JP2005097540A - Aromatic polycarbonate, method for producing the same, aromatic polycarbonate composition, hollow vessel made thereof and extrusion molded article produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate having excellent hue while keeping the molding characteristics. <P>SOLUTION: The aromatic polycarbonate having a viscosity-average molecular weight of ≥16,000 is produced by the transesterification reaction of a carbonic acid diester and an aromatic dihydroxy compound. The Mw/Mn ratio of the standard polystyrene equivalent weight-average molecular weight (Mw) measured by gel permeation chromatography to the number-average molecular weight (Mn) is ≥2.8 and ≤4.5 and the value (swell ratio) calculated by dividing the cross-section area of a strand extruded by a melt-index measurement at 280°C by applying 11 kg load on a molten resin by the cross-section area of an orifice is ≥1.2 and ≤4.0. The invention further provides an aromatic polycarbonate composition, a hollow vessel produced by using the composition and an extrusion molded article of the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an aromatic polycarbonate having excellent quality, a method for producing the same, a polycarbonate composition, a hollow container using the same, and a molded product obtained by extrusion molding the composition. More specifically, the molding properties are improved and the hue is even better, so extrusion processing and injection molding, especially water by blow molding that requires materials with high melt strength and excellent shape retention properties of the extrudate. The present invention relates to a molded product that is suitable for use in a bottle, extrusion of a different shape, twin wall sheet or multi-wall sheet.

  As a method for producing polycarbonate (hereinafter referred to as PC), a method of directly reacting an aromatic dihydroxy compound such as bisphenol and phosgene (interface method), or an aromatic dihydroxy compound such as bisphenol and a carbonic acid diester such as diphenyl carbonate; A method (transesterification method or melting method) in which a transesterification reaction is carried out in a molten state is known. Of the PCs obtained by such a method, linear PCs generally have room for improvement in molding characteristics such as melt elasticity and melt strength. As a method for improving such molding characteristics, a polyfunctional organic compound is commonly used. A method of branching PC by polymerizing has been proposed (for example, see Patent Documents 1 to 3).

Originally, when branching is to be introduced, the amount of branching agent should be determined in order to keep the melt flowability (MVR), flow characteristics (MVR-Ratio) and mechanical properties within an appropriate range. The relationship between the amount of the branching agent and the amount of the branching agent is complicated when the molecular weight is included, so the actual range is to determine the appropriate range while measuring the characteristics of the product with a certain amount of the branching agent introduced. It was. In addition, when such a branched PC is produced by the above melting method using a branching agent conventionally used in the interfacial method, the resulting branched PC causes the decomposition of the branching agent at a high temperature. The target molding characteristics cannot be obtained, and the hue deteriorates, resulting in a satisfactory product (for example, see Patent Documents 4 to 7).
Japanese Patent Publication No. 44-17149 Japanese Patent Publication No.47-23918 Japanese Patent Publication No. 60-11733 Japanese Patent Laid-Open No. 4-89824 JP-A-6-136112 Japanese Patent Publication No. 7-37517 Japanese Patent Publication No.7-116285

  The present invention relates to an aromatic polycarbonate having excellent quality, a method for producing the same, a polycarbonate composition, a hollow container using the same, and a molded product obtained by extrusion molding the composition. More particularly, the molding properties are improved and the hue is even better, so extrusion processing and injection molding, especially blow molding water that requires materials with high melt strength and excellent shape retention properties of the extrudate. The purpose of the present invention is to provide a molded product that is suitable for use of a bottle, extrusion of a different shape, twin wall sheet or multi-wall sheet.

The inventors of the present invention have intensively studied to provide an aromatic polycarbonate having a good color tone while maintaining molding characteristics. As a result, the main chain contains a specific amount of a specific structural unit, and the swell ratio is specific. It has been found that the aromatic polycarbonate in the range has improved molding characteristics and further excellent hue, and has completed the present invention.

That is, the gist of the present invention is an aromatic polycarbonate having a viscosity average molecular weight of 16,000 or more obtained by a transesterification method, and a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography and a number average. When the ratio (Mw / Mn) to the molecular weight (Mn) is in the range of 2.8 to 4.5 and the melt index is measured at 280 ° C., an extrusion of 11 kg is applied to the molten resin. A value obtained by dividing the obtained cross-sectional area of the strand by the cross-sectional area of the orifice (hereinafter referred to as swell ratio) is in the range of 1.2 or more and 4.0 or less.

  Another aspect of the present invention is that when the aromatic polycarbonate is produced, an alkali metal compound and / or an alkaline earth metal having a metal amount of 1.1 to 5 μm per 1 mol of the aromatic dihydroxy compound. The present invention resides in a method for producing an aromatic polycarbonate characterized by using a compound.

