JPH06298925A - Production of polycarbonate copolymer - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate copolymer having excellent non-volatility, impact resistance and weather resistance and useful as a board for outdoor use such as arcade and carport in high efficiency by copolymerizing a specific triphenol at a specific ratio. CONSTITUTION:The objective copolymer is produced by copolymerizing 0.1-5.0wt.% of a triphenol of formula I (R and R<1> to R<6> are H, halogen or 1-12C organic residue; at least one of Z<1> to Z<6> is group of formula II and the others are H, halogen or 1-12C organic residue) [e.g. 1,1,1-tris(4-hydroxyphenyl)ethane benzotriazole] by interfacial polycondensation or ester interchange process.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polycarbonate copolymer. More specifically, the present invention relates to a production method capable of efficiently obtaining a polycarbonate copolymer having excellent volatility during molding and outdoor use, as well as excellent impact resistance and weather resistance.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical strength such as heat resistance and impact resistance and transparency, and are engineering plastics such as optical parts, mechanical parts, electric / electronic parts. It is used in various fields such as parts, automobile parts, and various containers. When a polycarbonate resin having such characteristics is used outdoors for arcades, carports, etc., its weather resistance is not sufficient and improvement is desired. As a method for improving the weather resistance of a polycarbonate resin, a method of adding a small amount of an ultraviolet absorber has been generally adopted, as disclosed in Japanese Patent Publication No. 44-18989. However, the method of adding the ultraviolet absorber as described above has a drawback that the ultraviolet absorber is volatilized during the molding process or when the molded product is used outdoors. As a method for preventing the volatilization of the ultraviolet absorber, for example, JP-A-49-99596 and JP-A-1-
Each of Japanese Patent Laid-Open No. 201330 and JP-A-3-39326 discloses a method of copolymerizing an ultraviolet absorber.
In the conventional method of copolymerizing these ultraviolet absorbers, the weather resistance is, compared with the case where the same amount of ultraviolet absorber is added,
It has the disadvantage of being inferior.

[0003]

Therefore, the present inventor has conducted diligent research to develop a polycarbonate copolymer having excellent volatility during molding and outdoor use as well as excellent impact resistance and weather resistance. As a result of stacking, it was found that the desired polycarbonate copolymer can be obtained by copolymerizing a specific triphenol having an ultraviolet absorbing ability. The present invention has been completed based on such findings. That is, in the present invention, when the polycarbonate copolymer is produced by the interfacial polycondensation method or the transesterification method, the general formula (I)

[0004]

[Chemical 3]

[In the formula, R and R ^{1 to} R ⁶ each represent a hydrogen atom, a halogen atom or an organic residue having 1 to 12 carbon atoms. Further, at least one of Z ^{1 to} Z ⁶ is a formula

[0006]

[Chemical 4]

The rest are hydrogen atoms, halogen atoms or organic residues having 1 to 12 carbon atoms. ] 0.1 to 5.0% by weight of a monomer represented by the above formula is copolymerized to provide a method for producing a polycarbonate copolymer. First, in producing the polycarbonate copolymer (PC copolymer) of the present invention, triphenol used for copolymerization is represented by the general formula (I).

[0008]

[Chemical 5]

It is represented by R and R ^{1 to} R ⁶ in the general formula (I) each represent a hydrogen atom, a halogen atom (bromine, chlorine, fluorine, iodine) or an organic residue having 1 to 12 carbon atoms. Here, examples of the organic residue having 1 to 12 carbon atoms include an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group). Group) or carbon number 6
To 12 aryl groups (eg, phenyl group, tolyl group,
Xylyl group, naphthyl group, etc.), which may be the same or different. Also, Z ^{1 to} Z ⁶
Is at least one of the expressions

[0010]

[Chemical 6]

It is represented by The rest represents a hydrogen atom, a halogen atom (bromine, chlorine, fluorine, iodine) or an organic residue having 1 to 12 carbon atoms. This carbon number 1 to 1
The organic residue of 2 is the same as in the general formula (I). As the triphenol represented by the general formula (I), specifically, 1,1,1-tris (4-hydroxyphenyl) ethanebenzotriazole (THPE-BZT);
1,1,1-Tris (4-hydroxyphenyl) methanebenzotriazole; 1,1,1-Tris (4-hydroxyphenyl) propanebenzotriazole; 1,1,
1-Tris (4-hydroxyphenyl) butanebenzotriazole and the like can be mentioned. These triphenols constitute the main chain or end groups of the PC copolymer.

