Ester compounds and resin compositions

Abstract

The present invention provides a novel epoxy resin curing agent. The present invention provides a compound containing a structure represented by formula (1), a structure represented by formula (2), and a structure represented by formula (3) in one molecule (the meanings of the respective symbols are as described in the specification).

Description

Technical Field

[0001] This invention relates to novel ester compounds, epoxy resin curing agents, methods for manufacturing the same, products obtained therefrom, and resin compositions comprising the same. The invention also relates to cured products, sheet-like laminates, resin sheets, printed wiring boards, and semiconductor devices obtained using the resin compositions. Background Technology

[0002] Resin compositions containing epoxy resin and its curing agent are widely used as electronic component materials for semiconductors and printed wiring substrates because they impart excellent insulation, heat resistance, and adhesion to their cured products. On the other hand, to achieve high-speed communications such as 5G, circuit designs with low transmission loss in high-frequency environments are essential. Therefore, there is a search for developing new insulating materials with better dielectric properties (low dielectric constant, low dielectric loss tangent) than before.

[0003] As insulating materials with excellent dielectric properties, for example, Patent Document 1 discloses a resin composition in which an active ester compound containing aliphatic fluorinated groups such as trifluoromethyl is used as an epoxy curing agent. However, while the cured product using the compound of Patent Document 1 as a curing agent exhibits better dielectric properties than when using a general phenolic curing agent, it cannot be said to be at a completely satisfactory level. There is still a need for curing agents with excellent dielectric properties, curability, heat resistance, moisture resistance, and other properties. Therefore, we are seeking to develop novel ester compounds that can be used as curing agents for epoxy resins.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Re-publication Patent No. 2018 / 207532. Summary of the Invention

[0005] The technical problem that the invention aims to solve The subject of this invention is to provide novel ester compounds useful as epoxy resin curing agents.

[0006] The means used to solve technical problems The inventors have focused particularly on the introduction of fluorine atoms into the structure, specifically on where and what type of fluorine group can be introduced to achieve the highest level of dielectric properties. They discovered that introducing a structure where fluorine atoms are directly bonded to aromatic carbons is a means to achieve the aforementioned effects at a higher level, thus completing this invention. This invention includes the following contents.

[0007] [1] A compound having in one molecule the following structures: the structure shown in formula (1), the structure shown in formula (2), and the structure shown in formula (3): The structure shown in equation (1): [Chemical Formula 1] [In the formula, Ring A 1 And Ring A 2 Each of the optional aromatic rings with substituents can be represented independently. X represents a single bond or a divalent organic group. 'a' represents 0 or 1. *1 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure.

[0008] The structure shown in equation (2): [Chemical Formula 2] [In the formula, Ring B represents an aromatic ring substituted with one or more fluorine atoms. *2 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure.

[0009] The structure shown in equation (3): [Chemical Formula 3] [In the formula, Y represents a divalent organic group. *3 is the bonding site with an oxygen atom, which bonds to form an ester structure.

[0010] [2] According to the compound described in [2] above, ring B is an aromatic ring substituted with two or more fluorine atoms.

[0011] [3] According to the compound described in [1] or [2] above, wherein the structure shown in formula (1) contains more than 3 fluorine atoms in one unit of the structure.

[0012] [4] The compound described in [1] above is represented by formula (A1). [Chemical Formula 4]

[0013] [In the formula, Ring A 1 And Ring A 2 Each of the optional aromatic rings with substituents can be represented independently. Ring B independently represents an aromatic ring substituted with one or more fluorine atoms. X can independently represent a single bond or a divalent organic group. Y independently represents a divalent organic group. a can independently represent 0 or 1. n represents an integer greater than or equal to 1.

[0014] [5] The compound described in [4] above is represented by formula (A2). [Chemical Formula 5]

[0015] [In the formula, Ring A 1 And Ring A 2 Each of the optional aromatic rings with substituents can be represented independently. Ring B independently represents an aromatic ring substituted with one or more fluorine atoms. X 1 Each can be used independently to represent a single bond and -C(R) x -2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, R x Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; ring X 2 Each ring independently represents either an aromatic ring with substituents or a non-aromatic ring with substituents, ring Y. 1 Each can be independently represented as an aromatic carbon ring with optional substituents. a can independently represent 0 or 1. b can represent integers from 0 to 3 independently. n represents an integer greater than or equal to 1.

[0016] [6] The compound according to any one of [1] to [5] above, wherein the content of fluorine atoms is 28% by mass or more.

[0017] [7] An epoxy resin curing agent comprising any one of the compounds described in [1] to [6] above.

[0018] [8] A method for manufacturing a compound, wherein the compound contains, in one molecule, the structures shown in formula (1), formula (2), and formula (3): The structure shown in equation (1): [Chemical Formula 6]

[0019] [In the formula, Ring A 1 And Ring A 2 Each of the optional aromatic rings with substituents can be represented independently. X represents a single bond or a divalent organic group. 'a' represents 0 or 1. *1 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure.

[0020] The structure shown in equation (2): [Chemical Formula 7]

[0021] [In the formula, Ring B represents an aromatic ring substituted with one or more fluorine atoms. *2 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure.

[0022] The structure shown in equation (3): [Chemical Formula 8]

[0023] [In the formula, Y represents a divalent organic group. *3 is the bonding site with an oxygen atom, which bonds to form an ester structure.

[0024] The manufacturing method includes reacting a mixture comprising "the compound represented by formula (B1)", "the compound represented by formula (C1)" and "the compound represented by formula (D1-1) or (D1-2) or a salt thereof": The compound represented by formula (B1): [Chemical Formula 9] [In the formula, the meaning of each symbol is as described above].

[0025] The compound represented by formula (C1): [Chemical Formula 10] [In the formula, the meaning of each symbol is as described above].

[0026] The compound or its salt represented by formula (D1-1) or (D1-2): [Chemical Formula 11] [In the formula, Hal represents a halogen atom, and the meanings of other symbols are as described above].

[0027] [9] A product obtained by reacting a mixture comprising "a compound of formula (B1), a compound of formula (C1), and a compound of formula (D1-1) or (D1-2) or a salt thereof", wherein the compound of formula (B1) is: [Chemical Formula 12] [In the formula, the meaning of each symbol is as described above].

[0028] The compound represented by formula (C1): [Chemical Formula 13] [In the formula, the meaning of each symbol is as described above].

[0029] The compound or its salt represented by formula (D1-1) or (D1-2): [Chemical Formula 14] [In the formula, Hal represents a halogen atom, and the meanings of other symbols are as described above].

[0030]

[10] A resin composition comprising "a compound having in one molecule the structure shown in formula (1), the structure shown in formula (2), and the structure shown in formula (3)", and "an epoxy resin". The structure shown in equation (1): [Chemical Formula 15] [In the formula, Ring A 1 And Ring A 2 Each of the optional aromatic rings with substituents can be represented independently. X represents a single bond or a divalent organic group. 'a' represents 0 or 1. *1 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure by bonding with the carbonyl group's carbon atom.

[0031] The structure shown in equation (2): [Chemical Formula 16] [In the formula, Ring B represents an aromatic ring substituted with one or more fluorine atoms. *2 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure. The structure shown in equation (3): [Chemical Formula 17] [In the formula, Y represents a divalent organic group. *3 is the bonding site with an oxygen atom, which bonds with an oxygen atom to form an ester structure.

[0032]

[11] The resin composition according to

[10] above, wherein it further comprises an inorganic filler material.

[0033]

[12] According to the resin composition described in

[11] above, when the non-volatile component in the resin composition is set to 100% by mass, the content of inorganic filler material is 60% by mass or more.

[0034]

[13] The resin composition according to any one of

[10] to

[12] above is used to form an insulating layer of a printed wiring board.

[0035]

[14] The resin composition according to any one of

[10] to

[12] above is used to seal a semiconductor chip.

[0036]

[15] A cured product, which is a cured product of the resin composition described in any one of

[10] to

[14] above.

[0037]

[16] A sheet-like laminated material comprising the resin composition described in any one of

[10] to

[14] above.

[0038]

[17] A resin sheet having a support and a resin composition layer formed of any one of the resin compositions described in

[10] to

[14] disposed on the support.

[0039]

[18] A printed wiring board having an insulating layer formed from a cured product of the resin composition described in any one of

[10] to

[14] above.

[0040]

[19] A semiconductor device comprising the printed wiring board described in

[18] above.

[0041]

[20] The semiconductor device described in

[19] above is a fan-out type semiconductor device.

[0042] The effects of the invention According to the present invention, novel ester compounds that are useful as novel epoxy resin curing agents can be provided.

[0043] Brief description of the attached diagram Figure 1 The GPC spectrum of the product (A-1) in Example A-1 is shown. Figure 2 The IR spectrum of the product (A-1) in Example A-1 is shown. Figure 3 The GPC spectrum of product (A-2) in Example A-2 is shown. Figure 4 The IR spectrum of the product (A-2) in Example A-2 is shown. Figure 5 The GPC spectrum of the product (A-3) in Example A-3 is shown. Figure 6 The IR spectrum of the product (A-3) in Example A-3 is shown. Figure 7 The GPC spectrum of the product (A-4) in Example A-4 is shown. Figure 8 The IR spectrum of the product (A-4) in Example A-4 is shown. Figure 9 The GPC spectrum of the product (A-5) in Example A-5 is shown. Figure 10 The IR spectrum of the product (A-5) in Example A-5 is shown. Figure 11 The GPC spectrum of the product (A-1') in comparative example A-1 is shown. Figure 12 The IR spectrum of the product (A-1') in comparative example A-1 is shown. Detailed Implementation

[0044] The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the embodiments and examples described below, and may be implemented by any modifications without departing from the scope of the claims and their equivalents.

[0045] The present invention provides compounds containing, in one molecule, the structures shown in formula (1), formula (2), and formula (3) (hereinafter sometimes referred to as "ester compound (A)").

[0046] The structure shown in equation (1): [Chemical Formula 18]

[0047] [In the formula, Ring A 1 And Ring A 2 Each of the optional aromatic rings with substituents can be represented independently. X represents a single bond or a divalent organic group. 'a' represents 0 or 1. *1 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure by bonding with the carbonyl group's carbon atom.

[0048] The structure shown in equation (2): [Chemical Formula 19]

[0049] [In the formula, Ring B represents an aromatic ring substituted with one or more fluorine atoms. *2 is the binding site with the carbonyl carbon atom, which binds to the carbonyl carbon atom to form an ester structure.

[0050] The structure shown in equation (3): [Chemical Formula 20]

[0051] [In the formula, Y represents a divalent organic group. *3 is the bonding site with an oxygen atom, which bonds with an oxygen atom to form an ester structure.

[0052] In one embodiment, the number of structural units of the structure represented by formula (1) in one molecule of ester compound (A) is 1 or more, preferably 1 to 100, more preferably 1 to 10, further preferably 1, 2, 3, 4 or 5, and particularly preferably 1, 2 or 3. In one embodiment, the number of structural units of the structure represented by formula (2) in one molecule of ester compound (A) is 1 or more, preferably 2 or more, and particularly preferably 2. In one embodiment, the number of structural units of the structure represented by formula (3) in one molecule of ester compound (A) is 1 or more, preferably 2 or more, more preferably 2 to 100, further preferably 2 to 10, and even more preferably 2, 3, 4, 5 or 6, and particularly preferably 2, 3 or 4.

[0053] Ester compound (A) is an ester compound obtained by esterifying a hydroxyl compound with a carboxylic acid compound (the raw material may be a carboxyl halide or a carboxylic anhydride). The structures shown in formulas (1) and (2) are derived from the hydroxyl compound, and the structure shown in formula (3) is derived from the carboxylic acid compound. In one embodiment, ester compound (A) may further include: structures derived from other monohydroxyl compounds, other dihydroxyl compounds, trihydroxyl compounds, tetrahydroxyl compounds, and other hydroxyl compounds; and structures derived from other carboxylic acid compounds such as monocarboxyl compounds, tricarboxyl compounds, and tetracarboxyl compounds. In this embodiment, the total proportion of the structures derived from the hydroxyl compound in ester compound (A) of formula (1) and formula (2) is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, 98 mol% or more, or 100 mol%. The proportion of the structure of formula (3) derived from the structure of the carboxylic acid compound (A) in the ester compound (A) is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, 98 mol% or more, or 100 mol%.

[0054] In ester compound (A), it is preferable that at least one of the *1 binding sites in the structure shown in formula (1) is bound to the *3 binding site in the structure shown in formula (3), and more preferably that both *1 binding sites are bound to the *3 binding site. In ester compound (A), it is preferable that the *2 binding site in the structure shown in formula (2) is bound to the *3 binding site in the structure shown in formula (3). In ester compound (A), it is preferable that at least one of the *3 binding sites in the structure shown in formula (3) is bound to the *1 binding site in the structure shown in formula (1) or the *2 binding site in the structure shown in formula (2), and more preferably that both *3 binding sites are bound to the *1 binding site or the *2 binding site. Ester compound (A) is particularly preferably a compound of formula (A1) described below, formed by all the *1 binding sites in the structure shown in formula (1) and all the *2 binding sites in the structure shown in formula (2) are bound to the *3 binding sites in the structure shown in formula (3).

[0055] The structure shown in equation (1) will be explained below.

[0056] Ring A 1 And Ring A 2 Each of the aromatic rings with substituents can be represented independently.

[0057] An aromatic ring is a ring whose π-electron system contains 4p+2 electrons (p being a natural number) and follows Hückel's rule. The aromatic ring can be an aromatic carbon ring with carbon atoms as the ring-forming atoms, or an aromatic heteroring with oxygen, nitrogen, sulfur, or other heteroatoms in addition to carbon atoms as ring-forming atoms. In one embodiment, an aromatic carbon ring is preferred. In another embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, and even more preferably a 5- or 6-membered aromatic ring.

[0058] Preferred examples of aromatic rings include monocyclic aromatic rings such as benzene rings, furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyridine rings, pyridazine rings, pyrimidine rings, and pyrazine rings; and fused aromatic rings formed by the fusion of two or more monocyclic aromatic rings such as naphthyl rings, anthracene rings, phenanthrene rings, benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzoimidazolium rings, indazole rings, benzooxazole rings, benzoisooxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, borazine rings, and phthalazine rings. In one embodiment, it is preferable to be an aromatic carbon ring, more preferably a benzene ring or a naphthyl ring, and particularly preferably a benzene ring.

