KR102313046B1 - Polyarylate resin and its resin composition - Google Patents

Abstract

[식(1) 중, R¹, R², R³ 및 R⁴는 수소 원자, 탄소 원자수가 1∼12인 탄화수소기 또는 할로젠 원자를 나타내고, R⁵ 및 R⁶은 수소 원자 또는 탄소수가 1∼4인 탄화수소기를 나타낸다; m은 4∼12의 정수를 나타내고, X는 포화 지방족 탄화수소환을 형성하는 탄소 원자를 나타낸다].The present invention provides a polyarylate resin that has excellent heat resistance and dielectric properties, and is also excellent in fluidity during processing and solubility in non-halogenated solvents. The present invention is a polyarylate resin containing a dihydric phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component, wherein the content of the dihydric phenol represented by the general formula (1) in the total dihydric phenol component is 30 to 70 mol%, the content of the hydroxycarboxylic acid component in the total monomer component is 1 to 30 mol%, and the number average molecular weight is less than 10000 polyarylate resin:

[In formula (1), R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom, and R ⁵ and R ⁶ are a hydrogen atom or 1 carbon atom -4 represents a hydrocarbon group; m represents an integer of 4 to 12, and X represents a carbon atom forming a saturated aliphatic hydrocarbon ring].

Description

Polyarylate resin and its resin composition

The present invention relates to a polyarylate resin having excellent heat resistance and dielectric properties, and excellent fluidity during processing and solubility in a non-halogenated solvent, and a polyarylate resin composition containing the polyarylate resin.

DESCRIPTION OF RELATED ART In recent years, with the increase of the amount of information processing in various electronic devices, the high integration of the semiconductor device mounted, the density increase of wiring, and the multilayer technology are advancing rapidly. Insulating materials, such as printed wiring boards used in various electronic devices, are required to have a low dielectric constant in order to increase a signal transmission speed, and to have a low dielectric loss tangent in order to reduce loss during signal transmission. Moreover, the outstanding heat resistance, such as tolerating heat processing, such as a soldering process, is calculated|required by insulating materials, such as a printed wiring board.

Polyarylate resins are known as resins excellent in heat resistance and dielectric properties such as dielectric constant and dielectric loss tangent. For example, in patent document 1, using the resin composition which mix|blended the active ester compound, the hardening accelerator, and the epoxy resin with polyarylate resin for a printed wiring board is disclosed.

Japanese Patent Laid-Open No. 2004-224890

When using polyarylate resin for a printed wiring board etc., polyarylate resin is melt|dissolved in an organic solvent, and is used. However, in general, polyarylate resins have low solubility and are soluble in halogenated solvents, but have low solubility in non-halogenated solvents, which has been desired due to an increase in environmental awareness in recent years, or even when soluble in solutions. There is a problem that stability is bad. Furthermore, even if the polyarylate resin is dissolved in a non-halogenated solvent, there is a problem that the amount of dissolution is too small. In general, polyarylate resins have a high glass transition temperature and low fluidity during processing, so voids are likely to occur when prepreg is multilayered. there was.

In view of the prior art, the present invention provides a polyarylate resin having excellent heat resistance and dielectric properties, and excellent fluidity during processing and solubility in non-halogenated solvents, and a polyarylate resin composition containing the polyarylate resin aims to provide

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors WHEREIN: In the polyarylate resin containing a specific dihydric phenol component in a specific amount, the hydroxycarboxylic acid component is made to contain a specific amount, and a number average molecular weight is set to a specific range. It was discovered that the above object could be achieved by setting it as , and the present invention was reached.

That is, the summary of this invention is as follows.

<1>

A polyarylate resin containing a dihydric phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component, comprising:

The content of the dihydric phenol represented by the general formula (1) in the total dihydric phenol component is 30 to 70 mol%,

The content of the hydroxycarboxylic acid component in the total monomer component is 1 to 30 mol%,

Polyarylate resin characterized in that the number average molecular weight is less than 10000:

[In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom, and R ⁵ and R ⁶ are each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m represents an integer of 4 to 12, and X represents a carbon atom forming a saturated aliphatic hydrocarbon ring together with the carbon atom to which the hydroxyphenyl group is bonded].

<2>

The polyarylate resin has a structure represented by the following formula (2) and/or (3) as a terminal group,

The polyarylate resin according to <1>, wherein the total amount of the terminal groups of the following formulas (2) and (3) is 100 geq/t or more:

[The terminal group of formula (2) represents the structure derived from the monohydroxy compound component, the terminal group of the formula (3) represents the structure derived from the monocarboxylic acid component, and R ⁷ and R ⁸ are each independently an aliphatic hydrocarbon group or represents an aromatic hydrocarbon group].

<3>

The dihydric phenol represented by the formula (1) is 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and/or 1,1-bis(4-hydroxyphenyl) - The polyarylate resin according to <1> or <2>, characterized in that it is cyclododecaine.

<4>

The polyarylate resin according to any one of <1> to <3>, wherein the content of isophthalic acid in the wholly aromatic dicarboxylic acid component is 50 mol% or more.

<5>

The dihydric phenol component is 2,2-bis(4-hydroxyphenyl)propane (BisA) and/or 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BisAP), and the formula The polyarylate resin in any one of <1>-<4> containing the dihydric phenol represented by (1).

<6>

The content ratio of the total content of the BisA and/or the BisAP and the total content of the dihydric phenol represented by the formula (1) ((BisA+BisAP)/(dihydric phenol represented by the formula (1))) is 35 The polyarylate resin according to <5>, which is /65 to 65/35 (molar ratio).

<7>

The polyarylate resin according to any one of <1> to <6>, wherein the content ratio of the dihydric phenol component and the aromatic dicarboxylic acid component is 70/100 to 140/100 (molar ratio).

<8>

A polyarylate resin composition comprising the polyarylate resin according to any one of <1> to <7>, an epoxy resin, and a curing accelerator.

<9>

A coating film comprising the polyarylate resin according to any one of <1> to <7> or the polyarylate resin composition according to <8>.

<10>

A film comprising the polyarylate resin according to any one of <1> to <7> or the polyarylate resin composition according to <8>.

<11>

A resin solution comprising the polyarylate resin according to any one of <1> to <7> or the polyarylate resin composition according to <8>, and an organic solvent.

<12>

The resin solution according to <11>, wherein the organic solvent is a non-halogenated solvent.

<13>

A prepreg in which the resin solution according to <11> or <12> is impregnated or coated on a reinforcing fiber cloth.

<14>

The prepreg as described in <13> is laminated|stacked, The laminated body characterized by the above-mentioned.

According to the present invention, it is possible to provide a polyarylate resin having excellent heat resistance and dielectric properties, excellent fluidity during processing and solubility in non-halogenated solvents, and a polyarylate resin composition containing the polyarylate resin. . The polyarylate resin and polyarylate resin composition of the present invention can be suitably used as an insulating material for a printed wiring board.

The polyarylate resin of the present invention is composed of a dihydric phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component.

The dihydric phenol component is an organic compound containing two phenolic hydroxyl groups in one molecule, and includes an alicyclic dihydric phenol represented by the general formula (1). A phenolic hydroxyl group is the hydroxyl group couple|bonded with the aromatic ring directly.

In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom. The hydrocarbon group having 1 to 12 carbon atoms includes a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group and an aromatic hydrocarbon group. The saturated aliphatic hydrocarbon group contains an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n- A butyl group, an isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. are mentioned. The unsaturated aliphatic hydrocarbon group contains an alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and examples thereof include a vinyl group and an allyl group. The aromatic hydrocarbon group contains an aryl group having 6 to 10 carbon atoms, preferably 6, and examples thereof include a phenyl group and a naphthyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably they are a chlorine atom and a bromine atom.

In formula (1), preferred R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (particularly 1 to 3), or 6 to 10 carbon atoms (particularly 6). of an aryl group or a halogen atom (especially a chlorine atom or a bromine atom). More preferred R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (particularly 1 to 3). Some or all of R ¹ , R ² , R ³ and R ⁴ may contribute different from each other, or may contribute the same, and preferably represent the same group.

