KR20180133390A - Polyarylate resin and resin composition thereof - 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 having excellent heat resistance and dielectric properties, and having excellent flowability upon processing and solubility in a non-halogenated solvent. The present invention relates to a polyarylate resin containing a divalent phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component, wherein the content of the divalent phenol represented by the formula (1) 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 10,000.

Wherein 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, R ⁵ and R ^{6 each} represent a hydrogen atom or a carbon atom having a carbon number of 1 ≪ / RTI > m represents an integer of 4 to 12, and X represents a carbon atom which forms a saturated aliphatic hydrocarbon ring.

Description

Polyarylate resin and resin composition thereof

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

2. Description of the Related Art In recent years, with the increase of information processing amount in various electronic apparatuses, high integration of semiconductor devices to be mounted, high density wiring, and multilayering technology are rapidly progressing. 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 transmission speed of signals and a low dielectric tangent in order to reduce loss in signal transmission. In addition, an insulating material such as a printed wiring board is required to have excellent heat resistance such as to withstand a heat treatment such as soldering.

As a resin excellent in dielectric properties such as heat resistance, dielectric constant and dielectric loss tangent, polyarylate resin is known. For example, Patent Document 1 discloses the use of a resin composition comprising an active ester compound, a curing accelerator, and an epoxy resin in a polyarylate resin for a printed wiring board.

Japanese Patent Application Laid-Open No. 2004-224890

When a polyarylate resin is used for a printed wiring board or the like, the polyarylate resin is used by being dissolved in an organic solvent. However, in general, polyarylate resins are low in solubility and soluble in halogenated solvents. However, in recent years, solubility in a non-halogenated solvent which is desired due to enhancement of environmental consciousness is low, There is a problem that stability is poor. Even if the polyarylate resin is dissolved in the non-halogenated solvent, there is a problem that the amount of the polyarylate resin is too small. In general, the polyarylate resin has a high glass transition temperature and low fluidity at the time of processing, so voids tend to occur when the prepreg is multilayered, and a problem that a highly reliable multilayered printed circuit board can not be obtained there was.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior arts, and a polyarylate resin having excellent heat resistance and dielectric properties, And to provide the above objects.

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that, in a polyarylate resin containing a specific amount of a specific divalent phenol component, a specific amount of a hydroxycarboxylic acid component is further contained, , It is possible to achieve the above object, and the present invention has been reached.

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

<1>

A polyarylate resin containing a divalent phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component,

Wherein the content of the divalent phenol represented by the formula (1) in the entire divalent phenol component is 30 to 70 mol%

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

A polyarylate resin having a number average molecular weight of less than 10,000;

Wherein 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, R ⁵ and R ⁶ are each independently 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 which forms a saturated aliphatic hydrocarbon ring together with the carbon atom to which the hydroxyphenyl group is bonded.

&Lt; 2 &

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

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

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

&Lt; 3 &

Wherein the divalent phenol represented by the formula (1) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and / or 1,1- The polyarylate resin according to < 1 > or < 2 >, which is a cyclododecane.

&Lt; 4 &

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

&Lt; 5 &

Wherein the divalent phenol component is at least one selected from the group consisting of 2,2-bis (4-hydroxyphenyl) propane (BisA) and / or 1,1-bis (4-hydroxyphenyl) The polyarylate resin according to any one of <1> to <4>, wherein the polyarylate resin contains a divalent phenol represented by the following formula (1).

&Lt; 6 &

(BisA + BisAP) / (divalent phenol represented by the formula (1)) of the total content of the bisA and / or the bisAP and the total content of the divalent phenol represented by the formula (1) / 65 to 65/35 (molar ratio). &Lt; 5 > The polyarylate resin according to &lt; 5 &gt;

&Lt; 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).

&Lt; 8 &

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

&Lt; 9 &

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

&Lt; 10 &

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

&Lt; 11 &

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

&Lt; 12 &

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

&Lt; 13 &

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

&Lt; 14 &

The laminate according to < 13 >, wherein the prepreg is laminated.

According to the present invention, it is possible to provide a polyarylate resin having excellent heat resistance and dielectric properties, excellent in fluidity during processing and solubility in a non-halogenated solvent, 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 divalent phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component.

The bifunctional phenol component is an organic compound containing two phenolic hydroxyl groups in one molecule and includes an alicyclic divalent phenol represented by the formula (1). The phenolic hydroxyl group is a hydroxyl group directly bonded to an aromatic ring.

In the 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 includes an alkyl group having 1 to 12, preferably 1 to 6, more preferably 1 to 3, carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, Butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group and the like. The unsaturated aliphatic hydrocarbon group includes 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 includes an aryl group having 6 to 10 carbon atoms, preferably 6 carbon atoms, 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 preferably a chlorine atom and a bromine atom.

In the formula (1), preferable R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (particularly 1 to 3 carbon atoms) Or a halogen atom (in particular, a chlorine atom or a 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 (particularly 1 to 3 carbon atoms). R ¹ , R ² , R ³ and R ⁴ are partly or wholly different from each other, or represent the same group, and preferably represent the same group.

In the 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 includes an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t -Butyl group and the like. The unsaturated aliphatic hydrocarbon group includes 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 present in a plurality in accordance with the value of m to be described later, and the plurality of R ⁵ and the plurality of R ⁶ may independently be selected from within the above range.

In the formula (1), preferable 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, particularly a hydrogen atom.

In the formula (1), m represents an integer of 4 to 12, preferably an integer of 4 to 11, more preferably an integer of 5 to 11.

In the formula (1), X represents a carbon atom forming a saturated aliphatic hydrocarbon ring (monocyclic ring) together with the carbon atom to which the hydroxyphenyl group is 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 cyclopentane ring (m = 4), cyclohexane ring (m = 5), cycloheptane ring (m = 6), cyclooctane ring ), A cyclododecane ring (m = 8), a cyclodecane ring (m = 9), a cyclododecane ring (m = ).

Among the alicyclic divalent phenols represented by the formula (1), the solubility, heat resistance and dielectric properties of the polyarylate resin to a non-halogenated solvent (particularly methyl ethyl ketone), and the cured product of the polyarylate resin and the epoxy resin (1b), (1c), (1d), (1e), (1f), (1g), (1h) and (1b) 1i), particularly alicyclic divalent phenols represented by the formulas (1b) to (1h).

