JP2002080734A - Method for producing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymer including a step to remarkably improve the aging deterioration of the color of an organic solvent solution of a polymer having a constitution unit derived from a 9,9- bishydroxyphenylfluorene compound. SOLUTION: A polymer is produced from an aromatic dihydroxy compound containing 1-100 mol% 9,9-bishydroxyphenylfluorene compound component in the total aromatic dihydroxy compound component. The production process contains a step to mix 100 pts.wt. of the polymer with 0.0001-5 pts.wt. of a heavy metal inactivation agent and/or an active hydrogen-containing compound based on the synthesized organic solvent solution of the polymer or with 0.1-10 pts.wt. of an alcohol based on 100 pts.wt. of the organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer having a constitutional unit derived from a 9,9-bishydroxyphenylfluorene compound, and to a method for preventing coloring of a solution of the polymer in an organic solvent. More specifically, the present invention relates to a method for preventing coloring of an organic solvent solution over time during storage of the organic solvent solution of a polymer.

[0002]

2. Description of the Related Art Hitherto, polymers having structural units derived from 9,9-bishydroxyphenylfluorene-based compounds have been synthesized in various ways for the purpose of improving heat resistance, and are useful for various applications such as retardation films. Known (JP-A-6-25398, JP-A-6-49186)
JP, JP-A-6184288, JP-A-7-26
No. 132, JP-A-7-48424, JP-A-7-48424
1499881, JP-A-7-228669).

[0003] However, a polymer having a structural unit derived from a 9,9-bishydroxyphenylfluorene-based compound may cause color deterioration over time during storage in an organic solvent solution. The color of the color-deteriorated solution is transferred to the polymer, and only the colored polymer or molded article is obtained at the time of polymer recovery from the solution or casting from the solution, and this improvement is required.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to
Structural units derived from 9-bishydroxyphenylfluorene-based compounds, especially 9,9-bis (4-oxy-3)
An object of the present invention is to provide a method for producing a polymer, which comprises a step of remarkably improving the time-dependent deterioration of the hue of a polymer organic solvent solution having a (methylphenyl) fluorene structural unit.

The present inventors have conducted intensive studies in an attempt to achieve this object. As a result, by adding a specific amount of a heavy metal deactivator, an active hydrogen-containing compound or an alcohol to an organic solvent solution of the polymer, the polymer was obtained. The present inventors have found that the temporal deterioration of the hue of the organic solvent solution is remarkably improved, and arrived at the present invention.

[0006]

That is, according to the present invention, in the wholly aromatic dihydroxy compound component, the following formula [1]
In producing a polymer from an aromatic dihydroxy compound in which the compound component represented by is 1 to 100 mol%,
A solution of the polymer 10 in an organic solvent solution of the synthesized polymer
A method for producing a polymer, comprising a step of mixing 0.0001 to 5 parts by weight of a heavy metal deactivator and / or an active hydrogen-containing compound with respect to 0 parts by weight.

[0007]

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[In the formula, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. According to the present invention, among the wholly aromatic dihydroxy compound components, the compound represented by the formula [1] is 1 to 100.
In producing a polymer from an aromatic dihydroxy compound which is mol%, the method includes a step of mixing 0.1 to 10 parts by weight of an alcohol with 100 parts by weight of the organic solvent in a solution of the synthesized polymer in an organic solvent. A method for producing a polymer is provided.

In the present invention, the aromatic dihydroxy component represented by the formula [1] is a 9,9-bishydroxyphenylfluorene compound, for example, 9,9-bishydroxyphenylfluorene compound.
-Bis (4-hydroxyphenyl) fluorene, 9,9
-Bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-
4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, etc., among others, of the present invention 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is most preferable because the effect is remarkable.

These fluorene compounds are present in an amount of 1 to 100 mol%, preferably 1 to 100 mol%, of the total aromatic dihydroxy component.
99 mol%, more preferably 10 to 98 mol%, still more preferably 30 to 95 mol%, particularly preferably 40 to 9 mol%.
0 mol% is used.

In the present invention, the polymer having a structural unit of a 9,9-bishydroxyphenylfluorene compound represented by the above formula [1] is preferably a polycarbonate resin, a polyarylate resin or an epoxy resin.
Particularly, a polycarbonate resin is preferable.

