Ester compounds and resin compositions

Abstract

The present invention provides a novel ester compound that is useful as an epoxy resin curing agent. The present invention provides a compound that has at least two aromatic rings to which a fluorine-substituted arylcarbonyloxy group is directly bonded.

Description

[Technical Field]

[0001] The present invention relates to novel ester compounds, epoxy resin curing agents, methods for producing the same, products obtained thereby, and resin compositions containing the same. Furthermore, it relates to cured products, sheet-like laminated materials, resin sheets, printed circuit boards, and semiconductor devices obtained using the resin composition. [Background technology]

[0002] Resin compositions containing epoxy resins and their curing agents have been widely used as materials for electronic components such as semiconductors and printed circuit boards because they can impart excellent insulation, heat resistance, and adhesion to their cured products. On the other hand, in order to realize high-speed communication such as 5G, it is necessary to design circuits with low transmission loss in high-frequency environments. Therefore, there is a growing need for the development of new insulating materials with even better dielectric properties (low dielectric constant, low dielectric loss tangent).

[0003] As an insulating material with excellent dielectric properties, for example, Patent Document 1 discloses a resin composition using an active ester compound containing an aliphatic fluorine-containing group such as a trifluoromethyl group as an epoxy curing agent. However, although the cured product using the compound from Patent Document 1 as a curing agent exhibits superior dielectric properties compared to that using a general phenol-based curing agent, it is not necessarily at a satisfactory level. Furthermore, there is a need for a curing agent with excellent properties such as curability, heat resistance, and moisture resistance, thus creating a demand for the development of new ester compounds useful as curing agents for epoxy resins. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Republished Patent No. 2018 / 207532 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a novel ester compound useful as an epoxy resin curing agent. [Means for solving the problem]

[0006] The inventors of this invention have diligently studied the structure of introducing fluorine atoms into ester compounds, that is, where and what kind of fluorine group structure should be introduced to achieve the highest level of dielectric properties. As a result, they have found that the introduction of a fluorine-substituted arylcarbonyloxy group in which a fluorine atom is directly bonded to an aromatic ring is a means to achieve the above effect at an even higher level, and have completed the present invention. The present invention includes the following:

[0007] [1] A compound having two or more aromatic rings to which fluorine-substituted arylcarbonyloxy groups are directly bonded. [2] Formula (A1):

[0008] [ka]

[0009] [In the formula, Each Ar ring independently represents an aromatic ring which may have substituents; Each X independently represents an arylcarbonyloxy group or a hydroxyl group which may have substituents, and at least two X groups bonded to different ring Ars are fluorine-substituted arylcarbonyloxy groups; Each Z independently represents either a single bond or a divalent organic group; n represents an integer greater than or equal to 1; Each instance of m represents an integer between 1 and 3, independently of the others. The compound described above [1], represented by [1]. [3] Formula (A2):

[0010] [ka]

[0011] [In the formula, Each Ar ring independently represents an aromatic ring which may have substituents; Each X independently represents an arylcarbonyloxy group or a hydroxyl group which may have substituents, and at least two X groups bonded to different ring Ars are fluorine-substituted arylcarbonyloxy groups; Y 1 These are, independently, single bonds, -C(R 1 ) indicates -2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; R 1 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group; Ring Y 2 Each independently represents an aromatic ring which may have substituents, or an unaromatic ring which may have substituents; Each 'a' independently represents an integer between 0 and 3; n represents an integer greater than or equal to 1; Each instance of m represents an integer between 1 and 3, independently of the others. The compound described above [2], represented by [2]. [4] Ring Ar, ring Y 2 , and Y 1 At least one of the structural units represented by contains a fluorine atom, and the rings are Ar and Y. 2 , and Y 1 The compound described in [3] above, wherein the total number of fluorine atoms contained in the structural unit represented by is 3 or more. [5] A compound according to any of [2] to [4] above, wherein the ratio of fluorine-substituted arylcarbonyloxy groups to hydroxyl groups in X (fluorine-substituted arylcarbonyloxy group:hydroxyl group) is 20:80 to 100:0. [6] A compound according to any of [1] to [5] above, wherein the number of fluorine atoms in the fluorine-substituted arylcarbonyloxy group is 3 or more. [7] A fluorine-substituted arylcarbonyloxy group, formula (F1-1):

[0012] [Chemical formula]

[0013] [wherein, R f1 and R f2 each independently represents a hydrogen atom or a fluorine atom, and at least one of R f1 and R f2 is a fluorine atom; * represents the bonding site with the aromatic ring.] The compound according to any one of [1] to [6] above, which is a group represented by [8] The compound according to [7] above, wherein one of R f1 is a fluorine atom, and the other of R f1 and R f2 are a hydrogen atom or a fluorine atom. [9] The compound according to any one of [1] to [8] above, wherein the fluorine atom content is 20% by mass or more.

[10] An epoxy resin curing agent containing the compound according to any one of [1] to [9] above.

[11] A method for producing a compound having two or more aromatic rings directly bonded with a fluorine-substituted aryloxycarbonyl group, which includes reacting a fluorine-substituted aryl carboxylic acid, its acid halide, its acid anhydride, or its salt with a compound having two or more aromatic rings directly bonded with a hydroxy group.

[12] A product obtained by reacting a fluorine-substituted aryl carboxylic acid, its acid halide, its acid anhydride, or its salt with a compound having two or more aromatic rings directly bonded with a hydroxy group.

[13] A resin composition containing a compound having two or more aromatic rings directly bonded with a fluorine-substituted aryloxycarbonyl group and an epoxy resin.

[14] The resin composition according to

[13] above, further containing an inorganic filler.

[15] The resin composition according to

[14] above, wherein when the content of the inorganic filler is 100% by mass of the non-volatile components in the resin composition, it is 50% by mass or more.

[16] A resin composition according to any one of

[13] to

[15] above for forming an insulating layer on a printed circuit board.

[17] A resin composition according to any of

[13] to

[15] above for semiconductor chip encapsulation.

[18] A cured product of any of the resin compositions described in

[13] to

[17] above.

[19] A sheet-like laminated material containing the resin composition described in any of

[13] to

[17] above.

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

[13] to

[17] above, provided on the support.

[21] A printed circuit board comprising an insulating layer made of a cured resin composition described in any of

[13] to

[17] above.

[22] A semiconductor device including the printed circuit board described in

[21] above.

[23] The semiconductor device described in

[22] above, which is a fan-out type semiconductor device. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide novel ester compounds useful as epoxy resin curing agents. [Brief explanation of the drawing]

[0015] [Figure 1] Figure 1 shows the GPC charts for the product (A-1) (solid line) and raw material (bisphenol A) (dotted line) in Example A-1. [Figure 2] Figure 2 shows the IR charts for the product (A-1) (lower curve) and the raw material (bisphenol A) (upper curve) in Example A-1. [Figure 3] Figure 3 shows the GPC charts for the product (A-2) (solid line) and raw material (phenol novolac resin) (dotted line) in Example A-2. [Figure 4] Figure 4 shows the IR charts for the product (A-2) (lower curve) and raw material (phenol novolac resin) (upper curve) in Example A-2. [Figure 5]Figure 5 shows the GPC charts for the product (A-3) (solid line) and raw material (phenol novolac resin) (dotted line) in Example A-3. [Figure 6] Figure 6 shows the IR charts for the product (A-3) (lower curve) and raw material (phenol novolac resin) (upper curve) in Example A-3. [Figure 7] Figure 7 shows the GPC charts for the product (A-4) (solid line) and raw material (o-cresol novolac resin) (dotted line) in Example A-4. [Figure 8] Figure 8 shows the IR charts for the product (A-4) (lower curve) and the raw material (o-cresol novolac resin) (upper curve) in Example A-4. [Figure 9] Figure 9 shows the GPC charts for the product (A-5) (solid line) and raw material (o-cresol novolac resin) (dotted line) in Example A-5. [Figure 10] Figure 10 shows the IR charts for the product (A-5) (lower curve) and the raw material (o-cresol novolac resin) (upper curve) in Example A-5. [Figure 11] Figure 11 shows the GPC charts for the product (A-6) (solid line) and raw material (biphenyl aralkyl resin) (dotted line) in Example A-6. [Figure 12] Figure 12 shows the IR charts for the product (A-6) (lower curve) and raw material (biphenyl aralkyl resin) (upper curve) in Example A-6. [Figure 13] Figure 13 shows the GPC charts for the product (A-7) (solid line) and raw material (bisphenol AF) (dotted line) in Example A-7. [Figure 14] Figure 14 shows the IR charts for the product (A-7) (lower curve) and the starting material (bisphenol AF) (upper curve) in Example A-7. [Modes for carrying out the invention]

[0016] The present invention will be described in detail below with reference to its preferred embodiments. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with modifications as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0017] The present invention provides a compound having two or more aromatic rings to which fluorine-substituted arylcarbonyloxy groups are directly bonded (hereinafter sometimes referred to as "ester compound (A)"). In preferred embodiments, the fluorine-substituted arylcarbonyloxy groups are directly bonded to the aromatic carbon atoms of the aromatic rings.

[0018] In ester compound (A), each aromatic ring to which a fluorine-substituted arylcarbonyloxy group is directly bonded is directly or indirectly bonded via an organic group to one or more other aromatic rings to which a fluorine-substituted arylcarbonyloxy group is directly bonded via a single bond. In one embodiment, such an organic group is an organic group consisting of one or more skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50). In one embodiment, such an organic group may have a halogen atom as a non-skeletal atom, in addition to or instead of a hydrogen atom. Such an organic group may include a linear structure, a branched structure, and / or a cyclic structure. Such an organic group may be an organic group that does not contain an aromatic ring, or an organic group that contains an aromatic ring.

[0019] An aromatic ring is a ring that follows Hückel's rule, where the number of electrons in the π-electron system on the ring is 4p+2 (where p is a natural number). An aromatic ring can be an aromatic carbocyclic ring with carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms, but in one embodiment, an aromatic carbocyclic ring is preferred. In one embodiment, an aromatic ring with 5 to 14 members is preferred, an aromatic ring with 5 to 10 members is more preferred, and an aromatic ring with 5 or 6 members is even more preferred.

[0020] Suitable 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 condensed aromatic rings formed by the fusion of two or more monocyclic aromatic rings such as naphthalene rings, anthracene rings, phenanthrene rings, benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzimidazole rings, indazole rings, benzoxazole rings, benzoisoxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, sinnoline rings, and phthalazine rings. In one embodiment, the aromatic ring is preferably an aromatic carbon ring, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0021] A fluorine-substituted arylcarbonyloxy group is a group in which an aryl atom is bonded via a carbonyloxy group, and in which one or more hydrogen atoms on the aromatic carbon atoms of the aryl atom are substituted with fluorine atoms. In other words, a fluorine-substituted arylcarbonyloxy group is a group represented as (fluorine-substituted aryl)-C(=O)-O-.

[0022] An aryl group refers to a monovalent aromatic ring group consisting of an aromatic ring with one hydrogen atom removed. The aryl group may be an aryl group with carbon atoms as ring constituent atoms, or a heteroaryl group having heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms. In one embodiment, however, it is preferable that the aryl group has carbon atoms as ring constituent atoms. In one embodiment, the number of ring constituent atoms of the aryl group is preferably 5 to 14, more preferably 5 to 10, and even more preferably 5 or 6.

[0023] Suitable examples of aryl groups include aryl groups with carbon atoms as ring atoms, such as phenyl, naphthyl, anthryl, and phenantrenyl groups; furyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, imidazolyl, pyridyl, pyridadinyl, pyrimidinyl, pyrazinyl, benzofuranyl, isobenzofuranyl, indolyl, isoindolyl, benzothiophenyl, benzimidazolyl, and indazolyl groups. Examples of heteroaryl groups include heteroaryl groups having a heteroatom in addition to a carbon atom as a ring constituent atom, such as a benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, acridinyl group, quinazolinyl group, synnolinyl group, and phthalazinyl group. In one embodiment, it is preferably an aryl group having a carbon atom as a ring constituent atom, more preferably a naphthyl group or a phenyl group, and particularly preferably a phenyl group.

[0024] From the viewpoint of obtaining the desired effects of the present invention more significantly, it is preferable that at least one hydrogen atom on the ortho aromatic carbon atom (the aromatic carbon atom adjacent to the aromatic carbon atom at the carbonyl bond position) is substituted with a fluorine atom, and more preferably two hydrogen atoms are substituted with fluorine atoms.

[0025] The number of fluorine atoms in the fluorine-substituted arylcarbonyloxy group is 1 or more, and from the viewpoint of obtaining the desired effects of the present invention more significantly, it is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.

[0026] In one embodiment, the fluorine-substituted arylcarbonyloxy group is represented by formulas (F1-1) to (F1-3):

[0027] [ka]

[0028] [In the formula, R f1and R f2 Each of these independently represents a hydrogen atom or a fluorine atom, and R f1 and R f2 At least one of them is a fluorine atom; * indicates a bonding site with an aromatic ring. The group is preferably represented by any of the following, and more preferably by formula (F-1).

[0029] R f1 and R f2 In one embodiment, from the viewpoint of obtaining the desired effects of the present invention more significantly, preferably R f1 and R f2 At least two of them are fluorine atoms, and more preferably, R f1 and R f2 At least three of these are fluorine atoms, and more preferably, R f1 and R f2 At least four of them are fluorine atoms, R f1 and R f2 At least five of them are fluorine atoms.

[0030] R f1 and R f2 In one embodiment, from the viewpoint of obtaining the desired effects of the present invention more significantly, preferably R f1 If there are two of them, R f1 One of them is a fluorine atom, and R f1 The other side and R f2 However, it is a hydrogen atom or a fluorine atom, R f1 If there is one, then R f1 However, it is a fluorine atom, R f2 However, it is a hydrogen atom or a fluorine atom. More preferably, R f1 However, it is a fluorine atom, R f2 However, it is a hydrogen atom or a fluorine atom. More preferably, R f1 However, it is a fluorine atom, R f2 However, it is a hydrogen atom or a fluorine atom and R f2 At least one of them is a fluorine atom. Particularly preferably, R f1 and R f2 This is a fluorine atom.

[0031] Specific examples of fluorine-substituted arylcarbonyloxy groups include formulas (F2-1) to (F2-19):

[0032] [ka]

[0033] Groups represented by [wherein * indicates the bonding site with the aromatic ring] are examples, and among them, groups represented by formulas (F2-1) to (F2-4) are preferred, and the group represented by formula (F2-1) is particularly preferred.