[0059] As ring A 1 And Ring A 2 The substituents in the aromatic ring are not particularly limited, and examples include groups selected from halogen atoms, amino, mercapto, nitro, cyano, -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -O-COR, -NH-COR, -NR-COR, and -N(COR)2. R, for example, can be: (1) selected from halogen atoms, hydroxyl, amino, mercapto, nitro, cyano, -R a -OR b -SR b -SO2R b -NHR b -N(R) b )2、-COR b -CO-OR b -CO-NHR b -CO-N(R) b )2、-O-COR b -NH-COR b -NR-COR b and -N(COR) b (2) Alkyl groups substituted in 2; (2) may be selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R groups. a -ORb -SR b -SO2R b -NHR b -N(R) b )2、-COR b -CO-OR b -CO-NHR b -CO-N(R) b )2、-O-COR b -NH-COR b -NR b -COR b and -N(COR) b (2) The group substituted with an alkenyl group; or (3) The group may be selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R groups. b -OR b -SR b -SO2R b -NHR b -N(R) b )2、-COR b -CO-OR b -CO-NHR b -CO-N(R) b )2、-O-COR b -NH-COR b -NR b -COR b and -N(COR) b )2 substituted aryl groups, etc. R a It can be a halogen atom, a substituted or unsubstituted aryl group, etc., specifically a halogen atom, aryl group, haloaryl group, alkyl-aryl group (aryl group substituted by one or more alkyl groups), aryl-aryl group (aryl group substituted by one or more aryl groups), etc. R b It can be a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, etc. Specifically, it can be a halogen atom, an alkyl group, an alkenyl group, an aryl group, a haloalkyl group, a haloalkenyl group, a haloaryl group, an alkyl-aryl group, an aryl-aryl group, an aryl-alkyl group (an alkyl group substituted by one or more aryl groups), etc.

[0060] Alkyl refers to a straight-chain, branched, and / or cyclic monovalent saturated hydrocarbon group. No particular alkyl group is specified, but it is preferably an alkyl group with 1 to 14 carbon atoms, more preferably an alkyl group with 1 to 10 carbon atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 3,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl, etc.

[0061] An alkenyl group refers to a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. No particular alkenyl group is specified, but it is preferably an alkenyl group with 2 to 14 carbon atoms, more preferably an alkenyl group with 2 to 10 carbon atoms, and even more preferably an alkenyl group with 2 to 6 carbon atoms. Examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, etc.

[0062] An aryl group is a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. No particular aryl group is specified, but it is preferably an aryl group with 6 to 14 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms. Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 9-anthrayl, and 9-phenanthyl.

[0063] The halogen atom can be a fluorine, chlorine, bromine, or iodine atom, without special designation, but preferably a fluorine atom. Halogenated alkyl, halogenated alkenyl, and halogenated aryl refer to alkyl groups substituted with one or more halogen atoms, alkenyl groups substituted with one or more halogen atoms, and aryl groups substituted with one or more halogen atoms, respectively; preferably fluoroalkyl, fluoroalkenyl, and fluoroaryl refer to alkyl groups substituted with one or more fluorine atoms, alkenyl groups substituted with one or more fluorine atoms, and aryl groups substituted with one or more fluorine atoms, respectively.

[0064] In one implementation, ring A 1 And Ring A 2 Each and every one of them is preferably an aromatic carbon ring with a substituent.

[0065] In one implementation, ring A 1 And Ring A 2 It is preferable that either the benzene ring or the naphthalene ring is optionally substituted, and each is independent of the other.

[0066] In one implementation, ring A 1 And Ring A 2 More preferably, independently and separately, is: (1) a benzene ring optionally having a substituent selected from (a) a halogen atom; (b) an alkyl group optionally having a substituent selected from halogen atoms and aryl groups; (c) an alkyl-oxy group (i.e., an alkoxy group) optionally having a substituent selected from halogen atoms and aryl groups; (d) an alkenyl group optionally having a substituent selected from halogen atoms and aryl groups; (e) an aryl group optionally having a substituent selected from halogen atoms, aryl, alkenyl, and alkyl groups; and (f) an alkyl group optionally having a substituent selected from halogen atoms, aryl, alkenyl, and alkyl groups. (1) an aryl-oxy group, or (2) a naphthalene ring optionally having a substituent selected from (a) a halogen atom; (b) an alkyl group optionally having a substituent selected from halogen atoms and aryl groups; (c) an alkyl-oxy group optionally having a substituent selected from halogen atoms and aryl groups; (d) an alkenyl group optionally having a substituent selected from halogen atoms and aryl groups; (e) an aryl group optionally having a substituent selected from halogen atoms, aryl, alkenyl and alkyl groups; and (f) an aryl-oxy group optionally having a substituent selected from halogen atoms, aryl, alkenyl and alkyl groups.

[0067] In one implementation, ring A 1 And Ring A 2 More preferably, independently, is (1) a benzene ring having a substituent selected from halogen atoms, aryl, alkyl, aryl-oxy, alkyl-oxy, haloaryl and haloalkyl, or (2) a naphthalene ring having a substituent selected from halogen atoms, aryl, alkyl, aryl-oxy, alkyl-oxy, haloaryl and haloalkyl.

[0068] In one implementation, ring A 1 And Ring A 2 It is particularly preferred, independently, that (1) a benzene ring having a substituent selected from fluorine atom, aryl, alkyl, fluoroaryl and fluoroalkyl, or (2) a naphthalene ring having a substituent selected from fluorine atom, aryl, alkyl, fluoroaryl and fluoroalkyl.

[0069] X independently represents either a single bond or a divalent organic group. In one embodiment, the divalent organic group in X is preferably a divalent organic group formed by one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from carbon, oxygen, nitrogen, and sulfur atoms. In one embodiment, the divalent organic group in X may have a halogen atom as a non-skeletal atom other than a hydrogen atom or in place of a hydrogen atom. The divalent organic group in X comprises a straight-chain structure, a branched structure, and / or a cyclic structure. The divalent organic group in X may be a divalent organic group without an aromatic ring or a divalent organic group containing an aromatic ring.

[0070] 'a' represents 0 or 1. In one implementation, it is preferred to be 1, and in another implementation, it is preferred to be 0.

[0071] In one embodiment, the structure shown in equation (1) is preferably the structure shown in equation (1').

[0072] [Chemical Formula 21] [In the formula, each symbol has the same meaning as in the above text].

[0073] [Chemical Formula 22]

[0074] [In the formula, X] 1 Each can be used independently to represent a single bond and -C(R) x -2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R x Each of the following can independently represent a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; cyclo(X) 2 Each symbol independently represents an aromatic ring with a substituent or a non-aromatic ring with a substituent; b represents an integer from 0 to 3; other symbols have the same meaning as above.

[0075] The structure shown in equation (1) is better represented by either equation (1”-1) or (1”-2).

[0076] [Chemical Formula 23] [In the formula, R] 1 Each symbol independently represents a substituent; each 'c' independently represents an integer greater than or equal to 0 or 1; other symbols have the same meaning as described above.

[0077] The structure shown in equation (1) is further preferably represented by any of the equations (1”'-1) to (1”'-38).

[0078] [Chemical Formula 24]

[0079] [Chemical Formula 25]

[0080] [Chemical Formula 26]

[0081] [Chemical Formula 27] [In the formula, each symbol has the same meaning as in the above text].

[0082] As a specific example, without limitation, structures represented by equations (1””-1) to (1””-87) can be given.

[0083] [Chemical Formula 28]

[0084] [Chemical Formula 29]

[0085] [Chemical Formula 30]

[0086] [Chemical Formula 31]

[0087] [Chemical Formula 32]

[0088] [Chemical Formula 33]

[0089] [Chemical Formula 34]

[0090] [Chemical Formula 35]

[0091] [Chemical Formula 36]

[0092] [Chemical Formula 37]

[0093] [Chemical Formula 38]

[0094] [Chemical Formula 39]

[0095] [In the formula, R] 2 Each symbol independently represents a halogen atom, aryl, alkyl, aryl-oxy, alkyl-oxy, haloaryl, or haloalkyl; m represents 1 or 2; other symbols have the same meaning as above. It should be noted that unit b may be the same or different in each structural unit. Unit c may be the same or different in each structural unit.

[0096] X 1 Each can be used independently to represent a single bond and -C(R) x X = 2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-. In one embodiment, X 1 It is better to use single bonds and -C(R) independently. x -2-, -O-, -CO-, -S-, -SO-, or -SO2-, preferably a single bond, or -C(R) x )2-, especially good is -C(R) x )2-.

[0097] R x Each of the following can be independently represented: a hydrogen atom, an alkyl group optionally having a substituent, or an aryl group optionally having a substituent.

[0098] As R x The substituents in "optionally aryl groups with substituents" are not particularly limited, and examples include groups selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -O-COR, -NH-COR, -NR-COR, and -N(COR)2. As R x The substituents in "optionally alkyl groups having substituents" are not particularly limited, and examples include groups selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R', -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -O-COR, -NH-COR, -NR-COR, and -N(COR)2. R has the same meaning as described above (same meaning as described above), and R' can be, for example, selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R', -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -O-COR, -NH-COR, -NR-COR, and -N(COR)2. b -OR b -SR b -SO2R b -NHR b -N(R) b)2、-COR b -CO-OR b -CO-NHR b -CO-N(R) b )2、-O-COR b -NH-COR b -NR b -COR b and -N(COR) b )2 substituted aryl groups, etc. R b As stated above.

[0099] In one implementation, R x Preferably, independently, it is: (1) a hydrogen atom; (2) an alkyl group optionally having a substituent selected from halogen atoms, aryl, aryl-oxy, alkyl-oxy, and haloaryl; or (3) an aryl group optionally having a substituent selected from halogen atoms, aryl, alkenyl, alkyl, aryl-oxy, alkyl-oxy, haloaryl, and haloalkyl. In one embodiment, R x Each and every one of them is preferably a hydrogen atom, aryl, alkyl, haloaryl, or haloalkyl. In one embodiment, R x Each and every one of them is independently, preferably, a hydrogen atom, an aryl group, an alkyl group, a fluoroaryl group, or a fluoroalkyl group. In one embodiment, R x It is particularly good that each of the following is independent: hydrogen atom, methyl group, or trifluoromethyl group.

[0100] Ring X 2 Each can be independently represented as either an aromatic ring with a substituent or a non-aromatic ring with a substituent.

[0101] A non-aromatic ring refers to a ring other than an aromatic ring. A non-aromatic ring can be a non-aromatic carbon ring with carbon atoms as the ring-forming atoms, or a non-aromatic heteroring with oxygen, nitrogen, sulfur, or other heteroatoms in addition to carbon atoms as ring-forming atoms. In one embodiment, a non-aromatic carbon ring is preferred. A non-aromatic ring can be a saturated ring or an unsaturated non-aromatic ring; in one embodiment, a saturated ring is preferred. In one embodiment, the non-aromatic ring is preferably a 3- to 15-membered non-aromatic ring.

[0102] Examples of non-aromatic carbon rings include: (a1) monocyclic non-aromatic carbon rings, (a2) bridged carbon rings formed by two or more rings having two or more atoms in total, and (a3) ​​aromatic-non-aromatic compound fused carbon rings formed by fused one or more aromatic carbon rings onto one or more monocyclic non-aromatic carbon rings and / or bridged carbon rings.

[0103] A monocyclic nonaromatic carbon ring is a monocyclic nonaromatic ring with carbon atoms as the ring-forming atoms. It may have carbon-carbon double bonds, preferably a monocyclic nonaromatic carbon ring with 3 to 15 carbon atoms, and more preferably a monocyclic nonaromatic carbon ring with 3 to 8 carbon atoms. Examples include cycloalkanes (monocyclic nonaromatic saturated carbon rings) such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane; and cycloolefins (monocyclic nonaromatic unsaturated carbon rings) such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, cyclopentadiene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene.

[0104] Bridged carbon rings are bridging rings with carbon atoms as the ring-forming atoms. They may have carbon-carbon double bonds, and are preferably bridging carbon rings with 8 to 15 carbon atoms. Examples include: bicyclic [2.2.1]heptane ring (norbornene ring), bicyclic [4.4.0]decane ring (decahydronaphthalene ring), bicyclic [5.3.0]decane ring, bicyclic [4.3.0]nonane ring (hexahydroindene ring), bicyclic [3.2.1]octane ring, bicyclic [5.4.0]undecane ring, bicyclic [3.3.0]octane ring, bicyclic [3.3.1]nonane ring, etc., and other bicyclic saturated bridged carbon rings; tricyclic [5.2.1.0 2,6 Decane ring (tetrahydrobicyclopentadiene ring), tricyclic [3.3.1.1] 3,7 Decane ring (adamantane ring), tricyclic [6.2.1.0] 2,7 [Tricyclic saturated bridged carbon rings such as undecane ring; tetracyclic [6.2.1.1] 3,6 .0 2,7 Tetracyclic saturated bridged carbon rings such as dodecane rings; pentacyclic [6.5.1.1] 3,6 .0 2,7 .0 9,13 Pentadecane ring (tetrahydrotricyclopentadiene ring), etc., are saturated bridged carbon rings of the pentacyclic class; bicyclic [2.2.1]hept-2-ene ring (norbornene ring), bicyclic [2.2.1]hept-2,5-diene ring (norbornene ring), bicyclic [2.2.2]oct-5-ene ring, bicyclic [4.4.0]dec-2-ene ring, etc., are unsaturated bridged carbon rings of the bicyclic class; tricyclic [5.2.1.0] 2,6 Unsaturated bridged carbocyclic rings, such as dec-3,8-diene ring (bicyclopentadiene ring), are tricyclic unsaturated bridged carbocyclic rings.

[0105] As an aromatic-nonaromatic ring complex fused carbon ring, it is a complex fused ring with carbon atoms as the ring-forming atoms. Preferably, it is an aromatic-nonaromatic ring complex fused carbon ring with 8 to 15 carbon atoms. Examples include: bicyclic complex fused carbon rings such as indene ring, indene ring, tetrahydronaphthalene ring, 1,2-dihydronaphthalene ring, and 1,4-dihydronaphthalene ring; tricyclic complex fused carbon rings such as fluorene ring, 9,10-dihydroanthracene ring, and 9,10-dihydrophenanthrene ring; tetracyclic complex fused carbon rings such as 2,3-benzofluorene ring; and pentacyclic complex fused carbon rings such as 2,3,6,7-dibenzofluorene ring.

