TWI746536B - Polyarylate resin and resin composition thereof - Google Patents

Abstract

The present invention provides a polyarylate resin which has excellent heat-resisting properties and dielectric properties and is also excellent in flow properties during a processing treatment and solubility properties in a non-halogenated solvent. The present invention relate to a polyarylate resin comprising a dihydric phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component, wherein a content of the dihydric phenol component shown by the general formula (1) is 30 to 70 mol% in all of the dihydric phenol components, a content of the hydroxycarboxylic acid component is 1 to 30 mol% in all of the monomer components, and a number-average molecular weight of the polyarylate resin is less than 10000:

[wherein R¹, R², R³ and R⁴ represent respectively a hydrogen atom, a hydrocarbon group having 1 to 12 of carbon atoms or a halogen atom and R⁵ and R⁶ represent respectively a hydrogen atom or a hydrocarbon group having 1 to 4 of carbon atoms; and m is an integer of 4 to 12 and X represents a carbon atom to form 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 to non-halogenated solvents; and a composition of polyarylate resin containing the polyarylate resin Things.

In recent years, with the increase in the amount of information processing of various electronic equipment, the high integration of semiconductor devices, the high density of wiring, and the multi-layer technology have developed 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 the signal transmission speed, and further, require a low dielectric loss tangent to reduce the loss during signal transmission. In addition, insulating materials such as printed wiring boards are required to have excellent heat resistance that can withstand heat treatment such as soldering treatment.

Polyarylate resins are known as resins having excellent dielectric properties such as heat resistance, dielectric constant, and dielectric loss tangent. For example, Patent Document 1 discloses that a resin composition obtained by blending an active ester compound, a curing accelerator, and an epoxy resin in a polyarylate resin is used for a printed wiring board.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2004-224890

When the polyarylate resin is used for a printed wiring board or the like, the polyarylate resin is dissolved in an organic solvent and used. However, in general, although polyarylate resins have low solubility and dissolve in halogenated solvents, they have low solubility in non-halogenated solvents, or even in soluble ones, which have been expected in recent years due to increased environmental awareness. In this case, the stability of the solution is also poor. Furthermore, even if the polyarylate resin is dissolved in a non-halogenated solvent, there is a problem that the dissolved amount is too small. In addition, in general, polyarylate resin has a relatively high glass transition temperature and low fluidity during processing. Therefore, when the prepreg is multilayered, it is easy to produce voids and cannot obtain a multilayer with high reliability. Problems with printed wiring boards.

In view of this conventional technology, the purpose of the present invention is to provide a polyarylate resin with excellent heat resistance and dielectric properties, and excellent fluidity during processing and solubility in non-halogenated solvents; and containing the same Polyarylate resin composition of polyarylate resin.

The inventors of the present invention have made diligent studies to solve the above-mentioned problems. As a result, they have found that a specific amount of a specific dihydric phenol component in a polyarylate resin further contains a specific amount of hydroxycarboxylic acid component, and the number average molecular weight is set to The specific scope can achieve the above-mentioned object, thereby achieving the present invention.

That is, the gist of the present invention is as follows.

<1>

[式(1)中，R¹、R²、R³及R⁴分別獨立地表示氫原子、碳原子數為1~12之烴基或鹵素原子，R⁵及R⁶分別獨立地表示氫原子或碳數為1~4之烴基；m表示4~12之整數，X表示與羥基苯基鍵結之碳原子一起形成飽和脂肪族烴環之碳原子]。 A polyarylate resin containing a dihydric phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component, and is characterized in that: among all the dihydric phenol components, the dihydric phenol represented by the general formula (1) The content is 30~70 mol%, the content of hydroxycarboxylic acid in all monomer components is 1~30 mol%, and the number average molecular weight is less than 10,000;

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

<2>

[通式(2)之末端基表示源自單羥基化合物成分之結構，通式(3)之末端基表示源自單羧酸成分之結構，R⁷及R⁸分別獨立地表示脂 肪族烴基或芳香族烴基]。 The polyarylate resin as described in <1>, wherein the polyarylate resin has a structure represented by the following general formula (2) or/and (3) as a terminal group, and the following general formula (2) and (3) The total amount of the end groups of) is more than 100geq/t;

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

<3>

The polyarylate resin as described in <1> or <2>, wherein the dihydric phenol represented by the general formula (1) is 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl Cyclohexane and/or 1,1-bis(4-hydroxyphenyl)-cyclododecane.

<4>

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

<5>

The polyarylate resin according to any one of <1> to <4>, wherein the dihydric phenol component contains 2,2-bis(4-hydroxyphenyl)propane (BisA) and/or 1,1- Bis(4-hydroxyphenyl)-1-phenylethane (BisAP) and the dihydric phenol represented by the above general formula (1).

<6>

The polyarylate resin according to <5>, wherein the content ratio of the total content of the above BisA and/or the above BisAP to the total content of the dihydric phenol represented by the above general formula (1) ((BisA+BisAP)/( The dihydric phenol represented by the general formula (1)) is 35/65 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 to the aromatic dicarboxylic acid component is 70/100 to 140/100 (molar ratio) .

<8>

A polyarylate resin composition characterized by comprising the polyarylate resin described in any one of <1> to <7>, an epoxy resin, and a hardening accelerator.

<9>

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

<10>

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

<11>

A resin solution characterized by containing the polyarylate resin described in any one of <1> to <7> or the polyarylate resin composition described in <8>, and an organic solvent.

<12>

The resin solution as described in <11>, wherein the above-mentioned organic solvent is a non-halogenated solvent.

<13>

A prepreg characterized in that it is impregnated or coated on a reinforced fiber cloth with the resin solution described in <11> or <12>.

<14>

A laminated body characterized in that it is a prepreg described in the laminated layer <13>.

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

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 the alicyclic dihydric phenol represented by the general formula (1). The phenolic hydroxyl group is a hydroxyl group directly bonded to an aromatic ring.

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, more preferably 1 to 3, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl Base, isobutyl, tertiary butyl, n-pentyl, n-hexyl, etc. The unsaturated aliphatic hydrocarbon group includes an alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3, and examples thereof include vinyl groups, allyl groups, and the like. The aromatic hydrocarbon group includes an aryl group having 6 to 10 carbon atoms, preferably 6, and examples thereof include a phenyl group and a naphthyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.

In formula (1), preferred R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms (especially 1 to 3), and 6 to 10 carbon atoms ( Especially 6) aryl group or halogen atom (especially chlorine atom, bromine atom). More preferably, 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 (especially 1 to 3). R ¹ , R ² , R ³ and R ⁴ may be a part or all of groups different from each other, or may be the same group, 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 groups with 1 to 4 carbon atoms include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. The saturated aliphatic hydrocarbon group contains an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and Tributyl and so on. The unsaturated aliphatic hydrocarbon group includes an alkenyl group having 1 to 4, preferably 1 to 3 carbon atoms, and examples thereof include vinyl groups, allyl groups, and the like. There are several R ⁵ and R ⁶ depending on the value of m described below, and the several R ⁵ and several R ⁶ may be independently selected from the above-mentioned range.

In formula (1), preferred R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, especially a hydrogen atom.