[0034] The ester compound (A) may have, in addition to an aromatic ring to which a fluorine-substituted arylcarbonyloxy group is directly bonded, an aromatic ring to which a hydroxyl group is directly bonded (an aromatic ring having a phenolic hydroxyl group). The molar ratio of the fluorine-substituted arylcarbonyloxy group to the phenolic hydroxyl group (fluorine-substituted arylcarbonyloxy group:phenolic hydroxyl group) is not particularly limited, but in one embodiment, from the viewpoint of obtaining a better balance of properties such as solvent solubility, fluidity, curability, dielectric properties, and heat resistance, it is preferably 20:80 to 100:0, more preferably 30:70 to 100:0, even more preferably 40:60 to 100:0, and particularly preferably 50:50 to 100:0. The molar ratio of the fluorine-substituted arylcarbonyloxy group to the phenolic hydroxyl group can be arbitrarily adjusted to a desired range by a person skilled in the art by adjusting the type of raw materials and reaction ratio in the manufacturing method described later.

[0035] Ester compound (A) may have an aromatic ring to which a fluorine-substituted arylcarbonyloxy group is directly bonded, as well as an aromatic ring to which other substituted arylcarbonyloxy groups and / or (unsubstituted) arylcarbonyloxy groups are directly bonded. Here, the substituents of the "other substituted arylcarbonyloxy groups" are the same as the substituents in the "optional substituted arylcarbonyloxy groups" of X described below (except when the substituent is only a fluorine atom). The ratio of fluorine-substituted arylcarbonyloxy groups (fluorine-substituted arylcarbonyloxy groups / fluorine-substituted arylcarbonyloxy groups) in the optional arylcarbonyloxy groups (i.e., the total of fluorine-substituted arylcarbonyloxy groups, other substituted arylcarbonyloxy groups, and (unsubstituted) arylcarbonyloxy groups) is not particularly limited, but in one embodiment it may be preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more, and particularly preferably 100%. The proportion of fluorine-substituted arylcarbonyloxy groups in the optionally substituted fluorine-substituted arylcarbonyloxy groups can be arbitrarily adjusted to a desired range by a person skilled in the art by adjusting the type of raw materials and reaction ratio in the production method described later.

[0036] From the viewpoint of obtaining the desired effects of the present invention more significantly, the fluorine atom content in the ester compound (A) is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is not particularly limited, but for example, it can be 60% by mass or less. The fluorine atom content can be arbitrarily adjusted to a desired range by a person skilled in the art by adjusting the type of raw materials and reaction ratio in the manufacturing method described later.

[0037] The molecular weight (or weight-average molecular weight if n is 2 or more) of the ester compound (A) is not particularly limited, but in one embodiment, it is preferably 200,000 or less, more preferably 100,000 or less, more preferably 50,000 or less, and more preferably 30,000 or less. The lower limit of the molecular weight (or weight-average molecular weight if n is 2 or more) of the ester compound (A) is not particularly limited, but for example, it may be 400 or more, 450 or more, 500 or more, etc. The weight-average molecular weight can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0038] The equivalent amount of the fluorine-substituted arylcarbonyloxy group directly bonded to the aromatic ring of ester compound (A) (hereinafter sometimes referred to as "fluorine-substituted aryl ester group equivalent") is not particularly limited, but is preferably 5000 g / eq. or less, more preferably 2000 g / eq. or less, even more preferably 1000 g / eq. or less, even more preferably 800 g / eq. or less, particularly preferably 600 g / eq. or less, and most preferably 500 g / eq. or less. The lower limit of the fluorine-substituted aryl ester group equivalent of ester compound (A) is not particularly limited, but may be, for example, 150 g / eq. or more, 180 g / eq. or more, 200 g / eq. or more, etc.

[0039] The total equivalent amount (hereinafter sometimes referred to as "functional group equivalent") of arylcarbonyloxy groups (fluorine-substituted arylcarbonyloxy groups, arylcarbonyloxy groups with other substituents, and (unsubstituted) arylcarbonyloxy groups) and hydroxyl groups (i.e., phenolic hydroxyl groups) directly bonded to the aromatic ring of ester compound (A) is not particularly limited, but is preferably 5000 g / eq. or less, more preferably 2000 g / eq. or less, even more preferably 1000 g / eq. or less, even more preferably 800 g / eq. or less, particularly preferably 600 g / eq. or less, or 500 g / eq. or less. The lower limit of the functional group equivalent of ester compound (A) is not particularly limited, but may be, for example, 150 g / eq. or more, 180 g / eq. or more, 200 g / eq. or more, etc.

[0040] The ester compound (A) may be an ester of a compound having two or more aromatic rings to which hydroxyl groups are directly bonded (hereinafter sometimes referred to as "polyvalent aromatic hydroxy compound (B)") and a fluorine-substituted aryl carboxylic acid (i.e., an aryl carboxylic acid substituted with one or more fluorine atoms) (the raw material for production may be a halide or an anhydride, etc.) (in addition to the fluorine-substituted aryl carboxylic acid, it may also be a mixed ester of carboxylic acids containing aryl carboxylic acids with other substituents or (unsubstituted) aryl carboxylic acids). As the polyvalent aromatic hydroxy compound (B), a wide range of known phenolic compounds can be used and are not particularly limited, but examples include biphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AF, allylated bisphenol A, fluorenebisphenol, terpene diphenol, tetrabromobisphenol A, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-1,1'-biphenyl-4,4'-diol, phenol aralkyl type bisphenol, dicyclopentadiene type bisphenol, and other bisphenols. Trisphenols such as tris-(4-hydroxyphenyl)methane; tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; aromatic ring diols such as hydroquinone, resorcinol, catechol, 1,4-naphthalenediol, 1,6-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol; phenols (alkyl-substituted or unsubstituted phenols, alkyl-substituted or unsubstituted naphthols, alkyl-substituted or unsubstituted hydroquinones, alkyl-substituted or unsubstituted resorcinols, alkyl-substituted Examples include phenol polymers such as polycondensates or polyadditions of substituted or unsubstituted naphthalenediols (e.g., naphthalenediols) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, furfural, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, etc.In one embodiment, the polyvalent aromatic hydroxy compound (B) is preferably a polyvalent aromatic hydroxy compound containing a high concentration of fluorine atoms (e.g., bisphenol AF) or a polyvalent aromatic hydroxy compound having an alicyclic skeleton (e.g., a polyaddition reaction product of dicyclopentadiene and phenols), from the viewpoint of further improving properties such as dielectric properties, but is not particularly limited.

[0041] In one embodiment, the ester compound (A) is preferably of formula (A1):

[0042] [ka]

[0043] [In the formula, each Ar ring independently represents an optionally substituted aromatic ring; each X independently represents an optionally substituted arylcarbonyloxy group or hydroxyl group, and at least two X groups bonded to different Ar rings are fluorine-substituted arylcarbonyloxy groups; each Z independently represents a single bond or a divalent organic group; n represents an integer of 1 or more; and each m independently represents an integer from 1 to 3.] This is a compound represented by [formula]. Note that the n unit may be the same or different for each structural unit. The m unit may be the same or different for each structural unit.

[0044] Each Ar ring independently represents an aromatic ring that may have substituents.

[0045] The substituents on the aromatic ring of ring Ar are not particularly limited, but examples include 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 is, for example, (1) halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R 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-COR b 、 and -N(COR b )2, an alkyl group optionally substituted with a group selected from; (2) a halogen atom, a hydroxy group, an amino group, a mercapto group, a nitro group, a cyano group, -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 b -COR b 、 and -N(COR b )2, an alkenyl group optionally substituted with a group selected from; or (3) a halogen atom, a hydroxy group, an amino group, a mercapto group, a nitro group, a cyano group, -R b 、 -OR b 、 -SR b 、 -SO2R b ​​​​​​​​​​​​​​​​​​​​​​​​These include halogen atoms, substituted or unsubstituted aryl groups, and specifically, halogen atoms, aryl groups, halogen-substituted aryl groups, alkyl-aryl groups (aryl groups substituted with one or more alkyl groups), aryl-aryl groups (aryl groups substituted with one or more aryl groups), etc. b These include halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aryl groups, and more specifically, halogen atoms, alkyl groups, alkenyl groups, aryl groups, halogen-substituted alkyl groups, halogenated alkenyl groups, halogen-substituted aryl groups, alkyl-aryl groups, aryl-aryl groups, aryl-alkyl groups (alkyl groups substituted with one or more aryl groups), etc.

[0046] An alkyl group refers to a linear, branched, and / or cyclic monovalent saturated hydrocarbon group. Unless otherwise specified, alkyl groups are preferably those having 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 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, and 2-cyclohexylethyl.

[0047] An alkenyl group is a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl groups are preferably those having 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms. Examples of alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 3-methyl- Examples include 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0048] The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and unless otherwise specified, it is preferably a fluorine atom. Halogen-substituted alkyl groups, halogen-substituted alkenyl groups, and halogen-substituted aryl groups mean an alkyl group substituted with one or more halogen atoms, an alkenyl group substituted with one or more halogen atoms, and an aryl group substituted with one or more halogen atoms, respectively, and are preferably fluorine-substituted alkyl groups, fluorine-substituted alkenyl groups, and fluorine-substituted aryl groups. Fluorine-substituted alkyl groups, fluorine-substituted alkenyl groups, and fluorine-substituted aryl groups mean an alkyl group substituted with one or more fluorine atoms, an alkenyl group substituted with one or more fluorine atoms, and an aryl group substituted with one or more fluorine atoms, respectively.

[0049] In one embodiment, each Ar ring is an aromatic carbon ring that may, preferably, have substituents independently.

[0050] In one embodiment, the Ar ring is, more preferably, independently a substituted benzene ring or a substituted naphthalene ring.

[0051] In one embodiment, the ring Ar is independently and more preferably (1) (a) a halogen atom; (b) an alkyl group which may have substituents selected from a halogen atom and an aryl group; (c) an alkyl-oxy group (i.e., an alkoxy group) which may have substituents selected from a halogen atom and an aryl group; (d) an alkenyl group which may have substituents selected from a halogen atom and an aryl group; (e) an aryl group which may have substituents selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group; and (f) an aryl-oxy group which may have substituents selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group. The naphthalene ring may have substituents, or (2)(a) a halogen atom; (b) an alkyl group which may have substituents selected from a halogen atom and an aryl group; (c) an alkyl-oxy group which may have substituents selected from a halogen atom and an aryl group; (d) an alkenyl group which may have substituents selected from a halogen atom and an aryl group; (e) an aryl group which may have substituents selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group; and (f) an aryl-oxy group which may have substituents selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group.

[0052] In one embodiment, the ring Ar is independently, and more preferably, (1) a benzene ring which may have substituents selected from a halogen atom, an aryl group, an alkyl group, an aryl-oxy group, an alkyl-oxy group, a halogen-substituted aryl group, and a halogen-substituted alkyl group, or (2) a naphthalene ring which may have substituents selected from a halogen atom, an aryl group, an alkyl group, an aryl-oxy group, an alkyl-oxy group, a halogen-substituted aryl group, and a halogen-substituted alkyl group.

[0053] In one embodiment, the Ar ring is independently and particularly preferably (1) a benzene ring which may have substituents selected from a fluorine atom, an aryl group, an alkyl group, a fluorine-substituted aryl group, and a fluorine-substituted alkyl group, or (2) a naphthalene ring which may have substituents selected from a fluorine atom, an aryl group, an alkyl group, a fluorine-substituted aryl group, and a fluorine-substituted alkyl group.

[0054] Each of X independently represents an arylcarbonyloxy group which may have substituents, or a hydroxyl group, and at least two Xs bonded to different ring Ars are fluorine-substituted arylcarbonyloxy groups. In one embodiment, each of X independently preferably represents a fluorine-substituted arylcarbonyloxy group, an (unsubstituted) arylcarbonyloxy group, or a hydroxyl group, and at least two Xs bonded to different ring Ars are fluorine-substituted arylcarbonyloxy groups. In one embodiment, each of X independently more preferably represents a fluorine-substituted arylcarbonyloxy group or a hydroxyl group, and at least two Xs bonded to different ring Ars are fluorine-substituted arylcarbonyloxy groups. In one embodiment, X particularly preferably represents a fluorine-substituted arylcarbonyloxy group.

[0055] The substituents in the "optionally substituted arylcarbonyloxy group" of X are not particularly limited, but include, for example, halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, and groups selected from -R, -OR, -SR, -SO2R, -NHR, -NR2, -COR, -CO-OR, -CO-NHR, -CO-NR2, -NH-COR, -NR-COR, and -N(COR)2. The same applies to R.

[0056] The ratio of fluorine-substituted arylcarbonyloxy groups to hydroxyl groups in X (fluorine-substituted arylcarbonyloxy groups:hydroxyl groups) is not particularly limited, but from the viewpoint of obtaining a better balance of properties such as solvent solubility, fluidity, curability, dielectric properties, and heat resistance, it is preferably 20:80 to 100:0, more preferably 30:70 to 100:0, even more preferably 40:60 to 100:0, and particularly preferably 50:50 to 100:0.

[0057] The proportion of fluorine-substituted arylcarbonyloxy groups in the arylcarbonyloxy group in X, which may have substituents, is not particularly limited, but in one embodiment, it may be preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more, and particularly preferably 100%.

[0058] Each Z independently represents a single bond or a divalent organic group. In one embodiment, the divalent organic group in Z is preferably a divalent organic group consisting of one or more skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50). In one embodiment, the divalent organic group in Z may have a halogen atom as a non-skeletal atom, in addition to or instead of a hydrogen atom. The divalent organic group in Z includes linear, branched, and / or cyclic structures. The divalent organic group in Z may be a divalent organic group that does not contain an aromatic ring, or a divalent organic group that contains an aromatic ring.

[0059] n represents an integer greater than or equal to 1. In one embodiment, n is preferably an integer between 1 and 500, more preferably between 1 and 200, even more preferably between 1 and 100, even more preferably between 1 and 50, and particularly preferably between 1 and 20. In the first embodiment, n is preferably 1. In the second embodiment, n is preferably an integer between 2 and 500, more preferably between 2 and 200, even more preferably between 2 and 100, even more preferably between 2 and 50, and particularly preferably between 2 and 20 (including integers between 3 and 20, 4 and 20, and 5 and 20).

