WO2023048209A1

WO2023048209A1 - Resin composition, cured product, resin sheet, insulation layer, electric/electronic component, printed circuit board, and curing agent for epoxy resin

Info

Publication number: WO2023048209A1
Application number: PCT/JP2022/035310
Authority: WO
Inventors: 陽平青野; 隆明渡邊; 紀行木田; 雅翔西村; 正志横木; 裕一矢山
Original assignee: 三菱ケミカル株式会社
Priority date: 2021-09-24
Filing date: 2022-09-22
Publication date: 2023-03-30
Also published as: TW202317700A; CN117957264A

Abstract

This resin composition contains a phenol carbonate resin (A) and an epoxy resin (B), wherein the molar ratio (epoxy groups / terminal hydroxyl groups) of the epoxy groups of the epoxy resin (B) to the terminal hydroxyl groups of the phenol carbonate resin (A) is 3.0-100,000.

Description

Resin compositions, cured products, resin sheets, insulating layers, electrical/electronic components, printed wiring boards, and curing agents for epoxy resins

The present invention relates to a resin composition containing a phenol carbonate resin and an epoxy resin. Furthermore, a cured product of the resin composition, a resin sheet and an insulating layer obtained using the resin composition, an electric/electronic component and a printed wiring board provided with the insulating layer, and a curing for an epoxy resin containing a phenol carbonate resin Regarding agents.

In recent years, multilayer circuit boards used in electrical and electronic equipment have become smaller, lighter, and more functional. and reliability in harsh environments such as in-vehicle use. In addition, the speed and frequency of signals in various electronic devices are increasing, and there is a demand for substrates with low transmission loss. Therefore, the resin composition used for the substrate also has a well-balanced variety of properties such as heat resistance, adhesiveness, water resistance, low dielectric constant, low dielectric loss tangent, mechanical strength, film formability, low linear expansion, and flame resistance. There is a need for improved technology.

A resin composition containing an epoxy resin is known as a resin composition used for multilayer circuit boards. In this case, the epoxy resin is generally used in combination with a curing agent, so various required properties can be achieved. Therefore, it is important to select an appropriate curing system. In particular, when an epoxy resin is used as a lamination material for a multilayer circuit board, it must be able to achieve a low dielectric constant and a low dielectric loss tangent. Active esters are known as typical curing agents among curing agents. In the curing reaction of the epoxy resin and active esters, crosslinking can be achieved without generating polar functional groups such as secondary hydroxyl groups.

On the other hand, Non-Patent Document 1 discloses a method for synthesizing a polycarbonate by reacting an epoxy group of a bifunctional epoxy resin and a carbonate group of diphenyl carbonate. A cured product can be produced without generating a polar functional group such as a secondary hydroxyl group.

In Patent Document 1, a carbonate resin using diphenyl carbonate, tricyclodecanedimethanol and bisphenol F is disclosed as a phenol carbonate resin that can be used as an epoxy resin curing agent and provides a cured product with a low dielectric constant and a low dielectric loss tangent. A synthesized example is described. It also describes that a laminate was obtained by preparing a resin varnish containing the carbonate resin and the epoxy resin, impregnating the resin varnish into a fibrous base material, and curing the resin varnish.

In addition, Patent Document 2 discloses a resin composition containing an epoxy resin, a curing agent, a polycarbonate resin and an inorganic filler.

JP 2019-89965 A JP 2019-35056 A

In recent years, laminates for electrical and electronic circuits have become more complex and smaller in size. Furthermore, materials used, that is, resin compositions containing epoxy resins and curing agents and cured products thereof are also required to have higher heat resistance than ever before.

When the curing agent is an active ester, one equivalent of the ester group reacts with one equivalent of the epoxy group. However, in the case of a carbonate compound, one equivalent of the carbonate group reacts with two equivalents of the epoxy group. In principle, a cured product with a high Tg can be obtained.

The phenol carbonate resin described in Patent Document 1 and the polycarbonate resin described in Patent Document 2 are polymers of monomers having hydroxyl groups at both ends, and the hydroxyl group ends are high. Therefore, by cross-linking an epoxy resin with a phenol carbonate resin or a polycarbonate resin, a cured product having a relatively low dielectric constant and dielectric loss tangent can be obtained. However, since the reaction between the epoxy group and the hydroxyl group generates a secondary hydroxyl group, the dielectric constant and dielectric loss tangent of the resulting cured product may not be lowered.
In addition, the cured products obtained by the techniques described in these patent documents have a problem of moisture resistance due to their high water absorption. In addition, the solvent solubility of the phenol carbonate resin and polycarbonate resin used as curing agents is not sufficiently high, and the moldability of the epoxy resin composition is also insufficient.

An object of the present invention is to provide a resin composition containing a phenol carbonate resin and an epoxy resin that gives a cured product with a low dielectric constant, a low dielectric loss tangent and a high heat resistance. Another object of the present invention is to provide a cured product of the resin composition, and electric/electronic parts and printed wiring boards using the resin composition. Yet another object of the present invention is to provide a curing agent for epoxy resins comprising a phenolic carbonate resin.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that, in a resin composition containing an epoxy resin, a phenol carbonate resin containing a repeating unit having a viscosity average molecular weight within a specific range and having a specific structure is used as a curing agent. The above problem can be solved by blending such that the molar ratio of the epoxy group of the epoxy resin to the terminal hydroxyl group of the phenol carbonate resin (epoxy group/terminal hydroxyl group) is within a specific range. That is, the gist of the present invention resides in the following.

[1]
A resin composition containing a phenol carbonate resin (A) and an epoxy resin (B),
A resin composition wherein the molar ratio of the epoxy groups of the epoxy resin (B) to the terminal hydroxyl groups of the phenol carbonate resin (A) (epoxy group/terminal hydroxyl group) is 3.0 to 100,000.
[2]
The resin composition according to [1], wherein the phenol carbonate resin (A) contains a repeating unit represented by the following formula (1).

(In formula (1), A ¹ and A ² are each independently a group represented by the following formula (2) or (3); X is a direct bond, an optionally substituted carbon a divalent hydrocarbon group of numbers 1 to 15, -O-, -S-, -SO-, -SO ₂ -, -CO-, -OCO- or -COO-; n ¹ and n ² are Each is independently an integer from 1 to 50.)

(In formulas (2) and (3), R is each independently an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, arylalkoxy group, aryl group having 6 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, arylalkenyl group having 8 to 12 carbon atoms, alkynyl group having 2 to 12 carbon atoms, arylalkynyl group having 8 to 12 carbon atoms group, halogen atom, hydroxyl group, carboxy group, sulfone group, amino group, cyano group or nitro group; p is an integer from 0 to 4; q is an integer from 0 to 6; * is a bond position.)
[3]
The resin composition according to [1] or [2], wherein the phenol carbonate resin (A) has a viscosity average molecular weight (Mv) of 500 to 100,000.
[4]
The resin composition according to [2], wherein the phenol carbonate resin (A) further contains a repeating unit represented by the following formula (4).