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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

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

In the formula (1a), R ¹⁰ represents 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 includes an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t -Butyl group and the like. The unsaturated aliphatic hydrocarbon group includes 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 &lt; ¹⁰ &gt; s may be independently selected from within the above range. The bonding position of R &lt; ¹⁰ &gt; in the cyclopentane ring is not particularly limited. When the carbon atom of the cyclopentane ring to which the hydroxyphenyl group is bonded is 1, the carbon atom at the 3rd and 4th positions And each R &lt; ¹⁰ &gt; is bonded to a carbon atom selected from R &lt; ¹⁰ &gt;

Each of R &lt; ¹⁰ &gt; preferably independently represents an alkyl group having 1 to 4 carbon atoms. More preferable R &lt; ¹⁰ &gt; each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic divalent phenol represented by the formula (1a) include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy- 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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

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

In the formula (1b), R ²⁰ is the same as R ¹⁰ in the formula (1a). When n2 is an integer of 2 or more, a plurality of R &lt; ²⁰ &gt; s may be independently selected within the same range as that of R &lt; ¹⁰ &gt;. The bonding position of R ^{20 in} the cyclohexane ring is not particularly limited, but when the carbon atom of the cyclohexene ring to which the hydroxyphenyl group is bonded is 1 in the formula (1b), the bonding positions of the 3 rd, 4 th and 5 th on the carbon atoms selected from carbon atoms, especially 3 carbon atoms in the above and 5 above is preferred that each R ²⁰ is bonded.

Each R &lt; ²⁰ &gt; independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R &lt; ²⁰ &gt; each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic divalent phenol represented by the formula (1b) include 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5- (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, Methyl cyclohexane BisTMC, 1,1-bis (4-hydroxyphenyl) -3,3,5-triethylcyclohexane, 1,1-bis- (4-hydroxyphenyl) , 5,5-tetramethyl-cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,4-trimethyl-cyclohexane, 1,1- Phenyl) -3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -3,3,5- (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3-methyl- Lt; / RTI &gt; phenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- ) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5-dibromo-4-hydroxyphenyl) -3,3,5-trimethyl- . Above all, BisTMC is particularly preferable because of its high versatility.

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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

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

In the 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 &lt; ³⁰ &gt; s may be independently selected within the same range as that of R &lt; ¹⁰ &gt;. 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 is 1, the position of the 3 rd, 4 th, 5 th and the carbon atom selected from a carbon atom of the 6 above it is preferred that each R ³⁰ is bonded.

Each R &lt; ³⁰ &gt; independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, each R ³⁰ independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic divalent 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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

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

In the formula (1d), R ⁴⁰ is the same as R ¹⁰ in the formula (1a). When the n4 is an integer of 2 or more, when a plurality of R ⁴⁰ are each independently the same as R ¹⁰ and selected from the range of is. The bonding position of R ^{40 in} the cyclooctane ring is not particularly limited, but when the carbon atom of the cyclooctane ring bonded to the hydroxyphenyl group in Formula (1d) is set to 1, the 4th, 5th and 6th positions And each R &lt; ^{40 &} gt ^; is bonded to a carbon atom selected from carbon atoms of R &lt; ⁴⁰ &gt;

Each R &lt; ⁴⁰ &gt; independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R &lt; ⁴⁰ &gt; each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic divalent phenol represented by the 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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

In the formula (1e), n5 is an integer of 0 to 16, preferably 0 to 8, more preferably 0 to 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 &lt; ⁵⁰ &gt; s may be independently selected within the same range as that of R &lt; ¹⁰ &gt;. 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 is 1 in the formula (1e), the 4th, 5th, 6th and It is preferable that each R &lt; ⁵⁰ &gt; is bonded to a carbon atom selected from the 7th carbon atom.

Each R &lt; ⁵⁰ &gt; independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, each R &lt; ⁵⁰ &gt; independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic divalent phenol represented by the formula (1e) include 1,1-bis (4-hydroxyphenyl) -cyclo-nonene.

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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

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

In the formula (1f), R ⁶⁰ is the same as R ¹⁰ in the formula (1a). When the n6 is an integer 2 or more, plural R ⁶⁰ are each independently selected from the R ¹⁰ when the same selected from the range of. The bonding position of R ^{60 in} the cyclodecane ring is not particularly limited, but when the carbon atom of the cyclodecane ring bonded to the hydroxyphenyl group in Formula (1f) is set to 1, the 4th, 5th, 6th , the carbon atom to which the No. 7 and No. 8, in particular above 5, 6, selected from carbon atoms and the above seventh it is preferable that each of R ⁶⁰ are combined.

Each R &lt; ⁶⁰ &gt; independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R &lt; ⁶⁰ &gt; each independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic divalent phenol represented by the formula (1f) include, for example, 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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

In the formula (1g), n7 is an integer of 0 to 20, preferably 0 to 10, more preferably 0 to 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 &lt; ⁷⁰ &gt; s may be independently selected within the same range as that of R &lt; ¹⁰ &gt;. The bonding position of R &lt; ⁷⁰ &gt; in the cycloalkane ring is not particularly limited. When the carbon atom of the cyclohexane ring to which the hydroxyphenyl group is bonded is 1, the 4th, 5th, and the carbon atom selected from carbon atom 7 of the above it is preferred that each R ⁷⁰ is bonded.

Each R ⁷⁰ independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, R &lt; ⁷⁰ &gt; independently represents an alkyl group having 1 to 3 carbon atoms.

Specific examples of the alicyclic divalent phenol represented by the formula (1g) include, for example, 1,1-bis (4-hydroxyphenyl) -cyclo-decane.

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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

In the formula (1h), n8 is an integer of 0 to 22, preferably 0 to 11, more preferably 0 to 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 &lt; ^{80 &} gt ^{; s} may independently be selected from the same range as that of R &lt; ¹⁰ &gt;. The bonding position of R ^{80 in} the cyclododecane ring is not particularly limited, but when the carbon atom of the cyclododecane ring bonded to the hydroxyphenyl group in Formula (1h) is taken as the first carbon atom, the carbon atom of the fifth, sixth, seventh , a carbon atom selected from 8 carbon atoms to the above 9 and above it is preferable that each of R ⁸⁰ are combined.