Hereinafter, the present invention will be specifically described.
Production Method of Aromatic Polycarbonate The aromatic polycarbonate of the present invention may substantially contain polyester carbonate or polyarylate, using an aromatic dihydroxy compound and carbonic acid diester as raw materials, and in the presence of a transesterification catalyst, It can be obtained by a transesterification reaction (melt polycondensation reaction).
Carbonic acid diester The carbonic acid diester used in the present invention is represented by the following general formula.

O
‖
A-O-C-O-A '

(In the above formula, A and A ′ are an aliphatic group or substituted aliphatic group having 1 to 18 carbon atoms, or an aromatic group or substituted aromatic group, and A and A ′ are the same or different. May be.)
Examples of the carbonic acid diester represented by the above general formula include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, substituted diphenyl carbonates such as diphenyl carbonate, and ditolyl carbonate. Diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. These carbonic acid diesters may be used alone or in combination of two or more.
Further, together with the carbonic acid diester as described above, dicarboxylic acid or dicarboxylic acid ester may be used preferably in an amount of 50 mol% or less, more preferably 40 mol% or less. Examples of such dicarboxylic acid or dicarboxylic acid ester include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When such a dicarboxylic acid or dicarboxylic acid ester is used in combination with a carbonic acid diester, a polyester carbonate is obtained.
Aromatic dihydroxy compound The aromatic dihydroxy compound used in the present invention is usually represented by the following formula (2).

(In Formula (2), X is a single bond, a C1-C8 alkylene group, a C2-C8 alkylidene group, a C5-C15 cycloalkylene group, and a C5-C15 cycloalkylidene group. Or, it is selected from the group consisting of divalent groups represented by —O—, —S—, —CO—, —SO—, —SO ₂ —.)
Examples of the aromatic dihydroxy compound represented by the above formula (2) include 2,2-bis (4-hydroxyphenyl) propane (also referred to as “bisphenol A”), bis (4-hydroxyphenyl) sulfone, and bis ( 4-Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like are exemplified, and bisphenol A is particularly preferable. These aromatic dihydroxy compounds may be used alone or as a mixture of two or more.

  In order to produce an aromatic polycarbonate in the present invention, bisphenol A is usually used as the aromatic dihydroxy compound, and diphenyl carbonate is used as the carbonic acid diester, but the diphenyl carbonate is 1.01-1 with respect to 1 mol of bisphenol A. It is preferably used in an amount of .30 mol, preferably 1.02 to 1.20. When the molar ratio is smaller than 1.01, the terminal OH group of the produced aromatic polycarbonate is increased, and the thermal stability of the polymer is deteriorated. When the molar ratio is larger than 1.30, under the same conditions, The rate of the transesterification reaction decreases, making it difficult to produce an aromatic polycarbonate resin having the desired molecular weight, as well as increasing the amount of residual carbonate diester in the produced aromatic polycarbonate. Or undesirably causing odor of the molded product.

Transesterification Catalyst In the present invention, an alkali metal compound and / or an alkaline earth metal compound is used as the transesterification catalyst, and supplementarily a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound. It is also possible to use a basic compound such as, but it is particularly preferable that an alkali metal compound and / or an alkaline earth metal compound is used alone.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, carbonate Cesium, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, Sodium phenyl borohydride, potassium potassium phenide, lithium phenyl phenide, cesium phenyl phenide, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 hydrogen phosphates Lithium, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, and cesium salt.

Examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples thereof include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

Specific examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributyl. Sodium salts such as benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron, butyl triphenyl boron, sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, strontium salts, etc. Can be mentioned.
Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydrode Sid, butyl triphenyl ammonium hydroxide, and the like.
Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

  In order to obtain an aromatic polycarbonate excellent in molding characteristics and hue of the present application, the amount of the transesterification catalyst is, as an amount of metal, based on 1 mol of bisphenol A when an alkali metal compound and / or an alkaline earth metal compound is used. It is used within the range of 1.1 to 5 μmol, preferably within the range of 1.2 to 5 μmol, more preferably within the range of 1.3 to 4 μmol, and particularly preferably 1.3 to 3 μm. Within the range of 8 μmol. If the amount is less than the above lower limit, the amount of branching component that provides the polymerization activity and molding characteristics necessary for producing a polycarbonate having a desired molecular weight cannot be obtained. If the amount exceeds this amount, the polymer hue deteriorates and the amount of branching component Is too much, the fluidity is lowered, and an aromatic polycarbonate excellent in target molding characteristics cannot be produced.