[0060] Each of the values ​​of m independently represents an integer between 1 and 3. Each of the values ​​of m independently is preferably 1 or 2, and particularly preferably 1.

[0061] In one embodiment, the ester compound (A) is more preferably of formula (A2):

[0062] [ka]

[0063] [In the formula, Y 1 These are, independently, single bonds, -C(R 1 ) indicates -2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; R 1 Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group; ring Y 2 Each independently represents an aromatic ring that may have substituents, or an unaromatic ring that may have substituents; each independently represents an integer from 0 to 3; and the other symbols are the same as in formula (A1). It is a compound represented by. Note that the a units may be the same or different for each structural unit. The n units may be the same or different for each structural unit. The m units may be the same or different for each structural unit.

[0064] Y 1 each independently represents a single bond, -C(R 1 )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-. Y 1 In one embodiment, each independently is preferably a single bond, -C(R 1 )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, more preferably a single bond, -C(R 1 )2-, or -O-, and particularly preferably a single bond or -C(R 1 )2-.

[0065] R 1 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0066] R 1 The substituents in the "aryl group which may have a substituent" of R 1The substituents in the "alkyl group which may have substituents" are not particularly limited, but examples include 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 is the same as above, and R' is, for example, halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R 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 )These are aryl groups, etc., which may be substituted with a group selected from 2. b The same applies as above.

[0067] R 1In one embodiment, each is independently preferably (1) a hydrogen atom; (2) an alkyl group which may have substituents selected from halogen atoms, hydroxyl groups, aryl groups (the aryl group may have substituents selected from halogen atoms, hydroxyl groups, fluorine-substituted arylcarbonyloxy groups, (unsubstituted) arylcarbonyloxy groups, aryl groups, alkenyl groups and alkyl groups), aryl-oxy groups (the aryl-oxy group may have substituents selected from halogen atoms, hydroxyl groups, fluorine-substituted arylcarbonyloxy groups, (unsubstituted) arylcarbonyloxy groups, aryl groups, alkenyl groups and alkyl groups), and alkyl groups. (3) an aryl group; or (3) an aryl group which may have a substituent selected from a halogen atom, a hydroxyl group, an aryl group (the aryl group may have substituents selected from a halogen atom, a hydroxyl group, a fluorine-substituted arylcarbonyloxy group, an (unsubstituted) arylcarbonyloxy group, an aryl group, an alkenyl group and an alkyl group), an alkenyl group, an alkyl group, an aryl-oxy group (the aryl-oxy group may have substituents selected from a halogen atom, a hydroxyl group, a fluorine-substituted arylcarbonyloxy group, an (unsubstituted) arylcarbonyloxy group, an aryl group, an alkenyl group and an alkyl group), an alkyl-oxy group and a substituent selected from a halogen-substituted alkyl group. 1 In one embodiment, each is independently, and more preferably, a hydrogen atom, an aryl group, an alkyl group, a halogen-substituted aryl group, or a halogen-substituted alkyl group. 1 In one embodiment, each is independently, and more preferably, a hydrogen atom, an aryl group, an alkyl group, a fluorine-substituted aryl group, or a fluorine-substituted alkyl group. 1 In one embodiment, each of these is independently and particularly preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0068] Ring Y 2 Each of these independently represents an aromatic ring which may have substituents, or a non-aromatic ring which may have substituents.

[0069] A non-aromatic ring refers to a ring other than an aromatic ring. A non-aromatic ring may be a non-aromatic carbocyclic ring with carbon atoms as ring constituent atoms, or a non-aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms, but in one embodiment, it is preferable to be a non-aromatic carbocyclic ring. A non-aromatic ring may be a saturated ring or an unsaturated non-aromatic ring, but in one embodiment, it is preferable to be a saturated ring. In one embodiment, a non-aromatic ring with 3 to 15 members is preferred.

[0070] Examples of non-aromatic carbocyclic rings include (a1) monocyclic non-aromatic carbocyclic rings, (a2) bridged carbocyclic rings consisting of two or more rings sharing two or more atoms, and (a3) ​​aromatic-non-aromatic composite condensed carbocyclic rings in which one or more aromatic carbocyclic rings are fused to one or more monocyclic non-aromatic carbocyclic rings and / or bridged carbocyclic rings.

[0071] A monocyclic non-aromatic carbocycle is a monocyclic non-aromatic ring whose ring constituent atoms are carbon atoms, and may have a carbon-carbon double bond. Monocyclic non-aromatic carbocycles having 3 to 15 carbon atoms are preferred, and monocyclic non-aromatic carbocycles having 3 to 8 carbon atoms are more preferred. Examples include cycloalkane rings (monocyclic non-aromatic saturated carbocycles) such as cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, cyclononane rings, cyclodecane rings, cycloundecane rings, and cyclododecane rings; and cycloalkene rings (monocyclic non-aromatic unsaturated carbocycles) such as cyclobutene rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, cyclooctene rings, cyclononene rings, cyclodecene rings, cycloundecene rings, cyclododecene rings, cyclopentadiene rings, 1,3-cyclohexadiene rings, and 1,4-cyclohexadiene rings.

[0072] A bridged carbocyclic ring is a bridged ring in which carbon atoms constitute the ring atoms, and may have a carbon-carbon double bond. Bridged carbocyclic rings with 8 to 15 carbon atoms are preferred, for example, bicyclic saturated bridged carbocyclic rings such as bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decalin ring), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (hydrindane ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, and bicyclo[3.3.1]nonane ring; tricyclo[5.2.1.0 2,6 ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 ] Decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 ]Saturated bridged carbon rings of tricyclic systems such as undecane rings; tetracyclo[6.2.1.1 3,6 .0 2,7 ]Saturated bridged carbon rings of tetracyclic systems such as dodecane rings; pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 Saturated bridged carbocyclic rings such as pentadecane rings (tetrahydrotricyclopentadiene rings); unsaturated bridged carbocyclic rings such as bicyclo[2.2.1]hepta-2-ene rings (norbornene rings), bicyclo[2.2.1]hepta-2,5-diene rings (norbornadiene rings), bicyclo[2.2.2]octa-5-ene rings, bicyclo[4.4.0]deca-2-ene rings; tricyclo[5.2.1.0 2,6 Examples include unsaturated bridged carbocyclic rings such as deca-3,8-diene rings (dicyclopentadiene rings) and other tricyclic unsaturated bridged carbocyclic rings.

[0073] Aromatic-non-aromatic composite condensed carbocyclic rings are composite condensed rings in which carbon atoms are ring constituent atoms, and aromatic-non-aromatic composite condensed carbocyclic rings having 8 to 15 carbon atoms are preferred. Examples include bicyclic composite condensed carbocyclic rings such as indan rings, indene rings, tetralin rings, 1,2-dihydronaphthalene rings, and 1,4-dihydronaphthalene rings; tricyclic composite condensed carbocyclic rings such as fluorene rings, 9,10-dihydroanthracene rings, and 9,10-dihydrophenanthrene rings; tetracyclic composite condensed carbocyclic rings such as 2,3-benzofluorene rings; and pentacyclic composite condensed carbocyclic rings such as 2,3,6,7-dibenzofluorene.

[0074] Examples of non-aromatic heterocycles include (b1) monocyclic non-aromatic heterocycles, (b2) bridged heterocycles consisting of two or more rings sharing two or more atoms, and (b3) aromatic-non-aromatic composite fused heterocycles in which one or more aromatic rings (aromatic carbocycles and / or aromatic heterocycles) are fused to one or more monocyclic aromatic rings (monocyclic aromatic carbocycles and / or monocyclic non-aromatic heterocycles) and / or bridged rings (bridged carbocycles and / or bridged heterocycles).

[0075] A monocyclic non-aromatic heterocycle is a monocyclic non-aromatic ring having heteroatoms such as oxygen, nitrogen, and sulfur atoms in addition to carbon atoms as ring constituent atoms, and may have carbon-carbon double bonds and / or nitrogen-carbon double bonds. A 3- to 15-membered monocyclic non-aromatic heterocycle is preferred, and a 3- to 8-membered monocyclic non-aromatic heterocycle is more preferred. Examples include monocyclic non-aromatic saturated heterocycles such as pyrrolidine rings, pyrazolidine rings, imidazolidine 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 non-aromatic unsaturated heterocycles such as 2-pyrroline rings, 3-pyrroline rings, 2-pyrazoline rings, and 2-imidazoline rings.

[0076] A bridged heterocycle is a bridged heterocycle having heteroatoms such as oxygen, nitrogen, and sulfur atoms in addition to carbon atoms as ring constituent atoms, and may have carbon-carbon double bonds and / or nitrogen-carbon double bonds. 8 to 15-membered bridged heterocycles are preferred, for example, bicyclic saturated bridged heterocycles such as 7-oxabicyclo[4.1.0]heptane ring (1,2-epoxycyclohexane ring), 1-azabicyclo[2.2.2]octane (quinuclidine ring), decahydroquinoline ring, decahydroisoquinoline ring; 1-azabicyclo[3.3.1.1 3,7 ] Decane (1-azaadamantane ring), 2-azatricyclo[3.3.1.1 3,7 Examples include saturated bridged complex rings such as decanes (2-adamantane rings) and other tricyclic saturated bridged complex rings.

[0077] Aromatic-non-aromatic complex fused heterocycles are complex fused heterocycles that, in addition to carbon atoms, have heteroatoms such as oxygen, nitrogen, and sulfur atoms as ring constituent atoms. Preferably, aromatic-non-aromatic complex fused heterocycles have 8 to 15 members. Examples include bicyclic complex fused heterocycles such as 2,3-dihydrobenzofuran rings, 1,3-dihydroisobenzofuran rings, 2H-chromene rings, 4H-chromene rings, 1H-isochromene rings, 3H-isochromene rings, indoline rings, isoindoline rings, 2,3-dihydrobenzothiophene rings, 1,2-dihydroquinoline rings, 3,4-dihydroquinoline rings, 1,2,3,4-tetrahydroquinoline rings, and benzoxazine rings; and tricyclic complex fused heterocycles such as 1,2,3,4-tetrahydrocarbazole rings and 1,2,3,4-dibenzofuran rings.

[0078] As for the non-aromatic ring, in one embodiment, monocyclic non-aromatic carbocycles, bridged carbocycles, aromatic-non-aromatic complex condensed carbocycles, monocyclic non-aromatic heterocycles, bridged heterocycles, and aromatic-non-aromatic complex condensed heterocycles are more preferred; monocyclic non-aromatic carbocycles, bridged carbocycles, and aromatic-non-aromatic complex condensed carbocycles are even more preferred; and monocyclic non-aromatic carbocycles and bridged carbocycles are particularly preferred.

[0079] Ring Y 2The substituents in the "aromatic ring which may have substituents" are not particularly limited, but examples include 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. Ring Y 2 The substituents in the "non-aromatic ring which may have substituents" are not particularly limited, but include, for example, 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 groups selected from =O. R is the same as above.

[0080] Ring Y 2 In one embodiment, each is independently, preferably, an aromatic carbon ring having a substituent, or a non-aromatic carbon ring having a substituent.

[0081] Ring Y 2In one embodiment, each independently, and more preferably, (1) (a) a halogen atom; (b) an alkyl group which may have a substituent selected from a halogen atom and an aryl group; (c) an alkyl-oxy group which may have a substituent selected from a halogen atom and an aryl group; (d) an alkenyl group which may have a substituent selected from a halogen atom and an aryl group; (e) an aryl group which may have a substituent selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group; and (f) an aromatic group which may have a substituent selected from an aryl-oxy group which may have a substituent selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group. The group is a carbon ring, or (2)(a) a halogen atom; (b) an alkyl group which may have substituents selected from a halogen atom and an aryl group; (c) an alkyl-oxy group which may have substituents selected from a halogen atom and an aryl group; (d) an alkenyl group which may have substituents selected from a halogen atom and an aryl group; (e) an aryl group which may have substituents selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group; (f) an aryl-oxy group which may have substituents selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group; and (g) a non-aromatic carbon ring which may have substituents selected from an oxo group (=O).

[0082] Ring Y 2 In one embodiment, each is independently and more preferably (1) an aromatic carbon ring which may have substituents selected from a halogen atom, an aryl group, an alkyl group, a halogen-substituted aryl group, and a halogen-substituted alkyl group, or (2) a non-aromatic carbon ring which may have substituents selected from a halogen atom, an aryl group, an alkyl group, a halogen-substituted aryl group, a halogen-substituted alkyl group, and an oxo group.

[0083] Ring Y 2In one embodiment, each is independently, and more preferably, (1) an aromatic carbon ring which may have substituents selected from a fluorine atom, an aryl group, an alkyl group, a fluorine-substituted aryl group, and a fluorine-substituted alkyl group, or (2) a non-aromatic carbon ring which may have substituents selected from a fluorine atom, an aryl group, an alkyl group, a fluorine-substituted aryl group, a fluorine-substituted alkyl group, and an oxo group.

[0084] Ring Y 2 In one embodiment, each is independently and particularly preferably (1) an aromatic carbon ring which may have substituents selected from a fluorine atom, an alkyl group, and a fluorine-substituted alkyl group, or (2) a non-aromatic carbon ring which may have substituents selected from a fluorine atom, an alkyl group, and a fluorine-substituted alkyl group.

[0085] Each of a independently represents an integer from 0 to 3, preferably an integer from 0 to 2 in one embodiment, and more preferably 0 or 1. Each of a independently represents 0 in one embodiment of the first embodiment.

[0086] In one embodiment, the ester compound (A) is more preferably of formula (A3-1) or (A3-2):

[0087] [ka]

[0088] [In the formula, R 2 Each of the symbols independently represents a substituent; each of the symbols independently represents 0 or an integer greater than or equal to 1; and the other symbols are the same as in formulas (A1) and (A2). This is a compound represented by the formula shown. Note that the a unit may be the same or different for each structural unit. The n unit may be the same or different for each structural unit. The t unit may be the same or different for each structural unit.

[0089] R 2Each of these independently represents a substituent.

[0090] R 2 The substituents in are not particularly limited, but examples include 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 is the same as above.

