JP6899184B2 - Bisphenols having a fluorene skeleton and polyarylate resins derived from the bisphenols - Google Patents

Description

The present invention relates to bisphenols having a fluorene skeleton and a method for producing the same, and a polyarylate resin produced from the bisphenols and a method for producing the same.

Resins (polycarbonate resin, polyester resin, polyester carbonate resin, (meth) acrylic resin, polyurethane resin, etc.) produced from bisphenols having a fluorene skeleton are known to have features such as high heat resistance and high refractive index. There is. In particular, the polyarylate resin is a thermoplastic total aromatic polyester having a structural unit derived from bisphenols and a structural unit derived from aromatic dicarboxylic acids, and is known as a resin exhibiting particularly high heat resistance among these resins. ..

For example, Patent Document 1 is an invention relating to a heat transfer recording sheet using a polyarylate resin. In order to search for a polyarylate resin having better heat resistance, a polyarylate resin is produced from various bisphenols and has heat resistance. The result of measuring the glass transition temperature (Tg), which is one of the indexes of the above, is described (see Patent Document 1 and Table 1). Among these polyarylate resins, it is described that the glass transition temperature of the polyarylate resin having a structural unit derived from bisphenols having a fluorene skeleton is 288 ° C., which is particularly excellent in heat resistance.

Japanese Unexamined Patent Publication No. 2000-79768

Therefore, based on the description of Patent Document 1, the inventors of the present application tried to produce a polyarylate resin having a structural unit derived from bisphenols having a fluorene skeleton described in the reference, and found that the solvent solubility was poor and the polyarylate resin was poor. It was found that the 5% weight loss temperature, which is an index of chemical heat resistance, was about 400 ° C., and the difference from the glass transition temperature was small, making it difficult to produce a molded product using the polyarylate resin.

An object of the present invention is the same as a bisphenol having a fluorene skeleton capable of producing a resin having characteristics such as high heat resistance and a high refractive index, particularly a polyallylate resin having a structural unit derived from a known bisphenol having a fluorene skeleton. A polyallylate resin having a degree of physical heat resistance (glass transition temperature), excellent solvent solubility, and a high 5% weight loss temperature, which is an index of chemical heat resistance, and fluorene that can be provided by the polyallylate resin. The purpose is to provide bisphenols having a skeleton.

As a result of intensive studies to solve the above problems, the present inventors have found that bisphenols represented by the following general formula (1) and polyallylate resins having a structural unit derived from the bisphenols are solvent-soluble. It was found that it is excellent in physical heat resistance and chemical heat resistance. Specifically, the following inventions are included.

[1]
The following general formula (1)

（式中、Ｒ_１及びＲ_２は分岐を有してもよい炭素数１〜１２のアルキル基、炭素数５〜１２のシクロアルキル基又はアリール基を表し、ｎ_１及びｎ_２はそれぞれ同一又は異なって０〜２の整数を表す。ｎ_１及びｎ_２が２である場合、それぞれ対応するＲ_１及びＲ_２は同一であっても異なってもよい。）
で表されるビスフェノール類。

(In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group or an aryl group having 5 to 12 carbon atoms which may have a branch, and n ₁ and n ₂ are the same or n 2 respectively. Differently represent integers 0-2. When n ₁ and n ₂ are 2, the corresponding R ₁ and R ₂ may be the same or different, respectively.)
Bisphenols represented by.

[2]
In the presence of acid, 9-fluorenone and the following general formula (2)

（式中、Ｒ_３は分岐を有してもよい炭素数１〜１２のアルキル基、炭素数５〜１２のシクロアルキル基、又はアリール基を表し、ｎ_３は０〜２の整数を表す。ｎ_３が２である場合、それぞれ対応するＲ_３は同一であっても異なってもよい。）
で表される多価フェノール類、及び、以下一般式（３）

(In the formula, R ₃ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group which may have a branch, and n ₃ represents an integer of 0 to 2. If n ₃ is 2, R ₃ each corresponding may be the same or different.)
Multivalent phenols represented by, and the following general formula (3)

（式中、Ｒ_４は分岐を有してもよい炭素数１〜１２のアルキル基、炭素数５〜１２のシクロアルキル基、又はアリール基を表し、ｎ_４は０〜２の整数を表す。ｎ_４が２である場合、それぞれ対応するＲ_４は同一であっても異なってもよい。）
で表される多価フェノール類とを反応させる、［１］に記載のビスフェノール類の製造方法。

(In the formula, R ₄ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group which may have a branch, and n ₄ represents an integer of 0 to 2. When n ₄ is 2, the corresponding R _4s may be the same or different.)
The method for producing bisphenols according to [1], which reacts with the multivalent phenols represented by.

[3]
A polyarylate resin having a structural unit derived from bisphenols represented by the general formula (1) and a structural unit derived from an aromatic dicarboxylic acid.

[4]
The method for producing a polyarylate resin according to [3], wherein the bisphenol represented by the general formula (1) is polymerized with an aromatic dicarboxylic acid or a derivative thereof.

[5]
A molded product containing the polyarylate resin according to [3].

[6]
The molded product according to [5], wherein the molded product is an optical member.

The bisphenols represented by the above general formula (1) of the present invention are described below in the general formula (4).

（式中、Ｒ_５及びＲ_６はそれぞれ同一又は異なって分岐を有してもよい炭素数１〜１２のアルキル基、炭素数５〜１２のシクロアルキル基、又はアリール基を表し、ｎ_５及びｎ_６はそれぞれ同一又は異なって０〜２の整数を表す。ｎ_５及びｎ_６が２である場合、それぞれ対応するＲ_５及びＲ_６は同一であっても異なってもよい。）
で表されるビスフェノール類よりも高屈折率であるので、各種光学用途に用いられる樹脂（例えばポリカーボネート樹脂、ポリエステル樹脂、ポリエステルカーボネート樹脂、（メタ）アクリル樹脂、ポリウレタン樹脂等）に好適に用いることができる。特に本発明の上記一般式（１）で表されるビスフェノール類は、上記一般式（４）で表されるビスフェノール類よりも融点が低いことから、溶融重合法等、ビスフェノール類を溶融させた後重合することにより製造される樹脂の原料として好適である。

(In the formula, R ₅ and R ₆ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group, which may have the same or different branches, respectively, and represent n ₅ and an aryl group. n ₆ represents the same or different integers of 0 to 2, respectively. When n ₅ and n ₆ are 2, the corresponding R ₅ and R ₆ may be the same or different, respectively.)
Since it has a higher refractive index than the bisphenols represented by, it can be suitably used for resins used for various optical applications (for example, polycarbonate resin, polyester resin, polyester carbonate resin, (meth) acrylic resin, polyurethane resin, etc.). it can. In particular, since the bisphenols represented by the general formula (1) of the present invention have a lower melting point than the bisphenols represented by the general formula (4), after melting the bisphenols by a melt polymerization method or the like. It is suitable as a raw material for a resin produced by polymerization.