In formula (1), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group having 1 to 4 carbon atoms includes a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group contains an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t - A butyl group, etc. are mentioned. The unsaturated aliphatic hydrocarbon group contains an alkenyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and examples thereof include a vinyl group and an allyl group. R ⁵ and R ⁶ are when present in plural in accordance with the value of m, which will be described later, and a plurality of R ⁵ R ⁶ and a plurality of the art are each independently selected from the above range.

In Formula (1), preferable R<^5> and R<^6> respectively independently represent a hydrogen atom or a C1-C4 alkyl group. More preferable R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly a hydrogen atom.

In Formula (1), m is an integer of 4-12, Preferably the integer of 4-11, More preferably, the integer of 5-11 is shown.

In formula (1), X represents the carbon atom which forms a saturated aliphatic hydrocarbon ring (monocyclic) with the carbon atom to which the hydroxyphenyl group couple|bonded. The saturated aliphatic hydrocarbon ring represents a cycloalkane ring according to the number of m. Specific examples of the saturated aliphatic hydrocarbon ring include, for example, a cyclopentane ring (m = 4), a cyclohexane ring (m = 5), a cycloheptane ring (m = 6), and a cyclooctane ring (m = 7). ), cyclononane ring (m = 8), cyclodecane ring (m = 9), cyclodecane ring (m = 10), cyclododecaine ring (m = 11), cyclotridecane ring (m = 12) ) can be mentioned.

Among the alicyclic dihydric phenols represented by the formula (1), the solubility, heat resistance and dielectric properties of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone), and a cured product of the polyarylate resin and the epoxy resin From the viewpoint of further improvement of the heat resistance of this, as preferred specific examples, formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h) and ( 1i), in particular, alicyclic dihydric phenols represented by formulas (1b) to (1h) are mentioned.

Equation (1a) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1a), n1 is an integer of 0-8, Preferably it is an integer of 0-4, More preferably, it is an integer of 0-2.

In formula (1a), R<^10> represents a C1-C4 hydrocarbon group. The hydrocarbon group having 1 to 4 carbon atoms includes a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group contains an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t -Butyl group, etc. are mentioned. The unsaturated aliphatic hydrocarbon group contains an alkenyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and examples thereof include a vinyl group and an allyl group. When n1 is an integer of 2 or more, a plurality of R ¹⁰ may be each independently selected from within the above range. Although the bonding position of R ^{10 in} the cyclopentane ring is not particularly limited, when the carbon atom of the cyclopentane ring to which the hydroxyphenyl group is bonded in the formula (1a) is 1, the 3rd and 4th carbon atoms ^{It is preferable that each R 10} couple|bonds with the carbon atom selected from.

Preferred R ¹⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ¹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the formula (1a) include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxy-3, 5-dimethylphenyl)cyclopentane and 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane.

Equation (1b) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1b), n2 is an integer of 0-10, Preferably it is an integer of 0-5, More preferably, it is an integer of 2-4.

In Formula (1b), R ²⁰ is the same as ^{R 10} in Formula (1a). When n2 is an integer of 2 or more, a plurality of R ²⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{20 in} the cyclohexane ring is not particularly limited, when the carbon atom of the cyclohexane ring to which the hydroxyphenyl group is bonded in the formula (1b) is the 1st, 3rd, 4th and 5th positions It is preferable that ^{each R 20} is bonded to a carbon atom selected from carbon atoms of , particularly carbon atoms in the 3rd and 5th positions.

Preferred R ²⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ²⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the formula (1b) include 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl- 4-Hydroxyphenyl)cyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-tri Methylcyclohexane [BisTMC], 1,1-bis(4-hydroxyphenyl)-3,3,5-triethylcyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3 ,5,5-Tetramethyl-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,4-trimethyl-cyclohexane, 1,1-bis-(4-hydroxyl Phenyl)-3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane Sein, 1,1-bis-(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(3-methyl-4-hydride Roxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(3-phenyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1, 1-bis-(3,5-dichloro-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(3,5-dibromo-4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane. Especially, since versatility is high, BisTMC is especially preferable.

Equation (1c) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1c), n3 is an integer of 0-12, Preferably it is an integer of 0-6, More preferably, it is an integer of 0-2.

In formula (1c), R ³⁰ is the same as ^{R 10} in the formula (1a). When n3 is an integer of 2 or more, a plurality of R ³⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{30 in} the cycloheptane ring is not particularly limited, when the carbon atom of the cycloheptane ring to which the hydroxyphenyl group is bonded in the formula (1c) is 1, the 3rd, 4th, and 5th positions ^{and each R 30} is preferably bonded to a carbon atom selected from the carbon atom at the 6th position.

Preferred R ³⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ³⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the formula (1c) include 1,1-bis(4-hydroxyphenyl)-cycloheptane.

Formula (1d) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1d), n4 is an integer of 0-14, Preferably it is an integer of 0-7, More preferably, it is an integer of 0-2.

In the formula (1d), R ⁴⁰ is the same as ^{R 10} in the formula (1a). When n4 is an integer of 2 or more, a plurality of R ⁴⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{40 in} the cyclooctane ring is not particularly limited, when the carbon atom of the cyclooctane ring to which the hydroxyphenyl group is bonded in the formula (1d) is the 1st, 4th, 5th and 6th positions ^{It is preferable that each R 40} couple|bonds with the carbon atom selected from the carbon atom of.

Preferred R ⁴⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ⁴⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the general formula (1d) include 1,1-bis(4-hydroxyphenyl)-cyclooctane.

Formula (1e) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1e), n5 is an integer of 0-16, Preferably it is an integer of 0-8, More preferably, it is an integer of 0-2.

In the formula (1e), R ⁵⁰ is the same as ^{R 10} in the formula (1a). When n5 is an integer of 2 or more, a plurality of R ⁵⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{50 in} the cyclononeine ring is not particularly limited, when the carbon atom of the cyclononeine ring to which the hydroxyphenyl group is bonded in the formula (1e) is the 1st, 4th, 5th, 6th and ^{It is preferable that each R 50} couple|bonds with the carbon atom selected from the carbon atom at 7th-position.

Preferred R ⁵⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ⁵⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the general formula (1e) include 1,1-bis(4-hydroxyphenyl)-cyclononanein.

Formula (1f) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1f), n6 is an integer of 0-18, Preferably it is an integer of 0-9, More preferably, it is an integer of 0-2.

In the formula (1f), R ⁶⁰ is the same as ^{R 10} in the formula (1a). When n6 is an integer of 2 or more, a plurality of R ⁶⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{60 in} the cyclodecane ring is not particularly limited, when the carbon atom of the cyclodecane ring to which the hydroxyphenyl group is bonded in the formula (1f) is the 1st, 4th, 5th, and 6th positions , it is preferable that ^{each R 60} is bonded to a carbon atom selected from the carbon atoms in the 7th and 8th positions, particularly the carbon atoms in the 5th, 6th and 7th positions.

Preferred R ⁶⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ⁶⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the formula (1f) include 1,1-bis(4-hydroxyphenyl)-cyclodecane.

Formula (1g) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1g), n7 is an integer of 0-20, Preferably it is an integer of 0-10, More preferably, it is an integer of 0-2.

In the formula (1g), R ⁷⁰ is the same as ^{R 10} in the formula (1a). When n7 is an integer of 2 or more, a plurality of R ⁷⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{70 in} the cyclonedecane ring is not particularly limited, when the carbon atom of the cyclodecane ring to which the hydroxyphenyl group is bonded in the formula (1g) is 1st, 4th, 5th, and 6th positions ^{and each R 70} is preferably bonded to a carbon atom selected from the carbon atom at the 7th position.

Preferred R ⁷⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ⁷⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the general formula (1g) include 1,1-bis(4-hydroxyphenyl)-cycloundecane.

Formula (1h) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1h), n8 is an integer of 0-22, Preferably it is an integer of 0-11, More preferably, it is an integer of 0-2.

