JP2009144016A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition improving environment and resource maintenance even by a little and at the same time having characteristics suitable for a large-sized molded article. <P>SOLUTION: This thermoplastic resin composition is characterized by comprising (A) a polycarbonate containing a constituting unit derived from a dihydroxy compound expressed by general formula (1) and (B) a styrene-based resin, and having the (90/10) to (10/90) range of their constituting weight ratio. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a thermoplastic resin composition. More specifically, it is a thermoplastic resin composition comprising a carbonate polymer containing isosorbide, which is a biomass resource, and a styrene resin, and is excellent in fluidity, impact strength, weld strength and heat resistance during molding. Relates to the composition.

  Aromatic polycarbonate resins are used as engineering plastics with excellent mechanical properties such as impact strength, and styrene resins such as ABS resins are used as thermoplastic resins with excellent mechanical properties and excellent moldability. It is widely used for various applications such as. However, aromatic polycarbonate resins have the disadvantage of being inferior in moldability and chemical resistance. On the other hand, styrene resins such as ABS resin and ASA resin have a problem in terms of heat resistance and have a problem that their use in a high temperature atmosphere is limited.

  Numerous alloys of aromatic polycarbonate resin and styrene resin such as ABS resin have been developed as a material that solves these problems and has both excellent properties. Especially, TV cabinets, printer / copier housings, automobiles, etc. Widely used for large molded products such as dashboards. (Japanese Patent Publication No. 38-15225, Japanese Patent Publication No. 39-71, Japanese Patent Publication No. 42-11396). In particular, the fluidity during molding is improved, the molding shrinkage ratio is low, the heat resistance can be maintained at about 80 ° C., and the mechanical strength is also good. In addition, since both resins have an aromatic group, they have compatibility, and there is an advantage that color unevenness such as pearly luster does not occur and coloring is easy.

  By the way, styrene resins such as aromatic polycarbonate resin and ABS resin are generally manufactured using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and there is a demand for the provision of plastic molded products using raw materials obtained from biomass resources such as plants. In addition, it is feared that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., so that carbon-neutral plant-derived monomers are used as raw materials even after disposal after use. There is a demand for the development of plastic molded material parts from plastics, especially in the field of large molded products.

  Conventionally, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (see, for example, Patent Document 1). However, the polycarbonate obtained is brown and is not satisfactory. Further, as a copolymerized polycarbonate of isosorbide and another dihydroxy compound, a polycarbonate copolymerized with bisphenol A has been proposed (for example, see Patent Document 2), and further, by copolymerizing isosorbide and an aliphatic diol. Attempts have been made to improve the rigidity of homopolycarbonate composed of isosorbide (see, for example, Patent Document 3). These were insufficient in mechanical strength, particularly impact resistance, for application to large-sized molded articles.

  On the other hand, many polycarbonates obtained by polymerizing 1,4-cyclohexanedimethanol, which is an alicyclic dihydroxy compound, have been proposed (for example, Patent Documents 4 and 5). The molecular weight of these polycarbonates is as low as about 4000 at most. Therefore, many of them have a low glass transition temperature.

Although carbonate polymers using isosorbide have been proposed in this way, they are not yet a resin with a comprehensive balance of heat resistance, mechanical strength, fluidity, etc. for application to large molded products. Is the situation. In addition, these documents disclose only the glass transition temperature and the basic mechanical properties, and sufficiently disclose the properties such as fluidity and impact resistance that are important for the above-mentioned large molded products. It has not been.
GB1079686 Publication JP-A-56-55425 WO 2004/111106 gazette JP-A-6-145336 Japanese Patent Publication No. 63-12896

  As mentioned above, polycarbonate resins, styrene resins such as ABS resins, and their alloys, which are currently widely used for large molded products, are also in view of environmental and petroleum resource conservation in the construction of a better future society. In addition, there are some problems in the characteristics for the application. The purpose of the present invention was to provide a thermoplastic resin composition that has a slight improvement in environmental and resource conservation, and at the same time has properties suitable for large molded articles.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have secondary to molding products such as TV cabinets and automobile dashboards such as high surface hardness, low weathering discoloration, and self-extinguishing properties. Found that a carbonate (co) polymer composed of isosorbide, a plant-derived monomer, possesses important properties in order to balance mechanical strength, moldability, and heat resistance while utilizing this property. However, the present invention has been completed by alloying with styrene resins including ABS resin. Further, it has been found that a carbonate copolymer obtained by copolymerizing an alicyclic dihydroxy compound has a good balance between glass transition temperature and impact resistance and has good characteristics even in a wide range of blends.

That is, the gist of the present invention resides in the following [1] to [5].
[1] In a thermoplastic resin composition comprising (A) a polycarbonate containing a structural unit derived from a dihydroxy compound represented by the following general formula (1) and (B) a styrene-based resin, the structural weight ratio is 90 / A thermoplastic resin composition characterized by being in the range of 10 to 10/90.

[2] The thermoplastic resin composition according to [1], wherein the (A) polycarbonate has a glass transition temperature of 90 ° C. or higher.
[3] The thermoplastic resin composition according to [1] or [2], wherein the (A) polycarbonate further includes a structural unit derived from an alicyclic dihydroxy compound.
[4] The polycarbonate (A) is a polycarbonate copolymer containing a structural unit derived from the dihydroxy compound represented by the general formula (1) and a structural unit derived from the alicyclic dihydroxy compound, The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by Formula (1) and the structural unit derived from the alicyclic dihydroxy compound is in the range of 85:15 to 65:35 [3]. Thermoplastic resin composition.
[5] The (B) styrene resin is at least one selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, impact-resistant polystyrene, and acrylonitrile / styrene / acrylic rubber copolymer. The thermoplastic resin composition according to any one of [1] to [4].

  The thermoplastic resin composition of the present invention is a styrene-based material including a carbonate (co) polymer composed of isosorbide having excellent mechanical strength, impact strength, heat resistance, fluidity, surface hardness, weathering discoloration and the like, and ABS resin. Resin composition consisting of resin. Carbonate (co) polymers are derived from biomass resources such as plants. Even in the construction of a better future society, from the viewpoint of environmental and petroleum resource conservation, the environment and resource conservation is a little. Improvements are possible. In addition, it is extremely useful for various industrial uses such as the automotive field, OA equipment field, and electronic / electrical equipment field, and relatively large molded products such as exterior materials, interior materials, and electronic equipment casings in the automotive field. Ideal for required applications.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

(A) Polycarbonate The carbonate polymer of the present invention contains a structural unit derived from a dihydroxy compound represented by the following general formula (1). A copolymer obtained by replacing a dihydroxy compound such as a structural unit derived from an aliphatic or aromatic dihydroxy compound, or a copolymerized structural unit such as polyalkylene glycol may also be used.

  In the present invention, examples of the dihydroxy compound represented by the general formula (1) include isosorbide, isomannide, and isoidet, which are related to stereoisomers. These may be used alone or in combination of two kinds. A combination of the above may also be used.