Among the various resins described above, the polyallylate resin of the present invention produced from the bisphenols represented by the above general formula (1) is a bisphenol having a fluorene skeleton whose physical heat resistance (glass transition temperature) is known. It is about the same as polyallylate resin having a constituent unit of origin, has excellent solvent solubility, and has a 5% weight loss temperature, which is an index of chemical heat resistance, and a glass transition temperature, which is an index of physical heat resistance. Since there is a large difference from the above, it is possible to manufacture a molded product having excellent heat resistance by various methods such as a solution casting method and a heat melt molding method such as injection molding.

Further, since the polyarylate resin of the present invention has excellent transparency and high refractive index, it is particularly suitable for optical members (for example, prism sheets used in liquid crystal display devices, overcoating agents, hardcoating agents, antireflection films). , Optical film, optical sheet, optical fiber, optical waveguide, hologram, liquid crystal film, organic EL film, various optical lenses, etc.).

<Bisphenols represented by the above general formula (1)>
The bisphenols of the present invention are represented by the above general formula (1). In the general formula (1), the alkyl group of the substituents _{R 1} and _{R 2} carbon atoms from 1 to 12 optionally having a branch in a methyl group, propyl group, isopropyl group, butyl group, tert- butyl group , Hexyl group, octyl group and the like are exemplified. Examples of the cycloalkyl group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group. Examples of the aryl group include aromatic groups that may have a substituent such as a phenyl group and a tolyl group. Among the substituents mentioned above R ₁ and R ₂ also, in view of availability of bisphenols represented by the above general formula (1), is an alkyl group of 1 to 4 carbon atoms which may have a branched preferred.

_{N 1} and n ₂ representing the number of substituents (R ₁ and R ₂ ) are the same or different integers of 0 to 2, respectively, and the availability of bisphenols represented by the above general formula (1) as raw materials. From the viewpoint of, it is preferably an integer of 0 or 1, and more preferably 0. When the number of substituents is 2, the corresponding substituents may be the same or different.

The bisphenols represented by the general formula (1) of the present invention have a lower melting point than the bisphenols represented by the general formula (4). Specifically, in the above general formula (1) _{, the melting point of the bisphenols of the present invention in which n 1} = n ₂ = 0 is 232 ° C., whereas in the above general formula (4), n ₅ = n. The melting point of bisphenols at _{6 = 0 is 270 ° C.} Further, the bisphenols of the present invention have a feature that the refractive index of the bisphenols themselves is 1.62 or more, particularly 1.65 or more. The melting point and refractive index of the bisphenols of the present invention are determined by the methods described in Examples described later.

The bisphenols represented by the above general formula (1) of the present invention can also be used as a raw material (monomer) for various thermoplastic resins or thermosetting resins. Examples of the thermoplastic resin that can be used as a raw material include polycarbonate resin, polyester resin, polyester carbonate resin, (meth) acrylic resin, and polyurethane resin, and examples of the thermosetting resin include epoxy resin, (meth) acrylic resin, and polyurethane. Examples include resins and phenolic resins. Among these resins, the bisphenols represented by the general formula (1) have a characteristic of high refraction, and are therefore suitable as raw materials for the high refraction polyester resin and the polycarbonate resin. Further, since the melting point is lower than that of the bisphenols represented by the general formula (4), it is also suitable as a raw material for a resin produced by melting bisphenols and then polymerizing them by a melt polymerization method or the like. ..

<Method for producing bisphenols represented by the above general formula (1)>
The method for producing bisphenols represented by the above general formula (1) of the present invention will be described in detail.
The bisphenols represented by the above general formula (1) of the present invention are 9-fluorenone (hereinafter, also referred to as fluorenone) and the following general formula (2) in the presence of an acid.

（式中、Ｒ_３は分岐を有してもよい炭素数１〜１２のアルキル基、炭素数５〜１２のシクロアルキル基、又はアリール基を表し、ｎ_３は０〜２の整数を表す。ｎ_３が２である場合、それぞれ対応するＲ_３は同一であっても異なってもよい。）
で表される多価フェノール類、及び、以下一般式（３）

(In the formula, R ₃ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group which may have a branch, and n ₃ represents an integer of 0 to 2. If n ₃ is 2, R ₃ each corresponding may be the same or different.)
Multivalent phenols represented by, and the following general formula (3)

（式中、Ｒ_４は分岐を有してもよい炭素数１〜１２のアルキル基、炭素数５〜１２のシクロアルキル基、又はアリール基を表し、ｎ_４は０〜２の整数を表す。ｎ_４が２である場合、それぞれ対応するＲ_４は同一であっても異なってもよい。）
で表される多価フェノール類とを反応させることにより製造される（以下、ビスフェノール化反応と称することがある）。

(In the formula, R ₄ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group which may have a branch, and n ₄ represents an integer of 0 to 2. When n ₄ is 2, the corresponding R _4s may be the same or different.)
It is produced by reacting with a multivalent phenol represented by (hereinafter, may be referred to as a bisphenolization reaction).

_{The substituent R 3} and the number of substituents n ₃ in the polyhydric phenol represented by the general formula (2) correspond to the _{substituent R 1} and the number of substituents n ₁ of the bisphenol represented by the general formula (1). and, also, the substituents R ₄ and the number of substituents n ₄ in the polyhydric phenols represented by the general formula (3) is, substituents R ₂ and the number of substituents bisphenols represented by the above general formula (1) Corresponds to n _2. Therefore, the specific embodiment and the preferred embodiment of each substituent and the number of substituents are the same as those described in detail in the bisphenols represented by the above general formula (1).

