JPWO2017073549A1 - Polyarylate resin, method for producing the same, and polyarylate resin composition - Google Patents

Abstract

An object of the present invention is to provide a polyarylate resin excellent in fluidity and reactivity with an epoxy resin, and a method for producing the same, which can form a cured product sufficiently excellent in heat resistance and dielectric properties. The present invention provides a polyarylate resin containing a dihydric phenol component and an aromatic dicarboxylic acid component and having a hydroxyl group concentration of 100 geq / ton or more. The present invention is also a method for producing the polyarylate resin by performing an acetylation reaction and a deacetic acid polymerization reaction, wherein a hydroxycarboxylic acid component is added after the acetylation reaction and before the deacetic acid polymerization reaction. A method for producing a polyarylate resin is provided.

Description

  The present invention relates to a polyarylate resin, a method for producing the same, and a polyarylate resin composition.

  2. Description of the Related Art In recent years, with various types of electronic equipment, with the increase in the amount of information processing, high integration of semiconductor devices to be mounted, high density of wiring, and multilayer technology have rapidly advanced. Insulating materials such as printed wiring boards used in various electronic devices are required to have excellent dielectric properties. Specifically, in order to increase the transmission speed of a signal, a low dielectric constant and a low dielectric loss tangent are required to reduce loss during signal transmission. Further, an insulating material such as a printed wiring board is required to have excellent heat resistance that can withstand heat treatment such as soldering.

  Insulating materials such as printed wiring boards include thermosetting resins such as epoxy resins, but thermosetting resins are difficult to achieve both heat resistance and dielectric properties such as relative permittivity and dielectric loss tangent. On the other hand, it is known that polyarylate resin which is a thermoplastic resin is excellent in heat resistance and dielectric properties. Therefore, it is expected that the heat resistance and dielectric properties of the epoxy resin are improved by blending the polyarylate resin with the epoxy resin.

  For example, Patent Document 1 discloses a technique in which a resin composition in which an active ester compound, a curing accelerator, and an epoxy resin are blended with a specific polyarylate resin is used for a printed wiring board.

JP 2004-224890 A

  However, since the polyarylate resin contained in the resin composition in Patent Document 1 has low fluidity, it is inferior in workability. For example, when producing a multilayer printed wiring board, voids are generated when the prepreg is multilayered. However, there is a problem that a highly reliable multilayer printed wiring board cannot be obtained.

  The polyarylate resin is generally produced by an interfacial polymerization method or a melt polymerization method. However, for example, in the interfacial polymerization method, an end-blocking agent is usually used, so that the carboxyl group and hydroxyl group, which are polar groups excellent in reaction with an epoxy resin, hardly remain at the end of the molecular chain of the resulting polyarylate resin. Therefore, even if the polyarylate resin has a relatively high glass transition temperature, the reactivity to the epoxy resin is low, so that a cured product having a sufficiently high glass transition temperature cannot be obtained together with the epoxy resin. There was a problem with heat resistance. Furthermore, in the interfacial polymerization method, a large amount of organic solvent and water are used in the production of the polyarylate resin. Therefore, a large amount of energy such as electric power is required for the solvent recovery and regeneration treatment. Was big.

  In addition, for example, in the melt polymerization method, the raw divalent phenol is acetylated, and then the acetylated dihydric phenol and dicarboxylic acid are subjected to deacetic acid polymerization. For this reason, the hydroxyl group hardly remains at the molecular chain terminal of the polyarylate resin obtained by the melt polymerization method. Therefore, the polyarylate resin produced by a general melt polymerization method has a relatively high glass transition temperature even if it has a relatively high glass transition temperature. In some cases, a high cured product could not be obtained, resulting in problems in heat resistance.

  It is also known that an ester in the main chain of a polyarylate resin reacts with an epoxy in the presence of a catalyst such as a tertiary amine and a quaternary onium salt. However, since the reactivity to the epoxy resin is low, the reaction rate is slow, and even if the reaction proceeds, it is still impossible to obtain a cured product having a sufficiently high glass transition temperature together with the epoxy resin.

  On the other hand, polyarylate resins generally have low solubility in general-purpose solvents, are difficult to handle, and polyarylate resins excellent in solubility in general-purpose solvents are demanded. If the solubility in a general-purpose solvent is low, it is difficult to prepare a varnish with a high solid content concentration, and it is easy to gel or precipitate. In addition, the production of polyarylate resin may require a long reaction time, and polyarylate having good production efficiency is also demanded.

  An object of the present invention is to provide a polyarylate resin excellent in fluidity and reactivity with an epoxy resin, and a method for producing the same, which can form a cured product sufficiently excellent in heat resistance and dielectric properties.

  The present invention also provides a polyarylate resin that is capable of forming a cured product sufficiently excellent in heat resistance and dielectric properties, has excellent solubility in general-purpose solvents, fluidity, and reactivity with an epoxy resin, and a method for producing the same. For the purpose.

  The present invention also provides a polyarylate resin capable of forming a cured product sufficiently excellent in heat resistance and dielectric properties, having solubility in a general-purpose solvent, fluidity, reactivity with an epoxy resin, and production efficiency, and a production method thereof. The purpose is to provide.

As a result of intensive studies, the present inventors have found that the above object can be achieved, and have reached the present invention.
That is, the gist of the present invention is as follows.
<1> A polyarylate resin containing a dihydric phenol component and an aromatic dicarboxylic acid component and having a hydroxyl group concentration of 100 geq / ton or more.
<2> The polyarylate resin according to <1>, wherein the acetyl group concentration is 10 geq / ton or more.
<3> The polyarylate resin according to <1> or <2>, wherein the monomer concentration is 2% by mass or less.
<4> The polyarylate resin according to any one of <1> to <3>, further containing a hydroxycarboxylic acid component.
<5> The polyarylate resin according to <4>, wherein the hydroxycarboxylic acid component is contained in a proportion of 2 to 50 mol% with respect to all monomer components.
<6> The polyarylate resin according to any one of <1> to <5>, wherein the dihydric phenol component contains an alicyclic dihydric phenol represented by the general formula (1).
[In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms or a halogen atom; R ⁵ and R ⁶ are Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m represents an integer of 4 to 12; X represents a saturated aliphatic hydrocarbon ring together with the carbon atom to which the hydroxyphenyl group is bonded. Represents the carbon atom to be formed]
<7> The polyarylate resin according to <6>, wherein the alicyclic dihydric phenol is contained at a ratio of 15 mol% or more with respect to the total dihydric phenol component.
<8> The dihydric phenol component is 2,2-bis (4-hydroxyphenyl) propane (BisA) and / or 1,1-bis (4-hydroxyphenyl) -1-phenylethane (BisAP), , 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BisTMC) and / or 1,1-bis (4-hydroxyphenyl) -cyclododecane (BisCDE), <6> Or the polyarylate resin as described in <7>.
<9> The content ratio ((BisA + BisAP) / (BisTMC + BisCDE)) of the total content of the BisA and / or the BisAP and the total content of the BisTMC and / or the BisCDE is 15/85 to 85/15 ( The polyarylate resin according to <8>, which is a molar ratio).
<10> A method for producing a polyarylate resin according to any one of <1> to <9> by performing an acetylation reaction and a deacetic acid polymerization reaction,
A method for producing a polyarylate resin, comprising adding a hydroxycarboxylic acid component after the acetylation reaction and before the deacetic acid polymerization reaction.
<11> A preliminary step of adjusting the temperature and pressure for the deacetic acid polymerization reaction after the acetylation reaction and before the deacetic acid polymerization reaction,
The method for producing a polyarylate resin according to <10>, wherein the hydroxycarboxylic acid component is added in the preliminary stage.
<12> The preliminary step is a step of depressurizing after raising the temperature of the reaction system,
The method for producing a polyarylate resin according to <11>, wherein in the preliminary stage, the hydroxycarboxylic acid component is added before the temperature rise and / or after the temperature rise and before the pressure reduction.
<13> A polyarylate resin composition comprising the polyarylate resin and the epoxy resin according to any one of <1> to <9>.
<14> A film comprising the polyarylate resin according to any one of <1> to <9>.
<15> A film comprising the polyarylate resin according to any one of <1> to <9>.
<16> A resin solution containing the polyarylate resin according to any one of <1> to <9> and an organic solvent.
<17> A prepreg, wherein the resin solution according to <16> is impregnated or applied to a reinforcing fiber cloth.
<18> A laminate in which the prepreg according to <17> is laminated.

The polyarylate resin of the present invention is excellent in reactivity with an epoxy resin and fluidity.
The polyarylate resin of the present invention can also form a cured product sufficiently excellent in heat resistance and dielectric properties together with an epoxy resin.