[0091] R 2 In one embodiment, preferably each independently is (a) a halogen atom; (b) an alkyl group which may have a substituent selected from a halogen atom and an aryl group; (c) an alkyl-oxy group which may have a substituent selected from a halogen atom and an aryl group; (d) an alkenyl group which may have a substituent selected from a halogen atom and an aryl group; (e) an aryl group which may have a substituent selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group; or (f) an aryl-oxy group which may have a substituent selected from a halogen atom, an aryl group, an alkenyl group and an alkyl group. 2 In one embodiment, and more preferably, each is independently a halogen atom, an aryl group, an alkyl group, an aryl-oxy group, an alkyl-oxy group, a halogen-substituted aryl group, or a halogen-substituted alkyl group. 2 In one embodiment, and more preferably, each is independently a fluorine atom, an aryl group, an alkyl group, an aryl-oxy group, an alkyl-oxy group, a fluorine-substituted aryl group, or a fluorine-substituted alkyl group. 2 In one embodiment, particularly preferably, each is independently a fluorine atom, an aryl group, an alkyl group, a fluorine-substituted aryl group, or a fluorine-substituted alkyl group.

[0092] Each t independently represents an integer of 0 or 1 or more, and in one embodiment, is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

[0093] In one embodiment, the ester compound (A) is particularly preferably of formulas (A4-1) to (A4-36):

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [In the formulas, each symbol is the same as in formulas (A1), (A2), (A3-1), and (A3-2).] The compound is represented by any of the following. In one embodiment, it is preferable that the compound is represented by any of the formulas (A4-1), (A4-2), (A4-8), (A4-9), (A4-11), (A4-13), (A4-17), (A4-19), (A4-20), (A4-26), (A4-27), (A4-29), (A4-31), and (A4-35), and more preferably that the compound is represented by any of the formulas (A4-2), (A4-9), (A4-11), (A4-17), (A4-20), (A4-27), (A4-29), and (A4-35). The n unit may be the same for each structural unit or it may be different. The t unit may be the same for each structural unit or it may be different.

[0100] Examples of ester compounds (A) are not limited to those specified in formulas (A5-1) to (A5-90):

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [In the formula, X' independently represents an arylcarbonyloxy group or a hydroxyl group which may have substituents; R 3 Each of the following independently represents a halogen atom, an aryl group, an alkyl group, an aryl-oxy group, an alkyl-oxy group, a halogen-substituted aryl group, or a halogen-substituted alkyl group; n' represents an integer from 1 to 20; u independently represents 1 or 2; and other symbols are the same as in formulas (A1), (A2), (A3-1), and (A3-2). Examples of compounds represented by [formula] can be given.

[0116] R 3 Each of these independently represents a halogen atom, an aryl group, an alkyl group, an aryl-oxy group, an alkyl-oxy group, a halogen-substituted aryl group, or a halogen-substituted alkyl group. 3 In one embodiment, each is preferably independently a fluorine atom, an aryl group, an alkyl group, an aryl-oxy group, an alkyl-oxy group, a fluorine-substituted aryl group, or a fluorine-substituted alkyl group, and more preferably a fluorine atom, an aryl group, an alkyl group, a fluorine-substituted aryl group, or a fluorine-substituted alkyl group.

[0117] n' represents an integer between 1 and 20. Preferably, n' is an integer between 2 and 20.

[0118] In one embodiment, in formula (A1), at least one of the structural units represented by ring Ar and Z contains a fluorine atom, and the total number of fluorine atoms contained in the structural units represented by ring Ar and Z is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. In one embodiment, in formula (A2), ring Ar, ring Y 2 , and Y 1 At least one of the structural units represented by contains a fluorine atom, and the rings are Ar and Y. 2 , and Y 1 The total number of fluorine atoms contained in the structural unit represented by is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. In one embodiment, in formula (A3-1) or (A3-2), R 2 , ring Y 2 , and Y 1 At least one of the structural units represented by contains a fluorine atom, R 2 , ring Y 2 , and Y 1 The total number of fluorine atoms contained in the structural unit represented by is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. In one embodiment, in formulas (A4-1) to (A4-36), R 2 , and ring Y 2 At least one of the structural units represented by contains a fluorine atom, R 2 , and ring Y 2 The total number of fluorine atoms contained in the structural unit represented by is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. In one embodiment, in formulas (A5-1) to (A5-90), R 3 At least one of the structural units represented by contains a fluorine atom and / or a group represented by -CF3 is present, R 3 The total number of fluorine atoms contained in the structural unit represented by and the group represented by -CF3 is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more.

[0119] The method for producing ester compound (A) is described below.

[0120] The present invention provides a method for producing a compound having two or more aromatic rings to which fluorine-substituted arylcarbonyloxy groups are directly bonded (i.e., an ester compound (A)), comprising reacting (hereinafter sometimes referred to as "esterification reaction") a compound having two or more aromatic rings to which hydroxyl groups are directly bonded (i.e., a polyvalent aromatic hydroxy compound (B)) with a fluorine-substituted arylcarboxylic acid, its acid halide (preferably a chloride, bromide, or iodide), its acid anhydride, or a salt thereof (hereinafter sometimes referred to as "fluorine-substituted arylcarboxylic acids (C)") and a compound having two or more aromatic rings to which hydroxyl groups are directly bonded (i.e., a polyvalent aromatic hydroxy compound (B)). In the above production method, the fluorine-substituted arylcarboxylic acids (C) may be a mixture that further includes, in addition to the fluorine-substituted arylcarboxylic acid, its acid halide, its acid anhydride, or a salt thereof, other substituent arylcarboxylic acids and / or (unsubstituted) arylcarboxylic acids, their acid halides, their acid anhydrides, or salts thereof.

[0121] In one embodiment, a method for producing ester compound (A) is a method for producing compound represented by formula (A1), which preferably involves reacting a compound represented by any of formulas (C1) to (C3) or a salt thereof with a compound represented by formula (B1):

[0122] [ka]

[0123] [In the formula, FAr represents an aryl group which may have substituents, and in at least a portion of the compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group (i.e., an aryl group substituted with one or more fluorine atoms) (corresponding to the fluorine-substituted arylcarbonyloxy group of X in ester compound (A1)) (preferably, in all compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group); Hal represents a chlorine atom, a bromine atom, or an iodine atom; and the other symbols are the same as in formula (A1).]

[0124] In one embodiment, a method for producing ester compound (A) is a method for producing compound represented by formula (A2), which more preferably involves reacting a compound represented by any of formulas (C1) to (C3) or a salt thereof with a compound represented by formula (B2):

[0125] [ka]

[0126] [In the formulas, FAr represents an aryl group which may have substituents, and in at least a portion of the compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group (corresponding to the fluorine-substituted arylcarbonyloxy group of X in ester compound (A2)) (preferably, in all compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group); Hal represents a chlorine atom, a bromine atom, or an iodine atom; and the other symbols are the same as in formulas (A1) and (A2).]

[0127] In one embodiment, a method for producing ester compound (A) is a method for producing a compound represented by formula (A3-1) or (A3-2), which more preferably involves reacting a compound represented by any of formulas (C1) to (C3) or a salt thereof with a compound represented by formula (B3-1) or (B3-2):

[0128] [ka]

[0129] [In the formula, FAr represents an aryl group which may have substituents, and in at least a portion of the compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group (corresponding to the fluorine-substituted arylcarbonyloxy group of X in ester compounds (A3-1) or (A3-2)) (preferably, in all compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group); Hal represents a chlorine atom, a bromine atom, or an iodine atom; and the other symbols are the same as in formulas (A1), (A2), (A3-1), and (A3-2).]

[0130] Examples of salts include alkali metal salts such as cesium salts, potassium salts, and sodium salts.

[0131] In the production method of the present invention, fluorine-substituted aryl carboxylic acids (C) undergo a condensation reaction with some or all of the hydroxyl groups directly bonded to the aromatic ring of a polyhydric aromatic hydroxy compound (B), thereby esterifying and obtaining an ester compound (A).

[0132] In one embodiment, the fluorine-substituted arylcarboxylic acid (C) is preferably a halide, and among the compounds represented by formulas (C1) to (C3), it is preferably the compound represented by formula (C2).

[0133] In the esterification reaction of the method for producing ester compound (A), a base may be used in a preferred embodiment. Examples of bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and tertiary amines such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine (DMAP). The base may be used as is or diluted in a solution. A single base may be used, or two or more bases may be used in any combination.

[0134] When alkali metal hydroxides are used as the base, in one embodiment, reactivity is improved and less starting material remains, which is an advantage. When tertiary amines are used as the base, in one embodiment, the ester bonds formed under anhydrous conditions are less susceptible to hydrolysis, which is an advantage and improves the yield.

[0135] In one embodiment, the amount of base used is preferably 80 to 300 moles per 100 moles of fluorine-substituted arylcarboxylic acids (C), and more preferably 100 to 150 moles from the viewpoint of raw material residue rate, base removal efficiency, etc.

[0136] In the esterification reaction of the method for producing ester compound (A), a condensing agent may be used as needed in one embodiment. Examples of condensing agents include carbodiimide-based 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 their salts. The amount of condensing agent used may be, for example, 50 to 100 moles per 100 moles of fluorine-substituted arylcarboxylic acids (C). In the esterification reaction of the method for producing ester compound (A), a condensation accelerator may be added in addition to the condensing agent as needed in one embodiment. 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 per 100 moles of fluorine-substituted arylcarboxylic acids (C).

[0137] In the reaction system for the esterification reaction of the method for producing the ester compound (A), the mixing ratio of the number of moles (b) of the polyhydric aromatic hydroxy compound (B) and the number of moles (c) of the fluorine-substituted aryl carboxylic acid (C) is preferably in the range of ((n+1)×(b)):(c)=90:100 to 100:90, and more preferably in the range of ((n+1)×(b)):(c)=95:100 to 100:95.

[0138] In one embodiment, the esterification reaction of the method for producing ester compound (A) may proceed in a solvent-free system without using 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; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve 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. Among these, hydrophobic solvents such as ketone solvents (e.g., methyl isobutyl ketone) and aromatic hydrocarbon solvents (e.g., toluene) are preferred from the viewpoint of purification efficiency after the reaction. One type of organic solvent may be used alone, or two or more types may be used in any combination.

[0139] The reaction temperature in the esterification reaction of the method for producing ester compound (A) is not particularly limited, but in one embodiment, a range of 0 to 70°C is preferred.

[0140] The reaction time in the esterification reaction of the method for producing ester compound (A) is not particularly limited, but in one embodiment, a range of 30 minutes to 8 hours is preferred.

[0141] In one embodiment, the esterification reaction in the method for producing ester compound (A) can also be carried out by stirring a mixture (organic solvent system or solvent-free system) containing a polyhydric aromatic hydroxy compound (B) and fluorine-substituted aryl carboxylic acids (C), adding a base dropwise, and then stirring further after the addition of the base. In this case, the addition time is not particularly limited, but is preferably in the range of 10 minutes to 3 hours. The stirring time after addition is preferably in the range of 30 minutes to 5 hours.

[0142] In the method for producing ester compound (A), the ester compound (A) may be purified after the esterification reaction. After the esterification reaction, purification steps such as filtration or microfiltration may be performed to remove by-product salts and excess starting materials from the system. For example, in one embodiment, after the esterification reaction is complete, the amount of water necessary to dissolve the by-product salts is added, and the aqueous layer is discarded after standing separation. If necessary, an acid is added to neutralize the mixture, and the washing with water is repeated. After that, impurities are removed by microfiltration after a dehydration step using a chemical or azeotrope, and if necessary, the organic solvent is removed by distillation to obtain ester compound (A). The organic solvent can also be used as a solvent in the resin composition without completely removing it.

[0143] In the esterification reaction for the production of ester compound (A), in one embodiment, multiple ester compounds may be produced simultaneously. Therefore, the resulting product may contain one or more ester compounds (A) and optionally one or more ester compounds other than ester compound (A). Ester compounds other than ester compound (A) may include compounds with only one fluorine-substituted arylcarbonyloxy group, reaction intermediate compounds, compounds derived from raw material impurities (e.g., n=0 in formula (A1)), etc. The product obtained from the esterification reaction can be used as is as an epoxy resin curing agent, or it can be used after removing unwanted compounds as appropriate.

[0144] The "fluorine-substituted aryl ester group equivalent" of the product obtained by the esterification reaction of the present invention is not particularly limited, but is preferably 5000 g / eq. or less, more preferably 2000 g / eq. or less, even more preferably 1000 g / eq. or less, even more preferably 800 g / eq. or less, particularly preferably 600 g / eq. or less, and most preferably 500 g / eq. or less. The lower limit of the fluorine-substituted aryl ester group equivalent of ester compound (A) is not particularly limited, but may be, for example, 150 g / eq. or more, 180 g / eq. or more, 200 g / eq. or more, etc. If the product is a mixture, the ester group equivalent based on the mixture is indicated.

[0145] The functional group equivalent of the product obtained by the esterification reaction of the present invention is not particularly limited, but is preferably 5000 g / eq. or less, more preferably 2000 g / eq. or less, even more preferably 1000 g / eq. or less, even more preferably 800 g / eq. or less, particularly preferably 600 g / eq. or less, or 500 g / eq. or less. The lower limit of the functional group equivalent of the ester compound (A) is not particularly limited, but may be, for example, 150 g / eq. or more, 180 g / eq. or more, 200 g / eq. or more, etc. If the product is a mixture, the functional group equivalent is based on the mixture.

[0146] Ester compound (A) can be used as an epoxy resin curing agent. By using ester compound (A) as an epoxy resin curing agent, it is possible to obtain a cured product with excellent dielectric properties. Furthermore, by using ester compound (A) as an epoxy resin curing agent, it is possible to obtain a cured product with excellent curability, heat resistance, moisture resistance (hydrolysis resistance), etc. In addition, when ester compound (A) is used as an epoxy resin curing agent in the interlayer insulating material of printed circuit boards, it may also have the effect of reducing the occurrence of haloing defects after laser via formation. By using a sheet-like laminate material or semiconductor encapsulant using ester compound (A), it is possible to provide printed circuit boards and semiconductor devices, including fan-out type, that suppress transmission loss in the high-frequency range.

[0147] The resin composition of the present invention will be described below.

[0148] The present invention provides a resin composition comprising a compound having two or more aromatic rings to which fluorine-substituted arylcarbonyloxy groups are directly bonded (i.e., ester compound (A)) and an epoxy resin.

[0149] The epoxy resin used in the resin composition of the present invention is not limited to any type as long as it is a compound having one or more (preferably two or more) epoxy groups in one molecule.

[0150] 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-butyl-catechol 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 having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiroring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like. In particular, phenol 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 preferred from the viewpoint of further improving dielectric properties, moisture resistance, and flame retardancy. Two or more types of epoxy resin (Y) may be used in combination.