The total amount of the polyhydric phenols represented by the general formula (2) and the polyhydric phenols represented by the general formula (3) is usually 2 to 15 mol with respect to 1 mol of fluorenone, and more. From the viewpoint of obtaining bisphenols represented by the above general formula (1) in good yield, preferably 4 to 12 mol is used. The ratio of the polyhydric phenols represented by the general formula (2) to the polyhydric phenols represented by the general formula (3) is usually expressed in molar ratio and is represented by the general formula (2). Polyphenols: Polyphenols represented by the general formula (3) = 10: 90 to 90:10, from the viewpoint of obtaining bisphenols represented by the general formula (1) in better yield. It is preferably 20:80 to 60:40, and more preferably 20:80 to 50:50.

Various acids such as inorganic acids and organic acids can be used as the acids used in the bisphenolization reaction. Specifically, the inorganic acids include sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, heteropolyacid, zeolite, and clay minerals. Etc. are exemplified, and examples of the organic acid include methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, acidic ion exchange resin and the like. Among these acids, hydrochloric acid or p-toluenesulfonic acid is preferably used from the viewpoint of availability and handleability. Further, p-toluenesulfonic acid is particularly preferable because it improves the reaction selectivity. The amount of the acid used is usually 0.01 to 5.0 mol with respect to 1 mol of fluorenone, and is preferably 0.05 to 5.0 mol with respect to 1 mol of fluorenone from the viewpoint of obtaining a sufficient reaction rate and easiness of post-treatment. Use 1.0 mol. These acids may be used alone or in combination of two or more as required.

When carrying out the bisphenolization reaction, a sulfur-containing compound may coexist from the viewpoint of improving the reaction rate. Examples of sulfur-containing compounds that can be used include mercaptocarboxylic acids, alkyl mercaptans, aralkyl mercaptans, and salts thereof. _{Specifically, for example, C 1-16} alkyl mercaptans such as thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiosuccinic acid, mercaptosuccinic acid, mercaptobenzoic acid, n-butyl mercaptan, dodecyl mercaptan and the like. Can be mentioned. Among these sulfur-containing compounds, dodecyl mercaptan and β-mercaptopropionic acid are preferably used because of their good industrial handling. When these sulfur-containing compounds are used, the amount used is usually 0.01 to 1.0 parts by weight with respect to 1 part by weight of fluorenone, preferably from the viewpoint of obtaining a sufficient reaction rate and easiness of post-treatment. It is 0.01 to 0.50 parts by weight with respect to 1 part by weight. These sulfur-containing compounds may be used alone or in combination of two or more as required.

When carrying out the bisphenolization reaction, the reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent that can be used include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, and halogenated hydrocarbons. Examples of aliphatic hydrocarbons include hexane, heptane, octane, and decane, examples of aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene, and examples of ethers are dialkyls such as diethyl ether. Examples thereof include ethers, cyclic ethers such as tetrahydrofuran and dioxane, and examples of the halogenated hydrocarbons include aliphatic halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aromatics such as chlorobenzene and dichlorobenzene. Halogenized hydrocarbons are exemplified. Among these solvents, aromatic hydrocarbons such as toluene and xylene are preferably used from the viewpoint of availability, handleability, reaction rate, and reaction selectivity. When these solvents are used, the amount used is usually 0.1 to 20 parts by weight with respect to 1 part by weight of fluorenone, preferably 5 to 5 parts by weight with respect to 1 part by weight of fluorenone from the viewpoint of obtaining a sufficient reaction rate and economically. Use 10 parts by weight. These solvents may be used alone or in combination of two or more, if necessary.

In the bisphenolization reaction, fluorenone, polyhydric phenols represented by the general formula (2) and the above general formula (3), an acid, and if necessary, a sulfur-containing compound and a solvent are placed in a reactor, and the internal temperature is usually 50. It is carried out by stirring at ~ 200 ° C., preferably 80 to 140 ° C., more preferably 120 ° C. to 140 ° C. Further, from the viewpoint of obtaining a sufficient reaction rate, the reaction may be carried out while dehydrating under normal pressure or reflux under reduced pressure, if necessary.

After the bisphenolization reaction, the bisphenols represented by the above general formula (1) can be taken out by a conventional method such as neutralization, washing with water, concentration, crystallization, filtration and the like, if necessary. The obtained bisphenols represented by the general formula (1) can also be purified by a conventional method such as recrystallization, distillation, adsorption, or column chromatography. Further, if necessary, the obtained reaction solution may be used as it is for the production of the polyarylate resin described above.

<Polyarylate resin of the present invention>
The polyarylate resin of the present invention is a resin having a structural unit derived from bisphenols represented by the above general formula (1) and a structural unit derived from an aromatic dicarboxylic acid.

The polyarylate resin of the present invention may have a structural unit derived from other bisphenols other than the structural unit derived from bisphenols represented by the above general formula (1). Other bisphenols include, for example, bisphenol A, tetramethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 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) ) Methan, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (3-benzyl-4-hydroxyphenyl) fluorene, Spiro [Fluoren 9,9'-(2', 7'-dihydroxyxanthene) )], 1,1'-bi-2-naphthol and the like. The constituent units derived from these other bisphenols may have one kind, or two or more kinds if necessary.

When having a structural unit derived from other bisphenols, the ratio of the structural unit derived from bisphenol represented by the above general formula (1) is usually 80 mol% or more, preferably 80 mol% or more, based on the structural unit derived from all bisphenols. Is 90 mol% or more, more preferably 99 mol% or more.