In formula (1), m represents an integer of 4-12, preferably an integer of 4-11, more preferably an integer of 5-11. In the formula (1), X represents a carbon atom that forms a saturated aliphatic hydrocarbon ring (monocyclic) together with the carbon atom bonded to the hydroxyphenyl group. The saturated aliphatic hydrocarbon ring means a cycloalkane ring corresponding to the number of m. As specific examples of saturated aliphatic hydrocarbon rings, for example, cyclopentane ring (m=4), cyclohexane ring (m=5), cycloheptane ring (m=6), cyclooctane ring ( m=7), cyclononane ring (m=8), cyclodecane ring (m=9), cycloundecane ring (m=10), cyclododecane ring (m=11), ring thirteen Alkyl ring (m=12).

In the alicyclic dihydric phenol represented by the general formula (1), the solubility, heat resistance and dielectric properties of polyarylate resin to non-halogenated solvents (especially methyl ethyl ketone) And from the viewpoint of further improvement of the heat resistance of the cured product of the polyarylate resin and epoxy resin, preferred specific examples include general formulas (1a), (1b), (1c), ( 1d), (1e), (1f), (1g), (1h) and (1i), especially the alicyclic dihydric phenols represented by the general formulas (1b) to (1h).

In formula ^{(1a), R 1, R} 2, R 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

In formula (1a), n1 is an integer of 0-8, preferably an integer of 0-4, and more preferably an integer of 0-2.

In the formula (1a), R ¹⁰ represents a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon groups with 1 to 4 carbon atoms include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. The saturated aliphatic hydrocarbon group contains an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and Tributyl and so on. The unsaturated aliphatic hydrocarbon group includes an alkenyl group having 1 to 4, preferably 1 to 3 carbon atoms, and examples thereof include vinyl groups, allyl groups, and the like. When the above n1 is an integer of 2 or more, a plurality of R ¹⁰ may be independently selected from the above range. ^{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 taken as one position, it is preferable that each R ¹⁰ and the selected Bonding from the carbon atoms in the third and fourth positions.

Preferably, R ¹⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ¹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

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

In the formula ^{(1b), R 1, R} 2, R 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

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

In the formula (1b), R ²⁰ is the same as ^{R 10} in the above formula (1a). When the above n2 is an integer of 2 or more, a plurality of R ^{20 may be} independently selected from the same range as the ^{above R 10. 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 taken as one position, it is preferable that each R ²⁰ and the selected Bonding from the carbon atoms in the third, fourth, and fifth positions, especially the carbon atoms in the third and fifth positions.

Preferably, R ²⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ²⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic dihydric phenol represented by the general formula (1b) include, for example, 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-Trimethylcyclohexane [BisTMC], 1,1-bis(4-hydroxyphenyl)-3,3,5-triethylcyclohexane, 1,1-bis-(4-hydroxy Phenyl)-3,3,5,5-tetramethyl-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,4-trimethyl-cyclohexane, 1, 1-Bis-(4-hydroxyphenyl)-3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis-(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane , 1,1-bis-(3-methyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(3-phenyl-4-hydroxybenzene) Yl)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(3,5-dichloro-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane Alkyl, 1,1-bis-(3,5-dibromo-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane. Among them, in terms of higher versatility, BisTMC is particularly preferred.

In formula ^{(1c), R 1, R} 2, R 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

In formula (1c), n3 is an integer of 0-12, preferably an integer of 0-6, and more preferably an integer of 0-2.

In the formula (1c), R ³⁰ is the same as ^{R 10} in the above formula (1a). When the above n3 is an integer of 2 or more, a plurality of R ^{30 may be} independently selected from the same range as the ^{above R 10. 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 taken as one position, it is preferable that each R ³⁰ and the selected Bonding from carbon atoms of carbon atoms in the third, fourth, fifth, and sixth positions.

Preferably, R ³⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ³⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

As a specific example of the alicyclic dihydric phenol represented by general formula (1c), 1,1-bis(4-hydroxyphenyl)-cycloheptane is mentioned, for example.

Formula Example ^{(1d), R 1, R 2, R} 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

In formula (1d), n4 is an integer of 0-14, preferably an integer of 0-7, and more preferably an integer of 0-2.

In the formula (1d), R ⁴⁰ is the same as ^{R 10} in the above formula (1a). When the above n4 is an integer of 2 or more, a plurality of R ^{40 may be} independently selected from the same range as the ^{above R 10. 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 taken as one position, it is preferable that each R ⁴⁰ and the selected Bonding from carbon atoms in the fourth, fifth, and sixth carbon atoms.

Preferably, R ⁴⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ⁴⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

As a specific example of the alicyclic dihydric phenol represented by general formula (1d), 1,1-bis(4-hydroxyphenyl)-cyclooctane is mentioned, for example.

In the formula ^{(1e), R 1, R} 2, R 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

In formula (1e), n5 is an integer of 0-16, preferably an integer of 0-8, and more preferably an integer of 0-2.

In the formula (1e), R ⁵⁰ is the same as ^{R 10} in the above formula (1a). When the above n5 is an integer of 2 or more, a plurality of R ^{50 may be} independently selected from the same range as the ^{above R 10. The bonding position of R 50} in the cyclononane ring is not particularly limited. When the carbon atom of the cyclononane ring to which the hydroxyphenyl group is bonded in formula (1e) is taken as one position, it is preferable that each R ⁵⁰ and the selected Bonding from carbon atoms in the fourth, fifth, sixth, and seventh carbon atoms.

Preferably, R ⁵⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ⁵⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

As a specific example of the alicyclic dihydric phenol represented by general formula (1e), 1,1-bis(4-hydroxyphenyl)-cyclononane is mentioned, for example.

Of formula (1f) in ^{a, R 1, R 2, R} 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

In formula (1f), n6 is an integer of 0-18, preferably an integer of 0-9, and more preferably an integer of 0-2.

In the formula (1f), R ⁶⁰ is the same as ^{R 10} in the above formula (1a). When the above n6 is an integer of 2 or more, a plurality of R ^{60 may be} independently selected from the same range as the ^{above R 10. 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 formula (1f) is taken as one position, it is preferable that each R ⁶⁰ and the selected From the fourth, fifth, sixth, seventh and eighth positions, especially the fifth, sixth and seventh carbon atoms, the carbon atoms are bonded.

Preferably, R ⁶⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ⁶⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

As a specific example of the alicyclic dihydric phenol represented by general formula (1f), 1,1-bis(4-hydroxyphenyl)-cyclodecane is mentioned, for example.

^1, R ^2, the same as ^{(1g), R 1, R} 2, R 3 and R ⁴ of the formula R (1) in the respective formulas R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

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

In the formula (1g), R ⁷⁰ is the same as ^{R 10} in the above formula (1a). When the above n7 is an integer of 2 or more, a plurality of R ^{70 may be} independently selected from the same range as the ^{above R 10. The bonding position of R 70} in the cycloundecane ring is not particularly limited. When the carbon atom of the cycloundecane ring to which the hydroxyphenyl group is bonded in the formula (1g) is taken as one position, each R ^{70 is preferred} Bonds to a carbon atom selected from the four, five, six and seven carbon atoms.

Preferably, R ⁷⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ⁷⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

As a specific example of the alicyclic dihydric phenol represented by general formula (1g), 1,1-bis(4-hydroxyphenyl)-cycloundecane is mentioned, for example.

[化11]

In the formula ^{(1h), R 1, R} 2, R 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

In formula (1h), n8 is an integer of 0-22, preferably an integer of 0-11, and more preferably an integer of 0-2.