(In Formula (4), A ³ and A ⁴ are each independently synonymous with A ¹ in Formula (1) above; Y is a direct bond and optionally has a substituent of 6 to 15 divalent aromatic hydrocarbon groups or optionally substituted divalent heteroaromatic hydrocarbon groups having 6 to 15 carbon atoms; n ³ and n ⁴ are each independently 1 to is an integer of 50.)
[5]
The resin composition according to any one of [1] to [4], wherein the phenol carbonate resin (A) has a carbonate equivalent of 100 to 10,000 g/eq.
[6]
The resin composition according to any one of [1] to [5], wherein the weight ratio of the phenol carbonate resin (A) to the epoxy resin (B) is from 0.01 to 100.
[7]
Furthermore, a curing accelerator (C) is included, and the content of the curing accelerator (C) with respect to a total of 100 parts by weight of the phenol carbonate resin (A) and the epoxy resin (B) is 0.001 to 5 parts by weight. The resin composition according to any one of [1] to [6].
[8]
[7], wherein the curing accelerator (C) is at least one selected from the group consisting of phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators. of the resin composition.
[9]
A resin sheet having a resin composition layer formed of the resin composition according to any one of [1] to [8].
[10]
A cured product obtained by curing the resin composition according to any one of [1] to [8].
[11]
An insulating layer obtained by curing the resin composition according to any one of [1] to [8].
[12]
An electric/electronic component comprising the insulating layer of [11].
[13]
A printed wiring board having the insulating layer according to [11].
[14]
An epoxy resin curing agent containing a phenol carbonate resin (A)',
The phenol carbonate resin (A)' is an epoxy resin curing agent having a viscosity average molecular weight (Mv) of 500 to 20,000 and a terminal aromatic hydrocarbon group content of 95% by mass or more.

According to the present invention, it is possible to provide a resin composition containing a phenol carbonate resin and an epoxy resin that gives a cured product with a low dielectric constant, a low dielectric loss tangent and a high heat resistance. Moreover, using the resin composition, it is possible to provide a cured product, an electrical/electronic component, and a printed wiring board. Further, it is possible to provide an epoxy resin curing agent containing a phenol carbonate resin.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description unless it exceeds the gist of the present invention. .
In addition, when the expression "~" is used in this specification, it is used as an expression including numerical values or physical property values before and after it.

In the technical field of the present invention, the term "epoxy resin" includes polymers containing repeating structures and epoxy compounds with a monomolecular structure (i.e., non-polymeric compounds), both of which are expressed as "epoxy resins" and are commercially available. There is something. Also, a mixture of two or more epoxy resins may be simply referred to as an "epoxy resin". Also in this specification, the term "epoxy resin" means any of a polymer containing a repeating structure, an epoxy compound having a monomolecular structure, and a mixture of two or more epoxy resins.

[Resin composition]
The resin composition according to the first embodiment of the present invention is a resin composition containing a phenol carbonate resin (A) and an epoxy resin (B), wherein the epoxy resin for the terminal hydroxyl group of the phenol carbonate resin (A) It is characterized in that the epoxy group molar ratio (epoxy group/terminal hydroxyl group) of (B) is from 3.0 to 100,000.

Although the reason why the resin composition according to the present embodiment provides a cured product with a low dielectric constant, a low dielectric loss tangent and a high heat resistance is not sufficiently clear, it is presumed to be due to the following mechanism.
That is, the resin composition according to the present embodiment has a molar ratio of the epoxy group of the epoxy resin to the terminal hydroxyl group of the phenol carbonate resin (epoxy group/terminal hydroxyl group) within a certain range, so that the resin composition shown in Scheme 1 below at the time of heat curing. It is believed that two equivalents of the epoxy groups of the epoxy resin react with one equivalent of the carbonate groups of the phenol carbonate resin to form a high-density crosslinked structure without generating secondary hydroxyl groups. It is believed that a cured product with a low dielectric constant, a low dielectric loss tangent and a high heat resistance can be obtained by forming more of this crosslinked structure in the cured product.

<Phenol carbonate resin (A)>
In the resin composition according to the present embodiment, the molar ratio of the epoxy group of the epoxy resin (B) to the terminal hydroxyl group of the phenol carbonate resin (A) (epoxy group/terminal hydroxyl group) is 3.0 to 100,000. . The lower limit of the molar ratio is preferably 15 or more, more preferably 30 or more, still more preferably 60 or more, still more preferably 100 or more, particularly preferably 130 or more, particularly preferably 130 or more, in terms of reactivity between the epoxy group and the carbonate group. is preferably 140 or more, most preferably 150 or more. Moreover, the upper limit of the molar ratio is preferably 2,500 or less, more preferably 1,500 or less, and still more preferably 1,000 or less in terms of heat resistance of the cured product.

The phenol carbonate resin (A) in the resin composition according to this embodiment preferably has a viscosity average molecular weight (Mv) of 500 to 100,000. The lower limit of Mv is more preferably 1,000 or more, still more preferably 1,500 or more, and particularly preferably 2,000 or more. By setting the Mv of the phenol carbonate resin (A) to the above lower limit or more, the glass transition temperature (Tg) of the cured product of the resin composition is increased, and the phenol carbonate resin (A) is less likely to cause side reactions during the curing reaction. tend to become On the other hand, the upper limit of Mv of the phenol carbonate resin (A) is more preferably 50,000 or less, still more preferably 20,000 or less, particularly preferably 10,000 or less, and most preferably 8,000. It is below. By setting the Mv of the phenol carbonate resin (A) to the above upper limit or less, the solvent solubility tends to increase.

The viscosity average molecular weight (Mv) of the phenol carbonate resin (A) is determined by dissolving the phenol carbonate resin (A) in methylene chloride and measuring the intrinsic viscosity [η] (unit: dL/g) at 20°C with an Ubbelohde viscometer. It is calculated based on the measured and obtained intrinsic viscosity and Schnell's viscosity formula (the following formula).
[η]=1.23×10 ⁻⁴ Mv ^0.83

The constituent units of the phenol carbonate resin (A) are not particularly limited, but preferably contain repeating units represented by the following formula (1).

In formula (1), A ¹ and A ² are each independently a group represented by formula (2) or (3), X is a direct bond, optionally substituted, and has 1 to 15 carbon atoms a divalent hydrocarbon group of -O-, -S-, -SO-, -SO ₂ -, -CO-, -OCO- or -COO-, wherein n ¹ and n ² are Each is independently an integer from 1 to 50.

At least one of A ¹ and A ² in formula (1) is a group represented by formula (2) from the viewpoint of improving solvent solubility, and both are groups represented by formula (2). It is even more preferable to have The positions of the bonds of the benzene ring in formula (2) and the naphthalene ring in formula (3) are not particularly limited. However, 1 and 4-positions are preferable in that Tg tends to be improved. In addition, in the case of formula (3), 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2 , 6th, 2nd, 7th, etc., but 1st, 2nd, 1,4th, 1,5th, 2,6th, 2,7th in that Tg tends to improve is preferred.

X in formula (1) is a direct bond, an optionally substituted divalent hydrocarbon group having 1 to 15 carbon atoms, —O—, —S—, —SO—, —SO ₂ — , -CO-, -OCO- or -COO-.

Examples of divalent hydrocarbon groups having 1 to 15 carbon atoms include -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CHPh-, -C(CH ₃ )Ph -, -CPh ₂ -, 9,9-fluorenylene group, 1,1-cyclopropylene group, 1,1-cyclobutylene group, 1,1-cyclopentylene group, 1,1-cyclohexylene group, 3,3 ,5-trimethyl-1,1-cyclohexylene group, 1,1-cyclododecylene group, 1,2-ethylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-phenylene group, 1,3-propylene group, 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,3-cyclohexylene group, 1 ,3-phenylene group, 1,4-butylene group, 1,4-cyclohexylene group, 1,4-phenylene group and the like. Substituents which may be present include halogen atoms, hydroxyl groups, carboxy groups, sulfone groups, amino groups, cyano groups, nitro groups, etc., preferably fluorine atoms.