[Polyarylate resin]
The polyarylate resin of the present invention is a polyester containing a dihydric phenol component and an aromatic dicarboxylic acid component as monomer components.

  The dihydric phenol component may be any organic compound containing two phenolic hydroxyl groups in one molecule. A phenolic hydroxyl group is a hydroxyl group bonded directly to an aromatic ring.

  The dihydric phenol component is an alicyclic dihydric phenol represented by the general formula (1) from the viewpoint of improving the solubility in a general-purpose solvent and further improving the heat resistance of the cured product of the polyarylate resin and the epoxy resin. It is preferable to contain.

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

In formula (1), preferred R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (particularly 1 to 3), or 6 to 10 carbon atoms. (Especially 6) aryl group or halogen atom (especially chlorine atom, bromine atom). More preferable R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 (particularly 1 to 3) carbon atoms. R ¹ , R ² , R ³ and R ⁴ may be partially or completely 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 group having 1 to 4 carbon atoms includes a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group contains an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t -A butyl group etc. are mentioned. The unsaturated aliphatic hydrocarbon group 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. A plurality of R ⁵ and R ⁶ are present depending on the value of m described later, and the plurality of R ⁵ and the plurality of R ⁶ may be independently selected from the above range.

In 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 preferable R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly a hydrogen atom.

In formula (1), m represents an integer of 4 to 12, preferably an integer of 5 to 11.
In formula (1), X represents a carbon atom that forms a saturated aliphatic hydrocarbon ring (monocycle) together with the carbon atom to which the hydroxyphenyl group is bonded. The saturated aliphatic hydrocarbon ring represents a cycloalkane ring corresponding to the number of m. Specific examples of the saturated aliphatic hydrocarbon ring include, for example, a cyclopentane ring (m = 4), a cyclohexane ring (m = 5), a cycloheptane ring (m = 6), a cyclooctane ring (m = 7), and a cyclononane ring. (M = 8), cyclodecane ring (m = 9), cycloundecane ring (m = 10), cyclododecane ring (m = 11), cyclotridecane ring (m = 12).

  Among the alicyclic dihydric phenols represented by the general formula (1), from the viewpoint of further improving the heat resistance of the cured product of the polyarylate resin and the epoxy resin, the general formula (1a), ( 1b), (1c), (1d), (1e), (1f), (1g), (1h) and (1i), especially alicyclic dihydric phenols represented by general formulas (1b) to (1h) Is mentioned.

Wherein ^(1a), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In 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 contains an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t -A butyl group etc. are mentioned. The unsaturated aliphatic hydrocarbon group 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 the n1 is an integer of 2 or more, plural R ¹⁰ are each independently, may be selected from the above range. The bonding position of R ¹⁰ in the cyclopentane ring is not particularly limited, but is selected from the 3- and 4-position carbon atoms when the carbon atom of the cyclopentane ring to which the hydroxyphenyl group is bonded in the formula (1a). It is preferable that each R ¹⁰ is bonded to a carbon atom.

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

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

Wherein ^(1b), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

  In formula (1b), n2 is an integer of 0-10, preferably an integer of 0-5, 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 said n2 is an integer greater than or equal to 2, several R < ²⁰ > should just be independently selected from the same range as said R < ¹⁰ >. The bonding position of R ^{20 in} the cyclohexane ring is not particularly limited, but when the carbon atom of the cyclohexane ring to which the hydroxyphenyl group is bonded in the formula (1b) is selected from the carbon atoms at the 3-position, 4-position and 5-position. It is preferable that each R ²⁰ is bonded to the carbon atom to be formed, particularly the carbon atom at the 3rd and 5th positions.

Desirable R ²⁰ each independently represents an alkyl group having 1 to 4 carbon atoms. More preferred 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 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (3,5-dimethyl-4-hydroxyphenyl). ) Cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [BisTMC], 1,1-bis- (4-hydroxyphenyl) -3,3,5,5-tetramethyl Cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,4-trimethyl-cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3-dimethyl-5-ethyl-cyclohexane 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3 -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-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5-dichloro-4-hydroxyphenyl) -3,3,5-trimethyl- And cyclohexane, 1,1-bis- (3,5-dibromo-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane. Among them, BisTMC is particularly preferable because of its high versatility.

Wherein ^(1c), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In the formula (1c), R ³⁰ is the same as R ¹⁰ in the above formula (1a). When the n3 is an integer of 2 or more, plural R ³⁰ are each independently, may be selected from a range similar to the above R ^10. The bonding position of R ³⁰ in the cycloheptane ring is not particularly limited. However, when the carbon atom of the cycloheptane ring to which the hydroxyphenyl group is bonded is the first position in the formula (1c), the 3-position, 4-position, 5-position and 6-position It is preferable that each R ³⁰ is bonded to a carbon atom selected from the following carbon atoms.

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

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

Wherein ^(1d), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In the formula (1d), R ⁴⁰ is the same as R ¹⁰ in the above formula (1a). When the n4 is an integer of 2 or more, plural R ⁴⁰ are each independently, may be selected from a range similar to the above R ^10. The bonding position of R ⁴⁰ in the cyclooctane ring is not particularly limited. However, when the carbon atom of the cyclooctane ring to which the hydroxyphenyl group is bonded in the formula (1d) is the first position, the fourth, fifth and sixth position carbon atoms It is preferable that each R ⁴⁰ is bonded to a carbon atom selected from:

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

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

Wherein ^(1e), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In formula (1e), R ⁵⁰ is the same as R ¹⁰ in formula (1a). When the n5 is an integer of 2 or more, plural R ⁵⁰ is each independently may be selected from a range similar to the above R ^10. The bonding position of R ^{50 in} the cyclononane ring is not particularly limited, but when the carbon atom of the cyclononane ring to which the hydroxyphenyl group is bonded in the formula (1e) is the first position, the carbons at the 4-position, 5-position, 6-position and 7-position Each R ⁵⁰ is preferably bonded to a carbon atom selected from the atoms.

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

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

Wherein ^(1f), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In the formula (1f), R ⁶⁰ is the same as R ¹⁰ in the above formula (1a). When the n6 is an integer of 2 or more, plural R ⁶⁰ are each independently, may be selected from a range similar to the above R ^10. The bonding position of R ^{60 in} the cyclodecane ring is not particularly limited, but when the carbon atom of the cyclodecane ring to which the hydroxyphenyl group is bonded in the formula (1f) is selected from the 4-position, 5-position and 6-position carbon atoms It is preferable that each R ⁶⁰ is bonded to the carbon atom to be formed.

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

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

Wherein (1 ^g), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In the formula (1g), R ⁷⁰ is the same as R ¹⁰ in the above formula (1a). When the n7 is an integer of 2 or more, plural R ⁷⁰ are each independently, may be selected from a range similar to the above R ^10. The bonding position of R ^{70 in} the cycloundecane ring is not particularly limited, but when the carbon atom of the cycloundecane ring to which the hydroxyphenyl group is bonded in the formula (1g) is the first position, the fourth position, the fifth position, the sixth position and the seventh position. It is preferable that each R ⁷⁰ is bonded to a carbon atom selected from the following carbon atoms.

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

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

Wherein ^(1h), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In the formula (1h), R ⁸⁰ is the same as R ¹⁰ in the above formula (1a). When the n8 is an integer of 2 or more, plural R ⁸⁰ are each independently, may be selected from a range similar to the above R ^10. The bonding position of R ^{80 in} the cyclododecane ring is not particularly limited, but when the carbon atom of the cyclododecane ring to which the hydroxyphenyl group is bonded in the formula (1h) is the first position, the fifth position, the sixth position, the seventh position, the eighth position And each R ⁸⁰ is preferably bonded to a carbon atom selected from carbon atoms at the 9-position.

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

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

Wherein ^(1i), each R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferable R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (1).

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

In formula (1i), R ⁹⁰ is the same as R ¹⁰ in formula (1a). When the n9 is an integer of 2 or more, plural R ⁹⁰ are each independently, may be selected from a range similar to the above R ^10. The bonding position of R ⁹⁰ in the cyclotridecane ring is not particularly limited. However, when the carbon atom of the cyclotridecane ring to which the hydroxyphenyl group is bonded in the formula (1i) is the first position, the sixth position, the seventh position, the eighth position, and Each R ⁹⁰ is preferably bonded to a carbon atom selected from the carbon atoms at the 9th position.