[0106] Examples of non-aromatic heterocycles include: (b1) monocyclic non-aromatic heterocycles, (b2) bridged heterocycles formed by two or more rings having two or more atoms in common, and (b3) aromatic-non-aromatic ring complex fused heterocycles formed by fused one or more aromatic rings (aromatic carbon rings and / or aromatic heterocycles) onto one or more monocyclic aromatic rings (monocyclic aromatic carbon rings and / or monocyclic non-aromatic heterocycles) and / or bridged rings (bridged carbon rings and / or bridged heterocycles).

[0107] Monocyclic nonaromatic heterocycles are monocyclic nonaromatic rings that, in addition to carbon atoms, also have heteroatoms such as oxygen, nitrogen, and sulfur atoms as cyclic atoms. They may have carbon-carbon double bonds and / or nitrogen-carbon double bonds. Preferably, they are 3- to 15-membered monocyclic nonaromatic heterocycles, and more preferably, they are 3- to 8-membered monocyclic nonaromatic heterocycles. Examples include monocyclic nonaromatic saturated heterocycles such as pyrrolidine rings, pyrazolidine rings, imidazoline rings, tetrahydrofuran rings, piperidine rings, piperazine rings, tetrahydropyran rings, 1,3-dioxane rings, 1,4-dioxane rings, thiane rings, 1,3-dithiane rings, 1,4-dithiane rings, morpholine rings, thiomorpholine rings, and oxazolidine rings; and monocyclic nonaromatic unsaturated heterocycles such as 2-pyrrolidine rings, 3-pyrrolidine rings, 2-pyrazolidine rings, and 2-imidazoline rings.

[0108] Bridged heterocycles are bridging rings in which the cyclic atoms, in addition to carbon atoms, also contain heteroatoms such as oxygen, nitrogen, and sulfur. They may have carbon-carbon double bonds and / or nitrogen-carbon double bonds, and are preferably 8- to 15-membered bridged heterocycles. Examples include 7-oxabicyclic [4.1.0]heptane ring (1,2-epoxycyclohexane ring), 1-azabicyclic [2.2.2]octane (quinine ring), decahydroquinoline ring, decahydroisoquinoline ring, etc., which are bicyclic saturated bridged heterocycles; 1-azatricyclic [3.3.1.1] 3,7 Decane (1-azaadamantane ring), 2-azatricyclic [3.3.1.1] 3,7 Saturated bridged heterocycles such as decane (2-azaadamantane ring) and other tricyclic saturated bridged heterocycles.

[0109] Aromatic-nonaromatic ring complex fused heterocycles are complex fused rings in which the ring-forming atoms, in addition to carbon atoms, also have heteroatoms such as oxygen, nitrogen, and sulfur atoms. Preferably, they are 8- to 15-membered aromatic-nonaromatic ring complex fused heterocycles. Examples include bicyclic complex fused heterocycles such as 2,3-dihydrobenzofuran ring, 1,3-dihydroisobenzofuran ring, 2H-chromene ring, 4H-chromene ring, 1H-isochromene ring, 3H-isochromene ring, indoline ring, isoindoline ring, 2,3-dihydrobenzothiophene ring, 1,2-dihydroquinoline ring, 3,4-dihydroquinoline ring, 1,2,3,4-tetrahydroquinoline ring, and benzoxazine ring; and tricyclic complex fused heterocycles such as 1,2,3,4-tetrahydrocarbazole ring and 1,2,3,4-dibenzofuran ring.

[0110] In one embodiment, the non-aromatic ring is preferably a monocyclic non-aromatic carbon ring, a bridged carbon ring, an aromatic ring-non-aromatic ring complex fused carbon ring, a monocyclic non-aromatic heterocycle, a bridged heterocycle, and an aromatic ring-non-aromatic ring complex fused heterocycle. More preferably, it is a monocyclic non-aromatic carbon ring, a bridged carbon ring, and an aromatic ring-non-aromatic ring complex fused carbon ring. Particularly preferred are monocyclic non-aromatic carbon rings and bridged carbon rings.

[0111] As a ring X 2 The substituents in "optional aromatic rings with substituents" are not particularly limited, and examples include groups selected from halogen atoms, amino, mercapto, nitro, cyano, -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -NH-COR, -NR-COR, and -N(COR)2. As ring X 2 The substituents in "optional non-aromatic rings with substituents" are not particularly limited and can be, for example, selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -O-COR, -NH-COR, -NR-COR, -N(COR)2, and =O groups. R has the same meaning as described above.

[0112] In one implementation, ring X 2 It is preferable that each is independently an aromatic carbon ring with substituents, or a non-aromatic carbon ring with substituents.

[0113] In one implementation, ring X 2More preferably, independently, is: (1) an aromatic carbocyclic ring optionally having a substituent selected from (a) a halogen atom; (b) an alkyl group optionally having a substituent selected from halogen atoms and aryl groups; (c) an alkyl-oxy group optionally having a substituent selected from halogen atoms and aryl groups; (d) an alkenyl group optionally having a substituent selected from halogen atoms and aryl groups; (e) an aryl group optionally having a substituent selected from halogen atoms, aryl, alkenyl, and alkyl groups; and (f) an aryl-oxy group optionally having a substituent selected from halogen atoms, aryl, alkenyl, and alkyl groups, or (2) Optionally, a non-aromatic carbocyclic ring having a substituent selected from (a) a halogen atom; (b) an alkyl group having a substituent selected from halogen atoms and aryl groups; (c) an alkyl-oxy group having a substituent selected from halogen atoms and aryl groups; (d) an alkenyl group having a substituent selected from halogen atoms and aryl groups; (e) an aryl group having a substituent selected from halogen atoms, aryl, alkenyl and alkyl groups; (f) an aryl-oxy group having a substituent selected from halogen atoms, aryl, alkenyl and alkyl groups; and (g) an oxo group (=O).

[0114] In one implementation, ring X 2 Further preferably, independently, is: (1) an aromatic carbon ring having a substituent selected from halogen atoms, aryl, alkyl, haloaryl and haloalkyl, or (2) a non-aromatic carbon ring having a substituent selected from halogen atoms, aryl, alkyl, haloaryl, haloalkyl and oxo.

[0115] In one implementation, ring X 2 Further, independently, is (1) an aromatic carbide ring having a substituent selected from fluorine atom, aryl, alkyl, fluoroaryl and fluoroalkyl, or (2) a non-aromatic carbide ring having a substituent selected from fluorine atom, aryl, alkyl, fluoroaryl, fluoroalkyl and oxoyl.

[0116] In one implementation, ring X 2 It is particularly preferred, independently, that (1) an aromatic carbide ring having a substituent selected from fluorine atoms, alkyl groups and fluoroalkyl groups, or (2) a non-aromatic carbide ring having a substituent selected from fluorine atoms, alkyl groups and fluoroalkyl groups.

[0117] b represents an integer from 0 to 3 independently. In one implementation, it is preferable to be an integer from 0 to 2, and more preferably 0 or 1.

[0118] R 1 Substituents are represented independently.

[0119] As R 1The substituents in this group are not particularly limited and can be, for example, selected from halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -NH-COR, -NR-COR, and -N(COR)2. R has the same meaning as described above.

[0120] In one implementation, R 1 Preferably, each is independently: (a) a halogen atom; (b) an alkyl group optionally having a substituent selected from halogen atoms and aryl groups; (c) an alkyl-oxy group optionally having a substituent selected from halogen atoms and aryl groups; (d) an alkenyl group optionally having a substituent selected from halogen atoms and aryl groups; (e) an aryl group optionally having a substituent selected from halogen atoms, aryl groups, alkenyl groups, and alkyl groups; or (f) an aryl-oxy group optionally having a substituent selected from halogen atoms, aryl groups, alkenyl groups, and alkyl groups. In one embodiment, R 1 Preferably, each is independently a halogen atom, aryl group, alkyl group, aryl-oxy group, alkyl-oxy group, haloaryl group, or haloalkyl group. In one embodiment, R 1 Further preferably, each is independently a fluorine atom, aryl group, alkyl group, aryl-oxy group, alkyl-oxy group, fluoroaryl group, or fluoroalkyl group. In one embodiment, R 1 Ideally, each atom should be a fluorine atom, aryl group, alkyl group, fluoroaryl group, or fluoroalkyl group.

[0121] c represents an integer greater than or equal to 0 or 1. In one implementation, it is preferably 0, 1 or 2, more preferably 0 or 1, and especially preferably 0.

[0122] R 2 Each of these can be independently represented as a halogen atom, aryl, alkyl, aryl-oxy, alkyl-oxy, haloaryl, or haloalkyl. In one embodiment, R 2 It is preferred that the atom is fluorine, aryl, alkyl, aryl-oxy, alkyl-oxy, fluoroaryl, or fluoroalkyl, and even more preferably fluorine, aryl, alkyl, fluoroaryl, or fluoroalkyl.

[0123] In one embodiment, the structure shown in formula (1) (including the structures shown in formula (1'), (1”-1), or (1”-2) preferably contains a fluorine atom. For such a fluorine atom, for example, in the structure shown in formula (1), it may be contained in a divalent organic group represented by X, and / or in a ring A. 1 and Ring A 2 The substituents of the aromatic ring are indicated; if it is the structure shown in formula (1'), it may contain R. x The alkyl or aryl substituents are represented by ring A. 1 Ring A 2and Ring X 2 The substituents of the aromatic ring, and / or the ring X 2 The non-aromatic ring substituents are represented. In one embodiment, the structure shown in formula (1) preferably contains 3 or more fluorine atoms in one unit of the structure, more preferably 4 or more fluorine atoms, and even more preferably 5 or more fluorine atoms.

[0124] The structure shown in equation (2) will be explained below.

[0125] Ring B represents an aromatic ring that is substituted with one or more fluorine atoms. "An aromatic ring substituted with one or more fluorine atoms" in ring B means that at least one hydrogen atom on the aromatic carbon atom constituting the aromatic ring is substituted with a fluorine atom.

[0126] In one embodiment, ring B is preferably an aromatic carbon ring substituted with one or more fluorine atoms. In another embodiment, ring B is more preferably a benzene ring substituted with one or more fluorine atoms, or a naphthalene ring substituted with one or more fluorine atoms.

[0127] From the viewpoint of achieving the desired effect of the present invention more significantly, the number of fluorine atoms substituting in the aromatic ring of ring B is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and even more preferably 5 or more.

[0128] From the viewpoint of achieving the desired effect of the present invention more significantly, it is preferable that at least one of the hydrogen atoms on the aromatic carbon atom (the aromatic carbon atom adjacent to the "aromatic carbon atom at the oxygen atom bonding site") in the aromatic ring B, which is adjacent to the bonding site with the oxygen atom forming the ester structure, is replaced by a fluorine atom, and more preferably two of them are replaced by a fluorine atom.

[0129] In one embodiment, the structure shown in equation (2) is preferably the structure shown in equations (2'-1) to (2'-3).

[0130] [Chemical Formula 40]

[0131] [In the formula, each symbol has the same meaning as in the above text].

[0132] [Chemical Formula 41]

[0133] [In the formula, R] f1 and R f2 Each can independently represent a hydrogen atom or a fluorine atom, and R f1 and R f2At least one of them is a fluorine atom; the other symbols have the same meaning as above. As a specific example, without limitation, the structures shown in formulas (2”-1) to (2”-19) can be cited.

[0134] [Chemical Formula 42] [In the formula, each symbol has the same meaning as in the above text].

[0135] In one embodiment, the structure shown in formulas (2”-1) to (2”-4) is particularly preferred.

[0136] R f1 and R f2 Each can independently represent a hydrogen atom or a fluorine atom, and R f1 and R f2 At least one of them is a fluorine atom.

[0137] For R f1 and R f2 From the viewpoint of increasing the curing reaction rate of epoxy resin, in one embodiment, R is preferred. f1 and R f2 At least two of them are fluorine atoms, preferably R. f1 and R f2 At least three of them are fluorine atoms, and more preferably R f1 and R f2 At least four of them are fluorine atoms.

[0138] For R f1 and R f2 From the viewpoint of increasing the curing reaction rate of epoxy resin, in one embodiment, it is preferable to use R f1 When there are 2, R f1 One side is a fluorine atom, R f1 The other party and R f2 It is a hydrogen atom or a fluorine atom; in R f1 When there is only one, R f1 R is a fluorine atom. f2 It can be a hydrogen atom or a fluorine atom. R is preferable. f1 R is a fluorine atom. f2 It is a hydrogen atom or a fluorine atom. Even better is R. f1 R is a fluorine atom. f2 It is a hydrogen atom or a fluorine atom, and R f2 At least one of them is a fluorine atom. It is especially preferred to have R. f1 and R f2 It is a fluorine atom.

[0139] The structure shown in equation (3) will be explained below.

[0140] Y represents a divalent organic group. In one embodiment, the divalent organic group in Y is preferably a divalent organic group formed by one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from carbon, oxygen, nitrogen, and sulfur atoms. In one embodiment, the divalent organic group in Y may have a halogen atom as a non-skeletal atom other than a hydrogen atom or in place of a hydrogen atom. The divalent organic group in Y includes a straight-chain structure, a branched structure, and / or a cyclic structure. The divalent organic group in Y can be a divalent organic group without an aromatic ring or a divalent organic group containing an aromatic ring.

[0141] In one embodiment, Y is preferably a divalent hydrocarbon group having a substituent.

[0142] A divalent hydrocarbon group is a divalent hydrocarbon group whose backbone consists of only one or more carbon atoms (e.g., 1–50, 1–20, or 1–10). Divalent hydrocarbon groups can have straight-chain, branched, and / or cyclic structures. A divalent hydrocarbon group can be a hydrocarbon group without an aromatic ring or a hydrocarbon group containing an aromatic ring.

[0143] Examples of divalent hydrocarbon groups include: (1) alkylene groups optionally having an aryl group as a substituent; (2) alkenyl groups optionally having an aryl group as a substituent; (3) arylene groups optionally having a substituent selected from aryl, alkyl, and alkenyl groups; (4) (alkylene groups optionally having an aryl group as a substituent)-(arylene groups optionally having a substituent selected from aryl, alkyl, and alkenyl groups); (5) (arylene groups optionally having a substituent selected from aryl, alkyl, and alkenyl groups)-(arylene groups optionally having a substituent selected from aryl, alkyl, and alkenyl groups); (6) (arylene groups optionally having a substituent selected from aryl, alkyl, and alkenyl groups)-( (7) (optionally alkylene group having aryl as a substituent)-(optionally arylene group having substituents selected from aryl, alkyl and alkenyl) group, etc., in one embodiment, preferably alkylene, alkenyl, arylene, alkylene-arylene, arylene-arylene, arylene-alkylene-arylene, or alkylene-arylene-alkylene, more preferably arylene, arylene-arylene, or arylene-alkylene-arylene, and even more preferably arylene.