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

Specific examples of the alicyclic divalent phenol represented by the formula (1h) include 1,1-bis (4-hydroxyphenyl) -cyclododecane (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 preferably R ¹ , R ² , R ³ and R ⁴ are also the same as those in the formula (1).

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

In the formula (1i), R ⁹⁰ is the same as R ¹⁰ in the formula (1a). When n9 is an integer of 2 or more, a plurality of R &lt; ^{90 &} gt ^{; s} may be independently selected within the same range as that of R &lt; ¹⁰ &gt;. The bonding position of R ^{90 in} the cyclotridecane ring is not particularly limited. When the carbon atom of the cyclotridecane ring bonded to the hydroxyphenyl group in Formula (1i) is set to 1, the 6th, 7th, It is preferable that each R ⁹⁰ is bonded to a carbon atom selected from the 8th and 9th carbon atoms.

Each R &lt; ⁹⁰ &gt; independently represents an alkyl group having 1 to 4 carbon atoms. More preferably, each R &lt; ⁹⁰ &gt; independently represents an alkyl group having 1 to 3 carbon atoms.

As specific examples of the alicyclic divalent phenol represented by the formula (1i), for example, 1,1-bis (4-hydroxyphenyl) -cyclotridecane.

The content of the alicyclic divalent phenol represented by the above formula (1) is required to be 30 to 70 mol% with respect to the total divalent phenol component. The content is preferably 40 to 65 mol% with respect to the total divalent phenol component from the viewpoint of further improving the solubility, heat resistance and dielectric properties of the polyarylate resin to a non-halogenated solvent (particularly methyl ethyl ketone) , More preferably 45 to 65 mol%, and still more preferably 45 to 55 mol%. When the content of the alicyclic divalent phenol in the total divalent phenol component is less than 30 mol% and in the case of more than 70 mol%, the non-halogenated solvent of the polyarylate resin (particularly methyl ethyl ketone) The solubility in the solution is lowered. The alicyclic divalent phenol represented by the alicyclic divalent phenol represented by the above formula (1) may be used alone or in combination of two or more. In this case, the total amount of the alicyclic divalent phenol may be within the above range. The solubility of the polyarylate resin in the non-solubilized solvent is such that the solubility of the polyarylate resin in the non-halogenated solvent at a solids concentration of about 20% by mass is as high as 30% More preferably not less than 40% by mass, and more preferably not less than 50% by mass, in the non-halogenated solvent at a high concentration. 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. The dielectric properties include properties relating to dielectric constant and dielectric tangent.

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

The divalent phenol other than the alicyclic divalent phenol represented by the formula (1) is not particularly limited as long as it is a divalent phenol component not included in the alicyclic divalent phenol represented by the formula (1) , The following bifunctional phenols are exemplified: 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane BisA, 2,2- Dihydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2- Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy diphenyl ketone, 9,9-bis (4-hydroxyphenyl) fluorene , 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, N-phenyl- (4-hydroxyphenyl) phthalimidine, N-methyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 1,1- Bis (3,5-dimethylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis . Among them, BisA and / or BisAP are preferred because of their high solubility in general-purpose and non-halogenated solvents (particularly methyl ethyl ketone). The divalent phenol other than the alicyclic divalent phenol represented by the above formula (1) may be used alone or in combination of plural kinds.

The bivalent phenol component may be used alone or in combination of two or more of the above divalent phenols. However, since the solubility of the polyarylate resin in a non-halogenated solvent (particularly, methyl ethyl ketone) becomes higher, Is preferably used. Among them, from the standpoint of further improving the solubility of the polyarylate resin in a non-halogenated solvent (particularly, methyl ethyl ketone), the divalent phenol component can be obtained by reacting BisA and / or BisAP with an alicyclic (Particularly BisTMC and / or BisCDE), and more preferably BisA and a combination of alicyclic divalent phenols represented by the formula (1) (particularly BisTMC and / or BisCDE) . When BisA and / or BisAP and the alicyclic divalent phenols represented by the formula (1) (particularly BisTMC and / or BisCDE) are used, the total content of BisA and BisAP and the content of alicyclic bivalent phenol represented by the formula (1) ((BisA + BisAP) / (divalent phenol represented by the formula (1)) in the total content of the bisphenol A (particularly BisTMC and BisCDE) is preferably 10/90 to 90/10 (molar ratio) The molar ratio is more preferably 35/65 to 65/35 because the solubility, heat resistance and dielectric properties of the polyarylate resin to the non-halogenated solvent (particularly, methyl ethyl ketone) 60/40 (molar ratio).

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

As the aromatic dicarboxylic acid component, one kind of the above-mentioned compounds may be used alone, or plural kinds of compounds may be used in combination. Among them, it is preferable to use at least IPA from the viewpoint of further improving the solubility and dielectric properties of the polyarylate resin to a non-halogenating solvent (particularly methyl ethyl ketone), and it is preferable to use TPA and / or NDCA and IPA in combination It is more preferable to use TPA and IPA in combination. The content of IPA is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 50 to 90 mol%, further preferably 60 to 85 mol%, based on the entire aromatic dicarboxylic acid component % Is most preferable. From the viewpoint of further improving the solubility and dielectric properties of the polyarylate resin to a non-halogenating solvent (particularly methyl ethyl ketone) when the aromatic dicarboxylic acid component contains TPA and / or NDCA and IPA, (TPA + NDCA ) / IPA is preferably 10/90 to 70/30, more preferably 10/90 to 50/50, still more preferably 15/85 to 40/60, still more preferably 20/80 to 40/60, 60 is more preferable.

The content ratio of the dihydric phenol component and the aromatic dicarboxylic acid component (bivalent phenol component / aromatic dicarboxylic acid component) is usually 70/100 to 140/100 (molar ratio), and the non-halogenated solvent of the polyarylate resin 100 to 140/100 (molar ratio), more preferably 105/100 to 140/100 (molar ratio), and still more preferably 110/100 to 140/100, from the viewpoints of further improving the solubility and heat resistance of the polymer 100 to 135/100 (molar ratio), and most preferably from 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; 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, a benzene-based hydroxycarboxylic acid, especially PHBA, is preferable from the viewpoints of solubility in a non-halogenated solvent (particularly methyl ethyl ketone) of the polyarylate resin, heat resistance of the cured product of the polyarylate resin composition, desirable.

