JP2000290364A - Production of branched polycarbonate resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a branched polycarbonate resin having an arbitrarily controlled degree of branching by thermally melting and kneading a mixture comprising a linear polycarbonate resin, a branching agent and a transesterification catalyst. SOLUTION: A linear polycarbonate resin having a structural viscosity index (an N-value) of 1.1-1.4 is usually used. Preferably, the N value of the branched polycarbonate resin is controlled to 1.6 or higher. Preferably, the linear polycarbonate resin used has a viscosity average mol.wt. (Mv) of 15,000-50,000 and a phenolic OH content of 2,000 ppm or lower. The branching agent is used usually in an amount of 0.01-5 mol% based on a dihydric phenol compound from which the repeating units of the linear polycarbonate resin are derived. Preferably, the catalyst is used in an amount of 10-8-10-1 mol per mol of the dihydric phenol compound. Using a machine selected from among various extruders and molding machines for thermal melting is the most effective.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for obtaining a branched polycarbonate resin directly from a linear polycarbonate resin produced by an interfacial polymerization method or a transesterification method in a plasticizer, for example, an extruder or a molding machine. And a molded product obtained by processing the same.

[0002]

2. Description of the Related Art Polycarbonate resins are used in many fields because of their excellent mechanical and optical properties. In addition, ordinary polycarbonate resins are often branched at the time of resin production in order to improve moldability, dropping property during combustion, and birefringence as an optical material. Since ordinary polycarbonate resin exhibits Newtonian flow behavior under melt processing conditions, sagging occurs during injection molding, and drawdown occurs in which a parison extruded during blow molding hangs down due to its own weight and becomes thin. Therefore, in order to impart non-Newtonian behavior under melt processing conditions, a method of mixing a high molecular weight polycarbonate resin (Japanese Patent No. 2591546)
No. 2,608,188) and a method of improving the melting characteristics by blending a high-molecular-weight acrylic resin (Japanese Unexamined Patent Publication No.
-268761) has been proposed. Also, a method of branching a polycarbonate resin (JP-A-48-69)
No. 3, JP-B-53-28193) are known. Further, as an optical disk material, a branched polycarbonate resin optical molded product (JP-A-60-215019) is known for the purpose of preventing brittleness and stringing during molding.

[0003] In the method of mixing a high molecular weight polycarbonate resin, since the molecular weight of a high molecular weight polycarbonate mixed with a commercially available polycarbonate resin has a large difference, it becomes optically non-uniform and causes minute white streaks or silver or silver during molding. There are drawbacks such as delamination and uneven mechanical strength. Further, the method of blending another resin has problems such that the transparency of the polycarbonate resin is lost and the mechanical strength is similarly reduced.

[0004] The branched polycarbonate resin is prepared by using a solvent such as dichloromethane at the time of or immediately after treating a bifunctional phenol with carbonyl chloride by an interfacial polymerization method or a solution method. It is produced by adding and polymerizing a branching agent that can react with, for example, trifunctional phenol, trifunctional carboxylic acid, and isatin bisphenol. However, when producing a branched polycarbonate resin by this production method, it has been difficult to produce it according to the purpose and required amount. In addition, in this production method, it is difficult to purify unreacted substances and impurities, resulting in coloring of molded articles,
Further, there is a problem that equipment for adding a branching agent is required and the production conditions are narrow.

On the other hand, also in the transesterification method, a branched polycarbonate resin can be produced by adding a transesterifying branching agent to a bifunctional phenol and treating with diphenyl carbonate and a small amount of a transesterification catalyst. For example, various methods for producing a branched polycarbonate resin by transesterification have been proposed. Production method using a max blend type stirring blade or a double helical ribbon blade and a heater (Japanese Patent Laid-Open No. Hei 10-273528).
Is characterized by being able to efficiently produce a branched polycarbonate resin by using special wings. The method using a twin-screw extruder (Japanese Patent Publication No. 52-36159) is
There is a feature that a branched polycarbonate resin can be efficiently produced by shear melting and mixing with a vented twin screw extruder.
However, it is difficult to obtain a branched polycarbonate resin by a single-stage melt-kneading apparatus in these production methods, and since the molten resin adheres to the inside of the apparatus, the mixed product when switching between a general product and a branched product is used. The outbreak was not avoided. In addition, a new problem such as treatment of a used cleaning agent or solvent has arisen with the enlargement of the apparatus. Therefore, there are various disadvantages in producing a branched polycarbonate resin by this production method.

[0006]

Since the branched polycarbonate resin has an economical problem associated with product identification on the part of the manufacturer and raw material identification on the part of the molded article which occur at the time of production, the production amount of the branched polycarbonate resin is low. It was difficult to manufacture or use unless a certain amount was used. The present invention provides a method for producing a branched polycarbonate resin in which the degree of branching is arbitrarily controlled by adding a branching agent during extrusion or molding using a generally produced linear polycarbonate resin. Things.