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

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

  The content ratio of the alicyclic dihydric phenol represented by the general formula (1) is not particularly limited, and is usually 15 mol% or more (15 to 100 mol%) with respect to the total dihydric phenol component. The content ratio is preferably 15 to 90 mol%, more preferably 25 to 75 mol%, based on the total dihydric phenol component, from the viewpoint of improving the solubility of the polyarylate resin in a general-purpose solvent. The content ratio is preferably 40 to 100 mol%, more preferably 55 to 100 mol% with respect to the total dihydric phenol component, from the viewpoint of further improving the heat resistance of the cured product of the polyarylate resin. Preferably it is 90-100 mol%. The content ratio is the total dihydric phenol component from the viewpoint of the balance between the improvement of the solubility of the polyarylate resin in a general-purpose solvent and the further improvement of the reactivity of the polyarylate resin with the epoxy resin and the heat resistance of the cured product. It is preferably 40 to 90 mol%, more preferably 50 to 90 mol%. The alicyclic dihydric phenol represented by the alicyclic dihydric phenol represented by the general formula (1) may be used alone or in combination, and in that case, the total amount thereof. Should just be in the said range.

  The dihydric phenol component may contain a dihydric phenol other than the alicyclic dihydric phenol represented by the general formula (1). From the viewpoint of improving the solubility of the polyarylate resin in a general-purpose solvent, the dihydric phenol component preferably contains a dihydric phenol other than the alicyclic dihydric phenol represented by the general formula (1).

  The dihydric phenol other than the alicyclic dihydric phenol represented by the general formula (1) is not particularly limited as long as it is a dihydric phenol component not included in the alicyclic dihydric phenol represented by the general formula (1). Examples thereof include the following dihydric phenols: 2,2-bis (4-hydroxyphenyl) propane [BisA], 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2, 2-bis (3-methyl-4-hydroxyphenyl) propane, 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) Le) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane. Of these, BisA and / or BisAP are preferred because of their versatility and high solubility in general-purpose solvents. Divalent phenols other than the alicyclic dihydric phenol represented by the general formula (1) may be used alone or in combination of two or more.

  As the dihydric phenol component, the above dihydric phenol may be used alone, or a plurality of dihydric phenols may be used in combination. However, since the solubility in a general-purpose solvent is increased, it is preferable to use a plurality of dihydric phenol components. Among these, the dihydric phenol component preferably contains a combination of BisA and / or BisAP and BisTMC and / or BisCDE. When using BisA and / or BisAP and BisTMC and / or BisCDE, the content ratio of the total content of BisA and BisAP and the total content of BisTMC and BisCDE ((BisA + BisAP) / (BisTMC + BisCDE)) is 10/90 To 90/10 (molar ratio), and more preferably 15/85 to 85/15 (molar ratio), because solubility in methyl ethyl ketone is particularly high. 30/70 to 70 / More preferably, it is 30 (molar ratio). From the viewpoint of solubility in a general-purpose solvent, BisA / BisTMC is more preferably 30/70 to 70/30 (molar ratio).

  The aromatic dicarboxylic acid component may be any organic compound containing two carboxyl groups directly bonded to the aromatic ring in one molecule. Specific examples of the aromatic dicarboxylic acid component include, for example, terephthalic acid [TPA], isophthalic acid [IPA], orthophthalic acid, 4,4′-diphenyldicarboxylic acid, diphenylether-2,2′-dicarboxylic acid, diphenylether-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- And naphthalenedicarboxylic acid [NDCA].

  As the aromatic dicarboxylic acid component, one of the above compounds may be used alone, or a plurality of compounds may be used in combination. Among these, from the viewpoint of solubility of the polyarylate resin in a general-purpose solvent and reactivity with the epoxy resin, it is preferable to use IPA alone or to use TPA and / or NDCA and IPA in combination. The content ratio of IPA is preferably 20 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and more preferably 60 mol% with respect to the wholly aromatic dicarboxylic acid component. % Or more is most preferable. When the aromatic dicarboxylic acid component contains TPA and / or NDCA and IPA, from the viewpoint of solubility of the polyarylate resin in a general-purpose solvent, particularly methyl ethyl ketone, the content ratio of (TPA + NDCA) / IPA is 0 / 100-80 / 20 is preferable, 0 / 100-60 / 40 is more preferable, 0 / 100-50 / 50 is more preferable, 0 / 100-40 / 60 is more preferable, and 10 / 90-40 / 60 is the most preferable.

  The polyarylate resin of the present invention may further contain a hydroxycarboxylic acid component as a monomer component. 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, for example, p-hydroxybenzoic acid [PHBA], m-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, and 1-hydroxy-4- Naphthoic acid is mentioned. Of these, PHBA is preferred because of its high versatility.

  The content ratio of the hydroxycarboxylic acid component needs to be 2 to 50 mol% with respect to 100 mol% of all monomer components, and from the viewpoint of improving the solubility of the polyarylate resin in a general-purpose solvent, it is 2 to 35. From the viewpoint of further improving the solubility, the reactivity of the polyarylate resin with the epoxy resin and the heat resistance of the cured product, 5-30 mol% is more preferable. It is 5-25 mol%, More preferably, it is 10-25 mol%. When the content ratio of the hydroxycarboxylic acid component is less than 2 mol%, it is difficult to obtain a polyarylate resin having a predetermined hydroxyl group concentration, which is not preferable. When the content of the hydroxycarboxylic acid component exceeds 50 mol%, the solubility in a general-purpose solvent (particularly a non-halogenated solvent) and the solution stability are unfavorable. In addition, all the monomer components mean all the monomer components which comprise polyarylate resin. For example, when the polyarylate resin is composed of only a dihydric phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component, all monomer components are all dihydric phenol component, aromatic dicarboxylic acid component, and hydroxycarboxylic acid component ( Total amount). Further, for example, when the polyarylate resin contains other monomer components in addition to the dihydric phenol component, the aromatic dicarboxylic acid component, and the hydroxycarboxylic acid component, all of these components (total amount).

  The polyarylate resin may contain other monomer components other than the above-described dihydric phenol component, aromatic dicarboxylic acid component, and hydroxycarboxylic acid component as long as the effects of the present invention are not impaired. Specific examples of other monomer components include, for example, aliphatic diols such as ethylene glycol and propylene glycol; alicyclic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol; Examples thereof include aliphatic dicarboxylic acids such as acid and sebacic acid; and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid. The aliphatic dicarboxylic acid and alicyclic dicarboxylic acid may be derivatives or anhydrides thereof. The content ratio of the other monomer components is usually 10 mol% or less, preferably 5 mol% or less, more preferably 0 mol%, based on 100 mol% of all monomer components.

  The hydroxyl group concentration of the polyarylate resin of the present invention is required to be 100 geq / ton or more, from the viewpoint of improving solubility in general-purpose solvents, reactivity with epoxy resins, and further improving heat resistance of cured products. 200 geq / ton or more, preferably 300 geq / ton or more, and more preferably 500 geq / ton or more. When the hydroxyl group concentration is less than 100 geq / ton, the reactivity with the epoxy resin and the heat resistance of the cured product are lowered. Moreover, since the solubility to a general purpose solvent falls, it is not preferable. The upper limit of the hydroxyl group concentration is not particularly limited, but does not exceed the hydroxyl group concentration of the dihydric phenol component, and the hydroxyl group concentration is usually 2500 geq / ton or less, more preferably 1500 geq / ton or less, Preferably it is 1000 geq / ton or less.

Hydroxyl group concentration, a method of obtaining the group concentration if it is possible to quantify the hydroxyl group is not particularly limited, may be obtained by a known method such as neutralization titration method, but will be described in detail later ¹ H In -NMR analysis, it can be determined by calculating the peak area of protons located in the ortho position or meta position relative to the phenolic hydroxyl group and quantifying the group.

  The polyarylate resin of the present invention preferably has an acetyl group concentration of 10 geq / ton or more, more preferably 20 geq / ton or more, from the viewpoint of increasing the efficiency of production of the polyarylate resin by shortening the reaction time. More preferably, it is more than / ton. The acetyl group of the polyarylate resin is an acetylated hydroxyl group, and the polymerization reaction proceeds as the reaction between the carboxyl group and the acetyl group in the aromatic dicarboxylic acid component proceeds. The concentration of acetyl groups in the resin decreases. Even if the acetyl group concentration of the polyarylate resin is less than 10 geq / ton, the effect of the present invention is not affected, but in order to make the acetyl group concentration less than 10 geq / ton, the polymerization time must be lengthened. Therefore, it is not preferable because the production efficiency of the polyarylate resin is lowered. The upper limit of the acetyl group concentration is not particularly limited, but the acetyl group concentration is usually 2000 geq / ton or less, more preferably 1000 geq / ton or less, and further preferably 500 geq / ton or less.