The content of the hydroxycarboxylic acid component is required to be 1 to 30 mol% based on 100 mol% of the total monomer component. The content of the hydroxycarboxylic acid component in the polyarylate resin is preferably in the range of 1 to 30 mol% Is preferably from 4 to 21 mol%, more preferably from 4 to 19 mol%, from the viewpoints of further improving the heat resistance of the resin and the polyarylate resin composition and the dielectric properties of the polyarylate resin and the polyarylate resin composition cured product. Mol%, and more preferably 10 to 19 mol%. When the content of the hydroxycarboxylic acid component is less than 1 mol% or exceeds 30 mol%, the solubility of the polyarylate resin in a non-halogenated solvent (particularly methyl ethyl ketone) is lowered. On the other hand, the term "whole monomer component" means all monomer components constituting the polyarylate resin. For example, in the case where the polyarylate resin comprises only a divalent phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component, the total monomer component includes all of a divalent phenol component, an aromatic dicarboxylic acid component and a hydroxycarboxylic acid component )to be. Also, for example, when the polyarylate resin contains, in addition to the divalent phenol component, the aromatic dicarboxylic acid component and the hydroxycarboxylic acid component, other monomer components, all of these components (total amount). The monomer component means an organic compound having two or more functional groups capable of being polymerized. Therefore, when the polyarylate resin contains a monohydroxy compound component and / or a monocarboxylic acid component described later, the total monomer component does not include the monohydroxy compound component and / or the monocarboxylic acid component.

The polyarylate resin may contain monomer components other than the above-mentioned divalent phenol component, aromatic dicarboxylic acid component and hydroxycarboxylic acid component within the range not to impair the effect of the present invention. Specific examples of other monomer components include, for example, aliphatic diols such as ethylene glycol and propylene glycol; Cycloaliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol; Polyhydric alcohols such as trimethylol propane and pentaerythritol; Aliphatic dicarboxylic acids such as adipic acid and sebacic acid; Cycloaliphatic dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, and 1,2-cyclohexane dicarboxylic acid; And polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid. The aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and polyvalent carboxylic acids may be derivatives and anhydrides thereof. The content of the other monomer component is usually 10 mol% or less, preferably 5 mol% or less, and more preferably 0 mol%, based on 100 mol% of the total monomer component.

The method for producing the polyarylate resin of the present invention is not particularly limited, and examples thereof include a method of producing a polyarylate resin by performing an acetylation reaction and a deacetylation polymerization reaction.

The acetylation reaction is a reaction in which a bivalent phenol component is acetylated. In the acetylation reaction, the dicarboxylic acid component and acetic anhydride are added to the reaction can, and the reaction solution is purged with nitrogen and heated at a temperature of 100 to 240 캜, preferably 120 to 180 캜, for 5 to 8 hours , Preferably 30 minutes to 5 hours, at normal pressure or under pressure. The molar ratio of the acetic anhydride to the hydroxyl group of the dihydric phenol component and the hydroxycarboxylic acid component or the molar ratio of the acetic anhydride to the dihydroxy phenol component and the hydroxy group of the hydroxycarboxylic acid component and the monohydroxy compound is in the range of 1.00 - 1.20.

The deacetic acid polymerization reaction is a reaction of polycondensation by reacting an acetylated divalent phenol with an aromatic dicarboxylic acid. In the deacetic acid polymerization reaction, at a decompression degree 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, And stirred. When the temperature is less than 240 占 폚, the reduced pressure is more than 500 Pa, and the retention time is less than 30 minutes, the deacetylation reaction becomes insufficient and the amount of acetic acid in the resulting polyarylate resin becomes high, Or the polymer color tone may deteriorate.

There is usually a preliminary step of adjusting the temperature and pressure of the reaction system to the temperature and pressure for deacetic acid polymerization reaction during the period from the acetylation reaction to the deacetylation polymerization reaction. In the method for producing the polyarylate resin of the present invention, the hydroxycarboxylic acid component may be added in this preliminary step. Specifically, in the preliminary step, the hydroxycarboxylic acid component may be added prior to elevating the temperature in the reaction system after the temperature is elevated, or the hydroxycarboxylic acid component may be added before the decompression while the temperature is elevated. The hydroxycarboxylic acid component may be added before the temperature rise and after the temperature rise and both before the decompression.

In the acetylation reaction and the deacetylation polymerization reaction, a catalyst is preferably used if necessary. Examples of the catalyst include organic titanium 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, tin octylate , And heterocyclic compounds such as N-methylimidazole. The addition amount of the catalyst is preferably 1.0% by mass or less with respect to the amount of the resin to be obtained.

Examples of the apparatus for producing the polyarylate resin of the present invention include known reaction apparatuses, for example, a batch reaction apparatus and a continuous reaction apparatus.

The number average molecular weight of the polyarylate resin of the present invention is required to be less than 10,000, preferably less than 8,000, more preferably less than 6,000, more preferably 4,000 or less, most preferably 3,000 or less. When the number average molecular weight is 10,000 or more, the glass transition temperature of the polyarylate resin is increased and the fluidity at the time of processing is deteriorated. And the solubility of the polyarylate resin in a non-halogenated solvent (particularly methyl ethyl ketone) is lowered. The lower limit of the number average molecular weight of the polyarylate resin is not particularly limited and usually the number average molecular weight is 500 or more, and preferably 1000 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 lowered within the above range, the number average molecular weight is lowered. Further, for example, if the reaction time is increased within the above range or the reaction temperature is increased within the above range, the number average molecular weight increases.

Further, 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 difference between the molar ratio of the dicarboxylic acid component and the dihydric phenol component is increased within the above range, the number average molecular weight is lowered. Also, for example, if the difference in the molar ratio of the dicarboxylic acid component to the dihydric phenol component is reduced within the above range, the number average molecular weight increases.