As a preferred embodiment of such a polycarbonate resin, 1 to 99 mol% of the total aromatic dihydroxy component is used.
Is a compound component represented by the formula [1], 99 to 1 mol%
Is the following formula [2]

[0013]

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[Wherein, R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms or a halogen atom, and W is a single bond, a carbon atom A hydrocarbon group which may contain an aromatic group of the formulas 1 to 20, O,
S, SO, SO ₂ , CO or COO groups. ] It is a polycarbonate copolymer which consists of an aromatic dihydroxy component represented by these.

The 9,9-bishydroxyphenylfluorene compound represented by the formula [1] used in the present invention is usually obtained by a reaction between o-cresol and fluorenone.

The other aromatic dihydroxy component represented by the above formula [2] used in the aromatic polycarbonate copolymer may be any one which is usually used as an aromatic dihydroxy component of an aromatic polycarbonate. For example, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4- (Hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) ) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, α, α'-bis (4- (Hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, etc., among which bisphenol A, bisphenol Z, bisphenol C, bisphenol E, bisphenol M
Are preferred, and bisphenol A is particularly preferred.

The aromatic polycarbonate resin is produced by a reaction means known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting the above-mentioned aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. Next, basic means of these manufacturing methods will be briefly described.

The reaction by the interfacial polycondensation method is usually a reaction between an aromatic dihydroxy component and phosgene, and is carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. At that time, the reaction temperature is usually 0 to 40 ° C, and the reaction time is several minutes to 5 hours.

The reaction by the melting method is usually a transesterification reaction between an aromatic dihydroxy component and a carbonic acid diester, and is produced by stirring a predetermined ratio of the aromatic dihydroxy component with the carbonic acid diester while heating under an inert gas atmosphere. It is performed by a method of distilling alcohol or phenols. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, and is usually 120 to 30.
It is in the range of 0 ° C. The reaction is completed under reduced pressure from the beginning while distilling off alcohol or phenols produced. Further, a catalyst usually used in a transesterification reaction to promote the reaction can be used.
Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.

As the aromatic polycarbonate resin, monofunctional phenols which are usually used as a terminal stopper in the polymerization reaction can be used. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the obtained aromatic polycarbonate copolymer has a monofunctional phenol at the terminal. Since it is blocked by a group based on phenols, it has better heat stability than that which is not.

The monofunctional phenol may be any one used as a terminal terminator for an aromatic polycarbonate resin, and is generally phenol or a lower alkyl-substituted phenol and represented by the following formula [3]. Monofunctional phenols can be shown.

[0022]

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Wherein A is a hydrogen atom, a linear or branched alkyl or arylalkyl group having 1 to 9 carbon atoms, and r is an integer of 1 to 5, preferably 1 to 3. ]

Specific examples of the monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

The aromatic polycarbonate resin preferably has an intrinsic viscosity at 20 ° C. of a solution of the polymer in methylene chloride at 0.35 to 1.0, preferably 0.50 to 1.0.
0.80 is more preferred, and 0.55-0.80 is even more preferred. When the intrinsic viscosity is in such a range, the strength of a molded product, especially a film, is sufficient, and the melt viscosity and the solution viscosity are also appropriate, and the handling is easy and preferable.

In the present invention, a polyarylate resin is also preferably used.

The polyarylate resin is a polymer obtained by a reaction between an aromatic dihydroxy component and an aromatic dicarboxylic acid. In the present invention, the polyarylate resin is represented by the above-mentioned formula [1] in the wholly aromatic dihydroxy compound component. 9,9
The bishydroxyphenylfluorene compound component is 1
-100 mol%, preferably 1-99 mol%, more preferably 10-98 mol%, even more preferably 30-95 mol%.
Mol%, particularly preferably 40 to 90 mol%. 9,
As the aromatic dihydroxy compound other than the 9-bishydroxyphenylfluorene-based compound component, those similar to those described in the description of the polycarbonate resin are used.