[0151] In one embodiment, the epoxy resin preferably includes an epoxy resin containing fluorine atoms, such as a bisphenol AF type epoxy resin.

[0152] When the non-volatile components of the epoxy resin are considered to be 100% by mass, it is preferable that at least 50% by mass be epoxy resin having two or more epoxy groups per molecule. Furthermore, for interlayer insulating film applications for build-up multilayer circuit boards, it is preferable to contain an aromatic epoxy resin (liquid epoxy resin) having two or more epoxy groups per molecule and being liquid at 20°C, and it is more preferable to contain the liquid epoxy resin and an aromatic epoxy resin (solid epoxy resin) having three or more epoxy groups per molecule and being solid at 20°C. By using both liquid and solid epoxy resins as epoxy resins, when the resin composition is used in the form of a resin sheet, it is possible to form a film that exhibits sufficient flexibility and has excellent handling properties, while at the same time, the tensile strength of the cured resin composition is improved, and the durability of the build-up multilayer circuit board is improved. Furthermore, when using both liquid and solid epoxy resins as epoxy resins, the mixing ratio (liquid:solid) is preferably in the range of 1:0.1 to 1:2 by mass ratio. By using liquid epoxy resin within this range, sufficient flexibility can be obtained when used in the form of a resin sheet, improving handling and ensuring sufficient fluidity during lamination. On the other hand, by using solid epoxy resin within this range, the tackiness of the resin composition can be reduced, improving degassing during vacuum lamination when used in the form of a resin sheet. Furthermore, it is possible to improve the release properties of protective and support films during vacuum lamination and enhance heat resistance after curing.

[0153] In one embodiment, the content of fluorine atoms relative to the total mass of the ester compound (A) and epoxy resin is preferably 5% by mass or more, more preferably 10% by mass or more, even more 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, but for example, it may be 60% by mass or less.

[0154] In the resin composition of the present invention, the epoxy resin content is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, even more preferably 13% to 40% by mass, and particularly preferably 15% to 35% by mass, when the nonvolatile components in the resin composition are considered to be 100% by mass. In one embodiment, setting the epoxy resin content within this range tends to improve the curability of the resin composition.

[0155] In the resin composition of the present invention, the content of ester compound (A) is not particularly limited, but when the nonvolatile components in the resin composition are taken as 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, even more 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, but when the nonvolatile components in the resin composition are taken as 100% by mass, it may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, etc. In one embodiment, by setting the content of ester compound (A) within this range, it is possible to provide a cured product with excellent dielectric properties, as well as excellent curability, heat resistance, moisture resistance, etc.

[0156] The resin composition of the present invention may further contain an inorganic filler. In one embodiment, by including an inorganic filler in the resin composition of the present invention, the linear thermal expansion coefficient can be reduced and the dielectric loss tangent can be reduced.

[0157] Examples of inorganic fillers 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, silica such as amorphous silica, crushed silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica are preferred, with fused silica and spherical silica being more preferred in terms of reducing the surface roughness of the insulating layer, and spherical fused silica being even more preferred. These may be used individually or in combination of two or more. Examples of commercially available spherical fused silica include "SOC2" and "SOC1" manufactured by Admatex.

[0158] The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of achieving a low surface roughness of the insulating layer and enabling the formation of fine wiring, it is preferably 5 μm or less, more preferably 3 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and especially 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 handling ease, it is preferably 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 especially preferably 0.1 μm or more. The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be measured by creating a volume-based particle size distribution of the inorganic filler using a laser diffraction-scattering particle size distribution analyzer and using its median diameter as the average particle size. A sample of inorganic filler dispersed in water by ultrasound is preferably used for measurement. For laser diffraction scattering particle size distribution analyzers, devices such as the LA-950 manufactured by Horiba, Ltd. can be used.

[0159] Inorganic fillers are preferably surface-treated with surface treatment agents such as aminosilane coupling agents, ureidosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, vinylsilane coupling agents, styrylsilane coupling agents, acrylatesilane coupling agents, isocyanatesilane coupling agents, sulfidosilane coupling agents, organosilazane compounds, and titanate coupling agents to improve their moisture resistance and dispersibility. These may be used individually or in combination of two or more types.

[0160] In the resin composition of the present invention, the content of inorganic filler varies depending on the properties required of the resin composition, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and particularly preferably 70% by mass or less. The lower limit of the inorganic filler content is, for example, 0% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, and preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and particularly preferably 50% by mass or more. In one embodiment, if the inorganic filler content is too low, the linear thermal expansion coefficient of the cured product becomes high, on the other hand, if the content is too high, it may be difficult to form a film when manufacturing a resin sheet, or the cured product may become brittle.

[0161] The resin composition of the present invention may further contain a thermoplastic resin. In one embodiment, by including a thermoplastic resin in the resin composition of the present invention, the mechanical strength of the cured product can be improved, and the film molding ability when used in the form of a resin sheet can also be improved.

[0162] Examples of thermoplastic resins include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin, with phenoxy resin and polyvinyl acetal resin being particularly preferred. These thermoplastic resins may 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. The weight-average molecular weight in this invention is measured by gel permeation chromatography (GPC) (in polystyrene equivalent). Specifically, the weight-average molecular weight can be calculated using the GPC method by measuring with a Shimadzu LC-9A / RID-6A as the measuring instrument, a Showa Denko Shodex K-800P / K-804L / K-804L as the column, and chloroform or the like as the mobile phase, at a column temperature of 40°C, and then using a calibration curve for standard polystyrene.

[0163] In the resin composition of the present invention, the content of thermoplastic resin is not particularly limited, but when the non-volatile components in the resin composition are taken as 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, and preferably 0.1% by mass or more, more preferably 0.5% by mass or more. In one embodiment, by having a thermoplastic resin content in the range of 0.1 to 10% by mass, effects such as improved film molding ability and mechanical strength can be achieved, and furthermore, it may be possible to increase the melt viscosity and reduce the roughness of the insulating layer surface after the wet roughening process.

[0164] The resin composition of the present invention may further contain epoxy resin curing agents other than ester compound (A).

[0165] Other epoxy resin curing agents besides ester compounds (A) include TD2090, TD2131 (manufactured by DIC Corporation), MEH-7600, MEH-7851, MEH-8000H (manufactured by Meiwa Chemical Co., Ltd.), NHN, CBN, GPH-65, GPH-103 (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), LA7052, LA7054, LA3018, Examples of curing agents include phenol-based curing agents such as LA1356 (manufactured by DIC Corporation); benzoxazine-based curing agents such as Fa, Pd (manufactured by Shikoku Chemicals Co., Ltd.), and HFB2006M (manufactured by Showa Polymer Co., Ltd.); acid anhydride-based curing agents such as methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic anhydride; cyanate ester-based curing agents such as PT30, PT60, and BA230S75 (manufactured by Lonza Japan Co., Ltd.); and benzoxazine-based curing agents.

[0166] In the resin composition of the present invention, the content of epoxy resin curing agents other than the ester compound (A) is not particularly limited, but when the nonvolatile components in the resin composition are taken as 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, and the lower limit may be 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, etc.

[0167] The resin composition of the present invention may further contain an epoxy resin curing accelerator. In one embodiment, by including an epoxy resin curing accelerator in the resin composition of the present invention, the curing time and curing temperature can be efficiently adjusted.

[0168] Examples of epoxy resin curing accelerators include organophosphine compounds such as TPP, TPP-K, TPP-S, and TPTP-S (manufactured by Hokko Chemical Industry Co., Ltd.), imidazole compounds such as Curesol 2MZ, 2E4MZ, Cl1Z, Cl1Z-CN, Cl1Z-CNS, Cl1Z-A, 2MZ-OK, 2MA-OK, and 2PHZ (manufactured by Shikoku Chemicals Co., Ltd.), amine adduct compounds 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, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 4-dimethylaminopyridine, and organometallic complexes or organometallic salts such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Two or more curing accelerators may be used in combination.

[0169] In the resin composition of the present invention, the content of the epoxy resin curing accelerator is not particularly limited, but when the nonvolatile components in the resin composition are taken as 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, and the lower limit may be 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, etc.

[0170] The resin composition of the present invention may further contain a flame retardant. Examples of the flame retardant include phosphorus-based flame retardants such as phosphazene compounds, phosphates, phosphate esters, polyphosphates, phosphinates, phosphinate esters, phosphonates, and phosphonate esters; 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; 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. Among them, phosphorus-based flame retardants are preferred. The flame retardant may be used alone or in combination of two or more.

[0171] In the resin composition of the present invention, the content of the flame retardant is not particularly limited. However, when the non-volatile components in the resin composition are 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.

[0172] The resin composition of the present invention may further contain an organic filler. As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board may be used. For example, rubber particles, polyamide fine particles, silicone particles, etc. may be mentioned, and rubber particles are preferred. The rubber particles are not particularly limited as long as they are fine particles of a resin obtained by subjecting a resin exhibiting rubber elasticity to a chemical crosslinking treatment and being insoluble and infusible in an organic solvent. For example, acrylonitrile-butadiene rubber particles, butadiene rubber particles, acrylic rubber particles, etc. may be mentioned. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Stafiloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by Aika Kogyo Co., Ltd. above), Paraloid EXL2655, EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd. above), etc. The average particle diameter of the organic filler 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 diameter of the organic filler can be measured using the dynamic light scattering method. For example, the organic filler is uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and using a concentrated system particle size analyzer (FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.), the particle size distribution of the organic filler is created on a mass basis, and it can be measured by taking the median diameter as the average particle diameter.

[0173] In the resin composition of the present invention, the content of the organic filler is not particularly limited. However, when the non-volatile components in the resin composition are set to 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less. 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.

[0174] The resin composition of the present invention may further contain any additives as non-volatile components. Examples of such additives include: radical polymerizable compounds such as maleimide-based radical polymerizable compounds, vinylphenyl-based radical polymerizable compounds, (meth)acrylic-based radical polymerizable compounds, allyl-based radical polymerizable compounds, and polybutadiene-based radical polymerizable compounds; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, melamine resins, and silicone resins; organometallic compounds such as organocumeric 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 phenothiazine; and silicone-based Examples of materials include leveling agents such as bearing agents and acrylic polymer leveling agents; thickeners such as bentonite and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion fertilizers such as triazole-based adhesion fertilizers, tetrazole-based adhesion fertilizers, and triazine-based adhesion fertilizers; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. Other additives may be used individually or in combination of two or more in any ratio. The content of other additives can be appropriately determined by those skilled in the art.

[0175] The resin composition of the present invention may further contain any organic solvent as a volatile component, in addition to the non-volatile component described above. Any known organic solvent can be used as long as it is capable of dissolving at least a portion of the non-volatile component, and the 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, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of organic solvents include ether ester solvents; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents 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. Organic solvents may be used individually or in combination of two or more in any ratio.

[0176] The content of the organic solvent is not particularly limited, but in one embodiment, when the total components in the resin composition are considered to be 100% by mass, it may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc.

[0177] The resin composition of the present invention can be prepared by appropriately mixing the necessary components from the above components, and, if necessary, by kneading or mixing using kneading means such as a three-roll mill, ball mill, bead mill, or sand mill, or stirring means such as a super mixer or planetary mixer.

[0178] The resin composition of the present invention contains an ester compound (A). By using such a resin composition, it is possible to obtain a cured product with excellent dielectric properties. Furthermore, by using such a resin composition, it is possible to obtain a cured product with excellent curability, heat resistance, moisture resistance (hydrolysis resistance), etc. In addition, when such a resin composition is used as an interlayer insulating material for printed circuit boards, it may also have the effect of reducing the occurrence of haloing defects after laser via formation.

[0179] In one embodiment, the resin composition of the present invention may exhibit excellent curability. Therefore, in one embodiment, for example, the gel time measured by the method of Test Example 1 below may be preferably 100 seconds or less, more preferably 80 seconds or less, even more preferably 60 seconds or less, and particularly preferably 50 seconds or less.

[0180] In one embodiment, the cured product of the resin composition of the present invention may have excellent heat resistance or moisture resistance (hydrolysis resistance). Therefore, in one embodiment, for example, when a voltage of 3.3V is applied to wiring connected to a DC power supply for 200 hours under conditions of 130°C and 85%RH, as measured by the method of Test Example 2 below, the insulation resistance value of the evaluation substrate after 200 hours is preferably 1.0 × 10⁻⁶. 5 Ω or greater, more preferably 1.0 × 10 6 Ω or greater, more preferably 1.0 × 10⁻¹⁰ 7 Ω or greater, particularly preferably 1.0 × 10⁻⁶ 8It could be Ω or higher.

[0181] In one embodiment, the cured product of the resin composition of the present invention may have excellent dielectric properties. Therefore, in one embodiment, for example, as shown in Test Example 3 below, the dielectric loss tangent (Df) of the cured product of the resin composition (a cured product obtained by heating at 190°C for 90 minutes) when measured at 5.8 GHz and 23°C may be preferably 0.020 or less, 0.010 or less, more preferably 0.009 or less, even more preferably 0.008 or less, particularly preferably 0.007 or less, or 0.006 or less. Also, in one embodiment, for example, as shown in Test Example 3 below, the relative permittivity (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23°C may be preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.4 or less, even more preferably 3.2 or less, and particularly preferably 3.0 or less.

[0182] In one embodiment, the cured product of the resin composition of the present invention may have the characteristic of being less prone to haloing defects after laser via formation. In one embodiment, for example, the haloing ratio calculated as shown in Test Example 4 below may be preferably 45% or less, more preferably 40% or less, even more preferably 37% or less, and particularly preferably 35% or less.

[0183] The resin composition of the present invention can be suitably used as a resin composition for insulating applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (including a redistribution layer) on which a conductor layer (including a redistribution layer) is formed (a resin composition for forming an insulating layer for forming a conductor layer). Furthermore, in printed circuit boards described later, it can be suitably used as a resin composition for forming an insulating layer on a printed circuit board (a resin composition for forming an insulating layer on a printed circuit board). The resin composition of the present invention can also be used in a wide range of applications where a resin composition is required, such as sheet-like laminated materials like resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins.