X is preferably a direct bond, —CH ₂ —, —CH(CH ₃ )—, since the degree of freedom of rotation of the aromatic rings in A ¹ and A ² adjacent to X is reduced to increase chemical resistance. , -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CHPh-, -C(CH ₃ )Ph-, -CPh ₂ -, 9,9-fluorenylene group, 1,1-cyclohexylene 3,3,5-trimethyl-1,1-cyclohexylene group, 1,1-cyclododecylene group, —O—, —S—, —SO ₂ —, or —CO—, more preferably a direct bond , —CH ₂ —, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, 9,9-fluorenylene group, 3,3,5-trimethyl-1,1-cyclohexylene group, or 1, It is a 1-cyclododecylene group.

n ¹ and n ² in formula (1) are each independently an integer of 1 to 50, but are preferably 1 to 30 in terms of solvent solubility and compatibility with other resins tending to improve. Yes, more preferably 1-10.

In the above formulas (2) and (3), the substituents R are each independently an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a carbon arylalkoxy groups of 7 to 12 carbon atoms, aryl groups of 6 to 12 carbon atoms, alkenyl groups of 2 to 12 carbon atoms, arylalkenyl groups of 8 to 12 carbon atoms, alkynyl groups of 2 to 12 carbon atoms, and 8 to 12 carbon atoms. 12 arylalkynyl groups, halogen atoms, hydroxyl groups, carboxy groups, sulfone groups, amino groups, cyano groups or nitro groups; p is an integer of 0-4; q is an integer of 0-6. Alkyl groups, alkoxy groups and alkenyl groups are not limited to linear groups, and may have a branched structure or a cyclic structure. Moreover, the position and number of the double bond of the alkenyl group and the triple bond of the alkynyl group are not particularly limited.

Examples of alkyl groups having 1 to 12 carbon atoms include the following. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n- decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group and the like.

Examples of arylalkyl groups having 7 to 12 carbon atoms include the following. Examples include benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, 2-phenylisopropyl group and the like.

Examples of alkoxy groups having 1 to 12 carbon atoms include the following. For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, tert-pentoxy, cyclopentyl thoxy group, n-hexyloxy group, isohexyloxy group, cyclohexyloxy group, n-heptoxy group, cycloheptoxy group, methylcyclohexyloxy group, n-octyloxy group, cyclooctyloxy group, n-nonyloxy group, 3,3,5-trimethyl cyclohexyloxy group, n-decyloxy group, cyclodecyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclododecyloxy group and the like.

Examples of the arylalkyloxy group having 7 to 12 carbon atoms include the following. Examples include benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, naphthylmethoxy, phenethyloxy, 2-phenylisopropoxy and the like.

Examples of aryl groups having 6 to 12 carbon atoms include the following. For example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, xylyl group, n-propylphenyl group, isopropylphenyl group, mesityl group, ethynylphenyl group, naphthyl group, vinylnaphthyl group etc.

Examples of alkenyl groups having 2 to 12 carbon atoms include the following. For example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butandienyl group, cyclohexenyl group, cyclohexadienyl group groups, cinnamyl groups, naphthylvinyl groups, and the like.

Examples of arylalkenyl groups having 8 to 12 carbon atoms include the following. Examples include a styryl group, a cinnamyl group, a naphthylvinyl group, and the like.

Examples of alkynyl groups having 2 to 12 carbon atoms include the following. Examples include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group and the like.

Examples of arylalkynyl groups having 8 to 12 carbon atoms include the following. For example, phenylethynyl group, naphthylethynyl group and the like.

The substituent R is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of improving heat resistance due to better molecular packing. , and more preferably a methyl group.

p represents an integer of 0 to 4, and is preferably 0 to 2 from the viewpoint of improving solvent solubility and increasing the glass transition temperature (Tg) of the cured product. When p is 1 or 2, the dielectric loss tangent tends to decrease, which is particularly preferred.

q represents an integer of 0 to 6, and is preferably 0 to 2 from the viewpoint of improving solvent solubility and increasing the glass transition temperature (Tg) of the cured product. When q is 1 or 2, the dielectric loss tangent tends to decrease, which is particularly preferred.

The substitution position of R with respect to the aromatic ring in formulas (2) and (3) is not particularly limited, but a group represented by the following formula tends to reduce the dielectric loss tangent and is particularly preferred.

When the phenol carbonate resin (A) contains the repeating unit represented by the above formula (1), the proportion of the repeating unit represented by the formula (1) is not particularly limited, but the phenol carbonate resin (A) is composed of 80 mol % or more, more preferably 90 mol % or more, still more preferably 95 mol % or more, and particularly preferably 100 mol %, of all the structural units.
The phenol carbonate resin (A) is a copolymer containing repeating units with a plurality of different structures, regardless of whether the repeating unit consists of repeating units with a single structure or the structure represented by formula (1). May be combined. When the phenol carbonate resin (A) is a copolymer, the phenol carbonate resin (A) is represented by the following formula having a structure different from the repeating unit represented by the formula (1) and the repeating unit represented by the formula (1) More preferably, it contains a repeating unit represented by (4).

In formula (4), A ³ and A ⁴ are each independently synonymous with A ¹ above; Y is a direct bond or an optionally substituted divalent aromatic having 6 to 15 carbon atoms a hydrocarbon group or an optionally substituted divalent heteroaromatic hydrocarbon group having 6 to 15 carbon atoms; n ³ and n ⁴ are each independently an integer of 1 to 50 (provided that , A ³ , A ⁴ , n ³ and n ⁴ completely match the combination of A ¹ , A ² , n ¹ and n ² in formula (1)).

As an optionally substituted divalent aromatic hydrocarbon group having 6 to 15 carbon atoms or an optionally substituted divalent heteroaromatic hydrocarbon group having 6 to 15 carbon atoms, , phenylene group, naphthylene group, anthracenylene group, 2,7-fluorenylene group, 9,9-fluorenylene group, pyridylene group, thienylene group, furanylene group and the like. Among them, the 9,9-fluorenylene group is preferred because it tends to increase the Tg and decrease the dielectric loss tangent.

n ³ and n ⁴ are each independently an integer of 1 to 50, preferably 1 to 30, more preferably 1, in that solvent solubility and compatibility with other resins tend to be improved. ~10.

The carbonate equivalent of the phenol carbonate resin (A) is not particularly limited, but is preferably 100 g/eq or more, more preferably 110 g/eq or more, still more preferably 120 g/eq or more, and preferably 10,000 g/eq or less. It is preferably 5,000 g/eq or less, more preferably 1,000 g/eq or less, and particularly preferably 500 g/eq or less. When the carbonate equivalent of the phenol carbonate resin (A) is at least the above lower limit, curing shrinkage tends to decrease, and impact resistance and weather resistance of the cured product of the resin composition tend to improve. Further, by setting the carbonate equivalent weight of the phenol carbonate resin (A) to the above upper limit or less, the crosslink density of the cured product of the resin composition tends to increase and the Tg tends to improve.

The amount of terminal hydroxyl groups in the phenol carbonate resin (A) is not particularly limited, but is preferably 10 ppm or more, more preferably 50 ppm or more, still more preferably 100 ppm or more, and preferably 5,000 ppm or less, more preferably 1,000 ppm. 300 ppm or less, more preferably 300 ppm or less. When the amount of terminal hydroxyl groups of the phenol carbonate resin (A) is at least the above lower limit, a sufficient curing rate can be obtained, and when it is at most the above upper limit, the dielectric constant and dielectric loss tangent of the cured product can be reduced. The terminal hydroxyl group content of the phenol carbonate resin (A) can be measured by the colorimetric method used in the examples described later.