In order to produce a PC copolymer by the production method of the present invention, the triphenol represented by the above general formula (I) 0.1 to 0.1 is produced by an interfacial polycondensation method or a transesterification method.
5.0% by weight is copolymerized. The production method by the above interfacial polycondensation method or transesterification method,
Various methods can be adopted. That is, in the interfacial polycondensation method, for example, a dihydric phenol and phosgene are reacted in a mixed solution of an organic solvent and an alkaline aqueous solution to produce a polycarbonate oligomer (PC oligomer), and then the PC oligomer and the general formula By reacting the triphenol and dihydric phenol represented by (I) in a mixed solution of an organic solvent and an aqueous alkaline solution, P
C copolymers can be produced. Further, dihydric phenols, triphenol represented by the general formula (I) and phosgene are reacted in a mixed solution of an organic solvent and an aqueous alkaline solution to produce a PC oligomer having triphenol incorporated in its main chain. The PC copolymer can also be produced by reacting the PC oligomer and the dihydric phenol in a mixed solution of an organic solvent and an alkaline aqueous solution. Furthermore, for example, a PC copolymer can be produced from a dihydric phenol, a triphenol represented by the general formula (I) and a carbonate precursor such as a carbonic acid diester compound by a transesterification method.

First, in the production method of the present invention, the PC oligomer used to produce the PC copolymer by the interfacial polycondensation method has the general formula (II)

[0014]

[Chemical 7]

It is represented by Here, R ⁷ and R ⁸ in the general formula (II) are each a halogen atom (eg, bromine, chlorine, fluorine, iodine), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, Propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group) or an aryl group having 6 to 12 carbon atoms (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.), It may be the same or different. And m and n are integers of 0-4, respectively. Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylidene group (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group, etc.), carbon A cycloalkylene group or a cycloalkylidene group having a number of 5 to 20 (for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, a 3,3,5-trimethylcyclohexylidene group), or- O -, - S -, - SO -, - SO 2 -,
-CO- bond or formula (III) or (III ')

[0016]

[Chemical 8]

Is shown. Hal represents a halogen atom (for example, bromine, chlorine, fluorine, iodine), and t = 2 to
Twenty. This PC oligomer is easily produced by a solvent method, that is, by reacting a dihydric phenol with a carbonate precursor such as phosgene in the presence of a known acid acceptor and a terminal stopper in a solvent such as methylene chloride. be able to. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or a terminator, 2
It can be produced by the reaction of a phenol with a carbonate precursor such as phosgene.

Here, the above-mentioned dihydric phenols may be those usually used for producing a polycarbonate by an interfacial polycondensation method or a transesterification method,
There are various things. Specifically, bis (4-hydroxyphenyl) methane; 2,2-bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)
-(4-isopropylphenyl) methane; bis (3,5
-Dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane;
1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2,2 -Bis (4-hydroxyphenyl) propane [common name: bisphenol A]; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl-1-methylphenyl) propane 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-
1,1-bis (4-hydroxyphenyl) propane;
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane; 2,2-bis (3-
Chloro-4-hydroxyphenyl) propane; 2,2-
Bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 1,1-bis (4 -Hydroxyphenyl)
Butane; 2,3-bis (4-hydroxyphenyl) butane; 1,4-bis (4-hydroxyphenyl) butane;
2,2-bis (4-hydroxyphenyl) pentane; 4
-Methyl-2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4- Hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) nonane;
Bis (hydroxyaryl) alkanes such as 1,10-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-
Bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 1,1
-Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cyclodecane, bis (4-hydroxyphenyl) sulfone; bis (3,5-
Dimethyl-4-hydroxyphenyl) sulfone; dihydroxydiarylsulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-
4-hydroxyphenyl) ether and other dihydroxydiaryl ethers, 4,4′-dihydroxybenzophenone; 3,3 ′, 5,5′-tetramethyl-4,
Dihydroxydiarylketones such as 4'-dihydroxybenzophenone, bis (4-hydroxyphenyl)
Sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide; bis (3-methyl Examples thereof include dihydroxydiaryl sulfoxides such as -4-hydroxyphenyl) sulfoxide, dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl, thiobisphenol, bisphenol Z, bisphenolfluorene, and tetrabromobisphenol A. Also, the above 2
Besides dihydric phenols, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene; halogen- and alkyl-substituted dihydroxybenzenes such as 1,4-dihydroxy-3-methylbenzene, 1,
5-dihydroxynaphthalene; dihydroxynaphthalene such as 2,6-dihydroxynaphthalene, and the like. Of these, bisphenol A is preferably used. These dihydric phenols may be used alone or in combination of two or more.