As a method for producing a polyarylate resin,
For example, an interfacial polymerization method in which an alkali aqueous solution of an aromatic dihydroxy component and a solution of an aromatic dicarboxylic acid chloride such as terephthalic acid chloride or isophthalic acid chloride are mixed and reacted at the interface, or an aromatic dihydroxy component and an aromatic dicarboxylic acid chloride. In an organic solvent in the presence of an amine (such as triethylamine). As the solvent, halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene and the like are used.

In the polymerization reaction of the polyarylate resin, the same monofunctional phenols as those described in the description of the polycarbonate resin can be used as a terminal stopper. Since monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the obtained aromatic polycarbonate copolymer has a terminal blocked by a group based on the monofunctional phenol,
It has better thermal stability than those not.

The polyarylate resin is prepared by mixing 35% by weight in a phenol / tetrachloroethane mixed solvent (weight ratio 60/40).
The intrinsic viscosity measured at 0 ° C. is preferably 0.3 to 1.2 from the viewpoint of heat resistance and moldability, and is preferably 0.4 to 0.9.
Is particularly preferred.

In the present invention, an epoxy resin is also preferably used. The epoxy resin is a polymer obtained by a reaction between an aromatic dihydroxy component and epichlorohydrin. In the present invention, among such wholly aromatic dihydroxy compound components, the 9,9- Bishydroxyphenylfluorene compound component is 1 to 10
It is 0 mol%, preferably 1 to 99 mol%, more preferably 10 to 98 mol%, further preferably 30 to 95 mol%, particularly preferably 40 to 90 mol%. 9,9-
As the aromatic dihydroxy compound other than the bishydroxyphenylfluorene-based compound component, the same compounds as those described in the description of the polycarbonate resin are used.

As a method for producing an epoxy resin, for example, an epoxy resin is synthesized by adding epichlorohydrin to an aqueous alkali solution of an aromatic dihydroxy component (using an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide) and heating. I do. At that time, the reaction temperature is usually 80 to 120 ° C, and the reaction time is several minutes to 5 hours.

The polymer containing a structural unit derived from the 9,9-bishydroxyphenylfluorene compound to be used in the present invention includes polycarbonate resin,
A polyarylate resin or an epoxy resin may be mentioned, and these resins may be put into a solution state in the course of the manufacturing process, or may be put into a product state through a solution state such as a casting film or a paint application.

In particular, in a polycarbonate resin,
A polymer containing a structural unit derived from the 9,9-bishydroxyphenylfluorene-based compound is preferably used for a liquid crystal display film such as a heat-resistant placell substrate or a retardation film. Deterioration of the hue has a problem that the color tone of the color display becomes unclear, and a method for preventing the deterioration is desired.

The organic solvent solution of the polymer containing the constitutional unit derived from the 9,9-bishydroxyphenylfluorene compound of the present invention is left in a solution state, and particularly, when it is left in a dark place, the coloring deteriorates with time.

In the present invention, a solution of a polymer synthesized from an aromatic dihydroxy compound in which the 9,9-bishydroxyphenylfluorene-based compound component accounts for 1 to 100 mol% of the total aromatic dihydroxy compound component, in an organic solvent solution, By mixing 0.0001 to 5 parts by weight of a heavy metal deactivator and / or an active hydrogen-containing compound with respect to 100 parts by weight of the polymer, coloring of the polymer organic solvent solution is prevented.

Further, in the present invention, an organic solvent solution of a polymer synthesized from an aromatic dihydroxy compound in which the 9,9-bishydroxyphenylfluorene-based compound component is 1 to 100 mol% of the total aromatic dihydroxy compound component By mixing 0.1 to 10 parts by weight of alcohol with respect to 100 parts by weight of the organic solvent, coloring of the polymer organic solvent solution is prevented.

The heavy metal deactivator is a compound capable of forming a chelate having an unpaired electron in its structure.
For example, N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine {Irganox MD1024 (manufactured by Ciba Specialty Chemicals Co., Ltd.)}, oxalic bis (benzylidene) Hydrazide) @EastmanInhibit
or OABH (Eastman Kodak Co., Ltd.)｝,
1,2,3-benzotriazole, other Adecataps CDA-1 (made by Asahi Denka Co., Ltd.), Adecatapuas CDA
-6 (made by Asahi Denka Co., Ltd.), Quox (made by Mitsui Toatsu Fine Co., Ltd.), Naugard XL-1 (made by Uniroyal Co., Ltd.), and the like. In particular, N, N'-bis [3- has high solubility in organic solvents such as methylene chloride.
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyl] hydrazine @ IrganoxMD102
4 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is preferably used.