In the formula (1h), R ⁸⁰ is the same as ^{R 10} in the above formula (1a). When the above n8 is an integer of 2 or more, a plurality of R ^{80 may be} independently selected from the same range as the ^{above R 10. The bonding position of R 80 in} the cyclododecane ring is not particularly limited. When the carbon atom of the cyclododecane ring to which the hydroxyphenyl group is bonded in formula (1h) is taken as one position, each R ^{80 is preferred} Bonding with a carbon atom selected from the carbon atoms of the five, six, seven, eight, and ninth positions.

Preferably, R ⁸⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ⁸⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

As a specific example of the alicyclic dihydric phenol represented by General formula (1h), 1,1-bis(4-hydroxyphenyl)-cyclododecane (BisCDE) is mentioned, for example.

[化12]

In the formula ^{(1i), R 1, R} 2, R 3 and R ⁴ in the formula R (1) in the ^1, R ^2, the same as R ³ and R ^4, and preferably the R ^1, R ^2, R ³ And R ⁴ and more preferably R ¹ , R ² , R ³ and R ^{4 are} also the same as in the above formula (1).

In formula (1i), n9 is an integer of 0-24, preferably an integer of 0-12, and more preferably an integer of 0-2.

In the formula (1i), R ⁹⁰ is the same as ^{R 10} in the above formula (1a). When the above n9 is an integer of 2 or more, a plurality of R ^{90 may be} independently selected from the same range as the ^{above R 10. 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 is bonded in the formula (1i) is taken as one position, each R ^{90 is preferred} Bonds to a carbon atom selected from the carbon atoms of the sixth, seventh, eighth and ninth positions.

Preferably, R ⁹⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R ⁹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms.

As a specific example of the alicyclic dihydric phenol represented by general formula (1i), 1,1-bis(4-hydroxyphenyl)-cyclotridecane is mentioned, for example.

The content of the alicyclic dihydric phenol represented by the above general formula (1) must be 30 to 70 mole% with respect to all dihydric phenol components. For non-halogenated solvents (Especially methyl ethyl ketone) from the viewpoint of further improvement of solubility, heat resistance and dielectric properties, the content relative to all dihydric phenol components is preferably 40~65 mol%, more preferably 45~65 mole%, more preferably 45~55 mole%. When the content of the above-mentioned alicyclic dihydric phenol in all dihydric phenol components is less than 30 mol%, when it exceeds 70 mol%, in any case, the polyarylate resin is not halogenated Solvents (especially methyl ethyl ketone) have reduced solubility, which is not good. The alicyclic dihydric phenol represented by the above general formula (1) may be used alone or in combination of several types. In this case, the total amount of these may be within the above range. The solubility of polyarylate resin in non-halogenated solvents not only includes the solubility of polyarylate resin in non-halogenated solvents with a solid content concentration of about 20% by mass, but also includes the solid content concentration as described below, preferably 30% by mass Above, more preferably 40% by mass or more, and more preferably 50% by mass or more, high-concentration solubility in a non-halogenated solvent. 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 related to relative permittivity and dielectric loss tangent.

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

The dihydric phenols other than the alicyclic dihydric phenol represented by the above general formula (1) are not special as long as the dihydric phenol components are not included in the alicyclic dihydric phenol represented by the above general formula (1) Limited, for example, the following dihydric phenols: 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane [BisA], 2,2-bis(3,5-di Methyl-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane Alkane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 4,4 '-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 9,9-bis(4-hydroxyphenyl) sulfide, 9,9- Bis(4-hydroxy-3-methylphenyl) pyridium, N-phenyl-3,3-bis(4-hydroxyphenyl)phthalimide, N-methyl-3,3-bis (4-hydroxyphenyl)phthalimide, 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, in terms of versatility and higher solubility in non-halogenated solvents (especially methyl ethyl ketone), BisA and/or BisAP are preferred. Dihydric phenols other than the alicyclic dihydric phenol represented by the above general formula (1) may be used alone, or several types may be used in combination.

As the dihydric phenol component, the above dihydric phenols may be used alone, or several types may be used in combination. In terms of the solubility of polyarylate resin in non-halogenated solvents (especially methyl ethyl ketone) becomes higher, it is preferred To use several kinds. Among them, from the viewpoint of further improving the solubility of the polyarylate resin to non-halogenated solvents (especially methyl ethyl ketone), it is preferable that the dihydric phenol component combination contains BisA and/or BisAP and the general formula (1 ) Represented by the alicyclic dihydric phenol (especially BisTMC and/or BisCDE), more preferably a combination of BisA and the alicyclic dihydric phenol represented by the general formula (1) (especially BisTMC and/or BisCDE) . When BisA and/or BisAP and the alicyclic dihydric phenol represented by general formula (1) (especially BisTMC and/or BisCDE) are used, the total content of BisA and BisAP is the same as that represented by general formula (1) The content ratio of the total content of alicyclic dihydric phenols (especially BisTMC and BisCDE) ((BisA+BisAP)/(dihydric phenol represented by general formula (1))) is preferably set to 10/90~90 /10 (mole ratio), especially in terms of the solubility, heat resistance and dielectric properties of polyarylate resin to non-halogenated solvents (especially methyl ethyl ketone), more It is preferably set to 35/65 to 65/35 (molar ratio), and more preferably to be set to 40/60 to 60/40 (molar ratio).

The aromatic dicarboxylic acid component may be any organic compound containing two carboxyl groups directly bonded to an aromatic ring in one molecule. As specific examples of aromatic dicarboxylic acid components, for example, terephthalic acid [TPA], isophthalic acid [IPA], phthalic acid, 4,4'-diphenyl dicarboxylic acid, di Phenyl ether-2,2'-dicarboxylic acid, diphenyl 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-naphthalene dicarboxylic acid [NDCA], diphthalic acid bis(p-carboxyphenyl) Alkanes.

As the aromatic dicarboxylic acid component, one of the above-mentioned compounds may be used alone, or several compounds may be used in combination. Among them, from the viewpoint of further improvement of the solubility and dielectric properties of the polyarylate resin to non-halogenated solvents (especially methyl ethyl ketone), it is preferable to use at least IPA, and more preferably to use TPA and/or in combination. NDCA and IPA are used, and it is more preferable to use TPA and IPA in combination. The content of IPA relative to all aromatic dicarboxylic acid components is preferably 30 mol% or more, more preferably 50 mol% or more, and still more preferably 50-90 mol%, most preferably It is set to 60~85 mol%. In the case where 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 to non-halogenated solvents (especially methyl ethyl ketone) In other words, the content ratio of (TPA+NDCA)/IPA is calculated in molar ratio, preferably 10/90~70/30, more preferably 10/90~50/50, and more preferably 15/85~40/ 60, more preferably 20/80~40/60.

The content ratio of the dihydric phenol component to the aromatic dicarboxylic acid component (dihydric phenol component/aromatic dicarboxylic acid component) is usually 70/100~140/100 (mole ratio). Solvent (especially methyl ethyl ketone) solubility and heat resistance further From the viewpoint of step improvement, it is preferably 90/100~140/100 (molar ratio), more preferably 105/100~140/100 (molar ratio), and still more preferably 110/100~135/100 (Mole ratio), the best is 115/100~130/100 (Mole ratio).

The hydroxycarboxylic acid may be all organic compounds (especially aromatic compounds) containing one hydroxyl group and one carboxyl group in one molecule. Specific examples of hydroxycarboxylic acids include, for example, benzene-based hydroxycarboxylic acids such as p-hydroxybenzoic acid [PHBA] and m-hydroxybenzoic acid; 2-hydroxy-6-naphthoic acid (HNA), 2-hydroxy-3- Naphthalene-based hydroxycarboxylic acids such as naphthoic acid and 1-hydroxy-4-naphthoic acid. Among them, in terms of the solubility of the polyarylate resin in non-halogenated solvents (especially methyl ethyl ketone), the heat resistance and versatility of the cured product of the polyarylate resin composition are further improved, it is preferably Benzene-based hydroxycarboxylic acid, PHBA is particularly preferred.