Examples of the aromatic dicarboxylic acid constituting the constituent unit derived from the aromatic dicarboxylic acid constituting the polyarylate resin of the present invention include phthalates such as terephthalic acid, isophthalic acid and orthophthalic acid, methyl group, ethyl group and n-propyl. A phthalic acid derivative such as terephthalic acid and isophthalic acid in which one or two alkyl groups selected from the group consisting of a group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like are substituted. , 4,4'-biphenyldicarboxylic acid, biphenyldicarboxylic acid such as 2,2'-biphenyldicarboxylic acid, naphthalenedicarboxylic acid such as 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenylether-2, 2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4, Examples thereof include diphenyl ether dicarboxylic acids such as 4'-dicarboxylic acid. These aromatic dicarboxylic acids may be used alone or in combination of two or more as required. Among these aromatic dicarboxylic acids, phthalic acids (terephthalic acid, isophthalic acid, etc.), naphthalenedicarboxylic acids, and biphenyldicarboxylic acids are preferably used.

Derived from components other than the bisphenol-derived structural unit represented by the above general formula (1), other bisphenol-derived structural units, and aromatic dicarboxylic acid-derived structural units, as long as the effects of the present invention are not impaired. It may contain a structural unit of. Examples of other components that may be contained include aliphatic diols, alicyclic diols, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and the like, and examples of the aliphatic diols include ethylene glycol and propylene glycol. .. Examples of the alicyclic diols include 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol and the like. Examples of the aliphatic dicarboxylic acids include adipic acid and sebacic acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and the like.

The weight average molecular weight (Mw) of the polyarylate resin of the present invention can be selected from the range of about 5,000 to 200,000 from the viewpoint of handleability at the time of manufacture, for example, 6,000 to 150,000, particularly 8,000 to 120,000, and further 1,000 to 100,000. Is. The weight average molecular weight (Mw) is calculated by the method described in Examples described later.

The glass transition temperature (Tg) of the polyarylate resin of the present invention is preferably 250 ° C. or higher, particularly 270 ° C. or higher, from the viewpoint of heat resistance. The glass transition temperature is determined by the method described in Examples described later.

The 5% weight loss temperature of the polyarylate resin of the present invention is preferably 120 ° C. or higher higher than the glass transition temperature, and particularly preferably 140 ° C. or higher. If the 5% weight loss temperature is 120 ° C. or higher with respect to the glass transition temperature, the polyarylate resin can be heated to such an extent that sufficient fluidity is exhibited when molding is performed by heat melt molding such as injection molding. It becomes. The 5% weight loss temperature is measured by the method described in Examples described below.

The refractive index of the polyarylate resin of the present invention is, for example, 1.62 or more, particularly 1.65 or more at a temperature of 20 ° C. and a wavelength of 589 nm. Therefore, the polyarylate resin of the present invention can exhibit a refractive index equal to or higher than that of high-refractive polyester or the like used as an optical member. The refractive index is determined by the method described in Examples described later.

Although the polyarylate resin of the present invention has a rigid skeleton such as a structural unit derived from bisphenols represented by the above general formula (1) and a structural unit derived from an aromatic dicarboxylic acid, it is solvent-soluble. Excellent for. For example, the polyallylate resin of the present invention includes ethers (eg, tetrahydrofuran), cyclic ketones (eg, cyclohexanone), amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide), halogenated hydrocarbons. It can be dissolved in a general-purpose solvent such as Methylene chloride (for example, chloroform) and N-methylpyrrolidone. Therefore, the polyarylate resin of the present invention can be used not only for hot melt molding but also for molding (filming) using a solvent such as a solution casting method.

<Manufacturing method of polyarylate resin>
The polyarylate resin of the present invention can be produced by polymerizing the bisphenol represented by the above general formula (1) with an aromatic dicarboxylic acid or a derivative thereof.

The amount of aromatic dicarboxylic acid used is usually 0.9 to 1 mol with respect to the total amount of bisphenols represented by the above general formula (1), and when other bisphenols are used, with other bisphenols. It is 2.0 mol, preferably 1.0 to 1.2 mol. Further, when producing the polyarylate resin of the present invention, a derivative of an aromatic dicarboxylic acid can be used in addition to the aromatic dicarboxylic acid. As a derivative of the aromatic dicarboxylic acid that can be used, for example, an ester of an aromatic dicarboxylic acid {for example, an alkyl ester [for example, a lower alkyl ester such as a methyl ester or an ethyl ester (for example, a C _1-4 alkyl ester, particularly C _{1- 2} Alkyl esters], etc.}, acid halides (acid chlorides, etc.), acid anhydrides, etc. These aromatic dicarboxylic acid derivatives may be monoesters (half esters) or diesters, monoacid halides or dihalides. Good.

Examples of the polymerization method that can be used in producing the polyarylate resin of the present invention include an interfacial polymerization method, a solution polymerization method, and a melt polymerization method. Among them, the interfacial polymerization method is preferable. According to the interfacial polymerization method, the reaction is faster than that of the solution polymerization method or the melt polymerization method, and a high molecular weight polyarylate resin can be easily obtained. Further, the interfacial polymerization method is a polymerization method in which the molecular weight of the obtained polyarylate resin can be easily controlled, the obtained polyarylate resin has few impurities, and high transparency can be imparted. In the interfacial polymerization method, an alkaline suspension (aqueous phase) in which bisphenols represented by the above general formula (1) are mixed with an alkaline aqueous solution and dicarboxylic acid dihalide, which is a derivative of aromatic dicarboxylic acid, are mixed with water. It is carried out by mixing an organic phase mixed with an organic solvent insoluble in water in the presence of a polymerization catalyst, and specific methods for carrying out the interfacial polymerization method include, for example, W. M. EARECKSON, J. Mol. Poly. Sci. It is described in XL399 (1959), Japanese Patent Publication No. 40-1959, and the like. Hereinafter, the interfacial polymerization method in the present invention will be described in detail.

When the bisphenol represented by the general formula (1) and other bisphenols are used as the aqueous phase, the other bisphenols are mixed with the alkaline aqueous solution, and then the polymerization catalyst and, if necessary, the terminal are used. Add encapsulant. Separately from the aqueous phase, an aromatic dicarboxylic acid dihalide, which is a raw material for introducing a structural unit derived from an aromatic dicarboxylic acid, is dissolved in an organic solvent for preparing an organic phase, which will be described later, to prepare an organic phase. To do. Then, the aqueous phase and the organic phase are mixed and an interfacial polymerization reaction is carried out to produce a high molecular weight polyarylate resin in the organic phase. Then, the organic phase containing the polyarylate resin is washed with pure water, ion-exchanged water, or the like, and then the organic phase is dropped into a poor solvent to precipitate the polyarylate resin, and the precipitated resin is filtered off or the organic solvent is used. A polyarylate resin can be obtained by distilling off.