The transesterification reaction is generally carried out in a multistage process having two or more stages. Specifically, the first stage reaction is carried out at a temperature of 140 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 10 hours, preferably 0.5 to 3 hours. The reaction temperature is gradually raised while gradually reducing the pressure of the reaction system, and finally the polycondensation reaction is performed at a temperature of 240 to 320 ° C. under a reduced pressure of 200 Pa or less. Here, the final polymerization tank is preferably a horizontal type, and the reaction temperature of the horizontal final polymerization tank is preferably in the range of 280 to 300 ° C, more preferably in the range of 281 to 299 ° C. .
Further, the residence time of the final horizontal polymerization tank is preferably in the range of 50 to 140 minutes, and more preferably in the range of 60 to 130 minutes. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type, but the continuous type is particularly preferred.

Aromatic polycarbonate The aromatic polycarbonate of the present invention needs to have a viscosity average molecular weight of 16,000 or more, preferably 20,000 or more, and more preferably 21,000 or more. Those having a viscosity average molecular weight of less than 16,000 are not preferable because mechanical strength such as impact resistance is lowered.
In addition, the amount of terminal OH groups of the aromatic polycarbonate has a great influence on the thermal stability, hydrolysis resistance, hue, etc. of the product, and in order to maintain practical physical properties, , In the range of 100 to 1,500 ppm, preferably in the range of 150 to 1,200 ppm, and more preferably in the range of 200 to 1,000 ppm. If the terminal OH amount is 100 ppm or less, the amount of carbonic acid diester compound in the polycarbonate immediately after polymerization is large, and it is difficult to reduce the amount of carbonic acid diester compound to 200 ppm by weight or less by devolatilization.

The aromatic polycarbonate of the present invention is an aromatic polycarbonate having a viscosity average molecular weight of 16,000 or more obtained by a transesterification method, and further has a polystyrene-reduced weight average molecular weight (Mw) and number measured by gel permeation chromatography. One of the characteristics is that the ratio (Mw / Mn) to the average molecular weight (Mn) needs to be in the range of 2.8 to 4.5.
In the production method of the transesterification method (melting method) of polycarbonate, it has been conventionally known that the formulas (3) and (4) are produced by simultaneously carrying out the rearrangement reaction in the polymerization reaction system (for example, Encyclopedia of Polymer Science and Technology, vol.10, p.723 (1969) On the other hand, structural units of formula (5) and / or formula (6) are produced when polycarbonate is produced by the melting method under specific reaction conditions. Although the generation process of the structural units of the formulas (5) and (6) is not necessarily clear, it is assumed that they are generated through the following route.
When these structural units are formed, the ratio of the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) measured by gel permeation chromatography of an aromatic polycarbonate is a normal linear aromatic polycarbonate. It is necessary for the value to be within the specific range.

  Further, in the melt index measurement at 280 ° C., the value obtained by dividing the cross-sectional area of the extruded strand when the load of 11 kg is applied to the molten resin by the cross-sectional area of the orifice (hereinafter referred to as swell ratio) is 1.2 or more. It must be in a specific range of 4.0 or less.

It has been found that if a specific relationship between the two elements is satisfied, an aromatic polycarbonate having an excellent moldability and a good hue not found in the prior art can be obtained. A preferred range of the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography is within the range of 2.8 to 4.0. More preferably, it is in the range of 2.8 or more and 3.8 or less. Moreover, as a preferable range of the said swell ratio, it exists in the range of 1.4 or more and 3.5 or less, More preferably, it exists in the range of 1.4-3.0.
When the relationship between the swell ratio and the ratio (Mw / Mn) of the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) measured by gel permeation chromatography is smaller than the above range, melting during molding No tension can be obtained, and it is impossible to produce an aromatic polycarbonate with excellent target molding characteristics. If it is larger than the above range, the melt tension at the time of molding is too large and the fluidity is poor, and the target molding characteristics It is not possible to produce an excellent aromatic polycarbonate.

The aromatic polycarbonate of the present invention preferably has a flow rate ratio (MVR-R) represented by the following formula (7) in the range of 15 to 30, based on JIS K 7210, and more preferably MVR- R is in the range of 16-28. When MVR-R is smaller than the above range, melt tension cannot be obtained, and an aromatic polycarbonate excellent in target molding characteristics cannot be produced. On the other hand, if it is larger than the above range, the melt tension at the time of molding is too high, the fluidity is inferior, and an aromatic polycarbonate with excellent target molding characteristics cannot be produced.
MVR-R = MVR (21.6) / MVR (2.16) (7)

  The aromatic polycarbonate of the present invention has a melt tension of 30 to 30 measured at 250 ° C. using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.) with an extrusion speed of 10 mm / min and a take-up speed of 20 mm / min. The range is preferably 150 mN, and more preferably the melt tension is in the range of 40 to 130 mN. If the melt tension is smaller than the above range, the resin cannot maintain its shape, and an aromatic polycarbonate excellent in blow moldability cannot be produced. On the other hand, if it is larger than the above range, the melt tension is too large, the fluidity is inferior, and an aromatic polycarbonate excellent in target molding characteristics cannot be produced.