The content of the hydroxy carboxylic acid component relative to 100 mol% of all monomer components must be set to 1-30 mol%. As for the solubility of polyarylate resin to non-halogenated solvents (especially methyl ethyl ketone), From the viewpoint of further improving the heat resistance of the arylate resin and polyarylate resin composition, and the dielectric properties of the cured polyarylate resin and polyarylate resin composition, it is preferably 4-21 mol%, It is more preferably 4-19 mol%, and still more preferably 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 to non-halogenated solvents (especially methyl ethyl ketone) is reduced. Furthermore, all monomer components refer to all monomer components constituting the polyarylate resin. For example, when the polyarylate resin contains only dihydric phenol components, aromatic dicarboxylic acid components, and hydroxycarboxylic acid components, all monomer components are dihydric phenol components, aromatic dicarboxylic acid components, and hydroxycarboxylic acid components. All of them (total amount). Moreover, for example, when the polyarylate resin also contains other monomer components in addition to the dihydric phenol component, the aromatic dicarboxylic acid component, and the hydroxycarboxylic acid component, it is all of these components (total amount). The monomer component means a bifunctional or higher organic compound capable of undergoing a polymerization reaction. therefore, When the polyarylate resin contains the following monohydroxy compound component and/or monocarboxylic acid component, the monohydroxy compound component and/or monocarboxylic acid component is not included in all monomer components.

The polyarylate resin may contain monomer components other than the above-mentioned dihydric phenol component, aromatic dicarboxylic acid component, and hydroxycarboxylic acid component within a range that does not impair the effects of the present invention. Specific examples of other monomer components include, for example, aliphatic diols such as ethylene glycol and propylene glycol; 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanedi Alicyclic diols such as alcohols; polyols such as trimethylolpropane and pentaerythritol; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexane Alicyclic dicarboxylic acids such as alkanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid; polycarboxylic acids such as trimellitic acid and pyromellitic acid. Aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and polycarboxylic acids may be derivatives and anhydrides thereof. The content of the above-mentioned other monomer components is relative to 100 mol% of all monomer components, and is usually 10 mol% or less, preferably 5 mol% or less, and more preferably 0 mol%.

The manufacturing method of the polyarylate resin of this invention is not specifically limited, For example, the method of performing an acetylation reaction and a deacetic acid polymerization reaction to manufacture a polyarylate resin can be mentioned.

The acetylation reaction is a reaction in which the dihydric phenol component is acetylated. In the acetylation reaction, put the dicarboxylic acid component and acetic anhydride into the reaction tank, perform nitrogen replacement, under an inert atmosphere, at a temperature of 100-240 ℃, preferably 120-180 ℃, in normal Stir under pressure or pressure for 5 minutes to 8 hours, preferably 30 minutes to 5 hours. The molar ratio of acetic anhydride to the hydroxyl group of the dihydric phenol component and hydroxycarboxylic acid component, or the molar ratio of acetic anhydride to the hydroxyl group of the dihydric phenol component, hydroxycarboxylic acid component, and monohydroxy compound is preferably set to 1.00~ 1.20.

Deacetic acid polymerization reaction system to make acetylated dihydric phenol and aromatic dihydric The carboxylic acid reacts and undergoes a polycondensation reaction. In the deacetic acid polymerization reaction, at a temperature of 240°C or higher, preferably 260°C or higher, and more preferably 280°C or higher, 500 Pa or lower, preferably 260 Pa or lower, more preferably 130 Pa or lower under reduced pressure conditions Keep it for more than 30 minutes and stir. When the temperature is less than 240°C, when the pressure reduction degree exceeds 500 Pa, and when the holding time is less than 30 minutes, the deacetic acid reaction may be insufficient, and the amount of acetic acid in the obtained polyarylate resin may change. High, or the overall polymerization time becomes longer, or the color of the polymer deteriorates.

After the acetylation reaction is carried out, until the deacetic acid polymerization reaction is carried out, there is usually a preliminary stage of adjusting the temperature and pressure of the reaction system to the temperature and pressure for the deacetic acid polymerization reaction. In the manufacturing method of the polyarylate resin of the present invention, a hydroxycarboxylic acid component can be added in this preliminary stage. Specifically, in the preliminary stage, when the reaction system is heated up and then pressure is reduced, 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. The hydroxycarboxylic acid component may be added before the temperature rise, and after the temperature rise and before the pressure is reduced.

In the acetylation reaction and the deacetic acid polymerization reaction, it is preferable to use a catalyst as necessary. 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, hydroxybutyl tin oxide, and tin octoate Other organotin compounds; N-methylimidazole and other heterocyclic compounds. The addition amount of the catalyst is preferably 1.0% by mass or less with respect to the mass of the resin obtained.

As an apparatus for producing the polyarylate resin of the present invention, known reaction apparatuses can be cited, for example, a batch type reaction apparatus and a continuous type reaction apparatus can be cited.

The number average molecular weight of the polyarylate resin of the present invention must be less than 10,000, preferably less than 8,000, more preferably less than 6,000, and more preferably less than 4,000 The best is 3000 or less. When the number average molecular weight is 10,000 or more, the glass transition temperature of the polyarylate resin becomes high, and the fluidity during processing becomes poor, which is not good. In addition, the solubility of the polyarylate resin in non-halogenated solvents (especially methyl ethyl ketone) is reduced. The lower limit of the number average molecular weight of the polyarylate resin is not particularly limited. Generally, the number average molecular weight is 500 or more, preferably 1,000 or more.

The number average molecular weight of the polyarylate resin can be controlled by adjusting the reaction conditions. For example, if the reaction time is shortened within the above range, or the reaction temperature is decreased within the above range, the number average molecular weight will decrease. Also, for example, if the reaction time is extended within the above range or the reaction temperature is increased within the above range, the number average molecular weight will increase. In addition, it can be controlled by adjusting the molar ratio of the dicarboxylic acid component and the dihydric phenol component within the range of 200:100 to 100:200. For example, if the molar ratio difference between the dicarboxylic acid component and the dihydric phenol component is increased within the above range, the number average molecular weight will decrease. Also, for example, if the difference in molar ratio between the dicarboxylic acid component and the dihydric phenol component is reduced within the above range, the number average molecular weight will increase. In addition, it can be controlled by adjusting the total amount of the monohydroxy compound or/and the monocarboxylic acid component. For example, if the total amount of the monohydroxy compound or/and the monocarboxylic acid component is increased, the number average molecular weight will decrease. Also, for example, if the total amount of the monohydroxy compound or/and the monocarboxylic acid component is decreased, the number average molecular weight will increase.

The molecular chain end of the polyarylate resin of the present invention is not particularly limited. From the viewpoint of dielectric properties, it is preferable to have the structure represented by the following general formula (2) or/and (3) as the end group, The total amount of the terminal groups of the following general formulas (2) and (3) is 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. Generally, the total amount is less than 2000geq/t, which further improves the solubility of the polyarylate resin in non-halogenated solvents (especially methyl ethyl ketone) From the viewpoint of the balance between the solubility and the 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 total amount range of the terminal groups as described above is preferably that R ⁷ is the amount of the terminal groups of the general formula (2) of the following aliphatic hydrocarbon groups and aromatic hydrocarbon groups [preferably aryl groups (especially naphthyl groups)], And R ⁸ are the following aliphatic hydrocarbon groups [preferably alkyl (especially methyl and heptadecyl)] and aromatic hydrocarbon groups [preferably aryl (especially phenyl)] of the general formula (3) The total measurement range of the amount of end groups.