In the formula (1h), R ⁸⁰ is the same as ^{R 10} in the formula (1a). When n8 is an integer of 2 or more, a plurality of R ⁸⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{80 in} the cyclododecaine ring is not particularly limited, when the carbon atom of the cyclododecaine ring to which the hydroxyphenyl group is bonded in the formula (1h) is the 1st, the 5th, 6th and 7th positions ^{It is preferable that each R 80} couple|bonds with the carbon atom selected from the carbon atom of 8th-position and 9th-position.

Preferred R ⁸⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ⁸⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the general formula (1h) include 1,1-bis(4-hydroxyphenyl)-cyclododecaine (BisCDE).

Formula (1i) of, R ^1, R ^2, R ³ and R ⁴ each is the same as the formula (1) R ^1, R ^2, R ³ and R ⁴ in the preferred R ^1, R ^2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the formula (1).

In formula (1i), n9 is an integer of 0-24, Preferably it is an integer of 0-12, More preferably, it is an integer of 0-2.

In Formula (1i), R ⁹⁰ is the same as ^{R 10} in Formula (1a). When n9 is an integer of 2 or more, a plurality of R ⁹⁰ may be each independently selected from within the same range as that of ^{R 10 .} Although the bonding position of R ^{90 in} the cyclotridecane ring is not particularly limited, when the carbon atom of the cyclotridecane ring to which the hydroxyphenyl group in the formula (1i) is bonded is the 1st, 6th, 7th, ^{It is preferable that each R 90} couple|bonds with the carbon atom selected from the carbon atom of 8th-position and 9th-position.

Preferred R ⁹⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R ⁹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the formula (1i) include 1,1-bis(4-hydroxyphenyl)-cyclotridecaine.

The content of the alicyclic dihydric phenol represented by the general formula (1) needs to be 30 to 70 mol% based on the total dihydric phenol component. The content is preferably 40 to 65 mol% based on the total dihydric phenol component from the viewpoint of further improvement of the solubility, heat resistance and dielectric properties of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone). , More preferably, it is 45-65 mol%, More preferably, it is 45-55 mol%. When the content of the alicyclic dihydric phenol in the total dihydric phenol component is less than 30 mol%, or exceeds 70 mol%, in any case, the non-halogenated solvent of the polyarylate resin (especially methyl ethyl ketone) It is undesirable because the solubility for it decreases. The alicyclic dihydric phenol represented by the alicyclic dihydric phenol represented by the said General formula (1) may be used independently and may use multiple types together, and in that case, those total amounts should just exist in the said range. The solubility of the polyarylate resin in the non-halogenated solvent is not only the solubility of the polyarylate resin in the non-halogenated solvent with a solid content concentration of about 20 mass%, but also the solid content concentration is preferably 30 mass% or more, More preferably, it is 40 mass % or more, More preferably, it contains high concentration solubility which melt|dissolves in a non-halogenated solvent at a high concentration of 50 mass % or more. The heat resistance of the polyarylate resin includes not only the heat resistance of the polyarylate resin itself, but also the heat resistance of the cured product of the polyarylate resin composition containing the polyarylate resin. Dielectric properties include properties relating to relative permittivity and dielectric loss tangent.

The dihydric phenol component may contain dihydric phenols other than the alicyclic dihydric phenol represented by the general formula (1). From the viewpoint of further improving the solubility of the polyarylate resin in the non-halogenated solvent, it is preferable that the dihydric phenol component contains a dihydric phenol other than the alicyclic dihydric phenol represented by the formula (1).

The dihydric phenol other than the alicyclic dihydric phenol represented by the formula (1) is not particularly limited as long as it is a dihydric phenol component not included in the alicyclic dihydric phenol represented by the formula (1), for example, , and the following dihydric phenols: 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane [BisA], 2,2-bis(3,5- Dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 9,9-bis(4-hydroxyphenyl)fluorene , 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, N-methyl-3,3-bis (4 -Hydroxyphenyl)phthalimidine, 1,1-bis(4-hydroxyphenyl)-1-phenylethane [BisAP], 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis( 3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1-bis(3-methyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, bis(3,5- Dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)methane. Among them, BisA and/or BisAP are preferred because of their versatility and high solubility in non-halogenated solvents (especially methyl ethyl ketone). Dihydric phenols other than the alicyclic dihydric phenol represented by the general formula (1) may be used alone, or multiple types may be used in combination.

As the dihydric phenol component, the above dihydric phenols may be used alone or in combination of multiple types. It is preferable to use Among them, from the viewpoint of further improving the solubility of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone), the dihydric phenol component is BisA and/or BisAP and an alicyclic represented by the formula (1). It is preferable to contain a dihydric phenol (especially BisTMC and/or BisCDE) in combination, more preferably BisA and an alicyclic dihydric phenol represented by the formula (1) (especially BisTMC and/or BisCDE) in combination contains When using BisA and/or BisAP and an alicyclic dihydric phenol represented by the formula (1) (especially BisTMC and/or BisCDE), the total content of BisA and BisAP and the alicyclic dihydric phenol represented by the formula (1) It is preferable that the content ratio ((BisA+BisAP)/(dihydric phenol represented by formula (1)) of the total content of (especially BisTMC and BisCDE) is 10/90 to 90/10 (molar ratio), In particular, since the solubility, heat resistance and dielectric properties of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone) become higher, it is more preferably set to 35/65 to 65/35 (molar ratio), and 40/60 to It is more preferable to set it as 60/40 (molar ratio).

The aromatic dicarboxylic acid component may be any organic compound containing two carboxyl groups directly bonded to the aromatic ring in one molecule. Specific examples of the aromatic dicarboxylic acid component include terephthalic acid [TPA], isophthalic acid [IPA], orthophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenyl ether-2,2'-dicarboxylic acid, di Phenyl ether-2,3'-dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether -4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid [NDCA], and bis(p-carboxyphenyl)alkane diphenic acid are mentioned.

The aromatic dicarboxylic acid component may use individually 1 type of compound among the above, and may use multiple types of compounds together. Among them, from the viewpoint of further improvement of the solubility and dielectric properties of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone), it is preferable to use at least IPA, and TPA and/or NDCA and IPA are used in combination. It is more preferable to use, and it is still more preferable to use TPA and IPA together. The content of IPA is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 50 to 90 mol%, and 60 to 85 mol%, based on the total aromatic dicarboxylic acid component. % is most preferable. When the aromatic dicarboxylic acid component contains TPA and/or NDCA and IPA, from the viewpoint of further improvement of the solubility and dielectric properties of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone), (TPA+NDCA 10/90 to 70/30 are preferable in molar ratio, as for the content rate of )/IPA, 10/90-50/50 are more preferable, 15/85-40/60 are still more preferable, 20/80-40/ 60 is more preferable.

The content ratio of the dihydric phenol component and the aromatic dicarboxylic acid component (dihydric phenol component/aromatic dicarboxylic acid component) is usually 70/100 to 140/100 (molar ratio), and the non-halogenated solvent of the polyarylate resin (especially methyl ethyl From the viewpoint of further improvement of solubility in ketones) and heat resistance, preferably 90/100 to 140/100 (molar ratio), more preferably 105/100 to 140/100 (molar ratio), still more preferably 110/ 100 to 135/100 (molar ratio), most preferably 115/100 to 130/100 (molar ratio).

The hydroxycarboxylic acid may be any organic compound (especially an aromatic compound) containing one hydroxyl group and one carboxyl group in one molecule. Specific examples of the hydroxycarboxylic acid include benzene-based hydroxycarboxylic acids such as p-hydroxybenzoic acid [PHBA] and m-hydroxybenzoic acid; and naphthalene-based hydroxycarboxylic acids such as 2-hydroxy-6-naphthoic acid (HNA), 2-hydroxy-3-naphthoic acid, and 1-hydroxy-4-naphthoic acid. Among them, from the viewpoint of further improving the solubility of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone), the heat resistance and versatility of the cured product of the polyarylate resin composition, benzene-based hydroxycarboxylic acid, especially PHBA desirable.