  Among these dihydroxy compounds, isosorbide obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as resources and are readily available is easy to obtain and manufacture, optical properties, moldability From the viewpoint of

Since isosorbide is gradually oxidized by oxygen, in order to prevent decomposition due to oxygen during storage and handling during production, do not mix moisture, use an oxygen scavenger, or use a nitrogen atmosphere. It is important to set it down. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate is produced using isosorbide containing these decomposition products, the resulting polycarbonate is colored or causes a significant deterioration in physical properties. In addition, the polymerization reaction may be affected, and a high molecular weight polymer may not be obtained. In addition, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, coloring may occur in the obtained polycarbonate, or physical properties may be significantly deteriorated. As the stabilizer, a reducing agent or an antacid is used. Among them, examples of the reducing agent include sodium borohydride and lithium borohydride. Examples of the antacid include alkalis such as sodium hydroxide. Addition of such an alkali metal salt also serves as a polymerization catalyst, and if it is excessively added, the polymerization reaction may not be controlled.
In order to obtain isosorbide containing no oxidative decomposition product, isosorbide may be distilled as necessary. Moreover, also when the stabilizer is mix | blended in order to prevent the oxidation and decomposition | disassembly of isosorbide, you may distill isosorbide as needed. In this case, the distillation of isosorbide may be simple distillation or continuous distillation, and is not particularly limited. After the atmosphere is an inert gas atmosphere such as argon or nitrogen, distillation is performed under reduced pressure.
By performing such distillation of isosorbide, in the present invention, it is preferable to use a high purity isosorbide having a formic acid content of less than 20 ppm, more preferably 10 ppm or less, particularly 5 ppm or less.

  On the other hand, the dihydroxy compound of a copolymerization structural unit suitable for use in the present invention may be any of linear aliphatic, cycloaliphatic, and aromatic dihydroxy compounds. Examples of linear aliphatic dihydroxy compounds include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, Examples include 6- (2-ethyl) hexanediol, 1,6- (2,2,4-trimethyl) hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, and the like. it can.

  Examples of the cycloaliphatic (alicyclic) dihydroxy compound that can be used in the present invention include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1, Hexanediols such as 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,3-norbornanedimethanol, 2,5-norbornanedimethanol And norbornane dimethanols, tricyclodecane dimethanol, adamantane diols and the like. Of these, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,2-cyclohexanedimethanol are preferred.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxy diphenyl etc. are mentioned, Preferably bisphenol A is mentioned.

  Further, the polyalkylene glycol as the copolymerization unit preferably contains 2 to 40 carbonsyl groups having 2 to 4 carbon atoms per molecule, and examples thereof include polyethylene glycol and polypropylene glycol.

  The hydroxy compound which is these copolymerization structural units may be used individually by 1 type, and may mix and use 2 or more types. If a linear aliphatic dihydroxy compound or polyalkylene glycol is used as a copolymerization component, the glass transition temperature is drastically lowered, and the use as an automobile or electrical / electronic component is restricted, which is not preferable. When an aromatic dihydroxy compound is used as a copolymerization component, the reactivity is significantly different from that of the dihydroxy compound represented by the general formula (1), and transparency and the like deteriorate. It is difficult to obtain a high molecular weight polycarbonate resin of the dihydroxy compound represented by the general formula (1) alone. On the other hand, when a cycloaliphatic (sometimes referred to as alicyclic) dihydroxy compound is used as a copolymerization component, the dihydroxy compound represented by the general formula (1) and the alicyclic dihydroxy as shown below. Good balance of reactivity with compounds, relatively high molecular weight, relatively low glass transition temperature, less than linear aliphatic dihydroxy compounds, sufficiently high surface hardness and mechanical strength This is desirable.

  As described above, a polycarbonate obtained by copolymerizing a structural unit derived from the dihydroxy compound represented by the general formula (1) and a structural unit derived from the alicyclic dihydroxy compound, which is a preferred polycarbonate in the present invention, has not yet been reported. The details thereof will be described below, but the copolymers with other dihydroxy compounds are basically similar, and can be produced with reference to the above-mentioned patent documents.

  About the content rate of the structural unit derived from the dihydroxy compound represented by General formula (1), and the structural unit derived from an alicyclic dihydroxy compound, it can select in arbitrary ratios. However, when a differential scanning calorimetry (DSC) is performed, a single glass transition temperature is given. The carbonate copolymer of the present invention is a dihydroxy compound represented by the general formula (1) and an alicyclic dihydroxy compound. The glass transition temperature can be obtained as a polymer having an arbitrary glass transition temperature from about 45 ° C. to about 155 ° C. depending on the application.

  Therefore, for the resin composition of the present invention, by setting the glass transition temperature to 90 ° C. or higher, heat resistance (usable temperature) of 80 ° C. or higher can be secured, so that the dihydroxy represented by the general formula (1) It is necessary to appropriately select the ratio between the structural unit derived from the compound and the structural unit derived from the alicyclic dihydroxy compound. The ratio is preferably 100: 0 to 45:55 (mol%), particularly 95: 5 to 50:50 (mol%), more preferably 90:10 to 65:35 (mol%). If the number of structural units derived from the dihydroxy compound represented by the general formula (1) is larger than the above range and the number of structural units derived from the alicyclic dihydroxy compound is small, coloring tends to occur. Conversely, the structural formula is represented by the general formula (1). When the number of structural units derived from the dihydroxy compound is small and the number of structural units derived from the alicyclic dihydroxy compound is large, the molecular weight is difficult to increase and the glass transition temperature tends to decrease.

  Further, the degree of polymerization of the polycarbonate of the present invention is precisely determined by using a mixed solution of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 as a solvent, and the concentration of the polycarbonate is precisely 1.00 g / dl. The reduced viscosity measured at a temperature of 30.0 ° C. ± 0.1 ° C. (hereinafter simply referred to as “reduced viscosity of polycarbonate”) is 0.40 dl / g or more, particularly 0.40 dl / g or more and 2 The degree of polymerization is preferably 0.0 dl / g or less. When the reduced viscosity of this polycarbonate is extremely low, the mechanical strength when molded into civil engineering and building materials is weak. Further, when the reduced viscosity of the polycarbonate is increased, the fluidity at the time of molding is lowered, the cycle characteristics are lowered, the distortion of the molded product is increased, and it tends to be easily deformed by heat. Therefore, the reduced viscosity of the polycarbonate of the present invention is preferably in the range of 0.40 dl / g to 2.0 dl / g, particularly 0.45 dl / g to 1.5 dl / g.

  The polycarbonate of the present invention can be produced by a generally used polymerization method, and the polymerization method may be either a solution polymerization method using phosgene or a melt polymerization method in which it reacts with a carbonic acid diester. In the presence, a melt polymerization method in which a dihydroxy compound is reacted with a diester carbonate that is less toxic to the environment is preferred.