[The end group of the general formula (2) represents the structure derived from the monohydroxy compound component, and the end group of the general formula (3) represents the structure derived from the monocarboxylic acid component]

In the general formulas (2) and (3), R ⁷ and R ⁸ each independently represent an aliphatic hydrocarbon group with 1 to 21 carbon atoms or an aromatic hydrocarbon group with 1 to 21 carbon atoms, and may be a mixed group of these .

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

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

The alkenyl group as R ⁷ is an alkenyl group having 2 to 21 carbon atoms, preferably 2 to 18, and more preferably 15 to 18. As a specific example of this alkenyl group, an oleyl group can be mentioned, for example.

The cycloalkyl group as R ⁷ is a cycloalkyl group having 1 to 21 carbon atoms, preferably 3 to 18, and more preferably 4 to 8. As a specific example of this cycloalkyl group, a cyclohexyl group can be 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, and more preferably 7 to 10. The number of carbon atoms of the aryl-substituted alkyl group is the total number of carbon atoms of the aryl group and the alkyl group. As a specific example of the aryl-substituted alkyl group, for example, a benzyl group can be given.

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, and more preferably 6 to 10. As a specific example of this aryl group, a phenyl group and a naphthyl group are mentioned, for example.

The alkyl-substituted aryl group as R ⁷ is an alkyl-substituted aryl group having 7 to 21 carbon atoms, preferably 7 to 18, and more preferably 7 to 15. The number of carbon atoms of the alkyl-substituted aryl group is the total number of carbon atoms of the alkyl group and the aryl group. Specific examples of the alkyl-substituted aryl group include, for example, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, dimethylphenyl, diethylphenyl, and dipropylene. Base phenyl, dibutyl phenyl, trimethyl phenyl, triethyl phenyl, tripropyl phenyl, tributyl phenyl, tetramethyl phenyl, tetraethyl phenyl, tetrapropyl benzene Group, tetrabutylphenyl, methylpropylphenyl, methylbutylphenyl, nonylphenyl.

The aryl-substituted aryl group as R ⁷ is an aryl-substituted aryl group having 12 to 21 carbon atoms, preferably 12 to 18, and more preferably 12. The number of carbon atoms of the aryl group substituted by the aryl group is the total number of carbon atoms of all aryl groups. As a specific example of the aryl group substituted by the aryl group, for example, a biphenyl group can be given.

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. As a specific example of this alkyl group, the same alkyl group as the alkyl group which is ^{R 7 is mentioned, for example.}

The alkenyl group of R ⁸ is an alkenyl group having 2 to 21 carbon atoms, preferably 2 to 18, and more preferably 2 to 5. As a specific example of this alkenyl group, a vinyl group can be mentioned, for example.

The aromatic hydrocarbon group as R ⁸ includes an aryl group, an alkyl-substituted aryl group, an alkoxy-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, and more preferably 6 to 10. As a specific example of this aryl group, a phenyl group and a naphthyl group are mentioned, for example.

The alkyl-substituted aryl group as R ⁸ is an alkyl-substituted aryl group having 7 to 21 carbon atoms, preferably 7 to 18, and more preferably 7 to 15. The number of carbon atoms of the alkyl-substituted aryl group is the total number of carbon atoms of the alkyl group and the aryl group. Specific examples of the alkyl-substituted aryl group include, for example, the same alkyl-substituted aryl group as the alkyl-substituted aryl group ^{as R 7.}

The alkoxy-substituted aryl group as R ⁸ is an alkoxy-substituted aryl group having 7 to 21 carbon atoms, preferably 7 to 18, and more preferably 7 to 10. The number of carbon atoms of the alkoxy-substituted aryl group is the total number of carbon atoms of the alkoxy group and the aryl group. Specific examples of the alkoxy-substituted aryl group include, for example, a methoxyphenyl group, an ethoxyphenyl group, a propoxyphenyl group, and a butoxyphenyl group.

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

As the terminal group represented by the general formula (2) (hereinafter, sometimes referred to as "terminal End group (2)") Specific examples of the monohydroxy compound component introduced into the polyarylate resin include, for example, methanol, ethanol, propanol, butanol, octanol, lauryl alcohol, oleyl alcohol, cyclohexanol, Monohydric alcohols such as benzyl alcohol; phenol, o-cresol, p-cresol, m-cresol, phenyl phenol, ethyl phenol, n-propyl phenol, isopropyl phenol, tertiary butyl phenol, xylenol, methyl Propyl phenol, methyl butyl phenol, dipropyl phenol, dibutyl phenol, nonyl phenol, 2,4,6-trimethylphenol, 2,3,5-trimethylphenol, 2,3 ,6-Trimethylphenol, 1-naphthol, 2-naphthol and other phenols. A monohydroxy compound component may be used individually by 1 type, and may use 2 or more types together. Among them, in terms of excellent dielectric properties and reactivity, phenols are preferred, and 1-naphthol and 2-naphthol are particularly preferred.

As specific examples of the monocarboxylic acid component of the polyarylate resin that the terminal group represented by the general formula (3) (hereinafter, sometimes referred to as "terminal group (2)") can be introduced, for example, acetic acid, Propionic acid, valeric acid, trimethylacetic acid, caproic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, Aliphatic monocarboxylic acids such as stearic acid, behenic acid and acrylic acid; benzoic acid, dimethyl benzoic acid, trimethyl benzoic acid, tetramethyl benzoic acid, ethyl benzoic acid, propyl benzoic acid, butyl Benzoic acid, cuminic acid, p-tert-butyl benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, ethoxy benzoic acid, propoxy benzoic acid, naphthoic acid, nicotinic acid, furoic acid, large Aromatic monocarboxylic acids such as anisic acid. The monocarboxylic acid component may be chlorinated benzoyl and its derivatives, or may be anhydrides of the aforementioned aliphatic monocarboxylic acids and/or aromatic monocarboxylic acids. A monocarboxylic acid component may be used individually by 1 type, and may use 2 or more types together. Among them, acetic anhydride and stearic acid are particularly preferred in terms of excellent dielectric properties and reactivity.

The monohydroxy compound component and the monocarboxylic acid component are usually used because they exist in the reaction system before the acetylation reaction together with the aromatic dicarboxylic acid component and the dihydric phenol component during the production of the polyarylate resin. Monohydroxy compound component and monocarboxylic acid component Each of them may be used alone, or any of them may be used in combination.

When the terminal group of the structure represented by the general formula (2) or/and (3) reacts with the epoxy group, since the hydroxyl group with higher polarity is not generated, the polar group of the cured product obtained is reduced , Excellent dielectric properties.

The total amount of the terminal groups of the above general formulas (2) and (3) can be controlled by adjusting the reaction components and reaction conditions. For example, if the dihydric phenol component is present in a large amount relative to the dicarboxylic acid component, the total amount will increase. In addition, for example, if the above-mentioned monohydroxy compound component and/or monocarboxylic acid component is present in the reaction system together with the aromatic dicarboxylic acid component and the dihydric phenol component from before the acetylation reaction, the total amount increases. At this time, if the usage amount of the monohydroxy compound component and/or the monocarboxylic acid component is increased, the total amount will further increase. On the other hand, if the monohydroxy compound component and/or the monocarboxylic acid component are not used, the total amount will decrease.