The content of the hydroxycarboxylic acid component needs to be 1 to 30 mol% with respect to 100 mol% of the total monomer components, and the solubility of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone), polyarylate From the viewpoint of further improvement of the heat resistance of the resin and the polyarylate resin composition and the dielectric properties of the cured product of the polyarylate resin and the polyarylate resin composition, preferably 4 to 21 mol%, more preferably 4 to 19 mol% It is mol%, More preferably, it is 10-19 mol%. When the content of the hydroxycarboxylic acid component is less than 1 mol% or more than 30 mol%, the solubility of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone) is lowered. In addition, all monomer components mean all the monomer components which comprise polyarylate resin. For example, when the polyarylate resin consists only of a dihydric phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component, the total monomer component includes all of the dihydric phenol component, the aromatic dicarboxylic acid component, and the hydroxycarboxylic acid component (total amount). )am. Moreover, for example, when polyarylate resin contains another monomer component in addition to a dihydric phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component, it is all (total amount) of these components. The monomer component means a bifunctional or higher functional organic compound capable of a polymerization reaction. Therefore, when the polyarylate resin contains the monohydroxy compound component and/or the monocarboxylic acid component described later, the monohydroxy compound component and/or the monocarboxylic acid component are not included in the total monomer component.

Polyarylate resin may contain other monomer components other than said dihydric phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component in the range which does not impair the effect of this invention. As a specific example of another monomer component, For example, aliphatic diols, such as ethylene glycol and propylene glycol; alicyclic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol; polyhydric alcohols such as trimethylolpropane and pentaerythritol; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid; Polyhydric carboxylic acids, such as trimellitic acid and a pyromellitic acid, are mentioned. The aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and polyhydric carboxylic acid may be derivatives thereof or anhydrides thereof. Content of said other monomer component is 10 mol% or less normally with respect to 100 mol% of all monomer components, Preferably it is 5 mol% or less, More preferably, it is 0 mol%.

Although the manufacturing method of the polyarylate resin of this invention is not specifically limited, For example, the method of performing an acetylation reaction and deacetic acid polymerization reaction, and manufacturing polyarylate resin is mentioned.

An acetylation reaction is a reaction which acetylates a dihydric phenol component. In the acetylation reaction, a dicarboxylic acid component and acetic anhydride are put into a reaction can, nitrogen is substituted, and in an inert atmosphere, at a temperature of 100 to 240°C, preferably 120 to 180°C, for 5 minutes to 8 hours. , preferably 30 minutes to 5 hours, and stirring under normal pressure or pressure. The molar ratio of acetic anhydride to the hydroxyl groups of the dihydric phenol component and the hydroxycarboxylic acid component or the molar ratio of acetic anhydride to the hydroxyl groups of the dihydric phenol component, the hydroxycarboxylic acid component, and the monohydroxy compound is 1.00 to It is preferable to set it as 1.20.

The deacetic acid polymerization reaction is a reaction in which an acetylated dihydric phenol and an aromatic dicarboxylic acid are reacted and polycondensed. In the deacetic acid polymerization reaction, at a temperature of 240 ° C. or higher, preferably 260 ° C. or higher, more preferably 280 ° C. or higher, 500 Pa or lower, preferably 260 Pa or lower, more preferably 130 Pa or lower, at a reduced pressure of 130 Pa or lower, for 30 minutes or longer hold and stir. When the temperature is less than 240° C., when the degree of reduced pressure exceeds 500 Pa, and when the holding time is less than 30 minutes, the deacetic acid reaction becomes insufficient and the amount of acetic acid in the polyarylate resin obtained increases, or the overall polymerization time becomes long, The polymer color tone may deteriorate.

After performing the acetylation reaction until the deacetic acid polymerization reaction, there is usually a preliminary step of adjusting the temperature and pressure of the reaction system to the temperature and pressure for the deacetic acid polymerization reaction. In the method for producing the polyarylate resin of the present invention, a hydroxycarboxylic acid component may be added in this preliminary step. Specifically, in the preliminary step, after raising the temperature of the reaction system and then performing the pressure reduction, the hydroxycarboxylic acid component may be added before the temperature rise, or the hydroxycarboxylic acid component may be added after the temperature rise and before the pressure reduction. You may add a hydroxycarboxylic acid component at the time of both before a temperature rise and before a pressure reduction while after a temperature rise.

In acetylation reaction and deacetic acid polymerization reaction, it is preferable to use a catalyst as needed. Examples of the catalyst include organic titanic acid compounds such as tetrabutyl titanate, alkali metal salts such as zinc acetate and potassium acetate, alkaline earth metal salts such as magnesium acetate, antimony trioxide, hydroxybutyltin oxide, and tin octylate. Heterocyclic compounds, such as organotin compounds, such as N-methylimidazole, are mentioned. It is preferable that the addition amount of a catalyst shall be 1.0 mass % or less with respect to the resin mass obtained.

A well-known reaction apparatus is mentioned as an apparatus for manufacturing the polyarylate resin of this invention, For example, a batch type reaction apparatus and a continuous reaction apparatus are mentioned.

The number average molecular weight of the polyarylate resin of the present invention needs to be less than 10000, preferably less than 8000, more preferably less than 6000, still more preferably 4000 or less, and most preferably 3000 or less. When a number average molecular weight is 10000 or more, since the glass transition temperature of polyarylate resin becomes high and the fluidity|liquidity at the time of a process worsens, it is unpreferable. Also, the solubility of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone) is reduced. The lower limit of the number average molecular weight of polyarylate resin is not specifically limited, Usually, the said number average molecular weight is 500 or more, Preferably it is 1000 or more.

The number average molecular weight of polyarylate resin is controllable by adjusting reaction conditions. For example, when reaction time is shortened within the said range, or reaction temperature is lowered|hung within the said range, a number average molecular weight will fall. Further, for example, when the reaction time is lengthened within the above range or the reaction temperature is raised within the above range, the number average molecular weight increases.

Moreover, it is controllable by adjusting the molar ratio of a dicarboxylic acid component and a dihydric phenol component within the range of 200:100-100:200. For example, when the difference of the molar ratio of a dicarboxylic acid component and a dihydric phenol component is enlarged within the said range, a number average molecular weight will fall. Moreover, for example, when the difference of the molar ratio of a dicarboxylic acid component and a dihydric phenol component is made small within the said range, a number average molecular weight will increase.

Moreover, it can control by adjusting the total amount of a monohydroxy compound or/and a monocarboxylic acid component. For example, when the total amount of the monohydroxy compound and/or the monocarboxylic acid component is increased, the number average molecular weight is lowered. Further, for example, when the total amount of the monohydroxy compound or/and the monocarboxylic acid component is decreased, the number average molecular weight increases.

Although the molecular chain terminal of the polyarylate resin of the present invention is not particularly limited, from the viewpoint of dielectric properties, it has a structure represented by the following formula (2) and/or (3) as a terminal group, and has the following formula (2) and The total amount of the terminal groups in (3) is preferably 100 geq/t or more, more preferably 200 geq/t or more, still more preferably 400 geq/t or more, and most preferably 600 geq/t or more. The upper limit of the total amount of the terminal groups is not particularly limited, and the total amount is usually 2000 geq/t or less. From the viewpoint of balance of dielectric properties, it is preferably 1500 geq/t or less, more preferably 1000 geq/t or less, still more preferably 900 geq/t or less, and most preferably 800 geq/t or less. The range of the total amount of the terminal groups as described above is ^{the amount of the terminal groups in the formula (2) in which R 7} is an aliphatic hydrocarbon group and an aromatic hydrocarbon group [preferably an aryl group (particularly a naphthyl group)] ^{described later, and R 8 is a} It is preferable that it is in the range of the total amount of the amount of the terminal group of the formula (3) which is an aliphatic hydrocarbon group [preferably an alkyl group (especially a methyl group and a heptadecyl group)] and an aromatic hydrocarbon group [preferably an aryl group (especially a phenyl group)].

[The terminal group in the formula (2) represents the structure derived from the monohydroxy compound component, and the terminal group in the formula (3) represents the structure derived from the monocarboxylic acid component.]