[0007]

Means for Solving the Problems The present inventors have added a trace amount of an ester exchange catalyst and a desired branching agent to a linear polycarbonate resin produced by an interfacial polymerization method, a solution method or a transesterification method. It has been found that by kneading under heating in an extruder or a molding machine, the branching characteristics can be easily adjusted by performing the necessary branching in the pelletizing stage or the molding stage, and arrived at the present invention.

The present invention is a process for producing a branched polycarbonate resin, which comprises heating, melting and kneading a polycarbonate resin mixture obtained by adding a branching agent and a transesterification catalyst to a linear polycarbonate resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material linear polycarbonate resin used in the present invention has a measured structural viscosity index N
Is a polycarbonate resin usually in the range of 1.1 to 1.4. This polycarbonate resin is generally produced by various methods for producing a polycarbonate resin such as an interfacial polymerization method, a solution method or a transesterification method. When produced by these production methods, there may be slight branching due to impurities contained in a trace amount or a transfer reaction, but the structural viscosity index N is 1.4 or less, which is useful as a branched polycarbonate resin. Characteristics are not exhibited.

The structural viscosity index N here is derived from the following relational expression. Q = K × P ^N [where P is 280 ° C. using a Koka type flow tester.
(Load: 40 to 180 kgf). Q is
This is the flow rate (ml / sec) of the molten resin. K is an intercept of the regression equation and is an independent constant, which is derived from the molecular weight and structure of the polycarbonate resin. ]

The melting property can be evaluated by the structural viscosity index N value,
When N is 1, it exhibits Newtonian flow behavior, and the larger the N value, the greater the pressure dependence of fluidity and exhibits non-Newtonian flow behavior. In general, a non-Newtonian flow behavior having a large pressure dependency can prevent sagging and drawdown during extrusion and molding.

In general, the structural viscosity index N of a commercially available linear polycarbonate resin for molding is from 1.1 to 1.1.
1.4, and the N value of the branched polycarbonate resin according to the present invention is 1.5 or more. The polycarbonate resin of the present invention is preferably controlled to 1.6 or more by adjusting the amount of the branching agent and the melting conditions. If the molecular weight of the raw material linear polycarbonate resin used in the present invention is too small, the strength decreases, which is not preferable. When the molecular weight is too large, a high melting temperature is required when plasticizing with an extruder or a molding machine, and large shear heat is generated, so that the mixing of the branching agent becomes insufficient or the color is deteriorated. Absent. The optimum molecular weight is desirably in the range of 15,000 to 50,000, assuming that the viscosity average molecular weight is Mv.

The linear polycarbonate resin used in the present invention may be one produced by any of an interfacial polymerization method, a solution method, and a transesterification method, but may be used as a raw material for branching. It is not preferable that the raw material polycarbonate resin contains too much phenolic OH. In other words, extruders, injection molding machines, sheet molding machines, and other devices that produce pellets and molded products used for branching are limited in the plasticization zone, so when phenolic OH increases, diphenyl carbonate and other Need to be added, and the phenol coming out of the transesterification must be removed from the vent. Therefore, it is not preferable because phenol is easily recovered, the extruder and the molding machine are modified, and mold contamination and sheet roll contamination due to residual phenol are likely to occur. A linear polycarbonate resin desirable for use as a raw material has a phenolic OH content of 2000 ppm or less.

The branching agent used in the present invention includes phloroglucin, trimellitic acid, pyromellitic acid, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4, 6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) heptene-
2,1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl)
Ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 1- [α-methyl-
α- (4′-hydroxyphenyl) ethyl] benzene,
α, α ', α "-tri (4-hydroxyphenyl)-
Polyhydroxy compounds exemplified by 1,3,5-triisopropylbenzene and the like, and 3,3-bis (4-hydroxyphenyl) oxindole (= isatin bisphenol), isatin bis (o-cresol), 5-chlorisa Examples thereof include tin bisphenol, 5,7-dichloroisatin bisphenol, and 5-bromoisatin bisphenol. Among them, phloroglysin, 2,6-
Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,1,1-tri ( 4-hydroxyphenyl) ethane, α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 3,3-bis (4-hydroxyphenyl) oxindole (= isatin Bisphenol) and isatin bis (o-cresol) are preferred.

The amount of the branching agent used in the present invention is 0.01 to 5 mol%, preferably 0.1 to 2.0 mol, based on the dihydric phenol compound constituting the repeating unit of the starting polycarbonate resin. %, More preferably 0.1 to
In the range of 0.5 mol%, one or two or more of them can be used in combination. When the amount of the branching agent used in the present invention is 0.0
If it is less than 1 mol%, there is no effect due to branching. If it exceeds 5 mol%, it is not preferable because the molded article becomes brittle and the hue deteriorates.

Transesterification catalysts to be used together with the branching agent include all basic inorganic or organic compounds, for example, typical metal salts such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and zinc. , Transition metal salts such as tin,
Examples include hydroxides such as quaternary ammonium and phosphonium, carbonates, bicarbonates, halides, phenolates, diphenolates, halides, carboxylates, phosphates, hydrogen phosphates, borates, and the like.

