JPH08109249A - High-molecular weight polyester resin and production thereof - Google Patents

Abstract

PURPOSE: To improve the abrasion resistance, transparency, heat resistance, optical anisotropy, moldability, productivity and other properties by copolymerizing a dicarboxylic acid or an ester forming deriv. with a dial and a particular dihydroxy compd. CONSTITUTION: A dicarboxylic acid or an ester forming deriv. thereof, 10mol% or more dihydroxy compd. of the formula (wherein R1 is a 2-4C alkyl; and R2 to R5 are H, a 1-4 C alkyl, an aryl, or an aralkyl), and 5mol% or more, based on the whole hydroxy compd., diol are melt-polymerized to produce a high mol.wt. liner polyester polymer having an intrinsic viscosity of not less than 0.6 as measured in chloroform. If necessary, the polyester polymer is reacted with a diisocyanate in an amt. of 0.9 to 1.0 times by mole that of the polyester polymer, as calculated based on number average mol.wt., in the presence of a catalyst and an org. solvent at 130 to 150 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical polyester resin material having excellent transparency, heat resistance, abrasion and mechanical strength.

[0002]

2. Description of the Related Art Plastic is widely used in optical products because of its transparency, lightness, crack resistance, and safety. Polymethyl methacrylate (PM) is a typical optical material.
MA) and polycarbonate (PC) are well known. These optical resins are used by taking advantage of their respective characteristics. For example, PMMA is used for optical fibers, lenses, etc. because it has extremely small birefringence and high transparency. Further, since PC has high heat resistance and relatively low hygroscopicity, it is used as a substrate material for compact discs.

On the other hand, there are some problems in applying plastics to optical applications. For example, the resin PM described above
MA has a problem of high hygroscopicity and a low refractive index, while PC has a problem of large birefringence and poor moldability. By the way, as means for solving these problems, Japanese Patent Laid-Open No. 6-1
84288 proposes an amorphous polyester obtained by copolymerizing an aromatic dicarboxylic acid or its ester-forming derivative with a special dihydroxy compound typified by 9,9-bis (4-hydroxyphenyl) fluorene. Since the polyester resin has a low birefringence, a high refractive index and a high heat resistance, it can be used in a wide range of optical applications. However, when used in fields requiring special mechanical properties and abrasion resistance, such as electrophotographic photosensitive drums, liquid crystal display films, and outer layer lenses of projection TV, contact with other objects and The friction may cause the resin surface to be worn away, resulting in a problem in durability. On the other hand, it is known that in order to improve abrasion resistance, the molecular weight of polyester should be increased.

The molecular weight of polyester is usually determined by the degree of vacuum in the reaction vessel and the reaction temperature in the melt polymerization, although it depends on the kind and purity of the raw materials. Usually, it is difficult to reduce the vacuum of the reaction tank to 0.1 or less in practice, and the reaction temperature is practically 300 ° C as the upper limit. Therefore, the molecular weight of the polyester has an upper limit, and the amorphous polyester obtained by copolymerizing a dicarboxylic acid or its ester-forming derivative with a special dihydroxy compound represented by 9,9-bis (4-hydroxyphenyl) fluorene is Although it depends on the composition, in the usual method, the weight average molecular weight in terms of polystyrene is 50,000 (0.4 dl / g in intrinsic viscosity in chloroform), and even the highest is about 100,000 in weight average molecular weight in terms of polystyrene. Is the limit in the melt polymerization method (0.6 dl / g in intrinsic viscosity in chloroform).

As a method for increasing the molecular weight of polyester after polymerization, for example, as described in "Polyester Resin Handbook" edited by Kazuo Yuki, heat treatment is performed in vacuum at a temperature below the melting point of the resin and above the glass transition point. Solid state polymerization methods are known. This method is extremely effective for crystalline polyester and is used for producing tire cords and high strength monofilaments. When the solid-phase polymerization method is used, an increase in the molecular weight of 1.2 to 2 times is achieved in the intrinsic viscosity depending on the type of polyester. However, although this solid-state polymerization method is effective for crystalline polyester, it cannot be applied to amorphous polyester. This is because with amorphous polyester, the resin becomes a highly viscous fluid above the glass transition point, foams in the reaction tank, and is difficult to handle such as taking it out from the reaction system.