In formulas (2) and (3), R ⁷ and R ⁸ each independently represent an aliphatic hydrocarbon group having 1 to 21 carbon atoms or an aromatic hydrocarbon group having 1 to 21 carbon atoms, and may be a mixture thereof.

The ^{aliphatic hydrocarbon group as R 7 includes} an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl-substituted alkyl group.

The ^{alkyl group as R 7 is} an alkyl group having 1 to 21 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetra group. A decyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group are mentioned.

The ^{alkenyl group as R 7 is} an alkenyl group having 2 to 21 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 15 to 18 carbon atoms. As a specific example of the said alkenyl group, an oleyl group is mentioned, for example.

The ^{cycloalkyl group as R 7 is} a cycloalkyl group having 1 to 21 carbon atoms, preferably 3 to 18 carbon atoms, and more preferably 4 to 8 carbon atoms. As a specific example of the said cycloalkyl group, a cyclohexyl group is mentioned, for example.

The ^{aryl-substituted alkyl group as R 7 is} an aryl-substituted alkyl group having 7 to 21 carbon atoms, preferably 7 to 18 carbon atoms, and more preferably 7 to 10 carbon atoms. The number of carbon atoms in the aryl-substituted alkyl group is the total number of carbon atoms in the aryl group and the alkyl group. Specific examples of the aryl-substituted alkyl group include a benzyl group.

The ^{aromatic hydrocarbon group as R 7 includes} an aryl group, an alkyl-substituted aryl group, and an aryl-substituted aryl group.

The ^{aryl group as R 7 is} an aryl group having 6 to 21 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group and a naphthyl group.

The ^{alkyl-substituted aryl group as R 7 is} an alkyl-substituted aryl group having 7 to 21 carbon atoms, preferably 7 to 18 carbon atoms, and more preferably 7 to 15 carbon atoms. The number of carbon atoms in the alkyl-substituted aryl group is the total number of carbon atoms in the alkyl group and the aryl group. Specific examples of the alkyl-substituted aryl group include, for example, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a dimethylphenyl group, a diethylphenyl group, a dipropylphenyl group, a dibutylphenyl group, a trimethylphenyl group, a triethylphenyl group, and tripropylphenyl group, tributylphenyl group, tetramethylphenyl group, tetraethylphenyl group, tetrapropylphenyl group, tetrabutylphenyl group, methylpropylphenyl group, methylbutylphenyl group, and nonylphenyl group.

The ^{aryl-substituted aryl group as R 7 is} an aryl-substituted aryl group having 12 to 21 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 carbon atoms. The number of carbon atoms in the aryl-substituted aryl group is the total number of carbon atoms in all aryl groups. Specific examples of the aryl-substituted aryl group include a biphenyl group.

The ^{aliphatic hydrocarbon group as R 8} includes an alkyl group and an alkenyl group.

The ^{alkyl group as R 8 is} an alkyl group having 1 to 21 carbon atoms, preferably 1 to 18 carbon atoms. As a specific example of the said alkyl group, the alkyl group similar to the alkyl group as ^{R<7> is mentioned, for example.}

The ^{alkenyl group as R 8 is} an alkenyl group having 2 to 21 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 2 to 5 carbon atoms. As a specific example of the said alkenyl group, a vinyl group is mentioned, for example.

The ^{aromatic hydrocarbon group as R 8 includes} an aryl group, an alkyl-substituted aryl group, an alkyloxy-substituted aryl group, and a heterocyclic group.

The ^{aryl group as R 8 is} an aryl group having 6 to 21 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group and a naphthyl group.

The ^{alkyl-substituted aryl group as R 8 is} an alkyl-substituted aryl group having 7 to 21 carbon atoms, preferably 7 to 18 carbon atoms, and more preferably 7 to 15 carbon atoms. The number of carbon atoms in the alkyl-substituted aryl group is the total number of carbon atoms in the alkyl group and the aryl group. As a specific example of the said alkyl-substituted aryl group, the alkyl-substituted aryl group similar to the alkyl-substituted aryl group as ^{R<7> is mentioned, for example.}

The ^{alkyloxy-substituted aryl group as R 8 is} an alkyloxy-substituted aryl group having 7 to 21 carbon atoms, preferably 7 to 18 carbon atoms, and more preferably 7 to 10 carbon atoms. The number of carbon atoms in the alkyloxy-substituted aryl group is the total number of carbon atoms in the alkyloxy group and the aryl group. Specific examples of the alkyloxy-substituted aryl group include a methyloxyphenyl group, an ethyloxyphenyl group, a propyloxyphenyl group, and a butyloxyphenyl group.

The ^{heterocyclic group as R 8 is} a heterocyclic group having 2 to 9 carbon atoms, preferably 3 to 5, more preferably 4 to 5 carbon atoms. Specific examples of the heterocyclic group include a pyridyl group and a furyl group.

As a specific example of the monohydroxy compound component which can introduce|transduce the terminal group (Hereinafter, it may be called "terminal group (2)") represented by the general formula (2) into the polyarylate resin, for example, methyl monohydric alcohols such as alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol, lauryl alcohol, oleyl alcohol, cyclohexanol and benzyl alcohol; Phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, isopropylphenol, t-butylphenol, xyleneol, methylpropylphenol, methylbutylphenol, dipropylphenol, di and phenols such as butylphenol, nonylphenol, mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 1-naphthol, and 2-naphthol. A monohydroxy compound component may be used individually by 1 type, or may use 2 or more types together. Especially, since it is excellent in a dielectric characteristic and reactivity, phenols are preferable and 1-naphthol and 2-naphthol are especially preferable.

As a specific example of the monocarboxylic acid component which can introduce|transduce the terminal group (hereinafter, sometimes referred to as "terminal group (2)") represented by the general formula (3) into the polyarylate resin, for example, acetic acid, propionic acid , pentanoic acid, pivalic acid, caproic acid, caprylic acid, octylic acid, nonyl acid, decanoic acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, etc. of aliphatic monocarboxylic acids; Benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cumic acid, para-butylbenzoic acid, orthotoluic acid, metatoluic acid, paratoluic acid, ethoxybenzoic acid, propoxy and aromatic monocarboxylic acids such as benzoic acid, naphthoic acid, nicotinic acid, furoic acid, and anisic acid. The monocarboxylic acid component may be benzoyl chloride and a derivative thereof, or may be an anhydride of the above-described aliphatic monocarboxylic acid and/or aromatic monocarboxylic acid. A monocarboxylic acid component may be used individually by 1 type, or may use 2 or more types together. Among them, acetic anhydride and stearic acid are particularly preferable because of their excellent dielectric properties and reactivity.

A monohydroxy compound component and a monocarboxylic acid component are normally used by making it exist in a reaction system before an acetylation reaction together with an aromatic dicarboxylic acid component and a dihydric phenol component at the time of manufacture of polyarylate resin. The monohydroxy compound component and the monocarboxylic acid component may be used individually, or both may be used together.

When the terminal group of the structure represented by the general formula (2) or/and (3) reacts with an epoxy group, since a hydroxyl group with high polarity is not generated, the resulting cured product has fewer polar groups and has excellent dielectric properties. .

The total amount of the terminal groups in the formulas (2) and (3) can be controlled by adjusting the reaction components and reaction conditions.

For example, when many dihydric phenol components are made to exist with respect to a dicarboxylic acid component, the said total amount will increase.

Moreover, for example, when the said monohydroxy compound component and/or monocarboxylic acid component are made to exist in a reaction system before an acetylation reaction together with an aromatic dicarboxylic acid component and a dihydric phenol component, the said total amount will increase. At this time, if the usage-amount of the said monohydroxy compound component and/or a monocarboxylic acid component is increased, the said total amount will further increase. On the other hand, if the said monohydroxy compound component and/or a monocarboxylic acid component are not used, the said total amount will fall.

The polyarylate resin of the present invention, from the viewpoint of further improving the solubility of the polyarylate resin in a non-halogenated solvent (especially methyl ethyl ketone), without containing the monohydroxy compound component and the monocarboxylic acid component , it is preferable to have the terminal groups of the formulas (2) and (3) in the total amount.