The glass transition temperature (Tg) of the phenol carbonate resin (A) is not particularly limited, but is preferably 70°C or higher, more preferably 100°C or higher, still more preferably 120°C or higher, and usually 250°C. or less, and may be 200° C. or less or 180° C. or less. The higher the glass transition temperature of the phenol carbonate resin (A), the higher the Tg of the cured product.

A commercially available phenol carbonate resin (A) may be used. Moreover, when manufacturing, it can manufacture by the conventionally well-known polymerization method.

The polymerization method may be either a solution polymerization method using phosgene or a melt polymerization method in which a diester carbonate and a hydroxy compound are reacted.
Among them, in the presence of a polymerization catalyst, a dihydroxy compound having a structure represented by the above formula (1) and other dihydroxy compounds used as necessary, such as a dihydroxy compound having a structure represented by formula (4) Melt polymerization methods in which the compound is reacted with a diester carbonate are preferred.

As the carbonic acid diesters used in the melt polymerization method, one kind may be used alone, or two or more kinds may be mixed and used in an arbitrary combination and ratio. Carbonic acid diesters include, for example, aromatic carbonates and aliphatic carbonates. Examples of aromatic carbonates include diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate; and the like. Examples of aliphatic carbonates include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate.
Among these, aromatic carbonates are preferred, diphenyl carbonate or substituted diphenyl carbonate is more preferred, and diphenyl carbonate is particularly preferred.

In the melt polymerization method described above, the diester carbonate is preferably used in a molar ratio of 0.90 to 1.10 with respect to all dihydroxy compounds including the dihydroxy compound represented by formula (1) used in the reaction. It is more preferred to use a molar ratio of 96-1.04.
If the molar ratio of the diester carbonate used in the melt polymerization method is too small, the number of terminal hydroxyl groups in the produced polycarbonate resin increases, the thermal stability of the polymer deteriorates, and there is a tendency that the desired high molecular weight product cannot be obtained. be. On the other hand, if the molar ratio of the diester carbonate used is excessively large, the rate of the transesterification reaction will decrease under the same polymerization conditions, making it difficult to produce the phenol carbonate resin (A) having the desired viscosity average molecular weight. . Furthermore, the amount of carbonic acid diester remaining in the produced phenol carbonate resin (A) tends to increase, and the residual carbonic acid diester tends to cause odor during molding or molded products.

As described above, in the method for producing the phenol carbonate resin (A) used in the present embodiment, it is preferable to use an aromatic carbonate such as diphenyl carbonate as the carbonic acid diester. In this case, the phenol carbonate resin (A) to be produced is an aromatic hydrocarbon exemplified by the terminal group represented by the following formula (5) (hereinafter sometimes referred to as "phenyl group terminal") system terminal group (hereinafter sometimes referred to as "aromatic hydrocarbon group terminal"). The ratio (T1/T2) of the number of aromatic hydrocarbon group terminals (T1) to the total number of terminals (T2) of the phenol carbonate resin (A) is preferably 0.20 or more, more preferably 0.25 or more, It is more preferably 0.30 or more, and usually 1.00 or less.
If the ratio (T1/T2) of the number of aromatic hydrocarbon group terminals (T1) to the total number of terminals (T2) is excessively small, coloration increases under conditions where the polymerization reaction temperature, injection molding temperature, etc. are high. There is fear.

The method for adjusting the ratio (T1/T2) of the number of aromatic hydrocarbon group terminals (T1) to the total number of terminals (T2) of the phenol carbonate resin within the above range is not particularly limited. A method of adjusting the carbonic acid diester amount ratio to the compound within the range in which the desired high molecular weight is obtained; and the like;

The ratio (T1/T2) of the number of aromatic hydrocarbon group terminals (T1) in the phenol carbonate resin to the total number of terminals (T2) was measured by an NMR spectrometer using heavy chloroform to which TMS was added as a measurement solvent. It can be calculated by measuring ¹ H-NMR spectrum.

Alkali metal compounds and/or alkaline earth metal compounds are used as polymerization catalysts (transesterification catalysts) in melt polymerization. Basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used together with the alkali metal compounds and/or alkaline earth metal compounds. Particular preference is given to using only alkali metal compounds and/or alkaline earth metal compounds.

Examples of alkali metal compounds used as polymerization catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, and potassium carbonate. , lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, Cesium borohydride, sodium phenylborohydride, potassium phenylide, lithium borophenylide, cesium phenylide, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, hydrogen phosphate dipotassium, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates of sodium, potassium, lithium, cesium, phenolate, disodium salt, dipotassium salt, dilithium salt, dicesium salt of bisphenol A and the like.

Examples of alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, and magnesium carbonate. , strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like. One of these alkali metal compounds and/or alkaline earth metal compounds may be used alone, or two or more thereof may be used in any combination and ratio.

Specific examples of basic boron compounds used in combination with alkali metal compounds and/or alkaline earth metal compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenyl Sodium salts, potassium salts, lithium salts of boron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. , calcium salts, barium salts, magnesium salts, strontium salts and the like.

Examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

Examples of basic ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide and the like.

Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

Basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used alone, or two or more may be used in any combination and ratio. .

When an alkali metal compound and/or an alkaline earth metal compound is used, the amount of the polymerization catalyst used is usually in the range of 0.1 to 100 μmol in terms of metal, per 1 mol of all the dihydroxy compounds used in the reaction. is preferably within the range of 0.5 to 50 μmol, more preferably within the range of 1 to 25 μmol. If the amount of the polymerization catalyst used is too small, there is a tendency that the polymerization activity required to produce a polycarbonate resin with a desired molecular weight cannot be obtained. On the other hand, if the amount of polymerization catalyst used is excessively large, the hue of the phenol carbonate resin obtained will deteriorate, and by-products will be generated, resulting in a decrease in fluidity and a large amount of gel formation. Phenolic carbonate resins tend to be difficult to manufacture.

In the production of the phenol carbonate resin used in the present embodiment, the dihydroxy compound having the structure represented by the structural formula (1) may be supplied as a solid, or may be supplied in a molten state after being heated. Alternatively, it may be supplied as an aqueous solution.

In the present embodiment, a method of reacting a dihydroxy compound having a structure represented by formula (1), an alicyclic dihydroxy compound, and optionally other dihydroxy compounds with a diester carbonate in the presence of a polymerization catalyst. is usually carried out in a multistage process of two or more stages.
Specifically, the first stage reaction is carried out at a temperature of 140 to 220° C., preferably 150 to 200° C., for 0.1 to 10 hours, preferably 0.5 to 3 hours. From the second stage onwards, the pressure in the reaction system is gradually lowered from the pressure in the first stage while the reaction temperature is raised. Specifically, the polycondensation reaction is carried out at a reaction system pressure of 200 Pa or less and a temperature range of 210 to 280°C.
In reducing the pressure in the polycondensation reaction, it is important to control the balance between the temperature and the pressure in the reaction system. In particular, if either the temperature or the pressure is rapidly changed excessively, unreacted monomer may be distilled off, the molar ratio of the diester carbonate to the dihydroxy compound may be changed, and the degree of polymerization may be lowered.
The form of the reaction may be batch type, continuous type, or a combination of batch type and continuous type.

[Epoxy resin (B)]
Epoxy resin (B) is not particularly limited, but bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol C type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene. type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy Resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins , cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, and the like. Among these, the epoxy resin (B) is preferably an aromatic epoxy resin, more preferably an aromatic epoxy resin that is liquid at 20°C. One type of epoxy resin may be used alone, or two or more types may be used together in any combination and ratio.

