JP4097588B2 - Polycarbonate resin composition for extrusion molding using sizing die and molded body - Google Patents

Description

The present invention relates to a polycarbonate resin composition for extrusion using a sizing die and a molded product obtained by extruding the resin composition using a sizing die. More specifically, the present invention relates to a specific ¹ H-NMR spectrum. The present invention relates to a polycarbonate resin composition for extrusion molding using a sizing die and a molded article having an integral value of a signal, good moldability, low load on a molding machine, and excellent hue and impact strength.

  Polycarbonate is used in various fields as a resin excellent in heat resistance, mechanical properties, dimensional stability, transparency, and the like. By the way, the conventional general polycarbonate has a linear molecular structure. Polycarbonate having such a molecular structure has a large drawdown at the time of extrusion molding, particularly at the time of extrusion molding using a sizing die having a function of cooling the molten resin discharged from the extruder while imparting a desired shape. There is a tendency that the melt tension is insufficient. If the molecular weight of the polycarbonate is increased in order to improve the melt properties such as drawdown, the melt viscosity at the time of extrusion molding becomes too high, the load on the extruder becomes excessive, and the productivity does not increase. There was a desire for improvement.

As a method for improving the melt characteristics such as drawdown property of polycarbonate, it is an interfacial polymerization method together with 2,2-bis (4-hydroxydiphenyl) propane (hereinafter abbreviated as “bisphenol A” or “BPA”). As a branching agent, a polyfunctional compound such as 1,1,1-tris (4-hydroxylphenyl) ethane (THPE), 1,3,5-tris (4-hydroxyphenyl) benzene is used to branch the polycarbonate. There is known a method of making it (for example, see Patent Documents 1 to 4). However, it is necessary to copolymerize a large amount of polyfunctional compounds in order to obtain a branched polycarbonate having sufficient melting characteristics to stably perform profile extrusion molding (for example, twin wall molding) that gives a complicated shape by a die. There were problems such as coloring of product polycarbonate, contamination of the production line, and cost increase due to the polyfunctional compound.
In order to solve these problems, various attempts have been made in transesterification methods using carbonic diesters and aromatic dihydroxy compounds (see, for example, Patent Documents 5 to 8). Decomposition occurred at high temperature, branching effects did not appear, and coloring was caused during melt molding, and satisfactory products were not obtained.
Japanese Patent Publication No. 44-17149 Japanese Patent Publication No.47-2918 JP-A-2-55725 Japanese Patent Laid-Open No. 4-89824 Japanese Patent Laid-Open No. 4-89824 JP-A-6-136112 Japanese Patent Publication No. 7-37517 Japanese Patent Publication No.7-116285

  The object of the present invention is to provide the original mechanical properties of polycarbonate, transparency, good moldability, suitable for extrusion molding using a sizing die such as a deformed extrusion molded body such as a pipe or twin wall, and in hue. An object of the present invention is to provide an excellent polycarbonate-based resin composition and a molded body extruded from the polycarbonate-based resin composition using a sizing die.

The present inventors have made intensive studies to solve the above problems, a main repeating unit represented by the following formula (A), δ = 7 to ¹ H-NMR spectrum which is measured using deuterated chloroform as a solvent. The number of proton moles (Pa) in 1 g of polycarbonate calculated from the integrated values of the signal (a) detected at 96 to 8.02 ppm and the signal (b) detected at δ = 8.11 to 8.17 ppm and (Pb) satisfies the following formula (1), and the polycarbonate-based resin composition mainly comprising a polycarbonate having a viscosity average molecular weight of 17000 to 27000 is suitable for extrusion molding using a sizing die, and The resin composition has good moldability at the time of extrusion molding using a sizing die, and the molded body made of the composition has impact resistance, mechanical strength, heat resistance and color. Found to have excellent, it has been led to completion of the present invention.

4 <{(Pa) + (Pb)} <26 (1)
(However, the unit of (Pa) and (Pb) is μmol / g)

As a preferred embodiment of the present invention, the polycarbonate is calculated from an integral value of a signal (c) detected at δ = 10.35 to 10.50 ppm in a ¹ H-NMR spectrum measured using deuterated chloroform as a solvent. The ratio (Pc) / (Pa) between the number of proton moles (Pc) in 1 g of polycarbonate and the above (Pa) satisfies the following formula (2), and the ratio between (Pa) and (Pb) (Pa) / Provided is the above polycarbonate resin composition in which (Pb) satisfies the following formula (3); and the above (Pb) and (Pc) are in the relationship of the following formula (4).
Formula (2) 0 ≦ (Pc) / (Pa) <0.5
Formula (3) 0.5 <(Pa) / (Pb) <3
Formula (4) 0.70 <(Pb) / {(Pb) + (Pc)} <0.96 (wherein (Pa), (Pb) and (Pc) are expressed in μmol / g)

  The polycarbonate is preferably a polycarbonate obtained by a transesterification method, that is, a polycarbonate obtained by transesterification of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polymerization catalyst. More preferably, the composition contains

  As another embodiment of the present invention, a molded product obtained by extruding the polycarbonate resin composition using a sizing die; and the molded product that is a twin wall molded product or a molded product having three or more layers of walls. And further relates to a molded article having a coating layer on at least a part of the surface of the molded article, or a molded article laminated and integrated with another resin composition by a co-extrusion method.

  According to the present invention, the original mechanical properties of polycarbonate, transparency, and good moldability are suitable for extrusion using a sizing die such as a pipe or a modified extrusion molded body such as a twin wall. And a molded article obtained by extrusion molding from a polycarbonate resin composition using a sizing die.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be specifically described.
The polycarbonate used in the present invention is a polycarbonate calculated from the sum of integral values of the signal (a) detected at δ = 7.96 to 8.02 ppm of ¹ H-NMR spectrum measured using deuterated chloroform as a solvent. The number of proton moles (Pb) in 1 g of polycarbonate calculated from the sum of the integral number of protons (Pa) in 1 g and the signal (b) of δ = 8.11 to 8.17 ppm is represented by the following formula (1). The range shown,
4 <{(Pa) + (Pb)} <26 (1)
Preferably it is the range shown by following formula (5), More preferably, it is the range shown by following formula (6).
6 <{(Pa) + (Pb)} <26 (5)
(However, the unit of (Pa) and (Pb) is μmol / g)
7 <{(Pa) + (Pb)} <22 (6)
(However, the unit of (Pa) and (Pb) is μmol / g)

  The polycarbonate has a viscosity average molecular weight of 17000 to 27000, preferably 19000 to 26000, and more preferably 20000 to 24000. When (Pa) + (Pb) is 4 or less, the drawdown during profile extrusion molding becomes large, and the moldability is inferior. If it is 26 or more, the hue deteriorates and the impact strength decreases, which is not preferable. If the viscosity average molecular weight is less than 17000, gel formation and impact strength decrease occur, and if it exceeds 27000, the melt viscosity becomes excessively high and the load on the extruder increases.