  Examples of the carbonic acid diester used in the melt polymerization method include those represented by the following general formula (2).

(In General formula (2), A and A 'are the C1-C18 aliphatic groups which may have a substituent, or the aromatic group which may have a substituent, A and A ′ may be the same or different.)

  Examples of the carbonic acid diester represented by the general formula (2) include diphenyl carbonate, substituted diphenyl carbonate represented by ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Particularly preferred are diphenyl carbonate and substituted diphenyl carbonate. These carbonic acid diesters may be used alone or in combination of two or more.

  The carbonic acid diester is preferably used in a molar ratio of 0.96 to 1.10, more preferably 0.98 to 1.04, relative to the dihydroxy compound. When this molar ratio is less than 0.96, the terminal OH groups of the produced polycarbonate are increased and the thermal stability of the polymer is deteriorated. On the other hand, when the molar ratio is higher than 1.10. The rate of the exchange reaction is reduced, making it difficult to produce a polycarbonate copolymer having a desired molecular weight, and the amount of residual carbonate diester of the produced polycarbonate is increased. This is not preferable because it causes odor of the product.

  Moreover, as a polymerization catalyst (transesterification catalyst) in melt polymerization, an alkali metal compound and / or an alkaline earth metal compound is used. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with an alkali metal compound and / or an alkaline earth metal compound. It is particularly preferred to use only metal compounds and / or alkaline earth metal compounds.

  Examples of the alkali metal compound used as the polymerization catalyst 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, cesium carbonate, 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 phenyl borohydride, lithium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, benzoic acid Cium, 2 sodium hydrogen phosphate, 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, cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt and the like.

  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.

  These alkali metal compounds and / or alkaline earth metal compounds may be used alone or in combination of two or more.

  Specific examples of basic boron compounds used in combination with alkali metal compounds and / or alkaline earth metal compounds include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethyl Sodium salt such as phenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, butyltriphenyl boron, potassium salt, lithium Examples thereof include salts, calcium salts, barium salts, magnesium salts, and strontium salts.

  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 hydroxide 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.

  These basic compounds may be used alone or in combination of two or more.

  When the alkali metal compound and / or alkaline earth metal compound is used, the polymerization catalyst is used in an amount of metal with respect to 1 mol in total of the dihydroxy compound represented by the general formula (1) and the alicyclic dihydroxy compound. As a conversion amount, it is normally used within the range of 0.1 to 100 μmol, preferably within the range of 0.5 to 50 μmol, and more preferably within the range of 1 to 25 μmol. If the amount of the polymerization catalyst used is too small, the polymerization activity necessary to produce a polycarbonate having a desired molecular weight cannot be obtained. On the other hand, if the amount of the polymerization catalyst used is too large, the hue of the resulting polycarbonate deteriorates, By-products are generated and fluidity is lowered and gel is generated more frequently, making it difficult to produce polycarbonate having the target quality.

  In the production of the polycarbonate of the present invention, the dihydroxy compound such as the dihydroxy compound represented by the general formula (I) may be supplied as a solid, or heated and supplied in a molten state. Alternatively, it may be supplied as an aqueous solution. When these raw material dihydroxy compounds are supplied in a molten state or in an aqueous solution, there is an advantage that they can be easily measured and transported when industrially produced.

  In the present invention, the method of reacting the dihydroxy compound represented by the general formula (I) or the copolymer component with a carbonic acid diester in the presence of a polymerization catalyst is usually carried out in two or more multistage processes. Specifically, the first stage reaction is carried out at a temperature of 140 to 220 ° C, preferably 150 to 200 ° C for 0.1 to 10 hours, preferably 0.5 to 3 hours. From the second stage onward, the reaction temperature is raised while gradually reducing the pressure of the reaction system from the pressure of the first stage, and at the same time, the phenol generated at the same time is removed from the reaction system. Is 200 Pa or less and a polycondensation reaction is performed under the temperature range of 210-280 degreeC.

  In the pressure reduction in this polycondensation reaction, it is important to control the balance between temperature and pressure in the reaction system. In particular, if either one of the temperature and the pressure is changed too quickly, unreacted monomers are distilled out, the molar ratio of the dihydroxy compound and the carbonic acid diester may be changed, and the degree of polymerization may be lowered. For example, when isosorbide and 1,4-cyclohexanedimethanol are used as the dihydroxy compound, 1,4-cyclohexanedimethanol is used when the molar ratio of 1,4-cyclohexanedimethanol to the total dihydroxy compound is 50 mol% or more. Since methanol easily distills out as a monomer, the reaction is carried out under a reduced pressure of about 13 kPa while the temperature is increased at a rate of temperature increase of 40 ° C. or less per hour, and further up to about 6.67 kPa. When the temperature is increased at a temperature increase rate of 40 ° C. or less per hour under the pressure of, and finally the polycondensation reaction is performed at a temperature of 200 to 250 ° C. at a pressure of 200 Pa or less, the degree of polymerization is sufficiently increased. Since the obtained polycarbonate is obtained, it is preferable.

  In addition, when the molar ratio of 1,4-cyclohexanedimethanol is less than 50 mol% with respect to all dihydroxy compounds, particularly when the molar ratio is 30 mol% or less, 1,4-cyclohexanedimethanol Compared with the case where the molar ratio is 50 mol% or more, the viscosity rises rapidly. For example, the temperature is increased at a rate of 40 ° C. or less per hour until the pressure in the reaction system is reduced to about 13 kPa. And the reaction is carried out at a pressure of up to about 6.67 kPa while increasing the temperature at a rate of temperature rise of 40 ° C. or more, preferably at a rate of temperature rise of 50 ° C. or more per hour. When a polycondensation reaction is finally performed at a temperature of 220 to 290 ° C. under a reduced pressure of 200 Pa or less, a polycarbonate having a sufficiently high degree of polymerization is obtained, which is preferable.

  The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

  When the polycarbonate of the present invention is produced by a melt polymerization method, a phosphoric acid compound or a phosphorous acid compound can be added during polymerization for the purpose of preventing coloring.

  As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compound components. When the addition amount of the phosphorus compound is less than the above lower limit, the effect of preventing coloring is small, and when it is more than the above upper limit, haze is increased, or on the contrary, the coloring is promoted or the heat resistance is lowered.

  When adding a phosphorous acid compound, the heat stabilizer shown below can be selected arbitrarily and used. In particular, trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) One or more of pentaerythritol diphosphites can be suitably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compound component. It is preferable to do. If the amount of the phosphite compound is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, it may cause haze to increase, or conversely promote coloring or reduce heat resistance. Sometimes.

  The phosphoric acid compound and the phosphorous acid compound can be added in combination, but the addition amount in that case is the total amount of the phosphoric acid compound and the phosphorous acid compound, and the total hydroxy compound component described above, It is preferable to set it as 0.0001 mol% or more and 0.005 mol% or less, More preferably, it is 0.0003 mol% or more and 0.003 mol% or less. If the amount added is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, haze may be increased, or conversely, coloring may be promoted or heat resistance may be lowered.