[0184] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a redistribution-forming layer (resin composition for forming a redistribution-forming layer) as an insulating layer for forming a redistribution layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When the semiconductor chip package is manufactured, a redistribution layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto the substrate, (2) A step of temporarily fixing the semiconductor chip onto a temporary fixing film, (3) A step of forming a sealing layer on a semiconductor chip, (4) Steps to peel off the substrate and temporary fixing film from the semiconductor chip, (5) A step of forming a rewiring layer as an insulating layer on the surface from which the substrate and temporary fixing film of the semiconductor chip have been peeled off, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer.

[0185] Furthermore, since the resin composition of the present invention provides an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a circuit board with embedded components.

[0186] The resin composition of the present invention can be used by applying it in a varnish state, but industrially it is generally preferable to use it in the form of a sheet-like laminate material containing the resin composition.

[0187] As sheet-like laminated materials, the following resin sheets and prepregs are preferred.

[0188] In one embodiment, the resin sheet comprises a support and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.

[0189] From the viewpoints of thinning the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be 5 μm or more, 10 μm or more, etc.

[0190] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

[0191] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0192] When using a metal foil as the support, examples of the metal foil include a copper foil, an aluminum foil, etc., and a copper foil is preferable. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0193] The support may be subjected to a mat treatment, a corona treatment, an antistatic treatment on the surface that joins the resin composition layer.

[0194] Furthermore, as the support, a support with a release layer may be used, which has a release layer on the surface that is bonded to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may be used as the support with a release layer, for example, PET films having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1", "AL-5", and "AL-7" from Lintec Corporation, "Lumirror T60" from Toray Industries, Inc., "Purex" from Teijin Corporation, and "Unipeel" from Unitika Corporation.

[0195] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. 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.

[0196] In one embodiment, the resin sheet may further include any additional layer as needed. Such an additional layer may be, for example, a protective film similar to the support, provided 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, but is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of dust and other debris to the surface of the resin composition layer and scratches can be suppressed.

[0197] Resin sheets can be manufactured, for example, by applying a resin varnish prepared by directly using a liquid resin composition or by dissolving the resin composition in an organic solvent, coating it onto a support using a die coater or the like, and then drying it to form a resin composition layer.

[0198] Examples of organic solvents include those similar to those described as components of the resin composition. Organic solvents may be used individually or in combination of two or more.

[0199] Drying may be carried out by known methods such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer should be dried so that the content of the 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, when using a resin composition or resin varnish containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0200] The resin sheet can be stored by rolling it up. If the resin sheet has a protective film, it can be used after removing the protective film.

[0201] In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous substrate with the resin composition of the present invention.

[0202] The sheet-like fibrous substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed circuit board, the thickness of the sheet-like fibrous substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited, but is usually 10 μm or more.

[0203] Prepregs can be manufactured by known methods such as the hot melt method and the solvent method.

[0204] The thickness of the prepreg can be within the same range as the resin composition layer in the resin sheet described above.

[0205] The sheet-like laminated material of the present invention can be suitably used to form an insulating layer of a printed circuit board (for the insulating layer of a printed circuit board), and more suitably used to form an interlayer insulating layer of a printed circuit board (for the interlayer insulating layer of a printed circuit board).

[0206] The printed circuit board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0207] Printed circuit boards can be manufactured, for example, using the resin sheet described above, by a method including the following steps (I) and (II). (I) A process of laminating a resin sheet onto an inner layer substrate such that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., thermal curing) the resin composition layer to form an insulating layer.

[0208] The "internal layer substrate" used in process (I) is a material that serves as the substrate for a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. The substrate may also have a conductive layer on one or both sides, and this conductive layer may be patterned. An internal layer substrate in which a conductive layer (circuit) is formed on one or both sides of the substrate is sometimes called an "internal layer circuit board." Furthermore, an intermediate product on which an insulating layer and / or a conductive layer is to be formed during the manufacturing of a printed wiring board is also included in the "internal layer substrate" as defined in this invention. If the printed wiring board is a circuit board with embedded components, an internal layer substrate with embedded components may be used.

[0209] Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet onto the inner layer substrate from the support side. Examples of the member used to heat and press the resin sheet onto the inner layer substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the resin sheet via an elastic material such as heat-resistant rubber, rather than directly pressing the heat-pressing member onto the resin sheet, so that the resin sheet can adequately follow the surface irregularities of the inner layer substrate.

[0210] Lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the heat-pressure temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressure pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-pressure time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination may preferably be carried out under reduced pressure conditions of 26.7 hPa or less.

[0211] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch-type vacuum pressure laminators.

[0212] After lamination, the laminated resin sheets may be smoothed by pressing a heat-sealing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. The smoothing process can be performed using a commercially available laminator. Lamination and smoothing may be performed continuously using the commercially available vacuum laminator mentioned above.

[0213] The support may be removed between steps (I) and (II), or after step (II).

[0214] In step (II), the resin composition layer is cured (e.g., by thermal curing) to form an insulating layer made of the cured resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly used when forming an insulating layer for a printed circuit board may be used.

[0215] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but 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 can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0216] Prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermal curing the resin composition layer, it may 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 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0217] In manufacturing printed circuit boards, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer. These steps (III) through (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed circuit boards. If the support is removed after step (II), the removal of the support may be carried out between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (II) through (V) may be repeated to form a multilayer printed circuit board.

[0218] In other embodiments, the printed circuit board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when a resin sheet is used.

[0219] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed circuit board.

[0220] Step (IV) is a process for roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The procedure and conditions for the roughening process are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed circuit board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution in this order.

[0221] The swelling solution used for the roughening treatment is not particularly limited, but examples include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Examples of commercially available swelling solutions include "Swelling Dip Securing P" and "Swelling Dip Securing SBU" manufactured by Atotec Japan. The swelling treatment with the swelling solution is not particularly limited, but can be carried out, for example, 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 of 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.

[0222] The oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent 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. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Attec Japan.

[0223] Furthermore, an acidic aqueous solution is preferred as the neutralizing solution used in the roughening treatment. A commercially available example is "Reduction Solution Securigant P" manufactured by Attec Japan.

[0224] The neutralization treatment can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in a neutralization solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, it is preferable to immerse the object, which has been roughened with an oxidizing agent, in a neutralization solution at 40°C to 70°C for 5 to 20 minutes.

[0225] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment 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. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. Also, the root mean square roughness (Rq) of the insulating layer surface after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, 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.

[0226] Step (V) is a step of forming a conductive layer, in which a conductive layer is formed on an insulating layer. The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains 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 conductive layer may be a single-metal layer or an alloy layer, and examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). In particular, from the viewpoint of versatility in conductor layer formation, cost, and ease of patterning, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are more preferred, and single metal layers of copper are even more preferred.

[0227] The conductive layer may be a single-layer structure, or it may be a multi-layer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductive 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.

[0228] The thickness of the conductor layer depends on the desired printed circuit board design, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0229] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using conventionally known techniques such as the semi-additive method or the fully additive method. From the viewpoint of ease of manufacture, it is preferable to form it by the semi-additive method. An example of forming the conductor layer by the semi-additive method is shown below.

[0230] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. Then, the unnecessary plating seed layer can be removed by etching or other means to form a conductor layer having the desired wiring pattern.

[0231] 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 the metal foil is laminated onto the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Subsequently, the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern by conventional known techniques such as the subtractive method or the modified semi-additive method.

[0232] Metal foils can be manufactured by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Oil & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0233] The semiconductor device of the present invention includes the printed circuit board of the present invention. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

[0234] Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

[0235] In a preferred embodiment, the semiconductor device of the present invention is a fan-out type semiconductor device. [Examples]

[0236] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In the following, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "mass%", respectively. Unless otherwise specified, the temperature condition is room temperature (23°C). Unless otherwise specified, the pressure condition is atmospheric pressure (1 atm).

[0237] <Example A-1> In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 114 g (0.5 mol, 1.0 mol hydroxyl group) of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 219 g (0.95 mol, 0.95 equivalents per equivalent of hydroxyl group of bisphenol A), and 1000 g of methyl isobutyl ketone were charged and dissolved while purging the system with reduced pressure nitrogen. The system was heated to 50°C and 115 g (1.14 mol) of triethylamine was added dropwise over 1 hour with vigorous stirring. After the addition was complete, stirring was continued at 70°C for another hour. 300 g of water was added to dissolve the by-product salts, and the mixture was allowed to stand before separation, discarding the lower aqueous layer. The aqueous layer was then washed repeatedly with water until its pH reached 7, followed by dehydration and removal of insoluble impurities by microfiltration. The solution was heated under reduced pressure to 150°C and the solvent was dried to obtain 251 g of crystalline product (A-1). The fluorine-substituted aryl ester group equivalent (hereinafter abbreviated as "ester group equivalent") of product (A-1) was 324 g / eq., the hydroxyl group equivalent was 2280 g / eq., the total functional group equivalent was 298 g / eq., and the fluorine atom content was 29.3 mass%. The obtained product (A-1) was measured by gel permeation chromatography (GPC) and infrared spectroscopy (IR) based on the GPC and IR measurement conditions described below. Figure 1 shows the GPC chart of the obtained product (A-1) (solid line) and starting material (bisphenol A) (dotted line). Figure 2 shows the IR chart of the obtained product (A-1) (lower curve) and starting material (bisphenol A) (upper curve). Mass spectral analysis revealed peaks corresponding to the theoretical structural component at m / z;616 and the terminally esterified component at m / z;422.

[0238] (GPC measurement conditions) Measurement device: Tosoh Corporation "HPLC-8420GPC" Columns: TSKgel SuperHZ4000 (1 tube) + TSKgel SuperHZ3000 (1 tube) + TSKgel SuperHZ2000 (2 tubes) manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 1.0ml / min

[0239] (IR measurement conditions) Measurement device: JASCO Corporation "FT / IR-4600"

[0240] <Example A-2> Except for using 104 g of phenol novolac resin (PHENOLITE TD-2131, manufactured by DIC Corporation, hydroxyl group equivalent 104 g / eq., softening point 80°C) (1.0 mol of hydroxyl groups) instead of bisphenol A, changing the amount of pentafluorobenzoyl chloride used to 196 g (0.85 mol, 0.85 equivalents per 1 equivalent of hydroxyl groups in the phenol novolac resin) and changing the amount of triethylamine used to 101 g (1.0 mol), 228 g of amorphous product (A-2) was obtained in the same manner as in Example A-1. The ester group equivalent of product (A-2) was 281 g / eq., the hydroxyl group equivalent was 1793 g / eq., the total functional group equivalent was 269 g / eq., and the fluorine atom content was 25.8 mass%. The obtained product (A-2) was measured by GPC and IR in the same manner as in Example A-1. Figure 3 shows the GPC charts for the obtained product (A-2) (solid line) and raw material (phenol novolac resin) (dotted line). Figure 4 shows the IR charts for the obtained product (A-2) (lower curve) and raw material (phenol novolac resin) (upper curve).

[0241] <Example A-3> 168 g of amorphous product (A-3) was obtained in the same manner as in Example A-2, except that 135 g of 4-fluorobenzoyl chloride (0.85 mol, 0.85 equivalents per 1 equivalent of hydroxyl groups in the phenol novolac resin) was used instead of pentafluorobenzoyl chloride. The ester group equivalent of product (A-3) was 245 g / eq., the hydroxyl group equivalent was 1387 g / eq., the total functional group equivalent was 208 g / eq., and the fluorine atom content was 7.0 mass%. The obtained product (A-3) was measured by GPC and IR in the same manner as in Example A-1. Figure 5 shows the GPC chart of the obtained product (A-3) (solid line) and the raw material (phenol novolac resin) (dotted line). Figure 6 shows the IR chart of the obtained product (A-3) (lower curve) and the raw material (phenol novolac resin) (upper curve).

[0242] <Example A-4> Except for using 120 g of orthocresol novolac resin (DIC Corporation, "PHENOLTE KA-1163", hydroxyl group equivalent 120 g / eq., softening point 110°C) instead of phenol novolac resin, changing the amount of pentafluorobenzoyl chloride used to 116 g (0.5 mol, 0.5 equivalents per 1 equivalent of hydroxyl groups in orthocresol novolac resin), and changing the amount of triethylamine used to 61 g (0.6 mol), 185 g of amorphous product (A-4) was obtained in the same manner as in Example A-2. The ester group equivalent of product (A-4) was 434 g / eq., the hydroxyl group equivalent was 434 g / eq., the total functional group equivalent was 217 g / eq., and the fluorine atom content was 15.0 mass%. The obtained product (A-4) was measured by GPC and IR in the same manner as in Example A-1. Figure 7 shows the GPC charts for the obtained product (A-4) (solid line) and raw material (cresol novolac resin) (dotted line). Figure 8 shows the IR charts for the obtained product (A-4) (lower curve) and raw material (cresol novolac resin) (upper curve).

[0243] <Example A-5> 171 g of amorphous product (A-5) was obtained in the same manner as in Example A-4, except that 111 g of 4-fluorobenzoyl chloride (0.7 mol, 0.7 equivalents per 1 equivalent of hydroxyl groups in orthocresol novolac resin) was used instead of pentafluorobenzoyl chloride. The ester group equivalent of product (A-5) was 270 g / eq., the hydroxyl group equivalent was 630 g / eq., the total functional group equivalent was 189 g / eq., and the fluorine atom content was 3.9 mass%. The obtained product (A-5) was measured by GPC and IR in the same manner as in Example A-1. Figure 9 shows the GPC chart of the obtained product (A-5) (solid line) and the raw material (cresol novolac resin) (dotted line). Figure 10 shows the IR chart of the obtained product (A-5) (lower curve) and the raw material (cresol novolac resin) (upper curve).

[0244] <Example A-6> Except for using 231 g of biphenyl aralkyl resin (GPH-103, manufactured by Nippon Kayaku Co., Ltd., hydroxyl group equivalent 231 g / eq.) instead of phenol novolac resin (1.0 mol of hydroxyl groups), changing the amount of pentafluorobenzoyl chloride used to 208 g (0.9 mol, 0.9 equivalents per 1 equivalent of hydroxyl groups in biphenyl aralkyl resin), and changing the amount of triethylamine used to 121 g (1.2 mol), 318 g of amorphous product (A-6) was obtained in the same manner as in Example A-2. The ester group equivalent of product (A-6) was 451 g / eq., the hydroxyl group equivalent was 4060 g / eq., the total functional group equivalent was 406 g / eq., and the fluorine atom content was 21.0 mass%. The obtained product (A-6) was measured by GPC and IR in the same manner as in Example A-1. Figure 11 shows the GPC charts for the obtained product (A-6) (solid line) and raw material (biphenyl aralkyl resin) (dotted line). Figure 12 shows the IR charts for the obtained product (A-6) (lower curve) and raw material (biphenyl aralkyl resin) (upper curve).