Further, the polycarbonate of the present invention is obtained in 1 g of polycarbonate calculated from the integral value of signal (c) detected at δ = 10.35 to 10.50 ppm in ¹ H-NMR spectrum measured using deuterated chloroform as a solvent. The ratio (Pc) / (Pa) of the number of proton moles (Pc) and (Pa) satisfies the following formula (2), and the ratio (Pa) / (Pb) between (Pa) and (Pb) Preferably satisfies the following formula (3).
0 ≦ (Pc) / (Pa) <0.5 (2)
0.5 <(Pa) / (Pb) <3 (3)
(However, the unit of (Pa), (Pb) and (Pc) is μmol / g)
When the ratio (Pc) / (Pa) is 0.5 or more, the drawdown is large and the profile extrusion moldability is deteriorated. When (Pa) / (Pb) is 3 or more, the hue of the resin is deteriorated. There is a tendency, and when it is 0.5 or less, the profile extrusion moldability tends to deteriorate.

Moreover, it is preferable that the (Pb) and the (Pc) are in the relationship of the following formula (4). When the upper limit of formula (4) is exceeded, the hue of the resin composition deteriorates, and when the lower limit is exceeded, the drawdown during blow molding tends to increase.
Formula (4) 0.70 <(Pb) / {(Pb) + (Pc)} <0.96

  Regarding the signals (b) and (c) of the polycarbonate of the present invention, Polymer, 42 (2001) 7653, respectively, is a signal derived from a branched skeleton of a phenyl salicylate structure and an unbranched skeleton of a phenyl salicylate structure. Considering that the improvement in extrusion moldability depends only on the branched skeleton of the phenyl salicylate structure to which the signal (b) belongs, the higher the strength of the signal (b) in the polycarbonate, the better the profile extrusion moldability of the polycarbonate. Will be. However, according to the study of the present inventor, it has been found that it is difficult to control the profile extrusion moldability only by the high strength of the signal (b).

As described in Polymer, 42 (2001) 7653, the polycarbonate produced by the transesterification method is known to have a branched structure other than the branched structure to which the signal (b) belongs. It is clear as to which position in ¹ H-NMR the branch structure other than the branch structure to which signal (b) belongs, and the number of types of branch structures other than the structure to which signal (b) belongs. However, the inventors' investigation has revealed that there is a correlation between the strength of the signal (a) and the profile extrusion moldability of polycarbonate. It is not clear what chemical structure the signal (a) is derived from, and it is not always derived from one chemical structure. The signal (a) is a signal of a plurality of chemical structural species having similar structures. May be the total amount of those appearing in the specific range, but the present invention is that the sum ({Pa) + (Pb)} of the integral values of the signals (a) and (b) is in the specific range. Has been found to be important for the profile extrusion moldability of polycarbonate. Therefore, if {(Pa) + (Pb)} is 4 or less, the drawdown during the profile extrusion molding increases, and the moldability deteriorates. On the other hand, when it is 26 or more, swelling becomes too large, the extrusion moldability deteriorates, and the impact strength also decreases.

  Here, Polymer, 42 (2001) 7653 shows that the signal (a) includes an unbranched phenyl salicylate structure and an unknown structure. In the present invention, it is preferable that the proportion of the unbranched phenyl salicylate structure in the signal (a) is small. The amount of the unbranched phenyl salicylate structure in the signal (a) can be obtained by dividing the integral value of the signal (a), but it is often difficult to separate with high accuracy. It is preferable to obtain by (Pc) / (Pa) using c). In the present invention, the value of (Pc) / (Pa) is preferably in the range of 0 or more and less than 0.5. When (Pc) / (Pa) is 0.5 or more, the drawdown during profile extrusion molding is large, and the moldability tends to deteriorate.

  Although the degree of influence of the signal (a) and the signal (b) on the profile extrudability is not clear, the contribution to the improvement of the profile extrudability is presumed that the signal (a) is dominant. Is done. On the other hand, it is considered that the signal (b) greatly contributes to suppressing the coloring of the polycarbonate. Therefore, the balance between the effect of coloring but effective for drawing down (Pa) and the effect of not being effective for drawing down but difficult to be colored (Pb) is also important for the polycarbonate to maintain various properties in a balanced manner. From such a viewpoint, it is preferable that both the signal (a) and the signal (b) exist, and (Pa) / (Pb) is more preferably in the range of more than 0.5 and less than 3. When the ratio (Pa) / (Pb) is 0.5 or less, there are cases where the effect of improving the profile extrusion moldability is insufficient even if {(Pa) + (Pb)} satisfies the above formula (1). However, when the ratio (Pa) / (Pb) is 3 or more, the polycarbonate tends to be remarkably colored. According to the disclosure of Polymer, 42 (2001) 7653, the signal (b) and the signal (c) are signals derived from the branched skeleton of the phenyl salicylate structure and the unbranched skeleton of the phenyl salicylate structure, respectively. If the unbranched structure is reduced too much (the intensity of the signal (c) is reduced too much) in order to increase the structure (increase the intensity of the signal (b)), the polycarbonate tends to be colored. Thus, in a preferred embodiment of the polycarbonate of the present invention, the signals (a), (b) and (c) satisfy the above formulas (1), (2), (3) and (4). It is an aspect that exists in a well-balanced manner.

The measurement of ¹ H-NMR spectrum applied to the polycarbonate of the present invention needs to be performed with particularly high sensitivity since the signal intensity of the present invention is very small. For example, a signal / noise ratio (S / N ratio) sufficient for quantification can be obtained by integrating 6000 times or more at a polycarbonate solution concentration of 10 to 20% by weight with an NMR spectrometer having an operation frequency of about 400 MHz or more. it can. In addition, as for the quantification method, since a sufficient quantitative property cannot be obtained with a methyl group or the like in a polycarbonate repeating structural unit, which is usually used as a reference signal, tetraphenylmethane ( It is necessary to perform quantification by adding a small amount of a reference substance such as TPM). If the signal (c) is not detected even though the presence of the unbranched phenyl salicylate structure described in Polymer, 42 (2001) 7653 can be confirmed in the signal (a), the measurement resolution is insufficient. It is thought that. In such a case, it is necessary to further increase the number of integrations, but it is also possible to determine (Pc) from the integrated value of the signal detected in the vicinity of δ = 8.00 to 8.02 ppm according to the above document. . However, in this case, the measurement error becomes large.