Further, the above-mentioned end terminator is usually
Various materials used for polymerization of polycarbonate can be used. Specifically, as monohydric phenol,
Examples thereof include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, bromophenol, tribromophenol, pentabromophenol, trichlorophenol, nonylphenol and the like. And as other components, as a branching agent, for example, 1,1,1-
Tris (4-hydroxyphenyl) ethane; α, α ′,
α ″ -tris (4-hydroxyphenyl) -1,3,5
-Triisopropylbenzene; 1- [α-methyl-α-
(4'-Hydroxyphenyl) ethyl] -4- [α ',
A compound having three or more functional groups such as α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; phloroglysin, trimellitic acid, isatin bis (o-cresol) may be used. Siloxane can also be used.

In order to produce a PC oligomer using each of the above components, for example, phosgene 110-150 and branching agent 0-2 are added to bisphenol A100 (molar ratio).
The reaction is carried out at a molar ratio of 6. In this reaction, first,
Bisphenol A and a branching agent are dissolved in an aqueous solution of an alkali metal hydroxide to prepare an alkaline aqueous solution of bisphenol A and a branching agent. Then, as an alkaline organic solvent and an inert organic solvent, for example, phosgene or a phosgene derivative is introduced into a mixed solution of methylene chloride and reacted to synthesize a PC oligomer of bisphenol A, and the reaction solution is mixed with an aqueous phase and an organic phase. And separated to obtain an organic phase containing PC oligomer. At this time, the alkali concentration of the alkaline aqueous solution is preferably in the range of 1 to 15% by weight, and the volume ratio of the organic phase to the aqueous phase is 10: 1 to 1:10, preferably 5: 1.
It is preferably in the range of ˜1: 5. The reaction temperature is generally 0 to 70 ° C., preferably 5 to 65 ° C., and the reaction time is 15 minutes to 4 hours, preferably 3 after cooling with a water bath.
It is about 0 minutes to 3 hours. The thus-obtained PC oligomer has an average molecular weight of 2,000 or less and a polymerization degree of usually 20 or less, preferably 2 to 10 mer. Examples of phosgene or phosgene derivatives include phosgene, triphosgene, bromophosgene, bis (2,4,6-trichlorophenyl) carbonate, bis (2,4-dichlorophenyl) carbonate, bis (2-cyanophenyl) carbonate, and chloroform. Examples thereof include trichloromethyl acid.