The weight ratio of the phenol carbonate resin (A) to the epoxy resin (B) is not particularly limited, but is usually 0.01 or more, preferably 0.1 or more, and more preferably 0.2 or more from the viewpoint of reactivity. , more preferably 0.4 or more. The weight ratio is preferably 100 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less from the viewpoint of storage stability.

[Curing accelerator (C)]
The resin composition according to this embodiment may contain a curing accelerator (C). The curing accelerator (C) is not particularly limited, but includes phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among these, the curing accelerator (C) is preferably a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator or a metal curing accelerator, more preferably an amine curing accelerator. . The curing accelerator (C) may be used singly, or two or more thereof may be used in any combination and ratio.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1, 8-diazabicyclo(5,4,0)-undecene and the like can be mentioned, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred, and 4-dimethylaminopyridine being more preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; organocopper complexes such as copper (II) acetylacetonate; zinc (II) acetylacetonate; organic zinc complexes such as iron (III) acetylacetonate; organic iron complexes such as nickel (II) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Although the content of the curing accelerator (C) is not particularly limited, it is preferably 0.001 parts by weight or more with respect to a total of 100 parts by weight of the phenol carbonate resin (A) and the epoxy resin (B). From the viewpoint of properties, it is more preferably 0.01 parts by weight or more, and still more preferably 0.1 parts by weight or more. In addition, it is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 1 part by weight or less from the viewpoint of storage stability of the resin composition.

[Curing agent]
The resin composition according to the present embodiment may contain a curing agent (hereinafter referred to as "other curing agent") other than the phenol carbonate resin (A) within a range that does not impair the effects of the present invention. Other curing agents are not particularly limited, but phenolic curing agents, naphthol curing agents, amide curing agents, active ester curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, and Phenol carbonate resins other than phenol carbonate resin (A), etc. are mentioned. Among these, active ester curing agents, phenolic curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents are preferred, and active ester curing agents, phenolic curing agents and carbodiimide are more preferred. system curing agent. Other curing agents may be used alone, or two or more of them may be used in any combination and ratio.

[solvent]
The resin composition according to the present embodiment may be diluted by blending a solvent in order to appropriately adjust the viscosity of the resin composition during handling during coating film formation. In the resin composition according to the present embodiment, the solvent is used to ensure handleability and workability in molding the resin composition, and there is no particular limitation on the amount used. In the present specification, the term "solvent" and the term "solvent" are used separately according to the mode of use, but the same type or different types may be used independently.

Solvents that may be contained in the resin composition according to the present embodiment include, for example, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, ketones such as cyclohexanone; esters such as ethyl acetate; glycol ethers such as ethylene glycol monomethyl ether; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; alcohols such as methanol and ethanol; alkanes such as hexane and cyclohexane; aromatics such as toluene and xylene; The solvents listed above may be used alone, or two or more of them may be mixed and used in any combination and ratio.

[Other ingredients]
The resin composition according to the present embodiment contains components other than those listed above (hereinafter sometimes referred to as "other components") for the purpose of further improving its functionality. You can Such other components include thermosetting resins other than epoxy resins, photo-curing resins, curing accelerators (excluding those included in "curing agents"), UV inhibitors, antioxidants, Coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, ion trapping agents, inorganic fillers, organic fillers, and the like.

[Cured product of resin composition]
The method of curing the resin composition when curing the resin composition according to the present embodiment to obtain a cured product varies depending on the ingredients and the amount of the resin composition, but is usually 60 to 60 at 80 to 280 ° C. A heating condition of 360 minutes is mentioned. This heating is preferably a two-stage treatment of primary heating at 80 to 160° C. for 10 to 90 minutes and secondary heating at 120 to 200° C. for 60 to 150 minutes. It is preferable to further perform tertiary heating at 150 to 280° C. for 60 to 120 minutes in a blended system that exceeds the secondary heating temperature. Performing secondary heating and tertiary heating in this way is preferable from the viewpoint of reducing poor curing and residual solvent.

[Use of resin composition]
The resin composition according to this embodiment can form a cured product having a low dielectric constant, a low dielectric loss tangent and a high heat resistance. Therefore, the resin composition according to the present embodiment can be suitably used for electrical/electronic parts, insulating layers of printed wiring boards and the like; semiconductor sealing materials; and the like.

[Resin sheet]
A second embodiment of the present invention is a resin sheet having a resin composition layer formed of the resin composition according to the first embodiment of the present invention.
The resin sheet according to the present embodiment can form an insulating layer made of a cured product of the resin composition by curing the resin composition layer. Therefore, the resin sheet according to the present embodiment can be suitably used as a resin sheet for forming insulating layers of electronic/electronic parts, printed wiring boards, and the like.

Although the thickness of the resin composition layer is not particularly limited, it is usually 50 μm or less, and from the viewpoint of thinning the printed wiring board, it is preferably 25 μm or less, more preferably 15 μm or less, still more preferably 13 μm or less, and particularly preferably 10 μm. Below, it is most preferably 8 μm or less, and usually 1.0 μm or more, and may be 1.5 μm or more or 2.0 μm or more.

The resin sheet according to the present embodiment may be a sheet consisting only of a resin composition layer, or may be a sheet having a resin composition layer formed on a support. When the resin sheet according to the present embodiment is used to form an insulating layer for an electronic/electronic component, printed wiring board, or the like, the support may be removed from the insulating layer by peeling after the insulating layer is formed. It may be used as part of a wiring board or the like.

Examples of the support include plastic films, metal foils, release papers, etc. Plastic films and metal foils are preferred.
Materials constituting the plastic film include, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polycarbonates; acrylic resins such as polymethyl methacrylate (PMMA); cyclic polyolefins; triacetyl cellulose (TAC); polyether sulfide; polyether ketone; polyimide; and the like, preferably polyethylene terephthalate or polyethylene naphthalate.
Examples of the metal foil include copper foil, aluminum foil, copper alloy foil, aluminum alloy foil and the like, preferably copper foil.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer. Also, a release layer may be formed on the surface of the support that is to be bonded to the resin composition layer. As the mold release agent, it is possible to appropriately select and use known mold release agents such as alkyd resins, polyolefin resins, urethane resins, silicone resins, and the like.

Although the thickness of the support is not particularly limited, it is preferably 5 to 75 μm, more preferably 10 to 60 μm. When a release layer is provided on the support, the thickness of the entire support including the release layer is preferably within the above range.

The resin sheet according to this embodiment may contain other layers as necessary. Other layers include, for example, protective films. The protective film is usually provided on the surface of the resin composition layer that is not in contact with the support. The thickness of the protective film is not particularly limited, and is, for example, 1 to 40 μm.

The method for producing the resin sheet is not particularly limited. For example, a resin varnish obtained by dissolving a resin composition in an organic solvent is applied onto a support using a die coater or the like, and dried to form a resin composition layer. method.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; carbitols such as cellosolve and butyl carbitol; toluene and xylene. dimethylformamide (DMF), N-methylpyrrolidone (NMP) and other amide solvents; An organic solvent may be used individually by 1 type, and may mix and use 2 or more types by arbitrary combinations and ratios.

Drying may be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30 to 60% by mass of organic solvent, the resin composition layer is formed by drying at 50 to 150° C. for 3 to 10 minutes. can do.