  The polycarbonate of the present invention is preferably produced by an ester exchange reaction using an aromatic dihydroxy compound and a carbonic acid diester as raw materials.

Aromatic dihydroxy compounds:
In the transesterification method, the aromatic dihydroxy compound used as one of the raw materials is preferably a compound represented by the following general formula (A-1).

In formula (A-1), A represents a single bond, an optionally substituted linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -S-. , —CO— or —SO ₂ —, wherein X and Y are a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and p and q are each an integer of 0 or 1 is there. X and Y and p and q may be the same or different from each other.

  Typical aromatic dihydroxy compounds include, for example, bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy-3-methylphenyl) propane. 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5 '-Tetramethyl-4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone. These aromatic dihydroxy compounds can be used alone or in admixture of two or more. Furthermore, polyvalent phenols having three or more hydroxy groups in the molecule such as 1,1,1-tris (4-hydroxylphenyl) ethane (THPE), 1,3,5-tris (4-hydroxyphenyl) benzene Etc. can be used together in a small amount as a branching agent, but it is preferable not to use a branching agent. Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (hereinafter also referred to as “bisphenol A” and sometimes abbreviated as “BPA”) is particularly preferable.

These aromatic dihydroxy compounds may contain the above ¹ H-NMR signal (a), (b) or (c) as a minor component, but (a), (b) and (c) It is preferred that neither signal is substantially present. Here, “substantially” means that the number of proton moles (Pa), (Pb) and (Pc) calculated from the sum of integral values of signals per 1 g of aromatic dihydroxy compound are each less than 1 μmol, more preferably 0.1 μm. Less than a mole.

Carbonic acid diester:
The carbonic acid diester which is the other raw material is preferably a compound represented by the following formula (B).

Wherein (B), A ¹ and A ² are each independently optionally substituted good straight, a monovalent hydrocarbon group branched or cyclic, A ¹ and A ² may be the same or different from each other.

  Representative carbonic acid diesters include, for example, substituted diphenyl carbonates typified by diphenyl carbonate, ditolyl carbonate and the like, and dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) and substituted diphenyl carbonate are preferable.

  Moreover, said carbonic acid diester may substitute the quantity of the 50 mol% or less preferably 30 mol% or less with the dicarboxylic acid or dicarboxylic acid ester preferably. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  These carbonic acid diesters (including the above substituted dicarboxylic acids or esters of dicarboxylic acids; the same applies hereinafter) are usually used in excess relative to the aromatic dihydroxy compound. That is, it is used in a molar ratio within the range of 1.001 to 1.3, preferably 1.01 to 1.2 with respect to the aromatic dihydroxy compound. When the molar ratio is less than 1.001, the terminal OH groups of the produced polycarbonate are increased to deteriorate the thermal stability and hydrolysis resistance. When the molar ratio is greater than 1.3, the terminal of the polycarbonate is increased. Although the number of OH groups decreases, the rate of the transesterification reaction decreases under the same conditions, and it tends to be difficult to produce a polycarbonate having a desired molecular weight. In the present invention, it is preferable to use a polycarbonate adjusted to have a terminal OH group content of 50 to 1500 ppm, preferably 100 to 1000 ppm, and more preferably 200 to 800 ppm.

  As a method of supplying the raw material to the raw material mixing tank, since the measurement accuracy in the liquid state is easier to maintain high, one or both of the aromatic dihydroxy compound and the carbonic acid diester is melted and supplied in the liquid state. Is preferred. When the raw material is supplied in a liquid state, an oval flow meter, a micro motion type flow meter, or the like can be used as a metering device. On the other hand, when the raw material is supplied in a solid state, it is preferable to use a weight weighing device rather than a screw weighing device such as a screw feeder, and a weight feeder such as a belt type or a loss-in-weight type. However, the loss-in-weight method is particularly preferable.

Transesterification catalyst:
When producing a polycarbonate by the transesterification method, a catalyst is usually used. In the polycarbonate production method of the present invention, the catalyst species is not limited, but in general, an alkali metal compound, an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, etc. These basic compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferred. These may be used alone or in combination of two or more.

  Examples of the alkali metal compounds include inorganic alkali metal compounds such as lithium, sodium, potassium, rubidium, cesium hydroxide, carbonate, hydrogen carbonate compounds, and organic alkali metal compounds such as alcoholates, phenolates, and organic carboxylates. . Among these alkali metal compounds, cesium compounds are preferable, and specific examples of the most preferable cesium compounds are cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide.

  In addition, as alkaline earth metal compounds, inorganic alkaline earth metal compounds such as beryllium, magnesium, calcium, strontium, barium hydroxide and carbonate, organic alkaline earth metals such as alcoholate, phenolate, and organic carboxylate There are compounds.

Among these catalysts, an alkali metal compound is desirable in order to obtain a sufficient ¹ H-NMR signal. In the present invention, the transesterification catalyst is preferably used in the form of a catalyst solution dissolved in a solvent. Examples of the solvent include water, acetone, alcohol, toluene, phenol, a solvent that dissolves the raw material aromatic dihydroxy compound, carbonic acid diester, and the like. Among these solvents, water is preferable, and when an alkali metal compound is used as a catalyst, an aqueous solution is preferable. In the case of an alkali metal catalyst, the amount of the catalyst used is 4 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol, preferably 1 × 10 ^{−6 to} 6 × 10, per 1 mol of the aromatic dihydroxy compound. Used within the range of ^-6 mol. If the amount of the catalyst used is less than the above amount, the polymerization activity necessary for producing a polycarbonate having a desired molecular weight cannot be obtained, and it is necessary to lengthen the residence time during polymerization or raise the temperature. The hue deteriorates, and the structures of ¹ H-NMR signals (a) and (b) are not sufficiently obtained.
On the contrary, if the amount of the catalyst is too large, the hue and hydrolysis resistance deteriorate, and further, the mechanical strength and transparency are lowered, which is not preferable.