Examples of the alkali for preparing the alkaline aqueous solution include sodium hydroxide and potassium hydroxide, but sodium hydroxide is preferably used from the viewpoint of economic advantage and easy waste liquid treatment. The amount used is usually 2.0 to 8.0 mol with respect to 1 mol of the total amount of bisphenols represented by the above general formula (1) and, when other bisphenols are used, with other bisphenols. , Preferably 3.0-5.0 mol. One kind of alkali may be used, or two or more kinds may be used in combination if necessary.

Examples of the polymerization catalyst include tertiary amines such as triethylamine, tri-n-butylamine, trihexylamine, tridodecylamine, N, N-dimethylcyclohexylamine, pyridine, quinoline, and dimethylaniline, trimethylbenzylammonium halide, and tributylbenzylammonium. Quaternary ammonium salts such as halides, triethylbenzylammonium halides, tetrabutylammonium halides, trimethylbenzylphosphonium halides, tributylbenzylphosphonium halides, triethylbenzylphosphonium halides, tetrabutylphosphonium halides, triphenylbenzylphosphonium halides, tetraphenylphosphonium halides, etc. Quaternary phosphonium salt and the like. Of these, tributylbenzylammonium halide, tetrabutylammonium halide and tetrabutylphosphonium halide are preferable from the viewpoint of high reaction rate and minimizing hydrolysis of aromatic dicarboxylic acid halide. The amount used is usually 0.0001 to 0.05 mol with respect to 1 mol of the total amount of bisphenols represented by the above general formula (1) and, when other bisphenols are used, with other bisphenols. , Preferably 0.001 to 0.01 mol. One type of polymerization catalyst may be used, or two or more types may be used in combination as required.

The solvent for preparing the organic phase may be any solvent that is incompatible with water and in which the polyarylate resin is soluble. Examples of such a solvent include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-. Examples thereof include chlorine-based solvents such as dichlorobenzene, aromatic hydrocarbon-based solvents such as toluene, benzene, and xylene, and ether-based solvents such as cyclopentylmethyl ether. Among them, non-flammable and easy-to-handle. From the point of view, methylene chloride is preferable. The amount used is usually 3 to 30 parts by weight, preferably 3 to 30 parts by weight, based on 1 part by weight of the total amount of the bisphenols represented by the general formula (1) and other bisphenols when used. Is 10 to 20 parts by weight. One type of solvent may be used, or two or more types may be used in combination if necessary.

Examples of the terminal encapsulant used as needed include monohydric phenol, monohydric acid chloride, monohydric alcohol and monovalent carboxylic acid. As monovalent phenol, for example, phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-methoxyphenol, m-methoxyphenol , P-methoxyphenol, 2,3,6-trimethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol , 2-Phenyl-2- (4-hydroxyphenyl) propane, 2-phenyl-2- (2-hydroxyphenyl) propane, 2-phenyl-2- (3-hydroxyphenyl) propane. Examples of monovalent acid chloride include benzoyl chloride, benzoic acid chloride, methanesulfonyl chloride, and phenylchloroformate. Examples of monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol. Examples of the monovalent carboxylic acid include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid and p-methoxyphenylacetic acid. Among these terminal encapsulants, 2,3,6-trimethylphenol and p-tert-butylphenol are preferable because of their high thermal stability or ability to adjust the molecular weight. The amount used is usually 0.01 to 0.2 mol with respect to 1 mol of the total amount of bisphenols represented by the above general formula (1) and, when other bisphenols are used, with other bisphenols. , Preferably 0.03 to 0.1 mol. The end sealant may be used alone or in combination of two or more if necessary.

The temperature at which the interfacial polymerization is carried out is usually 0 to 50 ° C, preferably 10 to 40 ° C, and more preferably 20 to 30 ° C. A sufficient reaction rate can be obtained by setting the temperature to 0 ° C. or higher, and the polyarylate resin of the present invention having higher purity can be obtained by suppressing the formation of impurities by setting the temperature to 50 ° C. or lower. ..

After completion of the interfacial polymerization, a solution containing a polyarylate resin is usually obtained by separating and removing the aqueous phase. The obtained solution containing the polyarylate resin may be neutralized with an acid such as acetic acid, hydrochloric acid, or oxalic acid so that the pH becomes 4.0 to 8.0, and after neutralization, it is washed with water.・ Liquid separation may be repeated. In addition, the insoluble matter may be separated and removed by appropriately performing a filtration operation.

The solution containing the polyarylate resin obtained by the above operation may be used as it is for the production of a molded product containing the polyarylate resin of the present invention, which will be described later, or the obtained solution containing the polyarylate resin may be used as a poor solvent. The polyarylate resin may be taken out by dropping to precipitate the polyarylate resin and filtering the precipitated resin, or by distilling off an organic solvent from the solution. The polyarylate resin taken out can be made into a molded product containing the polyarylate resin of the present invention by the following method.

<Molded product containing the polyarylate resin of the present invention>
In order to obtain a molded product containing the polyarylate resin of the present invention, it is manufactured by using a casting method, an injection molding, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, or the like. However, it is not particularly limited and may be appropriately used depending on the intended use. An example thereof will be described below.

The casting method is a so-called solution casting method, in which the polyarylate resin of the present invention is dissolved in an organic solvent, and the solution is made of a metal drum or belt, or a film made of another resin different from the polyarylate resin of the present invention. After coating on the base material, the organic solvent is distilled off and the film is peeled off from the base material or the like to obtain a film containing the polyarylate resin of the present invention.

Examples of the organic solvent used in the solution casting method include N-methylpyrrolidone (NMP), N, N-dimethylformamide, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-. Examples thereof include tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-dichlorobenzene, toluene, benzene, xylene, tetrahydrofuran (THF), 1,4-dioxane and 1,3-dioxolane. Among them, from the viewpoint of halogen-free, NMP, toluene, benzene, xylene, THF, 1,4-dioxane and 1,3-dioxolane are preferable, and toluene or THF is more preferable. One kind of organic solvent may be used, or two or more kinds may be used in combination if necessary.

The thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm.

In addition, a molded product containing the polyarylate resin of the present invention can be produced by forming a film (or molding) using an extrusion molding method, a calender molding method, or the like. Further, by applying an injection molding method or the like, it is possible to manufacture molded products having various shapes.

Examples of the shape of the molded product include a two-dimensional structure (film-like, sheet-like, plate-like, etc.) and a three-dimensional structure (tubular, rod-like, tubular, hollow, etc.), and the polyarylate resin of the present invention can be used. The molded product containing the molded product is preferably used as an optical member because it has excellent optical characteristics such as transparency and high refractive index.

Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited thereto.

[1] HPLC analyzer / equipment: LC-2010C manufactured by Shimadzu Corporation,
-Column: L-volume ODS (5 μm, 4.6 mmφ x 250 mm) manufactured by the Chemical Substances Evaluation and Research Institute,
-Mobile phase: Liquid A = 50% methanol water, Liquid B = methanol. The concentration of solution B was changed as follows for analysis.
・ Solution B concentration: 0% (0 minutes) → 100% (30 minutes) → 100% (40 minutes),
・ Flow rate: 1.0 ml / min,
-Column temperature: 40 ° C,
-Detection wavelength: UV 254 nm.
The production rate and content of each component described in the following Examples are the area percentages of HPLC measured under the above conditions.

[2] Melting point (maximum melting heat absorption temperature by differential scanning calorimetry (DSC)) and glass transition temperature 5 mg of the sample is precisely weighed in an aluminum pan, and a differential scanning calorimeter (SII Nanotechnology Co., Ltd .: EXSTAR DSC7020) Was measured under the following operating conditions using aluminum oxide as a control, and the maximum temperature of the detected melting heat absorption was taken as the melting point. For the sample (polyarylate resin) in which the endothermic melting peak was not detected, the intersection of the tangents of the inflection point was defined as the glass transition temperature (Tg).
(Operating conditions)
・ Temperature rise rate: 10 ° C / min (bisphenols), 20 ° C / min (polyarylate resin),
-Measurement range: 30-350 ° C (bisphenols), 150-360 ° C (polyarylate resin),
-Atmosphere: Open, nitrogen 40 ml / min.

[3] NMR measurement
^{1 1} H-NMR and ¹³ C-NMR were recorded by a JEOL-ESC400 spectrometer using tetramethylsilane as an internal standard and DMSO-d6 as a solvent.

[4] LC-MS measurement / equipment: Waters Xevo G2 Q-Tof,
-Column: L-Column2 ODS (2 μm, 2.1 mmφ x 100 mm) manufactured by Chemical Substances Evaluation and Research Institute,
-Column temperature: 40 ° C,
-Detection wavelength: UV 220-500 nm,
-Mobile phase: Liquid A = 10 mM ammonium acetate water, Liquid B = methanol. The concentration of solution B was changed as follows for analysis.
Solution B concentration: 60% (0 min) → 65% (25 min) → 100% (35 min)
-Mobile phase flow rate: 0.3 ml / min,
-Detection method: Q-Tof,
-Ionization method: ESI (+,-) method,
-Ion Source: Voltage (+) 2.0 kV, (-) 1.5 kV, temperature 120 ° C,
-Sampling Connect: Voltage 30V, Gas flow 50L / h,
-Desolution Gas: Temperature 500 ° C., gas flow 1000 L / h.

[5] Refractive index and Abbe number The refractive index and Abbe number of bisphenols and polyarylate resins are values measured by the following methods and conditions.

・ Equipment: Abbe refractometer (“Multi-wavelength Abbe refractometer DR-2M” manufactured by Atago Co., Ltd.),
-Measurement wavelength: 589 nm (refractive index), 486, 589, 656 nm (Abbe number),
-Measurement temperature: 20 ° C.

Refractive index and Abbe number of bisphenols: 2.5% by weight, 5% by weight and 7.5% by weight of bisphenols dissolved in N-methyl-2-pyrrolidone (hereinafter, may be referred to as NMP). Solutions were prepared, and the refractive index of each solution was measured under the above-mentioned equipment and conditions. Next, an approximate curve was derived from the obtained measured values at the three points, and the value when this was extrapolated to 100% by weight was taken as the refractive index of each bisphenol. In addition, the Abbe number was calculated based on the refractive index of each wavelength obtained by the above method.

-Refractive index and Abbe number of polyarylate resin: Polyarylate resin powder is dissolved in NMP to prepare 1% by weight, 3% by weight and 5% by weight solutions, and the refractive index of each solution is determined by the above-mentioned equipment and conditions. It was measured. Next, an approximate curve was derived from the obtained measured values at the three points, and the value when this was extrapolated to 100% by weight was taken as the refractive index of each polyarylate resin. In addition, the Abbe number was calculated based on the refractive index of each wavelength obtained by the above method.

[6] 5% weight loss temperature Using a thermal analyzer (Thermo Plus Evo II TG-DTA8121 / S manufactured by Rigaku Co., Ltd.), the temperature was raised from room temperature to 500 ° C. at 10 ° C./min under a nitrogen stream and measured. did.

[7] Weight average molecular weight (Mw)
Using gel permeation chromatography (GPC), analysis was performed under the following conditions to calculate the polystyrene-equivalent weight average molecular weight (Mw).
-Equipment: EcoSEC HLC-8320GPC manufactured by TOSOH,
-Columns: TSKguardvolume SuperHZ-L, TSKgel SuperHZ4000, TSKgel SuperHZ2500, TSKgel SuperHZ1000,
・ Flow rate: 0.35 mL / min,
-Mobile phase: THF,
-Column temperature: 40 ° C,
-Detector: RI.

[8] Solvent solubility test of polyarylate resin The polyarylate resin and each organic solvent were mixed at room temperature, and the solubility was visually evaluated as follows.
◯: Completely dissolved even when the polyarylate resin concentration was 20% by weight.
Δ: Polyarylate resin was not completely dissolved at a concentration of 20% by weight, but was completely dissolved at a concentration of 10% by weight.
X: Not completely dissolved even when the polyarylate resin concentration was 10% by weight.