From the viewpoint of further improving the solubility of polyarylate resin in non-halogenated solvents (especially methyl ethyl ketone), it is preferable that the polyarylate resin of the present invention does not contain the above-mentioned monohydroxy compound component and monocarboxylic acid The components have the terminal groups of the above-mentioned general formulas (2) and (3) in the above-mentioned total amount.

The polyarylate resin of the present invention can be used in combination with an epoxy resin and a hardening accelerator to form a polyarylate resin composition. The polyarylate resin composition is a blend obtained by mixing only polyarylate resin, epoxy resin, and hardening 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 specific examples of epoxy resins, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, Dicyclopentadiene epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, isocyanide Urethane type epoxy resin, alicyclic epoxy resin, acrylic modified epoxy resin, multifunctional epoxy resin, brominated epoxy resin, phosphorus modified epoxy resin. The epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy equivalent of epoxy resin is usually 100-3000, preferably 150-300.

The softening point of epoxy resin is generally 200°C or less, preferably 100°C or less.

The blending amount of the polyarylate resin is preferably such that the functional group equivalent of the polyarylate resin is relative to the epoxy equivalent of the epoxy resin, which is preferably 0.5 to 1.5 equivalent ratio, more preferably 0.7 to 1.3 equivalent ratio. The functional group equivalent of the polyarylate resin is equivalent to the equivalent calculated from the content of the phenolic hydroxyl group and the ester group. The blending amount of such polyarylate resin is usually 20 to 80 parts by mass, preferably 35 to 65 parts by mass, more preferably 40 to 50 parts by mass relative to 100 parts by mass of the total amount of epoxy resin and polyarylate resin share.

The hardening accelerator used in the present invention is not particularly limited, and examples include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 4-dimethylimidazole Tertiary amines such as aminopyridine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol; triphenyl Organic phosphines such as phosphine and tributyl phosphine. The hardening accelerator may be used alone or in combination of two or more kinds.

In the resin composition of the present invention, a hardener may be used in combination. Examples of hardeners include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, dihydrazine adipate, and polyamide polyamines. Amine compounds; alicyclic polyamine compounds such as menthane diamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane and bis(4-aminocyclohexyl)methane; between Aromatic polyamine compounds such as xylylenediamine, diaminodiphenylmethane, diaminodiphenylmethane and m-phenylenediamine; phthalic anhydride, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, Monofunctional acid anhydrides such as chloro-bridged acid anhydride; bifunctional acid anhydrides such as pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (dehydrated trimellitate), methyl cyclohexane tetracarboxylic acid anhydride; Free acid carboxylic acid anhydrides such as trimellitic anhydride and polyazelaic anhydride. The curing agent may be used alone or in combination of two or more kinds.

In addition, in the resin composition of the present invention, thermosetting resins such as cyanate resin, isocyanate resin, maleimide resin, polyimide resin, urethane resin, and phenol resin can be used in combination. ; And silica, glass, alumina, talc, mica, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, titanium oxide, silicon nitride, boron nitride and other inorganic filler materials. The thermosetting resin and the inorganic filler may be used independently, respectively, or two or more types may be used in combination. In addition, the inorganic filler is preferably surface-treated with a surface treatment agent 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 form a resin solution. The preparation method of the resin solution is not particularly limited. In the case of preparing the resin solution of the polyarylate resin composition, compared to dissolving the polyarylate resin and the epoxy resin in an organic solvent at the same time, the polyarylate resin And the epoxy resin is dissolved in the organic solvent separately and then mixed these systems to easily obtain a uniform resin solution in a short time. Furthermore, when the polyarylate resin and epoxy resin are separately dissolved in an organic solvent and then mixed, the solid content of the two resin solutions is closer, which makes it easier to obtain a uniform resin in a shorter time. Solution.

烷、1,3-二氧雜環戊烷、四氫呋喃等醚化合物；甲基乙基酮、環戊酮、環己酮等酮化合物；甲苯、二甲苯等芳香族烴類；乙酸乙酯、丙二醇單乙醚乙酸酯等乙酸酯類。該等非鹵化溶劑均可用作為通用溶劑，酮化合物及芳香族烴類，尤其是甲基乙基酮及甲苯可用作為更通用之溶劑。最有用之非鹵化通用溶劑為甲基乙基酮。上述有機溶劑可單獨使用，亦可併用2種以上。 The organic solvent used in the resin solution of the polyarylate resin of the present invention is not particularly limited as long as it can uniformly dissolve the polyarylate resin. From the viewpoint of the impact on the environment, a non-halogenated solvent is preferred. The organic solvent used in the resin solution of the polyarylate resin composition of the present invention is not particularly limited as long as it can uniformly dissolve the epoxy resin and the polyarylate resin. From the viewpoint of the impact on the environment, it is preferably non- Halogenated solvents. The non-halogenated solvent used in the resin solution of the polyarylate resin of the present invention and the resin solution of the polyarylate resin composition of the present invention can be the same. Examples of such non-halogenated solvents include amide compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; 1 ,4-two

Ether compounds such as alkanes, 1,3-dioxolane, and tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl acetate, propylene glycol Acetate esters such as monoethyl ether acetate. These non-halogenated solvents can be used as general solvents, and ketone compounds and aromatic hydrocarbons, especially methyl ethyl ketone and toluene can be used as more general solvents. The most useful non-halogenated universal solvent is methyl ethyl ketone. The above-mentioned organic solvents may be used alone or in combination of two or more kinds.

Since the polyarylate resin and polyarylate resin composition of the present invention have excellent solubility in non-halogenated solvents, the solid content concentration of each resin solution can be higher. Specifically, it can be 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. In particular, the polyarylate resin of the present invention can be dissolved in a solid content concentration of, for example, 5-40% by mass, preferably 10-40% by mass, more preferably 20-40% by mass, and more preferably 30-40% by mass. In non-halogenated solvents. Methyl ethyl ketone and/or toluene, which are used as the solvent of the resin solution of the present invention, are widely used in the electrical and electronic fields, are easy to obtain, and are relatively inexpensive, so they are particularly convenient organic solvents. Conventionally, it is believed that polyarylate resins are difficult to dissolve in the above-mentioned solvents due to the high concentration of aromatic rings. However, it is known that by making the polyarylate resin a specific resin composition, it can be dissolved in a high concentration Solution in the above solvent. Therefore, the polyarylate resin and polyarylate resin composition of the present invention are used in the formation of film and film and the production of prepregs, and the operability is very high, and its industrial significance is very high.

After coating and drying the resin solution of the present invention on a substrate, a film is formed and peeled from the substrate to obtain a film. The resin solution when forming the film and the thin film may be a resin solution prepared by dissolving a polyarylate resin in an organic solvent, or may be a resin solution prepared by dissolving a polyarylate resin composition in an organic solvent.

Examples of the substrate include polyethylene terephthalate (PET) film, polyimide film, glass plate, and stainless steel plate. Examples of coating methods include: wire bar coater coating method, film applicator coating method, brush coating method, spray coating method, gravure coating method, screen printing method, reverse roll coating method , Die lip coating method, air knife coating method, curtain type plane coating method, dip coating method.