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

The molecular chain terminal end of the polyarylate resin of the present invention is not particularly limited, but has a structure represented by the following formula (2) or / and (3) as a terminal group from the viewpoint of dielectric properties, It is preferable that the total amount of terminal groups of the compound (3) is 100geq / t or more, more preferably 200geq / t or more, more preferably 400geq / t or more, most preferably 600geq / t or more. The upper limit of the total amount of the terminal groups is not particularly limited and usually the total amount is not more than 2000 g / t. However, the solubility of the polyarylate resin in non-halogenated solvents (particularly, methyl ethyl ketone) It is preferably not more than 1500geq / t, more preferably not more than 1000geq / t, still more preferably not more than 900geq / t, most preferably not more than 800geq / t from the viewpoint of balance of dielectric characteristics. Total amount of the range of the end groups as described above, R ⁷ is described aliphatic hydrocarbon group and aromatic hydrocarbon group [preferably, an aryl group (especially a naphthyl group)] in the amount of terminal group of formula (2), to R ⁸ are described below (3), which is an aliphatic hydrocarbon group (preferably an alkyl group (particularly a methyl group and a heptadecyl group)) and an aromatic hydrocarbon group (preferably an aryl group (particularly, a phenyl group)].

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

In the 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, or 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, preferably 1 to 18, more preferably 1 to 12 carbon atoms. Specific examples of the alkyl group include 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 decyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group.

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

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. Specific examples of the cycloalkyl group include, for example, a cyclohexyl group.

The aryl-substituted alkyl group as R ^{7 is} an aryl-substituted alkyl group having 7 to 21, preferably 7 to 18, more preferably 7 to 10 carbon atoms. 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. Specific examples of the aryl-substituted alkyl group include, for example, 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, preferably 6 to 18, 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, preferably 7 to 18, more preferably 7 to 15 carbon atoms. 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 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 tribopropylphenyl group, a tributylphenyl group, a tetramethylphenyl group, a tetraethylphenyl group, a tetrapropylphenyl group, a tetrabutylphenyl group, a methylpropylphenyl group, a methylbutylphenyl group and a nonylphenyl group.

The aryl-substituted aryl group as R ^{7 is} an aryl-substituted aryl group having 12 to 21, preferably 12 to 18, more preferably 12 carbon atoms. The number of carbon atoms of the aryl-substituted aryl group is the total number of carbon atoms of all aryl groups. Specific examples of the aryl-substituted aryl group include, for example, 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 specific examples of the alkyl group, there can be mentioned, for example, the same alkyl group as R ⁷ .

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

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, preferably 6 to 18, 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, preferably 7 to 18, more preferably 7 to 15 carbon atoms. 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 an alkyl-substituted aryl group similar to the alkyl-substituted aryl group as R ⁷ .

The alkyloxy-substituted aryl group as R ^{8 is} an alkyloxy-substituted aryl group having 7 to 21, preferably 7 to 18, more preferably 7 to 10 carbon atoms. The number of carbon atoms of the alkyloxy-substituted aryl group is the total number of carbon atoms of 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, preferably 3 to 5, more preferably 4 to 5 carbon atoms. Specific examples of the heterocyclic group include, for example, a pyridyl group and a furyl group.

Specific examples of the monohydroxy compound component capable of introducing the terminal group represented by the formula (2) (hereinafter sometimes referred to as "terminal group (2)") into the polyarylate resin include, for example, methyl Monohydric alcohols such as alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol, lauryl alcohol, oleyl alcohol, cyclohexanol and benzyl alcohol; But are not limited to, phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, isopropylphenol, t-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, Butylphenol, nonylphenol, mesityl, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 1-naphthol and 2-naphthol. The monohydroxy compound component may be used singly or in combination of two or more. Among them, phenols are preferable, and 1-naphthol and 2-naphthol are particularly preferable because of excellent dielectric properties and reactivity.

Specific examples of the monocarboxylic acid component capable of introducing the terminal group represented by the formula (3) (hereinafter occasionally referred to as "terminal group (2)") into the polyarylate resin include, for example, acetic acid, , Stearic acid, behenic acid, acrylic acid, and the like, which may be used alone or in a mixture of two or more kinds selected from the group consisting of citric acid, tartaric acid, citric acid, Aliphatic monocarboxylic acids; Benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, quinic acid, paratintyl tilobenzoic acid, orthotolyl acid, metatolyl acid, paratoluic acid, ethoxybenzoic acid, 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 derivatives thereof, or an anhydride of the above-mentioned aliphatic monocarboxylic acid and / or aromatic monocarboxylic acid. The monocarboxylic acid component may be used singly or in combination of two or more. Of these, acetic anhydride and stearic acid are particularly preferred because of their excellent dielectric properties and reactivity.

The monohydroxy compound component and the monocarboxylic acid component are usually used in the production of the polyarylate resin by allowing the aromatic dicarboxylic acid component and the divalent phenol component to exist in the reaction system before the acetylation reaction. The monohydroxy compound component and the monocarboxylic acid component may be used alone or in combination.

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

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

For example, when a dicarboxylic acid component is present in a large amount of a divalent phenol component, the total amount of the dicarboxylic acid component increases.

For example, when the monohydroxy compound component and / or the monocarboxylic acid component together with the aromatic dicarboxylic acid component and the divalent phenol component are present in the reaction system before the acetylation reaction, the total amount is increased. At this time, when the amount of the monohydroxy compound component and / or the monocarboxylic acid component used is increased, the total amount of the monohydroxy compound component and the monocarboxylic acid component is further increased. On the other hand, if the monohydroxy compound component and / or the monocarboxylic acid component is not used, the total amount is reduced.

The polyarylate resin of the present invention is preferably a polyarylate resin in which the monohydroxy compound component and the monocarboxylic acid component are not contained in the polyarylate resin from the viewpoint of further improving the solubility of the polyarylate resin in a non-halogenating solvent (particularly methyl ethyl ketone) , And the total amount of the terminal groups of the above formulas (2) and (3).

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. Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, Novolak type epoxy resins, cresol novolak type epoxy resins, isocyanurate type epoxy resins, alicyclic epoxy resins, acrylic acid modified epoxy resins, polyfunctional epoxy resins, brominated epoxy resins and phosphorus modified epoxy resins. The epoxy resin may be used alone, or two or more epoxy resins may be used in combination.

The epoxy equivalent of the epoxy resin is usually from 100 to 3,000, and preferably from 150 to 300. [

The softening point of the epoxy resin is usually 200 DEG C or lower, preferably 100 DEG C or lower.

The blending amount of the polyarylate resin is preferably such that the functional equivalent of the polyarylate resin is in the range of preferably 0.5 to 1.5 equivalents, more preferably 0.7 to 1.3 equivalents, based on the epoxy equivalent of the epoxy resin. The functional equivalent of the polyarylate resin corresponds to the equivalent calculated from the content of the phenolic hydroxyl group and the ester group. The blending amount of such a 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 the epoxy resin and the polyarylate resin Mass part.