Specific examples of the basic metal salt include metal salts of typical elements, for example, hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide and calcium hydroxide; Sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, carbonates such as cesium hydrogencarbonate and hydrogencarbonate, sodium formate, lithium acetate, sodium acetate,
Potassium acetate, calcium acetate, sodium oxalate,
Aliphatic carboxylic salts such as potassium oxalate, sodium succinate, potassium succinate, sodium benzoate,
Aromatic carboxylate such as potassium benzoate, sodium phthalate, sodium hydrogen phthalate, sodium phenolate, sodium salt of cresols, sodium p- (t-butyl) phenolate, 2,2-bis (4-
Metal salts of phenolates such as mono- or bis-metal salts of hydroxyphenyl) propane; 2,2-bis (4
-Hydroxyphenyl) propane, 1,1-bis (4-
Mono-, bis-, or polyvalent metal salts such as (hydroxyphenyl) cyclohexane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, and 1,1,1-tri (4-hydroxyphenyl) ethane Metal salts of polyfunctional phenolates, sulfonic acid metal salts such as sodium decanesulfonate, sodium di (4-t
Metal salts of phosphoric acid such as -butylphenyl) phosphate and sodium 2,2-methylenebis (4,6-di-t-butylphenyl) phosphate.

Specific examples of the metal salt of the transition element include zinc compounds such as zinc oxide, zinc acetate and zinc phenoxide; silicon compounds such as sodium silicate, tetraalkylsilicon, tetraarylsilicon and diphenylethylethoxysilicon; Germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide, and germanium phenoxide; tin compounds bonded to alkoxy or aryloxy groups such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate, and ethyltin tributoxide Compounds, arsenic compounds such as quaternary arsonium salts, lead compounds combined with lead oxide, lead acetate, lead carbonate, alkoxy or aryloxy groups, and antimony compounds such as antimony oxide and antimony acetate Manganese compounds such as manganese acetate, manganese carbonate, manganese borate, titanium compounds bound to titanium oxide, alkoxy or aryloxy group, zirconium oxide, zirconium acetate, zirconium acetylacetone, titanium bound to alkoxy or aryloxy group Basic salt catalysts such as compounds are exemplified, and from the viewpoint of safety, hydroxides, carbonates, phenolates and phosphates of typical elements including alkali metals and alkaline earth metals are desirable. In particular, metal salts of phenols such as sodium carbonate, magnesium carbonate, bisphenol A, and sodium di (4-t-
Metal salts of phosphoric acid such as butylphenyl) phosphate and sodium 2,2-methylenebis (4,6-di-t-butylphenyl) phosphate are preferable because the resulting branched polycarbonate resin has good thermal stability.

As the basic organic salt, a phosphorus base such as a quaternary phosphonium salt can be suitably used. For example, tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium Tetra (aryl or alkyl) phosphonium hydroxides such as hydroxide, tetramethylphosphonium tetraphenylborate, tetramethylphosphonium methyltriphenylborate, tetraethylphosphoniumethyltoluphenylborate,
Tetraethyl phosphonium tetraphenyl borate, trimethyl ethyl phosphonium trimethyl phenyl borate, tetrapropyl phosphonium propyl triphenyl borate, tetrabutyl phosphonium butyl toluphenyl borate, tetrabutyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetraphenyl borate, methyl triphenyl phosphonium tetraphenyl Borate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, triphenylbutylphosphonium tetraphenylborate, trimethylbenzylphosphonium benzyltriphenylborate, trimethylenebis (triphenyl (Aryl or alkyl) phosphonium borates such as cyclophosphyl) -bis (tetraphenyl borate), cyclohexyl triphenyl phosphonium tetraphenyl bilate, and cyclopentyl triphenyl phosphonium teto phenyl borate, and further tetramethyl ammonium tetraphenyl borate and tetraethyl ammonium (Aryl or alkyl) ammonium borates such as tetraphenylborate, tetrapropylammonium tetraphenylborate, tetrabutylammonium tetraphenylborate, (aryl or alkyl) phosphonium halides such as tetraphenylphosphonium bromide, ethylenebis (triphenylphosphonium) dibromide , Tetra (pt-butylphenyl) phosphonium (Aryl or alkyl) phosphonium phosphate such as diphenyl phosphate and the like. Among them, tetraphenylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetrabutylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate are preferred.