The method for obtaining the concentration of the acetyl group is not particularly limited as long as the acetyl group concentration can be quantified. However, in ¹ H-NMR analysis described in detail later, the peak area of the proton of the methyl group of the acetyl group is determined. It can be determined by calculating and quantifying the group.

  The monomer concentration in the polyarylate resin of the present invention is preferably 2% by mass or less from the viewpoint of improving the solubility in a general-purpose solvent and further improving the reactivity with the epoxy resin and the heat resistance of the cured product. Preferably it is 1.5 mass% or less, More preferably, it is 1.0 mass% or less, Most preferably, it is 0.5 mass% or less. When the monomer concentration exceeds 2% by mass, when the polyarylate resin is dissolved in a solvent, insoluble matter precipitates in the solution and / or the solution becomes cloudy, so that the solubility of the polyarylate resin decreases. For this reason, when it uses for uses, such as a coating agent, since quality worsens, it is unpreferable. The lower limit of the monomer concentration is not particularly limited, and the monomer concentration is usually 0.01% by mass or more, particularly 0.1% by mass or more.

  In the present invention, the monomer concentration in the polyarylate resin refers to the monomer used in the production of the polyarylate resin but remaining unreacted and the polymer chain of the polyarylate resin, but released (decomposed) from the polymer chain. And the ratio of the total amount of monomers produced to the total amount of polyarylate resin. The monomer component contained in the polyarylate resin is difficult to separate and precipitates as an insoluble substance when the polyarylate resin is dissolved in a solvent. It is considered that the solubility of the polyarylate resin in a general-purpose solvent depends not only on the structure and monomer composition of the polymer itself of the polyarylate resin but also on the presence of the monomer contained in the polyarylate resin.

  The monomer concentration can be measured from a polyarylate resin solution by high performance liquid chromatography. Specifically, the measurement by high performance liquid chromatography is performed by the method described later.

  The number average molecular weight of the polyarylate resin of the present invention is preferably less than 20,000, more preferably less than 10,000, still more preferably less than 6000, and particularly preferably less than 3000. When the number average molecular weight is 20000 or more, the hydroxyl group concentration becomes low, and the reactivity with the epoxy resin may decrease. The lower limit of the number average molecular weight of the polyarylate resin is not particularly limited, but the number average molecular weight is usually 500 or more, particularly 1000 or more.

  In the polyarylate resin of the present invention, the hydroxyl group may be modified with a compound having an epoxy group, an acrylate group, a vinyl group, an isocyanate group, an oxazoline group, a carbodiimide group, or a silanol group as long as the properties are not impaired. Good. By modifying the hydroxyl group with a compound having an epoxy group, an acrylate group, a vinyl group, an isocyanate group, an oxazoline group, a carbodiimide group, or a silanol group, thermosetting reactivity and / or photocuring reactivity is improved. .

[Production method of polyarylate resin]
The production method of the polyarylate resin of the present invention is not particularly limited as long as the hydroxyl group concentration can be within a predetermined range. However, since the control of the hydroxyl group concentration is easy, control is performed using a hydroxycarboxylic acid component during melt polymerization. Is preferred.

  As a method for increasing the hydroxyl group concentration of polyester, a method of adding a polyvalent glycol component and carrying out a depolymerization reaction after completion of the polycondensation reaction is widely known. However, in the case of a polyarylate resin, the progress of the depolymerization reaction by the polyhydric glycol component, the dihydric phenol component, or the hydroxycarboxylic acid component is slow, and the reaction time of the whole reaction becomes long. In addition, a part of the monomer component added during the depolymerization reaction remains unreacted, and a part of the monomer component constituting the polyarylate resin is generated as a monomer by the depolymerization reaction. For this reason, the method of performing a depolymerization reaction is not preferable.

  In the present invention, the method of controlling the hydroxyl group concentration using a hydroxycarboxylic acid component at the time of melt polymerization refers to a method of performing an acetylation reaction and a deacetic acid polymerization reaction, after the acetylation reaction and before the deacetic acid polymerization reaction. This is a method of adding a hydroxycarboxylic acid component. That is, the hydroxycarboxylic acid component is added after the acetylation reaction and before the deacetic acid polymerization reaction. Such a method is also preferable from the viewpoint of solubility of the polyarylate resin in a general-purpose solvent. As long as the effect of the present invention is not impaired, after the acetylation reaction is carried out by adding a part of the hydroxycarboxylic acid component, the remaining hydroxy group is added after the acetylation reaction and before the deacetic acid polymerization reaction. A carboxylic acid component may be added.

  The acetylation reaction is a reaction for acetylating a dihydric phenol component or a dihydric phenol component and a hydroxycarboxylic acid component. In the acetylation reaction, an aromatic dicarboxylic acid component, a dihydric phenol component, and acetic anhydride are charged into a reaction vessel, or an aromatic dicarboxylic acid component, a dihydric phenol component, hydroxycarboxylic acid, and acetic anhydride are charged. Thereafter, nitrogen substitution is performed, and the mixture is stirred under an inert atmosphere at a temperature of 100 to 240 ° C., preferably 120 to 180 ° C., for 5 minutes to 8 hours, preferably 30 minutes to 5 hours, at normal pressure or under pressure. The molar ratio of acetic anhydride to the hydroxyl group of the dihydric phenol component is preferably 1.00 to 1.20.

  The deacetic acid polymerization reaction is a reaction in which acetylated dihydric phenol and aromatic dicarboxylic acid are reacted and polycondensed. In the deacetic acid polymerization reaction, it is maintained at a temperature of 240 ° C. or higher, preferably 260 ° C. or higher, more preferably 280 ° C. or higher, 500 Pa or lower, preferably 260 Pa or lower, more preferably 130 Pa or lower, for 30 minutes or longer. Stir. When the temperature is less than 240 ° C., when the degree of vacuum exceeds 500 Pa, or when the holding time is less than 30 minutes, the amount of acetic acid in the polyarylate resin that can result in insufficient deacetic acid reaction increases, There are cases where the polymerization time becomes longer or the polymer color tone deteriorates.

  In general, there is a preliminary stage for adjusting the temperature and pressure of the reaction system to the temperature and pressure for the deacetic acid polymerization reaction after the acetylation reaction and before the deacetic acid polymerization reaction. In the production method of the present invention, a hydroxycarboxylic acid component may be added in this preliminary stage. Specifically, in the preliminary stage, when the pressure is reduced after raising the temperature of the reaction system, a hydroxycarboxylic acid component may be added before raising the temperature, or after raising the temperature and before reducing the pressure, A carboxylic acid component may be added. The hydroxycarboxylic acid component may be added both before the temperature rise and after the temperature rise and before the pressure reduction.

  In the present invention, the hydroxycarboxylic acid component is added after reacting acetic anhydride with the dihydric phenol component or with the dihydric phenol component and the hydroxycarboxylic acid component. For this reason, the hydroxyl group of the hydroxycarboxylic acid component added after the acetylation reaction is not acetylated. As a result, among the terminal groups of the hydroxycarboxylic acid component, the carboxyl group having excellent reactivity proceeds with the polyarylate resin in the deacetic acid polymerization reaction stage, but the hydroxyl group that is not acetylated is polyarylate. The reaction with the resin does not proceed. For this reason, it is estimated that the hydroxyl group concentration of the polyarylate resin obtained can be made into a predetermined range.

  In the acetylation reaction and deacetic acid polymerization reaction, it is preferable to use a catalyst, if necessary. Examples of the catalyst include organic titanate compounds such as tetrabutyl titanate; zinc acetate; alkali metal salts such as potassium acetate; alkaline earth metal salts such as magnesium acetate; antimony trioxide; hydroxybutyltin oxide, tin octylate, etc. Organic tin compounds; heterocyclic compounds such as N-methylimidazole are included. The addition amount of the catalyst is usually 1.0 mol% or less, more preferably 0.5 mol% or less, further preferably 0.2 mol% or less, based on all monomer components of the polyarylate resin obtained. It is.

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

[Polyarylate resin composition]
The present invention also provides a polyarylate resin composition. The polyarylate resin composition of the present invention includes at least the polyarylate resin and the epoxy resin described above.

  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, phenol novolac type epoxy resin. , Cresol novolac type epoxy resin, isocyanurate type epoxy resin, alicyclic epoxy resin, acrylic acid modified epoxy resin, polyfunctional epoxy resin, brominated epoxy resin, phosphorus modified epoxy resin. An epoxy resin may be used independently and may use 2 or more types together.