The curing accelerator used in the present invention is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, 4- Tertiary amines such as dimethylaminopyridine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol, triphenylphosphine, tributylphosphine Of organic phosphines. The curing accelerator may be used alone or in combination of two or more.

In the resin composition of the present invention, a curing agent may be used in combination. Examples of the curing agent include aliphatic polyamine compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamine, adipic acid dihydrazide and polyamide polyamines, menendaiamine, isophorone Alicyclic polyamine compounds such as diamine, bis (4-amino-3-methylcyclohexyl) methane and bis (4-aminocyclohexyl) methane, meta-xylene diamine, diaminodiphenylmethane, Aromatic polyamine compounds such as diphenyl sulfone and metaphenylene diamine, aromatic polyamine compounds such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, , Monofunctional acid anhydride such as chlorogenic anhydride, anhydrous pyromellitic acid, benzophenone tetracarboxylic acid Bifunctional acid anhydrides such as ethylene glycol bis (anhydrotrimate) and methylcyclohexane tetracarboxylic acid anhydride, and free acid anhydride carboxylic acids such as trimellitic anhydride and polyazelaic acid anhydride. The curing agent may be used alone, or two or more kinds of curing agents may be used in combination.

The resin composition of the present invention may contain a thermosetting resin such as a cyanate resin, an isocyanate resin, a maleimide resin, a polyimide resin, a uretene resin and a phenol resin, and a thermosetting resin such as silica, glass, alumina, talc, , 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. The thermosetting resin and the inorganic filler may be used independently or in combination of two or more. The inorganic filler is preferably surface-treated with a surface treating agent such as an epoxy silane coupling agent or an amino silane coupling agent.

The polyarylate resin and polyarylate resin composition of the present invention can be dissolved in an organic solvent to prepare a resin solution. The method of preparing the resin solution is not particularly limited. However, in the case of preparing the resin solution of the polyarylate resin composition, the polyarylate resin and the epoxy resin are preliminarily mixed before the polyarylate resin and the epoxy resin are simultaneously dissolved in the organic solvent It is easy to obtain a homogeneous resin solution in a short period of time by mixing them after dissolving them in an organic solvent. On the other hand, when the polyarylate resin and the epoxy resin are respectively dissolved in an organic solvent and then mixed, it is easy to obtain a homogeneous resin solution in a shorter time, as the solids concentration of the resin solution of both is close.

The organic solvent used in 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 environmental impact. The organic solvent used in 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 . A common non-halogenated solvent may be used for the resin solution of the polyarylate resin of the present invention and the resin solution of the polyarylate resin composition of the present invention. Examples of such a non-halogenating solvent include amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, , Ether compounds such as 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 And acetic acid esters such as monoethyl ether acetate. All of these non-halogenated solvents are useful as general-purpose solvents, and ketone compounds and aromatic hydrocarbons, especially methyl ethyl ketone and toluene, are useful as more general-purpose solvents. The most useful non-halogenated general purpose solvent is methyl ethyl ketone. These organic solvents may be used alone or in combination of two or more.

Since the polyarylate resin and the polyarylate resin composition of the present invention have excellent solubility in a non-halogenated solvent, the solid concentration of each resin solution can be increased. Specifically, it may be 20 mass% or more, preferably 30 mass% or more, more preferably 40 mass% or more, and further preferably 50 mass% or more . Particularly, the polyarylate resin of the present invention has a solid content of 5 to 40 mass%, preferably 10 to 40 mass%, more preferably 20 to 40 mass%, and still more preferably 30 to 40 mass% Concentration in the non-halogenated solvent. The methyl ethyl ketone and / or toluene used as the solvent of the resin solution of the present invention is widely used in the field of electric and electronic devices, and is an organic solvent particularly convenient because it is easy to obtain and inexpensive. Conventionally, it has been considered that polyarylate resins are difficult to dissolve in the above solvents because of the high concentration of aromatic rings. However, it was found that the polyarylate resin was dissolved in the solvent at a high concentration by using a specific resin composition. Therefore, the polyarylate resin and the polyarylate resin composition of the present invention are very easy to handle in the formation of coatings and films and in the production of prepregs, and their industrial significance is very high.

After the resin solution of the present invention is applied to a substrate and dried, a film is formed, and the film is peeled off from the substrate. The resin solution for forming the coating film and the film may be a resin solution obtained by dissolving the polyarylate resin in an organic solvent or a resin solution obtained by dissolving the polyarylate resin composition in an organic solvent.

Examples of the substrate include a PET film, a polyimide film, a glass plate, and a stainless steel plate. Examples of the coating method include a wire bar coating method, a film applicator coating method, a brush coating method, a spray coating method, a gravure roll coating method, a screen printing method, a reverse roll coating method, a lip coating method, an air knife coating method, , And an immersion coating method.

The resin solution of the present invention can be impregnated or coated with a reinforcing fiber cloth and then dried to obtain a prepreg. The resin solution for preparing the prepreg may be a resin solution obtained by dissolving a polyarylate resin or polyarylate resin composition in an organic solvent.

Examples of the reinforcing fiber constituting the reinforcing fiber cloth include glass fiber, carbon fiber, organic fiber and ceramic fiber. Any of these woven or nonwoven fabrics can be used. A synthetic paper obtained by mixing and fibrillating these fibers in a short fiber state using fibrids may also be used. Above all, glass fibers and carbon fibers are preferable because of excellent workability. The thickness of the reinforcing fiber cloth is preferably 5 to 50 mu m, more preferably 10 to 45 mu m, and further preferably 15 to 40 mu m.

A method of impregnating the reinforcing fiber cloth with the resin solution is not particularly limited, and a known method can be used. Examples of the impregnating method include a method of using a continuous impregnation apparatus commercially available or a self-working apparatus, a method of immersing a reinforcing fiber in a resin solution made of a polyarylate resin, a method of spreading reinforcing fibers on a plate such as a release paper, a glass plate or a stainless steel plate , And a method of coating a resin solution comprising a polyarylate resin. The prepreg is obtained by evaporating and drying the organic solvent from the coated resin solution after the coating.