Examples of the organic salt include (aryl or alkyl) phosphonium phenols such as tetraphenylphosphonium phenolate, triphenylbutylphosphonium phenolate and bis-tetraphenylphosphonium salt of 2,2-bis (4-hydroxyphenyl) propane. Rates, and other carboxylate salts, such as tetramethylphosphonium acetate, tetraethylphosphonium acetate, tetrapropylphosphonium acetate, tetrabutylphosphonium acetate, tetrapentylphosphonium acetate, tetrahexylphosphonium acetate, tetraheptylphosphonium acetate, tetraoctylphosphonium acetate, tetradecyl Phosphonium acetate, tetradodecyl phosphonium acetate, tetrafe Le phosphonium acetate, (aryl or alkyl) phosphonium acetates, such as tetra-tolyl phosphonium acetate, tetramethyl phosphonium benzoate, tetraethyl phosphonium benzoate, tetrapropylammonium phosphonium benzoate,
(Aryl or alkyl) phosphonium formates such as tetraphenylphosphonium benzoate, (aryl or alkyl) phosphonium formates such as tetramethylphosphonium formate, tetraethylphosphonium formate, tetrapropylphosphonium formate, tetraphenylphosphonium formate,
(Aryl or alkyl) phosphonium propionates such as tetramethylphosphonium propionate, tetraethylphosphonium propionate, tetrapropylphosphonium propionate, tetraphenylphosphonium propionate, tetramethylphosphonium butyrate, tetraethylphosphonium butyrate, (Aryl or alkyl) phosphonium butyrates, such as tetrapropylphosphonium butyrate, tetraphenylphosphonium butyrate, or phosphazenes, for example the phosphazene base Pt-oct = t-octyl-imino-tris- (dimethylamino) -phosphorane Phosphazene base Pt-butyl = t-butyl-imino-tris- (dimethylamino) -phosphorane, or BEM
P = 2-t-butylimino-2-diethylamino-1,
3-dimethyl-perhydro-1,3-diaza-2-phosphorin and the like can also be used.

Further, phosphonium salts of sulfates and sulfites may be used. For example, tetraethyl phosphonium sulfate, tetraphenyl phosphonium sulfate, methyl triphenyl phosphonium sulfate, butyl triphenyl phosphonium sulfate, hexyl phosphonium sulfate, 4-carboxybutyl triphenyl phosphonium sulfate, 2-dimethylaminoethyl triphenyl phosphonium sulfate, tetrakis (hydroxy) Methyl) phosphonium and the like. Examples of the sulfonium phosphonium salt include tetraethylphosphonium sulfite, tetraphenylphosphonium sulfite, methyltriphenylphosphonium sulfite, butyltriphenylphosphonium sulfite, hexylphosphonium sulfite, 4-carboxybutyltriphenylphosphonium sulfite, and sulfite. 2-dimethylaminoethyltriphenylphosphonium, tetrakisulphite (hydrogen Kishimechiru) phosphonium and the like.

Also, nitrogen bases may be used. Examples thereof include quaternary ammonium salts, and (aryl, alkyl, or arylaryl) ammoniums such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and tetramethylbenzylammonium hydroxide. (Aryl, alkyl, or arylaryl) ammonium hydroxides such as hydroxides, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetramethylammonium acetate, tetramethylammonium fluoride, phenylphosphonium fluoride, hydroxide Dimethyldiphenylammonium, a tertiary amine compound may be used, or may be used in combination.
Tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, trimethylbenzylamine, and triphenylamine, or guanidines, for example, DBU (1,8-diazabicyclo [5.4. 0] undecene-7-ene), DBN (1,5-diazabicyclo [4.3.0] non-5-ene), 1,5,7-triazabicyclo- [4.4.0] -dece -5-ene, 7-
Phenyl-1,5,7-triazabicyclo- [4.4.
0] -dec-5-ene, MTBD (7-methyl-1,
5,7-Triazabicyclo- [4.4.0] -dec-5
-Ene, 7,7'-hexylidene-di-1,5,7-triazabicyclo- [4.4.0] -dec-5-ene,
7,7′-decylidene-di-1,5,7-triazabicyclo- [4.4.0] -dec-5-ene;
7'-dodecylidene-di-1,5,7-triazabicyclo- [4.4.0] -dec-5-ene and the like, and aromatic amines such as N, N-dimethyl-4-aminopyridine 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-piperidinopyridine, 4-aminopyridine,
2-aminopyridine, 4-hydroxypyridine, 2-hydroxypyridine, 4-methoxypyridine, 2-methoxypyridine, imidazole, 2-methylimidazole,
4-methylimidazole, 2-methoxyimidazole,
Examples thereof include 2-mercaptoimidazole, aminoquinoline, and diazabicyclooctane (DABCO).

In the present invention, a metal salt, a quaternary phosphonium salt, a nitrogen-containing organic basic compound or the like may be used alone or in combination of two or more. In the present invention, 10 ^-8 to 10 per mol of the dihydroxy compound is used.
^-1 mol, preferably 10 ^-7 to 10 ^-2 mol, is desirably used. 10 ^-1 transesterification catalyst
Use in excess of the moles is not preferred because it not only leads to coloring and cost increase, but also causes a decrease in heat resistance and hydrolysis resistance. On the other hand, when the amount is less than 10 ^-8 mol, the catalytic activity becomes insufficient, and the branching effect may not be sufficiently exhibited.