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

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

The compounding amount of the polyarylate resin is such that the functional group equivalent of the polyarylate resin is preferably 0.5 to 1.5 equivalent ratio, more preferably 0.7 to 1.3 equivalent ratio with respect to the epoxy equivalent of the epoxy resin. Preferably, the amount is such that The functional group equivalent of the polyarylate resin corresponds to an equivalent calculated from the contents 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 40 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin and the polyarylate resin. 50 parts by mass.

  The polyarylate resin composition of the present invention usually contains a curing accelerator. The curing accelerator is not particularly limited, but examples thereof include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 4-dimethylaminopyridine, benzyldimethylamine, 2- (dimethylamino) And tertiary amines such as methyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; and organic phosphines such as triphenylphosphine and tributylphosphine. A hardening accelerator may be used independently and may use 2 or more types together.

  A curing agent can be used in combination with the resin composition of the present invention. Examples of the curing agent include aliphatic polyamine compounds such as diethylenetriamine, triethylenetetonramine, tetraethylenepentamine, dicyandiamine, adipic acid dihydrazide, and polyamide polyamine; mensendiamine, isophoronediamine, bis (4-amino-3) -Alicyclic polyamine compounds such as methylcyclohexyl) methane and bis (4-aminocyclohexyl) methane; aromatic polyamine compounds such as metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and metaphenylenediamine; phthalic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorinated anhydride Monofunctional acid anhydrides such as dick acid; bifunctional acid anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexanetetracarboxylic acid anhydride; Examples include free acid carboxylic anhydrides such as trimellitic acid and polyazeline acid anhydride. A hardening | curing agent may be used independently and may use 2 or more types together.

  The resin composition of the present invention may further contain a thermosetting resin such as a cyanate resin, an isocyanate resin, a maleimide resin, a polyimide resin, a urethane resin, or a phenol resin.

  The resin composition of the present invention may contain a resin having two or more terminal groups in one molecule that reacts favorably with phenolic hydroxyl groups, instead of the epoxy resin. Examples of the resin that may be contained instead of the epoxy resin include a cyanate resin, an isocyanate resin, and a maleimide resin.

  The resin composition of the present invention may be used by adding to a high molecular weight resin. Depending on the application, it can be used for molded products, films, sheets, adhesives, coatings, conductive pastes, film-in-molded transfer foils, and the like. By adding the resin composition of the present invention to a high molecular weight resin, fluidity and coating properties can be improved while improving or maintaining the heat resistance of the high molecular weight resin. The high molecular weight resin is not particularly limited as long as it has a weight average molecular weight (Mw) of 10,000 or more. Examples of the high molecular weight resin include polyester resin, polyarylate resin, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polyetherimide resin, polyimide resin, polyamideimide resin, and polyamide resin. A high molecular weight resin may be used independently and may use 2 or more types together.

  The resin composition of the present invention may further contain an inorganic filler. Examples of the inorganic filler include silica, glass, alumina, talc, mica, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, titanium oxide, silicon nitride, and boron nitride. An inorganic filler may be used independently and may use 2 or more types together. The inorganic filler is preferably surface-treated with a surface treatment 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 may contain an antioxidant as long as the properties are not impaired. For example, as a hindered phenol-based antioxidant, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy-2) -Methyl-5-t-butylphenyl) butane, 1,1-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4 -Hydroxy-benzenepropanoic acid, pentaerythrityl tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl- Benzenepropanoic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxy And benzyl) benzene. As phosphorus antioxidants, 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ( Octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tri (monononylphenyl) phosphite, triphenoxyphosphine, isodecylphosphite, iso Decylphenyl phosphite, diphenyl 2-ethylhexyl phosphite, dinonylphenylbis (nonylphenyl) ester phosphoric acid, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) ) Butane, tris (2,4-di-t-butylphenyl) phosphite, pentaerythritol (2,4-di-t-butylphenyl phosphite), 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, bis (2,6-di-t-) Butyl-4-methylphenyl) pentaerythritol diphosphite and the like. 4,4′-thiobis [2-tert-butyl-5-methylphenol] bis [3- (dodecylthio) propionate], thiobis [2- (1,1-dimethylethyl) -5-methyl as a thioether antioxidant -4,1-phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-dodecylthiopropionate), bis (tridecyl) thiodipropionate. An antioxidant may be used independently and may use 2 or more types together.

  The resin composition of the present invention may contain a flame retardant. Non-halogen flame retardants are preferred from the viewpoint of environmental impact. Examples of the flame retardant include phosphorus-based flame retardant, nitrogen-based flame retardant, and silicone-based flame retardant. A flame retardant may be used independently and may use 2 or more types together.

[Solution of polyarylate resin and polyarylate resin composition and use thereof]
The polyarylate resin and the polyarylate resin composition of the present invention can be dissolved in an organic solvent to form a resin solution. The method for preparing the resin solution is not particularly limited. However, when preparing the resin solution of the polyarylate resin composition, the polyarylate resin and the epoxy resin are respectively organically prepared in advance rather than simultaneously dissolving the polyarylate resin and the epoxy resin in an organic solvent. It is easier to obtain a uniform resin solution in a shorter time by mixing them after dissolving in a solvent. In the latter case, it is easier to obtain a uniform resin solution in a shorter time when the solid concentration of both resin solutions is closer.

  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 influence on the environment. 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 influence on the environment. Examples of such a non-halogenated solvent include amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; 1,4-dioxane, 1,3-dioxolane, Ether compounds such as tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclopentanone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; and acetates such as ethyl acetate and propylene glycol monoethyl ether acetate. All of these non-halogenated solvents are useful as general-purpose solvents, and ketone compounds and aromatic hydrocarbons, particularly methyl ethyl ketone and toluene are useful as more general-purpose solvents. The most useful general purpose solvent is methyl ethyl ketone. The said organic solvent may be used independently and may use 2 or more types together.

  Since the polyarylate resin and the polyarylate resin composition of the present invention are very excellent in solubility in a non-halogenated solvent, the solid content concentration of each resin solution can be increased, specifically, 20 mass. % Or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. In particular, the polyarylate resin is, for example, 5 to 40% by mass, preferably 10 to 40% by mass, more preferably 20 to 40% by mass, and further preferably 30 to 40% by mass in a non-halogenated solvent. Can be made. Methyl ethyl ketone and toluene used as the solvent for the resin solution of the present invention are widely used in the electrical and electronic field, are easily available, and are inexpensive, and are particularly convenient organic solvents. Conventionally, polyarylate resins have been thought to be difficult to dissolve in the solvent because of the high concentration of aromatic rings. However, it has been found that, when the polyarylate resin has a specific resin composition as described above, the polyarylate resin dissolves in the solvent at a high concentration. 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 the preparation 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 can be obtained by forming a film and peeling it from the substrate. The resin solution for forming the coating and film may be a resin solution in which a polyarylate resin is dissolved in an organic solvent, or a resin solution in which a polyarylate resin composition is dissolved in an organic solvent, or a polyarylate resin composition The resin solution which melt | dissolved the thing and high molecular weight resin in the organic solvent may be sufficient.

  Examples of the substrate include a PET film, a polyimide film, a glass plate, and a stainless plate. Application methods include, for example, wire bar coater coating method, film applicator coating method, brush coating method, spray coating method, gravure roll coating method, screen printing method, reverse roll coating method, lip coating method, air knife coating method, curtain Examples thereof include a flow coating method and a dip coating method.

  The resin solution of the present invention can be impregnated or coated on a reinforcing fiber cloth and then dried to obtain a prepreg. The resin solution for producing the prepreg is a resin solution in which the polyarylate resin composition is dissolved in an organic solvent.

  Examples of the reinforcing fiber constituting the reinforcing fiber cloth include glass fiber, carbon fiber, organic fiber, and ceramic fiber. These reinforcing fibers can be used in any form such as woven fabric and non-woven fabric. Moreover, you may use the synthetic paper which mixed paper-made these fibers in the state of the short fiber using fibrid. Among these, glass fiber and carbon fiber are preferable because of excellent processability. The thickness of the reinforcing fiber cloth is preferably 5 to 50 μm, more preferably 10 to 45 μm, and still more preferably 15 to 40 μm.

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

  The method for 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, coating can be performed using a commercially available coating machine. When performing double-sided coating, after single-sided coating, once dried and then coated again on the opposite side, after single-sided coating and then coated on the opposite side without drying, both sides simultaneously The method of coating is mentioned. These coating methods can be appropriately selected in consideration of workability and performance of the obtained prepreg. The prepreg is obtained by evaporating and drying an 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 μm, more preferably 20 to 140 μm, and further preferably 30 to 130 μm. The prepreg is obtained by impregnating or applying a resin solution to the reinforcing fiber cloth, and then drying, but heat resistance is obtained by obtaining the prepreg so that the thickness of the reinforcing fiber cloth used is approximately three times the thickness. A prepreg excellent in mechanical properties, adhesiveness and appearance can be obtained.