The polyarylate resin of the present invention can be used in combination with an epoxy resin and a curing accelerator to form a polyarylate resin composition. The polyarylate resin composition is a blend obtained by simply mixing a polyarylate resin, an epoxy resin and a curing accelerator.

The epoxy resin used in the present invention is not particularly limited as long as it is an organic compound having two or more epoxy groups in one molecule. As a specific example of an epoxy resin, For example, bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, phenol and a novolak-type epoxy resin, a cresol novolak-type epoxy resin, an isocyanurate-type epoxy resin, an alicyclic epoxy resin, an acrylic acid-modified epoxy resin, a polyfunctional epoxy resin, a brominated epoxy resin, and a phosphorus-modified epoxy resin. An epoxy resin may be used independently and may use 2 or more types together.

The epoxy equivalent of an epoxy resin is 100-3000 normally, Preferably it is 150-300.

The softening point of an epoxy resin is 200 degrees C or less normally, Preferably it is 100 degrees C or less.

The blending amount of the polyarylate resin is preferably such that the functional group equivalent of the polyarylate resin is in a ratio of 0.5 to 1.5 equivalents, more preferably 0.7 to 1.3 equivalents, with respect to the epoxy equivalent of the epoxy resin. The functional group equivalent of the polyarylate resin corresponds to the equivalent calculated from the content of the phenolic hydroxyl group and the ester group. The compounding quantity of such polyarylate resin is 20-80 mass parts normally with respect to 100 mass parts of total amounts of an epoxy resin and polyarylate resin, Preferably it is 35-65 mass parts, More preferably, it is 40-50 mass parts. is the mass part.

The curing accelerator used in the present invention is not particularly limited, and for example, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, 4- Tertiary amines such as dimethylaminopyridine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, triphenylphosphine, tributylphosphine, etc. organic phosphines of A hardening accelerator may be used independently and may use 2 or more types together.

A hardening|curing agent can be used together with the resin composition of this invention. Examples of the curing agent include aliphatic polyamine compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamine, adipic acid dihydrazide and polyamide polyamine, mensendiamine, and isophorone. alicyclic polyamine compounds such as diamine, bis(4-amino-3-methylcyclohexyl)methane and bis(4-aminocyclohexyl)methane; metaxylenediamine, diaminodiphenylmethane, diamino Aromatic polyamine compounds such as diphenylsulfone and metaphenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic anhydride , monofunctional acid anhydrides such as chlorendic acid anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bis(anhydrotrimate), and difunctional acid anhydrides such as methylcyclohexanetetracarboxylic acid anhydride and free acid carboxylic acids such as trimellitic anhydride and polyazelaic anhydride. A hardening|curing agent may be used independently and may use 2 or more types together.

In the resin composition of the present invention, thermosetting resins such as cyanate resin, isocyanate resin, maleimide resin, polyimide resin, urethane resin, phenol resin, and silica, glass, alumina, talc, mica and inorganic fillers such as barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, titanium oxide, silicon nitride, and boron nitride may be used in combination. A thermosetting resin and an inorganic filler may be used independently, respectively, and may use 2 or more types together. Moreover, it is preferable that the inorganic filler was surface-treated with surface treatment agents, such as an epoxysilane coupling agent and an aminosilane coupling agent.

The polyarylate resin and polyarylate resin composition of the present invention can be dissolved in an organic solvent to obtain a resin solution. The preparation method of the resin solution is not particularly limited, but when preparing the resin solution of the polyarylate resin composition, the polyarylate resin and the epoxy resin are preliminarily prepared rather than simultaneously dissolving the polyarylate resin and the epoxy resin in an organic solvent. It is easy to obtain a uniform resin solution in a short time to mix them after each melt|dissolving in an organic solvent. On the other hand, in the case where the polyarylate resin and the epoxy resin are each dissolved in an organic solvent in advance and then mixed, the closer the solid content concentration of the resin solution of both is, the easier it is to obtain a uniform resin solution in a shorter time.

The organic solvent used for the resin solution of the polyarylate resin of the present invention is not particularly limited as long as the polyarylate resin can be uniformly dissolved, and a non-halogenated solvent is preferable from the viewpoint of the influence on the environment. The organic solvent used for the resin solution of the polyarylate resin composition of the present invention is not particularly limited as long as the epoxy resin and the polyarylate resin can be uniformly dissolved, and a non-halogenated solvent is preferable from the viewpoint of environmental impact. . As for the non-halogenated solvent used for the resin solution of the polyarylate resin of this invention and the resin solution of the polyarylate resin composition of this invention, a common thing can be used. Examples of the non-halogenated solvent include amide compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, and 1,4-dioxane. , 1,3-dioxolane, ether compounds such as tetrahydrofuran, ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, propylene glycol Acetic acid esters, such as monoethyl ether acetate, are mentioned. All of these non-halogenated solvents are useful as general-purpose solvents, and ketone compounds and aromatic hydrocarbons, particularly methyl ethyl ketone and toluene, are useful as more general-purpose solvents. The most useful non-halogenated universal solvent is methyl ethyl ketone. The said organic solvent may be used independently and may use 2 or more types together.

Since the polyarylate resin and polyarylate resin composition of the present invention have very excellent solubility in a non-halogenated solvent, the solid content concentration of each resin solution can be increased. Specifically, it can be 20 mass % or more, Preferably it can be 30 mass % or more, More preferably, it can be 40 mass % or more, More preferably, it can be 50 mass % or more. . In particular, the polyarylate resin of the present invention is, for example, 5 to 40 mass%, preferably 10 to 40 mass%, more preferably 20 to 40 mass%, still more preferably 30 to 40 mass% of solid content. concentration in a non-halogenated solvent. Methyl ethyl ketone and/or toluene used as a solvent for the resin solution of the present invention are widely used in the field of electric and electronic fields, are readily available, and are inexpensive, so they are particularly convenient organic solvents. Conventionally, since polyarylate resin has a high density|concentration of an aromatic ring, it was thought that it is hard to melt|dissolve in the said solvent. However, it turned out that it melt|dissolves in the said solvent at high concentration by making polyarylate resin into a specific resin composition. Therefore, the polyarylate resin and polyarylate resin composition of the present invention have very high handleability in the formation of films and films, and the preparation of prepregs, and their industrial significance is very high.

After coating and drying the resin solution of this invention to a base material, a film can be obtained by forming a film and peeling from a base material. The resin solution which melt|dissolved the polyarylate resin in the organic solvent may be sufficient as the resin solution at the time of forming a film and a film, or the resin solution which melt|dissolved the polyarylate resin composition in the organic solvent may be sufficient as it.

As a base material, a PET film, a polyimide film, a glass plate, and a stainless plate are mentioned, for example. As the coating method, for example, wire bar coating method, film applicator coating method, brush coating method, spray coating method, gravure roll coating method, screen printing method, reverse roll coating method, lip coating method, air knife coating method, curtain flow coating method , dip coating method is mentioned.

A prepreg can be obtained by drying the resin solution of the present invention after impregnating or applying the reinforcing fiber cloth. The resin solution at the time of manufacturing a prepreg may be the resin solution which melt|dissolved polyarylate resin or polyarylate resin composition in the organic solvent.

Examples of the reinforcing fibers constituting the reinforcing fiber cloth include glass fibers, carbon fibers, organic fibers, and ceramic fibers. Any form, such as these woven fabrics and nonwoven fabrics, can be used. Alternatively, synthetic paper obtained by mixing and papermaking these fibers in a short-fiber state using fibrids may also be used. Especially, since it is excellent in workability, glass fiber and carbon fiber are preferable. The thickness of the reinforcing fiber cloth is preferably 5 to 50 μm, more preferably 10 to 45 μm, and still more preferably 15 to 40 μm.