[Curing agent for epoxy resin]
The epoxy resin curing agent according to the third embodiment of the present invention contains a phenol carbonate resin (A)'. The epoxy resin curing agent according to the present embodiment can be used as a curing agent for curing the epoxy resin (B) in the first embodiment of the present invention. It can also be used as a curing agent for curing epoxy resins. By using the epoxy resin curing agent according to the present embodiment, it is possible to obtain an epoxy resin cured product having a low dielectric constant, a low dielectric loss tangent and a high heat resistance.
In addition, the epoxy resin curing agent according to the present embodiment includes other components, such as a curing accelerator which is an optional component of the resin composition according to the first embodiment of the present invention, as long as the effect of the present invention is not impaired. A solvent or the like may be contained.

<Phenol carbonate resin (A)'>
The phenol carbonate resin (A)' is obtained by changing the viscosity average molecular weight (Mv) and the amount of terminal aromatic hydrocarbon groups of the phenol carbonate resin (A) in the first embodiment of the present invention to specific ranges. That is, elements other than the Mv range and the terminal aromatic hydrocarbon group amount range of the phenol carbonate resin (A) '(e.g., Mv measurement method, structural unit, carbonate equivalent, terminal hydroxyl group amount, glass transition temperature, and production method, etc.) are the same as those for the phenol carbonate resin (A), including preferred embodiments thereof. Therefore, the elements other than the Mv range and the terminal aromatic hydrocarbon group amount range of the phenol carbonate resin (A)' are as described in the above item <Phenol carbonate resin (A)>, and the description of the item to invoke.

The phenol carbonate resin (A)' has a viscosity average molecular weight (Mv) of 500 to 20,000. The lower limit of Mv is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. By setting the Mv of the phenol carbonate resin (A)' to the above lower limit or more, the glass transition temperature (Tg) of the cured product of the resin composition increases, and the phenol carbonate resin (A)' does not cause a side reaction during the curing reaction. It tends to be harder to wake up. On the other hand, the upper limit of Mv of the phenol carbonate resin (A)' is preferably 10,000 or less, more preferably 8,000 or less. By setting the Mv of the phenol carbonate resin (A)' to the above upper limit or less, the solvent solubility tends to increase.

The lower limit of the amount of terminal aromatic hydrocarbon groups in the phenol carbonate resin (A)', that is, the amount of aromatic hydrocarbon groups at the ends of the molecular chains, is not particularly limited, but is 95.0% by mass, preferably 96.0% by mass. Above, more preferably 97.0% by mass or more, still more preferably 98.0% by mass or more, particularly preferably 99.0% by mass or more. Most preferably, it is 99.5% by mass or more. By setting the amount of the terminal aromatic hydrocarbon group of the phenol carbonate resin (A)' to the above lower limit or more, the dielectric loss tangent of the cured product of the resin composition tends to decrease. The upper limit of the amount of terminal aromatic hydrocarbon groups in the phenol carbonate resin (A)' is not particularly limited, and is usually 100% by mass or less.

The amount of terminal aromatic hydrocarbon groups of phenol carbonate resin (A)' is calculated by subtracting the amount of terminal hydroxyl groups from the total amount of terminal groups of phenol carbonate resin (A)'.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited by the following examples. Various production conditions and values of evaluation results in the following examples have the meaning of preferable upper or lower limits in the embodiments of the present invention. , the range defined by the values in the following examples or a combination of the values in the examples.

[Evaluation method of physical properties and characteristics]
In the following examples, physical properties and characteristics were evaluated by the methods described in 1) to 8) below.

1) Viscosity average molecular weight (Mv) of phenol carbonate resin
The viscosity average molecular weight (Mv) of the phenol carbonate resin is measured using methylene chloride as a solvent and using an Ubbelohde viscosity tube (manufactured by Moritomo Rika Kogyo Co., Ltd.) at 20 ° C. The intrinsic viscosity (intrinsic viscosity) [η] (unit: dL/ g) was determined and calculated from the Schnell viscosity formula (the following formula).
[η]=1.23×10 ⁻⁴ Mv ^0.83

2) Terminal hydroxyl group content of phenol carbonate resin The terminal hydroxyl group content of the phenol carbonate resin was measured by a colorimetric method using titanium tetrachloride/acetic acid. Specifically, it was measured by the method described below. As a result, the amount of terminal hydroxyl groups measured by the colorimetric method using titanium tetrachloride/acetic acid in the examples can be measured.

(a) Preparation of 5 v/v % acetic acid solution 50 mL of acetic acid was added to a 1,000 mL volumetric flask, and the contents were made up with methylene chloride and mixed to prepare a 5 v/v % acetic acid solution.

(b) Preparation of titanium tetrachloride solution Put 90 mL of methylene chloride in a 300 mL flask with a graduated cylinder, add 10 mL of a 5 v / v% acetic acid solution with a graduated cylinder, add a stirrer and stir with a magnetic stirrer to 5 mL. A titanium tetrachloride solution was prepared by slowly adding 2.5 mL of titanium tetrachloride solution and 2.0 mL of methanol with a graduated pipette.

(c) Preparation of Calibration Curve Sample A methylene chloride solution was prepared so that the terminal hydroxyl group content of the starting dihydroxy compound was 10 ppm by weight, and 0, 3, and 5 mL were added to each 25-mL volumetric flask. Subsequently, 5 mL each of 5 v/v % acetic acid and 10 mL each of titanium tetrachloride solution were added. Each was made up to volume with methylene chloride and mixed well.

(d) Preparation of calibration curve The absorbance of each prepared calibration sample was measured at a detection wavelength of 546 nm. The absorbance obtained was plotted against the concentration of the standard curve samples. The reciprocal of this slope was used as a factor.

(e) Preparation of Measurement Sample and Absorbance Measurement 0.2 g of a polycarbonate resin composition and 5 mL of methylene chloride were added to a 25 mL volumetric flask and dissolved. Next, 5 mL of 5 v/v % acetic acid solution and 10 mL of titanium tetrachloride solution were added, and the mixture was made up with methylene chloride and mixed well. The absorbance of the solution thus prepared was measured at a detection wavelength of 546 nm.

(f) Calculation of terminal hydroxyl group amount The terminal hydroxyl group amount in the polycarbonate resin composition was calculated by dividing the product of the measured absorbance and the factor by the concentration of the measurement sample.
In the case of a polycarbonate resin composition in which the starting material dihydroxy compound has a plurality of structures, a sample obtained by mixing the corresponding starting material dihydroxy compound according to the copolymerization ratio is prepared at a minimum of three concentrations, and from the data of the three or more points, After drawing a calibration curve, the amount of terminal hydroxyl groups is measured. Also, the detection wavelength is assumed to be 546 nm.

3) Amount of terminal aromatic hydrocarbon groups of phenol carbonate resin The amount of terminal aromatic hydrocarbon groups of phenol carbonate resin is, as shown in the following formula, the amount of terminal hydroxyl groups measured by the method described above from the total amount of terminal groups of phenol carbonate resin. Calculated by subtracting the amount.
Terminal aromatic hydrocarbon group amount (mass%) of phenol carbonate resin = 100 - {terminal hydroxyl group amount (mass%) of phenol carbonate resin}

4) Weight average molecular weight (Mw) and number average molecular weight (Mn) of epoxy resin
TSK Standard Polystyrene F-128 (Mw: 1,090,000, Mn: 1,030,000), F -10 (Mw: 106,000, Mn: 103,000), F-4 (Mw: 43,000, Mn: 42,700), F-2 (Mw: 17,200, Mn: 16,900), Calibration using A-5000 (Mw: 6,400, Mn: 6,100), A-2500 (Mw: 2,800, Mn: 2,700), A-300 (Mw: 453, Mn: 387) A line was drawn and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured as polystyrene conversion values.