In the aromatic polycarbonate produced by the transesterification method of the present invention, raw material monomers, catalysts, and low molecular weight compounds such as aromatic monohydroxy compounds and polycarbonate oligomers by-produced by the transesterification reaction usually remain. Among these, the raw material monomer and the aromatic monohydroxy compound have a large residual amount, which adversely affects physical properties such as heat aging resistance and hydrolysis resistance. From such a viewpoint, in the aromatic polycarbonate of the present invention, the residual amount of the aromatic dihydroxy compound is preferably 300 ppm by weight or less, and the aromatic monohydroxy compound is preferably 300 ppm by weight or less. Further, among the raw material monomers, the carbonic acid diester compound has an odor remaining in the hollow container by melt molding or blow molding, and this odor becomes a problem particularly when used for food applications. Therefore, the residual amount of the carbonic acid diester compound in the polycarbonate is preferable. Needs to be removed so as to be 200 ppm by weight or less, more preferably 100 ppm by weight or less, and most preferably 60 ppm by weight.

Transesterification method There is no particular limitation on the method of reducing the residual amount of raw material monomer and aromatic monohydroxy compound in the polycarbonate. For example, after polymerization, by continuously devolatilizing with a vent type extruder, the transesterification method A method of removing the residual carbonic acid diester compound and the like in the polycarbonate and a method of heat-treating the obtained pellets under reduced pressure are possible. Among these methods, when devolatilizing continuously with a vent-type extruder, the basic transesterification catalyst remaining in the resin is previously deactivated by adding an acidic compound or a precursor thereof. By doing so, side reactions during devolatilization can be suppressed, and the aromatic dihydro compound, carbonic acid diester compound, and aromatic monohydroxy compound, which are raw material monomers, can be efficiently removed.

  There is no restriction | limiting in particular in the acidic compound to add, or its precursor, As long as it has an effect which neutralizes the basic transesterification catalyst used for a polycondensation reaction, all can be used. Specifically, hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid, Formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid, picrine Examples thereof include Bronsted acids such as acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof. These may be used alone or in combination of two or more. Of these acidic compounds or precursors thereof, sulfonic acid compounds or ester compounds thereof, such as p-toluenesulfonic acid, methyl p-toluenesulfonate, butyl p-toluenesulfonate, and the like are particularly preferable.

The addition amount of these acidic compounds or precursors thereof is 0.1 to 50 times mol, preferably 0.5 to 40 times mol, of the neutralization amount of the basic transesterification catalyst used in the polycondensation reaction. Add in range. The timing of adding the acidic compound or its precursor may be any time after the polycondensation reaction, and there is no particular limitation on the addition method, depending on the properties of the acidic compound or its precursor and the desired conditions, Any method such as a method of adding directly, a method of adding by dissolving in an appropriate solvent, a method of using a pellet or a flaky master batch may be used.

  The extruder used for the devolatilization of low molecular weight compounds such as a carbonic acid diester compound may be uniaxial or biaxial. The twin screw extruder is a meshing type twin screw extruder, and the rotation direction may be the same direction or different direction. For the purpose of devolatilization, those having a vent part after the acidic compound addition part are preferred. The number of vents is not limited, but usually a multistage vent of 2 to 10 stages is used. Moreover, in this extruder, additives, such as a stabilizer, a ultraviolet absorber, a mold release agent, and a coloring agent, can be added and knead | mixed with resin as needed.

  Moreover, the aromatic polycarbonate of this invention can add a coloring agent for the purpose of coloring the molded article. Although there is no restriction | limiting in particular as a coloring agent, The effect by which 1 or more types of dye and pigment type coloring agents chosen from phthalocyanine blue and anthraquinone type dye improve the odor by the residual carbonic acid diester in branched polycarbonate, and a molded article The hydrolyzability, initial haze, and the like are favorable. Among the phthalocyanine blues, Pigment Blue 15: 3 (CI Generic Name) is preferable, and among the anthraquinone dyes, blue or violet dyes are preferable, and Solvent Blue 90, Solvent Blue 97, Solvent Violet 36, Solvent. Violet 13 (CI Generic Name each) is preferred. Of these, Pigment Blue 15: 3 (CI Generic Name) is most preferable. The blending amount of the colorant is not particularly limited as long as the molded product is colored to a desired hue, but is preferably 100 ppm by weight or less, more preferably 0.1 to 40 ppm by weight from the viewpoint of improving odor. More preferred is 30 ppm by weight or less. Even if the blending amount of the colorant exceeds 100 ppm by weight, the effect of reducing odor is small. The blending method and timing of the colorant to the transesterification polycarbonate are in accordance with the blending method and timing of the additive.

Aromatic polycarbonate composition The aromatic polycarbonate according to the present invention may be blended with at least one additive selected from a stabilizer, an ultraviolet absorber, a release agent and the like, if necessary. it can. There is no restriction | limiting in particular as such an additive, The thing normally used for the polycarbonate can be used.