  The polycarbonate of the present invention thus produced can be blended with a heat stabilizer in order to prevent a decrease in molecular weight and a deterioration in hue during molding.

  Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate , Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethylbenzenephosphonate , Diethyl benzenephosphonate, dipropyl benzenephosphonate and the like. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate, and further blending a phosphorous acid compound by a blending method described later, an increase in haze during polymerization, coloring, and By avoiding a decrease in heat resistance, more heat stabilizers can be blended, and hue deterioration can be prevented.

  The blending amount of these heat stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.2 part by weight when polycarbonate is 100 parts by weight. Part is more preferred.

  The polycarbonate of the present invention can be blended with an antioxidant generally known for the purpose of antioxidant.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4 -Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2, One type or two or more types such as 4,8,10-tetraoxaspiro (5,5) undecane may be mentioned.

  The blending amount of these antioxidants is preferably 0.0001 to 0.5 parts by weight when the polycarbonate is 100 parts by weight.

(B) Styrenic resin The styrenic resin (component B) used in the thermoplastic resin composition of the present invention is a styrene monomer and, if necessary, other vinyl monomers and rubbers copolymerizable therewith. It is a polymer obtained by polymerizing one or more kinds selected from a porous polymer.

  Examples of the styrene monomer used in the styrene resin component include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl. Examples include styrene derivatives such as naphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable. Furthermore, these can be used alone or in combination of two or more.

  Other vinyl monomers copolymerizable with the styrenic monomer include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate, methyl acrylate, and ethyl acrylate. Alkyl esters of acrylic acid such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, dodecyl acrylate, aryl methacrylates such as phenyl methacrylate, benzyl methacrylate, methyl methacrylate, ethyl Methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate Methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, and dodecyl methacrylate; epoxy group-containing methacrylic acid esters such as glycidyl methacrylate; maleimides such as maleimide, N-methylmaleimide, and N-phenylmaleimide And α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof.

  Examples of the rubbery polymer copolymerizable with the styrenic monomer include polybutadiene, polyisoprene, random copolymer and block copolymer of styrene / butadiene, acrylonitrile / butadiene copolymer, alkyl acrylate ester or methacrylic ester. Copolymers of acid alkyl esters and butadiene, diene copolymers such as butadiene / isoprene copolymers, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers and block copolymers Copolymers of ethylene and α-olefin, etc., ethylene / methacrylate copolymers, copolymers of ethylene and unsaturated carboxylic esters such as ethylene / butyl acrylate copolymers, ethylene / vinyl acetate copolymers, etc. Of ethylene and aliphatic vinyl , Terpolymers of ethylene, propylene and nonconjugated dienes such as ethylene / propylene / hexadiene copolymers, acrylic rubbers such as polybutyl acrylate, and polyorganosiloxane rubber components and polyalkyl (meth) acrylate rubber components Composite rubber (hereinafter referred to as IPN type rubber) having a structure in which they are intertwined so that they cannot be separated.

  Examples of the styrene resin include polystyrene, styrene / butadiene / styrene copolymer (SBS), hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS), hydrogenated styrene / isoprene / styrene copolymer (SEPS). ), Impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl methacrylate / Acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / styrene / acrylic rubber copolymer (ASA resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin) and styrene / IPN Resins such as rubber copolymer, or mixtures thereof.

  Such a styrenic thermoplastic resin may have high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst at the time of production. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution, block copolymers, and polymers and copolymers having high stereoregularity obtained by methods such as anion living polymerization and radical living polymerization are used. It is also possible. These may be used alone or in combination of two or more.

  Among these, polystyrene (hereinafter abbreviated as “PS”), impact-resistant polystyrene (hereinafter abbreviated as “HIPS resin”), acrylonitrile / styrene copolymer (hereinafter abbreviated as “AS resin”). ), Acrylonitrile / butadiene / styrene copolymer (hereinafter abbreviated as “ABS resin”), acrylonitrile / styrene / acrylic rubber copolymer (hereinafter abbreviated as “ASA resin” or “AAS resin”), From the group consisting of acrylonitrile / ethylene propylene rubber / styrene copolymer (hereinafter abbreviated as “AES resin”) and methyl methacrylate / butadiene / styrene copolymer (hereinafter abbreviated as “MBS resin”). It is preferable to use one or a mixture of two or more selected, among which ABS resin, ASA resin, AES Fat is preferable. Further, among these, ABS resin is preferable in a comprehensive balance, and the ASA resin has characteristics of excellent thermal stability and chemical resistance when melted. Moreover, if there are few compounding quantities, a HIPS resin is preferable from a cost surface. The resin composition of the present invention is a resin that is more suitable for large molded articles in that it can sufficiently compensate for the drawbacks of polycarbonate alone.

  The ABS resin used in the present invention is a mixture of a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is. As the diene rubber component forming this ABS resin, for example, a rubber having a glass transition point of 10 ° C. or less such as polybutadiene, polyisoprene and styrene-butadiene copolymer is used, and the proportion thereof is 100% by weight of the ABS resin component. It is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight. Examples of the vinyl cyanide compound grafted onto the diene rubber component include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound grafted onto the diene rubber component, those described above can be used as well, and styrene and α-methylstyrene are particularly preferably used. The ratio of the component grafted to the diene rubber component is preferably 95 to 20% by weight, particularly preferably 50 to 90% by weight, based on 100% by weight of the ABS resin component. Furthermore, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight with respect to 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for a part of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally well-known various things can be used for the initiator, serial transfer agent, emulsifier, etc. which are used by reaction as needed.

  The ASA resin used in the present invention is a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to an acrylic rubber component, or the thermoplastic graft copolymer, a vinyl cyanide compound and an aromatic resin. A mixture with a copolymer of a group vinyl compound. The acrylic rubber referred to in the present invention contains an alkyl acrylate unit having 2 to 10 carbon atoms, and further contains styrene, methyl methacrylate, butadiene as other copolymerizable components as necessary. Also good. Preferred examples of the alkyl acrylate having 2 to 10 carbon atoms include 2-ethylhexyl acrylate and n-butyl acrylate. The alkyl acrylate is preferably contained in an amount of 50% by weight or more in 100% by weight of the acrylate rubber. Furthermore, such acrylate rubbers are at least partially crosslinked, and examples of such crosslinking agents include ethylene glycol diacrylate, butylene glycol diacrylate, ethylene glycol dimethacrylate, allyl methacrylate, polypropylene glycol diacrylate, and the like. The crosslinking agent is preferably used in an amount of 0.01 to 3% by weight based on the acrylate rubber. The ratio of the vinyl cyanide compound and the aromatic vinyl compound is 5 to 50% by weight of the vinyl cyanide compound and 95 to 50% by weight of the aromatic vinyl compound with respect to the total amount of 100% by weight. It is preferable that the vinyl compound is 15 to 35% by weight and the aromatic vinyl compound is 85 to 65% by weight.