[0144] Alkylene refers to a straight-chain, branched, and / or cyclic divalent saturated hydrocarbon group. No particular alkylene is specified, but it is preferably an alkylene with 1 to 14 carbon atoms, more preferably an alkylene with 1 to 10 carbon atoms, and even more preferably an alkylene with 1 to 6 carbon atoms. Examples of alkylene include: straight-chain alkylenes such as methylene, ethylene group, trimethylene group, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylenes such as ethylidene group, propylidene group, isopropylidene, ethylmethylmethylene, and diethylmethylene; and cyclic alkylenes such as 1,4-cyclohexylene, 1,3-cyclohexylene, or 1,2-cyclohexylene, 1,3-cyclopentylene, and 1,2-cyclopentylene.

[0145] An alkenyl group refers to a straight-chain, branched, and / or cyclic divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. No particular alkenyl group is specified, but it is preferably an alkenyl group with 2 to 14 carbon atoms, more preferably an alkenyl group with 2 to 10 carbon atoms, and even more preferably an alkenyl group with 2 to 6 carbon atoms. Examples of alkenyl groups include -CH2=CH2-, -C(=CH2)-, -CH=CH-CH2-, -CH2-CH=CH-, -CH=CH-CH2-CH2-, -CH2-CH=CH-CH2-, and -CH2-CH2-CH=CH-.

[0146] Alemines refer to divalent aromatic hydrocarbon groups. There is no specific designation for arylemines, but they are preferably arylemines with 6 to 14 carbon atoms, and more preferably arylemines with 6 to 10 carbon atoms. Examples of arylemines include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,6-naphthylene, and 2,7-naphthylene.

[0147] The substituents in "optionally divalent hydrocarbon groups with substituents" in Y are not particularly limited, and can be, for example, selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -O-COR, -NH-COR, -NR-COR, and -N(COR)2. R has the same meaning as described above.

[0148] In one embodiment, the structure shown in equation (3) is preferably represented by equation (3').

[0149] [Chemical Formula 43] [In the formula, each symbol has the same meaning as in the above text].

[0150] [Chemical Formula 44]

[0151] [In the formula, each symbol has the same meaning as in the above text].

[0152] The structure shown in equation (3) is better represented by either equation (3”-1) or (3”-2).

[0153] [Chemical Formula 45] [In the formula, R] 3 Each symbol independently represents a substituent; each 'd' independently represents an integer greater than or equal to 0 or 1; other symbols have the same meaning as described above.

[0154] As a specific example, without limitation, the structures shown in equations (3”'-1) to (3”'-12) can be cited.

[0155] [Chemical Formula 46] [In the formula, R] 4 Each symbol independently represents a halogen atom, aryl group, alkyl group, aryl-oxy group, alkyl-oxy group, haloaryl group, or haloalkyl group; other symbols have the same meaning as above.

[0156] It should be noted that element d may be the same or different in each structural element.

[0157] Y-shaped ring 1 Each of these can be independently represented as an aromatic carbon ring with a substituent.

[0158] Aromatic carbon rings are aromatic rings with carbon atoms as the ring-forming atoms. In one embodiment, the aromatic carbon ring is preferably a 6- to 14-membered aromatic carbon ring, more preferably a 6- to 10-membered aromatic carbon ring. Specific examples of preferred aromatic carbon rings include benzene rings, naphthalene rings, anthracene rings, etc., with benzene rings or naphthalene rings being more preferred, and benzene rings being particularly preferred.

[0159] As a ring Y 1The substituents in "optional aromatic carbon rings with substituents" are not particularly limited and can be, for example, selected from halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -O-COR, -NH-COR, -NR-COR, and -N(COR)2. R has the same meaning as described above.

[0160] R 3 Substituents are represented independently.

[0161] As R 3 The substituents in this text are not particularly limited and can be, for example, selected from halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -NH-COR, -NR-COR, and -N(COR)2. R has the same meaning as described above.

[0162] In one implementation, R 3 Preferably, each is independently: (a) a halogen atom; (b) an alkyl group optionally having a substituent selected from halogen atoms and aryl groups; (c) an alkyl-oxy group optionally having a substituent selected from halogen atoms and aryl groups; (d) an alkenyl group optionally having a substituent selected from halogen atoms and aryl groups; (e) an aryl group optionally having a substituent selected from halogen atoms, aryl groups, alkenyl groups, and alkyl groups; or (f) an aryl-oxy group optionally having a substituent selected from halogen atoms, aryl groups, alkenyl groups, and alkyl groups. In one embodiment, R 3 Preferably, each is independently a halogen atom, aryl group, alkyl group, aryl-oxy group, alkyl-oxy group, haloaryl group, or haloalkyl group. In one embodiment, R 3 Further preferably, each is independently a fluorine atom, aryl group, alkyl group, aryl-oxy group, alkyl-oxy group, fluoroaryl group, or fluoroalkyl group. In one embodiment, R 3 Ideally, each atom should be a fluorine atom, aryl group, alkyl group, fluoroaryl group, or fluoroalkyl group.

[0163] d represents an integer greater than or equal to 0 or 1. In one implementation, it is preferable to be 0, 1 or 2, more preferably 0 or 1, and especially preferably 0.

[0164] R 4 Each of these can be independently represented as a halogen atom, aryl, alkyl, aryl-oxy, alkyl-oxy, haloaryl, or haloalkyl. In one embodiment, R 4It is preferred that the atom is fluorine, aryl, alkyl, aryl-oxy, alkyl-oxy, fluoroaryl, or fluoroalkyl, and even more preferably fluorine, aryl, alkyl, fluoroaryl, or fluoroalkyl.

[0165] In one embodiment, the ester compound (A) is preferably a compound represented by formula (A1).

[0166] [Chemical Formula 47] [In the formula, ring A] 1 And Ring A 2 Each of the following independently represents an aromatic ring with optional substituents; each of the following independently represents an aromatic ring substituted with one or more fluorine atoms; each of the following independently represents a single bond or a divalent organic group; each of the following independently represents a divalent organic group; each of the following independently represents 0 or 1; and each of the following independently represents an integer greater than 1.

[0167] The ester compound (A) is preferably the compound represented by formula (A2).

[0168] [Chemical Formula 48] [In the formula, ring A] 1 And Ring A 2 Each ring B independently represents an aromatic ring optionally having substituents; each ring B independently represents an aromatic ring substituted with one or more fluorine atoms; X 1 Each can be used independently to represent a single bond and -C(R) x -2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R x Each of the following can independently represent a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; cyclo(X) 2 Each can be independently represented as either an aromatic ring with substituents or a non-aromatic ring with substituents; ring Y 1 Each of the following groups independently represents an aromatic carbon ring with optional substituents; a independently represents 0 or 1; b independently represents an integer from 0 to 3; n represents an integer greater than 1.

[0169] In equations (A1) and (A2), element a can be the same or different in each structural element. Element b can be the same or different in each structural element. Element n can be the same or different in each structural element.

[0170] n represents an integer greater than or equal to 1. In one embodiment, n is preferably an integer from 1 to 100, more preferably an integer from 1 to 20, even more preferably an integer from 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), even more preferably 1, 2, 3, 4, or 5, and particularly preferably 1, 2, or 3. When the value of n is large, the crosslinking density increases during epoxy resin curing, thereby improving curability. When the value of n is small, the solvent solubility is high and the viscosity is low, thus improving operability and processability (engineering).

[0171] In one embodiment, the structure shown in equation (1) of equation (A1) is preferably represented by equation (1'), more preferably by any one of equation (1”-1) or (1”-2), and even more preferably by any one of equation (1”'-1) to (1”'-38). As a specific example, without limitation, structures represented by equations (1””-1) to (1””-87) can be given.

[0172] In one embodiment, the structure shown in equation (2) of equations (A1) and (A2) is preferably represented by equations (2'-1) to (2'-3). As a specific example, without limitation, structures represented by equations (2”-1) to (2”-19) can be cited. In one embodiment, the structure represented by equations (2”-1) to (2”-4) is particularly preferred.

[0173] In one embodiment, the structure shown in equation (3) of equation (A1) is preferably represented by equation (3'), more preferably by any one of equation (3”-1) or (3”-2). As a specific example, without limitation, structures represented by equations (3”'-1) to (3”'-12) can be given.

[0174] In one embodiment, the structure represented by formula (1') in formula (A2) is preferably a structure represented by either formula (1”-1) or (1”-2), and more preferably a structure represented by any of formulas (1”'-1) to (1”'-38). As a specific example, without limitation, structures represented by formulas (1””-1) to (1””-87) can be given.

[0175] In one embodiment, the structure represented by equation (3') in equation (A2) is preferably a structure represented by either equation (3”-1) or (3”-2). As a specific example, without limitation, structures represented by equations (3”'-1) to (3”'-12) can be given.

[0176] From the viewpoint of achieving the desired effects of the present invention more significantly, the fluorine atom content in the ester compound (A) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more or 28% by mass or more. There is no particular upper limit, and it can be set to, for example, 60% by mass or less. Regarding the fluorine atom content, in the manufacturing method described later, those skilled in the art can arbitrarily adjust it to the desired range by changing the type of raw material.

[0177] The weight-average molecular weight of ester compound (A) is not particularly limited, but is preferably below 100,000, more preferably below 50,000, even more preferably below 20,000, and even more preferably below 10,000. The lower limit of the weight-average molecular weight of ester compound (A) is not particularly limited, and may be, for example, above 400, above 600, above 800, etc. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0178] The total ester equivalent (hereinafter sometimes referred to as "ester equivalent") of the ester compound (A) based on the ester structures formed by the structures shown in formula (1) and formula (3), and the ester structures formed by the structures shown in formula (2) and formula (3) is not particularly limited, but is preferably 700 g / eq. or less, more preferably 500 g / eq. or less, further preferably 450 g / eq. or less, even more preferably 400 g / eq. or less, and particularly preferably 350 g / eq. or less. The lower limit of the ester equivalent of the ester compound (A) is not particularly limited, and may be, for example, 150 g / eq. or more, 180 g / eq. or more, 200 g / eq. or more, etc.

[0179] The method for manufacturing ester compound (A) will be described below.

[0180] The present invention provides a method for manufacturing an ester compound (A), the method comprising: reacting (i.e., esterification) a mixture comprising "a compound represented by formula (B1)," "a compound represented by formula (C1)," and "a compound represented by formula (D1-1) or (D1-2) or a salt thereof".

[0181] The compound represented by formula (B1) (hereinafter sometimes referred to as "hydroxy compound (B1)"): [Chemical Formula 49]

[0182] [In the formula, the meaning of each symbol is as described above].

[0183] The compound represented by formula (C1) (hereinafter sometimes referred to as "hydroxy compound (C1)"): [Chemical Formula 50]

[0184] [In the formula, the meaning of each symbol is as described above].

[0185] Compounds or their salts represented by formula (D1-1) or (D1-2) (hereinafter sometimes collectively referred to as "carboxylic acid compounds (D1)"): [Chemical Formula 51]

[0186] [In the formula, Hal represents a halogen atom (preferably a chlorine atom, bromine atom, or iodine atom); the meanings of other symbols are as described above].

[0187] In one embodiment, in the method for manufacturing ester compound (A), each molecule of carboxylic acid compound (D1), which is a component of carboxylic acid compound, undergoes a condensation reaction with hydroxyl compound (B1), which is a component of hydroxyl compound, or both hydroxyl compound (B1) and hydroxyl compound (C1), to achieve esterification, thereby obtaining the ester compound (A1) of the present invention. In one embodiment, in addition to hydroxyl compound (B1), hydroxyl compound (C1), and carboxylic acid compound (D1), other hydroxyl compound components and other carboxylic acid compound components, which are components of carboxylic acid compound, are simultaneously mixed during esterification.

[0188] In one embodiment, the method for producing the ester compound (A) preferably includes a method for producing the compound of formula (A1) by reacting "hydroxy compound (B1) and hydroxy compound (C1)" with "carboxylic acid compound (D1)" (i.e., esterification).

[0189] [Chemical Formula 52]

[0190] [In the formula, each symbol has the same meaning as in the above text].

[0191] In one embodiment, the method of producing the ester compound (A) is more preferably a method of producing the compound represented by formula (A2) by reacting "a compound represented by formula (B2) as a hydroxy compound (B1) and a hydroxy compound (C1)" with "a compound represented by formula (D2-1) or (D2-2) as a carboxylic acid compound (D1) or a salt thereof (hereinafter sometimes collectively referred to as "carboxylic acid compound (D2)")" (i.e., esterification).

[0192] [Chemical Formula 53]

[0193] [In the formula, each symbol has the same meaning as in the above text].

[0194] Examples of salts include alkali metal salts such as cesium salts, potassium salts, and sodium salts.

[0195] In one embodiment, the carboxylic acid compound (D1) is preferably a compound represented by formula (D1-2). In one embodiment, the carboxylic acid compound (D2) is preferably a compound represented by formula (D2-2).

[0196] In a preferred embodiment, a base can be used in the esterification reaction of the method for producing ester compound (A). Examples of bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; tertiary amines such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine (DMAP). The base can be used directly or after dilution in solution. One base can be used alone, or two or more bases can be used in any combination.

[0197] When an alkali metal hydroxide is used as the base, one embodiment has the advantages of increased reactivity and less residue of starting materials. When a tertiary amine is used as the base, one embodiment has the advantages of less susceptibility to hydrolysis of ester bonds formed under anhydrous conditions and increased yield.

[0198] In one embodiment, the amount of base used is preferably 80 to 300 moles relative to 100 moles of carboxyl groups (-COOH) or carboxyl halides (-COHal) in the carboxylic acid compound (D1), and preferably 100 to 150 moles from the viewpoints of raw material residue rate and base removal.

