4)" and L is "R 3 = hydrogen, and p is 0 to 120.

[0126] 2. Methacryloylation of anthracene resin 3 A 500 mL separable flask was charged with 60.0 g of anthracene resin 3, 1.21 g of dimethylaminopyridine, 120.0 g of toluene, and 20.0 g of triethylamine. The mixture was heated to 60°C. 38.8 g of methacrylic anhydride was added dropwise to the mixture over 30 minutes, and the mixture was allowed to react at 60°C for 9 hours. 72.2 g of water was then added to the solution, which was then allowed to cool to room temperature. 115.1 g of 5% aqueous sodium hydroxide solution was added to the reaction solution. The reaction solution was then stirred at 40°C for 1 hour to hydrolyze unreacted methacrylic anhydride. The lower layer was then discarded. 34.5 g of 30% aqueous sodium phosphate dibasic and 120.0 g of toluene were then added to the upper layer. The solution was washed five times with 120 g of water. The solvent was then removed under reduced pressure to obtain anthracene resin 4. The Mn of anthracene resin 4 was 1096 and the Mw was 2220. The hydroxyl group equivalent weight of anthracene resin 4 was 1475 g / equivalent. The GPC chart of anthracene resin 4 is shown in FIG. 2. Anthracene resin 4 is a compound represented by the general formula (1), in which A is "two R 2 = methyl group, one R 2 = methacryloyl group, m = 3, general formula (3)" and B is "R 1 = hydrogen, n=8, general formula (4)" and L is "R 3 = hydrogen, and p is 0 to 120.

[0127] Examples 4 to 8 and Comparative Examples 1 to 2 Curable resin compositions were prepared according to the formulations shown in Table 1.

[0128] [Table 1]

[0129] The curable resin composition was pressed using a vacuum press at 200°C for 2 hours, and then heat-cured at 250°C for 2 hours to obtain a cured product. The cured products of Examples 4 to 8 contained a Diels-Alder adduct of the anthracene ring of the anthracene resin and the maleimide ring of the maleimide resin. Furthermore, this Diels-Alder adduct contained at least a structure in which the anthracene ring was added at the 9- and 10-positions, i.e., a structure corresponding to general formula (10). The dielectric tangent and appearance of the cured products were evaluated using the following methods.

[0130] Dielectric properties In accordance with JIS-C-6481, the dielectric loss tangent at 1 GHz and 10 GHz of the test specimens was measured by the cavity resonance method using an Agilent Technologies network analyzer "E8362C" after bone drying and then storing them indoors at 23°C and 50% humidity for 24 hours. From the viewpoint of reducing transmission loss as an electronic material, the dielectric loss tangent is preferably 0.0030 or less, and more preferably 0.0025 or less.

[0131] Glass transition temperature (Tg) The 2.4 mm thick cured product was cut into a 5 mm wide and 54 mm long test piece. Using a viscoelasticity measuring device, the temperature (°C) at which the change in elastic modulus was greatest (the rate of change in tan δ was greatest) was evaluated as the glass transition temperature (Tg).

[0132] Appearance evaluation Letters were printed on the back of the 2.0 mm thick cured product in a 5 mm square. Transparency was visually evaluated based on the readability of the letters.

[0133] As shown in Table 1, the present invention was able to provide a curable resin composition that can achieve an excellent dielectric loss tangent (ie, a low dielectric loss tangent) and uniform appearance upon curing.

[0134] Example 9 and Comparative Example 3 A varnish solution was prepared according to the formulation shown in Table 2.

[0135] [Table 2]

[0136] The appearance of the resulting varnish solution was evaluated visually. 1 g of each varnish solution was placed in a metal dish, which was heated to 150°C to volatilize the toluene in the varnish solution and dry it. The appearance of the resin component remaining in the dish was then evaluated visually.

[0137] As shown in Table 2, in Example 9, both the varnish solution and the resin component after drying were uniform and transparent, confirming that the anthracene resin of the present invention has excellent compatibility with maleimide resins. [Industrial Applicability]

[0138] According to the present invention, it is possible to provide an anthracene resin that can contribute to the development of heat resistance and a low dielectric dissipation factor when cured. It is also possible to provide a curable resin composition that can achieve an excellent dielectric dissipation factor (i.e., a low dielectric dissipation factor) and uniformity in appearance. Furthermore, according to the present invention, it is possible to provide a cured product having an excellent dielectric dissipation factor and uniformity in appearance. Furthermore, according to the present invention, it is possible to provide a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that include such a curable resin composition or cured product.