Specific examples of the heating and melting apparatus used in the present invention include a single screw extruder, a co-direction twin screw extruder, a different direction twin screw extruder, a sheet extruder, a film extruder, and a heat extruder. Examples of the apparatus include a kneader, an injection molding machine, a blow molding machine, a heating and melting tank with a stirrer, a heating tank cascade with a stirrer, a thin layer evaporator, a liquid film evaporator, and a disk reactor. In particular, various extruders and various molding machines from which an intermediate product and a final product are obtained are most economically effective.

As a method of adding the branching agent, it may be added in advance to a crushed product of a molded product such as a polycarbonate powder, a pellet, a sheet, or the like. You may. In addition, when the melting point of the branching agent is low, or other additives heated and supplied,
For example, it may be melt-injected from an upstream vent of an extruder, a kneader, or a molding machine together with a release agent, a lubricant and the like. In particular, it is also possible to prevent the adverse effect of the catalyst by pre-mixing or press-fitting from the upstream vent port and then pressurizing the transesterification catalyst deactivator at the downstream vent port side using a multi-vented device. In any case, in order to maintain a uniform product and an operating state, it is necessary to supply the extruder and the extruder at a place where uniform mixing is possible in a molding machine.

The transesterification agent in the present invention can be previously mixed or quantitatively supplied to a polycarbonate product to be branched by a master batch or the like while the solid is in a powder state as a solid,
It can also be melt-pressed into a plasticizing kneading section of a processing and molding apparatus. The branching agent and the ester exchange agent may be mixed at the same time, or may be separately compounded or press-fitted.

The linear polycarbonate resin used in the method of the present invention may be prepared by any method, for example, by reacting a bisphenol compound with phosgene in the presence of an organic solvent and an aqueous alkali solution. Polycarbonate resin (interfacial polymerization method), a polycarbonate resin obtained by polymerizing a bisphenol compound and phosgene in the presence of pyridine or a tertiary amine (solution method), a transesterification reaction between a bisphenol compound and diphenyl carbonate in the presence of a transesterification catalyst ( A transesterification method).

The polycarbonate resin referred to herein is:
Viscosity average molecular weight of 15,000 to 50,000, such as aromatic homo- or co-polycarbonate resin using a normal bisphenol compound, and those branched to some extent in advance or those having a long-chain alkyl group introduced at the terminal.
0. In the production method of these polycarbonate resins, a polycarbonate resin having a carbon-carbon unsaturated double bond or other graftable point is produced as a terminal stopper or a comonomer, and a resin obtained by grafting polystyrene or the like, or a phenol-based material such as polystyrene is used. A compound obtained by copolymerizing a hydroxyl group and another compound having a graft polymerization start point of a polycarbonate resin may be used, and a compound obtained by graft-polymerizing a polycarbonate resin thereto may be used. The present invention can be used in any of these.

As the bisphenol compound used as the raw material for the linear polycarbonate resin of the present invention, specifically, bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3- Chloro-4-hydroxyphenyl) methane, bis (3,5-dibro-4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 1,
1-bis (2-t-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-t-butyl-
4-Hydroxy-5-methylphenyl) ethane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane , Bisphenol A
Abbreviated. ), 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane (hereinafter abbreviated as TBA), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,
5-dibromophenyl) propane, 2,2-bis (4-
(Hydroxy-3,5-dichlorophenyl) propane,
2,2-bis (4-hydroxy-3,5-difluorophenyl) propane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3-chlorophenyl)
Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-
3-fluorophenyl) propane, 2,2-bis (4-
(Hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) octane, 2,2
-Bis (4-hydroxyphenyl) phenylmethane,
2,2-bis (4-hydroxy-1-methylphenyl)
Propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4 -Hydroxy-3,5
-Dibromophenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (4 -Hydroxyphenyl) butane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenylbutane, 1,1-bis (2-t
-Butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-t-butyl-4-hydroxy-
5-methylphenyl) isobutane, 1,1-bis (2-
t-amyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) butane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) ) Butane, 4,4-bis (4
-Hydroxyphenyl) heptane, 1,1-bis (2-
bis (hydroxyaryl) alkanes such as t-butyl-4-hydroxy-5-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane and 1,1-bis (4-hydroxyphenyl) ethane; 1,1
-Bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter abbreviated as bisphenol Z), 1,1-
Bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-
Phenyl-4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5,5
Bis (4-hydroxyphenyl) cycloalkanes such as -trimethylcyclohexane; 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3 '
-Dimethylbiphenyl, 4,4'-dihydroxy-3,
Dihydroxybiphenyls such as 3'-dicyclohexylbiphenyl; bis (hydroxyaryl) ethers such as bis (4-hydroxyphenyl) ether and bis (4-hydroxy-3-methylphenyl) ether; bis (4-hydroxyphenyl) ) Sulfones, bis (hydroxyaryl) sulfones such as bis (3-methyl-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-
Bis (hydroxyaryl) sulfoxides such as hydroxyphenyl) sulfoxide and bis (3-phenyl-4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) sulfide, bis (3-methyl4
Bis (hydroxyaryl) sulfides such as -hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) ketone; phenol-modified siloxanes at both ends; phenol-modified silanes at both ends; and the like. These may be used in combination of two or more. Among them, bisphenol A, bisphenol Z, TB
Those selected from A are preferred.