  The AES resin used in the present invention is a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound on an ethylene-propylene rubber component or an ethylene-propylene-diene rubber component, or the thermoplastic graft copolymer. And a mixture of a vinyl cyanide compound and a copolymer of an aromatic vinyl compound.

  In the ABS, ASA, and AES resin of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles, but preferably has a large proportion of rubber particles forming a single phase.

  Further, it is well known that ABS, ASA and AES resins contain a vinyl cyanide compound and an aromatic vinyl compound which are not grafted to a diene rubber component. In the ABS, ASA and AES resins of the present invention, too. It may contain a free polymer component generated during such polymerization. The molecular weight of the copolymer comprising such free vinyl cyanide compound and aromatic vinyl compound is 10,000 to 500,000, preferably 50,000 to 200,000 in terms of weight average molecular weight (Mw) calculated by GPC measurement. 000. The weight average molecular weight shown here is calculated by GPC measurement using a calibration curve with a standard polystyrene resin.

  The ABS, ASA, and AES resins in the present invention may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, and may be copolymerized in one stage or in multiple stages. May be. Moreover, what blended the vinyl compound polymer obtained by copolymerizing an aromatic vinyl compound and a vinyl cyanide component separately to the ABS resin obtained by this manufacturing method can also be used preferably. The vinyl compound polymer obtained by separately copolymerizing the aromatic vinyl compound and the vinyl cyanide component has a weight average molecular weight (Mw) of 10,000 to 500,000, preferably 50,000 to 200,000. It is what is.

  The HIPS resin used in the present invention is obtained by mixing a rubbery polymer in polystyrene. The mixing method may be a simple mechanical blending method, but in order to obtain good compatibility, so-called graft copolymerization is carried out by graft copolymerization of a styrene monomer in the presence of a rubbery polymer. More preferred are those obtained by formulation. It is also desirable to use a rubber-modified polystyrene resin (graft polymer) obtained by the above method, which is obtained by a so-called graft-blend method in which polystyrene obtained by a separate method is mixed. As the polymerization method, emulsion polymerization, solution polymerization, suspension polymerization and the like can be applied.

  Specific examples of the rubbery polymer include conjugated diene rubbers such as polybutadiene, styrene-butadiene copolymer, hydrogenated styrene-butadiene block copolymer, and non-conjugated diene systems such as ethylene-propylene copolymer. Although rubber is mentioned, polybutadiene is particularly preferable.

  Examples of the styrenic monomer include styrene, α-methylstyrene, p-methylstyrene, bromostyrene, and the like. Among these, it is optimal to use styrene and / or α-methylstyrene. Examples of the monomer other than the styrene monomer include vinyl monomers such as acrylonitrile and methyl methacrylate.

  The rubber content in the HIPS resin is preferably 1 to 40% by weight, more preferably 3 to 30% by weight. Further, even when a monomer component other than the styrene monomer is included, the rubber and styrene monomer component content in the HIPS resin is desirably 90% by weight or more, and more preferably 95% by weight. % Or more.

  The MFR reflecting the molecular weight of the HIPS resin is preferably 0.5 to 15 g / 10 min at 200 ° C. and a load of 5 kg, more preferably 1.0 to 10 g / 10 min.

  Hydrogenated styrene / butadiene / styrene copolymer (hereinafter referred to as “hydrogenated SBS”), hydrogenated styrene / ethylene / butadiene / styrene copolymer (hereinafter referred to as “hydrogenated SEBS”) and water used in the present invention. Hydrogenated block copolymers represented by styrene / isoprene / styrene (hereinafter referred to as “SEPS”) include a block made of a polymer of a styrene monomer and a conjugated diene monomer such as polybutadiene and polyisoprene. And those obtained by hydrogenating (hydrogenating) unsaturated bonds of a block copolymer comprising a block of a polymer. The block copolymer may take any form of diblock, triblock and multiblock. Furthermore, as the shape of the block, any form such as a linear shape, a radial shape, and a branched shape can be basically taken, but a linear shape is more preferable.

  Here, examples of the styrene monomer include styrene and α-methylstyrene, and those in which 80% by weight or more of the styrene monomer is styrene are preferable. Examples of the conjugated diene monomer component include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like. In particular, butadiene and isoprene are preferable, and copolymers of both can also be used. Further, the hydrogenated block copolymer that can be used in the present invention is a hydrogenated block of 50% or more, more preferably 80% or more of the carbon-carbon unsaturated bond in the polymer block of the conjugated diene monomer. is there.

  For block copolymers before hydrogenation, conjugated diene and styrene monomers are sequentially polymerized using alkyllithium such as butyllithium and styryllithium as a catalyst, or separately for each monomer. It can be obtained by, for example, a method of reacting and bonding the obtained polymer with a bifunctional coupling agent.

Furthermore, as a method of hydrogenating the obtained block polymer, a metal such as nickel, palladium, platinum or ruthenium supported on a material having a small surface area such as carbon, alumina or diatomaceous earth, Raney nickel, lacquer raw nickel or the like Using a homogeneous catalyst such as a Ziegler catalyst such as a heterogeneous catalyst or a combination of a transition metal compound and an alkylated product of aluminum, alkaline earth metal, alkali metal, etc., under a condition of 20 to 200 ° C., 1 to 200 kgf / The method of making it contact with hydrogen gas of cm < ² > for 0.1 to 100 hours can be mentioned.

  The amount of the styrenic polymer block in the hydrogenated block copolymer of the present invention is 10 to 50% by weight, particularly preferably 15 to 35% by weight. The molecular weight of the styrenic polymer block is 4,000 to 80,000 in terms of number average molecular weight, and preferably 8,000 to 60,000. The molecular weight of the hydrogenated block copolymer is in the range of 30,000 to 500,000 in terms of number average molecular weight.

  The constituent ratio (weight) of (A) polycarbonate and (B) styrenic resin in the thermoplastic resin composition of the present invention is in the range of 90/10 to 10/90, preferably 85/15 to 20/80. Yes, more preferably 85/15 to 40/60. When the content of the component (A) is less than 10%, the effect on resource / environmental conservation, which is an important target of the present invention, is small. Moreover, when there is more content of a component (A) than 90%, the fluid improvement effect is not enough.

  Even if the polycarbonate of the present invention does not contain an aromatic group, the compatibility with the styrenic polymer is good, and the occurrence of defects associated with poor compatibility such as peeling and pearl luster is hardly observed. In order to further improve, a compatibilizer may be blended. Examples of the compatibilizer include an epoxy compound, an epoxy-modified styrene elastomer and a styrene-maleic anhydride copolymer.