In the production method of the present invention, the PC copolymer can be produced by an interfacial polycondensation method or a transesterification method. First, when it is produced by the interfacial polycondensation method, for example, it is produced by reacting the PC oligomer, the triphenol of the general formula (I) and the dihydric phenol in a mixed solution of an organic solvent and an alkaline aqueous solution. can do. That is, PC
Triphenol and bisphenols are added to the organic phase containing the oligomer and reacted. This reaction is usually
Triphenol 0.1 per 100 parts by weight of oligomer
˜6.0 parts by weight and bisphenols in an amount of 5 to 40 parts by weight. And the reaction temperature is usually 10 to 50.
C., preferably at a temperature in the range of 20 to 40.degree. C., and for a reaction time of about 30 minutes to 2 hours. In this reaction, dihydric phenols such as bisphenol A and triphenol are added as an aqueous alkaline solution. The addition order is not particularly limited,
It is desirable to add bisphenol A last. At that time, it is desirable to simultaneously add the alkaline aqueous solution. In the case of the interfacial polycondensation method, a PC oligomer is produced from a dihydric phenol, the triphenol of the general formula (I) and phosgene, and then the PC oligomer and the dihydric phenol are mixed with an organic solvent and an alkaline aqueous solution. It can also be produced by reacting under a mixed solution of. In this reaction, the above-mentioned terminal terminator and catalyst can be used if desired.

In the production of the PC copolymer, there are various organic solvents. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane;
1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; chlorinated hydrocarbons such as pentachloroethane and chlorobenzene; and acetophenone. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferable. Further, various kinds of catalysts can be used. In particular,
Examples include quaternary ammonium salts, quaternary phosphonium salts, and tertiary amines. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide and the like. Further, as the quaternary phosphonium salt, for example,
Examples thereof include tetrabutylphosphonium chloride and tetrabutylphosphonium bromide. Examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaminopyridine, dimethylaniline and the like. Among these, triethylamine is preferably used. As the alkaline aqueous solution, for example, an aqueous solution of an alkaline compound such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide or sodium carbonate can be used. Of these, sodium hydroxide and potassium hydroxide are preferred.
The polymer thus produced can be used as a PC copolymer by performing a recovery operation according to a usual method.

On the other hand, when the PC copolymer is produced by the transesterification method, it can be produced from, for example, a dihydric phenol, the triphenol of the general formula (I) and a carbonic acid diester compound by the transesterification method.
In the case of producing by this transesterification method, the same dihydric phenols, terminal terminators, branching agents and the like as those used in the interfacial polycondensation method can be used. There are various kinds of carbonic acid diester compounds. For example, it is at least one compound selected from diaryl carbonate compounds, dialkyl carbonate compounds or alkylaryl carbonate compounds. Here, as the carbonic acid diaryl compound, specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (m-cresyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bisphenol A bisphenyl carbonate. Etc.
Specific examples of the dialkyl carbonate compound include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. Specific examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. Among these,
Particularly, diphenyl carbonate is preferably used.

When a PC copolymer is produced by the transesterification method, a catalyst is not particularly required, but a known catalyst may be used to accelerate the transesterification reaction.
Specific examples of such a catalyst include alkali metal or alkaline earth metal simple substance, oxide, hydroxide, amide compound, alcoholate, phenolate, or Zn.
Basic metal oxides such as O, PbO and Sb ₂ O ₃ , organic titanium compounds, soluble manganese compounds, Ca, Mg,
Acetates of Zn, Pb, Sn, Mn, Cd, Co or nitrogen-containing basic compounds and boron compounds, nitrogen-containing basic compounds and alkali (earth) metal compounds, nitrogen-containing basic compounds and alkali (earth) metals Examples thereof include a combined catalyst of a compound and a boron compound.

In order to produce a PC copolymer by the transesterification method, specifically, the reaction may be carried out according to the known transesterification method. That is, the dihydric phenol and the triphenol of the general formula (I) are added in an amount of 0.1
The required amount for copolymerizing 5.0 wt% and the carbonic acid diester compound are
React at 1.5 times the molar amount. Depending on the situation, it is preferable that the amount of the carbonic acid diester compound is 1.02 to 1.20 times by mole, which is a slight excess.