Examples of the active hydrogen-containing compound include a hindered phenol-based antioxidant, and specifically, triethylene glycol-bis [3- (3-ter
t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di- tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-ter
t-butyl-4-hydroxy-benzylphosphonate-
Diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
3,9-bis {1,1-dimethyl-2- [β- (3-t
tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {-2,4,8,10
-Tetraoxaspiro (5,5) undecane and the like. Particularly, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate having high solubility in an organic solvent such as methylene chloride is preferable.

Such a heavy metal deactivator and / or active hydrogen-containing compound is used in an amount of 0.0
001 to 5 parts by weight, preferably 0.001 to 1 part by weight,
More preferably, 0.01 to 0.5 part by weight is blended.
If the amount is less than 0.0001 part by weight, the effect of preventing the coloration of the polymer solution is not obtained. If the amount exceeds 5 parts by weight, the improvement in the effect of preventing the coloration of the polymer solution is low, which is disadvantageous in terms of cost, which is not preferable.

As the alcohols, lower alcohols having 1 to 3 carbon atoms are preferable, and specific examples include methanol, ethanol, propanol and isopropanol. Of these, methanol and ethanol are preferably used.

The alcohol is used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the organic solvent.
5 parts by weight, more preferably 0.5 to 2 parts by weight. If the amount is less than 0.1 part by weight, the effect of preventing the coloration of the polymer solution is not obtained. If the amount exceeds 10 parts by weight, the improvement in the effect of preventing the coloration of the polymer solution is low, and the polymer may be precipitated, which is not preferable.

Further, a higher fatty acid ester of a monohydric or polyhydric alcohol can be added to the polymer of the present invention, if necessary.

The higher fatty acid ester is preferably a partial ester or a whole ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Further, as a partial ester or a whole ester of such a monohydric or polyhydric alcohol and a saturated fatty acid, stearic acid monoglyceride, stearic acid monosorbitate, behenic acid monoglyceride,
Pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, and the like. However, stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used.

The amount of the ester of the alcohol and the higher fatty acid is 0.0 to 100 parts by weight of the polymer.
1 to 2 parts by weight is preferable, 0.015 to 0.5 part by weight is more preferable, and 0.02 to 0.2 part by weight is further preferable. When the compounding amount is within this range, the releasing property is excellent, and the releasing agent is preferable because it does not migrate and adhere to the metal surface.

In the present invention, if necessary, at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof may be added to the polymer. it can. The compounding amount of the phosphorus compound is preferably 0.0001 to 0.05 parts by weight based on 100 parts by weight of the polymer.
The amount is more preferably from 0.05 to 0.02 parts by weight, and
0.01 part by weight is particularly preferred. By incorporating this phosphorus compound, the thermal stability of such a polymer is improved,
A decrease in molecular weight and a deterioration in hue during molding are prevented.

The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof.

As such phosphorus compounds, for example, triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl)
Phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, mono Octyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2
4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite,

Tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate,
Examples thereof include diisopropyl phosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, dimethyl benzenephosphonate, diethylbenzenebenzene and dipropylbenzenebenzene.

Among these phosphorus compounds, trisnonylphenyl phosphite, tris (2,4-di-ter
t-butylphenyl) phosphite, tetrakis (2,
4-Di-tert-butylphenyl) -4,4-diphenylenephosphonite is preferably used.

The polymer of the present invention further comprises a light stabilizer,
Additives such as a coloring agent, an antistatic agent, a lubricant, and a filler may be added in a small proportion as long as the object of the present invention is not impaired.

From a solution of the polymer of the present invention in an organic solvent, particularly a solution of a polycarbonate resin in an organic solvent, an optical film such as a liquid crystal display film is prepared.