Examples of the stabilizer include hindered phenol compounds, phosphorus compounds, sulfur compounds, epoxy compounds, hindered amine compounds, and the like. Among these, at least one kind of antioxidant selected from hindered phenol compounds and phosphorus compounds is preferably used.

  Specific examples of the hindered phenol compound include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate], 3, 9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5 , 5] undecane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] 3,5-di-tert-butyl-4- Droxybenzyl phosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylene Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, N, N′- And hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide). Among these, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 ′, 5′- t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl ] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred.

  The phosphorus compound is preferably a trivalent phosphorus compound. In particular, at least one ester in the phosphite ester is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms. It is preferably at least one selected from phosphites or tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphonite. Specific examples of phosphites include 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditri). Decyl phosphite-5-tert-butylphenyl) butane, trisnonylphenyl phosphite, dinonylphenyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4- Di-t-butylphenyl) pentaerythritol diphosphite, di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-ethylidene-bis (4,6-di) -T-butylphenyl) fluorinated phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) octylphos Phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, phosphite ester composed of monononylphenol and dinonylphenol, phosphite ester having hindered phenol represented by the above formula (3), etc. Can be mentioned.

  In the present invention, as the phosphorus compound, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphonite, or tris (2,4-di-t-butylphenyl) phosphite, 2 2,2'-methylene-bis (4,6-di-t-butylphenyl) octyl phosphite is preferred.

  The blending amount of the stabilizer is 1 part by weight or less, preferably 0.4 part by weight or less based on 100 parts by weight of the aromatic polycarbonate. When it exceeds 1 part by weight, there are problems such as deterioration of hydrolysis resistance. In addition, the blending ratio in the case of using a stabilizer in combination can be arbitrarily determined, and which to use or in combination is appropriately determined depending on the use of the polycarbonate or the like. For example, phosphorus compounds are generally highly effective in retention stability at high temperatures when molding polycarbonate, and heat stability during use of molded products, and phenolic compounds generally use polycarbonates such as heat aging as molded products. Highly effective in heat resistance during use. Moreover, the improvement effect of coloring property increases by using a phosphorus compound and a phenol compound together.

  Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as titanium oxide, cerium oxide, and zinc oxide. In the present invention, among these, organic ultraviolet absorbers are preferred, and in particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy]- Phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) It is preferably at least one selected from bis [4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester.

Specific examples of the benzotriazole compound include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], [methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol ] A condensate etc. can be mentioned.
Among these, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl are particularly preferable. ] -2H-benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (4 6-Diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazin-2-yl] -5- (octyloxy) phenol.

  The compounding quantity of a ultraviolet absorber is 10 weight part or less with respect to 100 weight part of polycarbonate, Preferably it is 1 weight part or less. If it exceeds 10 parts by weight, there is a problem such as mold contamination during injection molding. The ultraviolet absorber can be used alone or in combination.

As the release agent, aliphatic carboxylic acid, aliphatic carboxylic acid ester, number average molecular weight 200
˜15000 aliphatic hydrocarbon compounds and at least one compound selected from polysiloxane-based silicone oils. Among these, at least one selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters is preferably used.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellic acid, tetrariacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 40 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 40 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

  The compounding amount of the release agent is 5 parts by weight or less, preferably 1 part by weight or less with respect to 100 parts by weight of the polycarbonate. When it exceeds 5 parts by weight, there are problems such as degradation of hydrolysis resistance and mold contamination during injection molding. The release agent can be used alone or in combination.

  There are no particular restrictions on the addition timing and addition method of additives such as colorants and stabilizers, UV absorbers, mold release agents and the like according to the present invention. For example, the addition timing is a) during the polymerization reaction, b) polymerization. At the end of the reaction or c) after the catalyst used for the polymerization is deactivated with the catalyst deactivator, before the pelletization, and further during the kneading of the polycarbonate, etc., the polycarbonate can be added in the molten state, It can be kneaded with an extruder or the like after blending with a polycarbonate in a solid state such as powder. However, it is possible to add these additives either during a) during the polymerization reaction, b) at the end of the polymerization reaction, or c) after deactivation with the catalyst deactivator and before pelletization. It is preferable from the viewpoint of suppressing decomposition and suppressing coloring.

  As an addition method, additives such as a colorant and a stabilizer, an ultraviolet absorber, and a release agent can be directly mixed or kneaded with polycarbonate, but it is dissolved in a suitable solvent, or a small amount of polycarbonate or other resin. It can also be added as a high-concentration master batch prepared by the above method. When these compounds are used in combination, they may be added separately to the polycarbonate or simultaneously.