  The epoxy compound may be monofunctional, bifunctional, trifunctional, or polyfunctional, or a mixture of two or more of these. In particular, bifunctional, trifunctional, and polyfunctional epoxy compounds, that is, compounds having two or more epoxy groups in one molecule are preferable. Further, the epoxy compound may be any of alcohol, phenolic compound, glycidyl compound obtained from the reaction of carboxylic acid and epichlorohydrin, alicyclic epoxy compound, and the like.

  Specific examples of epoxy compounds include glycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, and allyl glycidyl ether; neopentyl glycol Diglycidyl ethers such as diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether; fatty acid glycidyl esters such as benzoic acid glycidyl ester and sorbic acid glycidyl ester; Glycidyl ester, terephthalic acid diglycidyl ester, ortho Diglycidyl esters such as diglycidyl tartrate; alicyclic diepoxy compounds such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate; glycidylimide compounds such as N-glycidylphthalimide . Of these, glycidyl ether compounds obtained from the reaction of bisphenol A and epichlorohydrin, particularly bisphenol A diglycidyl ether, are preferred. In particular, bisphenol A glycidyl ether having an epoxy equivalent of 100 to 200 g / eq equivalent is preferred.

  The compounding quantity of an epoxy compound is 0.1-3 weight part with respect to 100 weight part of component (A), Preferably it is 0.15-2 weight part. When the amount is less than 0.1 parts by weight, the compatibility improving effect is not recognized, and when the amount is more than 3 parts by weight, the fluidity at the time of melt molding is lowered.

  The epoxy-modified styrene elastomer is a graft copolymer of glycidyl (meth) acrylate with the hydrogenated styrene block copolymer. For example, epoxy-modified styrene-butadiene-styrene block copolymer (ESBS) is Daicel Chemical Industries. The product sold under the trade name Efrent A1010 by the company can be used.

  The styrene-maleic anhydride copolymer has a weight average molecular weight of 150,000 to 400,000, and the content of maleic anhydride is usually 1 to 40% by weight, preferably 2 to 30% by weight, more preferably 3 to 20%. % By weight. These copolymerization forms may be block copolymers or graft copolymers in addition to ordinary copolymers. An example of such a copolymer is the trade name Dailaque sold by Nova Chemical Japan.

  In addition, a release agent can be blended in the thermoplastic resin of the present invention within a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding. Examples of the release agent include olefin wax, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax and the like. The compounding amount of the release agent is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the A component polycarbonate.

  The thermoplastic resin composition of the present invention can be blended with an ultraviolet absorber and a light stabilizer as long as the object of the present invention is not impaired. Examples of such a compound include 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-p -Phenylenebis (1,3-benzoxazin-4-one) and the like. The blending amount of the stabilizer is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the carbonate (co) polymer which is the component A.

  An antistatic agent can be blended with the thermoplastic resin composition of the present invention as long as the object of the present invention is not impaired. Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like.

  The thermoplastic resin composition used in the present invention is produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. be able to. Furthermore, a nucleating agent, a flame retardant, an inorganic filler, an impact modifier, a foaming agent, a dye / pigment and the like that are usually used in the resin composition may be contained within a range not impairing the object of the present invention.

  You may mix | blend a flame retardant etc. with the thermoplastic resin composition of this invention in the range which does not impair the objective of this invention. Examples of the flame retardant to be added include bromine-based flame retardants, phosphate ester-based flame retardants, and red phosphorus-based flame retardants.

  First, examples of brominated flame retardants include halogenated flame retardants represented by brominated bisphenol, brominated polystyrene, carbonate oligomers of brominated bisphenol A, copolymers of brominated bisphenol A and bisphenol A, and copolymerized oligomers. Among the phosphate ester flame retardants, triphenyl phosphate as the monophosphate compound and resorcinol bis (dixylenyl phosphate) as the condensed phosphate ester have good flame retardancy and fluidity during molding. It can be preferably used for reasons such as being good.

  The red phosphorus flame retardant to be used may be red phosphorus in which the surface of red phosphorus is microencapsulated with a thermosetting resin and / or an inorganic material in addition to general red phosphorus. Furthermore, the use of such red microencapsulated red phosphorus is preferably used in the form of master pellets in order to improve safety and workability. Examples of inorganic materials used for such microencapsulation include magnesium hydroxide, aluminum hydroxide, titanium hydroxide, tin hydroxide, cerium hydroxide, and the like. Thermosetting resins include phenol / formalin, urea / formalin. And melamine / formalin resin. Further, red phosphorus or the like, which is formed by coating a thermosetting resin on a material coated with such an inorganic material and performing a double coating treatment, can be preferably used. The red phosphorus used can be electroless plated, and the electroless plating film is a metal plating film selected from nickel, cobalt, copper, iron, manganese, zinc, or alloys thereof. be able to. Further, red phosphorus coated with the inorganic material and the thermosetting resin described above may be used on red phosphorus plated without electrolysis. The amount of components used for microencapsulation such as inorganic material, thermosetting resin and electroless plating is desirably 20% by weight or less, more preferably 5 to 15% in 100% by weight of red phosphorus flame retardant. % By weight. Exceeding 20% by weight is not preferable because adverse effects such as a reduction in flame retardancy and a decrease in mechanical properties become larger than effects such as suppression of phosphine and ensuring safety. The average particle size of the red phosphorus flame retardant is 1 to 100 μm, preferably 1 to 40 μm. Commercially available products of such microencapsulated red phosphorus flame retardants are Nova Excel 140, Nova Excel F-5 (Rin Chemical Industry Co., Ltd .: trade name), Hishigard TP-10 (Nippon Chemical Industry Co., Ltd.). : Product name), Hostafram RP614 (manufactured by Clariant Japan Co., Ltd .: product name), and the like. Furthermore, the use of a red phosphorus flame retardant in which such microencapsulated red phosphorus is further master-pelletized with a thermoplastic resin achieves good flame retardancy and mechanical properties, and also increases safety during production. Therefore, it can be preferably used. In the present invention, it is more preferable to use a material that has been pelletized with a thermoplastic resin mainly composed of an aromatic polycarbonate resin.

  Further, additives such as antimony trioxide and sodium antimonate can be added as flame retardant assistants, and additives such as polytetrafluoroethylene having fibril-forming ability can be added as anti-drip agents.

  The inorganic filler used in the present invention is generally used in a resin composition such as a fiber, plate or granule, and includes a mixture thereof. Specifically, fibrous materials such as glass fibers, basalt fibers, ceramic whiskers, wollastonite, carbon fibers; plate-like materials such as glass flakes, mica, talc; silica, alumina, glass beads, carbon black, calcium carbonate, etc. Well-known things, such as a granular material, are mentioned. The criteria for these selections depend on the required properties of the product, but for mechanical strength and rigidity, fibrous materials, especially glass fibers, are selected, and when it is important to reduce the anisotropy and warpage of molded products, A material, particularly mica, is selected. In addition, an optimum granular material is selected based on an overall balance in consideration of fluidity during molding.