As described above, a method for increasing the molecular weight of polymerization applicable to amorphous polyester has not been found yet. Therefore, a high molecular weight material is obtained by copolymerizing a dicarboxylic acid or its ester-forming derivative, which is a type of amorphous polyester, with a special dihydroxy compound represented by 9,9-bis (4-hydroxyphenyl) fluorene as a representative example. Hard to get. However, as described above, since the polyester shows extremely excellent optical characteristics, it is necessary to develop a resin having a high molecular weight and abrasion resistance.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors in view of the drawbacks of the prior art, dicarboxylic acid or its ester-forming derivative and 9,9-bis (4-hydroxyphenyl) fluorene are obtained. In a polyester copolymerized with a special dihydroxy compound represented by, the present invention has been completed, and the purpose is to have excellent transparency and practically sufficient heat resistance, The object of the present invention is to provide a polyester resin having a small physical anisotropy, excellent moldability and dimensional stability, a high refractive index, excellent abrasion resistance, and excellent productivity.

[0008]

Means for Solving the Problems The present inventors have completed the present invention as a result of repeated studies for solving the above-mentioned drawbacks. That is, the above-mentioned problems are caused by the dicarboxylic acid or its ester-forming derivative and 10 mol% or more of the general formula (1).

Embedded image (R ₁ is an alkylene group having 2 to 4 carbon atoms, R ₂ , R ₃ ,
R ₄ and R ₅ are hydrogen or an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, which may be the same or different, and
A substantially linear polyester polymer composed of an aliphatic glycol having 2 to 4 carbon atoms, which is achieved by a high molecular weight polyester resin having an intrinsic viscosity of 0.6 or more in chloroform. To be done.

The present invention will be described in detail below. The general formula (1) of the polyester

[Chemical 4] It is a key part of the present invention to use a dihydroxy compound represented by as a copolymerization component. It has been found that by using this, the heat resistance is improved and the optical anisotropy is reduced without impairing the moldability of the polyethylene terephthalate resin. In particular, the latter is considered to be due to the relative special molecular structure of the fluorene moiety and the two phenol groups. When this component is less than 10 mol% with respect to the total dihydroxy component, the molded body is easily deformed by heat, the heat resistance is insufficient, the optical anisotropy is large, and the refractive index is less than 1.60. However, the stability of the molded product is also reduced.

The polyester polymer of the present invention has an intrinsic viscosity of 0.6 or more measured in chloroform at 20 ° C., preferably 0.6 to 2.0, more preferably 0.8 to 1.5. Is. If the intrinsic viscosity is less than 0.6, the mechanical properties of the molded product, especially abrasion resistance, will be insufficient. However, if the intrinsic viscosity is 0.6 or more, a molded product having sufficient mechanical properties can be obtained. Molding becomes more difficult as the intrinsic viscosity increases, and it is not preferable for practical use if it is 2.0 or more. The polyester polymer having such an intended intrinsic viscosity can be easily obtained by adjusting melt polymerization conditions such as a molecular weight modifier, polymerization time and polymerization temperature and conditions of a chain extension reaction in the subsequent step.

Examples of the dicarboxylic acid used as an ester-forming derivative such as a dicarboxylic acid or its alkyl ester to be used in the polyester polymer of the present invention include terephthalic acid, isophthalic acid, 2,6 naphthalenedicarboxylic acid,
1,8 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,2 naphthalenedicarboxylic acid, 1,
3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,2′- Aromatic dicarboxylic acids such as biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 9,9-bis (4-carboxyphenylene) fluorene, maleic acid, adipic acid, sebacic acid, Aliphatic dicarboxylic acids such as decamethylene dicarboxylic acid or their ester-forming derivatives are mentioned. These may be used alone or in combination of two or more as needed.

In the present invention, examples of the fluorene type dihydroxy compound represented by the general formula (1) include:
9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9
-Bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2
-Hydroxyethoxy) -3-ethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)
-3,5-Diethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-propylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5 -Dipropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)
-3-Isopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] fluorene, 9,9-bis [4-
(2-Hydroxyethoxy) -3-n-butylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-di-n-butylphenyl] fluorene, 9,9-bis [ 4- (2-hydroxyethoxy)
-3-isobutylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisobutylphenyl] fluorene, 9,9-bis [4- (2-
Hydroxyethoxy) -3- (1-methylpropyl) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-bis (1-methylpropyl)
Phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)-
3,5-Diphenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-benzylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5- Examples thereof include dibenzylphenyl] fluorene, 9,9-bis [4- (3-hydroxypropoxy) phenyl] fluorene 9,9-bis [4- (4-hydroxybutoxy) phenyl] fluorene and the like, which may be used alone or in combination with 2 You may use it in combination of 2 or more types. Among these, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is preferable in terms of optical properties and moldability.