The present invention further includes other thermoplastic resins, flame retardants, impact resistance improvers, antistatic agents, slip agents, antiblocking agents, lubricants, antibacterial agents, as long as the object of the present invention is not impaired. A polycarbonate resin composition having desired physical properties to which additives such as a clouding agent, natural oil, synthetic oil, wax, organic filler, and inorganic filler are added is also an object.

  The hollow container obtained by blow molding according to the present invention can be molded by applying a generally known blow molding method such as injection blow or injection stretch blow in addition to direct blow. For example, in direct blow molding, polycarbonate pellets are supplied to a single-screw or twin-screw extruder with a cylinder set temperature of 240 to 270 ° C., melted and kneaded under screw shear, and a tube-shaped molten parison is passed through a nozzle. The food container is molded by extruding and then sandwiching it in a mold having a predetermined shape and set at 70 to 110 ° C., and blowing air or inert gas. Furthermore, in the case of a dairy product bottle, a soft drink bottle, or a water bottle, it can be molded by biaxial stretch blow molding disclosed in JP-A-6-122140, etc., in order to improve the gas barrier property of polycarbonate. It can also be molded by multilayer blow molding with polyethylene terephthalate or polyamide.

The size of the hollow container obtained by blow molding of the present invention is not particularly limited, but the thickness is preferably 0.1 to 7 mm, more preferably 0.2, from the viewpoint of strength and shape retention of the hollow container. -5 mm, most preferably 0.3-3 mm.
The hollow volume obtained by blow molding according to the present invention can be used for a wide variety of applications, but is preferably a dairy product bottle, a soft drink bottle, and a water bottle.

The polycarbonate for extrusion molding according to the present invention can be molded into a molded product by applying a known extrusion molding method such as ordinary sheet molding provided with a polishing roll, corrugated sheet or pipe molding, or profile extrusion such as twin wall. However, among these, it can be particularly suitably used for profile extrusion. For example, polycarbonate pellets are supplied to a single-screw or twin-screw extruder having a cylinder set temperature of 240 to 290 ° C., melted and kneaded under screw shear, and the molten resin is extruded in a fixed shape through a die head, and then has a predetermined shape. Then, it is molded by cooling with a former, a sizing die, a polishing roll or the like whose temperature is set to 20 to 110 ° C. and fixing the shape.
The polycarbonate for extrusion molding of the present invention is preferably used for a twin wall or a multi-walled multi-wall, and further has a surface layer having a thickness of, for example, about 0.01 to 1 mm by co-extrusion with the same resin or another material, a twin wall sheet Can also be molded and can be used for multilayer extrusion molding with polyethylene terephthalate or polyamide to improve the gas barrier properties of polycarbonate.

  The size of the extruded product of the present invention is not particularly limited, but the thickness of the extruded product is preferably 0.1 to 7 mm, more preferably 0.2 to 5 mm, from the viewpoint of strength and shape retention. Most preferably, it is 0.3-3 mm. When the molded product is a twin wall sheet or a multi-wall sheet, the product thickness is generally 2 to 50 mm.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
In the following Examples and Comparative Examples, bisphenol A used and the obtained aromatic polycarbonate were analyzed by the following measuring methods.
(1) Viscosity average molecular weight (Mv)
Using an Ubbelohde viscometer, the intrinsic viscosity [η] of an aromatic polycarbonate (sample) at 20 ° C. in methylene chloride was measured and determined from the following equation.
η _sp /C=〔ita〕×(1tasu0.28Ita _sp)
[Η] = 1.23 × 10 ⁻⁴ × (Mv) ^0.83
(Wherein η _sp is the specific viscosity measured at 20 ° C. for the methylene chloride solution of polycarbonate resin, and C is the concentration of this methylene chloride solution. As the methylene chloride solution, the concentration of polycarbonate resin is 0.6 g / dl. Use the ones.)

(2) Weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn
The analyzer used was HLC-8020 (manufactured by Tosoh Corporation), and the columns were filled with four columns (each of which was manufactured by TSK 5000HLX, 4000HLX, 3000HLX and 2000HLX (both manufactured by Tosoh Corporation)). A diameter of 7.8 mmφ and a length of 300 mm) was connected and used. Tetrahydrofuran was used as the eluent, and standard polystyrene (Molecular weight; 761 (Mw / Mn ≦ 1.14), 2,000 (Mw / Mn ≦ 1.20), 000 (Mw / Mn ≦ 1.06), 9,000 (Mw / Mn ≦ 1.04), 17,500 (Mw / Mn ≦ 1.03), 50,000 (Mw / Mn ≦ 1.03), It was prepared using 233,000 (Mw / Mn ≦ 1.05), 600,000 (Mw / Mn ≦ 1.05) and 900,000 (Mw / Mn ≦ 1.05).
The measurement calculated | required Mw and Mn in polystyrene conversion from the chart detected by the refractive index, and computed Mw / Mn.