After impregnating or coating the resin solution of the present invention on the reinforced fiber cloth, it is dried to obtain a prepreg. The resin solution when manufacturing the prepreg may be a resin solution obtained by dissolving polyarylate resin or polyarylate resin composition in an 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 woven fabric and non-woven fabric can be used. In addition, synthetic paper obtained by mixing fibrids in the state of short fibers for papermaking can be used. Among them, glass fiber and carbon fiber are preferable in terms of excellent processability. The thickness of the reinforced fiber cloth is preferably 5 to 50 μm, more preferably 10 to 45 μm, and still more preferably 15 to 40 μm.

The method of impregnating the resin solution in the reinforced fiber cloth is not particularly limited, and a known method can be used. As the above-mentioned impregnation method, for example, a method of using a commercially available or self-made continuous impregnation device; impregnating a reinforcing fiber in a resin containing polyarylate The method in the resin solution of grease; the method of spreading the reinforcing fiber on the release paper, glass plate, stainless steel plate, etc., and coating the resin solution containing polyarylate resin. The prepreg is obtained by evaporating and drying the organic solvent from the resin solution applied after the above-mentioned coating.

The method of applying the resin solution to the reinforced fiber cloth is not particularly limited, and a known method can be used. As the above-mentioned coating method, for example, a commercially available coater can be used for coating. In the case of double-sided coating, it can be mentioned: after single-sided coating, temporarily dry, and then apply to the opposite side; after single-sided coating, apply to the opposite side without drying The method; the method of coating on both sides at the same time. These coating methods can be appropriately selected with reference to the workability and the properties of the obtained prepreg. The prepreg is obtained by evaporating and drying the organic solvent from the resin solution applied after the above-mentioned coating.

The thickness of the prepreg varies according to the thickness of the reinforced fiber cloth used, and is preferably 10 to 150 μm, more preferably 20 to 140 μm, and even more preferably 30 to 130 μm. Furthermore, the prepreg is obtained by impregnating or coating the resin solution on the reinforced fiber cloth and then drying it to obtain the prepreg in a way that the thickness of the reinforced fiber cloth is approximately 3 times the thickness of the reinforced fiber cloth used. In this way, a prepreg with excellent heat resistance, mechanical properties, adhesiveness, and appearance can be obtained.

The prepreg of the present invention can be used directly without heating treatment for hardening, etc. In addition, if the polyarylate resin contained in the prepreg is heated above its glass transition temperature, it will melt and exhibit fluidity. Therefore, the prepreg is heated and pressurized directly or laminated several pieces to achieve densification. To make a laminated body. Since the above-mentioned laminate has excellent adhesion between prepregs, the mechanical strength is sufficiently improved and the heat resistance is also excellent. In addition, the above-mentioned laminated body can be used in the form of a high-strength plate-shaped molded body. Furthermore, the plate-shaped molded body can also be molded into a desired shape. Regarding the formability, it also depends on the material of the reinforced fiber cloth used and the solid content of the prepreg, but it can be Perform shaping processing corresponding to the established mold. Perforation can be carried out within the range that does not significantly impair the mechanical characteristics. When a thermosetting resin is not used, the prepreg of the present invention is particularly excellent in workability such as adhesiveness, shaping processability, and punching properties. Furthermore, the shaping process and perforation can also be cold processed, and can also be processed under heating as needed.

By heating the film, film, prepreg and laminate obtained by using the solution of the polyarylate resin composition of the present invention, the polyarylate resin can react with the epoxy resin to achieve complete curing. The heating temperature (hardening temperature) is usually 110 to 250°C, preferably 130 to 220°C. The heating time (hardening time) is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours.

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

[Example]

Hereinafter, the present invention will be specifically explained through examples, but the present invention is not limited by these. In addition, the physical properties of the polyarylate resin were measured by the following methods.

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

Using a high-resolution nuclear magnetic resonance device (LA-400 NMR manufactured by JEOL Ltd.), ¹ H-NMR analysis was performed to determine the resin composition and end groups (2) and (3) based on the peak intensity of each copolymer component The total amount (resolution: 400MHz, solvent: a mixed solvent with a volume ratio of deuterated trifluoroacetic acid and deuterated tetrachloroethane of 1/11, temperature: 50°C).

(II) Glass transition temperature of polyarylate resin

Using a differential scanning calorimetry device (DSC7 manufactured by PerkinElmer), the temperature was raised from 40°C to 340°C at a heating rate of 20°C/min, and the obtained temperature rise curve was derived from the discontinuous change in the glass transition temperature The starting temperature is taken as the glass transition temperature.

S (best): above 144℃;

A (good): 130°C or higher and less than 144°C.

B (pass): 60°C or higher and less than 130°C. (There is no problem in practice)

C (unqualified): less than 60°C. (There are practical problems)

(III) Number average molecular weight of polyarylate resin

Using chloroform as a solvent, the particles of the polyarylate resin were dissolved to obtain a concentration of 1000 ppm to obtain a solution. By gel permeation chromatography (GPC, gel permeation chromatography) analysis, the number average molecular weight was calculated in terms of polystyrene.

(IV) Solubility of polyarylate resin

The polyarylate resin and methyl ethyl ketone were weighed so that the total amount was 30 g and the solid content concentration was 20, 30, 40, and 50% by mass, and put into a glass screw-top bottle with an inner volume of 50 mL. Thereafter, the glass screw-top bottle was sealed, rotated (stirred) at 70 rpm using a mixing rotator at a room temperature of 23°C for 24 hours, and was allowed to stand at a room temperature of 23°C for 2 weeks. After standing still, observe the resin solution visually, and judge the dissolution stability of the resin solution according to the following criteria. The polyarylate resin is in the state of coarsely pulverizing with a pulverizer (DAS-28; manufactured by Daiko Seiki Co., Ltd.). The maximum diameter of the polyarylate resin particles is 5mm. The maximum diameter is the average of the maximum sizes of any 100 particles.

○: The transparency is maintained and the viscosity is not increased.

△: Transparency is not maintained, or viscosity is increased.

×: The transparency is not maintained, and the viscosity is increased.

In addition, in the same manner as when the solvent is methyl ethyl ketone, the solvent is toluene, cyclohexanone, tetrahydrofuran, 1,3-dioxolane, N-methylpyrrolidone, N,N -In the case of dimethylformamide, the stability of the resin solution is also confirmed.

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

Mix 50 parts by mass of polyarylate resin, epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin, epoxy equivalent 184~194g/eq, viscosity 120~150 (25℃), softening point 20 (°C or less) 50 parts by mass, 0.2 parts by mass of a hardening accelerator (2-ethyl-4-methylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.), and 100 parts by mass of methyl ethyl ketone, and stirred until it becomes transparent to obtain a resin solution. The obtained resin solution was poured into an aluminum cup and dried at room temperature for 2 hours. After that, it was dried under vacuum at 170° C. for 2 hours using a vacuum dryer, and then dried under vacuum at 200° C. for 3 hours to perform solvent removal and curing to obtain a cured product. Furthermore, since the polyarylate resins obtained in Comparative Examples 1 to 4 and 6 were not dissolved 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, which was prepared Hardened object. Cut the hardened plate obtained by cutting, and measure the dielectric constant and dielectric loss tangent under the following conditions.