The 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is obtained, for example, by adding ethylene oxide (hereinafter, EO) to 9,9-bis (4-hydroxyphenyl) fluorene. . At this time, in addition to the 2EO adduct (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene) in which ethylene oxide was added to each hydroxyl group of phenol one molecule at a time, several molecules were further added in excess. Impurities such as 3EO adducts and 4EO adducts may be contained. When the amount of impurities such as 3EO and 4EO increases, the heat resistance of the polyester polymer is lowered. At this time, the purity of the 2EO adduct is 8
It may be 5% or more, but is preferably 95% or more.

In the present invention, as the diol, ethylene glycol, 1,3-propanediol, 1,2-
Propanediol, 1,4-butanediol, 1,2-
Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-
Aliphatic glycols such as pentanediol, 1,
1-bis [4- (2-hydroxyethoxy) phenyl]
Dihydroxy compound having aromatic ring in main chain and side chain such as -1-phenylethane, compound having aromatic ring and sulfur in main chain such as bis [4- (2-hydroxyethoxy) phenyl] sulfone, or other dihydroxy compound Compounds can be used. More specifically, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3-methylphenyl] cyclohexane, 1,1-
Bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] cyclohexane, 1,1-bis [4-
(2-Hydroxyethoxy) -3-ethylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxy) Ethoxy)-
3-propylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] cyclohexane, 1,1-bis [4- (2
-Hydroxyethoxy) -3-isopropylphenyl]
Cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3-n-butylphenyl] cyclohexane, 1,
1-bis [4- (2-hydroxyethoxy) -3,5-
Di-n-butylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] cyclohexane, 1,1-bis [4- (2-
Hydroxyethoxy) -3,5-diisobutylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3- (1-methylpropyl) phenyl] cyclohexane, 1,1-bis [4- (2 -Hydroxyethoxy) -3,5-bis (1-methylpropyl)
Phenyl] cyclohexane, 1,1-bis [4- (2-
Hydroxyethoxy) -3-phenylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diphenylphenyl] cyclohexane,
1,1-bis [4- (2-hydroxyethoxy) -3-
Benzylphenyl] cyclohexane, 1,1-bis [4
-(2-Hydroxyethoxy) -3,5-dibenzylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -4-methylcyclohexane, 1,1-bis [4- (2 -Hydroxyethoxy)
Phenyl] -2,4,6-trimethylcyclohexane,
1,1-bis [4- (2-hydroxypropoxy) phenyl] cyclohexane, 1,1-bis [4- (2-hydroxybutoxy) phenyl] cyclohexane and the like can be mentioned. Further bis- [4- (2-hydroxyethoxy)
Phenyl] -sulfone, bis- [4- (2-hydroxyethoxy) -3-methylphenyl] -sulfone, bis- [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] -sulfone, bis- [ 4- (2-hydroxyethoxy) -3-ethylphenyl] -sulfone, bis- [4- (2-hydroxyethoxy) -3,5
-Diethylphenyl] -sulfone, bis- [4- (2
-Hydroxyethoxy) -3-propylphenyl] -sulfone, bis- [4- (2-hydroxyethoxy)-
3,5-Dipropylphenyl] -sulfone, bis-
[4- (2-hydroxyethoxy) -3-isopropylphenyl] -sulfone, bis- [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] -sulfone, bis- [4- (2-hydroxyethoxy) ) −
3-n-butylphenyl] -sulfone, bis- [4-
(2-Hydroxyethoxy) -3,5-di-n-butylphenyl] -sulfone, bis- [4- (2-hydroxyethoxy) -3-isobutylphenyl] -sulfone, bis- [4- (2-hydroxy) Ethoxy) -3,5
-Diisobutylphenyl] -sulfone, bis- [4-
(2-Hydroxyethoxy) -3- (1-methylpropyl) phenyl] -sulfone, bis- [4- (2-hydroxyethoxy) -3,5-di (1-methylpropyl)
Phenyl] -sulfone, bis- [4- (2-hydroxyethoxy) -3-phenylphenyl] -sulfone,
Bis- [4- (2-hydroxyethoxy) -3,5-diphenylphenyl] -sulfone, bis- [4- (2-
Hydroxyethoxy) -3-benzylphenyl] -sulfone, bis- [4- (2-hydroxyethoxy)-
3,5-Dibenzylphenyl] -sulfone, bis-
[4- (2-Hydroxypropoxy) phenyl] -sulfone, bis- [4- (2-hydroxybutoxy) phenyl] -sulfone and the like can be mentioned, and further tricyclodecane dimethylol, tricyclodecanediethylol, tricyclo. Decanedipropyrrole, tricyclodecane dibutyrol, dimethyltricyclodecane dimethylol, diethyl tricyclodecane dimethylol, diphenyltricyclodecane dimethylol, dibenzyltricyclodecane dimethylol, tetramethyltricyclodecane dimethylol, hexamethyltri Cyclodecane dimethylol,
Octamethyltricyclodecane dimethylol, 1,1-
Bis [4- (2-hydroxyethoxy) phenyl] -1
-Phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3-methylphenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy)
-3,5-dimethylphenyl] -1-phenylethane,
1,1-bis [4- (2-hydroxyethoxy) -3-
Ethylphenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] -1-phenylethane, 1,1-bis [4-
(2-Hydroxyethoxy) -3-propylphenyl]
-1-Phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] -1
-Phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3-isopropylphenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diisopropyl Phenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3-n-butylphenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy) −
3,5-n-butylphenyl] -1-phenylethane,
1,1-bis [4- (2-hydroxyethoxy) -3-
Isobutylphenyl] -1-phenylethane, 1,1-
Bis [4- (2-hydroxyethoxy) -3,5-isobutylphenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3- (1-methylpropyl) phenyl]- 1-phenylethane, 1,1-
Bis [4- (2-hydroxyethoxy) -3,5-di (1-methylpropyl) phenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy)-
3-Phenylphenyl] -1-phenylethane, 1,1
-Bis [4- (2-hydroxyethoxy) -3,5-diphenylphenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxyethoxy) -3-benzylphenyl] -1-phenylethane , 1,1-bis [4-
(2-Hydroxyethoxy) -3,5-dibenzylpheniper] -1-phenylethane, 1,1-bis [4-
(2-hydroxyethoxy) phenyl] -1- (4-methylphenyl) ethane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -1- (2,4,6-trimethylphenyl) ethane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -1-phenylpropane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -1-phenyl-n-butane, 1,1 -Bis [4- (2-hydroxyethoxy) phenyl] -1-phenyl-2-methylpropane, 1,1-bis [4- (2
-Hydroxyethoxy) phenyl] -1-phenyl-2
-Methylbutane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -1-phenyl-2-ethylbutane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -diphenylmethane, 1,1 -Bis [4- (2
-Hydroxyethoxy) phenyl] -1,2-diphenylethane, 1,1-bis [4- (2-hydroxypropoxy) phenyl] -1-phenylethane, 1,1-bis [4- (2-hydroxybutoxy) Examples thereof include phenyl] -1-phenylethane, and these diols may be used alone or in combination of two or more kinds.