The method for impregnating the reinforcing fiber cloth with the resin solution is not particularly limited, and a known method can be used. As the impregnation method, for example, a method of using a commercially available or self-made continuous impregnation apparatus, a method of immersing the reinforcing fibers in a resin solution made of polyarylate resin, a release paper, a glass plate, a stainless steel plate, etc. Spread the reinforcing fibers on a plate , the method of coating the resin solution which consists of polyarylate resin is mentioned. A prepreg is obtained by evaporating and drying an organic solvent from the coated resin solution after the said coating.

The method for coating the resin solution on the reinforcing fiber cloth is not particularly limited, and a known method can be used. As the said coating method, coating is possible using a commercially available coating machine, for example. In the case of performing double-sided coating, a method of coating on the opposite side after single-sided coating, drying once and then coating on the opposite side, a method of coating on the opposite side without drying after one-side coating, and a method of coating on both sides at the same time . These coating methods can be suitably selected in consideration of workability and the performance of the prepreg obtained. A prepreg is obtained by evaporating and drying an organic solvent from the coated resin solution after the said coating.

Although the thickness of a prepreg changes with the thickness of the reinforcing fiber cloth used, it is preferable that it is 10-150 micrometers, It is more preferable that it is 20-140 micrometers, It is more preferable that it is 30-130 micrometers. On the other hand, the prepreg is obtained by impregnating or coating the reinforcing fiber cloth with a resin solution and then drying it. It can be set as a prepreg with excellent external appearance.

The prepreg of the present invention can be used as it is without heat treatment or the like for curing. In addition, since the polyarylate resin contained in the prepreg melts and exhibits fluidity when heated above its glass transition temperature, the prepreg can be densified as it is or by laminating several sheets and hot pressing to obtain a laminate. have. Since the said laminated body is excellent in adhesiveness between prepregs, mechanical strength is fully improved and it is excellent also in heat resistance. Moreover, the said laminated body can be used as a high-strength plate-shaped molded object. Moreover, this plate-shaped molded object can also be shape|molded into a desired shape. The moldability also differs depending on the material of the reinforcing fiber cloth used and the solid content of the prepreg, but it is possible to perform the shaping process according to a predetermined mold. It is a range which does not impair a mechanical characteristic significantly WHEREIN: You may perform punching etc. When a thermosetting resin is not used, the prepreg of the present invention is particularly excellent in workability such as adhesiveness, shaping workability, and punching property. On the other hand, although cold working is also possible for shaping|shaping and punching, you can also perform working under heating as needed.

By heating the coating film, film, and prepreg obtained by using the solution of the polyarylate resin composition of the present invention, and the laminate thereof, the polyarylate resin and the epoxy resin can be reacted to achieve complete curing. Heating temperature (curing temperature) is 110-250 degreeC normally, Preferably it is 130-220 degreeC. Heating time (curing time) is 1 minute - 20 hours normally, Preferably it is 5 minutes - 10 hours.

The polyarylate resin of the present invention has excellent heat resistance and dielectric properties, and excellent fluidity during processing and solubility in non-halogenated solvents, and therefore can be suitably used as an insulating material for printed wiring boards and the like.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these. In addition, the measurement of the physical property of polyarylate resin was performed by the following method.

(I) Resin composition of polyarylate resin, total amount of terminal groups (2) and (3)

^{By 1} H-NMR analysis using a high-resolution nuclear magnetic resonance apparatus (LA-400 NMR manufactured by Nippon Electronics Co., Ltd.), the resin composition and the total amount of terminal groups (2) and (3) were determined from the peak intensity of each copolymerization component. (resolution: 400 MHz, solvent: a mixed solvent in which the volume ratio of deuterated trifluoroacetic acid and deuterated tetrachloroethane is 1/11, temperature: 50°C).

(II) Glass transition temperature of polyarylate resin

Using a differential scanning calorimetry device (DSC7 manufactured by Perkin Elmer), the temperature was raised from 40°C to 340°C at a temperature increase rate of 20°C/min. did with

S (best): 144° C. or higher;

A (amount): 130°C or higher and lower than 144°C.

B (Pass): 60°C or higher, less than 130°C. (No practical problem)

C (rejected): less than 60°C. (There is a practical problem)

(III) number average molecular weight of polyarylate resin

Chloroform was used as a solvent, and the polyarylate resin pellet was dissolved so that it might become a density|concentration of 1000 ppm, and the solution was obtained. By GPC analysis, the number average molecular weight was calculated|required in conversion of polystyrene.

(IV) solubility of polyarylate resin

The polyarylate resin and methyl ethyl ketone were weighed and put into a glass screw-neck bottle with an internal capacity of 50 mL so that the total amount was 30 g and the solid content concentration was 20, 30, 40, or 50 mass%. Thereafter, the glass screwdriver bottle was sealed, rotated (stirred) at 70 rpm for 24 hours at a room temperature of 23°C using a mixing rotor (stirred), and left still for 2 weeks at a room temperature of 23°C. After standing still, the resin solution was visually observed, and the dissolution stability of the resin solution was judged on the basis of the following criteria. As the polyarylate resin, a state in which it was coarsely pulverized using a pulverizer (DAS-28; manufactured by Daiko Seiki Co., Ltd.) was used. The particles of the polyarylate resin had a maximum diameter of 5 mm. The maximum diameter is the average of the maximum dimensions of any 100 particles.

(circle): Transparency was maintained and it was not thickened.

(triangle|delta): Transparency was not maintained, or it had thickened.

x: Transparency was not maintained, but it was thickening.

In the same manner as in the case where the solvent is methyl ethyl ketone, when the solvent is toluene, cyclohexanone, tetrahydrofuran, 1,3-dioxolin, N-methylpyrrolidone, or N,N-dimethylformamide Also, the stability of the resin solution was confirmed.

(V) dielectric constant and dielectric loss tangent of polyarylate resin composition

50 parts by mass of polyarylate resin, 50 parts by mass of an epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin, epoxy equivalent 184 to 194 g/eq, viscosity 120 to 150 (25° C.), softening point 20° C. or less) , 0.2 mass parts of hardening accelerators (2-ethyl-4-methylimidazole, the Tokyo Chemical Industry company make) and 100 mass parts of methyl ethyl ketones were mixed, it stirred until it became transparent, and the resin solution was obtained.

The obtained resin solution was poured into an aluminum cup and dried at room temperature for 2 hours. Then, using a vacuum dryer, it dried at 170 degreeC under vacuum for 2 hours and then at 200 degreeC under vacuum for 3 hours, solvent removal and hardening were performed, and the hardened|cured material was obtained.

On the other hand, since the polyarylate resins obtained in Comparative Examples 1 to 4 and 6 did not dissolve in methyl ethyl ketone, 300 parts by mass of tetrahydrofuran was used instead of 100 parts by mass of methyl ethyl ketone to obtain a resin solution, and the cured product was made

The plate of the obtained cured product was cut, and the dielectric constant and dielectric loss tangent were measured under the following conditions.

Apparatus: Agilent Technologies, Inc., E4991A RF impedance/material analyzer Sample dimensions: 60 mm long x 60 mm wide x 100 μm thick

Frequency: 1GHz

Measuring temperature: 23℃

Test environment: 23℃±1℃, 50%RH±5%RH

permittivity

S (best): 2.84 or less;

A (amount): greater than 2.84, less than or equal to 2.85;

B (Pass): greater than 2.85, less than or equal to 2.89 (no problem in practice);

C (fail): greater than 2.89 (problems in practice).

hereditary tangent

S (best): 0.010 or less;

A (amount): greater than 0.010, less than or equal to 0.011;

B (pass): greater than 0.011, less than or equal to 0.013 (no problem in practice);

C (fail): greater than 0.013 (problems in practice).

(VI) Flowability of polyarylate resin composition

The plate of the cured product obtained in (V) was observed, and the fluidity of the polyarylate resin composition was judged on the basis of the following criteria.

(circle): Bubbles were not seen in hardened|cured material.

x: Bubbles were seen in hardened|cured material.

(VII) Glass transition temperature of polyarylate resin composition

The glass transition temperature of the polyarylate resin composition was measured by the method similar to the measuring method of the glass transition temperature of polyarylate resin except having used the hardened|cured material obtained in (V).