[0199] In one embodiment, a condensing agent may be used as needed in the esterification reaction of the method for producing ester compound (A). Examples of condensing agents include carbodiimide condensing agents such as 1,3-dicyclohexylcarbodiimide, 1-cyclohexyl-3-morpholinoethylcarbodiimide, 1-cyclohexyl-3-(4-diethylaminocyclohexyl)carbodiimide, 1,3-diethylcarbodiimide, 1,3-diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, or salts thereof. The amount of condensing agent used may be, for example, 50 to 100 moles relative to 100 moles of carboxyl groups (-COOH) or carboxyl halides (-COHal) in the carboxylic acid compound (D1). In one embodiment, a condensation accelerator may be added as needed in addition to the condensing agent in the esterification reaction of the method for producing ester compound (A). Examples of condensation accelerators include 1-hydroxybenzotriazole (HOBt), N-hydroxysuccinimide (HOSu), 1-hydroxy-7-azabenzotriazole (HOAt), and hydroxy-3,4-dihydro-4-oxo-1,2,3-benzotriazine (HOOBt). The amount of condensation accelerator used may be, for example, 50 to 100 moles of the carboxyl group (-COOH) or carboxyl halogen group (-COHal) in the carboxylic acid compound (D1).

[0200] Regarding the method for manufacturing ester compound (A), the mixing ratio of hydroxyl compound (B1), hydroxyl compound (C1), and carboxylic acid compound (D1) in the esterification reaction system can be selected appropriately based on the properties of the target product and the properties of the epoxy resin cured product. When implementing a design focused on the dielectric properties and moisture resistance of the epoxy resin cured product, it is preferable that no unreacted carboxyl halides and aromatic hydroxyl groups remain in the synthesized reactants. Therefore, the mixing ratio of the molar number (d) of carboxylic acid compound (D1), the molar number (b) of hydroxyl compound (B1), and the molar number (c) of hydroxyl compound (C1) is preferably in the range of 2(d):(2(b)+(c)) = 90:100 to 100:90, and more preferably in the range of 2(d):(2(b)+(c)) = 95:100 to 100:95. Furthermore, the mixing ratio (molar ratio) of the hydroxyl compound (B1), the hydroxyl compound (C1), and the carboxylic acid compound (D1) is preferably in the range of (b):(d):(c) = 0.5:1.5:2.0 (equivalent to n = 0.5) to 5.0:6.0:2.0 (equivalent to n = 5), and more preferably in the range of (b):(d):(c) = 1.0:2.0:2.0 (equivalent to n = 1) to 2.5:3.5:2 (equivalent to n = 2.5).

[0201] In one embodiment, the esterification reaction in the method for producing ester compound (A) can be carried out in a solvent-free system without the use of a solvent, or in an organic solvent system using an organic solvent. Examples of organic solvents for the esterification reaction include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, acetic acid solvents, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as solvents and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. From the viewpoint of purification efficiency after the reaction, hydrophobic solvents such as ketone solvents (e.g., methyl isobutyl ketone) and aromatic hydrocarbon solvents (e.g., toluene) are preferred. One organic solvent can be used alone, or two or more can be used in any combination.

[0202] The reaction temperature in the esterification reaction of the method for producing ester compound (A) is not particularly limited, but in one embodiment, it is preferably in the range of 0 to 70°C.

[0203] The reaction time in the esterification reaction of the method for producing ester compound (A) is not particularly limited, but in one embodiment, it is preferably in the range of 30 minutes to 8 hours.

[0204] In one embodiment of the esterification reaction for the production of ester compound (A), the esterification can also be carried out by adding a base dropwise to a mixture (organic solvent system or solvent-free system) containing hydroxyl compound (B1), hydroxyl compound (C1) and carboxylic acid (D1) while stirring, followed by further stirring. In this case, the dropping time is not particularly limited, but is preferably in the range of 10 minutes to 3 hours. The stirring time after dropping is preferably in the range of 30 minutes to 5 hours.

[0205] In the method for manufacturing ester compound (A), the ester compound (A) can be purified after the esterification reaction. After the esterification reaction, in order to remove by-product salts and excess starting materials from the system, purification steps such as water washing and precision filtration can be performed. For example, in one embodiment, after the esterification reaction is completed, the amount of water required to dissolve the by-product salts is added, the mixture is allowed to stand and separate, and the aqueous layer is discarded. Then, acid is added as needed for neutralization, and repeated water washing is performed. Then, after purification by a dehydration step using a reagent or azeotropic method and removing impurities by precision filtration, the organic solvent is removed by distillation as needed to obtain the ester compound (A). It can also be used directly as a solvent in the resin composition without completely removing the organic solvent.

[0206] In one embodiment, during the esterification reaction of the method for manufacturing ester compound (A), multiple ester compounds may be generated simultaneously. Therefore, as a mixture, a product may sometimes be obtained containing one or more ester compounds (A) and any one or more ester compounds other than ester compound (A). Among the ester compounds other than ester compound (A), there may be compounds that do not have the structure shown in formula (1) (e.g., n=0 in formula (A1)), reaction intermediate compounds (e.g., compounds with a hydroxyl or carboxyl group at one end), compounds derived from raw material impurities, etc. The product obtained by the esterification reaction can be used directly as an epoxy resin curing agent, or it can be used after removing unwanted compounds as appropriate.

[0207] Ester compound (A) can be used as an epoxy resin curing agent. By using ester compound (A) as an epoxy resin curing agent, cured products with excellent dielectric properties can be obtained. Furthermore, by using ester compound (A) as an epoxy resin curing agent, cured products with excellent curability, heat resistance, and moisture resistance (hydrolysis resistance) can be obtained. By employing sheet-like laminates or semiconductor sealing materials using ester compound (A), printed wiring substrates that suppress transmission losses in high-frequency regions and fan-out type semiconductor devices can be provided.

[0208] The resin composition of the present invention will be described below.

[0209] The present invention provides a resin composition comprising an ester compound (A) and an epoxy resin.

[0210] The epoxy resin used in the resin composition of the present invention is not limited in type as long as it is a compound having one or more, preferably two or more, epoxy groups in one molecule.

[0211] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butylcatechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene skeleton type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexanediol type epoxy resin, tris(hydroxymethyl) type epoxy resin, halogenated epoxy resin, etc. From the viewpoint of further improving dielectric properties, moisture resistance, and flame retardancy, phenolic aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, fluorene skeleton type epoxy resins, dicyclopentadiene type epoxy resins, and bisphenol AF type epoxy resins are particularly preferred. Two or more types of epoxy resin (Y) can be used in combination.

[0212] In one embodiment, the epoxy resin is preferably a fluorine-containing epoxy resin, including bisphenol AF type epoxy resins, etc.

[0213] When the non-volatile component of the epoxy resin is set to 100% by mass, it is preferable that at least 50% by mass is an epoxy resin having two or more epoxy groups per molecule. Furthermore, in applications using interlayer insulating films for built-up multilayer circuit boards, it is preferable to have an aromatic epoxy resin (liquid epoxy resin) containing two or more epoxy groups per molecule and being liquid at 20°C; more preferably, it is preferably a form containing both the liquid epoxy resin and an aromatic epoxy resin (solid epoxy resin) containing three or more epoxy groups per molecule and being solid at 20°C. By using both liquid and solid epoxy resins, when the resin composition is used in the form of a resin sheet, sufficient flexibility is exhibited, a film with excellent processability can be formed, and the tensile strength of the cured resin composition is improved, thereby enhancing the durability of the built-up multilayer circuit board. Furthermore, when using both liquid and solid epoxy resins as the epoxy resin, the mixing ratio (liquid:solid) is preferably in the range of 1:0.1 to 1:2 by mass. By using liquid epoxy resin within this range, sufficient flexibility and processability are obtained when used in the form of resin sheets, and sufficient flowability during lamination is also obtained. On the other hand, by using solid epoxy resin within this range, the adhesiveness of the resin composition is reduced, and the degassing property during vacuum lamination is improved when used in the form of resin sheets. In addition, the peelability of the protective film or support film is good during vacuum lamination, and the heat resistance after curing is also improved.

[0214] In one embodiment, the fluorine atom content relative to the total mass of the ester compound (A) and the epoxy resin is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit is not particularly limited and may be, for example, 60% by mass or less.

[0215] In the resin composition of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the content of epoxy resin is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, even more preferably 20% to 40% by mass, and particularly preferably 20% to 35% by mass. In one embodiment, by setting the epoxy resin content within this range, the curability of the resin composition tends to be improved.

[0216] In the resin composition of the present invention, the content of ester compound (A) is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. Furthermore, the lower limit of the content of ester compound (A) is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it can be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, etc. In one embodiment, by keeping the content of ester compound (A) within this range, the dielectric properties of the cured product are excellent, and a cured product with excellent curability, heat resistance, and moisture resistance is also provided.

[0217] The resin composition of the present invention may further contain inorganic filler materials. In one embodiment, by containing inorganic filler materials in the resin composition of the present invention, the coefficient of linear thermal expansion and the dielectric loss tangent can be reduced.

[0218] Examples of inorganic filler materials include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, amorphous silica, powdered silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica are preferred. Spherical silica is particularly preferred from the viewpoint of reducing the surface roughness of the insulating layer, and spherical fused silica is even more preferred. One or more of these can be used in combination. Commercially available spherical fused silica includes, for example, "SOC2" and "SOC1" manufactured by Admatechs Co., Ltd.

[0219] The average particle size of the inorganic filler material is not particularly limited. From the viewpoint of achieving low surface roughness of the insulating layer and enabling the formation of fine wiring, it is preferable to be 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.8 μm or less. On the other hand, from the viewpoint of preventing an increase in the viscosity of the resin composition and a decrease in processability, it is preferable to be 0.01 μm or more, more preferably 0.03 μm or more, even more preferably 0.05 μm or more, even more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle size of the aforementioned inorganic filler material can be determined by laser diffraction scattering based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler material can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median particle size can be used as the average particle size for measurement. The sample for measurement is preferably a sample obtained by dispersing the inorganic filler material in water using ultrasound. As a laser diffraction scattering particle size distribution measuring device, the LA-950 manufactured by Horiba Corporation can be used.

[0220] Inorganic filler materials are preferably surface-treated with surface treatment agents to improve their moisture resistance and dispersibility. These surface treatment agents include aminosilane coupling agents, ureasilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, vinylsilane coupling agents, styrenesilane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, organosilazane compounds, titanate coupling agents, etc. One or more of these can be used in combination.

[0221] In the resin composition of the present invention, the content of inorganic filler varies depending on the desired characteristics of the resin composition. When the non-volatile component in the resin composition is set to 100% by mass, the content of inorganic filler is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less. The lower limit of the content of inorganic filler is, for example, 0% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, etc., preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. In one embodiment, if the content of inorganic filler is too low, the coefficient of linear thermal expansion of the cured product increases; on the other hand, if the content is too high, it may be difficult to form a film when preparing resin sheets or the cured product may become brittle.

[0222] The resin composition of the present invention may further contain a thermoplastic resin. In one embodiment, by containing a thermoplastic resin in the resin composition of the present invention, the mechanical strength of the cured product can be improved, and the film-forming ability when used in the form of a resin sheet can also be improved.

[0223] Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamide-imide resins, polyether-imide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins, with phenoxy resins and polyvinyl acetal resins being particularly preferred. These thermoplastic resins can be used individually or in combination of two or more. The weight-average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 200,000, and more preferably in the range of 12,000 to 100,000. It should be noted that the weight-average molecular weight in this invention is determined by gel permeation chromatography (GPC) (polystyrene conversion). The weight-average molecular weight determined by GPC method can be measured using an LC-9A / RID-6A manufactured by Shimadzu Corporation as the measuring device, a Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation as the column, and chloroform or the like as the mobile phase. The measurement is performed at a column temperature of 40°C, and the weight-average molecular weight is calculated using a calibration curve of standard polystyrene.

[0224] In the resin composition of the present invention, the content of thermoplastic resin is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, and the lower limit is, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, etc., preferably 0.1% by mass or more, more preferably 0.5% by mass or more. In one embodiment, by keeping the content of thermoplastic resin in the range of 0.1% to 10% by mass, the effect of improving film forming ability and mechanical strength is achieved, thereby increasing melt viscosity and decreasing the surface roughness of the insulating layer after the wet roughening process.

[0225] The resin composition of the present invention may further contain an epoxy resin curing agent other than ester compound (A).

[0226] Examples of epoxy resin curing agents other than ester compounds (A) include: TD2090, TD2131 (manufactured by DIC Corporation), MEH-7600, MEH-7851, MEH-8000H (manufactured by Meiwa Kasei Corporation), NHN, CBN, GPH-65, GPH-103 (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, and SN39. Phenolic curing agents such as 5 (manufactured by Nippon Steel Chemical Co., Ltd.), LA7052, LA7054, LA3018, LA1356 (manufactured by DIC Co., Ltd.); benzoxazine curing agents such as Fa, Pd (manufactured by Shikoku Chemical Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.); anhydride curing agents such as methyl hexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride; cyanate ester curing agents such as PT30, PT60, BA230S75 (manufactured by Lonza Japan Co., Ltd.); benzoxazine curing agents, etc.

[0227] In the resin composition of the present invention, the content of epoxy resin curing agent other than ester compound (A) is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The lower limit is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, and 0.1% by mass or more.

[0228] The resin composition of the present invention may further contain an epoxy resin curing accelerator. In one embodiment, by containing an epoxy resin curing accelerator in the resin composition of the present invention, the curing time and curing temperature can be adjusted efficiently.

[0229] Examples of epoxy resin curing accelerators include: organophosphorus compounds such as TPP, TPP-K, TPP-S, and TPTP-S (manufactured by Hokuko Chemical Industry Co., Ltd.); imidazole compounds such as Curezol 2MZ, 2E4MZ, Cl1Z, Cl1Z-CN, Cl1Z-CNS, Cl1Z-A, 2MZ-OK, 2MA-OK, and 2PHZ (manufactured by Shikoku Chemical Industry Co., Ltd.); amine adducts such as NOVACURE (manufactured by Asahi Kasei Corporation) and Fujicure (manufactured by Fuji Chemical Industry Co., Ltd.); amine compounds such as 1,8-diazabicyclo[5.4.0]undecene-7,4-dimethylaminopyridine, benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 4-dimethylaminopyridine; and organometallic complexes or organometallic salts of cobalt, copper, zinc, iron, nickel, manganese, and tin. Two or more curing accelerators can be used together.

[0230] In the resin composition of the present invention, the content of epoxy resin curing accelerator is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit is 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, etc.