[9] Total light transmittance of polyarylate resin The total light transmittance of the polyarylate resin was measured by the following apparatus.
Equipment: Haze meter NDH4000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

(1) Production of bisphenols <Example 1 Of the bisphenols represented by the above general formula (1), a production example of bisphenol represented by the following formula (1-1)>

9-Fluorenone 45.00 g (0.250 mol), hydroquinone 123.74 g (1.124 mol), resorcin 41.25 g (0.375 mol), p in a glass reaction vessel equipped with a stirrer, cooler and thermometer. 4.75 g (0.025 mol) of −toluenesulfonic acid and 450.00 g of p-xylene were charged and the temperature was raised to 120 ° C. After stirring at the same temperature for 3 hours, the reaction solution was analyzed by HPLC, and no peak of 9-fluorenone was detected. The production rate of bisphenol represented by the above formula (1-1) was 51.7%.

Subsequently, ion-exchanged water was added to the obtained reaction solution to cool it to 70 ° C., and a 24 wt% sodium hydroxide aqueous solution was added at the same temperature for neutralization, and then 45.00 g of p-xylene was added. Then, the reaction solution was heated to 86 ° C. and filtered at 86 ° C. to remove the inorganic salt. After filtration, p-xylene and isopropyl acetate were added to the filtrate, stirred and allowed to stand, and then the aqueous phase was separated and removed. Next, the organic phase was washed with ion-exchanged water at 80 ° C., and then the organic phase was concentrated to dryness to obtain 69.87 g of pale orange crystals. When the obtained crystals were analyzed by HPLC, the content of bisphenol represented by the above formula (1-1) was 54.9%.

Next, 15.0 g of the obtained crystals were purified by a silica gel column (developing solvent chloroform: ethyl acetate = 12/1), so that the content of bisphenol represented by the above formula (1-1) was 93.9%. 2.59 g of crystals and 4.93 g of crystals having a bisphenol content of 88.7% represented by the above formula (1-1) were obtained.

Among the crystals obtained in the above examples, crystals having a content (purity) of 93.9% were subjected to ¹ H-NMR, ¹³ C-NMR and LC-MS analysis. The results of each analysis are shown below.

_{^{1 H-NMR (DMSO-d}} 6, 400MHz, TMS) δ (ppm): 5.64 (d, J = 2.8Hz, 2H), 6.00 (d, J = 8.8Hz, 2H), 6 .21 (dd, J = 2.8Hz, 8.4Hz, 2H), 6.55 (d, J = 2.0Hz, 2H), 6.58 (dd, J = 2.8Hz, 8.8Hz, 2H) ), 7.04 (d, J = 8.0, 4H), 7.05 (d, J = 8.8, 2H), 7.23 (dt, J = 1.2Hz, 8.0Hz, 4H) 7.36 (dt, J = 0.8Hz, 7.2Hz, 4H), 7.93 (d, J = 7.6Hz, 4H), 9.20 (bs, 2H).

_{^{13 C-NMR (DMSO-d}} 6, 400MHz, TMS) δ (ppm): 53.6,102.5,111.3,112.3,113.8,115.6,117.4,120.3 , 125.1, 125.3, 127.6, 127.8, 128.1, 128.4, 139.1, 143.8, 151.8, 152.7, 154.7, 157.6.

Mass spectral values ^(MH -): 363.10

<Example 2>
In a glass reaction vessel equipped with a stirrer, cooler and thermometer, 9-fluorenone 45.00 g (0.250 mol), hydroquinone 82.49 g (0.749 mol), resorcin 82.49 g (0.749 mol), p. -4.75 g (0.025 mol) of toluenesulfonic acid and 450.00 g of p-xylene were heated to 120 ° C. After stirring at the same temperature for 1 hour, the reaction solution was analyzed by HPLC, and no peak of 9-fluorenone was detected. The production rate of bisphenol represented by the above formula (1-1) was 49.8%.

Subsequently, ion-exchanged water was added to the obtained reaction solution to cool it to 65 ° C., a 24 wt% sodium hydroxide aqueous solution was added to neutralize it, the mixture was cooled to 40 ° C., and filtered at 40 ° C. to form an inorganic salt. Was removed. After filtration, the filtrate was allowed to stand and the aqueous phase was separated and removed. Next, the organic phase was washed with ion-exchanged water at 60 ° C., and then the organic phase was concentrated to dryness to obtain 23.58 g of pale orange crystals. When the obtained crystals were analyzed by HPLC, the content of bisphenol represented by the above formula (1-1) was 56.3%.

Next, 15.0 g of the obtained crystals were purified by a silica gel column (developing solvent chloroform: ethyl acetate = 6/1), so that the content of bisphenol represented by the above formula (1-1) was 90.3%. 3.5 g of crystals and 2.3 g of crystals having a bisphenol content of 78.7% represented by the above formula (1-1) were obtained.

<Example 3>
In a glass reaction vessel equipped with a stirrer, a cooler and a thermometer, 20.00 g (0.111 mol) of 9-fluorenone, 29.34 g (0.266 mol) of hydroquinone, 87.98 g (0.799 mol) of resorcin, p. -2.11 g (0.011 mol) of toluenesulfonic acid and 200.00 g of toluene were charged and the temperature was raised to 90 ° C. After stirring at the same temperature for 3.5 hours, the reaction solution was analyzed by HPLC, and no peak of 9-fluorenone was detected. The production rate of bisphenol represented by the above formula (1-1) was 33.3%.

Subsequently, ion-exchanged water was added to the obtained reaction solution to cool it to 70 ° C., and a 24 wt% sodium hydroxide aqueous solution was added to neutralize it, then cooled to 57 ° C. and filtered at 57 ° C. to obtain an inorganic salt. Was removed. After filtration, the filtrate was allowed to stand and the aqueous phase was separated and removed. Next, the organic phase was washed 3 times with ion-exchanged water at 60 ° C., and then the organic phase was concentrated to dryness to obtain 12.64 g of pale orange crystals. When the obtained crystals were analyzed by HPLC, the content of bisphenol represented by the above formula (1-1) was 45.7%.