[0245] <Example A-7> 299 g of amorphous product (A-7) was obtained in the same manner as in Example A-1, except that 168 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF, hydroxyl group equivalent 168 g / eq.) (1.0 mol of hydroxyl groups) was used instead of bisphenol A. The ester group equivalent of product (A-7) was 270 g / eq., the hydroxyl group equivalent was 630 g / eq., the total functional group equivalent was 352 g / eq., and the fluorine atom content was 39.9 mass%. The obtained product (A-7) was measured by GPC and IR in the same manner as in Example A-1. Figure 13 shows the GPC chart of the obtained product (A-7) (solid line) and the starting material (bisphenol AF) (dotted line). Figure 14 shows the IR chart of the obtained product (A-7) (lower curve) and the starting material (bisphenol AF) (upper curve). Mass spectral analysis revealed peaks corresponding to the theoretical structural component at m / z;724 and the terminally esterified component at m / z;530.

[0246] <Comparative example A-1> 194 g of amorphous product (A-1') was obtained in the same manner as in Example A-1, except that 134 g of benzoic acid chloride (benzoyl chloride) (0.95 mol, 0.95 equivalents per 1 equivalent of hydroxyl groups of bisphenol A) was used instead of 219 g of pentafluorobenzoyl chloride. The ester group equivalent of product (A-1') was 203 g / eq., the hydroxyl group equivalent was 4270 g / eq., the total functional group equivalent was 213 g / eq., and the fluorine atom content was 0% by mass.

[0247] <Comparative example A-2> 196 g of amorphous product (A-2') was obtained in the same manner as in Example A-2, except that 120 g (0.85 mol, 0.85 equivalents per 1 equivalent of hydroxyl groups of phenol novolac resin) of benzoic acid chloride (benzoyl chloride) was used instead of pentafluorobenzoyl chloride. The ester group equivalent of product (A-2') was 226 g / eq., the hydroxyl group equivalent was 1280 g / eq., the total functional group equivalent was 192 g / eq., and the fluorine atom content was 0% by mass.

[0248] <Comparative example A-3> 217 g of amorphous product (A-3') was obtained in the same manner as in Example A-2, except that 177 g of 4-trifluoromethylbenzoyl chloride (0.85 mol, 0.85 equivalents per 1 equivalent of hydroxyl groups in the phenol novolac resin) was used instead of pentafluorobenzoyl chloride. The ester group equivalent of product (A-3') was 294 g / eq., the hydroxyl group equivalent was 1667 g / eq., the total functional group equivalent was 250 g / eq., and the fluorine atom content was 17.3% by mass.

[0249] The structures, ester group equivalents, hydroxyl group equivalents, functional group equivalents, and fluorine atom content of the main components contained in the above products (A-1) to (A-7) and (A-1') to (A-3') are summarized in Tables 1A to 1C.

[0250] [Table 1A]

[0251] [Table 1B]

[0252] [Table 1C]

[0253] <Example B-1: Preparation of resin composition (B-1)> 29.8 g of the product (A-1) obtained in Example A-1 and 27.5 g of biphenylaralkyl epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275 g / eq.) were dissolved in 57 g of methyl ethyl ketone, and 0.6 g of dimethylaminopyridine was added as a curing accelerator to prepare a resin composition (B-1) for curing evaluation.

[0254] <Example B-2: Preparation of resin composition (B-2)> Resin composition (B-2) was prepared in the same manner as in Example B-1, except that 27.3 g of product (A-2) obtained in Example A-2 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0255] <Example B-3: Preparation of resin composition (B-3)> Resin composition (B-3) was prepared in the same manner as in Example B-1, except that 21.2 g of product (A-3) obtained in Example A-3 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0256] <Example B-4: Preparation of resin composition (B-4)> Resin composition (B-4) was prepared in the same manner as in Example B-1, except that 21.9 g of product (A-4) obtained in Example A-4 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0257] <Example B-5: Preparation of resin composition (B-5)> Resin composition (B-5) was prepared in the same manner as in Example B-1, except that 20.7 g of product (A-5) obtained in Example A-5 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0258] <Example B-6: Preparation of resin composition (B-6)> Resin composition (B-6) was prepared in the same manner as in Example B-1, except that 40.6 g of product (A-6) obtained in Example A-6 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0259] <Example B-7: Preparation of resin composition (B-7)> Resin composition (B-7) was prepared in the same manner as in Example B-1, except that 35.2 g of product (A-7) obtained in Example A-7 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0260] <Comparative Example B-1: Preparation of Resin Composition (B-1')> Resin composition (B-1') was prepared in the same manner as in Example B-1, except that 21.3 g of product (A-1') obtained in Comparative Example A-1 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0261] <Comparative Example B-2: Preparation of Resin Composition (B-2')> Resin composition (B-2') was prepared in the same manner as in Example B-1, except that 18.5 g of product (A-2') obtained in Comparative Example A-2 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0262] <Comparative Example B-3: Preparation of Resin Composition (B-3')> Resin composition (B-3') was prepared in the same manner as in Example B-1, except that 25.4 g of product (A-3') obtained in Comparative Example A-3 was used instead of 29.8 g of product (A-1) obtained in Example A-1.

[0263] <Test Example 1: Evaluation of curing properties by measuring gel time> The gel times of the above resin compositions (B-1) to (B-7) and (B-1') to (B-3') were measured using a 160°C curing plate, and the results are shown in Table 2.

[0264] [Table 2]

[0265] <Example C-1: Preparation of resin composition (C-1)> Fifteen parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "828US" manufactured by Mitsubishi Chemical Corporation) and fifteen parts of biphenyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.) were heated and dissolved in fifteen parts of methyl ethyl ketone (hereinafter abbreviated as "MEK") and 30 parts of cyclohexanone while stirring. To this, 38 parts of the product (A-1) obtained in Example A-1 (functional group equivalent 298 g / eq.), 0.15 parts of a curing accelerator (manufactured by Koei Chemical Industry Co., Ltd., "4-dimethylaminopyridine"), 100 parts of spherical silica (average particle size 0.5 μm, phenylaminosilane treated "SO-C2", manufactured by Admatex Co., Ltd., carbon content per unit mass 0.18%), and 15 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YL6954BH30", MEK solution with 30% solids by mass, weight-average molecular weight 40000) were mixed and uniformly dispersed in a high-speed rotary mixer to prepare resin composition (C-1).

[0266] <Example C-2: Preparation of resin composition (C-2)> Resin composition (C-2) was prepared in the same manner as in Example C-1, except that 35 parts of product (A-2) obtained in Example A-2 (functional group equivalent 273 g / eq.) were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0267] <Example C-3: Preparation of resin composition (C-3)> Resin composition (C-3) was prepared in the same manner as in Example C-1, except that 27 parts of product (A-3) (functional group equivalent 212 g / eq.) obtained in Example A-3 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0268] <Example C-4: Preparation of resin composition (C-4)> Resin composition (C-4) was prepared in the same manner as in Example C-1, except that 28 parts of product (A-4) (functional group equivalent 219 g / eq.) obtained in Example A-4 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0269] <Example C-5: Preparation of resin composition (C-5)> Resin composition (C-5) was prepared in the same manner as in Example C-1, except that 26 parts of product (A-5) (functional group equivalent 207 g / eq.) obtained in Example A-5 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0270] <Example C-6: Preparation of resin composition (C-6)> Resin composition (C-6) was prepared in the same manner as in Example C-1, except that 52 parts of product (A-6) (functional group equivalent 406 g / eq.) obtained in Example A-6 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0271] <Example C-7: Preparation of resin composition (C-7)> Resin composition (C-7) was prepared in the same manner as in Example C-1, except that 45 parts of product (A-7) (functional group equivalent 352 g / eq.) obtained in Example A-7 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0272] <Comparative Example C-1: Preparation of Resin Composition (C-1')> Resin composition (C-1') was prepared in the same manner as in Example C-1, except that 27 parts of product (A-1') (functional group equivalent 213 g / eq.) obtained in Comparative Example A-1 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0273] <Comparative Example C-2: Preparation of Resin Composition (C-2')> Resin composition (C-2') was prepared in the same manner as in Example C-1, except that 24 parts of product (A-2') (functional group equivalent 185 g / eq.) obtained in Comparative Example A-2 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0274] <Comparative Example C-3: Preparation of Resin Composition (C-3')> Resin composition (C-3') was prepared in the same manner as in Example C-1, except that 33 parts of product (A-3') (functional group equivalent 254 g / eq.) obtained in Comparative Example A-3 were used instead of 38 parts of product (A-1) obtained in Example A-1.

[0275] <Test Example 2: Evaluation of Insulation Reliability> (1) Preparation of resin sheets The resin compositions (C-1) to (C-7) and (C-1') to (C-3') obtained in the examples and comparative examples were applied to polyethylene terephthalate (38 μm thick, hereinafter abbreviated as "PET") using a die coater so that the resin thickness after drying was 40 μm, and the mixture was dried at 80 to 120°C (average 100°C) for 6 minutes to produce resin sheets.

[0276] (2) Surface treatment of laminated boards A double-sided copper-clad laminate made of epoxy resin on a glass cloth substrate with an inner layer circuit (copper foil thickness 18 μm, residual copper content 60%, substrate thickness 0.3 mm, manufactured by Matsushita Electric Works, Ltd., R5715ES) was subjected to a copper surface roughening treatment by immersing both sides in MEC's ​​CZ8100.

[0277] (3) Lamination of resin sheets The resin sheet prepared in (1) was laminated to both sides of the laminate using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho Co., Ltd.). Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds.

[0278] (4) Curing of the resin composition The PET film was peeled from the laminated resin sheet, and the resin composition was cured at 170°C for 30 minutes.

[0279] (5) Laser via processing Using a CO2 laser processing machine (Mitsubishi Electric "605GTWIII(-P)"), the insulating layer was irradiated with laser light to form multiple via holes with a top diameter (diameter) of approximately 30 μm in the insulating layer. The laser irradiation conditions were a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, 2 shots, and burst mode (10 kHz). The cured substrate A, in which via holes were formed in the insulating layer in this manner, is called evaluation substrate A.

[0280] (6) Roughening treatment Evaluation substrate A was immersed in a swelling solution, Sweling Dip Securigand P containing diethylene glycol monobutyl ether, manufactured by Attec Japan, at 60°C for 10 minutes. Next, as a roughening solution, it was immersed in Concentrate Compact P (an aqueous solution of KMnO4: 60 g / L and NaOH: 40 g / L), manufactured by Attec Japan, at 80°C for 20 minutes. Finally, as a neutralizing solution, it was immersed in Reduction Sulfuricine Securigand P, manufactured by Attec Japan, at 40°C for 5 minutes. The laminate after this roughening treatment was designated as Sample A.

[0281] (7) Plating by semi-additive method To form a circuit on the insulating layer surface, the laminate was immersed in an electroless plating solution containing PdCl2, and then in an electroless copper plating solution. After annealing by heating at 150°C for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductive layer with a thickness of 30 μm. Next, annealing was performed at 180°C for 60 minutes. This laminate was designated as Sample B.

[0282] (8) Evaluation of insulation reliability (evaluation of heat resistance and moisture resistance) A circular cutout of resist tape (Nitto Denko Corporation, Elep Masking Tape N380) was applied to the conductive layer of sample B and immersed in a ferric chloride aqueous solution for 30 minutes. The conductive layer in the areas where the resist tape was not applied was removed to create an evaluation board with a circular conductive layer formed on the insulating layer. Subsequently, a portion of the insulating layer was scraped to expose the underlying copper foil. The exposed copper foil and the circular conductive layer were then connected with wiring (wire). A DC power supply (Takasago Seisakusho Co., Ltd., TP018-3D) was connected to the wiring of the evaluation board, and a voltage of 3.3V was applied for 200 hours under conditions of 130°C and 85%RH. After 200 hours, the insulation resistance value was measured, and if the insulation resistance value was 1.0 × 10⁻⁶ 8 Values ​​greater than or equal to Ω are marked with "○", and 1.0 × 10 7 Ω or more 1.0×10 8 Values ​​less than Ω are represented as "△", and 1.0 × 10 7Values ​​less than Ω were marked with "×".

[0283] <Test Example 3: Measurement of Dielectric Properties (Relative Permittivity and Dielectric Loss Tangent)> The resin sheet prepared in Test Example 2(1) was heat-cured at 190°C for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured material. This cured material was cut into test pieces with a width of 2 mm and a length of 80 mm, and the relative permittivity and dielectric loss tangent were measured using the cavity resonance method at a measurement frequency of 5.8 GHz and 23°C with a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technologies. Measurements were performed on two test pieces, and the average value was calculated.

[0284] <Test Example 4: Evaluation of Haloing Properties> The evaluation substrate A, fabricated in Test Example 2, was observed in cross-section using a FIB-SEM combined system (SMI3050SE, manufactured by SII Nanotechnology). Specifically, the insulating layer was cut using a FIB (focused ion beam) so that a cross-section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole was revealed. This cross-section was observed using a SEM. The bottom diameter and top diameter of the via hole were measured from the observed image.

[0285] Furthermore, the images observed by SEM showed a gap formed by the delamination of the insulating layer from the copper foil layer of the inner substrate, extending continuously from the edge of the via bottom. Therefore, from the observed images, the distance r1 from the center of the via bottom to the edge of the via bottom (corresponding to the inner radius of the gap) and the distance r2 from the center of the via bottom to the far end of the gap (corresponding to the outer radius of the gap) were measured, and the difference r2-r1 between these distances r1 and r2 was calculated as the haloing distance from the edge of the via bottom at that measurement point.

[0286] The above measurements were performed at five randomly selected via holes. The average of the top diameters of the five via holes was adopted as the top diameter Lt of the sample after roughening. The average of the bottom diameters of the five via holes was adopted as the bottom diameter Lb of the sample after roughening. Furthermore, the average of the halloing distances of the five via holes was adopted as the halloing distance Wb from the edge of the via bottom of the sample.

[0287] From the measurement results mentioned above, the taper ratio (the ratio of the top diameter Lt to the bottom diameter Lb of the via hole after roughening, "Lb / Lt") and the haloing ratio Hb (the ratio of the haloing distance Wb from the edge of the via bottom after roughening to the radius of the via bottom of the via hole after roughening (Lb / 2), "Wb / (Lb / 2)") were calculated. If the haloing ratio Hb was 35% or less, it was judged as "○", and if the haloing ratio Ht was greater than 35%, it was judged as "×".