Polycarbonate production method:
In the present invention, the polycarbonate production method is preferably based on a transesterification reaction, and the proton amount and signal integral value ratio calculated from the sum of integral values of signals detected in the specific ¹ H-NMR spectrum. However, as long as it is in a specific range, it can be polymerized with ordinary melt-process polycarbonate production equipment and is not particularly limited, but polymerization such as catalyst type, catalyst amount, monomer charge ratio, polymerization temperature, residence time, degree of vacuum, etc. Depending on the conditions, these values will vary.
For example, in the present invention, the polymerization reaction (transesterification reaction) of polycarbonate is generally carried out continuously in two or more polymerization tanks, that is, in two or more stages, usually in a multistage process of 3 to 7 stages. Is preferred. Specific reaction conditions include temperature: 150 to 320 ° C., pressure: normal pressure to 2.0 Pa, average residence time: 5 to 150 minutes, and in each polymerization tank, phenol by-produced as the reaction proceeds. In order to make the discharge of water more effective, the temperature is set to higher temperature and higher vacuum stepwise within the above reaction conditions. The ¹ H-NMR signals (a) and (b) of the polycarbonate obtained are larger as the amount of the alkali metal catalyst used is larger, and the value of (Pa) / (Pb) ratio and formula (4) is larger as the residence time is longer. Tend to be. Note that the automatic control of the actual catalyst amount in the case of using a plurality of polymerization tanks in a multi-stage process is preferably continuous automatic control of the catalyst supply amount. In that case, 1 / of the residence time of the first polymerization tank Measurement and control must be completed within 3 minutes.

  The molecular weight distribution of the polycarbonate of the present invention thus produced is generally wider than that of a normal polycarbonate. For example, the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC). ) And the number average molecular weight ratio (Mw / Mn) is generally 2.6 or more, preferably 2.75 to 4.5.

  The apparatus used in the transesterification reaction may be any of a vertical type, a tube type, a tower type, and a horizontal type. Turbine blades, paddle blades, anchor blades, full-zone blades (manufactured by Shinko Pantech Co., Ltd.), Sun Meller blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max Blend blades (manufactured by Sumitomo Heavy Industries, Ltd.), helical ribbons Following one or more vertical polymerization tanks equipped with blades, torsion lattice blades (manufactured by Hitachi, Ltd.), etc., horizontal type uniaxial polymerization tanks such as disk type and cage type, HVR, SCR, N-SCR (Mitsubishi) Heavy Industries Co., Ltd.), Vivolak (Sumitomo Heavy Industries, Ltd.), Glasses Wings, Lattice Wings (Hitachi, Ltd.), or Glasses Wings and Polymer Feeding Function, eg Twist and Twist A horizontal biaxial type polymerization tank equipped with a combination of blades containing etc. and / or blades with an inclination, etc. can be used.

  The polycarbonate produced by the above method usually does not contain chlorine element and is 1 ppm or less. However, raw material monomers, catalysts, aromatic monohydroxy compounds by-produced by transesterification, polycarbonate oligomers and other low molecular weight compounds are present. Remains. Among them, the raw material monomer and the aromatic monohydroxy compound have a large residual amount and adversely affect the quality such as heat aging resistance and hydrolysis resistance, and thus are preferably removed upon commercialization. The residual amount of the aromatic monohydroxy compound is 200 ppm by weight or less, preferably 100 ppm by weight or less, the residual amount of the aromatic dihydroxy compound is 100 ppm by weight or less, preferably 50 ppm by weight or less, the residual amount of the carbonic acid diester compound Is 200 ppm by weight or less, preferably 150 ppm by weight or less, more preferably 100 ppm by weight or less.

  The method for removing them is not particularly limited, and may be continuously devolatilized by, for example, a vent type extruder. At that time, the basic transesterification catalyst remaining in the resin is preliminarily added with an acidic compound or a precursor thereof to deactivate, thereby suppressing side reactions during devolatilization, and efficiently starting monomer and Aromatic hydroxy compounds can be removed.

  There is no restriction | limiting in particular about the acidic compound to add, or its precursor, As long as it has the 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 30 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, and it can be directly applied depending on the properties of the acidic compound or its precursor and the desired conditions. Any method such as a method of adding, 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 devolatilization 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.

Polycarbonate resin composition:
The polycarbonate resin composition of the present invention comprises a stabilizer, an ultraviolet absorber, a release agent, a colorant, a plasticizer, an antistatic agent, a filler, a flame retardant, an impact modifier, other resins, and an epoxy compound as necessary. You may mix | blend the at least 1 sort (s) of additive chosen from these. There is no restriction | limiting in particular as such an additive, What is normally used for the polycarbonate resin composition can be used. Also, within the scope of the present invention, a plurality of polycarbonate resins having different molecular weights, production methods, and branching degrees can be mixed and 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.
As the hindered phenol compound, a compound represented by the following formula (C) is preferable.

In the formula (C), R ^x and R ^y each represent a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different, and Y ⁰ is a functional group selected from an ester group, an ether group, and an amide group A hydrocarbon group having 1 to 20 carbon atoms which may contain a group and / or a phosphorus atom, and Z ⁰ is a hydrocarbon group having 1 to 6 carbon atoms which may contain an oxygen atom and / or a nitrogen atom , A sulfur atom or a single bond, and g represents an integer of 1 to 4.

  Specifically, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3 ′, 5′-di-t-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, tri Ethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] 3,5-di-tert-butyl-4-hydroxybenzyl phosphone To-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, N, N′-hexamethylenebis (3 , 5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. 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, and 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 and 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-t-butylphenyl) butane, trisnonylphenyl phosphite, dinonylphenylpentaerythritol diphosphite, tris (2,4-di-t-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, mono- nonylphenol and phosphite consisting dinonyl like.

  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 compounding amount of the stabilizer is 1 part by weight or less, preferably 0.4 parts by weight or less, particularly preferably 0.01 to 0.2 part, based on 100 parts by weight of the 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 stability at high temperatures when molding polycarbonate, and heat stability during use of molded articles, and phenolic compounds generally use polycarbonates such as heat aging as molded articles. 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 ultraviolet absorbers include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, triazine compounds, cyanoacrylate compounds, and malonic acid 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 preferable, and in addition to the benzotriazole compound, the triazine compound 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, malonic acid compounds [ (4-Methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate of cyanoacrylate compound, and 2,2 ′-(1,4- It is preferably at least one selected from phenylene) bis [4H-3,1-benzoxazin-4-one].