However, a low boiling point diol such as ethylene glycol is required to be at least 5 mol%, preferably 10 mol% or more based on the total hydroxy compound group. When the low boiling point diol such as ethylene glycol is 5 mol% or less with respect to the total hydroxy compound group, problems such as that the melt polymerization does not proceed or the heavy time becomes extremely long occur.

The polyester polymer can be produced by selecting an appropriate method from known methods such as a transesterification method, a melt polymerization method such as a direct polymerization method, a solution polymerization method and an interfacial polymerization method. The reaction conditions of the polymerization catalyst and the like at that time may be the same as those conventionally used, and known methods can be used, but in general, the melt polymerization method is preferably used.

To produce the polyester polymer of the present invention by the transesterification method of the melt polymerization method, the fluorene dihydroxy component represented by the general formula (1) is 10 to 95 mol% of the glycol component in the resin. It is preferable. If this content is more than 95 mol%, problems such as that the melt polymerization reaction does not proceed or the polymerization time becomes extremely long may occur. When it is more than 95 mol%, it can be produced by a solution polymerization method or an interfacial polymerization method.

The amorphous polyester obtained by copolymerizing this dicarboxylic acid or its ester-forming derivative with a special dihydroxy compound represented by 9,9-bis (4-hydroxyphenyl) fluorene is a polystyrene-equivalent weight average. The molecular weight of 100,000 (the intrinsic viscosity in chloroform is 0.6 dl / g) is a limit in the commonly known polymerization method.