The reaction temperature of the transesterification reaction is not particularly limited, but is usually in the range of 100 ° C. to 330 ° C., preferably 180 ° C. to 300 ° C., more preferably 180 ° C. to 300 ° C. gradually according to the progress of the reaction. A good way is to raise the temperature to ℃. And the transesterification reaction is 100
If the temperature is below ℃, the reaction progresses slowly, and if it exceeds 330 ℃,
Polymer is thermally deteriorated, which is not preferable. The pressure during the reaction is set according to the vapor pressure of the triphenol used. This is not limited as long as it is set so that the reaction is efficiently performed. Usually, in the initial stage of the reaction, 1 to 50 atm (760 to 38,000)
to atmospheric pressure or pressurized condition up to the torr) and reduced pressure in the latter half of the reaction, preferably 0.01 to
It is often 100 torr. The reaction time may be such that it reaches a target molecular weight, and is usually about 0.2 to 10 hours. The above-mentioned transesterification reaction is carried out in the absence of an inert solvent, but if necessary, it may be carried out in the presence of an inert solvent of 1 to 150% by weight of the obtained PC copolymer. Then, as the transesterification reaction proceeds, phenols, alcohols, or their esters or an inert solvent (when used) corresponding to the used carbonic acid diester compound are desorbed from the reactor. These desorbed substances can be separated, purified and recycled, and it is preferable to have a facility for removing them.

As described above, in the production method of the present invention, the triphenol represented by the general formula (I) having an ultraviolet absorbing ability can be copolymerized by the interfacial polycondensation method or the transesterification method, whereby It is possible to obtain a PC copolymer having excellent impact resistance and weather resistance. The transesterification method is particularly preferable from the viewpoint of weather resistance. The PC copolymer excellent in such characteristics is obtained by copolymerizing 0.1 to 5.0% by weight of triphenol with respect to the PC copolymer. The amount of copolymerization of this triphenol
If it is less than 0.1% by weight, the weather resistance is insufficient, and it is 5.0% by weight.
If it exceeds, mechanical strength such as impact resistance decreases, which is not preferable. And the viscosity average molecular weight is 10,000.
〜5,000,000, preferably 13,000〜40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength such as impact resistance decreases. On the other hand, when it exceeds 50,000, the fluidity is lowered and the moldability is deteriorated, which is not preferable.

In order to obtain a molded article using the PC copolymer obtained by the production method of the present invention, it may be mixed with a commercially available polycarbonate resin within the range not impairing the object of the present invention. Then, if necessary, various additives or inorganic fillers may be mixed and kneaded to prepare a desired resin composition, which may be used for molding. Where the formulation,
For kneading, a commonly used method such as ribbon blender, Henschel mixer, Banbury mixer,
It can be carried out by a method using a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder or the like. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The resin composition of the PC copolymer thus obtained is subjected to various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, etc. for automobile glass, sunroof, etc. We can manufacture molded products in the automobile field, molded products in the home appliance field, and boards for outdoor use such as arcades, carports, and soundproof plates on the side walls of highways. As various additives, hindered phenol type,
Antioxidants such as phosphite ester and phosphoric acid ester, UV absorbers such as benzotriazole and benzophenone, light stabilizers such as hindered amine, external lubricants such as aliphatic carboxylic acid ester and paraffin, Colorants, flame retardants, flame retardant aids, antistatic agents, inorganic fillers and the like can be mentioned.

Here, various kinds of inorganic fillers can be used. Specifically, glass, carbon fiber, and other inorganic fillers are used. First, as the glass material, for example, glass fiber, glass beads, glass flakes, glass powder or the like can be used. Here, the glass fiber used may be any of alkali-containing glass, low-alkali glass and non-alkali glass. Its fiber length is 0.1 to 8 mm, preferably 0.1.
3 to 6 mm, and the fiber diameter is 0.1 to 30 μm,
It is preferably 0.5 to 25 μm. And the form of this glass fiber is not particularly limited, for example, roving,
There are various types such as milled fiber and chopped strand. These glass fibers may be used alone or in combination of two or more. These glass materials are surface-treated with a silane coupling agent such as aminosilane, epoxysilane, vinylsilane or methacrylsilane, a chromium complex compound or a boron compound in order to enhance the affinity with the resin. It may be one. As such a glass material, for example, commercially available MA-4 manufactured by Asahi Fiber Glass Co., Ltd.
09C (average fiber diameter 13 μm) or TA-409C
(Average fiber diameter 23 μm) and the like can be preferably used.