  The prepreg of the present invention can be used as it is without being subjected to a heat treatment for curing. In addition, since the polyarylate resin contained in the prepreg melts and exhibits fluidity when heated above its glass transition temperature, it is densified by laminating the prepreg as it is or by laminating and heating and forming a laminate. be able to. Since the laminate is excellent in adhesion between prepregs, the mechanical strength is sufficiently improved and the heat resistance is also excellent. Moreover, the said laminated body can be used as a high intensity | strength plate-shaped molded object. Furthermore, this plate-shaped molded body can be molded into a desired shape. The moldability varies depending on the material of the reinforcing fiber cloth to be used and the amount of the solid content containing the prepreg, but can be formed according to a predetermined mold. Punching or the like may be performed as long as the mechanical characteristics are not significantly impaired. Since the prepreg of the present invention does not use a thermosetting resin, it is particularly excellent in workability such as adhesion, moldability, and punchability. The forming and punching can be performed by cold working, but can be performed under heating as necessary.

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

  Since the polyarylate resin of the present invention has heat resistance and dielectric properties, and is excellent in fluidity and reactivity with epoxy resin, it can be suitably used as an insulating material for printed wiring boards and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The physical properties of the polyarylate resin and the resin composition were measured by the following method.

(1) Resin composition, hydroxyl group concentration, and acetyl group concentration of polyarylate resin Each copolymer is obtained by ¹ H-NMR analysis using a high-resolution nuclear magnetic resonance apparatus (LA-400 NMR manufactured by JEOL Ltd.). The resin composition was determined from the peak areas of the components. Moreover, by analyzing the ¹ H-NMR, the peak area of the proton located at the ortho position or the meta position with respect to the phenolic hydroxyl group was calculated, and the hydroxyl group concentration was determined by quantifying the hydroxyl group. Moreover, the peak area of the proton of the methyl group of the acetyl group was calculated, and the acetyl group concentration was determined by quantifying the acetyl group. (Resolution: 400 MHz, solvent: mixed solvent having a volume ratio of deuterated trifluoroacetic acid to deuterated tetrachloroethane of 1/11, temperature: 50 ° C.).

(2) Glass transition temperature of polyarylate resin Using a differential scanning calorimeter (DSC7 manufactured by PerkinElmer Co., Ltd.), the temperature was raised from 40 ° C. to 340 ° C. at a temperature rising rate of 20 ° C./min. The onset temperature of the discontinuous change derived from the glass transition temperature inside was defined as the glass transition temperature.

(3) Number average molecular weight of polyarylate resin A solution was obtained by dissolving pellets of polyarylate resin to a concentration of 1000 ppm using chloroform as a solvent. The number average molecular weight was calculated in terms of polystyrene by GPC analysis.

(4) Manufacturing time Each Example / Comparative Example was carried out using a reaction vessel having a capacity of 150 L so that the resulting polyarylate resin would be 45 to 55 kg. The time from the start of depressurization in the deacetic acid polymerization reaction to the start of extraction of the polyarylate resin was shown as “production time of polyarylate resin” and evaluated.
“Polyarylate resin production time” indicates the reaction time of the deacetic acid polymerization reaction in Examples 1-21, 24 and Comparative Examples 1-6, and the reaction time of the deacetic acid polymerization reaction in Examples 22 and 23. The total time of time and reaction time of depolymerization reaction (2 hours) is shown.
S (best): less than 4 hours;
A (excellent): 4 hours or more and less than 5 hours;
B (good): 5 hours or more and less than 7 hours;
C (pass): 7 hours or more and less than 8 hours;
D (failure): 8 hours or more.

(5) Soluble Solid Concentration Polyarylate resin and toluene were weighed in a glass screw cap bottle with an internal volume of 50 mL so that the total amount was 30 g and the solution concentrations were 5, 10, 20, and 30% by mass. Then, the glass screw cap bottle was sealed, rotated at 70 rpm for 24 hours at room temperature of 23 ° C., and allowed to stand at room temperature of 23 ° C. for 48 hours. After standing, the resin solution was visually observed, and the solution stability was judged according to the following criteria.
Good: Transparency was maintained and the viscosity was not increased.
Poor: The transparency was not maintained, the viscosity was increased, or there was an undissolved residue.
Among the solution concentrations of 5, 10, 20, and 30% by mass, the solution concentration of the solution having the highest solution concentration and the highest solution concentration was defined as the soluble solid content concentration.
In addition, when the result with favorable solution stability was not obtained in any solution concentration, it described as "0" in the table | surface.
Further, in the same manner as when the solvent was toluene, the soluble solid content concentration was also obtained when the solvent was methyl ethyl ketone.
If the polyarylate resin of the present invention has good solubility in at least one of toluene and methyl ethyl ketone, the solubility in general-purpose solvents is good. The polyarylate resin of the present invention preferably has good solubility in both of these solvents, particularly good solubility in methyl ethyl ketone. The higher the solution concentration, the better the solubility in the solvent.

(6) Reactivity of polyarylate resin (glass transition temperature of reaction product)
An epoxy resin (EOCN-1020-55, manufactured by Nippon Kayaku Co., Ltd., o-cresol novolak type epoxy resin, softening point 55 ° C., epoxy equivalent 195) and polyarylate resin so as to be 100 parts by mass in a ratio of 50/50 Further, 0.2 part by mass of a curing accelerator (2-ethyl-4-methylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts by mass of toluene were mixed and stirred until it became transparent. After stirring at room temperature (25 ° C.), the solvent was removed and dried to obtain a resin composition. When not dissolved in toluene, methylene chloride was used.
The obtained resin composition was heated from 30 ° C. to 300 ° C. at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter (DSC7 manufactured by PerkinElmer Co.), and after the temperature was lowered, the temperature was again reduced from 30 ° C. to 300 ° C. The temperature was raised to ° C., and the onset temperature of the discontinuous change derived from the glass transition temperature in the obtained temperature rise curve was defined as the glass transition temperature (Tga).
S (best): 200 ° C. ≦ Tga;
A (excellent): 190 ° C. ≦ Tga <200 ° C .;
B (good): 180 ° C. ≦ Tga <190 ° C .;
C (pass): 170 ° C. ≦ Tga <180 ° C .;
D (failure): Tga <170 ° C.

(7) Cured product properties of polyarylate resin composition (glass transition temperature, relative permittivity, dielectric loss tangent)
50 parts by mass of polyarylate resin and 50 parts by mass of epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 184 to 194 g / eq, viscosity 120 to 150 (25 ° C.), softening point 20 ° C. or less) Then, 0.2 part by mass of a curing accelerator (2-ethyl-4-methylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts by mass of tetrahydrofuran 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 dryer, drying was performed at 200 ° C. and 170 ° C. for 2 hours, followed by drying at 200 Pa and 200 ° C. for 3 hours to perform solvent removal and curing to obtain a cured product. In addition, when not melt | dissolving in toluene, the resin solution was obtained using the methylene chloride, and hardened | cured material was produced.
The obtained cured plate was cut, and a differential scanning calorimeter (DSC7, manufactured by Perkin Elmer) was measured. The temperature was raised from 30 ° C. to 300 ° C. at a rate of temperature rise of 20 ° C./min. After the temperature was lowered, the temperature was raised again from 30 ° C. to 300 ° C. The starting temperature was the glass transition temperature Tgb.
S (best): 190 ° C. ≦ Tgb;
A (excellent): 180 ° C. ≦ Tgb <190 ° C .;
B (good): 170 ° C. ≦ Tgb <180 ° C .;
C (pass): 160 ° C. ≦ Tgb <170 ° C .;
D (failure): Tgb <160 ° C.

The relative dielectric constant and dielectric loss tangent were measured under the following conditions.
Equipment: E4991A RF impedance / material analyzer manufactured by Agilent Technologies, Inc. Sample dimensions: length 60 mm × width 60 mm × thickness 100 μm
Frequency: 1GHz
Measurement temperature: 23 ° C
Test environment: 23 ° C. ± 1 ° C., 50% RH ± 5% RH

(8) Fluidity of polyarylate resin composition The plate of the cured product of the polyarylate resin composition obtained in (7) was observed, and the fluidity of the polyarylate resin composition was judged according to the following criteria.
○: No bubbles were observed in the cured product.
X: Bubbles were observed in the cured product.