In order to obtain the high molecular weight polyester polymer of the present invention, it is obtained by polymerizing by the above-mentioned usual method and then reacting the above-mentioned polyester with diisocyanate. By this post-treatment, the chain extension of the polyester becomes possible, and the intrinsic viscosity in chloroform is increased to 0.6 or more, and the increase in molecular weight is achieved. The reason is not clear, but mechanical properties such as abrasion properties jump at this limiting viscosity. Improve.

The diisocyanate used in the present invention contains 2
All compounds in which two isocyanate groups are present in the same molecule are included. More specifically, for example, hexamethylene diisocyanate, 2,4-tolylene diisocyanate
2,6-tolylene diisocyanate, methylene-
4,4'-bisphenyl diisocyanate, xylylene diisocyanate, 3-isocyanatomethyl-3,
Examples include 5,5-trimethylcyclohexyl isocyanate, and these may be used alone or in combination of two or more kinds. Among these, methylene-4,
4'-Bisphenyl diisocyanate is preferred.

The amount of diisocyanate reacted with the polyester polymer is usually in the range of 0.9 to 1.3 times, preferably 0.9 to 1 based on the number of moles of the polyester calculated based on the number average molecular weight. A range of 0.1 is suitable.
The end of the polyester molecule is alcoholic OH,
The diisocyanate reacts with the alcohol to form a urethane bond, whereby the chain extension of the polyester is achieved. A urethane bond is introduced into the polyester in the subsequent step, but the amount of the urethane bond is 5% or less of the total mole fraction, usually 1% or less. Therefore, the refractive index of the resin as a whole, birefringence, glass Physical properties such as transition point and transparency are the same as those of the untreated polyester resin.

A suitable catalyst may be used if necessary in the above chain extension reaction. As the catalyst, metal catalysts such as tin octylate, dibutyltin dilaurate and lead naphthenate, diazobiscyclo [2.2.2] octane and tri-N-butylamine are preferable. Although the amount of the catalyst added depends on the chain extension reaction temperature, it is usually 0.01 mol or less, preferably 0.001 mol per 1 mol of diisocyanate.
It is added in an amount of not more than mol.

The reaction proceeds by adding an appropriate amount of the catalyst and diisocyanate to the above-mentioned polyester in a liquid state and stirring the mixture while flowing dry nitrogen. If necessary, the reaction may be carried out in an appropriate organic solvent which is a good solvent for the polyester and diisocyanate. At this time, the concentration of the polyester must maintain the thickness required for the intermolecular reaction. This concentration varies depending on the molecular weight of the polyester, but is usually 20% by weight or more, preferably 40% or more. If the concentration is lower than the proper concentration, the intramolecular reaction occurs preferentially, so-called cyclic polymer is formed, which is not preferable.
The organic solvent used is preferably a stable compound having a boiling point as high as possible, and usually trichlorobenzene, dimethyl sulfoxide, N, N-dimethylformamide, xylene and the like are used.

The reaction temperature of the chain extension reaction varies depending on the conditions, but when it is carried out in an organic solvent, it should be set to a temperature below the boiling point of the solvent, or to a temperature above the glass transition point of the polyester when no organic solvent is used. is there. Since the molecular weight that can be reached and the degree of coloration due to side reactions are determined by the reaction temperature, consider the target molecular weight and the molecular weight of the polyester before the reaction, and select an appropriate reaction system and an appropriate reaction temperature suitable for it. There is a need. For example, when trichlorobenzene is used as the organic solvent, 130 ° C
The reaction can be carried out in the temperature range from 1 to 150 ° C, and there is almost no coloring due to side reaction. However, since the reaction temperature is relatively low, it takes several hours to complete the reaction, and the obtained molecular weight is also low.

The chain extension reaction of the above-mentioned polyester significantly increases the molecular weight and achieves an increase in intrinsic viscosity.
Although the final attainable molecular weight varies depending on the molecular weight before the reaction, the molecular weight can be easily controlled by the polymerization conditions. Usually, the molecular weight of the chain-extended polyester is adjusted to a desired value by changing the reaction temperature, the reaction time, and the amount of diisocyanate. This cannot be specified because it varies depending on the case, but the higher the temperature and the longer the reaction time, the higher the molecular weight. Further, the amount of diisocyanate is equal to the number of moles of the polyester determined from the number average molecular weight, or 1.1 equivalent, and the amount of diisocyanate is maximal.