  Examples of the benzotriazole compound include those represented by the following formula (D) and methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. These condensates are preferred.

In formula (D), R ^{a to} R ^d represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Y ¹ and Y ² represent a hydrogen atom, a nitrogen atom having 1 to 40 carbon atoms, and And / or a hydrocarbon group which may contain an oxygen atom.

  Specific examples of the benzotriazole compound of the formula (D) include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzo Triazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-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, [methyl-3- [3-t-butyl-5- (2H-be Nzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate, and a compound represented by the following formula (E).

In the formula, R ¹ and R ² are independently of each other hydrogen, halogen atom, alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, aralkyl group having 7 to 13 carbon atoms, and 6 to 14 carbon atoms. An aryl group of

Or —C—O—R ⁵ , wherein R ⁵ represents hydrogen or an alkyl group having 1 to 4 carbon atoms; R ³ and R ⁴ represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or 5 carbon atoms. Or a cycloalkyl group having 6 carbon atoms, a benzyl group, or an aryl group having 6 to 14 carbon atoms; m represents 1, 2 or 3, and n represents 1, 2, 3 or 4.

  Among the compounds represented by the formula (E), particularly preferred are 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis- [4- (1,1,3,3, -tetramethylbutyl) -6- (2N-benzotriazole-2- Yl) phenol], 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) 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-triazine-2 -Ill]- 5- (Octyloxy) phenol.

  The compounding quantity of a ultraviolet absorber is 20 weight part or less with respect to 100 weight part of polycarbonate. If it exceeds 20 parts by weight, there will be problems such as mold contamination during molding. The ultraviolet absorber can be used alone or in combination.

  The polycarbonate resin composition of the present invention preferably contains at least one release agent. When the resin composition of the present invention contains a release agent, it is preferable that an appearance defect of the molded product does not occur even if the extrusion speed is increased during extrusion molding with a sizing die. The release agent is preferably an aliphatic carboxylic acid, an aliphatic alcohol, an aliphatic carboxylic acid ester, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000 or a polysiloxane silicone oil. Among these, at least one selected from the group consisting of 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, and 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 one as the aliphatic carboxylic acid 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 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 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. can be mentioned. 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.

  In the present invention, it is preferable to use a release agent having a molecular weight of 500 or more, more preferable to use a release agent having a molecular weight of 1000 or more, and particularly preferable to use pentaerythritol tetrastearate having a molecular weight in the above range. . Use of a release agent having a molecular weight of 500 or more is preferable because it can solve the problem of poor surface appearance that occurs during high-speed extrusion molding of 0.01 m / second.

  In general, the blending amount of the release agent in the polycarbonate resin composition of the present invention is preferably 5 parts by weight or less, more preferably 1 part by weight or less, and still more preferably 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate. ~ 0.05 parts by weight. When the amount exceeds 5 parts by weight, hydrolysis resistance tends to be lowered, vent clogging due to gas generation during molding, appearance defects on the surface of the molded product, and the like. Moreover, the effect of addition may not be acquired as a compounding quantity is less than a lower limit. The release agent can be used alone or in combination.

  As the colorant, any of organic dyes, organic pigments, and inorganic pigments can be used, but as organic dyes and pigments, compounds having anthraquinone skeleton, compounds having phthalocyanine skeleton, etc., inorganic pigments such as titanium oxide, carbon black, Ultramarine blue, cobalt blue, etc. can be used. These inorganic pigments may be surface-treated with a silicon compound or the like. Among these, a compound having an anthraquinone skeleton is preferably used from the viewpoint of heat resistance and the like.

  Specific examples of the colorant include phthalocyanine blue, MACROLEX Blue RR, MACROLEX Violet 3R, MACROREX Violet B (manufactured by Bayer), Sumiplast Violet RR, Sumiplast Violet B, Sumilast Blue Industrial Co., Ltd. Violet D, Diaresin Blue G, Diaresin Blue N (made by Mitsubishi Chemical Corporation), etc. are mentioned.

  In general, the blending amount of the colorant is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and further preferably 0.00001 to 0.05 parts by weight with respect to 100 parts by weight of the polycarbonate. is there. The colorant can be used alone or in combination.

  There are no particular restrictions on the addition timing and addition method of additives such as stabilizers, ultraviolet absorbers, mold release agents, and colorants. For example, the addition timing is (i) during the polymerization reaction, (ii) completion of the polymerization reaction. Or (iii) after the catalyst used for the polymerization is deactivated with a catalyst deactivator, before pelletization, and further in the state where the polycarbonate is melted, such as during the kneading of the polycarbonate, etc. It is also possible to knead with an extruder or the like after blending with a polycarbonate in a solid state. However, (i) during the polymerization reaction, (ii) at the end of the polymerization reaction, or (iii) after adding the catalyst used for the polymerization after deactivation with the catalyst deactivator, before adding the pellet, It is preferable from the viewpoint of suppressing coloration and suppressing decomposition of the additive.

  As an addition method, additives such as a stabilizer, an ultraviolet absorber, a release agent, and a colorant 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. Moreover, when using these compounds together, you may add these to a polycarbonate separately, or may add 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, diffusing agent, organic filler, and inorganic filler are added is also an object.

  The resin composition of the present invention exhibits particularly excellent performance when producing a profile extrusion molded body such as a pipe, twin wall or multi-wall by extrusion using a sizing die. Extrusion molding using a sizing die is performed by a method of first extruding a molten resin composition, performing sizing using a sizing die, and cooling. This sizing means that the extruded molten resin is given a predetermined shape and size, and is preliminarily cooled so that no deformation occurs until the next cooling step. Further, the sizing die refers to a die having a function of imparting a predetermined shape and dimensions to an extruded product obtained by melting and extruding a resin composition.

Extruded body:
The molded product of the present invention is characterized by being formed by extrusion molding the resin composition of the present invention using a sizing die. Among these, a twin wall molded body or a multi-wall molded body having three or more layers is preferable. There are no particular restrictions on the various conditions of extrusion molding in producing the molded article of the present invention. An example is shown below.
Pellets of the polycarbonate resin composition of the present invention are supplied to a single-screw or twin-screw extruder having a cylinder set temperature of 240 to 290 ° C., and melted and kneaded under screw shear. This molten resin is extruded in a fixed shape through a die head, and then fixed in shape by, for example, cooling the resin along the die under reduced pressure with a sizing die having a predetermined shape and temperature set to 20 to 110 ° C. To obtain a molded body. The extrusion speed in the present invention is preferably 0.01 m / second or more, more preferably 0.02 m / second or more. As described above, when the composition of the present invention contains a release agent, the extrusion molding speed can be increased, and a molded article having a good appearance can be obtained even at 0.03 m / second or more. Sometimes.