As a method for producing a film from a solution of a polymer in an organic solvent, generally, a casting method in which the solution is extruded from a die, a doctor knife method, and the like are preferably used. As the solvent, for example, organic solvents such as methylene chloride, dioxolan, toluene, dioxane, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable. These may be one kind or a mixture of two or more kinds. The liquid crystal display film is a thick film, and a high concentration solution having a solution concentration of 10% by weight or more, preferably 20% by weight or more is preferably used.

The thickness of the polymer film may be selected according to the application, but is preferably in the range of 50 to 500 μm.
The range of 80 to 300 μm is more preferably used. Within this range, a sufficient retardation based on the refractive index anisotropy is obtained in the retardation film, and a sufficiently stiff (rigid) film is obtained in the liquid crystal substrate film (placell substrate). Film formation is easy and preferable. Further, the retardation film is preferable because the desired retardation can be obtained with high precision by stretching.

The film obtained from the polymer solution of the present invention has excellent film strength, good heat resistance and good hue, and can be provided with a gas barrier film and a solvent resistant film on both sides of the film, a transparent conductive film and a polarizing film. It is suitably used as a liquid crystal display film such as a liquid crystal substrate film or a retardation film together with the plate, and more specifically, it can be advantageously used for pagers, mobile phones, handy terminals, various display devices and the like. Further, the polymer solution of the present invention can be suitably used for production of a retardation film, a film for a liquid crystal substrate, and the like because the deterioration of the solution hue with time is suppressed.

[0056]

The present invention will be further described below with reference to examples. Parts in Examples are parts by weight, and% is% by weight. The evaluation was based on the following method. (1) Absorbance of polymer solution: Measured using a Hitachi U-2001 spectrophotometer in a quartz cell having an optical path length of 10 mm. (2) Intrinsic viscosity: Dissolve the polymer in methylene chloride and add 20
Measured at a temperature of ° C. (3) Glass transition temperature (Tg): Measured by using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. (4) b value of film: A 0.2 mm thick film obtained by casting the polymer solution on a glass plate was measured using a Hitachi U-3000 spectrophotometer.

Reference Example 1 In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 24623 parts of ion-exchanged water and 4153 parts of a 48% aqueous sodium hydroxide solution were charged, and 9,9-bis (4
-Hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "biscresolfluorene")
After dissolving 4439.4 parts, 1147.8 parts of 2,2-bis (4-hydroxyphenyl) propane (hereinafter may be abbreviated as “bisphenol A”) and 8 parts of hydrosulfite, 18188 parts of methylene chloride are added. After the addition, 1994 parts of phosgene were blown in at 15 to 25 ° C. with stirring over 60 minutes. After the injection of phosgene, p-te
38.4 parts of rt-butylphenol was added to methylene chloride 33.
0 part of the solution and 692.1 parts of a 48% aqueous sodium hydroxide solution were added thereto, and emulsified.
8 parts were added and the mixture was stirred at 28 to 33 ° C. for 1 hour to complete the reaction.

After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was added. The phases were separated. The methylene chloride phase is concentrated and dehydrated to a polycarbonate concentration of 20%.
Was obtained. The solvent was removed from this solution and dried to obtain a polycarbonate copolymer. The obtained polycarbonate copolymer had a molar ratio of structural units of biscresol fluorene to bisphenol A of 70:30 (polymer yield: 97%). This polymer had an intrinsic viscosity of 0.714 and a Tg of 230 ° C. The b value of the film obtained from this polymer was 0.55.

[Examples 1 to 4, Comparative Example 1] (Blending of heavy metal deactivator) 10 g of the polycarbonate copolymer obtained in Reference Example 1 was dissolved in 50 ml of methylene chloride, and the heavy metal was deactivated in this solution. As an agent, N, N'-bis [3- (3,5-di-t
tert-butyl-4-hydroxyphenyl) propionyl] hydrazine {Irganox MD1024 (Ciba.
Specialty Chemicals Co., Ltd.) was added to the polycarbonate copolymer for 250, 500, 1000, 20
00 ppm was added. The absorbance of these solutions at 434 nm was measured using a quartz cell having a 10 mm optical path length by Hitachi U.S.A.
It was measured using a -2001 spectrophotometer at the time of dissolution, one day after storage in a dark place, and two days after. Also, IrganoxMD10
The solution to which 24 was not added was also measured as a comparative example. The results are shown in Table 1. I as a metal deactivator
By adding rganoxMD1024, the color change of the methylene chloride solution of the polycarbonate copolymer was significantly suppressed. A film was prepared from the solution two days after storage in a dark place, and its hue was evaluated.
B value of the film of Comparative Example 1 was 0.60.
The value was 1.55.