Examples of the terminal terminator or molecular weight regulator used in the interfacial polymerization method or the solution method include compounds having a monovalent phenolic hydroxyl group.
Tert-butylphenol, p-cumylphenol, p-phenylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-di-
Other than cumylphenol, 3,5-di-cumylphenol tribromophenol, etc., p-octylphenol, p
-Long-chain alkylphenols including dodecylphenol, phenol-modified siloxane at one end, silane-modified phenol at one end, and other aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, aromatic carboxylic acids, aromatic acid chlorides, hydroxy acids Alkyl benzoate,
Alkyl ether phenol and the like.

Further, a terminal terminator having a reactive double bond may be used. In this case, acrylic acid, vinyl acetic acid, 2-pentenoic acid, 3-pentenoic acid, 5-hexenoic acid, 9-hexenoic acid, Unsaturated carboxylic acids such as undecenoic acid; acid chlorides or chloroformates such as acrylic acid chloride, sorbic acid chloride, allyl alcohol chloroformate, isopropenylphenol chloroformate or hydroxystyrene chloroformate; isopropenylphenol, hydroxy Examples include phenols having an unsaturated group such as styrene, hydroxyphenylmaleimide, allyl hydroxybenzoate or methyl allyl hydroxybenzoate. These compounds can be used in combination with the above-mentioned terminal terminators.

The terminating agent or the molecular weight regulator is usually used in an amount of 1 mole per 1 mole of the above-mentioned dihydric phenol compound.
２５25 mol%, preferably 1.5 to 10 mol%.

Solvents used in the interfacial polymerization method and the solution method include halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, toluene, chlorobenzene, 1,1,1-trichloroethane and the like for the polymerization reaction of polycarbonate resin and the like. It is exemplified as a good solvent to be used, and dichloromethane is particularly preferred.

On the other hand, examples of the carbonate source used in the transesterification method include diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, methyl phenyl carbonate, ethyl phenyl carbonate, propyl phenyl carbonate, butyl phenyl carbonate and the like. Particularly, diphenyl carbonate is preferred.

The conditions for processing and molding can be carried out within the temperature range in which the polycarbonate product used as a raw material is plasticized and molded. It is desirable to adjust. Generally, the flowability is slightly changed by branching, so that the processing and molding conditions need to be adjusted in a moderate direction.

In the present invention, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a weathering agent, an antistatic agent, a plasticizer, a coloring agent, a concealing agent, a filler including glass fiber, carbon fiber and the like may be used. Agents, reinforcing agents, mold release agents, flame retardants, heat ray shielding agents,
Dyes and pigments, fluorescent agents, rubbers, elastomers, other resins, and the like may be compounded before heat plasticization, or may be compounded or mixed with a fixed-quantity feeder or a press-fit pump during heat plasticization or molding.

[0037]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples, the viscosity average molecular weight M
v is the intrinsic viscosity η obtained by measuring a 0.5 g / dl methylene chloride solution at 20 ° C. using an Ubbelohde viscometer.
From sp, it was calculated using the following equation. η _SP /C=[η](1+0.28η _SP ), C = 0.5 [η] = 1.23 × 10 ⁻⁴ Mv ^0.83

A flow tester (manufactured by Shimadzu Corporation: Model CFT-500C) was used as a measure of molding fluidity.
The flow value (Q value) at 0 ° C and 160 kgf is 280
The structural viscosity index (N value) was calculated from the flow values at 160 ° C., 100 kgf, and 40 kgf by the following equation. Q = K × P ^N

The phenolic OH is obtained by dissolving a polycarbonate resin in anhydrous dichloromethane, adding a solution of titanium tetrachloride in anhydrous dichloromethane, and reacting the titanium tetrachloride with the phenolic OH to form a reddish-brown color using a spectrophotometer (Shimadzu Corporation) (Model UV-1200 manufactured by K.K.). In the present invention, the phenolic OH is determined by the weight pp of phenol group by a calibration curve prepared based on bis (4-hydroxyphenyl) propane.
Quantify as m.