  Two or more of the polycarbonate resin compositions of the present invention are coextruded, or the polycarbonate resin composition of the present invention is coextruded with other resin compositions, and a layer composed of two or more compositions is laminated. An integrated molded body can be produced. By adjusting the amount at the time of extruding the formed body, a formed body having a layer structure with a desired thickness can be obtained. Although the thickness, layer structure, and the like are not particularly limited, it is preferable that the base is made of the resin composition of the present invention having a thickness of usually 10 to 200 μm and twice or more the thickness of the coating layer. Other resin compositions that are co-extruded with the polycarbonate resin composition of the present invention are not particularly limited, such as a composition containing polycarbonate as a main component and a composition containing methyl methacrylate as a main component. Products, compositions based on polyethylene terephthalate, compositions based on polyamide, and the like can be used. In the present specification, the “other resin composition” is not only a different type of polymer as a main component but also a composition having a different blending amount even if the same type of polymer as a main component is the same. In addition, the term “additive” is used in the sense of including any composition having a different kind of additive component, its blending amount, or its composition ratio.

One embodiment of the molded body of the present invention is a molded body having a coating layer on at least a part of its surface. The molded body according to the present embodiment can be produced by the above-described coextrusion, and can also be produced by lamination. In particular, it is preferable to produce by coextrusion. The other resin composition constituting the coating layer is not particularly limited, but is preferably a polycarbonate resin composition. The main repeating unit is represented by the above formula (A) and measured using deuterated chloroform as a solvent. Of the ¹ H-NMR spectrum calculated from the integrated values of signal (a) detected at δ = 7.96 to 8.02 ppm and signal (b) detected at δ = 8.11 to 8.17 ppm. A polycarbonate resin composition mainly composed of polycarbonate having 1 mol of protons (Pa) and (Pb) in 1 g of polycarbonate satisfying the following formula (x) and having a viscosity average molecular weight of 17,000 to 40,000. Is more preferable.
Formula (x) {(Pa) + (Pb)} <26
(However, the unit of (Pa) and (Pb) is μmol / g)

  Furthermore, it is more preferable that the other resin composition contains 1 to 25 parts by weight of at least one ultraviolet absorber with respect to 100 parts by weight of the polycarbonate in the composition. The UV absorber is more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the polycarbonate. If the content of the ultraviolet absorber exceeds 25 parts by weight, there are problems such as gas generation during molding and mold contamination, and if it is less than 1 part by weight, sufficient effects may not be obtained. Examples of the ultraviolet absorber include those described above. As described above, at least one selected from triazole compounds, triazine compounds, cyanoacrylate compounds, and benzophenone compounds is preferable, and benzophenone is particularly preferable. It is a triazole compound. The ultraviolet absorber can be used alone or in combination.

  In the molded product of this embodiment, the polycarbonate resin composition of the present invention does not contain an ultraviolet absorber at all, or even when it contains it, the blending amount is preferably 1 part by weight or less.

  In the present embodiment, the coating layer can be provided on a plurality of surfaces as well as one surface of an extruded body (substrate) using a sizing die. The coating layer preferably has a thickness of 10 to 200 μm. Further, when the coating layer is a polycarbonate resin composition, the viscosity average molecular weight of the polycarbonate is more preferably in the range of −4000 to +8000 with respect to the viscosity average molecular weight of the polycarbonate of the substrate. If the value of (Pa) + (Pb) in the above-mentioned formula (1) of the polycarbonate of the coating layer is out of the above range, appearance defects such as fish eyes are unfavorable. On the other hand, if the thickness of the coating layer is less than 10 μm, it is difficult to coat with a uniform thickness, so that it is difficult to obtain the effect of improving weather resistance, and if it exceeds 200 μm, the hue deterioration due to the ultraviolet absorber becomes remarkable. In addition to the ultraviolet absorber, the polycarbonate resin composition for the coating layer contains, as necessary, an antistatic agent, a conductive agent, a heat ray shielding agent, an antireflection agent, etc. in addition to the thermal stabilizer, release agent, and colorant. Can be added.

  In this embodiment mode, a plurality of coating layers may be provided. For example, when the coating layer is a layer of the polycarbonate resin composition, a layer of polyethylene terephthalate or polyamide is further provided by multilayer extrusion molding (composite extrusion molding) in order to improve the gas barrier property of the polycarbonate. Is also effective. Further, depending on the purpose, the surface of the molded product can be treated with an acrylic or silicon hard coating agent, an antistatic agent, a heat ray shielding agent, an antireflection agent, a conductive agent, or the like, or can be printed.

  The size of the extruded product of the present invention is not particularly limited. For example, in the case of a modified extruded product, the thickness is preferably 0.1 to 7 mm, more preferably 0.2, from the viewpoint of strength and shape retention. -5 mm, most preferably 0.3-3 mm. When the molded body is a plate-like twin wall or multi-wall, the thickness of the product is generally about 2 to 50 mm.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The analysis and physical properties were evaluated by the following measurement methods. The hue (YI) in (6) and the Izod impact strength in (7) show the values evaluated by preparing a general test piece. It was.

(1) ¹ H-NMR measurement After the polycarbonate is dissolved in chloroform, it is dropped into a mixed solvent of normal hexane / methanol = 4/1, the resin content is reprecipitated, filtered and dried to remove the additive component. Was used as a sample. About 0.18 g of the treated polycarbonate and about 3 mg of triphenylmethane (TPM) as an internal standard substance were dissolved in 1 g of deuterated chloroform containing 0.05% by weight of tetramethylsilane (TMS) to prepare a sample. This sample was subjected to ¹ H-NMR measurement using “JMN-AL400” manufactured by JEOL Ltd. at a temperature of 50 ° C. and a cumulative number of 8000 times. After the measurement, the integrated intensity of the signals detected at δ = 7.96 to 8.02 ppm, δ = 8.11 to 8.17 ppm, and δ = 10.35 to 10.5 ppm was measured, and 5.5 to 5. From the integrated intensity of the signal of TPM appearing at 6 ppm, the proton amount per 1 g of polycarbonate was calculated by the following formula.
Proton amount (μmol / g) = (signal integrated intensity / TPM signal integrated intensity) × TPM weight / 244.3 / polycarbonate weight × 10 ⁻⁶

(2) Viscosity average molecular weight (Mv)
The intrinsic viscosity [η] at 20 ° C. in methylene chloride was measured using an Ubbelohde viscometer, and the viscosity average molecular weight (Mv) was determined from the following formula.
[Η] = 1.23 × 10 ⁻⁴ × (Mv) ^0.83

(3) Terminal OH group content Colorimetric determination was carried out by the titanium tetrachloride / acetic acid method (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.
(4) Quantification of residual monomer Phenol, aromatic as an aromatic monohydroxy compound in a high performance liquid chromatograph equipped with a water detector μ-Bondersphere, acetonitrile / acetic acid water as a solvent, and a UV detector. The amount of bisphenol A (BPA) as a group dihydroxy compound and the amount of diphenyl carbonate (DPC) as a diphenyl carbonate compound were measured and expressed in ppm by weight relative to the polycarbonate.