Device: manufactured by Agilent Technologies Co., Ltd., E4991A RF impedance/material analyzer, sample size: length 60mm×width 60mm×thickness 100μm

Frequency: 1GHz

Measuring temperature: 23℃

Test environment: 23℃±10℃, 50%RH±5%RH

Dielectric constant

S (best): 2.84 or less; A (good): more than 2.84 and 2.85 or less; B (eligible): more than 2.85 and less than 2.89 (practically no problem); C (unqualified): more than 2.89 (practically existing problem).

Dielectric loss tangent

S (best): less than 0.010; A (good): more than 0.010 and less than 0.011; B (pass): more than 0.011 and less than 0.013 (practically no problem); C (unqualified): more than 0.013 (practically exist problem).

(VI) Fluidity of polyarylate resin composition

Observe the plate of the cured product obtained in (V), and judge the fluidity of the polyarylate resin composition according to the following criteria.

○: No bubbles are seen in the cured product.

×: Air bubbles are visible in the cured product.

(VII) Glass transition temperature of polyarylate resin composition

Except for using the cured product obtained in (V), the glass transition temperature of the polyarylate resin composition is measured by the same method as the method for measuring the glass transition temperature of the polyarylate resin.

S (best): above 163℃; A (good): above 150℃ and less than 163℃; B (pass): 110°C or higher and less than 150°C (practically no problem); C (unqualified): less than 110°C (practical problem).

[Example 1]

Put 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 mass of PHBA, and 32.2 parts by mass of acetic anhydride into a reaction vessel equipped with a stirring device (TPA: IPA: BisA: BisTMC: PHBA: Acetic anhydride (mole ratio) = 50: 50: 63: 63: 50: 315), stir and mix for 2 hours under the conditions of atmospheric pressure and 140°C under nitrogen atmosphere. reaction. Then, the temperature was increased to 280°C over 3 hours, and the temperature was maintained at 280°C for 1 hour. Thereafter, the pressure was reduced to 130 Pa over 90 minutes, and the mixture was stirred for 2 hours to obtain a polyarylate resin. The resin composition of the obtained polyarylate resin was analyzed, and the result was TPA: IPA: BisA: BisTMC: PHBA (mole ratio)=50:50:63:63:50, which was the same as the added composition.

[Examples 2 to 16 and Comparative Examples 1 to 6]

Except for changing the composition of the addition of raw materials as described in the following table, the same operation as in Example 1 was performed to obtain a polyarylate resin.

[Example 17]

Put 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) into a reaction vessel equipped with a stirring device (Mole ratio)=30:70:62.5:62.5:250), under nitrogen atmosphere, at normal pressure, 140℃ Stir and mix for 2 hours to make the reaction. Then, after adding 5.1 parts by mass of PHBA at 140°C, the temperature was raised to 280°C over 3 hours, and after keeping at 280°C for 1 hour, the pressure was reduced to 130 Pa at 280°C over 90 minutes and stirred for 2 hours to obtain polyaramide Ester resin. The resin composition of the obtained polyarylate resin was analyzed, and the result was TPA: IPA: BisA: BisTMC: PHBA (molar ratio) = 30: 70: 63: 63: 37, which was the same as the added composition.

[Examples 18-19]

Except for changing the composition of the addition of the raw materials as described in the following table, the same operation as in Example 17 was performed to obtain a polyarylate resin.

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

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: p-Hydroxybenzoic acid

HNA: 2-hydroxy-6-naphthoic acid

Ac ₂ O: Acetic anhydride

BA: Benzoic acid

St: Stearic acid

1-NPOH: 1-Naphthol

Regarding the polyarylate resins of Examples 1 to 19, they are excellent in heat resistance and solubility in non-halogenated solvents, and are excellent in dielectric properties and fluidity during processing when they are made into resin compositions.

Regarding the polyarylate resins of Comparative Examples 1 and 2, since no hydroxycarboxylic acid component was used, the solubility was poor. Regarding the polyarylate resin of Comparative Example 3, since the content of the dihydric phenol represented by the general formula (1) is more than the range specified in the present invention, the solubility is poor. Regarding the polyarylate resin of Comparative Example 4, since the content of the dihydric phenol represented by the general formula (1) is less than the range specified in the present invention, the solubility is poor. Regarding the polyarylate resin of Comparative Example 5, since the hydroxycarboxylic acid component is more than the range specified in the present invention, the solubility is poor. Also, because it is not dissolved in methyl ethyl ketone, toluene, cyclohexanone, tetrahydrofuran, 1,3-dioxolane, N-methylpyrrolidone, and N,N-dimethylformamide can be used in any solvent, so hardened products cannot be produced. Regarding the polyarylate resin of Comparative Example 6, since the number average molecular weight is higher than the range specified in the present invention, the solubility is poor. In addition, when it is made into a resin composition, the fluidity during processing is poor.

(Industrial availability)

The polyarylate resin and its resin composition of the present invention can be used 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, and is characterized in that: among all the dihydric phenol components, the dihydric phenol represented by the general formula (1) The content is 30-70 mol%, the content of hydroxycarboxylic acid in all monomer components is 1-30 mol%, and the number average molecular weight is less than 10,000;

[In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 12 carbon atoms or a halogen atom, and R ⁵ and R ⁶ each independently represent a hydrogen atom or A hydrocarbon group with a carbon number of 1 to 4; m represents an integer from 4 to 12, and X represents a carbon atom that forms a saturated aliphatic hydrocarbon ring together with the carbon atom bonded to the hydroxyphenyl group]. The polyarylate resin of claim 1, wherein the polyarylate resin has a structure represented by the following general formula (2) or/and (3) as a terminal group, and the following general formula (2) and (3) The total amount of the end groups is more than 100geq/t; [化2]

[The terminal group of general formula (2) represents a structure derived from a monohydroxy compound component, and the terminal group of general formula (3) represents a structure derived from a monocarboxylic acid component. R ⁷ and R ⁸ each independently represent an aliphatic hydrocarbon group or Aromatic hydrocarbon group]. The polyarylate resin of claim 1 or 2, wherein the dihydric phenol represented by the general formula (1) is 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane Alkane and/or 1,1-bis(4-hydroxyphenyl)-cyclododecane. The polyarylate resin of claim 1 or 2, wherein the content of phthalic acid in all aromatic dicarboxylic acid components is 50 mol% or more. The polyarylate resin of claim 1 or 2, wherein the dihydric phenol component contains 2,2-bis(4-hydroxyphenyl)propane (BisA) and/or 1,1-bis(4-hydroxyphenyl) )-1-phenylethane (BisAP), and the dihydric phenol represented by the above general formula (1). The polyarylate resin of claim 5, wherein the content ratio of the total content of the above BisA and/or the above BisAP and the total content of the dihydric phenol represented by the above general formula (1) ((BisA+BisAP)/(General The dihydric phenol represented by the formula (1))) is 35/65 to 65/35 (molar ratio). The polyarylate resin of claim 1 or 2, 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 characterized by comprising the polyarylate resin according to any one of claims 1 to 7, an epoxy resin, and a hardening accelerator. A film comprising the polyarylate resin of any one of claims 1 to 7 or the polyarylate resin composition of claim 8. A film comprising the polyarylate resin of any one of claims 1 to 7 or the polyarylate resin composition of claim 8. A resin solution characterized by containing the polyarylate resin of any one of claims 1 to 7 or the polyarylate resin composition of claim 8, and an organic solvent. The resin solution of claim 11, wherein the above-mentioned organic solvent is a non-halogenated solvent. A prepreg characterized in that it is impregnated or coated on a reinforced fiber cloth with the resin solution of claim 11 or 12. A laminated body characterized in that it is a prepreg of laminated claim 13.