Next, the carbon fiber used is generally produced by calcining cellulose fiber, acrylic fiber, lignin, petroleum or coal-based pitch as a raw material, and has flame resistance, carbon quality or There are various types such as graphite. The fiber length of the carbon fiber is usually 0.01 to 10 mm, preferably 0.02 to 8 m.
The fiber diameter is in the range of m, and the fiber diameter is 1 to 15 μm, preferably 5 to 13 μm. The form of the carbon fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, chopped strand, and strand. These glass fibers may be used alone or in combination of two or more. The surface of these carbon fibers, in order to increase the affinity with the resin,
It may be one that has been surface-treated with an epoxy resin or a urethane resin. As such a carbon fiber, for example, a commercially available product such as Vesphite (average fiber diameter 7 μm) manufactured by Toho Rayon Co., Ltd. can be preferably used.

Other inorganic fillers include, for example, aluminum fibers, calcium carbonate, magnesium carbonate,
Dolomite, silica, diatomaceous earth, alumina, titanium oxide,
Iron oxide, zinc oxide, magnesium oxide, calcium sulfate, magnesium sulfate, calcium sulfite, talc, clay, mica, asbestos, calcium silicate, montmorillonite, bentonite. Carbon black, graphite, iron powder, lead powder, aluminum powder, etc. can also be used.

[0032]

The present invention will be further described in detail with reference to Examples and Comparative Examples. Example 1 2,275 g (10 mol) of bisphenol A (BPA) and methylene chloride were placed in a stirrer container having an internal volume of 50 liters.
8.25 liters and 14 liters of 2.0N sodium hydroxide aqueous solution were put, stirred and dissolved, and while cooling, phosgene was blown thereinto at a flow rate of 0.3 mol / min for 70 minutes to carry out a reaction. After the reaction, the mixture was allowed to stand to separate into an aqueous phase and a methylene chloride phase to obtain a methylene chloride solution of a polycarbonate oligomer (PC oligomer). The concentration of this PC oligomer was 330 g / liter, and the chloroformate group content was 0.70 N. Next, 10 liters of this PC oligomer solution was charged into a vessel with an internal volume of 50 liters equipped with a stirrer, and 40 g of p-tert-butylphenol (0.2
67 mol), 1,1,1-tris (4-hydroxyphenyl) ethanebenzotriazole [THPE-BZT;
Hoechst Celanese] 85 g (0.20 mol), sodium hydroxide 140 g (3.5 mol), water 1.8 liters,
As a catalyst, add 6 ml of triethylamine,
The mixture was stirred at 400 rpm for 30 minutes. After that, BPA79
0 g (3.46 mol), 360 g of sodium hydroxide (9.0
Mol), 4.6 liters of water and 10 liters of methylene chloride were added, and the mixture was further stirred for 60 minutes. The obtained reaction product was allowed to stand and separated, and a methylene chloride solution of a polycarbonate copolymer (PC copolymer) was extracted. The methylene chloride solution was washed with water, an acid (0.1N hydrochloric acid) and water in this order, and then methylene chloride was removed under reduced pressure at 40 ° C. to obtain a white powder of a PC copolymer. Further, after drying at 120 ° C. for 24 hours, it was melted by an extruder and pelletized. The glass transition temperature (Tg) of this pellet was measured and found to be 154 ° C. The viscosity average molecular weight was 24,700.
Then, the obtained pellets are heated at a temperature of 30 with an injection molding machine.
A test piece was prepared by injection molding at 0 ° C. and an injection pressure of 55 kg / cm ² . For the quality of the obtained test pieces, Izod impact strength and weather resistance were measured.
The results are shown in Table 1.

Examples 2 to 3 A PC copolymer was obtained in the same manner as in Example 1 except that the amount of THPE-BZT was changed as shown in Table 1. Hereinafter, quality evaluation was performed in the same manner as in Example 1.
The results are shown in Table 1. In Example 3, trisnonylphenyl phosphite (TN) was used as an antioxidant.
200 ppm of P) was added.