Next, 1000 ppm of Irganox MD1024 was added to the polycarbonate copolymer.
The polycarbonate copolymer solution stored in the dark for 2 days is
Cast at 20 ° C. onto a stainless steel plate moving from a T-die, evaporate methylene chloride while gradually increasing the temperature, peel off from the stainless steel plate, and further heat to remove methylene chloride, and remove the methylene chloride to a thickness of 200 μm. A film was obtained. These films were uniaxially stretched at 230 ° C. to a stretching ratio of 2.0 by a tenter method. After the barrier layer and the transparent electrode for liquid crystal were sputtered on these uniaxially stretched films, they were adhered to one surface of the deflecting plate using an adhesive so that the optical axis was at 45 degrees to obtain a composite deflecting plate. Then this is STN
When used by being bonded between the liquid crystal cell of the liquid crystal display device and the upper polarizing plate, a black-and-white display having a wide viewing angle, a white background color, and a black display color with good contrast was obtained. In addition, a color filter was put on the upper part, and the cells of RGB were colored and displayed with black and white gray density, whereby a clear full color display was obtained.

Examples 5 to 8 (Blending of Active Hydrogen-Containing Compound) Irganox MD1024 was prepared using octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was measured in the same manner as in Examples 1 to 4 except that {Irganox 1076 (manufactured by Ciba Specialty Chemicals)} was used. The results are shown in Table 1. Irgano as an active hydrogen-containing compound
By adding x1076, the color change of the methylene chloride solution of the polycarbonate copolymer was significantly suppressed. A film was prepared from the solution two days after storage in a dark place, and its hue was evaluated. As a result, the b value of the film of Example 8 was as good as 0.65.

Next, 1000 ppm of Irganox 1076 was added to the polycarbonate copolymer, and a polycarbonate copolymer solution stored in a dark place for 2 days was obtained in the same manner as in Example 3 to obtain a film having a thickness of 200 μm. The film was uniaxially stretched to 2.0. When this film was liquid crystal-displayed in the same manner as in Example 3, a clear full-color display with a wide viewing angle was obtained.

[0063]

[Table 1]

Example 9 (Blending of alcohols) 10 g of the polycarbonate copolymer obtained in Reference Example 1
Was dissolved in a solvent prepared by mixing 0.67 g of methanol with 66.7 g of methylene chloride. The absorbance at 434 nm of this solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Next, the polycarbonate copolymer solution stored in a dark place for 2 days was prepared in the same manner as in Example 3 for 20 minutes.
A film having a thickness of 0 μm was obtained and uniaxially stretched to a stretching ratio of 2.0. When this film was liquid crystal-displayed in the same manner as in Example 3, a clear full-color display with a wide viewing angle was obtained.

Example 10 Evaluation was performed in the same manner as in Example 9 except that 0.67 g of methanol was changed to 1.34 g. The results are shown in Table 2. Also,
A film was prepared from the solution two days after storage in a dark place, and its hue was evaluated. As a result, the b value of the film was as good as 0.63.

Example 11 Evaluation was performed in the same manner as in Example 9 except that ethanol was used instead of methanol. The results are shown in Table 2.

Example 12 Evaluation was made in the same manner as in Example 9 except that ethanol was used instead of methanol. The results are shown in Table 2. A film was prepared from the solution two days after storage in a dark place, and its hue was evaluated. As a result, the b value of the film was as good as 0.62.

Comparative Example 2 Evaluation was made in the same manner as in Example 9 except that no methanol was used. The results are shown in Table 2.

Example 13 1901.3 parts of biscresol fluorene of Reference Example 1 and 26 of bisphenol A were used.
A polycarbonate copolymer having a constitutional ratio of biscresol fluorene to bisphenol A of 30:70 in molar ratio was obtained in the same manner as in Reference Example 1 except that 76.7 parts was used (polymer yield: 99%). This polymer had an intrinsic viscosity of 0.727 and a Tg of 195 ° C.