Claims

1. An anthracene resin represented by general formula (1): 【Chemical 1】 In general formula (1), Each A independently has a structure represented by general formula (2) or (3), B each independently has a structure represented by general formula (4) or (5), L each independently has a structure selected from the group consisting of general formula (6), general formula (7), general formula (8), and general formula (9), p is an integer from 0 to 1000; However, at least one of A and B has a structure represented by general formula (2) or a structure represented by general formula (4), 【Chemistry 2】 【change】 In general formula (2), R １ are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R ４ O group, R ４ ２ N group, COR ４ Group and COOR ４ is selected from the group consisting of R ４ are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; n is an integer from 1 to 9, * represents the point of attachment to L; In general formula (3), R ２ are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R ４ O group, R ４ ２ N group, COR ４ Group and COOR ４ groups, with the proviso that at least one is an alkyl group; R ４ are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; m is an integer from 1 to 5, * represents the point of attachment to L; In general formula (4), R １ are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R ４ O group, R ４ ２ N group, COR ４ Group and COOR ４ is selected from the group consisting of R ４ are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; n is an integer from 1 to 8, * represents the point of attachment to L; In general formula (5), R ２ are independently hydrogen, an alkyl group, an aryl group, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, R ４ O group, R ４ ２ N group, COR ４ Group and COOR ４ groups, with the proviso that at least one is an alkyl group; R ４ are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; m is an integer from 1 to 4, * represents the point of attachment to L; In the general formula (6), the general formula (8) and the general formula (9), R ３ are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and vinyl groups; In the general formula (6), the general formula (7), the general formula (8) and the general formula (9), * indicates an anthracene resin, one of which is a bond point to A and the other is a bond point to B.

2. 2. The anthracene resin according to claim 1, wherein the hydroxyl equivalent is 1000 g / equivalent or more.

3. A has at least a structure represented by general formula (3), in which m is 2 to 5, and at least two R ２ is an alkyl group; and B has at least a structure represented by general formula (5), in which m is 2 to 4, and at least two R ２ The anthracene resin of claim 1 , wherein is an alkyl group.

4. A has at least a structure represented by general formula (3), in which m is 2 to 5, and at least one R ２ is an alkyl group, and at least one R ２ is a methacryloyloxy group, an acryloyloxy group, or —OCH ２ is a styryl group; and B has at least a structure represented by general formula (5), in which m is 2 to 4, and at least one R ２ is an alkyl group, and at least one R ２ is a methacryloyloxy group, an acryloyloxy group, or —OCH ２ 2. The anthracene resin of claim 1, wherein the anthracene resin is a styryl group.

5. A curable resin composition comprising the anthracene resin of claim 1 and a maleimide resin.

6. 6. The curable resin composition according to claim 5, wherein the curable resin composition comprises a Diels-Alder adduct of an anthracene ring of the anthracene resin and a maleimide ring of the maleimide resin.

7. The Diels-Alder adduct has one or more structural units selected from the group consisting of general formula (10), general formula (11), and general formula (12), 【Chemistry 3】 【change】 In general formulas (10) to (12), R １ and n is as defined in general formula (4), R ５ are independently an organic substituent having an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a maleimide group, L and p are as defined in general formula (1), The curable resin composition according to claim 6, wherein the * on the right side represents a bonding point with A, and the * on the left side represents a bonding point with L on the left side of general formula (1).

8. A cured product of the curable resin composition according to claim 5.

9. The cured product according to claim 8 , comprising a Diels-Alder adduct of an anthracene ring of the anthracene resin and a maleimide ring of the maleimide resin.

10. A reinforcing substrate; A semi-cured product of the curable resin composition according to claim 5 impregnated into the reinforcing substrate; A prepreg having

11. A circuit board comprising the cured product according to claim 8.

12. A build-up film comprising the curable resin composition according to claim 5 .

13. A semiconductor encapsulant comprising the curable resin composition according to claim 5 .

14. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 13.

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