Next, 3.0 g of the obtained crystals were purified by a silica gel column (developing solvent hexane: ethyl acetate = 2/1), so that the content of bisphenol represented by the above formula (1-1) was 95.8%. 0.48 g of crystals and 0.23 g of crystals having a bisphenol content of 94.1% represented by the above formula (1-1) were obtained.

<Example 4>
In a glass reaction vessel equipped with a stirrer, a cooler and a thermometer, 20.00 g (0.111 mol) of 9-fluorenone, 29.33 g (0.266 mol) of hydroquinone, 43.99 g (0.400 mol) of resorcin, p. -Toluenesulfonic acid 2.11 g (0.011 mol) and p-xylene 200.00 g were charged and the temperature was raised to 137 ° C. After stirring at the same temperature for 3 hours, the reaction solution was analyzed by HPLC, and no peak of 9-fluorenone was detected. The production rate of bisphenol represented by the above formula (1-1) was 42.5%.

(2) Physical Properties of Bisphenols The melting point, refractive index and Abbe number of the bisphenols obtained in Example 1 were measured under the above-mentioned conditions. The results are shown in Table 1. In addition, the following formula (4-1), which is a known bisphenol,:

The measurement results of bisphenol represented by are also shown.

(3) Production of Polyarylate Resin <Example 4>
51.53 g of water, 1.26 g (30 mmol) of sodium hydroxide, 2.91 g (8 mmol) of bisphenol represented by the above formula (1-1) in a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer. ), 0.07 g (0.5 mmol) of p-tert-butylphenol as an end-capping agent, and 0.02 g (0.05 mmol) of tributylbenzylammonium chloride as a polymerization catalyst, and vigorously stirring to form an alkaline suspension. Prepared.
0.84 g (4.1 mmol) of terephthalic acid dichloride and 0.84 g (4.1 mmol) of isophthalic acid dichloride were added to another container and dissolved in 39.89 g of methylene chloride. This methylene chloride solution was mixed with the previously prepared alkaline suspension with stirring, and then polymerization was carried out by stirring at 18 to 21 ° C. for 2 hours, and then the stirring was stopped and the reaction solution was allowed to stand still. The aqueous phase and the organic phase are separated from each other, only the aqueous phase is extracted from the reactor, 0.09 g of acetic acid and 61.82 g of water are added to the remaining organic phase, the mixture is stirred for 30 minutes, and the mixture is left to stand and separated again to water. I pulled out the phase. This washing operation was repeated until the aqueous phase after washing with water reached pH 7.
After washing with water, the obtained organic phase is gradually added to about 600 g of methanol to precipitate a resin, and the precipitated powdery resin is filtered and dried to be represented by the above general formula (1). 4.24 g of a polyarylate resin having a structural unit derived from bisphenol and a structural unit derived from an aromatic dicarboxylic acid was obtained.

The weight average molecular weight (Mw), glass transition temperature (Tg), 5% weight loss temperature (Td ₅ ), solvent solubility, refractive index and Abbe number of the obtained polyarylate resin were measured by the above methods. The measurement results are shown in Table 2 below.

Next, the obtained polyarylate resin was dissolved in methylene chloride so as to be 10% by weight, and a coating film having a thickness of about 25 μm was formed on a glass plate using an applicator, and in an environment of about 23 ° C. Pre-dry for 2 hours, then put in a vacuum dryer and gradually raise the temperature to 40 ° C x 30 minutes, 60 ° C x 30 minutes, 80 ° C x 30 minutes to dry, and a transparent polyarylate with a thickness of 90 μm. A resin film was obtained. The total light transmittance of the obtained polyarylate resin film was measured. These results are shown in Table 2. In the following comparative examples, since the polyarylate resin was not dissolved in methylene chloride, it was dissolved in tetrahydrofuran to prepare a polyarylate film resin in the same manner.

<Comparative example 1>
A polyarylate resin and a polyarylate resin film were obtained in the same manner as in Example 4 except that the bisphenols used in Example 4 were changed to 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The weight average molecular weight (Mw), glass transition temperature (Tg), 5% weight loss temperature (Td ₅ ), solvent solubility, refractive index, Abbe number and total light transmittance of the obtained polyarylate resin are described above. Measured by method. The measurement results are shown in Table 2 below.

Abbreviations in Table 2 above-THF: tetrahydrofuran-NMP: N-methylpyrrolidone-DMA: N, N-dimethylacetamide

Claims (5)

The following general formula (1)

(In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group or an aryl group having 5 to 12 carbon atoms which may have a branch, and n ₁ and n ₂ are the same or n 2 respectively. Differently represent integers 0-2. When n ₁ and n ₂ are 2, the corresponding R ₁ and R ₂ may be the same or different, respectively.)
A bisphenol compound represented by. In the presence of acid, 9-fluorenone and the following general formula (2)

(In the formula, R ₃ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group which may have a branch, and n ₃ represents an integer of 0 to 2. If n ₃ is 2, R ₃ each corresponding may be the same or different.)
The multivalent phenol compound represented by, and the following general formula (3)

(In the formula, R ₄ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group which may have a branch, and n ₄ represents an integer of 0 to 2. When n ₄ is 2, the corresponding R _4s may be the same or different.)
The method for producing a bisphenol compound according to claim 1, wherein the bisphenol compound is reacted with the polyvalent phenol compound represented by. The following general formula (1)

(In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group or an aryl group having 5 to 12 carbon atoms which may have a branch, and n ₁ and n ₂ are the same or n 2 respectively. Differently represent integers 0-2. When n ₁ and n ₂ are 2, the corresponding R ₁ and R ₂ may be the same or different, respectively.)
A polyarylate resin obtained by polymerizing a bisphenol compound represented by (1) with an aromatic dicarboxylic acid, an ester of an aromatic dicarboxylic acid, an acid halide of an aromatic dicarboxylic acid, or an acid anhydride of an aromatic dicarboxylic acid. A molded product containing the polyarylate resin according to claim 3. The molded product according to claim 4 , wherein the molded product is an optical member.