To a 20% by weight methylene chloride solution of this polymer, methanol was added at 2% by weight of methylene chloride, and the mixture was stored in a dark place for 2 days. Two days after storage in a dark place, the polymer solution was cast on a stainless steel plate moving from a T-die.
In the same manner as in the above, a film having a thickness of 100 μm was obtained.

The film was coated with a solvent-resistant layer on both sides and cured using a high-pressure mercury lamp to a thickness of 4.5 μm.
Was formed. Further, a siloxane gas barrier layer of 30 nm was formed on one side. A 30 nm indium / tin oxide conductive film was formed on the surface opposite to the gas barrier layer.

Next, two samples of 7 cm square were cut out from this, each was coated with a low-temperature curing type polyimide as an aligning agent, and after hardening, micropearl made of Sekisui Fine Chemical was sprayed as a spacer, and Ciba Geigy araldite was used as a sealant. Screen printed.

Next, the two samples were bonded to form a liquid crystal cell having a cell gap of 6 μm. Kiracol 6228 manufactured by Asahi Denka was injected into this using a liquid crystal injection device. After the injection, the mixture was heated to a liquid crystal phase transition temperature and then gradually cooled to room temperature to complete the alignment.

The cell obtained as a result exhibited a STN liquid crystal cell having a uniform color tone and an ON response of 60 msec or less and an OFF response of 25 msec or less at an applied voltage of 1.8 V.

[0076]

[Table 2]

[0077]

According to the method for producing a polymer of the present invention,
The color change of the hue in the solution can be remarkably suppressed, a polymer having a good hue can be obtained, and it can be suitably used as a retardation film or a film for a liquid crystal substrate.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) C08L 63/00 C08L 63/00 C 67/03 67/03 69/00 69/00 F-term (reference) 4J002 AA051 CD051 CF161 CG001 CG011 EJ016 EJ026 EJ036 EJ046 EP026 EQ026 EU176 EU196 EW126 FD076 FD206 HA05 4J029 AA03 AA09 AB04 AC01 AC02 AE03 BB10A BB12A BB12C BB13A BB13 DCB DCB ADB DCB AD8

Claims (8)

[Claims] An organic solvent solution of a synthesized polymer in producing a polymer from an aromatic dihydroxy compound in which a compound component represented by the following formula [1] is 1 to 100 mol% of a wholly aromatic dihydroxy compound component: And a heavy metal deactivator and / or 100 parts by weight of the polymer.
Alternatively, a method for producing a polymer, comprising a step of mixing 0.0001 to 5 parts by weight of an active hydrogen-containing compound. Embedded image [Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ] 2. A method for preparing a polymer from an aromatic dihydroxy compound in which the compound represented by the formula [1] is 1 to 100 mol% of the total aromatic dihydroxy compound component, an organic solvent solution of the synthesized polymer. The alcohol is added in an amount of 0.1 to 100 parts by weight of the organic solvent.
A method for producing a polymer, comprising a step of blending 10 parts by weight. 3. The compound represented by the formula [1] is 9,9-bis (4-hydroxy-3-methylphenyl)
3. The method for producing a polymer according to claim 1, which is fluorene. 4. The method according to claim 1, wherein the polymer is a polycarbonate resin, a polyarylate resin, or an epoxy resin. 5. The method for producing a polymer according to claim 1, wherein the polymer is a polycarbonate resin. 6. A polycarbonate resin, wherein 1 to 99 mol% of a wholly aromatic dihydroxy component is a compound component represented by the formula [1], and 99 to 1 mol% is a compound represented by the following formula [2]: [Wherein, R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom, and W is a single bond, 1 to 9 carbon atoms. 20 hydrocarbon groups which may contain an aromatic group, O, S, SO, S
O ₂ , CO or COO groups. The method for producing a polymer according to claim 5, which is a polycarbonate copolymer comprising an aromatic dihydroxy component represented by the following formula: 7. The method for producing a polymer according to claim 1, wherein the active hydrogen-containing compound is a hindered phenolic antioxidant. 8. The method for producing a polymer according to claim 2, wherein the alcohol is a lower alcohol having 1 to 3 carbon atoms.