Column: "TSKGEL SuperHM-H + H5000 + H4000 + H3000 + H2000" manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Flow rate: 0.5 mL/min
Detection: UV (wavelength 254 nm)
Temperature: 40°C
Sample concentration: 0.1% by weight
Injection volume: 10 μL

5) Epoxy equivalent Measured according to JIS K 7236 and expressed as a solid content conversion value.

6) Molar ratio of epoxy group of epoxy resin to terminal hydroxyl group of phenol carbonate resin (epoxy group/terminal hydroxyl group)
It was calculated according to the following formula.
Epoxy group/terminal hydroxyl group=(weight of epoxy resin/epoxy equivalent)/(weight of phenol carbonate resin×amount of terminal hydroxyl group of phenol carbonate resin/17.0)

7) Heat resistance of cured product: glass transition temperature (Tg)
The cured epoxy resin films (thickness: about 50 μm) obtained in Examples 1 to 7 were heated to 30 to 250° C. at a rate of 10° C./min using “DSC7020” manufactured by SII Nano Technology Co., Ltd. was used to measure the glass transition temperature. The glass transition temperature referred to here was measured based on the "middle point glass transition temperature: Tmg" described in JIS K 7121 "Method for measuring transition temperature of plastics".

8) Dielectric properties The cured epoxy resin films obtained in Examples 1 to 7 were cut into test pieces having a width of 2 mm and a length of 80 mm. Relative permittivity (εr) and dielectric loss tangent (tan δ) were measured at 1 GHz and 10 GHz at a measurement temperature of 23°C.

[Components of resin composition]
Various components used in the resin compositions of the following examples are as follows.

[Low molecular weight epoxy resin]
(B-1): Trade name “jER 828US” manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent 185 g/equivalent)

[Polymer epoxy resin]
(B-2): Mitsubishi Chemical Corporation, trade name "YL7891T30", Mn: 10,000, Mw: 30,000, epoxy equivalent: 6,000 g/equivalent, 30 wt% toluene solution of high molecular weight epoxy resin

[Phenol carbonate resin (A)]
(A-1): 2,2-bis(4-hydroxyphenyl)propane-type phenol carbonate resin (n=7)
(A-2): 2,2-bis(4-hydroxy-3-methylphenyl)propane-type phenol carbonate resin (n=5)
(A-3): 9,9-bis(4-hydroxy-3-methylphenyl)fluorene-type phenol carbonate resin (n=4)
(A-4): Copolymerized phenol carbonate resin of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 2,2-bis(4-hydroxy-3-methylphenyl)propane (n = 9)
(A-5): Copolymerized phenol carbonate resin of 1,1-bi-2-naphthol and 4,4-(3,3,5-trimethyl-1,1-cyclohexanediyl)bisphenol (n=2)
(A-6): Copolymerized phenol carbonate resin of 1,1-bi-2-naphthol and 4,4-(3,3,5-trimethyl-1,1-cyclohexanediyl)bisphenol (n=2)
(A-7): 2,2-bis(4-hydroxyphenyl)propane-type phenol carbonate resin (n=7)
The above (A-1) to (A-7) were synthesized in Synthesis Examples 1 to 7 below, respectively, and have the following repeating units.

[Curing accelerator]
(C-1): N,N'-dimethylaminopyridine (DMAP), 5 wt% toluene solution

[Leveling agent]
S-651: Fluorosurfactant (nonionic type) manufactured by AGC Seimi Chemical Co., Ltd.

[Synthesis of phenol carbonate resin (A)]
[Synthesis Example 1: Synthesis of phenol carbonate resin (A-1)]
116.71 g of 2,2-bis(4-hydroxyphenyl)propane (BPA) (approx. 5112 mol), 137.99 g (about 0.6442 mol) of diphenyl carbonate (DPC), and a 0.04% by mass aqueous solution of cesium carbonate as a catalyst were added so that the amount of cesium carbonate was 1 μmol per 1 mol of the dihydroxy compound to prepare a raw material mixture. bottom.

Next, the pressure inside the glass reactor was reduced to about 100 Pa (0.75 Torr), and then the pressure was restored to atmospheric pressure with nitrogen, which was repeated three times to replace the inside of the reactor with nitrogen. After purging with nitrogen, the external temperature of the reactor was set to 220° C., and the internal temperature of the reactor was gradually increased to dissolve the raw material mixture. The stirrer was then rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.0 kPa (760 Torr) in absolute pressure over 40 minutes while distilling off the phenol that was a by-product of the oligomerization reaction of the dihydroxy compound and DPC that took place inside the reactor. The pressure was reduced to 3 kPa (100 Torr).

Subsequently, the pressure in the reactor was maintained at 13.3 kPa, and transesterification was carried out for 80 minutes while further distilling off phenol. Thereafter, the internal pressure of the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in terms of absolute pressure over 40 minutes to remove distilled phenol out of the system. Furthermore, the absolute pressure in the reactor was reduced to 70 Pa (about 0.5 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the stirrer of the reactor reached a predetermined stirring power.

Then, after restoring the pressure inside the reactor to 101.3 kPa in absolute pressure with nitrogen, the phenol carbonate resin (A-1) was extracted from the reactor into an aluminum container, and the solidified (A-1) was pulverized. Table 1 shows the Mv, terminal hydroxyl group content, terminal aromatic hydrocarbon group content, carbonate equivalent weight, and Tg of the phenol carbonate resin (A-1).

[Synthesis Example 2: Synthesis of phenol carbonate resin (A-2)]
116.71 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) was added to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure regulator. (about 0.4553 mol), 146.30 g (about 0.6829 mol) of diphenyl carbonate (DPC), and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst were added so that the cesium carbonate was 3 μmol per 1 mol of the dihydroxy compound. A raw material mixture was prepared.

Subsequently, the pressure in the reactor was maintained at 13.3 kPa, and transesterification was carried out for 80 minutes while further distilling off phenol. After that, the reactor external temperature was raised to 260° C., and the reactor internal pressure was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 40 minutes to remove the distilled phenol out of the system. . Furthermore, the absolute pressure in the reactor was reduced to 70 Pa (about 0.5 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the stirrer of the reactor reached a predetermined stirring power.

Next, after restoring the pressure inside the reactor to 101.3 kPa in absolute pressure with nitrogen, the phenol carbonate resin (A-2) was extracted from the reactor into an aluminum container, and the solidified (A-2) was pulverized. Table 1 shows the Mv, terminal hydroxyl group content, terminal aromatic hydrocarbon group content, carbonate equivalent weight, and Tg of the phenol carbonate resin (A-2).

[Synthesis Example 3: Synthesis of phenol carbonate resin (A-3)]
116.71 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCF) was added to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure regulator. (approximately 0.3083 mol), 99.08 g (approximately 0.4625 mol) of DPC, and a 4% by mass aqueous solution of cesium carbonate as a catalyst were added so that the amount of cesium carbonate was 100 μmol per 1 mol of all dihydroxy compounds to prepare a raw material mixture. Except for this, the method described in Synthesis Example 2 was used.

Table 1 shows the Mv, terminal hydroxyl group content, terminal aromatic hydrocarbon group content, carbonate equivalent weight, and Tg of the obtained phenol carbonate resin (A-3).

[Synthesis Example 4: Synthesis of phenol carbonate resin (A-4)]
80.41 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCF) was added to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure regulator. (about 0.2124 mol), 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) 36.30 g (about 0.1416 mol), DPC 113.77 g (about 0.5311 mol), and as a catalyst The method described in Example 2 was followed except that a 4% by mass aqueous solution of cesium carbonate was added so that the amount of cesium carbonate was 60 μmol per 1 mol of all dihydroxy compounds to prepare a raw material mixture.