Example 4 In a container equipped with a stirrer and having an internal volume of 1 liter, 228 g of BPA was used.
(1 mol), diphenyl carbonate 224.8 g (1.05 mol), THPE-BZT 2.1 g (0.005 mol), charged with 2 mg of lithium hydroxide as a catalyst, 180
The temperature was raised to ℃ and the stirring was started. While removing the distilled phenol with a nitrogen stream of 0.5 l / min, 30
Let react for minutes. Furthermore, at 210 ℃ for 30 minutes, 240 ℃
After reacting for 30 minutes at 270 ° C., the temperature is raised to 270 ° C. and the system is gradually evacuated to 1 mmHg for 1 hour.
The reaction was allowed for 0 minutes. The reaction contents were taken out, crushed and then pelletized. As a result of measuring the glass transition temperature (Tg) of this pellet, it was 150 ° C. The viscosity average molecular weight was 20,500. The obtained pellets were molded in the same manner as in Example 1 and evaluated for quality. The results are shown in Table 1.

Comparative Examples 1 and 2 A PC copolymer was obtained in the same manner as in Example 1 except that the amount of THPE-BZT was changed as shown in Table 1. Hereinafter, quality evaluation was performed in the same manner as in Example 1.
The results are shown in Table 1.

Comparative Example 3 In Example 1, instead of THPE-BZT, 2-
(2-Hydroxy-5-tert-octylphenyl) benzotriazole [Kemipro Kasei Co., Ltd., Chemisorb 7
9] was used in the same manner as in Example 1 to obtain a PC copolymer. Hereinafter, quality evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 In Example 1, instead of THPE-BZT, 2-
Example 2 except that [2-hydroxy-3- (3,4,5,6-tetrahydrocyclohexyl imidazolemethyl) -5-methylphenyl] benzotriazole [Sumitomo 250, manufactured by Sumitomo Chemical Co., Ltd.] was used. PC as well as
A copolymer was obtained. Hereinafter, quality evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[0038]

[Table 1]

The types of triphenol in the table are as follows. A: 1,1,1-tris (4-hydroxyphenyl) ethanebenzotriazole (THPE-BZT) B: 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole C: 2- [2-hydroxy- 3- (3,4,5,6-Tetrahydrocyclohexylimidamethyl) -5-methylphenyl] benzotriazole Further, the Tg, viscosity average molecular weight, Izod impact strength and weather resistance were measured as follows. 1) Measured by Tg DSC (Differential Scanning Calorimeter). 2) Viscosity average molecular weight (Mv) The viscosity of the methylene chloride solution at 20 ° C was measured using an Ubbelohde type viscosity tube, and the intrinsic viscosity [η] was calculated from this, and then calculated by the following formula. [Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 3) Izod impact strength (with notch) It was measured according to JIS-K-7110 using a test piece having a thickness of 3.2 mm. 4) Weather resistance Measured under the following conditions using a sunshine weather meter. Measurement conditions Black panel temperature 63 ℃ Rain cycle 12 minutes / 60 minutes 1,000 hours Measure YI (Yellow Index) value after irradiation

[0040]

As described above, according to the present invention, it is possible to obtain a polycarbonate copolymer which is excellent in volatility during molding and outdoor use, and is also excellent in impact resistance and weather resistance. Therefore, the polycarbonate copolymer obtained by the production method of the present invention is suitably used for boards for outdoor use such as arcades and carports.

Claims (1)

[Claims] 1. In producing a polycarbonate copolymer by an interfacial polycondensation method or a transesterification method,
General formula (I) [In formula, R and R < ¹ > -R < ⁶ > show a hydrogen atom, a halogen atom, or a C1-C12 organic residue, respectively. Also,
At least one of Z ^{1 to} Z ⁶ has the formula: And the rest each represent a hydrogen atom, a halogen atom or an organic residue having 1 to 12 carbon atoms. ] 0.1-5.0 weight% of triphenols represented by these are copolymerized, The manufacturing method of the polycarbonate copolymer characterized by the above-mentioned.