Usually, the molecular weight of an amorphous polyester obtained by copolymerizing a dicarboxylic acid or its ester-forming derivative with a special dihydroxy compound represented by 9,9-bis (4-hydroxyphenyl) fluorene is about 50,000 ( The intrinsic viscosity is 0.4 dl / g) and the maximum is about 100,000 (the intrinsic viscosity is 0.6 dl / g). For example, when the chain extension reaction is carried out using about 50,000 polyesters that can be most easily produced, the intrinsic viscosity is 0.6 or more,
High molecular weight polyesters of 0.7 to 1.5 are usually obtained.

The chain-extended polyester generally has a wide molecular weight distribution. The molecular weight distribution of the amorphous polyester copolymerized with a special dihydroxy compound represented by fluorene, which is produced by melt polymerization, varies depending on the reaction conditions, but is usually about 2 (ratio of weight average molecular weight and number average molecular weight). is there. It usually becomes 4 or more after the chain extension reaction. For applications where a molecular weight distribution is not desirable, the distribution can be controlled using commonly known molecular weight fractionation methods.

As the molecular weight fractionation method, a reprecipitation method with a poor solvent and a method of passing through a column packed with a gel and sieving according to the size of the molecule are known. For example, molecular weight can be fractionated by dropping a poor solvent such as alcohol or acetone into a solution of 10% or less, preferably 5% or less of a polar organic solvent such as chloroform or DMSO of the polyester of the present invention. In this case, the high molecular weight polymer precipitates first. Although not particularly limited, the polymer solution of the present invention is placed in a container having a temperature control function, a poor solvent is added dropwise, and after cloudy precipitation, the temperature of the container is raised to redissolve the precipitate and again. It is possible to improve the accuracy of molecular weight fractionation by a method of obtaining a cloudy precipitate by returning the temperature to and. The method of molecular weight fractionation is not limited to this, and for example, Analysis of polymers, T. et al.
R. Crompton, Pergamon Pre
The method described in ss can also be used.

The amorphous polyester plastic material obtained by copolymerizing the dicarboxylic acid or its ester-forming derivative of the present invention and a special dihydroxy compound represented by 9,9-bis (4-hydroxyphenyl) fluorene is a high molecular weight compound. The glass transition temperature is 90 ° C. or more and the heat resistance is excellent. Further, since it has excellent melt viscosity characteristics, it has excellent moldability, and residual stress strain and molecular orientation during molding are excellent. In addition to being unlikely to occur, it has a characteristic that the optical anisotropy is extremely small even if they remain. Therefore, it is a resin that is extremely useful and well suited as an optical material.

[0030]

EXAMPLES The present invention will be specifically described with reference to the following examples. Properties such as the intrinsic viscosity, glass transition temperature, and abrasion resistance of the copolymers in the examples were measured by the methods described below.

1. Intrinsic Viscosity 0.15-0.5 g of the copolymer was dissolved in chloroform, and then the viscosity was measured at 20 ° C. for determination.

2. Glass transition temperature About 10 mg of a sample was used for a differential scanning calorimeter (Rigaku Denki DSC-8230), and heating was performed at a temperature rising rate of 10 ° C./min for measurement. The glass transition temperature Tg was determined as defined in JIS K 7121-1987.

3. Molecular weight Toyo Soda column G3000H, 7.5 x 60 cm
The elution volume of the sample was measured at 35 ° C. using chloroform as the solvent. The number average molecular weight and the weight average molecular weight were determined from a calibration curve prepared using standard polystyrene.

4. NMR A proton NMR spectrum of the polyester copolymer was measured using an FT-NMR apparatus manufactured by Varian (300 mHZ). A mixed solvent of trifluoroacetic acid and chloroform (1: 1) was used as a solvent, and a chemical shift was determined based on tetramethylsilane.

5. Measurement of abrasion resistance Polyester resin and carbazol, which is a model compound of a functional dye, are mixed in a volume ratio of 1: 1 and dissolved in chlorofocum, and a disk having a diameter of 30 mm and a wall thickness of 2 to 4 mm is prepared from this solution. The amount of wear is measured by sliding on PPC paper at a speed of 10 cm / sec by applying a weight of gram.