Table 1 shows the Mv, terminal hydroxyl group content, terminal aromatic hydrocarbon group content, carbonate equivalent weight, and Tg of the obtained phenol carbonate resin (A-4).

[Synthesis Example 5: Synthesis of phenol carbonate resin (A-5)]
4,4′-(3,3,5-trimethylcyclohexylidene)bisphenol (BP-TMC) was added to a 150 mL glass reactor equipped with a reactor agitator, a reactor heating device, and a reactor pressure regulator. ) 60.71 g (about 0.196 mol), 1,1′-bi-2-naphthol (BN) 56.00 g (about 0.196 mol), DPC 108.93 g (about 0.5085 mol), and cesium carbonate as a catalyst The method described in Example 2 was followed except that a 4% by mass aqueous solution was added so that the amount of cesium carbonate was 64 μmol per 1 mol of all dihydroxy compounds to prepare a raw material mixture.

Table 1 shows the Mv, terminal hydroxyl group content, terminal aromatic hydrocarbon group content, carbonate equivalent weight, and Tg of the obtained phenol carbonate resin (A-5).

[Synthesis Example 6: Synthesis of phenol carbonate resin (A-6)]
4,4′-(3,3,5-trimethylcyclohexylidene)bisphenol (BP-TMC) was added to a 150 mL glass reactor equipped with a reactor agitator, a reactor heating device, and a reactor pressure regulator. ) 60.71 g (about 0.196 mol), 1,1′-bi-2-naphthol (BN) 56.00 g (about 0.196 mol), DPC 108.93 g (about 0.5085 mol), and cesium carbonate as a catalyst The method described in Example 2 was followed except that a 4% by mass aqueous solution was added so that the amount of cesium carbonate was 64 μmol per 1 mol of all dihydroxy compounds to prepare a raw material mixture.

Table 1 shows the Mv, terminal hydroxyl group content, terminal aromatic hydrocarbon group content, carbonate equivalent weight, and Tg of the obtained phenol carbonate resin (A-6).

[Synthesis Example 7: Synthesis of phenol carbonate resin (A-7)]
116.71 g of 2,2-bis(4-hydroxyphenyl)propane (BPA) (approx. 5112 mol), 102.95 g (about 0.4806 mol) of diphenyl carbonate (DPC), and a 0.04% by mass aqueous solution of cesium carbonate as a catalyst were added so that the amount of cesium carbonate was 0.5 μmol per 1 mol of the dihydroxy compound. was prepared.

Subsequently, the pressure in the reactor was maintained at 13.3 kPa, and transesterification was carried out for 80 minutes while further distilling off phenol. After that, the temperature outside the reactor was raised to 280° C., the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 40 minutes, and the distilled phenol was removed from the system. . Furthermore, the absolute pressure in the reactor was reduced to 70 Pa (about 0.5 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the stirrer of the reactor reached a predetermined stirring power.

Next, after restoring the pressure inside the reactor to 101.3 kPa in absolute pressure with nitrogen, the phenol carbonate resin (A-7) was extracted from the reactor into an aluminum container, and the solidified (A-7) was pulverized.

Table 1 shows the Mv, terminal hydroxyl group content, terminal aromatic hydrocarbon group content, carbonate equivalent weight, and Tg of the obtained phenol carbonate resin (A-7).

[Production and evaluation of resin composition / cured product]
<Examples 1 to 7>
Cyclohexanone solutions of epoxy resin (B-1) and phenol carbonate resins (A-1) to (A-7) (Examples 1 and 7 are 20 wt%, Examples 2 to 6 are 30 wt%), a curing accelerator (C-1), a polymer epoxy resin (B-2) as another epoxy resin that serves as a filming agent, and a leveling agent to obtain a resin composition. . The resulting resin composition solution was applied to a separator (polyethylene terephthalate film treated with silicone) using an applicator, dried at 160°C for 1.5 hours, and then dried at 200°C for 1.5 hours to form a cured epoxy resin film. Obtained. The obtained film was evaluated for heat resistance and dielectric properties according to the methods described above. Table 2 shows the results.

From the results in Table 2, it can be seen that the cured products obtained using the resin compositions of Examples 1 to 7 are excellent in heat resistance and dielectric properties in a well-balanced manner.

Claims

A resin composition containing a phenol carbonate resin (A) and an epoxy resin (B),
A resin composition wherein the molar ratio of the epoxy groups of the epoxy resin (B) to the terminal hydroxyl groups of the phenol carbonate resin (A) (epoxy group/terminal hydroxyl group) is 3.0 to 100,000.
The resin composition according to claim 1, wherein the phenol carbonate resin (A) contains a repeating unit represented by the following formula (1).

(In formula (1), A 1 and A 2 are each independently a group represented by the following formula (2) or (3); X is a direct bond, an optionally substituted carbon a divalent hydrocarbon group of numbers 1 to 15, -O-, -S-, -SO-, -SO 2 -, -CO-, -OCO- or -COO-; n 1 and n 2 are Each is independently an integer from 1 to 50.)

(In formulas (2) and (3), R is each independently an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, arylalkoxy group, aryl group having 6 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, arylalkenyl group having 8 to 12 carbon atoms, alkynyl group having 2 to 12 carbon atoms, arylalkynyl group having 8 to 12 carbon atoms group, halogen atom, hydroxyl group, carboxy group, sulfone group, amino group, cyano group or nitro group; p is an integer from 0 to 4; q is an integer from 0 to 6; * is a bond position.)
The resin composition according to claim 1, wherein the phenol carbonate resin (A) has a viscosity average molecular weight (Mv) of 500 to 100,000.
The resin composition according to claim 2, wherein the phenol carbonate resin (A) further contains a repeating unit represented by the following formula (4).

(In Formula (4), A 3 and A 4 are each independently synonymous with A 1 in Formula (1) above; Y is a direct bond and optionally has a substituent of 6 to 15 divalent aromatic hydrocarbon groups or optionally substituted divalent heteroaromatic hydrocarbon groups having 6 to 15 carbon atoms; n 3 and n 4 are each independently 1 to is an integer of 50.)
The resin composition according to claim 1 or 2, wherein the phenol carbonate resin (A) has a carbonate equivalent of 100 to 10,000 g/eq.
The resin composition according to claim 1 or 2, wherein the weight ratio of said phenol carbonate resin (A) to said epoxy resin (B) is 0.01 or more and 100 or less.
Furthermore, a curing accelerator (C) is included, and the content of the curing accelerator (C) with respect to a total of 100 parts by weight of the phenol carbonate resin (A) and the epoxy resin (B) is 0.001 to 5 parts by weight. 3. The resin composition according to claim 1 or 2.
The curing accelerator (C) is one or more selected from the group consisting of phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metal curing accelerators, according to claim 7. of the resin composition.
A resin sheet having a resin composition layer formed of the resin composition according to claim 1 or 2.
A cured product obtained by curing the resin composition according to claim 1 or 2.
An insulating layer formed by curing the resin composition according to claim 1 or 2.
An electric/electronic component having the insulating layer according to claim 11.
A printed wiring board having the insulating layer according to claim 11.
An epoxy resin curing agent containing a phenol carbonate resin (A)',
The phenol carbonate resin (A)' is an epoxy resin curing agent having a viscosity average molecular weight (Mv) of 500 to 20,000 and a terminal aromatic hydrocarbon group content of 95% by mass or more.