The method of applying the resin solution to the reinforcing fiber cloth is not particularly limited, and a known method can be used. As the coating method, for example, it is possible to coat using a commercially available coating machine. In the case of performing both-side coating, there is a method in which a single-side coating is performed, a method in which drying is performed once and then coating is conducted on the opposite side, a method in which coating is performed on the opposite side without performing drying after the single- side coating is applied, . These coating methods can be appropriately selected in consideration of workability and the performance of the resulting prepreg. The prepreg is obtained by evaporating and drying the organic solvent from the coated resin solution after the coating.

The thickness of the prepreg varies depending on the thickness of the reinforcing fiber cloth used, but is preferably 10 to 150 占 퐉, more preferably 20 to 140 占 퐉, and still more preferably 30 to 130 占 퐉. On the other hand, the prepreg is obtained by impregnating or coating with a resin solution in a reinforcing fiber cloth and then drying the reinforcing fiber cloth. However, by obtaining a prepreg so as to have a thickness three times as large as the thickness of the reinforcing fiber cloth used, heat resistance, mechanical characteristics, A prepreg having excellent appearance can be obtained.

The prepreg of the present invention can be used as it is without any heat treatment or the like for curing. Since the polyarylate resin contained in the prepreg is melted when heated to a temperature not lower than its glass transition temperature and exhibits fluidity, the prepreg can be laminated as it is or several times, and can be densified by hot pressing to form a laminate have. Since the laminate has excellent adhesiveness between prepregs, the laminate has sufficiently improved mechanical strength and excellent heat resistance. Further, the laminate can be used as a plate-shaped formed body having high strength. Furthermore, the plate-shaped formed body may be molded into a desired shape. With respect to the moldability, although it depends on the material of the reinforcing fiber cloth to be used and the solid content of the prepreg, it is possible to perform shaping according to a predetermined mold. The punching may be carried out in a range not largely deteriorating the mechanical characteristics. When the thermosetting resin is not used in the prepreg of the present invention, the prepreg of the present invention is excellent in workability such as adhesiveness, formability and puncture. On the other hand, cold working can be applied to the form processing and punching, but it is also possible to carry out under-temperature processing as required.

By curing the film, film, prepreg and laminate thereof obtained by using the solution of the polyarylate resin composition of the present invention, the polyarylate resin and the epoxy resin are reacted to complete the curing. The heating temperature (curing temperature) is usually 110 to 250 캜, preferably 130 to 220 캜. The heating time (curing time) is usually from 1 minute to 20 hours, preferably from 5 minutes to 10 hours.

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

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited thereto. On the other hand, the physical properties of the polyarylate resin were measured by the following methods.

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

¹ H-NMR analysis was performed using a high-resolution nuclear magnetic resonance apparatus (LA-400 NMR manufactured by Nippon Denshi KK) to determine the resin composition and the total amount of the terminal groups (2) and (3) from the peak intensities of the respective copolymer components (Resolution: 400 MHz, solvent: mixed solvent having a volume ratio of deuterated trifluoroacetic acid and deuterated tetrachloroethane of 1/11, temperature: 50 ° C).

(II) Glass transition temperature of polyarylate resin

The temperature was raised from 40 DEG C to 340 DEG C at a temperature raising rate of 20 DEG C / min using a differential scanning calorimeter (DSC7, manufactured by Perkin Elmer), and the initiation temperature of the discontinuous change derived from the glass transition temperature in the obtained temperature rising curve was set at a glass transition temperature .

S (optimum): 144 占 폚 or higher;

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

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

C (fail): less than 60 ℃. (Problems in practical use)

(III) Number average molecular weight of polyarylate resin

Using chloroform as a solvent, the pellets of the polyarylate resin were dissolved at a concentration of 1000 ppm to obtain a solution. The number average molecular weight was determined by GPC analysis in terms of polystyrene.

(IV) Solubility of polyarylate resin

A polylaurate resin and methyl ethyl ketone were weighed and added to a glass or sludge bottle having an internal volume of 50 mL so that the total amount was 30 g and the solid content concentration was 20, 30, 40 and 50 mass%. Thereafter, the glass or dust bottle was sealed, and the mixture was rotated (stirred) at 70 rpm for 24 hours at room temperature of 23 DEG C using a mix rotor and allowed to stand at room temperature of 23 DEG C for 2 weeks. After standing, the resin solution was visually observed, and the dissolution stability of the resin solution was judged based on the following criteria. The polyarylate resin was ground in a pulverizer (DAS-28; manufactured by Daicose Chemical Industry Co., Ltd.). The particles of the polyarylate resin had a maximum diameter of 5 mm. The maximum diameter is the average of the largest dimension of any 100 particles.

?: Transparency was maintained, and no thickening was observed.

?: Transparency was not maintained or thickened.

X: Transparency was not maintained, and the film was thickened.

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

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

50 parts by mass of a polyarylate resin and 50 parts by mass of an epoxy resin (jER 828, bisphenol A type epoxy resin, epoxy equivalent 184 to 194 g / eq, viscosity 120 to 150 (25 캜) , 0.2 parts by mass of a curing accelerator (2-ethyl-4-methylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts by mass of methyl ethyl ketone were mixed and stirred until transparent to obtain a resin solution.

The obtained resin solution was poured into an aluminum cup and dried at room temperature for 2 hours. Thereafter, using a vacuum drier, it was desolvated and cured by drying under vacuum at 170 DEG C for 2 hours and then in vacuum at 200 DEG C for 3 hours to obtain a cured product.

On the other hand, since the polyarylate resins obtained in Comparative Examples 1 to 4 and 6 were not dissolved in methyl ethyl ketone, a resin solution was obtained by using 300 parts by mass of tetrahydrofuran instead of 100 parts by mass of methyl ethyl ketone, .

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

Device: manufactured by Agilent Technologies, Inc. E4991A RF Impedance / Material Analyzer Sample size: 60 mm in length × 60 mm in width × 100 μm in thickness

Frequency: 1GHz

Measuring temperature: 23 ° C

Test environment: 23 ° C ± 1 ° C, 50% RH ± 5% RH

permittivity

S (optimum): not more than 2.84;

A (quantity): more than 2.84, not more than 2.85;

B (pass): more than 2.85, 2.89 or less (practically no problem);

C (Failed): exceeded 2.89 (practical problem).