The draw-down property was as follows: pellets dried at 120 ° C. for 8 hours were extruded from a 30 mm extruder (Nakatani Co., Ltd.).
(VSK-30 type, die nozzle 4 mmφ), extruding at an extrusion temperature of 280 ° C. and a screw rotation speed of 25 rpm, cutting the hanging strand, obtaining the characteristic curve shown in FIG. 1 from the length and weight, and calculating the origin from this curve. Is drawn, and an intersection W2 between the weight W1 obtained from the measurement curve for the strand length L (300 mm) and the tangent is drawn.
The drawdown rate Rd (%) was calculated from the following equation. Drawdown rate Rd (%) = [(W2-W1) / W2]
× 100

Example 1 Polycarbonate resin powder and E-2000 powder obtained by an interfacial polymerization method using dichloromethane as a solvent [manufactured by Mitsubishi Gas Chemical Co., Ltd., viscosity average molecular weight (hereinafter abbreviated as Mv value): 2.8] × 10 ⁴ , structural viscosity index (hereinafter abbreviated as N value): 1.2, phenolic OH group: 132 ppm] 2
To 0 kg, 0.5 mol% of 1,1,1-tri (4-hydroxyphenyl) ethane and 150 ppm of sodium di (4-t-butylphenyl) phosphate were blended for 20 minutes using a V-type tumbler. The mixture, 50mmφ,
Using a vented single screw extruder with L / D = 32, 320 ° C.
Extruded with. The drawdown property measured for the obtained strand was 32.7%, and the structural viscosity index N value measured for the pellet was 1.8.

Example 2 Polycarbonate resin pellets obtained by a transesterification method [Mv value: 2.4 × 1 manufactured by Mitsubishi Gas Chemical Co., Ltd.]
0 ^4, N values: 1.2, phenolic OH groups: 235pp
m] To 20 kg, 0.5 mol% of 1,1,1-tri (4-hydroxyphenyl) ethane and 200 ppm of sodium 2,2-methylenebis (4,6-di-t-butylphenyl) phosphate were added to a V-type tumbler. For 20 minutes. The mixture was extruded at 320 ° C. using a vented single screw extruder with 50 mmφ and L / D = 32. The drawdown property of the obtained strand was 47.
The structural viscosity index N value measured for 6% of the pellets was 1.7.

Example 3 A polycarbonate resin powder obtained by an interfacial polymerization method using dichloromethane as a solvent, E-2000 [manufactured by Mitsubishi Gas Chemical Co., Ltd., Mv value: 2.9 × 10 ⁴ , N value: 1.
2] To 20 kg, 0.5 mol% of 1,1,1-tri (4-hydroxyphenyl) ethane and 100 ppm of tetraphenylphosphonium tetraphenylborate were blended for 20 minutes using a V-type tumbler. Using a direct injection molding machine (M140-SJ type, manufactured by Meiki Seisakusho Co., Ltd.),
As a result of molding 100 sheets of 100 mm × 100 mm × 150 mm, the resulting molded product was cut out with a saw and the N value was measured.

Example 4 Polycarbonate resin powder and E-1000 pellets obtained by an interfacial polymerization method using dichloromethane as a solvent [manufactured by Mitsubishi Gas Chemical Co., Ltd., Mv value: 3.2 × 104, N
Value: 1.3] To 20 kg, 0.5 mol% of 1,1,1-tri (4-hydroxyphenyl) ethane and 100 ppm of tetraphenylphosphonium tetraphenylborate were added.
It was blended in a V-type tumbler for 20 minutes. The mixture is
Extruded at 340 ° C. using a vented single screw extruder with 0 mmφ and L / D = 32. The pellets were extruded at 320 ° C. using a sheet forming machine (50 mmφ, L / D = 32 vented single-screw extruder), and were 500 mm wide × 1 mm thick.
Was formed. The obtained sheet was cut out with a saw and the N value was measured. As a result, it was 1.8.

Example 5 Polycarbonate resin powder, E-1000 (manufactured by Mitsubishi Gas Chemical Co., Ltd., Mv value: 3.2 × 10 ⁴ , N value: 1.) obtained by an interfacial polymerization method using dichloromethane as a solvent.
2) 0.5 mol% of α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and 100 ppm of tetraphenylphosphonium tetraphenylborate were added to 20 kg with a V-type tumbler. 20
Minutes. The mixture is fed to a sheet forming machine (50 mmφ,
L / D = 32 vented single screw extruder)
The sheet was extruded at 500 ° C. to form a sheet having a width of 500 mm and a thickness of 1 mm. The obtained sheet was cut out with a saw and the N value was measured. As a result, it was 1.8.

Comparative Example 1 The same polycarbonate resin 20 used in Example 1
150 kg of sodium di (4-t-butylphenyl) phosphate was added to the kg by a V-type tumbler for 20 minutes. The mixture was extruded at 320 ° C. with a vented single screw extruder having a diameter of 50 mmφ and L / D = 32. The drawdown property measured on the obtained strand was 54.8.
%, The structural viscosity index N value measured for the pellets is 1.
It was one.

Comparative Example 2 0.5 mol% of 1,1,1-tri (4-hydroxyphenyl) ethane was added to 20 kg of the same polycarbonate resin pellets used in Example 2 using a V-type tumbler.
0 minutes. The mixture was made 50 mmφ, L / D = 3
The mixture was extruded at 320 ° C. using a vented single screw extruder.
The drawdown property of the obtained strand was 62.1%, and the structural viscosity index N of the pellet was measured.
The value was 1.2.