(3) Swell ratio In melt index measurement at 280 ° C., a value obtained by dividing the cross-sectional area of the extruded strand when the load of 11 kg was applied to the molten resin by the cross-sectional area of the orifice.

(4) MVR-R
According to JIS K 7210, per unit time measured at 280 ° C. under a load of 21.6 kg for an aromatic polycarbonate (sample) dried at 130 ° C. for 5 hours using a melt indexer manufactured by Takara Industries Co., Ltd. Using the melt flow volume MVR (21.6) and the melt flow volume MVR (2.16) per unit time similarly measured at 280 ° C. and a load of 2.16 kg, the following formula was used.
MVR-R = MVR (21.6) / MVR (2.16)

(5) Hue (YI)
A molded article was obtained from an aromatic polycarbonate (sample) dried at 130 ° C. for 5 hours under the following conditions using an injection molding machine.
For a 100 mm × 100 mm × 3 mm thick press sheet injected at 360 ° C., the tristimulus value XYZ, which is the absolute value of the color, is measured with a color tester (SC-1-CH manufactured by Suga Test Instruments Co., Ltd.), and the following relationship The YI value, which is an index of yellowness, was calculated from the formula.
YI = (100 / Y) × (1.28 × X−1.06 × Z)
It shows that it colors, so that this YI value is large.

(6) Melt tension (mN)
Using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.), the sample dried at 130 ° C. for 5 hours was measured at 250 ° C. with an extrusion speed = 10 mm / min and a take-up speed = 20 mm / min.
(7) Quantitative determination of carbonic acid diester compound 1.25 g of polycarbonate was dissolved in 7 ml of methylene chloride and reprecipitated with 18 ml of acetone. After filtration, the filtrate was measured by reverse phase liquid chromatography. Reverse-phase liquid chromatography uses a mixed solvent consisting of 30% acetonitrile aqueous solution and acetonitrile as an eluent, and starts with a 30% acetonitrile aqueous solution / acetonitrile ratio starting from 100/0 and grading to 0/100 with a column temperature of 40 Measurement was performed at 0 ° C., and detection was performed using a UV detector with a wavelength of 219 nm (manufactured by Shimadzu Corporation, SPD-6A), and quantification was obtained by converting each peak area to a weight relative to the polymer weight from each calibration curve. .

(8) Quantification of terminal OH Colorimetric determination was performed by the titanium tetrachloride / acetic acid method (the method described in Makromol. Chem. 88 215 (1965)). The measured value was expressed in ppm unit weight of the terminal OH group with respect to the polycarbonate weight.

(9) Blow moldability About the sample dried at 130 degreeC for 5 hours, after supplying the resin fuse | melted at 250 degreeC with the extruder to a metal mold | die, 18L bottle was blow-molded and the moldability was confirmed.
(10) Pipe moldability test Using a 50 mm single-screw extruder, polycarbonate was extruded at a barrel temperature of 255 to 270 ° C. and a screw rotation speed: 41 rpm, and the die head portion had an outer diameter of 4.1 mm and an inner diameter of 3.8 mm. When performing profile extrusion into a cylindrical shape, the pipe take-up speed was changed, and the take-up speed range in which the pipe could be stably formed was examined.
(11) Twin Wall Sheet Molding Using a single-screw extruder, a twin wall having a product thickness of 6 mm was molded at a barrel temperature of 250 to 265 ° C., the molded product was bent by hand, and the presence or absence of cracks was confirmed.

[Example 1]
A melt prepared by mixing and preparing diphenyl carbonate and bisphenol A at a constant molar ratio (DPC / BPA = 1.040) under a nitrogen gas atmosphere at a flow rate of 88.7 kg / hour through a raw material introduction pipe, It was continuously provided in a first vertical stirring polymerization tank with a capacity of 100 L controlled at 220 ° C. and 1.33 × 10 ⁴ Pa, and was provided in the polymer discharge line at the bottom of the tank so that the average residence time was 60 minutes. The liquid level was kept constant while controlling the valve opening. In addition, simultaneously with the start of the supply of the above mixture, an aqueous cesium carbonate solution was continuously supplied as a catalyst at a ratio of 0.6 μmol (as a metal amount, 1.2 μmol with respect to 1 mol of bisphenol A) with respect to 1 mol of bisphenol A. .