(9) Monomer concentration in polyarylate resin (Preparation of sample solution A)
0.2 g of freeze-pulverized polyarylate resin was immersed in 3 mL of acetonitrile and extracted by standing at room temperature for 3 days. Thereafter, the extract was filtered through a filter having a pore size of 0.45 μm and diluted with acetonitrile to prepare a sample solution for measurement.
(Preparation of sample solution B)
0.2 g of freeze-pulverized polyarylate resin was immersed in 3 mL of methanol and extracted by standing at room temperature for 3 days. Thereafter, the extract was filtered through a filter having a pore size of 0.45 μm to prepare a measurement sample solution.

(Calculation of monomer concentration)
Sample solution A and sample solution B were measured using an HPLC apparatus (HP1100 manufactured by Hewlett Packard). From the measurement results of the sample solution A, the monomer concentrations of the dihydric phenol component and the hydroxycarboxylic acid component were determined. Further, from the measurement result of the sample solution B, the monomer concentration of the aromatic dicarboxylic acid component was determined. From the sum of the monomer concentrations of the dihydric phenol component, hydroxycarboxylic acid component and aromatic dicarboxylic acid component, the monomer concentration in the polyarylate resin was determined. (Column: Waters Atlantis T3 5 μm φ4.6 × 15 mm, temperature: 40 ° C., detector: UV 275 nm, eluent A: 0.1% formic acid aqueous solution, eluent B: acrylonitrile / formic acid = 100/2, flow rate: 0.5 mL / min)
S (best): the monomer concentration in the polyarylate resin is 0.5% by mass or less;
A (excellent): the monomer concentration in the polyarylate resin is more than 0.5% by mass and 1.0% by mass or less;
B (good): the monomer concentration in the polyarylate resin exceeds 1.0 mass% and is 1.5 mass% or less;
C (accepted): the monomer concentration in the polyarylate resin exceeds 1.5% by mass and is 2.0% by mass or less;
D (failure): The monomer concentration in the polyarylate resin is more than 2.0% by mass.

Example 1 (melt polymerization method)
A reaction vessel equipped with a stirrer was charged with 6.7 parts by mass of TPA, 6.7 parts by mass of IPA, 31.0 parts by mass of BisTMC, and 20.4 parts by mass of acetic anhydride (TPA: IPA: BisTMC: acetic anhydride (molar ratio)). = 50: 50: 125: 250), under a nitrogen atmosphere, the mixture was stirred and mixed at normal pressure and 140 ° C. for 2 hours (acetylation reaction).
Subsequently, 5.5 parts by mass of PHBA was added at 140 ° C., and then the temperature was raised to 280 ° C. over 3 hours and held at 280 ° C. for 1 hour. Thereafter, the pressure was reduced to 130 Pa over 90 minutes at 280 ° C., and the mixture was stirred for 2 hours to obtain a polyarylate resin. Then, the polyarylate resin was extracted from the reaction vessel (deacetic acid polymerization reaction).
When the resin composition of the obtained polyarylate resin was analyzed, it was TPA: IPA: BisTMC: PHBA = 50: 50: 125: 50 (molar ratio), which was the same as the charged composition.

Example 2 (melt polymerization method)
A reaction vessel equipped with a stirrer was charged with 6.7 parts by mass of TPA, 6.7 parts by mass of IPA, 31.0 parts by mass of BisTMC, and 20.4 parts by mass of acetic anhydride (TPA: IPA: BisTMC: acetic anhydride (molar ratio)). = 50: 50: 125: 250), under a nitrogen atmosphere, the mixture was stirred and mixed at normal pressure and 140 ° C. for 2 hours (acetylation reaction).
Then, after heating up to 280 degreeC over 3 hours and hold | maintaining at 280 degreeC for 1 hour, 5.5 mass parts of PHBA was thrown in at 280 degreeC. Thereafter, the pressure was reduced to 130 Pa over 90 minutes at 280 ° C., and the mixture was stirred for 2 hours to obtain a polyarylate resin. Then, the polyarylate resin was extracted from the reaction vessel (deacetic acid polymerization reaction).

Examples 3 to 17 and 19 to 21 and Comparative Examples 1 to 6 (melt polymerization method)
Except for changing the resin composition of the raw material charge as described in Table 1, Table 2, Table 3 or Table 4 and changing the “production time of polyarylate resin” as described in these tables, The same operation as in Example 1 was performed to obtain a polyarylate resin.

Comparative Example 7 (interfacial polymerization method)
In a reaction vessel equipped with a stirrer, 51.1 parts by mass of 2,2-bis (4-hydroxyphenyl) propane (BisA) as the bisphenol component and 2.01 parts by mass of p-tert-butylphenol (PTBP) as the end-capping agent ), 36.5 parts by mass of sodium hydroxide as an alkali, and 0.56 parts by mass of a 50% by mass aqueous solution of tri-n-butylbenzylammonium chloride (TBBAC) as a polymerization catalyst were dissolved in 1200 parts by mass of water (water phase). Separately, 23.4 parts by mass of terephthalic acid chloride and 23.4 parts by mass of isophthalic acid chloride were dissolved in 700 parts by mass of methylene chloride (organic phase) (TPC: IPC: PTBP: BisA (molar ratio). ) = 50: 50: 7: 97). The aqueous phase was previously stirred, the organic phase was added to the aqueous phase under strong stirring, and polymerization was performed at 20 ° C. for 2 hours by the interfacial polymerization method. Thereafter, stirring was stopped, and the aqueous phase and the organic phase were decanted and separated. After removing the aqueous phase, 1 part by mass of acetic acid was added to stop the reaction. Thereafter, washing of the organic phase with pure water was repeated until the pH reached around 7, and then the methylene chloride was evaporated while gradually pouring the organic phase into a 50 ° C. hot water tank equipped with a homomixer. To form a polymer. The obtained polymer was dehydrated and dried to obtain a polyarylate resin.

Example 18 (melt polymerization method)
A reaction vessel equipped with a stirrer was charged with 5.5 parts by mass of TPA, 12.8 parts by mass of IPA, 15.7 parts by mass of BisA, 21.3 parts by mass of BisTMC, 8.7 parts by mass of PHBA, and 22.6 parts by mass of acetic anhydride ( TPA: IPA: BisA: BisTMC: PHBA: acetic anhydride (molar ratio) = 30: 70: 62.5: 62.5: 57.7: 307.5), 2 at atmospheric pressure and 140 ° C. under nitrogen atmosphere The mixture was stirred for a period of time and reacted (acetylation reaction).
Subsequently, 8.7 parts by mass of PHBA was added at 140 ° C., and then the temperature was raised to 280 ° C. over 3 hours and held at 280 ° C. for 1 hour. Thereafter, the pressure was reduced to 130 Pa over 90 minutes at 280 ° C., and the mixture was stirred for 2 hours to obtain a polyarylate resin. Then, the polyarylate resin was extracted from the reaction vessel (deacetic acid polymerization reaction).

Example 22 (melt polymerization method)
A reaction vessel equipped with a stirrer was charged with 5.0 parts by mass of TPA, 11.6 parts by mass of IPA, 14.3 parts by mass of BisA, 19.4 parts by mass of BisTMC, and 25.5 parts by mass of acetic anhydride (TPA: IPA: BisA: BisTMC: acetic anhydride (molar ratio) = 30: 70: 62.5: 62.5: 250), under a nitrogen atmosphere, the mixture was stirred and mixed at normal pressure and 140 ° C. for 2 hours (acetylation reaction).
Then, after heating up to 280 degreeC over 3 hours and hold | maintaining at 280 degreeC for 1 hour, it pressure-reduced to 130 Pa over 90 minutes, and stirred for 2 hours (deacetic acid polymerization reaction). Thereafter, the pressure is brought to normal pressure in a nitrogen atmosphere, 6.9 parts by mass of PHBA is added at 280 ° C., the mixture is stirred at 280 ° C. for 2 hours to perform a depolymerization reaction, and a polyarylate resin is obtained. It was extracted from the container (depolymerization reaction).

Example 23 (melt polymerization method)
A reaction vessel equipped with a stirrer was charged with 5.0 parts by mass of TPA, 11.6 parts by mass of IPA, 8.6 parts by mass of BisA, 19.4 parts by mass of BisTMC, 6.9 parts by mass of PHBA, and 25.5 parts by mass of acetic anhydride ( TPA: IPA: BisA: BisTMC: PHBA: acetic anhydride (molar ratio) = 30: 70: 37.5: 62.5: 50: 250), mixed under a nitrogen atmosphere at normal pressure and 140 ° C. for 2 hours. (Acetylation reaction).
Then, it heated up to 280 degreeC over 3 hours, and hold | maintained at 280 degreeC for 1 hour. Thereafter, the pressure was reduced to 130 Pa at 280 ° C. over 90 minutes, followed by stirring for 2 hours to obtain a polyarylate resin (deacetic acid polymerization reaction). Thereafter, normal pressure was set in a nitrogen atmosphere, 5.7 parts by mass of BisA was added at 280 ° C., and stirred at 280 ° C. for 2 hours to perform a depolymerization reaction. After obtaining a polyarylate resin, the polyarylate resin was reacted. It was extracted from the container (depolymerization reaction).