[0288] The measurement and evaluation results for Test Examples 2-4 are shown in Table 3 below.

[0289] [Table 3]

[0290] As shown in Tables 2 and 3, when ester compound (A) is used as a component of the resin composition, it is clear that curability, structural reliability, dielectric properties, and haloing properties are superior to those when conventional ester compounds are used. In other words, resin compositions and cured products using ester compound (A) are materials that can achieve a high level of low transmission loss, which is required in high-frequency environments such as 5G devices, without sacrificing processability or reliability.

Claims

1. Formula (A1): 【Chemistry 1】 [In the formula, Each Ar ring independently represents an aromatic ring which may have substituents; Each X independently represents an arylcarbonyloxy group or a hydroxyl group which may have substituents, and at least two Xs bonded to different rings Ar are fluorine-substituted arylcarbonyloxy groups; The substituents in the aromatic ring of ring Ar, and the substituents in X, are halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, and -SO. ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ -NH-COR, -NR-COR, and -N(COR) ２ It is a base chosen from; R is an alkyl group optionally substituted with a group selected from (1) a halogen atom, a hydroxy group, an amino group, a mercapto group, a nitro group, a cyano group, -R ａ , -OR ｂ , -SR ｂ , -SO ２ R 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 ; (2) an alkenyl group optionally substituted with a group selected from a halogen atom, a hydroxy group, an amino group, a mercapto group, a nitro group, a cyano group, -R ａ , -OR ｂ , -SR ｂ , -SO ２ R 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​​​​​​​​​​​​​​​​​​​​​​​​​​​​​,-CO-NHR ｂ , -CO-N(R ｂ ) ２ , -O-COR ｂ ,-NH-COR ｂ , -NR ｂ -COR ｂ , and -N(COR ｂ ) ２ An aryl group which may be substituted with a group selected from; R ａ is a halogen atom, an aryl group, a halogen-substituted aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), or an aryl-aryl group (an aryl group substituted with one or more aryl groups); R ｂ is a halogen atom, alkyl group, alkenyl group, aryl group, halogen-substituted alkyl group, halide alkenyl group, halogen-substituted aryl group, alkyl-aryl group, aryl-aryl group, or aryl-alkyl group (alkyl group substituted with one or more aryl groups); Each Z independently represents a single bond or a divalent group consisting of one or more skeletal atoms selected from carbon, oxygen, nitrogen, and sulfur atoms; n represents an integer between 1 and 500; Each 'm' independently represents an integer between 1 and 3. An epoxy resin curing agent containing a compound represented by [the formula shown].

2. The compound represented by formula (A1) is given by formula (A2): 【Chemistry 2】 [In the formula, Each Ar ring independently represents an aromatic ring which may have substituents; Each X independently represents an arylcarbonyloxy group or a hydroxyl group which may have substituents, and at least two Xs bonded to different rings Ar are fluorine-substituted arylcarbonyloxy groups; Y １ These are, independently, single bonds, -C(R) １ ) ２ -, -O-, -CO-, -S-, -SO-, -SO ２ -, -CONH-, -NHCO-, -COO-, or -OCO- are indicated; R １ Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group; Ring Y ２ Each independently represents an aromatic ring which may have a substituent, or an unaromatic ring which may have a substituent; The substituents in the aromatic ring of ring Ar, and the substituents in X, are halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, and -SO. ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ -NH-COR, -NR-COR, and -N(COR) ２ It is a base chosen from; R １ If R is an aryl group which may have substituents, １ The substituents in this compound are halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, and -SO. ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ , -O-COR, -NH-COR, -NR-COR, and -N(COR) ２ It is a base chosen from; R １ If R is an alkyl group which may have substituents, １ The substituents in this compound are halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R', -OR, -SR, and -SO. ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ , -O-COR, -NH-COR, -NR-COR, and -N(COR) ２ It is a base chosen from; Ring Y ２ When Ring Y is an aromatic ring which may have a substituent, the substituent in Ring Y ２ is a group selected from a halogen atom, an amino group, a mercapto group, a nitro group, a cyano group, -R, -OR, -SR, -SO ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ , -NH-COR, -NR-COR, and -N(COR) ２ ; and is a group selected from Ring Y ２ If ring Y is a non-aromatic ring which may have substituents, ２ The substituents in this compound are halogen atoms, hydroxyl groups, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, and -SO. ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ , -O-COR, -NH-COR, -NR-COR, -N(COR) ２ A base chosen from , and = O; R is an alkyl group optionally substituted with a group selected from (1) a halogen atom, a hydroxy group, an amino group, a mercapto group, a nitro group, a cyano group, -R ａ , -OR ｂ , -SR ｂ , -SO ２ R 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) an alkenyl group optionally substituted with a group selected from a halogen atom, a hydroxy group, an amino group, a mercapto group, a nitro group, a cyano group, -R ２ , -OR ａ , -SR ｂ , -SO ｂ , -SR ２ , -SO ｂ R ｂ , -NHR ｂ , -N(R ２ ), 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 ); or (3) a halogen atom, a hydroxy group, an amino group, a mercapto group, a nitro group, a cyano group, -R ２ , -OR ｂ , -SR ｂ , -SO ｂ , -SR ２ , -SO ｂ R ｂ , -NHR ｂ , -N(R ２ ), ｂ , -COR , -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 An aryl group which may be substituted with a group selected from; R' represents a halogen atom, hydroxyl group, amino group, mercapto group, nitro group, cyano group, -R ｂ , -OR ｂ , -SR ｂ , -SO ２ R 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 An aryl group which may be substituted with a group selected from; R ａ is a halogen atom, an aryl group, a halogen-substituted aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), or an aryl-aryl group (an aryl group substituted with one or more aryl groups); R ｂ is a halogen atom, alkyl group, alkenyl group, aryl group, halogen-substituted alkyl group, halide alkenyl group, halogen-substituted aryl group, alkyl-aryl group, aryl-aryl group, or aryl-alkyl group (alkyl group substituted with one or more aryl groups); Each 'a' independently represents an integer between 0 and 3; n represents an integer between 1 and 500; Each 'm' independently represents an integer between 1 and 3. The epoxy resin curing agent according to claim 1, represented as follows:

3. In the compound represented by formula (A2), ring Ar, ring Y ２ , and Y １ At least one of the structural units represented by contains a fluorine atom, and the ring Ar, ring Y ２ , and Y １ The epoxy resin curing agent according to claim 2, wherein the total number of fluorine atoms contained in the structural unit represented by is 3 or more.

4. The epoxy resin curing agent according to claim 2 or 3, wherein in the compound represented by formula (A1), the ratio of fluorine-substituted arylcarbonyloxy groups to hydroxyl groups in X (fluorine-substituted arylcarbonyloxy groups:hydroxyl groups) is 20:80 to 100:

0.

5. The epoxy resin curing agent according to any one of claims 1 to 4, wherein the compound represented by formula (A1) has three or more fluorine atoms in the fluorine-substituted arylcarbonyloxy group.

6. In the compound represented by formula (A1), the fluorine-substituted arylcarbonyloxy group is represented by formula (F1-1): 【Transformation 3】 [In the formula, R ｆ１ and R ｆ２ Each of these independently represents a hydrogen atom or a fluorine atom and R ｆ１ and R ｆ２ At least one of these atoms is a fluorine atom; * indicates the bonding site with the aromatic ring. An epoxy resin curing agent according to any one of claims 1 to 5, wherein the group is represented by .

7. In the group represented by formula (F1-1), R ｆ１ One of them is a fluorine atom, R ｆ１ The other and R ｆ２ The epoxy resin curing agent according to claim 6, wherein the atom is a hydrogen atom or a fluorine atom.

8. The epoxy resin curing agent according to any one of claims 1 to 7, wherein the compound represented by formula (A1) has a fluorine atom content of 20% by mass or more.

9. The epoxy resin curing agent according to claim 1, wherein the compound represented by formula (A1) is obtained by reacting a compound represented by any one of formulas (C1) to (C3) or a salt thereof with the compound represented by formula (B1). 【Chemistry 4】 [In the formulas, FAr represents an optionally substituted aryl group, and in at least a portion of the compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group; Haal represents a chlorine atom, a bromine atom, or an iodine atom; substituents in FAr include halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, and -SO] ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ -NH-COR, -NR-COR, and -N(COR) ２ It is a base chosen from; other symbols are the same as in formula (A1).

10. A method for producing a resin composition containing an epoxy resin curing agent and an epoxy resin, This includes mixing an epoxy resin curing agent and an epoxy resin. The epoxy resin curing agent is formula (A1): 【Transformation 5】 [In the formula, Each Ar ring independently represents an aromatic ring which may have substituents; Each X independently represents an arylcarbonyloxy group or a hydroxyl group which may have substituents, and at least two Xs bonded to different rings Ar are fluorine-substituted arylcarbonyloxy groups; The substituents in the aromatic ring of ring Ar, and the substituents in X, are halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, and -SO. ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ -NH-COR, -NR-COR, and -N(COR) ２ It is a base chosen from; R is (1) a halogen atom, hydroxyl group, amino group, mercapto group, nitro group, cyano group, -R ａ , -OR ｂ , -SR ｂ , -SO ２ R 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 (2) Alkyl groups which may be substituted with a group selected from; (2) Halogen atom, hydroxyl group, amino group, mercapto group, nitro group, cyano group, -R ａ , -OR ｂ , -SR ｂ , -SO ２ R 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 Alkenyl groups which may be substituted with a group selected from (3) halogen atom, hydroxyl group, amino group, mercapto group, nitro group, cyano group, -R ｂ , -OR ｂ , -SR ｂ , -SO ２ R 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 An aryl group which may be substituted with a group selected from; R ａ is a halogen atom, an aryl group, a halogen-substituted aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), or an aryl-aryl group (an aryl group substituted with one or more aryl groups); R ｂ is a halogen atom, alkyl group, alkenyl group, aryl group, halogen-substituted alkyl group, halide alkenyl group, halogen-substituted aryl group, alkyl-aryl group, aryl-aryl group, or aryl-alkyl group (alkyl group substituted with one or more aryl groups); Each Z independently represents a single bond or a divalent group consisting of one or more skeletal atoms selected from carbon, oxygen, nitrogen, and sulfur atoms; n represents an integer between 1 and 500; Each 'm' independently represents an integer between 1 and 3. It contains a compound represented by, A method for producing a resin composition, wherein the compound represented by formula (A1) is produced by reacting a compound represented by any one of formulas (C1) to (C3) or a salt thereof with a compound represented by formula (B1). 【Transformation 6】 [In the formulas, FAr represents an optionally substituted aryl group, and in at least a portion of the compounds represented by formulas (C1) to (C3), FAr is a fluorine-substituted aryl group; Haal represents a chlorine atom, a bromine atom, or an iodine atom; substituents in FAr include halogen atoms, amino groups, mercapto groups, nitro groups, cyano groups, -R, -OR, -SR, and -SO] ２ R, -NHR, -NR ２ , -COR, -CO-OR, -CO-NHR, -CO-NR ２ -NH-COR, -NR-COR, and -N(COR) ２ It is a base chosen from; other symbols are the same as in formula (A1).

11. An epoxy resin curing agent and a resin composition containing epoxy resin, The epoxy resin curing agent is formula (A1): 【Transformation 7】 [In the formula, Each Ar ring independently represents an aromatic ring which may have substituents; Each X independently represents an arylcarbonyloxy group or a hydroxyl group which may have substituents, and at least two Xs bonded to different rings Ar are fluorine-substituted arylcarbonyloxy groups; The substituents on the aromatic ring of ring Ar, and the substituents on X, are groups that can be selected from among the possible groups; R is (1) a halogen atom, hydroxyl group, amino group, mercapto group, nitro group, cyano group, -R ａ , -OR ｂ , -SR ｂ , -SO ２ R 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 (2) Alkyl groups which may be substituted with a group selected from; (2) Halogen atom, hydroxyl group, amino group, mercapto group, nitro group, cyano group, -R ａ , -OR ｂ , -SR ｂ , -SO ２ R 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 Alkenyl groups which may be substituted with a group selected from (3) halogen atom, hydroxyl group, amino group, mercapto group, nitro group, cyano group, -R ｂ , -OR ｂ , -SR ｂ , -SO ２ R 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 An aryl group which may be substituted with a group selected from; R ａ is a halogen atom, an aryl group, a halogen-substituted aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), or an aryl-aryl group (an aryl group substituted with one or more aryl groups); R ｂ is a halogen atom, alkyl group, alkenyl group, aryl group, halogen-substituted alkyl group, halide alkenyl group, halogen-substituted aryl group, alkyl-aryl group, aryl-aryl group, or aryl-alkyl group (alkyl group substituted with one or more aryl groups); Each Z independently represents a single bond or a divalent group consisting of one or more skeletal atoms selected from carbon, oxygen, nitrogen, and sulfur atoms; n represents an integer between 1 and 500; Each 'm' independently represents an integer between 1 and 3. A resin composition containing a compound represented by [formula].

12. The resin composition according to claim 11, further comprising an inorganic filler.

13. The resin composition according to claim 12, wherein the inorganic filler content is 50% by mass or more, when the non-volatile components in the resin composition are considered to be 100% by mass.

14. The resin composition according to any one of claims 11 to 13, wherein the content of the compound represented by formula (A1) is 0.01% by mass or more and 40% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass.

15. Furthermore, it contains thermoplastic resin, The resin composition according to any one of claims 11 to 14, wherein the content of thermoplastic resin is 0.1% by mass or more and 10% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

16. A resin composition according to any one of claims 11 to 15 for forming an insulating layer on a printed wiring board.

17. A resin composition according to any one of claims 11 to 15 for semiconductor chip encapsulation.

18. A cured product of the resin composition according to any one of claims 11 to 17.

19. A sheet-like laminated material containing the resin composition according to any one of claims 11 to 17.

20. A resin sheet having a support and a resin composition layer formed from the resin composition described in any one of claims 11 to 17, provided on the support.

21. A printed circuit board comprising an insulating layer made of a cured resin composition according to any one of claims 11 to 17.

22. A semiconductor device comprising a printed circuit board as described in claim 21.

23. The semiconductor device according to claim 22, which is a fan-out type semiconductor device.

Images