The polymerization liquid discharged from the bottom of the tank is continuously continuously supplied to the second and third vertical stirring polymerization tanks (capacity 100 L) and the fourth horizontal polymerization tank (capacity 150 L). It was extracted from the polymer outlet. Next, in the molten state, this polymer was fed into a twin screw extruder, and butyl p-toluenesulfonate (4 times the amount of cesium carbonate used as a catalyst) was continuously kneaded, As a strand shape, a pellet was obtained by cutting with a cutter. The reaction conditions in the second to fourth polymerization tanks were the second polymerization tank (240 ° C., 2.00 × 10 ³ Pa, 75 rpm), the third polymerization tank (270 ° C., 67 Pa, 75 rpm), and the fourth polymerization tank, respectively. (280 ° C., 67 Pa, 5 rpm) The conditions were set to high temperature, high vacuum, and low stirring speed as the reaction proceeded. During the reaction, the liquid level was controlled so that the average residence time in the second to fourth polymerization tanks was 60 minutes, and at the same time, the by-produced phenol was distilled off.
A polycarbonate having a viscosity average molecular weight of 24,000 was obtained, and Mw / Mn, swell ratio, MVR-R, hue (YI) and melt tension measurement, blow moldability, pipe moldability test and twin wall sheet molding were carried out. The results are shown in Table-1.

[Examples 2 to 11, Comparative Examples 1 to 4]
In Example 1, except that it manufactured on the conditions of Table 1, it superposed | polymerized by the method similar to Example 1, and manufactured the aromatic polycarbonate. The results are shown in Table-1.

According to the present invention, the aromatic polycarbonate has a better hue while maintaining the molding characteristics, so that the material having processing and injection molding by extrusion, particularly high melt strength and excellent shape retention characteristics of the extrudate. The present invention relates to a molded product which is suitable for use in a water bottle by blow molding, extrusion of a different shape, a twin wall sheet or a multi-wall sheet.

Claims (17)

A ratio of a weight average molecular weight (Mw) in terms of polystyrene and a number average molecular weight (Mn) measured by gel permeation chromatography, which is an aromatic polycarbonate having a viscosity average molecular weight of 16,000 or more obtained by a transesterification method ( Mw / Mn) is 2.8 or more 4
. A value obtained by dividing the cross-sectional area of the extruded strand when the load of 11 kg is applied to the molten resin in the melt index measurement at 280 ° C. by the orifice cross-sectional area (hereinafter referred to as swell ratio). An aromatic polycarbonate characterized by having a range of 1.2 to 4.0. The aromatic polycarbonate according to claim 1, wherein the swell ratio is in the range of 1.4 to 3.0. The aromatic polycarbonate according to any one of claims 1 to 2, wherein a flow rate ratio (MVR-R) represented by the following formula (1) is in the range of 15 to 30 in accordance with JIS K 7210.
MVR-R = MVR (21.6) / MVR (2.16) Formula (1) The aromatic polycarbonate according to any one of claims 1 to 3, wherein the branch unit is derived from a rearrangement reaction of an aromatic polycarbonate in an aromatic polycarbonate production reaction step. The aromatic polycarbonate according to any one of claims 1 to 4, which is an aromatic polycarbonate having a viscosity average molecular weight of 21,000 or more obtained by a transesterification method. In the manufacturing method of the aromatic polycarbonate in any one of Claims 1 thru | or 5, when making an aromatic polycarbonate by making a carbonic acid diester and an aromatic dihydroxy compound react, with respect to 1 mol of aromatic dihydroxy compounds, A method for producing an aromatic polycarbonate, wherein an alkali metal compound and / or an alkaline earth metal compound having a metal content of 1.1 to 5 μm is used. 7. The aromatic polycarbonate according to claim 6, wherein the alkali metal compound and / or the alkaline earth metal compound is used in an amount of 1.3 to 3.8 μm with respect to 1 mol of the aromatic dihydroxy compound. Manufacturing method. A method for producing a branched aromatic polycarbonate comprising a step of polymerizing in at least two polymerization tanks, wherein the final polymerization tank is a horizontal type, and the reaction temperature in the final polymerization tank is in the range of 280 ° C to 300 ° C. A process for producing an aromatic polycarbonate according to claim 6 or 7. 6. An aromatic polycarbonate composition containing the aromatic polycarbonate according to claim 1 and a carbonic acid diester compound, wherein the content of the carbonic acid diester compound is 200 ppm by weight or less. The aromatic polycarbonate composition containing the aromatic polycarbonate and the dye according to any one of claims 1 to 5, wherein the dye is one or more compounds selected from a phthalocyanine blue dye or an anthraquinone dye, An aromatic polycarbonate composition having a content of 0.01 ppm to 100 ppm by weight. A hollow container obtained by blow molding the aromatic polycarbonate according to any one of claims 1 to 5. The hollow container obtained by blow-molding the aromatic polycarbonate composition of Claim 9 or 10. The hollow container according to claim 11 or 12, wherein the hollow container is a dairy product bottle, a soft drink bottle, or a water bottle. A molded article obtained by extruding the composition containing the polycarbonate according to any one of claims 1 to 5. The extruded product according to claim 14, wherein the extruded product is a sheet. The extrusion-molded product according to claim 14, wherein the extrusion-molded product is formed by a modified extrusion. The extruded product according to claim 14, wherein the extruded product is a twin wall sheet or a multi-wall sheet.