[0231] The resin composition of the present invention may further contain a flame retardant. Examples of flame retardants include phosphorus-based flame retardants such as phosphazene compounds, phosphates, phosphate esters, polyphosphates, phosphines, phosphines, phosphonates, phosphonates, and phosphonates; nitrogen-based flame retardants such as aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, and urea compounds; inorganic flame retardants such as metal hydroxides such as magnesium hydroxide and aluminum hydroxide, and antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate; and halogen-based flame retardants such as hexabromobenzene, chlorinated paraffin, brominated polycarbonate resin, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, and brominated benzyl polyacrylate resin. Phosphorus-based flame retardants are preferred. One flame retardant may be used alone, or two or more may be used in combination.

[0232] In the resin composition of the present invention, the content of flame retardant is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or less, more preferably 9% by mass or less, and the lower limit can be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, etc.

[0233] The resin composition of the present invention may further contain an organic filler material. As the organic filler material, any organic filler material that can be used in forming the insulating layer of the printed wiring board can be used, such as rubber particles, polyamide microparticles, and organosilicon particles, with rubber particles being preferred. As the rubber particles, there is no particular limitation as long as they are microparticles of a resin that exhibits rubber elasticity and is insoluble and infusible in an organic solvent after chemical cross-linking treatment; examples include acrylonitrile-butadiene rubber particles, butadiene rubber particles, and acrylic rubber particles. Specific examples of rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), STAPHYLOID AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by AICA Industries, Ltd.), and PARALOID EXL2655 and EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.). The average particle size of the organic filler material is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler material can be determined using dynamic light scattering. For example, the organic filler material is uniformly dispersed in a suitable organic solvent by means of ultrasound, and the particle size distribution of the organic filler material is prepared on a mass basis using a thick particle size analyzer (Otsuka Electronics Co., Ltd. "FPAR-1000"), and the median particle size is used as the average particle size for measurement.

[0234] In the resin composition of the present invention, the content of organic filler material is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, and the lower limit can be 0% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, etc.

[0235] The resin composition of the present invention may further include any additives as non-volatile components. Examples of such additives include: free radical polymerizable compounds such as maleimide-based free radical polymerizable compounds, vinylphenyl-based free radical polymerizable compounds, (meth)acrylic acid-based free radical polymerizable compounds, allyl-based free radical polymerizable compounds, and polybutadiene-based free radical polymerizable compounds; free radical polymerization initiators such as peroxide-based free radical polymerization initiators and azo-based free radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, polyurethane acrylate resins, polyurethane resins, cyanate ester resins, benzoxazine resins, unsaturated polyester resins, melamine resins, and organosilicon resins; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and thiophene; and organosilicon leveling agents. Leveling agents such as acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; defoamers such as silicone defoamers, acrylic defoamers, fluorinated defoamers, and vinyl resin defoamers; ultraviolet absorbers such as benzotriazole ultraviolet absorbers; adhesion enhancers such as ureasilanes; adhesion enhancers such as triazole, tetraazole, and triazine adhesion enhancers; antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as zirconia derivatives; surfactants such as fluorinated and silicone surfactants; dispersants such as phosphate ester dispersants, polyoxyethylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate ester stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. Other additives may be used alone or in combination of two or more in any ratio. Those skilled in the art can appropriately determine the content of other additives.

[0236] In addition to the non-volatile components mentioned above, the resin composition of the present invention sometimes further contains any organic solvent as a volatile component. As an organic solvent, any known organic solvent may be used as long as it can dissolve at least a portion of the non-volatile component, and its type is not particularly limited. Examples of organic solvents include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and ethyl diglycol acetate. Organic solvents include ether esters such as acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohols such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohols such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. One organic solvent can be used alone, or two or more can be combined in any ratio.

[0237] The content of organic solvent is not particularly limited. In one embodiment, when all components in the resin composition are set to 100% by mass, it can be, for example, 60% or less by mass, 40% or less by mass, 30% or less by mass, 20% or less by mass, 15% or less by mass, 10% or less by mass, etc.

[0238] The resin composition of the present invention can be prepared by appropriately mixing the essential components in the above-mentioned components and, as needed, by using a mixing device such as a three-roll mill, ball mill, bead mill, sand mill, or a stirring device such as a super mixer or planetary mixer.

[0239] The resin composition of the present invention comprises an ester compound (A). By using such a resin composition, a cured product with excellent dielectric properties can be obtained. By using such a resin composition, a cured product with excellent curing properties, heat resistance, and moisture resistance (hydrolysis resistance) can be obtained.

[0240] In one embodiment, the resin composition of the present invention exhibits excellent curability. Therefore, in one embodiment, for example, the gel time measured by the method of Test Example 1 below is preferably less than 100 seconds, more preferably less than 80 seconds, further preferably less than 70 seconds, and particularly preferably less than 60 seconds.

[0241] In one embodiment, the cured resin composition of the present invention exhibits excellent heat resistance or moisture resistance (hydrolysis resistance). Therefore, in one embodiment, for example, the insulation resistance value of the evaluation substrate after 200 hours of applying a 3.3V voltage to the wiring connected to a DC power supply for 200 hours at 130°C and 85% RH, as measured by the method described in Example 2 below, is preferably 1.0 × 10⁻⁶. 5 Ω or higher, preferably 1.0 × 10 6 Ω or higher, and even better is 1.0 × 10⁻⁶. 7 Ω or higher, especially 1.0×10 8 Ω and above.

[0242] In one embodiment, the cured resin composition of the present invention may have excellent dielectric properties. Therefore, in one embodiment, for example, the dielectric loss tangent (tanδ) of the cured resin composition (obtained by heating at 190°C for 90 minutes) measured at 5.8 GHz and 23°C as described in Test Example 3 below may preferably be 0.0200 or less, 0.0100 or less, or 0.0090 or less, more preferably 0.0080 or less, or 0.0070 or less, further preferably 0.0065 or less, or 0.0060 or less, and particularly preferably 0.0055 or less, or 0.0050 or less.

[0243] In one embodiment, the cured resin composition of the present invention exhibits excellent heat resistance. Therefore, in one embodiment, for example, the glass transition temperature of the cured resin composition (the cured product obtained by heating at 190°C for 90 minutes), as measured by the method described in Test Example 4 below, is preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, and still more preferably 150°C or higher, and particularly preferably 160°C or higher.

[0244] The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, and in particular as a resin composition for forming an insulating layer. Specifically, it can be suitably used as: a resin composition for forming an insulating layer for forming a conductor layer (the conductor layer is formed on an insulating layer, the conductor layer including a redistribution layer) (resin composition for forming an insulating layer for forming a conductor layer). Additionally, in the printed wiring board described later, it can be suitably used as: a resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can also be widely used in applications requiring resin compositions, such as resin sheets, sheet laminates like prepregs, solder resists, underfill materials, chip bonding materials, semiconductor sealing materials, filling resins, and component embedding resins.

[0245] Furthermore, for example, when manufacturing a semiconductor chip package through the following processes (1) to (6), the resin composition of the present invention can also be suitably used as: a resin composition for forming a redistribution layer as an insulating layer for forming a redistribution layer (resin composition for forming a redistribution layer), and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). During the manufacturing of the semiconductor chip package, a redistribution layer can be further formed on the sealing layer; (1) The process of laminating a temporary fixing film on a substrate. (2) The process of temporarily fixing the semiconductor chip onto the temporary fixing film. (3) The process of forming a sealing layer on a semiconductor chip. (4) The process of peeling the substrate and temporary fixing film from the semiconductor chip. (5) The process of forming a rewiring layer as an insulating layer on the surface of a semiconductor chip where the substrate and temporary fixing film have been stripped, and (6) The process of forming a redistribution layer as a conductor layer on the redistribution layer.

[0246] Furthermore, the resin composition of the present invention can form an insulating layer with good component embedding properties, and therefore can also be suitably applied to situations where the printed wiring board is a circuit board with components embedded in it.

[0247] The resin composition of the present invention can also be used by coating in the form of a varnish, but in industry, it is generally preferred to use it in the form of a sheet-like laminate containing the resin composition.

[0248] As sheet-like laminated materials, resin sheets and prepregs as shown below are preferred.

[0249] In one embodiment, the resin sheet comprises a support and a resin composition layer disposed on the support, the resin composition layer being formed of the resin composition of the present invention.

[0250] From the viewpoint of achieving thinner printed wiring boards and providing a cured product of the resin composition that exhibits excellent insulation properties even as a thin film, the thickness of the resin composition layer is preferably 50 μm or less, and more preferably 40 μm or less. There is no particular limitation on the lower limit of the resin composition layer thickness; it is typically set to 5 μm or more, 10 μm or more, etc.

[0251] Examples of supports include films made of plastic materials, metal foils, and release paper, with films and metal foils made of plastic materials being preferred.

[0252] When a film formed of a plastic material is used as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), acrylic polymers such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0253] When using metal foil as a support, examples of metal foils include copper foil and aluminum foil, with copper foil being preferred. Copper foil can be used as the support, either as a single metal such as copper or as an alloy of copper with other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0254] The surface of the support that is bonded to the resin composition layer can be treated with matte finish, corona treatment, and antistatic treatment.

[0255] Furthermore, as a support, a support with a release layer can be used on the surface bonded to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include, for example, one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, polyurethane resin, and silicone resin. Commercially available products can be used as the support with the release layer, such as PET films having a release layer with an alkyd resin-based release agent as the main component, such as "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Ltd., "Purex" manufactured by Teijin Corporation, and "Unipeel" manufactured by Unitech Co., Ltd.

[0256] The thickness of the support is not particularly limited, but it is preferably in the range of 5μm to 75μm, and more preferably in the range of 10μm to 60μm. It should be noted that when using a support with a release layer, it is preferable that the overall thickness of the support with the release layer is within the above range.

[0257] In one embodiment, the resin sheet may further comprise any layer as needed. Examples of such arbitrary layers include, for instance, a protective film selected according to the support, disposed on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, dust and other contaminants can be prevented from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer.

[0258] Resin sheets can be manufactured, for example, by directly coating a liquid resin composition onto a support using a die coater or similar machine, or by dissolving the resin composition in an organic solvent to prepare a resin varnish, coating it onto a support using a die coater or similar machine, and then drying it to form a resin composition layer.

[0259] As an organic solvent, the same organic solvents described as components of the resin composition can be cited. One organic solvent may be used alone, or two or more may be used in combination.

[0260] Drying can be carried out by known methods such as heating or hot air blowing. There are no particular limitations on the drying conditions, but drying is carried out when the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, if a resin composition or resin varnish containing 30% to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0261] Resin sheets can be stored by rolling them into rolls. If the resin sheet has a protective film, it can be used by peeling off the protective film.

[0262] In one embodiment, the prepreg can be formed by impregnating a sheet fiber substrate with the resin composition of the present invention.

[0263] There are no particular limitations on the sheet fiber substrate used for prepregs; commonly used substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning printed wiring boards, the thickness of the sheet fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular limitation on the lower limit of the sheet fiber substrate thickness. It is typically 10 μm or more.

[0264] Prepregs can be manufactured using known methods such as hot-melt methods and solvent methods.

[0265] The thickness of the prepreg can be the same range as the resin composition layer in the resin sheet described above.

[0266] The sheet-like laminated material of the present invention can be suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and is more suitable for forming an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[0267] The printed wiring board of the present invention comprises an insulating layer formed from a cured product obtained by curing the resin composition of the present invention.

[0268] Printed wiring boards can be manufactured, for example, using the resin sheet described above and by a method including the following steps (I) and (II); Step (I) involves laminating a resin sheet onto an inner substrate by bonding a resin composition layer of the resin sheet to the inner substrate. Step (II) involves curing the resin composition layer (e.g., thermosetting) to form an insulating layer.

[0269] The "inner layer substrate" used in process (I) refers to a component that becomes the substrate of a printed wiring board, such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. Additionally, this substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. Sometimes, an inner layer substrate with conductor layers (circuits) formed on one or both sides of the substrate is called an "inner layer circuit substrate." Furthermore, intermediate products for which insulating layers and / or conductor layers are to be further formed during the manufacture of the printed wiring board are also included in the "inner layer substrate" as described in this invention. When the printed wiring board is a component-integrated circuit board, an inner layer substrate with built-in components can be used.

[0270] The lamination of the inner substrate and the resin sheet can be achieved, for example, by heat-pressing the resin sheet onto the inner substrate from the support side. Examples of components for heat-pressing the resin sheet onto the inner substrate (hereinafter also referred to as "heat-pressing components") include, for example, heated metal plates (SUS end plates, etc.) or metal rollers (SUS rollers). It should be noted that, preferably, the heat-pressing components are not directly pressed onto the resin sheet, but rather pressed through an elastic material such as heat-resistant rubber, so that the resin sheet fully follows the surface irregularities of the inner substrate.

[0271] The lamination of the inner substrate and the resin sheet can be carried out by vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60℃ to 160℃, more preferably in the range of 80℃ to 140℃; the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa; and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions below 26.7 hPa.

[0272] Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include the vacuum pressure laminator manufactured by Meiki Manufacturing Co., Ltd., the vacuum applicator manufactured by Nikko-Materials Co., Ltd., and batch vacuum pressure laminators.

[0273] After lamination, the heated pressing members can be pressed under normal pressure (atmospheric pressure), for example, from the support side, thereby performing a smoothing treatment on the laminated resin sheets. The pressing conditions for the smoothing treatment can be set to the same conditions as the heated pressing conditions for the lamination described above. The smoothing treatment can be performed using a commercially available laminating machine. It should be noted that lamination and smoothing treatment can be performed continuously using the aforementioned commercially available vacuum laminating machine.

[0274] The support can be removed between process (I) and process (II), or it can be removed after process (II).

[0275] In step (II), the resin composition layer is cured (e.g., heat-cured) to form an insulating layer formed from the cured resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions typically used when forming insulating layers for printed wiring boards can be used.

[0276] For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc. In one embodiment, the curing temperature is preferably 120°C to 250°C, more preferably 150°C to 240°C, and even more preferably 170°C to 230°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0277] The resin composition layer can be preheated at a temperature lower than the curing temperature before heat curing. For example, the resin composition layer can be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for at least 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes before heat curing.

[0278] In manufacturing a printed wiring board, steps (III) of opening holes in the insulating layer, (IV) of roughening the insulating layer, and (V) of forming a conductor layer can be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art in the manufacture of printed wiring boards. It should be noted that if the support is removed after step (II), the removal of the support can be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). In addition, as needed, the formation of the insulating layer and conductor layer in steps (II) to (V) can be repeated to form a multilayer printed wiring board.

[0279] In other embodiments, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as that used when resin sheets are used.