Example 1 and Comparative Example 1 terephthalic acid dimethyl ester 55 mol, 10.6
8 kg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 38.5 mol, 16.8
8 kg, ethylene glycol 116 mol, 7.2 k
g as raw material and as catalyst, calcium acetate 0.09
Using 1 mol and 15.99 g, these were put into a reaction tank and gradually heated from 190 ° C. to 230 ° C. according to a conventional method with stirring to perform a transesterification reaction. After extracting a predetermined amount of methanol out of the system, 0.066 mol of germanium oxide as a polymerization catalyst, 6.9 g, and phosphoric acid trimethyl ester 0.1 mo to prevent coloring.
1 and 14 g are gradually added, the temperature is gradually raised and the pressure is reduced, and the heating tank temperature is 280 ° C. and the degree of vacuum is 1 Torr or less while removing the generated ethylene glycol. This condition was maintained, the increase in viscosity was waited, the reaction was terminated after reaching a predetermined stirring torque (after about 2 hours), and the reaction product was extruded into water to obtain pellets. (Comparative Example 1)

The intrinsic viscosity of this copolymer was 0.38. The weight average molecular weight determined by GPC is 55,000.
And the number average molecular weight was 25,000. The glass transition temperature was 145 ° C. The measurement result of NMR is shown in FIG.

30 g of the above-mentioned polyester copolymer was dissolved in trichlorobenzene to prepare a 40 wt% solution. Methylenebis (4-phenylisocyanate) 0.337 g and 0.175 mg diazobiscyclo [2.2.2] octane 1.1 times the number of moles of the polyester copolymer calculated from the number average molecular weight. Was added to the above solution, and the mixture was heated and stirred at 150 ° C. for 10 hours under a nitrogen stream. The resulting reaction product was reprecipitated in methanol and washed with a large amount of methanol and distilled water to obtain a chain-extended polyester resin of the present invention. (Example 1)

The intrinsic viscosity of the above chain-extended polyester resin is 0.76 dl / g, the weight average molecular weight determined by GPC is 120,000, and the number average molecular weight is 3800.
It was 0. The glass transition temperature was 145 ° C.
The measurement result of NMR is shown in FIG. Glass transition point, NMR
In both cases, there was no change from that before the chain extension reaction.

Abrasivity was measured on the polyester before and after the chain extension reaction. A comparison was made of the time required to abrade 10 micrometers by rubbing with paper. However, since the abrasion time greatly changed depending on the type of paper, the sample before the chain extension reaction (intrinsic viscosity 0.38) was set to 100 and the relative comparison value is shown. Table 1 shows the results.

[Table 1]

Examples 2 to 4 and Comparative Example 2 The high molecular weight polyester after the chain extension reaction obtained in Example 1 was dissolved in chloroform to prepare a solution having a weight concentration of 5%. 1 liter of this polymer solution was placed in a water tank controlled at 25 ° C., and methanol was added dropwise while stirring. The solution became cloudy at the time when the total amount dropped was about 370 cc.
Next, when the temperature of the water tank was raised to 50 ° C., the cloudiness disappeared. When the temperature of the water tank was returned to 25 ° C. again, it became cloudy. Stop stirring 25
Upon standing overnight at ° C, a cloudy precipitate accumulated at the bottom of the container. After taking this out and dissolving it in chloroform, methanol
It was reprecipitated in water and washed with a large amount of methanol and distilled water to obtain a fractionation section F-1 (Example 2) of this example.

The above-mentioned supernatant liquid was placed again in a flask in a water tank whose temperature was controlled at 25 ° C., and methanol was added dropwise with stirring. When 20 cc was dropped, it became cloudy again. The same method as described above is repeated to perform the classification classification F-2 (Example 3).
I got Further, by repeating the same method, the classification F-
3 (Example 4) was obtained. A large amount of methanol was added to the residual liquid after removing the category F-3 to precipitate the polymer, and the category F-4
(Comparative example 2) was obtained. The glass transition point of these four categories is 1
It was at 45 ° C and the NMR spectrum was the same as in Example 1. Table 2 shows a comparison of abrasion resistance together with the value of intrinsic viscosity.

[Table 2]

Example 5 and Comparative Example 3 terephthalic acid dimethyl ester 55 mol, 10.6
8 kg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 22 mol, 9.65 k
g, ethylene glycol 116 mol, 7.2 kg,
1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane 22 mol, 7.83 kg as a raw material, as a catalyst, calcium acetate 0.091 mol,
Using 15.99 g, these were put into a reaction tank and gradually heated from 190 ° C. to 230 ° C. while stirring to carry out a transesterification reaction. After extracting a predetermined amount of methanol out of the system, germanium oxide 0.066 mol, 6.9 g, which is a polymerization catalyst, and phosphoric acid trimethyl ester 0.1 mol, 14 g, in order to prevent coloring.
And gradually increase the temperature and reduce the pressure, and while removing the generated ethylene glycol, the heating tank temperature is 280 ° C.,
The degree of vacuum reaches 1 Torr or less. This condition was maintained, the increase in viscosity was waited, the reaction was terminated after reaching a predetermined stirring torque (after about 2 hours), and the reaction product was extruded into water to obtain pellets. Comparative Example 3 The intrinsic viscosity value of this copolymer was 0.50. GP
The weight average molecular weight determined from C was 80,000 and the number average molecular weight was 38,000.