Dielectric tangent

S (optimum): 0.010 or less;

A (quantity): more than 0.010, not more than 0.011;

B (acceptance): more than 0.011, less than 0.013 (practically no problem);

C (failure): exceeding 0.013 (there is a problem in practical use).

(VI) Flowability of polyarylate resin composition

The plate of the cured product obtained in the step (V) was observed to determine the fluidity of the polyarylate resin composition on the basis of the following criteria.

○: No air bubbles were observed in the cured product.

X: Bubbles were observed in the cured product.

(VII) Glass transition temperature of polyarylate resin composition

The glass transition temperature of the polyarylate resin composition was measured in the same manner as in the method of measuring the glass transition temperature of the polyarylate resin in addition to using the cured product obtained in the step (V).

S (optimum): 163 DEG C or higher;

A (quantity): 150 占 폚 or higher, lower than 163 占 폚;

B (pass): 110 ° C or more, less than 150 ° C (no problem in practical use);

C (Fail): Less than 110 ℃ (Practical problem).

Example 1

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 were charged (TPA: BisA: BisTMC: PHBA: acetic anhydride (molar ratio) = 50: 50: 63: 63: 50: 315) and the mixture was stirred and reacted under normal pressure and at 140 DEG C for 2 hours.

Subsequently, the temperature was raised to 280 deg. C over 3 hours and maintained at 280 deg. 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 composition of TPA: IPA: BisA: BisTMC: PHBA (molar ratio) = 50: 50: 63: 63:

Examples 2 to 16 and Comparative Examples 1 to 6?

A polyarylate resin was obtained in the same manner as in Example 1 except that the composition of the feedstock was changed as shown in the following table.

Example 17

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 were fed into a reaction vessel equipped with a stirrer (TPA: IPA: BisA: BisTMC: acetic anhydride = 30: 70: 62.5: 62.5: 250), and the mixture was stirred and reacted at 140 ° C for 2 hours under atmospheric pressure in a nitrogen atmosphere.

Subsequently, 5.1 parts by mass of PHBA was added at 140 占 폚, the temperature was raised to 280 占 폚 over 3 hours, the temperature was maintained at 280 占 폚 for 1 hour, the pressure was reduced to 130 Pa at 280 占 폚 over 90 minutes, To obtain a polyarylate resin.

The resin composition of the obtained polyarylate resin was analyzed, and the composition of the TPA: IPA: BisA: BisTMC: PHBA (molar ratio) = 30: 70: 63: 63:

Examples 18 to 19?

A polyarylate resin was obtained in the same manner as in Example 17 except that the composition of the feedstock was changed as shown in the following table.

The resin compositions of the polyarylate resins obtained in Examples 1 to 19 and Comparative Examples 1 to 6 and the evaluation thereof and the evaluation of the polyarylate resin composition are shown in the following Tables.

TPA: terephthalic acid

NDCA: 2,6-naphthalene dicarboxylic 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 a non-halogenated solvent, and had excellent dielectric properties and fluidity at the time of processing in the case of a resin composition.

The polyarylate resins of Comparative Examples 1 and 2 had poor solubility because they did not use the hydroxycarboxylic acid component.

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

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

The polyarylate resin of Comparative Example 5 had poor solubility because the hydroxycarboxylic acid component was larger than the range specified in the present invention. In addition, since it is not dissolved in any solvent such as methyl ethyl ketone, toluene, cyclohexanone, tetrahydrofuran, 1,3-dioxolane, N-methylpyrrolidone and N, N-dimethylformamide, I could not do it.

The polyarylate resin of Comparative Example 6 had a higher number-average molecular weight than the range specified in the present invention, and thus had poor solubility. Further, when the resin composition is used, the fluidity at the time of processing is poor.

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

Claims (14)

A polyarylate resin containing a divalent phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component,
Wherein the content of the divalent phenol represented by the formula (1) in the entire divalent phenol component is 30 to 70 mol%
The content of the hydroxycarboxylic acid component in the total monomer component is 1 to 30 mol%
A polyarylate resin having a number average molecular weight of less than 10,000;

Wherein 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, R ⁵ and R ⁶ are each independently 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 which forms a saturated aliphatic hydrocarbon ring together with the carbon atom to which the hydroxyphenyl group is bonded. The method according to claim 1,
Wherein the polyarylate resin has a structure represented by the following formula (2) or / and (3) as an end group,
A polyarylate resin characterized in that the total amount of terminal groups of the following formulas (2) and (3) is 100 g / t or more:

[Wherein the terminal group in the formula (2) represents a structure derived from a monohydroxy compound component, the terminal group in the formula (3) represents a structure derived from a monocarboxylic acid component, and R ⁷ and R ⁸ each independently represent an aliphatic hydrocarbon group or An aromatic hydrocarbon group]. 3. The method according to claim 1 or 2,
Wherein the divalent phenol represented by the formula (1) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and / or 1,1- - &lt; / RTI &gt; cyclododecane. 4. The method according to any one of claims 1 to 3,
Wherein the content of isophthalic acid in the entire aromatic dicarboxylic acid component is 50 mol% or more. 5. The method according to any one of claims 1 to 4,
Wherein the divalent phenol component is at least one selected from the group consisting of 2,2-bis (4-hydroxyphenyl) propane (BisA) and / or 1,1-bis (4-hydroxyphenyl) A polyarylate resin containing a divalent phenol represented by the following formula (1). 6. The method of claim 5,
(BisA + BisAP) / (divalent phenol represented by the formula (1)) of the total content of the bisA and / or the bisAP and the total content of the divalent phenol represented by the formula (1) / 65 to 65/35 (molar ratio). 7. The method according to any one of claims 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). A polyarylate resin composition comprising the polyarylate resin according to any one of claims 1 to 7, an epoxy resin, and a curing accelerator. A coating film comprising the polyarylate resin according to any one of claims 1 to 7 or the polyarylate resin composition according to claim 8. A film comprising the polyarylate resin according to any one of claims 1 to 7 or the polyarylate resin composition according to claim 8. A resin solution characterized by containing the polyarylate resin according to any one of claims 1 to 7 or the polyarylate resin composition according to claim 8 and an organic solvent. 12. The method of claim 11,
Wherein the organic solvent is a non-halogenated solvent. A prepreg characterized in that the resin solution according to claim 11 or 12 is impregnated or coated with a reinforcing fiber cloth. A laminate characterized in that the prepreg according to claim 13 is laminated.