[0280] Step (III) is the process of creating holes in the insulating layer, thereby forming through holes, vias, etc. Step (III) can be performed using tools such as drills, lasers, or plasma, depending on the composition of the resin composition used in forming the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed circuit board.

[0281] Step (IV) is a roughening process for the insulating layer. Typically, this step (IV) also includes the removal of contaminants. The roughening steps and conditions are not particularly limited, and well-known steps and conditions commonly used in forming the insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by sequentially performing a swelling treatment based on a swelling solution, a roughening treatment based on an oxidizing agent, and a neutralization treatment based on a neutralizing solution.

[0282] The swelling solution used in the roughening treatment is not particularly limited, and examples include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred as alkaline solutions. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN Co., Ltd. The swelling treatment based on the swelling solution is not particularly limited; for example, it can be carried out by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0283] The oxidant used in the roughening treatment is not particularly limited, and examples include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment based on oxidants such as alkaline permanganate solutions is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidants include alkaline permanganate solutions such as "Concentrate Compact CP" and "DosingSolution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0284] Furthermore, the neutralizing liquid used in the roughening process is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction Solution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0285] The treatment based on the neutralizing solution can be performed by immersing the surface that has undergone roughening treatment based on the oxidant in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From an operational perspective, it is preferable to immerse the surface that has undergone roughening treatment based on the oxidant in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0286] In one embodiment, the arithmetic mean roughness (Ra) of the roughened insulating layer surface is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular limitation on the lower limit, and it can be set to, for example, 1 nm or more, 2 nm or more, etc. Furthermore, the root mean square roughness (Rq) of the roughened insulating layer surface is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular limitation on the lower limit, and it can be set to, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0287] Step (V) is the step of forming a conductor layer, which is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility, cost, and ease of patterning in conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium, copper-nickel, or copper-titanium alloys, is preferred. More preferably, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloys, is even more preferred. A single metal layer of copper is also preferred.

[0288] The conductor layer can be a single-layer structure or a multi-layer structure consisting of two or more single-metal or alloy layers made of different types of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0289] The thickness of the conductor layer depends on the desired printed wiring board design, typically 3μm to 35μm, preferably 5μm to 30μm.

[0290] In one embodiment, the conductor layer can be formed by plating. For example, known techniques such as semi-additive and fully additive methods can be used to plate the surface of the insulating layer to form a conductor layer with the desired wiring pattern. From the viewpoint of ease of manufacturing, it is preferable to use the semi-additive method. An example of forming a conductor layer using the semi-additive method is shown below.

[0291] First, a seed layer is formed on the surface of an insulating layer using electroless plating. Next, a mask pattern is formed on the formed seed layer, corresponding to the desired wiring pattern, exposing a portion of the seed layer. A metal layer is formed on the exposed seed layer using electrolytic plating, and then the mask pattern is removed. Finally, the unwanted seed layer is removed using etching or the like, forming a conductor layer with the desired wiring pattern.

[0292] In other embodiments, the conductor layer may be formed using metal foil. When forming the conductor layer using metal foil, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and metal foil is laminated onto the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be legally performed using a vacuum layer. The lamination conditions can be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer with the desired wiring pattern can be formed using existing known techniques such as subtractive processing or modified semi-additive processing.

[0293] Metal foils can be manufactured using known methods such as electrolysis and rolling. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Minerals & Metals Co., Ltd., and 3EC-III foil and TP-III foil manufactured by Mitsui Metals & Minerals Co., Ltd.

[0294] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0295] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and aircraft).

[0296] In a preferred embodiment, the semiconductor device of the present invention is a fan-out type semiconductor device. Example

[0297] The present invention will now be specifically described through examples. The present invention is not limited to these examples. It should be noted that, unless otherwise explicitly stated, "parts" and "%" in the following text refer to "parts by mass" and "% by mass," respectively. The temperature condition, unless otherwise specified, is room temperature (25°C). The pressure condition, unless otherwise specified, is atmospheric pressure (1 atm).

[0298] <Example A-1> 228 g (1.0 mol) of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 184 g (1.0 mol) of pentafluorophenol, 305 g (1.5 mol) of isophthaloyl chloride, and 800 g of methyl isobutyl ketone were added to a flask equipped with a thermometer, dropping funnel, condenser, and stirrer. The system was purged with nitrogen under reduced pressure to dissolve the bisphenol A. The system was heated to 50 °C, and 404 g (4.0 mol) of triethylamine was added dropwise over 1 hour with vigorous stirring. After the addition was complete, stirring was continued for another hour. 300 g of water was added to dissolve the byproduct salts, and the mixture was allowed to stand and separated, discarding the lower aqueous layer. The mixture was then repeatedly washed with water until the pH of the aqueous layer reached 7, followed by dehydration and removal of insoluble impurities by precision filtration. The liquid was heated to 170 °C under reduced pressure to dry the solvent, yielding 540 g of product (A-1). The ester equivalent of product (A-1) was 203 g / eq., and the fluorine atom content was 15.6% by mass. For the obtained product (A-1), the determination was performed using gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the GPC and IR determination conditions described below. Figure 1 The GPC spectrum of the resulting product (A-1) is shown. Figure 2 The image shows the IR spectrum of the resulting product (A-1). Mass spectrometry analysis confirmed peaks at m / z = 498 (n=0 component), m / z = 856 (n=1 component), and m / z = 1214 (n=2 component).

[0299] (GPC measurement conditions) Measuring apparatus: Tosoh Corporation "HPLC-8420GPC" Column: "TSKgel SuperHZ4000" manufactured by Tosoh Corporation (1 column) + "TSKgel SuperHZ3000" manufactured by Tosoh Corporation (1 column) + "TSKgel SuperHZ2000" manufactured by Tosoh Corporation (2 columns) Detector: RI (Differential Refractometer) Column temperature: 40℃ Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min.

[0300] (IR measurement conditions) Measurement apparatus: JASCO Corporation, "FT / IR-4600".

[0301] <Example A-2> Except that 160 g (1.0 mol) of 2,7-dihydroxynaphthalene was used instead of bisphenol A, the procedure was the same as in Example A-1 to obtain 601 g of product (A-2) (a mixture of ester compounds). The ester equivalent of product (A-2) was 194 g / eq., and the fluorine atom content was 24.1% by mass. The resulting product (A-2) was subjected to GPC and IR determinations in the same manner as in Example A-1. Figure 3 The GPC spectrum of the resulting product (A-2) is shown. Figure 4 The image shows the IR spectrum of the resulting product (A-2). Furthermore, mass spectrometry analysis confirmed peaks at m / z = 498 (n=0 component), m / z = 788 (n=1 component), and m / z = 1078 (n=2 component).

[0302] <Example A-3> Except for replacing bisphenol A with 330 g (2.0 mol) of dicyclopentadiene-phenol addition polymer (softening point 85°C, hydroxyl equivalent 165 g / eq.), the procedure was performed in the same manner as in Example A-1 to obtain 642 g of product (A-3). Product (A-3) had an ester equivalent of 233 g / eq. and a fluorine content of 13.6% by mass. The resulting product (A-3) was subjected to GPC and IR-based determinations in the same manner as in Example A-1. Figure 5 The GPC spectrum of the resulting product (A-3) is shown. Figure 6 The image shows the IR spectrum of the resulting product (A-3). Furthermore, mass spectrometry analysis confirmed peaks at m / z = 498 (n=0 component), m / z = 948 (n=1 component), and m / z = 1399 (n=2 component).

[0303] <Example A-4> Except that 336 g (1.0 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF) was used instead of bisphenol A, the procedure was performed in the same manner as in Example A-1 to obtain 640 g of product (A-4). The ester equivalent of product (A-4) was 238 g / eq., and the fluorine atom content was 29.2% by mass. The resulting product (A-4) was subjected to GPC and IR determinations in the same manner as in Example A-1. Figure 7 The GPC spectrum of the resulting product (A-4) is shown. Figure 8 The image shows the IR spectrum of the resulting product (A-4). Furthermore, mass spectrometry analysis confirmed peaks at m / z = 498 (n=0 component), m / z = 964 (n=1 component), and m / z = 1430 (n=2 component).

[0304] <Example A-5> Except that 121 g (1.0 mol) of 4-fluorophenol was used instead of pentafluorophenol, the procedure was performed in the same manner as in Example A-4 to obtain 535 g of product (A-5). The ester equivalent of product (A-5) was 215 g / eq., and the fluorine atom content was 20.7% by mass. The resulting product (A-5) was subjected to GPC and IR determinations in the same manner as in Example A-1. Figure 9 The GPC spectrum of the resulting product (A-5) is shown. Figure 10 The image shows the IR spectrum of the resulting product (A-5). Furthermore, mass spectrometry analysis confirmed peaks at m / z = 354 (n=0 component), m / z = 820 (n=1 component), and m / z = 1286 (n=2 component).

[0305] <Comparative Example A-1> Except that 94 g (1.0 mol) of phenol was used instead of pentafluorophenol, the procedure was the same as in Example A-1 to obtain 502 g of product (A-1'). The ester equivalent of product (A-1') was 208 g / eq., and the fluorine atom content was 18.2% by mass. The resulting product (A-1') was subjected to GPC and IR determinations in the same manner as in Example A-1. Figure 11 The GPC spectrum of the resulting product (A-1') is shown. Figure 12 The IR spectrum of the resulting product (A-1') is shown. Furthermore, mass spectrometry analysis confirmed peaks at m / z = 318 (n=0 component), m / z = 784 (n=1 component), and m / z = 1250 (n=2 component).

[0306] The compounds, ester equivalents, and fluorine atom contents of the main components contained in the above-mentioned products (A-1) to (A-5) and (A-1') are summarized in Table 1.

[0307] [Table 1] (Table 1)

[0308] <Example B-1: Preparation of Resin Composition (B-1)> 203g of the product (A-1) obtained in Example A-1 and 275g of biphenyl aryl epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275g / eq.) were dissolved in 500g of methyl ethyl ketone, and 5.0g of dimethylaminopyridine as a curing accelerator were added to prepare a resin composition (B-1) for curing evaluation.

[0309] <Example B-2: Preparation of Resin Composition (B-2)> Except that 194g of the product (A-2) obtained in Example A-2 was used instead of the product (A-1) obtained in Example A-1, the same procedure as in Example B-1 was followed to prepare the resin composition (B-2).

[0310] <Example B-3: Preparation of Resin Composition (B-3)> Except that 233g of the product (A-3) obtained in Example A-3 was used instead of the product (A-1) obtained in Example A-1, the same procedure as in Example B-1 was followed to prepare the resin composition (B-3).

[0311] <Example B-4: Preparation of Resin Composition (B-4)> Except that 238g of the product (A-4) obtained in Example A-4 was used instead of the product (A-1) obtained in Example A-1, the same procedure as in Example B-1 was followed to prepare the resin composition (B-4).

[0312] <Example B-5: Preparation of Resin Composition (B-5)> Except that 215g of the product (A-5) obtained in Example A-5 was used instead of the product (A-1) obtained in Example A-1, the same procedure as in Example B-1 was followed to prepare the resin composition (B-5).

[0313] <Comparative Example B-1: Preparation of Resin Composition (B-1')> Except that 208g of the active product (A-1') obtained in Comparative Example A-1 was used instead of the product (A-1) obtained in Example A-1, the same procedure as in Example B-1 was followed to prepare the resin composition (B-1').

[0314] <Experimental Example 1: Evaluation of Curability Based on Gel Time Measurement> The gel times of the resin compositions (B-1) to (B-5) and (B-1') were measured using a curing plate at 160°C. The results of the evaluation of the curability of the resin compositions (B-1) to (B-5) and (B-1') prepared in Examples B-1 to 5 and Comparative Example B-1 are shown in Table 2.

[0315] [Table 2] (Table 2)

[0316] The structure formed by the direct bonding of fluorine atoms and aromatic carbons in the compounds of this invention results in a rapid transesterification reaction (crosslinking reaction of active esters) due to the electron density, which is believed to contribute to improved curability.

[0317] <Example C-1: Preparation of Resin Composition (C-1)> While stirring, 15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, manufactured by Mitsubishi Chemical Corporation "828US") and 15 parts of biphenyl type epoxy resin (epoxy equivalent 291, manufactured by Nippon Kayaku Co., Ltd. "NC3000H") were heated and dissolved in 15 parts of methyl ethyl ketone (hereinafter referred to as "MEK") and 15 parts of cyclohexanone. 40 parts of the product (A-1) obtained in Example A-1 (toluene solution with ester equivalent of 203 g / eq. and 65% solids content), 0.15 parts of curing accelerator (manufactured by Kōei Chemical Industry Co., Ltd., "4-dimethylaminopyridine"), 100 parts of spherical silica (average particle size of 0.5 μm, treated with phenylaminosilane "SO-C2", manufactured by Yadoma Co., Ltd., with 0.18% carbon per unit mass), and 15 parts of phenoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., "YL6954BH30", MEK solution with 30% by mass of solids content and 40,000 weight average molecular weight) were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a resin composition (C-1).

[0318] <Example C-2: Preparation of Resin Composition (C-2)> Except that 38 parts of the product (A-2) obtained in Example A-2 were used instead of 40 parts of the product (A-1), the same procedure as in Example C-1 was followed to prepare the resin composition (C-2).

[0319] <Example C-3: Preparation of Resin Composition (C-3)> Except that 40 parts of product (A-1) were replaced with 46 parts of product (A-3) obtained in Example A-3, the same procedure as in Example C-1 was followed to prepare the resin composition (C-3).

[0320] <Example C-4: Preparation of the resin composition (C-4)> Except that 47 parts of the product obtained in Example A-4 (A-4) were used instead of 40 parts of the product (A-1), the same procedure as in Example C-1 was followed to prepare the resin composition (C-4).

[0321] <Example C-5: Preparation of Resin Composition (C-5)> Except that 42 parts of the product obtained in Example A-5 (A-5) were used instead of 40 parts of the product (A-1), the same procedure as in Example C-1 was followed to prepare the resin composition (C-5).

[0322] <Comparative Example C-1: Preparation of Resin Composition (C-1')> Except that 40 parts of product (A-1) were used instead of 41 parts of product (A-1') obtained in Comparative Example A-1, the same procedure as in Example C-1 was followed to prepare the resin composition (C-1').

[0323] <Example 2: Evaluation of Insulation Reliability> (1) Fabrication of resin sheets Using a die coater, the resin compositions (C-1) to (C-5) and (C-1') obtained in Examples C-1 to 5 and Comparative Example C-1 were coated onto polyethylene terephthalate (38 μm thick, hereinafter referred to as "PET") with a dried resin thickness of 40 μm, and dried at 80 to 120°C (average 100°C) for 6 minutes to produce resin sheets.