(5) Molecular weight distribution (Mw / Mn) measurement The analyzer uses HLC-8020 (manufactured by Tosoh Corporation), and TSK 5000HLX, 4000HLX, 3000HLX and 2000HLX (all manufactured by Tosoh Corporation) as fillers. 4 columns (diameter 7.8 mmφ, length 300 mm) packed with each of the above were used. Tetrahydrofuran was used as the eluent, and the calibration curves were standard polystyrenes manufactured by Chemco Corporation (molecular weight: 761 (Mw / Mn ≦ 1.14), 2,000 (Mw / Mn ≦ 1.20), 4,000. (Mw / Mn ≦ 1.06), 9,000 (Mw / Mn ≦ 1.04), 17,5000 (Mw / Mn ≦ 1.03), 50,000 (Mw / Mn ≦ 1.03), 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.

(6) Hue (YI)
A 3 mm thick test piece was molded from a polycarbonate pellet (sample) dried at 120 ° C. for 5 hours by an injection molding machine M150AII-SJ (manufactured by Meiki Seisakusho Co., Ltd.) with a cylinder set temperature of 280 ° C. (Nippon Denshoku) The YI value was measured with a spectroscopic colorimeter SE2000 manufactured by Kogyo Co., Ltd. It shows that it colors, so that this YI value is large.
(7) Izod impact strength A 3.2 mm thick test piece from polycarbonate pellets (sample) dried at 120 ° C. for 5 hours by an injection molding machine M150AII-SJ (manufactured by Meiki Seisakusho) with a cylinder set temperature of 280 ° C. The Izod impact strength with a notch was measured according to ASTM D256.

(8) Pipe moldability test Using a 50 mm single-screw extruder, a polycarbonate resin composition with a barrel temperature of 255 to 270 ° C. and a screw rotation speed of 41 rpm, conditions of an outer diameter of the die head portion of 4.1 mm and an inner diameter of 3.8 mm The profile was extruded into a cylindrical shape. At that time, the pipe take-up speed was changed, and the take-up speed range in which the pipe could be stably formed was examined.
A wider take-off speed range indicates easier molding.
(9) Twin wall sheet molding Using a single-screw extruder, the barrel thickness is 250 to 265 ° C, the sizing die temperature is 20 to 90 ° C, the product thickness is 6 mm, the outer layer thickness is 0.4 to 0.6 mm, and the product weight is 1200 to 1300 g / The m ² twin wall was molded at an extrusion speed of 0.026 m / sec (Examples 1 to 4 and Comparative Examples 1 and 2), and the molded body was bent by hand to check for the occurrence of cracks.

[Example 1]
Under a nitrogen gas atmosphere, a melt prepared by mixing diphenyl carbonate and bisphenol A was continuously fed into a first vertical stirring polymerization tank controlled at 220 ° C. and 1.33 × 10 ⁴ Pa, and an average residence time of 60 The liquid level was kept constant while controlling the opening of the valve provided in the polymer discharge line at the bottom of the tank so that the minute amount could be reached. At the same time as the supply of the above mixture was started, an aqueous cesium carbonate solution was continuously supplied as a catalyst at a ratio of 1.2 × 10 ⁻⁶ mol 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 and the fourth horizontal polymerization tank, and is withdrawn from the polymer outlet at the bottom of the fourth polymerization tank. It was. The conditions of each reaction tank are set to high temperature, high vacuum, and low stirring speed as the reaction proceeds. In the fourth tank, the temperature is controlled at 290 ° C., 66 to 330 Pa, and the average residence time is 60 to 120 minutes. Distilling off the phenol was also performed. After the polymerization was completed, the polycarbonate was fed in a molten state into a twin screw extruder (46 mm φ twin screw extruder manufactured by Kobe Steel), and butyl p-toluenesulfonate (4 relative to cesium carbonate used as a catalyst). Twice the molar amount) was continuously kneaded, and after devolatilization, it was made into a strand shape through a die and cut with a cutter to obtain a pellet. The obtained polycarbonate resin was used as it was to prepare test pieces and to form pipes and twin walls.
The analysis results and the extrusion molding evaluation results are shown in Table 1.

[Examples 2 to 4, Comparative Examples 1 and 2]
In Example 1, except having changed into the catalyst amount of Table 1, it superposed | polymerized by the method similar to Example 1, the aromatic polycarbonate was manufactured, and extrusion molding was performed about each resin. The results are shown in Table 1.

[Examples 5 to 7]
In Examples 5 to 7, a polycarbonate obtained by polymerization in the same manner as in Example 3 was used, and the additives shown in Table 2 below were further kneaded to prepare compositions, and pellets comprising the compositions Was made. The additives were kneaded from the downstream side of the addition port of butyl p-toluenesulfonate by the twin-screw extruder used at the time of kneading of butyl p-toluenesulfonate in Examples 1 to 4. Each additive was added. Using this pellet, it was formed into a twin wall sheet using a sizing die in the same manner as in Examples 1 to 4, ie, under the conditions shown in (9) above. However, the extrusion speed at the time of molding was 0.03 m / second and 0.04 m / second, respectively, and the appearance of the obtained twin wall molded body was visually observed and evaluated. The case where there was no wrinkle or irregularity on the appearance was indicated by “◯”, and the case where the appearance was irregular or wrinkled was indicated by “X”. The results are shown in Table 2.