  The glass fiber is not particularly limited as long as it is generally used for resin reinforcement. For example, a long fiber type (roving) or a short fiber type (chopped strand) can be selected and used. The fiber cross section may be circular or irregular, and the fiber diameter (the irregular cross section is the cross-sectional area). The diameter is generally 6 to 25 μm when expressed in terms of a circle. Further, the glass fiber may be treated with a sizing agent (for example, polyvinyl acetate, polyester, etc.), a coupling agent (for example, silane compound, boron compound, etc.), other surface treatment agents, and the like.

  The blending amount of the inorganic filler (C) is 0 to 100 parts by weight, preferably 0.01 to 80 parts by weight, based on 100 parts by weight of the total amount of (A) polycarbonate and (B) styrene resin. is there. When the amount is more than 100 parts by weight, the mechanical properties are deteriorated, but the amount of the inorganic filler is preferably 5 parts by weight or more when improvement of mechanical strength is a target.

  Other impact modifiers include, for example, an acrylic-butadiene impact modifier, a composite rubber having a structure intertwined so that it cannot be separated from a polyorganosiloxane component and a poly (meth) alkyl acrylate component, alkyl ( Mention may be made of polymers grafted with (meth) acrylates and optionally copolymerizable vinyl polymers. Specific examples of the former include HIA15 (trade name) manufactured by Kureha Chemical Co., Ltd., and specific examples of the latter include Metablene S2001 (trade name) manufactured by Mitsubishi Rayon Co., Ltd. Such impact modifiers usually contain a component in which the monomer component is polymerized without being copolymerized with the base rubber component, and the molecular weight of such component is usually calculated by GPC measurement in terms of standard polystyrene. The average molecular weight is from 50,000 to 500,000.

  The thermoplastic resin composition obtained in the present invention can be applied to known molding methods such as normal injection molding, extrusion molding, blow molding, compression molding, and in particular to obtain a large molded article. It is suitable for the molding method. The resin temperature for injection molding is 230 to 270 ° C. Further, in the case of large molded products, the residence time becomes longer in the injection molding machine, so it is necessary to consider the thermal stability of the styrenic resin, preferably 235 to 260. ° C.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In the following, the physical properties and characteristics of polycarbonate were evaluated by the following methods. (1) Reduced viscosity
Using an Ubbelohde viscometer, a mixed solution of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 was used as a solvent, the concentration was precisely adjusted to 1.00 g / dl, and a temperature of 30. Measurement was performed at 0 ° C. ± 0.1 ° C. The higher this number, the greater the molecular weight.

(2) Glass transition temperature (Tg)
Using a differential scanning calorimeter ("DSC822" manufactured by METTLER) with a sample of about 10mg, heated at a rate of temperature increase of 10 ° C / min, measured according to JIS K 7121 (1987). The extrapolated glass transition start temperature Tg, which is the temperature at the intersection of the straight line obtained by extending the line to the high temperature side and the broken line drawn at the point where the slope of the step change portion of the glass transition is maximized, was determined. .

In addition, the resin composition in this invention was evaluated with the evaluation item and the method of the following (3)-(5).
(3) Fluidity: The Archimedean spiral length of the 6 mm diameter semicircular flow path was measured at a cylinder temperature of 250 ° C., a mold temperature of 40 ° C., and an injection pressure of 98.1 MPa using an injection molding machine (IS150 manufactured by Toshiba Machine Co., Ltd.). 30 cm or more is a rough guide for large molded products.

(4) Thermal deformation temperature: Thermal deformation using an ISO test piece obtained at an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: model SG-75 MIII) at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. The temperature was measured according to ISO 75. The load was measured at 0.45 MPa. A target of 80 ° C. or higher is used for large molded articles in automobiles, electrical / electronics, and OA.

(5) Impact strength, weld strength ratio Using Custom Scientific's minimax injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., a length of 31.5 mm and a width of 6 A rod-shaped test piece having a thickness of 2 mm and a thickness of 3.2 mm was obtained by injection molding.
A notch with a depth of 1.2 mm was attached to this rod-shaped test piece with a notching machine to obtain a test piece for measuring Izod impact strength. With respect to this test piece for impact strength, the Izod impact strength with a notch at 23 ° C. was measured using a custom scientific mini-max Izod impact tester “CS-183TI type”. The target is 100 J / m ² or more for large molded article applications in automobiles, electrical / electronics and OA applications.

On the other hand, a weld strength measurement test piece (a weld occurs in the middle of the test piece) having gates installed at both ends of the rod-like test piece shape was obtained by injection molding in the same manner as described above. A tensile test is performed on the rod-shaped test piece and the test piece for measuring the weld strength at a tensile speed of 10 mm / min, the tensile strength is measured, and the tensile strength ratio with and without weld (referred to as the weld strength ratio) is measured. did. If the weld strength ratio is 80% or more, it is judged that the strength is practically sufficient.
In addition, the (B) styrene resin used in the Example is as follows.
-ABS resin: Product name Techno ABS130 manufactured by Technopolymer
(220 ° C, 10kg MVR is 18g / 10min)
-HIPS resin: Product name PSJ polystyrene HT60 manufactured by PS Japan
(200 ° C, 5kg MVR 6.2g / 10min)
-ASA resin: Product name Techno ASA manufactured by Techno Polymer
Moreover, the formic acid content of isosorbide used in the following Production Examples 1 to 5 was 5 ppm. The formic acid was quantified by the following method.

(6) Quantitative determination of formic acid About 0.5 g of isosorbide was collected in a 50 ml volumetric flask and made up to volume with pure water. The formic acid concentration in the solution was measured by ion chromatography. For the measurement by ion chromatography, the above solution was injected into a 100 μl sample loop, and the peak having the same retention time as that of the standard sample was used as formic acid to quantify it from the peak area by the absolute calibration curve method. As a standard sample, an aqueous sodium formate solution was used.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As the measurement column, AG-15 was used for the guard column, AS-15 was used for the separation column, and the eluent concentration was 10 mM NaOH. The flow rate was 1.2 ml / min, and the thermostat temperature was 35 ° C.
A membrane suppressor was used as the suppressor, and 25 mM-H2SO4 was used as the regenerating solution.

[Production Example 1]
(A) Production of Polycarbonate With respect to 27.7 parts by weight (0.516 mol) of isosorbide (Rocket Fleure), 1,4-cyclohexanedimethanol (Eastman, hereinafter referred to as “1,4-CHDM”) 13.0 parts by weight (0.221 mol), diphenyl carbonate (Mitsubishi Chemical Co., Ltd., hereinafter abbreviated as “DPC”) 59.2 parts by weight (0.752 mol), and carbonic acid as a catalyst. Cesium (manufactured by Wako Pure Chemical Industries, Ltd.) 2.21 × 10 ⁻⁴ parts by weight (1.84 × 10 ⁻⁶ mol) was charged into the reaction vessel, and the first step of the reaction under a nitrogen atmosphere, The temperature of the heating tank was heated to 150 ° C., and the raw materials were dissolved while stirring as necessary (about 15 minutes).
Subsequently, the pressure was changed from normal pressure to 13.3 kPa, and the generated phenol was extracted out of the reaction vessel while the heating bath temperature was increased to 190 ° C. over 1 hour.