S (best): 163° C. or higher;

A (amount): 150°C or higher and lower than 163°C;

B (Pass): 110°C or higher and lower than 150°C (no problem in practical use);

C (rejected): less than 110°C (there is a problem in practice).

Example 1

In a reaction vessel equipped with a stirring device, 8.3 parts by mass of TPA, 8.3 parts by mass of IPA, 14.3 parts by mass of BisA, 19.4 parts by mass of BisTMC, 6.9 parts by weight of PHBA, and 32.2 parts by mass of acetic anhydride (TPA:IPA:BisA:BisTMC: PHBA: acetic anhydride (molar ratio) = 50: 50: 63: 63: 50: 315), under a nitrogen atmosphere, under normal pressure, at 140 ° C. for 2 hours, stirred and mixed to react.

Then, it heated up to 280 degreeC over 3 hours, and hold|maintained at 280 degreeC for 1 hour.

Then, it pressure-reduced to 130 Pa over 90 minutes, it stirred for 2 hours, and obtained polyarylate resin.

When the resin composition of the obtained polyarylate resin was analyzed, TPA:IPA:BisA:BisTMC:PHBA (molar ratio) = 50:50:63:63:50, which was the same as the composition of the preparation.

Examples 2 to 16 and Comparative Examples 1 to 6?

As described in the table below, except for changing the composition of the feed of the raw material, the same operation as in Example 1 was performed to obtain a polyarylate resin.

Example 17

To a reaction vessel equipped with a stirring device, 5.0 parts by mass of TPA, 11.6 parts by mass of IPA, 14.3 parts by mass of BisA, 19.4 parts by mass of BisTMC, and 25.5 parts by mass of acetic anhydride (TPA: IPA: BisA: BisTMC: acetic anhydride (molar ratio)) =30:70:62.5:62.5:250), under a nitrogen atmosphere, at normal pressure, 140° C. for 2 hours, followed by stirring and mixing.

Subsequently, after adding 5.1 parts by mass of PHBA at 140 ° C., the temperature was raised to 280 ° C. over 3 hours, maintained at 280 ° C. for 1 hour, and then reduced to 130 Pa over 90 minutes at 280 ° C., and stirred for 2 hours. , to obtain a polyarylate resin.

When the resin composition of the obtained polyarylate resin was analyzed, TPA:IPA:BisA:BisTMC:PHBA (molar ratio) = 30:70:63:63:37, which was the same as the composition of the preparation.

Examples 18-19?

As described in the table below, except for changing the composition of the input of the raw material, the same operation as in Example 17 was performed to obtain a polyarylate resin.

The resin composition of the polyarylate resin obtained in Examples 1-19 and Comparative Examples 1-6, its evaluation, and evaluation of the polyarylate resin composition are shown in the following table|surface.

TPA: terephthalic acid

NDCA: 2,6-naphthalenedicarboxylic acid

IPA: isophthalic acid

BisA: 2,2-bis (4-hydroxyphenyl) propane

BisAP: 1,1-bis(4-hydroxyphenyl)-1-phenylethane

BisTMC: 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane

BisCDE: 1,1-bis(4-hydroxyphenyl)-cyclododecane

PHBA: parahydroxybenzoic acid

HNA: 2-hydroxy-6-naphthoic acid

Ac ₂ O: acetic anhydride

BA: benzoic acid

St: stearic acid

1-NPOH: 1-naphthol

The polyarylate resins of Examples 1 to 19 were excellent in heat resistance and solubility in non-halogenated solvents, and were excellent in dielectric properties and fluidity during processing when used as a resin composition.

The polyarylate resins of Comparative Examples 1 and 2 had poor solubility because no hydroxycarboxylic acid component was used.

The polyarylate resin of Comparative Example 3 had poor solubility because the content of the dihydric phenol represented by the formula (1) was higher than the range prescribed in the present invention.

The polyarylate resin of Comparative Example 4 had poor solubility because the content of the dihydric phenol represented by the formula (1) was less than the range prescribed in the present invention.

Since the polyarylate resin of Comparative Example 5 contained more hydroxycarboxylic acid components than the range prescribed by the present invention, the solubility thereof was poor. In addition, methyl ethyl ketone, toluene, cyclohexanone, tetrahydrofuran, 1,3-dioxolin, N-methylpyrrolidone, N,N-dimethylformamide did not dissolve in any solvent, so preparation of a cured product could not do

Since the polyarylate resin of Comparative Example 6 had a number average molecular weight higher than the range prescribed in the present invention, the solubility was poor. Moreover, when it was set as the resin composition, the fluidity|liquidity at the time of a process was bad.

The polyarylate resin and its resin composition of the present invention are useful as insulating materials used in the electronic field. The polyarylate resin and its resin composition of the present invention are particularly useful as insulating materials for printed wiring boards and the like.

Claims (14)

A polyarylate resin containing a dihydric phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component, comprising:
The content of the dihydric phenol represented by the general formula (1) in the total dihydric phenol component is 30 to 70 mol%,
The content of the hydroxycarboxylic acid component in the total monomer component is 1 to 30 mol%,
Polyarylate resin characterized in that the number average molecular weight is less than 10000:

[In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom, and R ⁵ and R ⁶ are the values of m a plurality of R ⁵ and a plurality of R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m represents an integer of 4 to 12, and X represents a carbon atom forming a saturated aliphatic hydrocarbon ring together with the carbon atom to which the hydroxyphenyl group is bonded]. The method of claim 1,
The polyarylate resin has a structure represented by the following formula (2) and/or (3) as a terminal group,
A polyarylate resin characterized in that the total amount of the terminal groups of the following formulas (2) and (3) is 100 geq/ton or more:

[The terminal group of formula (2) represents the structure derived from the monohydroxy compound component, the terminal group of the formula (3) represents the structure derived from the monocarboxylic acid component, and R ⁷ and R ⁸ are each independently an aliphatic hydrocarbon group or represents an aromatic hydrocarbon group]. The method of claim 1,
The dihydric phenol represented by the formula (1) is 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and/or 1,1-bis(4-hydroxyphenyl) - Polyarylate resin, characterized in that cyclododecaine. The method of claim 1,
The content of isophthalic acid in the wholly aromatic dicarboxylic acid component is 50 mol% or more, The polyarylate resin characterized by the above-mentioned. 5. The method according to any one of claims 1 to 4,
The dihydric phenol component is 2,2-bis(4-hydroxyphenyl)propane (BisA) and/or 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BisAP), and the formula A polyarylate resin containing the dihydric phenol represented by (1). 6. The method of claim 5,
The content ratio of the total content of the BisA and/or the BisAP and the total content of the dihydric phenol represented by the formula (1) ((BisA+BisAP)/(dihydric phenol represented by the formula (1))) is 35 /65 to 65/35 (molar ratio), polyarylate resin. 5. The method according to any one of claims 1 to 4,
The polyarylate resin, wherein the content ratio of the dihydric phenol component and the aromatic dicarboxylic acid component is 70/100 to 140/100 (molar ratio). A polyarylate resin composition comprising the polyarylate resin according to any one of claims 1 to 4, an epoxy resin, and a curing accelerator. The polyarylate resin according to any one of claims 1 to 4; or a polyarylate resin composition comprising the polyarylate resin according to any one of claims 1 to 4, an epoxy resin, and a curing accelerator. The polyarylate resin according to any one of claims 1 to 4; or a polyarylate resin composition comprising the polyarylate resin according to any one of claims 1 to 4, an epoxy resin, and a curing accelerator; a film comprising. The polyarylate resin according to any one of claims 1 to 4 and an organic solvent; or the polyarylate resin composition comprising the polyarylate resin according to any one of claims 1 to 4, an epoxy resin and a curing accelerator, and an organic solvent; a resin solution comprising. 12. The method of claim 11,
The resin solution, wherein the organic solvent is a non-halogenated solvent. A prepreg in which the resin solution according to claim 11 is impregnated or coated on a reinforcing fiber cloth. A laminate, wherein the prepreg according to claim 13 is laminated.