Comparative Example 3 To 20 kg of the same polycarbonate resin powder used in Example 3, 100 ppm of tetraphenylphosphonium tetraphenylborate was blended for 20 minutes using a V-type tumbler. Using a direct injection molding machine (M140-SJ type, manufactured by Meiki Seisakusho Co., Ltd.), the mixture was 3 mm thick and 100 mm long.
100 sheets of mm × 150 mm width were formed. The obtained molded product was cut out with a saw and the N value was measured. As a result, it was 1.1.

Comparative Example 4 To 20 kg of the same polycarbonate resin powder used in Example 4, 100 ppm of tetraphenylphosphonium tetraphenylborate was blended for 20 minutes using a V-type tumbler. The mixture was extruded at 340 ° C. with a vented single screw extruder having a diameter of 50 mmφ and L / D = 32. The pellets were extruded at 320 ° C. using a sheet forming machine (50 mmφ, L / D = 32 vented single screw extruder),
A sheet having a width of 500 mm and a thickness of 1 mm was formed. The obtained sheet was cut out with a saw and the N value was measured. As a result, it was 1.2.

Comparative Example 5 0.5 kg of α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene was added to 20 kg of the same polycarbonate resin pellets used in Example 5. % Was blended in a V-type tumbler for 20 minutes, and the mixture was mixed with a sheet forming machine (50 mmφ, L / D =
(A single screw extruder with 32 vents) at 320 ° C. to form a sheet having a width of 500 mm and a thickness of 1 mm. The resulting sheet was cut out with a saw and the N value was measured.
It was one.

Comparative Example 6 Polycarbonate resin pellets obtained by the transesterification method [Mitsubishi Gas Chemical Co., Ltd., Mv value: 2.4 × 10
4, N value: 1.2, phenolic OH group 3650 pp
m] To 20 kg, 0.5 mol% of 1,1,1-tri (4-hydroxyphenyl) ethane and 200 ppm of sodium 2,2-methylenebis (4,6-di-t-butylphenyl) phosphate were added to a V-type tumbler. For 20 minutes. The mixture was extruded at 320 ° C. with a vented single screw extruder having a diameter of 50 mmφ and L / D = 32. The drawdown property measured for the obtained strand was 56.4.
%, The structural viscosity index N value measured for the pellets is 1.
It was one.

[0052]

According to the production method of the present invention, a branched polycarbonate resin suitable for a flame-retardant material, a blow molding material, and the like, including an optical disk molding material having excellent molding characteristics, is usually produced. Can be easily manufactured using extruders, injection molding machines, sheet molding machines, and other molding equipment, using raw polycarbonate resin products as raw materials. Burden can be greatly reduced.

[Brief description of the drawings]

FIG. 1 is a diagram for measuring a drawdown property.

Claims (9)

[Claims] 1. A method for producing a branched polycarbonate resin, comprising heating, melting and kneading a polycarbonate resin mixture obtained by adding a branching agent and a transesterification catalyst to a linear polycarbonate resin. 2. The method for producing a branched polycarbonate resin according to claim 1, wherein a linear polycarbonate resin having a structural viscosity index N value of 1.1 to 1.4 is used. 3. The linear polycarbonate resin has a viscosity average molecular weight (Mv) of 15,000 to 50,000, and the mole% of the branching agent with respect to the bisphenol compound constituting the repeating unit of the polycarbonate resin is:
The method for producing a branched polycarbonate resin according to claim 1, wherein the ratio is 0.1 to 2.0. 4. The method for producing a branched polycarbonate resin according to claim 1, wherein the phenolic OH group contained in the starting polycarbonate resin is 2000 ppm or less. 5. The method for producing a branched polycarbonate resin according to claim 1, wherein an apparatus selected from an extruder, an injection molding machine, a sheet molding machine, a film molding machine, and a blow molding machine is used as an apparatus for heating, melting and kneading. 6. From 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane The method for producing a branched polycarbonate resin according to claim 1, which is a linear polycarbonate resin produced from at least one selected monomer. 7. As a branching agent, phloroglysin, 2,
6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-2,1,1,1-
Tri (4-hydroxyphenyl) ethane, α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 3,3-bis (4-hydroxyphenyl) oxindole (= At least one selected from isatin bisphenol) and isatin bis (o-cresol)
The method for producing a branched polycarbonate resin according to claim 1, wherein a kind of compound is used. 8. The heating and melting temperature is 270 ° C. to 370 ° C.
The method for producing a branched polycarbonate resin according to claim 1, wherein 9. A molded product obtained by heating and melting and kneading a polycarbonate resin mixture obtained by adding a branching agent and a transesterification catalyst to a linear polycarbonate resin, and molding the branched polycarbonate resin.