  After maintaining the entire reaction vessel at 190 ° C. for 15 minutes, as a second step, the pressure in the reaction vessel is set to 6.67 kPa, the heating bath temperature is increased to 230 ° C. in 15 minutes, and the generated phenol is removed. It was extracted out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was raised to 250 ° C. in 8 minutes, and the pressure in the reaction vessel was allowed to reach 0.200 kPa or less in order to remove the generated phenol. After reaching a predetermined stirring torque, the reaction was terminated, and the produced reaction product was extruded into water to obtain polycarbonate pellets. The properties (reduced viscosity, glass transition temperature) of the obtained polycarbonate were measured according to the methods (1) and (2), respectively, and the results are shown in Table 1. The polycarbonate obtained in this production example was designated as “ISOB-PC1”.

[Production Example 2]
In Production Example 1, 19.7 parts by weight (0.363 moles) of isosorbide, 21.6 parts by weight of 1,4-CHDM (0.404 moles), 58.8 parts by weight of DPC (0.741 moles), carbonic acid as a catalyst. It implemented similarly except having changed into 2.19 * 10 <-4> weight part (1.82 * 10 <^-6> mol) of cesium. The results obtained by measuring the physical properties of this polycarbonate are shown in Table 1. The polycarbonate obtained in this production example was designated as “ISOB-PC2”.

[Production Example 3]
In Production Example 1, 25.8 parts by weight (0.480 moles), 58.6 parts by weight (0.734 moles) DPC, and 15.7 parts by weight (0.288 moles) of isosorbide, and The same procedure was performed except that the catalyst was changed to 2.18 × 10 ⁻⁴ parts by weight (1.80 × 10 ⁻⁶ mol) of cesium carbonate. The results obtained by measuring the physical properties of this polycarbonate are shown in Table 1. The polycarbonate obtained in this production example was designated as “ISOB-PC3”.

[Production Example 4]
In Production Example 1, isosorbide 35.9 parts by weight (0.674 mol), 1,4-CHDM 4.4 parts by weight (0.083 mol), DPC 59.7 parts by weight (0.764 mol), carbonic acid as a catalyst. It implemented similarly except having changed to cesium 2.22 * 10 <^-4> weight part (1.87 * 10 <^-6> mol). The obtained results are shown in Table 1. The results obtained by measuring the physical properties of this polycarbonate are shown in Table 1. The polycarbonate obtained in this production example was designated as “ISOB-PC4”.

[Production Example 5]
In Production Example 1, 59.9 parts by weight of DPC (0.592 mol, cesium carbonate 2.23 × 10 ⁻⁴ parts by weight (1.45 as a catalyst) with respect to 40.1 parts by weight (0.581 mol) of isosorbide × was changed to 10 ^-6 mol), it was carried out in the same manner. was polycarbonate obtained results this obtained by measuring physical properties of the polycarbonate in. this production example shown in Table 1 as "ISOB-PC 5" .

[Examples 1 to 8]
The resin compositions of Examples and Comparative Examples were obtained as follows.
Using a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12), the components (A ) Polycarbonate and (B) styrenic resin were uniformly mixed with a tumbler mixer, then fed from the barrel 1 and melt mixed to prepare a composition. Said evaluation was performed with respect to the obtained composition. In addition, all the test pieces for evaluation had a good white opaque appearance with no color unevenness such as pearl luster. About the obtained thermoplastic resin, the evaluation test of said (3)-(5) was done. The results are shown in Table 2.

[Comparative Examples 1-8]
A thermoplastic resin was produced in the same manner as in Example 1 except that the component (A) polycarbonate alone or (B) styrene resin alone was used at the ratio shown in Table 3. Said evaluation was performed with respect to the obtained composition. In addition, all the test pieces for evaluation had a good white opaque appearance with no color unevenness such as pearl luster. About the obtained thermoplastic resin, the evaluation test of said (3)-(5) was done. The results are shown in Table 3.

1) As shown in Comparative Examples 6-8, the styrene resin alone, especially HIPS, has some problems in heat resistance and impact strength, but it has good flowability and is a resin for large molded articles. It is suitable as.
2) Further, as shown in Comparative Examples 1 to 5, the polycarbonates containing isosorbide do not achieve the target of fluidity, and some of them have remarkably poor impact strength.
3) On the other hand, as shown in Examples 1 to 8, the alloy of polycarbonate and styrene resin containing isosorbide within the scope of the present invention achieved all of the goals of fluidity, heat resistance, impact strength, and weld strength ratio. In addition, it is a material suitable for large molded products, and at the same time contains plant-derived isosorbide.

  The thermoplastic resin composition of the present invention is a resin composition excellent in mechanical strength, impact strength, heat resistance, fluidity, surface hardness, weather discoloration, etc., and polycarbonate containing isosorbide is derived from biomass resources such as plants. Even in the construction of a better future society, it has become possible to improve the environment and resource conservation as much as possible from the viewpoint of environment and oil resource conservation. In addition, it is extremely useful for various industrial uses such as the automotive field, OA equipment field, and electronic / electrical equipment field, and relatively large molded products such as exterior materials, interior materials, and electronic equipment casings in the automotive field. Ideal for required applications.

Claims (5)

(A) In the thermoplastic resin composition which consists of a polycarbonate containing the structural unit derived from the dihydroxy compound represented by the following general formula (1) and (B) a styrene-based resin, the structural weight ratio is 90/10 to 10 A thermoplastic resin composition characterized by being in the range of / 90.

  The thermoplastic resin composition according to claim 1, wherein the glass transition temperature of the (A) polycarbonate is 90 ° C or higher.   The thermoplastic resin composition according to claim 1 or 2, wherein the (A) polycarbonate further comprises a structural unit derived from an alicyclic dihydroxy compound.   The (A) polycarbonate is a polycarbonate copolymer containing a structural unit derived from a dihydroxy compound represented by the general formula (1) and a structural unit derived from an alicyclic dihydroxy compound, wherein the general formula (1) 4. The thermoplastic resin according to claim 3, wherein the ratio (mol%) of the structural unit derived from the dihydroxy compound represented by) and the structural unit derived from the alicyclic dihydroxy compound is in the range of 85:15 to 65:35. Composition.   The (B) styrene resin is at least one selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, impact-resistant polystyrene, and acrylonitrile / styrene / acrylic rubber copolymer. Item 5. The thermoplastic resin composition according to any one of Items 1 to 4.