[0324] (2) Substrate treatment of laminated PCBs The copper surface of a glass cloth substrate with an epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, residual copper rate 60%, substrate thickness 0.3mm, Panasonic Electric Works R5715ES) with inner circuits was roughened by immersing both sides in MEC CZ8100.

[0325] (3) Lamination of resin sheets The resin sheet prepared in (1) was laminated onto both sides of the laminate using a batch vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho Co., Ltd.). The lamination was performed by depressurizing for 30 seconds to bring the air pressure down to below 13 hPa, and then pressing at 30 seconds, 100°C and 0.74 MPa.

[0326] (4) Curing of the resin composition The PET film is peeled off from the laminated resin sheet, and the resin composition is cured at 170°C for 30 minutes.

[0327] (5) Roughening treatment The laminated plate was immersed in Swelling Dip Securiganth P (containing diethylene glycol monobutyl ether), manufactured by Ammet Japan Co., Ltd., at 60°C for 10 minutes as a swelling solution. Then, it was immersed in Concentrate Compact P (an aqueous solution of KMnO4: 60 g / L and NaOH: 40 g / L), manufactured by Ammet Japan Co., Ltd., at 80°C for 20 minutes as a roughening solution. Finally, it was immersed in Reduction solution Securiganth P, manufactured by Ammet Japan Co., Ltd., at 40°C for 5 minutes as a neutralization solution. This roughened laminated plate was designated as sample A.

[0328] (6) Coating formation using a semi-additive method To form a circuit on the surface of the insulating layer, the laminate was immersed in an electroless plating solution containing PdCl2, followed by immersion in an electroless copper plating solution. After annealing at 150°C for 30 minutes, a resist layer was formed. Following the formation of the etch-based pattern, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. This was then annealed at 180°C for 60 minutes. This laminate was designated as sample B.

[0329] (7) Evaluation of insulation reliability (evaluation of heat and moisture resistance) A circular piece of resist tape (manufactured by Nitto Denko Co., Ltd., ELEP masking tape N380) was applied to the conductor layer of sample B and immersed in a ferric chloride aqueous solution for 30 minutes. The portion of the conductor layer without the resist tape was removed, creating an evaluation substrate with a circular conductor layer formed on an insulating layer. Then, a portion of the insulating layer was shaved away to expose the copper foil of the substrate. The exposed copper foil was then connected to the circular conductor layer using wires. A DC power supply (manufactured by Takasago Manufacturing Co., Ltd., TP018-3D) was connected to the wires on the evaluation substrate, and a voltage of 3.3V was applied for 200 hours at 130°C and 85% RH. After 200 hours, the resistance value was measured, and the resistance was set to 1.0 × 10⁻⁶. 8 Samples with a resistance greater than Ω are rated as "○", and a resistance value of 1.0 × 10⁻⁶ is assigned. 7 Ω or higher and lower than 1.0 × 10 8 Samples with a resistance of Ω are evaluated as "△", and those with a resistance value below 1.0 × 10⁻⁶ are considered to have a resistance value below 1.0 × 10⁻⁶. 7 The sample with Ω was rated as "×".

[0330] <Experimental Example 3: Determination of Dielectric Properties (Dielectric Loss Tangent)> The resin sheet prepared in Experiment 2(1) was heat-cured at 190°C for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into test pieces with a width of 2 mm and a length of 80 mm. The dielectric constant of the test piece was measured using a resonant cavity perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technologies Co., Ltd., at a measurement frequency of 5.8 GHz and a temperature of 23°C by the resonant cavity method. The dielectric loss tangent (tanδ) of the two test pieces was measured and the average value was calculated.

[0331] <Experimental Example 4: Determination of Glass Transition Temperature> The sheet-like cured material obtained in Example 3 was cut into specimens approximately 5 mm wide and 15 mm long. Thermomechanical analysis was performed using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nanotechnology Co., Ltd.) via tensile loading. The specimens were loaded onto the device and measured under the following conditions: load 200 mN, heating rate 2 °C / min. The peak value of tanδ was used as the glass transition temperature (°C).

[0332] The measurement and evaluation results of test examples 2 to 4 are shown in Table 3 below.

[0333] [Table 3] (Table 3)

[0334] As shown in Tables 2 and 3, it can be seen that when ester compound (A) is used as a component of the resin composition, the cured product exhibits superior curability, dielectric properties, heat resistance, and moisture resistance compared to the conventional use of active ester compounds.

[0335] In particular, for structures formed by the direct combination of fluorine atoms and aromatic carbon, the rigidity is high and the fluctuation (change) of the molecular chain is small in response to temperature or electric field changes. Therefore, it is believed to contribute to the improvement of insulation reliability and even dielectric properties.

[0336] That is, the resin composition and cured product using ester compound (A) are materials that can achieve a high level of low transmission loss required in high-frequency environments such as 5G devices without sacrificing processability and reliability.

Claims

1. A compound represented by formula (A2), In the formula, Ring A 1 And Ring A 2 Each of the following can be independently represented as a benzene ring or naphthalene ring having a substituent selected from fluorine atoms, alkyl groups having 1 to 6 carbon atoms, and fluoroalkyl groups having 1 to 6 carbon atoms; Ring B independently represents a benzene ring or naphthalene ring substituted with one or more fluorine atoms; X 1 Each can be used independently to represent a single bond or -C(R) x )2-; R x Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; Ring X 2 Each of the above independently represents a saturated carbon ring having 3 to 15 carbon atoms, which may be selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms. Y-shaped ring 1 Each independently represents a benzene ring or naphthalene ring having substituents selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms; a can independently represent 0 or 1; b represents 0 or 1 independently; n represents an integer from 1 to 100.

2. The compound according to claim 1, wherein, Ring A 1 And Ring A 2 Each can be a benzene ring or a naphthalene ring, independently.

3. The compound according to claim 1, wherein, R x Each can be independently a hydrogen atom, a methyl group, or a trifluoromethyl group.

4. The compound according to claim 1, wherein, Ring X 2 Each is an independent saturated carbon ring with 3 to 15 carbon atoms.

5. The compound according to claim 1, wherein, Y-shaped ring 1 Each can be a benzene ring or a naphthalene ring, independently.

6. The compound according to claim 1, wherein, Ring B is either a benzene ring or a naphthalene ring that is substituted with two or more fluorine atoms.

7. The compound according to claim 1, wherein, Ring B is either a benzene ring or a naphthalene ring that is substituted with five or more fluorine atoms.

8. The compound according to claim 1, wherein, The structure shown in formula (1') contained in formula (A2) contains more than 3 fluorine atoms in a single unit. 。 9. The compound according to claim 1, wherein, The structure shown in formula (1') contained in formula (A2) contains more than 5 fluorine atoms in a single unit. 。 10. The compound according to claim 1, wherein, The structure represented by the following formula (1') contained in formula (A2) is expressed by formula (1''-1) or (1''-2). In the formula, X 1 Each can be used independently to represent a single bond or -C(R) x )2-; R x Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; Ring X 2 Each of the above independently represents a saturated carbon ring having 3 to 15 carbon atoms, which may be selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms. R 1 Each substituent is independently selected from fluorine atoms, alkyl groups having 1 to 6 carbon atoms, and fluoroalkyl groups having 1 to 6 carbon atoms; 'a' represents 0 or 1; b represents 0 or 1; c represents an integer of 0 or higher, respectively. *1 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure.

11. The compound according to claim 1, wherein, The structure represented by the following formula (1') contained in the formula (A2) is expressed by any of the formulas (1'''-1) to (1'''-3), (1'''-9), (1'''-10), (1'''-20) to (1'''-22), (1'''-28), and (1'''-29). In the formula, Ring X 2 Each of the above independently represents a saturated carbon ring having 3 to 15 carbon atoms, which may be selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms. R 1 Each substituent is independently selected from fluorine atoms, alkyl groups having 1 to 6 carbon atoms, and fluoroalkyl groups having 1 to 6 carbon atoms; R x Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; c represents an integer of 0 or higher, respectively. *1 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure.

12. The compound according to claim 1, wherein, The structure represented by the following formula (1') contained in the formula (A2) is expressed by any of the formulas (1'''-1) to (1''''-28), (1''''-34) to (1''''-39), (1''''-49), (1''''-50), (1''''-54) to (1''''-59), (1''''-78), (1''''-79), (1''''-83), and (1''''-84). In the formula, R 2 Each can be independently represented by a fluorine atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; c represents an integer of 0 or higher, respectively. m represents 1 or 2; *1 indicates the bonding site with the carbonyl group's carbon atom, forming an ester structure.

13. The compound according to claim 1, wherein, The structure shown in equation (2) contained in equation (A2) is represented by any of equations (2'-1) to (2'-3). In the formula, R f1 and R f2 Each can independently represent a hydrogen atom or a fluorine atom, and R f1 and R f2 At least one of them is a fluorine atom; *2 represents the bonding site with the carbonyl group's carbon atom, forming an ester structure.

14. The compound according to claim 1, wherein, The structure shown in the following formula (2) contained in the formula (A2) is represented by any of the formulas (2''-1) to (2''-19). In the formula, *2 represents the bonding site with the carbonyl group's carbon atom, forming an ester structure.

15. The compound according to claim 14, wherein, The structure shown in the above formula (2) contained in formula (A2) is represented by any of the formulas (2''-1) to (2''-4).

16. The compound according to claim 1, wherein, The structure represented by the following formula (3') contained in formula (A2) is expressed by formula (3''-1) or (3''-2). In the formula, R 3 Each substituent is independently selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms; d represents an integer of 0 or higher, respectively. *3 is the bonding site with an oxygen atom, which bonds with the oxygen atom to form an ester structure.

17. The compound according to claim 1, wherein, The structure shown in the following formula (3') contained in formula (A2) is represented by any of the formulas (3'''-1) to (3'''-12). In the formula, R 4 Each substituent is independently selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms; d represents an integer of 0 or higher, respectively. *3 is the bonding site with an oxygen atom, which bonds with the oxygen atom to form an ester structure.

18. The compound according to claim 1, wherein, The fluorine atom content is more than 5% by mass.

19. The compound according to claim 1, wherein, The fluorine atom content is over 28% by mass.

20. The compound according to claim 1, wherein, The fluorine atom content is less than 60% by mass.

21. A mixture comprising the compound according to any one of claims 1 to 20.

22. An epoxy resin curing agent comprising any one of claims 1 to 20.

23. A method for manufacturing a compound, wherein, The compound is represented by formula (A2). In the formula, Ring A 1 And Ring A 2 Each of the following can be independently represented as a benzene ring or naphthalene ring having a substituent selected from fluorine atoms, alkyl groups having 1 to 6 carbon atoms, and fluoroalkyl groups having 1 to 6 carbon atoms; Ring B independently represents a benzene ring or naphthalene ring substituted with one or more fluorine atoms; X 1 Each can be used independently to represent a single bond or -C(R) x )2-; R x Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; Ring X 2 Each of the above independently represents a saturated carbon ring having 3 to 15 carbon atoms, which may be selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms. Y-shaped ring 1 Each independently represents a benzene ring or naphthalene ring having substituents selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms; a can independently represent 0 or 1; b represents 0 or 1 independently; n represents an integer from 1 to 100. The manufacturing method includes reacting a mixture containing the following components: The compound represented by formula (B2): In the formula, the meanings of each symbol are as described above; The compound represented by formula (C1): In the formula, the meanings of each symbol are as described above; and The compound or its salt represented by formula (D2-1) or (D2-2): In the formula, Hal represents a halogen atom, and the meanings of the other symbols are as described above.

24. A product containing the compound of claim 1, which is obtained by reacting a mixture comprising the following components, The compound represented by formula (B2): In the formula, the meanings of each symbol are as described above; The compound represented by formula (C1): In the formula, the meanings of each symbol are as described above; and The compound or its salt represented by formula (D2-1) or (D2-2): In the formula, Hal represents a halogen atom, and the meanings of the other symbols are as described above.

25. A resin composition comprising a compound represented by formula (A2) and an epoxy resin, In the formula, Ring A 1 And Ring A 2 Each of the following can be independently represented as a benzene ring or naphthalene ring having a substituent selected from fluorine atoms, alkyl groups having 1 to 6 carbon atoms, and fluoroalkyl groups having 1 to 6 carbon atoms; Ring B independently represents a benzene ring or naphthalene ring substituted with one or more fluorine atoms; X 1 Each can be used independently to represent a single bond or -C(R) x )2-; R x Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; Ring X 2 Each of the above independently represents a saturated carbon ring having 3 to 15 carbon atoms, which may be selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms. Y-shaped ring 1 Each independently represents a benzene ring or naphthalene ring having substituents selected from fluorine atoms and fluoroalkyl groups having 1 to 6 carbon atoms; a can independently represent 0 or 1; b represents 0 or 1 independently; n represents an integer from 1 to 100.

26. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of epoxy resin is 5% to 60% by mass.

27. The resin composition according to claim 26, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of epoxy resin is 20% by mass or more.

28. The resin composition according to claim 26, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of epoxy resin is 35% by mass or less.

29. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of the compound represented by formula (A2) is 0.01% by mass or more.

30. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of the compound represented by formula (A2) is 0.1% by mass or more.

31. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of the compound represented by formula (A2) is 60% by mass or less.

32. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of the compound represented by formula (A2) is 30% by mass or less.

33. The resin composition according to claim 25, wherein, It further includes inorganic filler materials.

34. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of inorganic filler material is 5% by mass or more.

35. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of inorganic filler material is 60% by mass or more.

36. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of inorganic filler material is 90% by mass or less.

37. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of inorganic filler material is 70% by mass or less.

38. The resin composition according to claim 25, used to form an insulating layer of a printed wiring board.

39. The resin composition according to claim 25, used for sealing semiconductor chips.

40. A cured product, which is a cured product of the resin composition according to any one of claims 25 to 39.

41. A sheet-like laminated material comprising the resin composition according to any one of claims 25 to 39.

42. A resin sheet having a support and a resin composition layer formed of the resin composition according to any one of claims 25 to 39 disposed on the support.

43. A printed wiring board having an insulating layer formed from a cured product of the resin composition according to any one of claims 25 to 38.

44. A semiconductor device comprising the printed wiring board of claim 43.

45. The semiconductor device according to claim 44, wherein it is a fan-out type semiconductor device.

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