Example 24 (melt polymerization method)
A reaction vessel equipped with a stirrer is charged with 5.5 parts by weight of TPA, 12.8 parts by weight of IPA, 15.7 parts by weight of BisA, 21.3 parts by weight of BisTMC, and 22.5 parts by weight of acetic anhydride (TPA: IPA: BisA: BisTMC: acetic anhydride (molar ratio) = 30: 70: 62.5: 62.5: 200), under nitrogen atmosphere, stirring and mixing at normal pressure and 140 ° C. for 2 hours (acetylation reaction).
Then, it heated up to 280 degreeC over 3 hours, and hold | maintained at 280 degreeC 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, and then the polyarylate resin was extracted from the reaction vessel (deacetic acid polymerization reaction).

Reference Example 100 parts by mass of epoxy resin (EOCN-1020-55, manufactured by Nippon Kayaku Co., Ltd., o-cresol novolak type epoxy resin, softening point 55 ° C., epoxy equivalent 195) and curing accelerator (2-ethyl-4-methylimidazole) (Manufactured by Tokyo Chemical Industry Co., Ltd.) 0.2 parts by mass and 100 parts by mass of toluene were mixed and stirred until transparent. After stirring, the solvent was removed and dried to obtain a resin composition.
The obtained resin composition was heated from 30 ° C. to 300 ° C. at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter (DSC7 manufactured by PerkinElmer Co.), and after the temperature was lowered, the temperature was again reduced from 30 ° C. to 300 ° C. The temperature was raised to 0 ° C., and the presence or absence of a discontinuous change start temperature derived from the glass transition temperature in the obtained temperature rise curve was examined.
The glass transition temperature was not in the range of 30 ° C to 300 ° C.

  Physical properties of the polyarylate resins and compositions obtained in Examples and Comparative Examples were measured. The results are shown in Tables 1 to 4.

  The polyarylate resins obtained in Examples 1 to 24 were able to form a cured product sufficiently excellent in heat resistance and dielectric properties, and were excellent in fluidity and reactivity with epoxy resins.

  Since all the polyarylate resins of Comparative Examples 1 to 7 had a low hydroxyl group concentration, the reactivity with the epoxy resin was low, and the glass transition temperature of the cured product of the polyarylate resin and the epoxy resin was low.

  From comparison between Examples 1-21 and Examples 22-24, it is clear that the solubility in a general-purpose solvent is improved by setting the monomer concentration in the polyarylate resin within a predetermined range.

  From comparison between Examples 1 to 20 and Example 21, it is clear that the production efficiency of the polyarylate resin is improved by setting the acetyl group concentration in the polyarylate resin within a predetermined range.

From the examples, from the viewpoint of further improving the solubility in methyl ethyl ketone, the polyarylate resin preferably has a monomer concentration of 2% by mass or less and further satisfies the following compositional condition. The polyarylate resin preferably satisfies the following composition condition (1), more preferably satisfies the composition condition (2), further preferably satisfies the composition condition (3), and satisfies the composition condition (4). Most preferred:
Composition condition (1): ratio of hydroxycarboxylic acid component to all monomer components = 2 to 30 mol%.
Composition condition (2): ratio of hydroxycarboxylic acid component to all monomer components = 5-30 mol% and content ratio of (BisA + BisAP) / (BisTMC + BisCDE) = 15 / 85-85 / 15 (molar ratio).
Composition condition (3): ratio of hydroxycarboxylic acid component to all monomer components = 5 to 25 mol%, (BisA + BisAP) / (BisTMC + BisCDE) content ratio = 30/70 to 70/30 (molar ratio) and (TPA + NDCA) / Content ratio of IPA = 0/100 to 60/40 (molar ratio).
Composition condition (4): ratio of hydroxycarboxylic acid component to all monomer components = 10-25 mol%, (BisA + BisAP) / (BisTMC + BisCDE) content ratio = 30 / 70-70 / 30 (molar ratio) and (TPA + NDCA) / Content ratio of IPA = 10/90 to 40/60 (molar ratio).

  Examples 1 to 21 are polyarylate resins obtained by the preferred method for producing the polyarylate resin of the present invention, and the monomer concentration in the polyarylate resin was 2% by mass or less.

  In Examples 22 and 23, although a predetermined hydroxyl group concentration was obtained, a desired monomer concentration was not obtained for the following reason. A depolymerization reaction with a hydroxycarboxylic acid component or a dihydric phenol component was performed, but some of the monomer components added during the depolymerization reaction remained unreacted and / or polyarylate by the depolymerization reaction. A part of the monomer component constituting the resin was produced as a monomer. For this reason, the monomer concentration in the polyarylate resin exceeded 2 mass%.

  In Example 24, in order to leave a part of the hydroxyl group of the dihydric phenol component without acetylation, the reaction was carried out by reducing the amount of acetic anhydride added. Although the predetermined hydroxyl group concentration was obtained, the divalent phenol component that was not acetylated remained unreacted, so that the monomer concentration in the polyarylate resin exceeded 2% by mass.

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

Claims (18)

  A polyarylate resin comprising a dihydric phenol component and an aromatic dicarboxylic acid component, and having a hydroxyl group concentration of 100 geq / ton or more.   The polyarylate resin according to claim 1, wherein the acetyl group concentration is 10 geq / ton or more.   The polyarylate resin according to claim 1 or 2, wherein the monomer concentration is 2% by mass or less.   The polyarylate resin according to any one of claims 1 to 3, further comprising a hydroxycarboxylic acid component.   The polyarylate resin according to claim 4, wherein the hydroxycarboxylic acid component is contained in a proportion of 2 to 50 mol% with respect to the total monomer components. The polyarylate resin in any one of Claims 1-5 in which the said dihydric phenol component contains the alicyclic dihydric phenol shown by General formula (1).
[In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms or a halogen atom; R ⁵ and R ⁶ are Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m represents an integer of 4 to 12; X represents a saturated aliphatic hydrocarbon ring together with the carbon atom to which the hydroxyphenyl group is bonded. Represents the carbon atom to be formed]   The polyarylate resin according to claim 6, wherein the alicyclic dihydric phenol is contained at a ratio of 15 mol% or more with respect to the total dihydric phenol component.   The dihydric phenol component is 2,2-bis (4-hydroxyphenyl) propane (BisA) and / or 1,1-bis (4-hydroxyphenyl) -1-phenylethane (BisAP) and 1,1- 8 or 7 comprising bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BisTMC) and / or 1,1-bis (4-hydroxyphenyl) -cyclododecane (BisCDE). The polyarylate resin described.   The content ratio ((BisA + BisAP) / (BisTMC + BisCDE)) of the total content of the BisA and / or the BisAP and the total content of the BisTMC and / or the BisCDE is 15/85 to 85/15 (molar ratio) The polyarylate resin according to claim 8, wherein A method for producing a polyarylate resin according to any one of claims 1 to 9 by performing an acetylation reaction and a deacetic acid polymerization reaction,
A method for producing a polyarylate resin, comprising adding a hydroxycarboxylic acid component after the acetylation reaction and before the deacetic acid polymerization reaction. A preliminary step of adjusting the temperature and pressure for the deacetic acid polymerization reaction after the acetylation reaction and before the deacetic acid polymerization reaction;
The method for producing a polyarylate resin according to claim 10, wherein the hydroxycarboxylic acid component is added in the preliminary stage. The preliminary step is a step of depressurizing after raising the temperature of the reaction system,
The method for producing a polyarylate resin according to claim 11, wherein, in the preliminary stage, the hydroxycarboxylic acid component is added before the temperature rise and / or after the temperature rise and before the pressure reduction.   A polyarylate resin composition comprising the polyarylate resin according to claim 1 and an epoxy resin.   The film containing the polyarylate resin in any one of Claims 1-9.   The film containing the polyarylate resin in any one of Claims 1-9.   A resin solution containing the polyarylate resin according to claim 1 and an organic solvent.   A prepreg, wherein the resin solution according to claim 16 is impregnated or applied to a reinforcing fiber cloth.   A laminate comprising the prepreg according to claim 17 laminated thereon.