[Examples 8 to 10]
In Examples 8 to 10, two types of resin compositions were coextruded to produce a twin wall molded body having a coating layer on the surface. As the resin composition for the substrate, a polycarbonate resin obtained by polymerization in exactly the same manner as in Example 3 was used, and the additives shown in Table 3 below were further kneaded to prepare a composition. The pellet which consists of a thing was produced. The additives were kneaded from the downstream side of the addition port of butyl p-toluenesulfonate by the twin-screw extruder used at the time of kneading of butyl p-toluenesulfonate in Examples 1 to 4. Each additive was added. On the other hand, as the resin composition for the coating layer, various polycarbonates and various additives shown in Table 3 below were kneaded and prepared by extrusion with a 30 mmφ twin-screw extruder to prepare pellets composed of the respective compositions. Using the pellets made of the composition for the substrate and the pellets made of the composition for the coating layer, respectively, co-extruded to produce a twin wall molded body having a coating layer of 30 μm on one side. The molding conditions were the same as the conditions shown in (9) above, except that the extrusion speed during molding was 0.04 m / sec. The appearance of the twin wall molded body having the obtained coating layer was visually observed and evaluated. The case where there was no wrinkle or irregularity on the appearance was indicated by “◯”, and the case where the appearance was irregular or wrinkled was indicated by “X”. Moreover, the value (Mv difference) which subtracted the viscosity average molecular weight of the polycarbonate of the polycarbonate resin composition which forms a base | substrate from the viscosity average molecular weight of the polycarbonate of the polycarbonate resin composition which forms a coating layer was measured. The results are shown in Table 3.

Abbreviations in Table AO-1: Tris (2,4-di-t-butylphenyl) phosphite AO-2: Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] Methane PTS: Pentaerythritol tetrastearate monoglyceride: monoglyceride stearate UVA-1: 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole UVA-2 : 2,2′-methylenebis- [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol]
UVA-3: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol UVA-4: 2- (2'-hydroxy-5 ' -T-octylphenyl) benzotriazole PC-1: manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon (registered trademark) E-2000F: (Pa), (Pb) and (Pc) are each 0 μmol / g Viscosity average molecular weight 28000.

From the results shown in Table 2, it was confirmed that when a release agent was included in the composition, the appearance of the molded article could be maintained well even when the extrusion speed was increased. Moreover, it has confirmed from the result shown in Table 3 that the molded object which integrally formed the coating layer about 30 micrometers thick by coextrusion can be produced. In particular, when a polycarbonate whose {(Pa) + (Pb)} is less than 26 is used as a main component in the composition for the coating layer, a molded article having a good appearance even when the extrusion speed is increased to 0.04 m / sec. It was confirmed that

Claims (14)

The main repeating unit is represented by the following formula (A), and the signal (a) detected at δ = 7.96 to 8.02 ppm in the ¹ H-NMR spectrum measured using deuterated chloroform as a solvent and δ = 8.11 The number of proton moles (Pa) and (Pb) in 1 g of polycarbonate calculated from the integrated values of signals (b) detected at ˜8.17 ppm satisfy the following formula (1), and the viscosity average molecular weight is 17, A polycarbonate-based resin composition for extrusion using a sizing die mainly composed of polycarbonate of 000 to 27,000.

Formula (1) 4 <{(Pa) + (Pb)} <26
(However, the unit of (Pa) and (Pb) is μmol / g) The number of proton moles in 1 g of polycarbonate calculated from the integrated value of signal (c) detected at δ = 10.35 to 10.50 ppm in ¹ H-NMR spectrum measured using deuterated chloroform as a solvent. The ratio (Pc) / (Pa) between Pc) and (Pa) satisfies the following formula (2), and the ratio (Pa) / (Pb) between (Pa) and (Pb) is The polycarbonate-type resin composition for extrusion molding using the sizing die of Claim 1 which satisfy | fills 3).
Formula (2) 0 ≦ (Pc) / (Pa) <0.5
Formula (3) 0.5 <(Pa) / (Pb) <3
(However, the unit of (Pa), (Pb) and (Pc) is μmol / g) The polycarbonate-based resin composition for extrusion using the sizing die according to claim 1 or 2, wherein the (Pb) and the (Pc) are in a relationship represented by the following formula (4).
Formula (4) 0.70 <(Pb) / {(Pb) + (Pc)} <0.96
(However, the unit of (Pb) and (Pc) is μmol / g) The polycarbonate resin composition for extrusion using the sizing die according to any one of claims 1 to 3, wherein the polycarbonate is a polycarbonate obtained by transesterifying an aromatic dihydroxy compound and a carbonic acid diester compound. The polycarbonate-type resin composition for extrusion molding using the sizing die of any one of Claims 1-4 which contains 0.001-5 weight part with respect to 100 weight part of said polycarbonates at least 1 type of mold release agent. object. The mold release agent is at least one selected from the group consisting of hydrocarbons, aliphatic carboxylic acids, aliphatic alcohols, esters of aliphatic carboxylic acids and alcohols, and polysiloxane silicone oils. A polycarbonate resin composition for extrusion molding using a sizing die. The molded object formed by extrusion-molding the resin composition of any one of Claims 1-6 using a sizing die. The molded article according to claim 7, which is a twin-wall molded article or a molded article having three or more layers of walls. The molded product according to claim 7 or 8, which has a coating layer on at least a part of its surface. Other resin composition with the resin composition by using a sizing die coextrusion city according to any one of claims 1 to 6, Ru formed feature name by integrally laminated. Molded body according to claim 10, wherein at least a portion of the front surface other resin composition is allowed to integrate the product layer. In the other resin composition, the main repeating unit is represented by the following formula (A), and a signal detected at δ = 7.96 to 8.02 ppm in a ¹ H-NMR spectrum measured using deuterated chloroform as a solvent ( The number of proton moles (Pa) and (Pb) in 1 g of polycarbonate calculated from the integral values of the signals (b) detected at a) and δ = 8.11 to 8.17 ppm are expressed by the following formula (x). The molded article according to claim 10 or 11, wherein the molded article is a polycarbonate resin composition mainly composed of polycarbonate having a viscosity average molecular weight of 17,000 to 40,000.

Formula (x) {(Pa) + (Pb)} <26
(However, the unit of (Pa) and (Pb) is μmol / g) The said other resin composition contains 1-25 weight part of at least 1 sort (s) of ultraviolet absorber with respect to 100 weight part of polycarbonate in the said other resin composition. The molded body described. The molded article according to claim 13, wherein the ultraviolet absorber is at least one selected from the group consisting of triazole compounds, triazine compounds, cyanoacrylate compounds, and benzophenone compounds.