30 g of the above polyester copolymer was dissolved in trichlorobenzene to prepare a 40 wt% solution. 0.222 g of methylenebis (4-phenylisocyanate) and 1.150 mg of diazobiscyclo [2.2.2] octane, 1.1 times the number of moles of the polyester copolymer calculated from the number average molecular weight. Was added to the above solution, and the mixture was heated and stirred at 160 ° C. for 10 hours under a nitrogen stream. The resulting reaction product was reprecipitated in methanol and washed with a large amount of methanol and distilled water to obtain a chain-extended polyester resin of the present invention. (Example 5) The intrinsic viscosity of the obtained chain-extended polyester resin was 1.2, the weight average molecular weight was 200,000, and the number average molecular weight was 530.
It was 00. The abrasion resistance of this resin is shown in Table 3 together with other examples.

[Table 3]

Examples 6 to 10 A chain-extended polyester resin was obtained in the same manner as in Example 2 except that the raw material composition and the diol component and dicarboxylic acid were changed, and the abrasion resistance was evaluated. The results are shown in Table 4.

[Table 4]

Examples 12 to 16 and Comparative Examples 6 to 10 Samples of Examples 12 to 16 and Comparative Examples 6 to 10 were prepared by changing the conditions of the chain extension reaction in Example 1 as shown in the table. Table 5 shows the results of evaluation of abrasion resistance. Further, FIG. 3 shows a summary of the relationship between the intrinsic viscosity and the amount of wear of all the examples and comparative examples.

[Table 5] Although the reason is not clear, a polyester having an intrinsic viscosity of 0.6 or more, which has been difficult to produce by the conventional method, is produced by the present invention, and thereby the abrasion property is dramatically improved.

[0047]

As described above, the dicarboxylic acid or its ester-forming derivative of the present invention and 9,9-bis (4
Amorphous polyester plastic materials obtained by copolymerizing a special dihydroxy compound represented by (hydroxyphenyl) fluorene as a typical example have a high molecular weight and are excellent in transparency and are suitable as an optical material. Further, it is resistant to abrasion, has good transparency and heat resistance, has small optical anisotropy, and has excellent moldability, dimensional stability and chemical resistance, and is industrially useful.

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[Procedure amendment]

[Submission date] February 21, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is an NMR diagram of terephthalic acid dimethyl ester / 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene / ethylene glycol copolymer.

FIG. 2 is an NMR diagram of a terephthalic acid dimethyl ester / 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene / ethylene glycol / methylenebis (4-phenylisocyanate) copolymer.

FIG. 3 is a graph showing the relationship between the intrinsic viscosity and the amount of wear of the polymers obtained in Examples 1 to 16 and Comparative Examples 1 to 10.

Front page continued (72) Inventor Kazuro Sakurai 117-7 Nishishinmachi, Himeji-shi (72) Inventor Yukio Horikawa 1-27-112 Shigaki, Matsubara-shi

Claims (2)

[Claims] 1. A dicarboxylic acid or an ester-forming derivative thereof and 10 mol% or more of the general formula (1): (R ₁ is an alkylene group having 2 to 4 carbon atoms, R ₂ , R ₃ ,
R ₄ and R ₅ are hydrogen or an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, which may be the same or different, and
A high molecular weight polyester resin, which is a substantially linear polyester polymer composed of diol and has an intrinsic viscosity of 0.6 or more in chloroform. 2. A dicarboxylic acid or an ester-forming derivative thereof and 10 mol% or more of the general formula (1): (R ₁ is an alkylene group having 2 to 4 carbon atoms, R ₂ , R ₃ ,
R ₄ and R ₅ are hydrogen or an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, which may be the same or different, and
A high molecular weight polyester obtained by polymerizing a substantially linear polyester composed of diol and then reacting the polyester with diisocyanate, which has an intrinsic viscosity in chloroform of 0.6 or more. Resin and method for producing the resin.