JP2009144017A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition improving environment and resource maintenance even by a little and at the same time improved with chemical resistance and excellent in mechanical characteristics and heat resistance. <P>SOLUTION: This resin composition is obtained by blending (B) 1 to 80 pts.wt. aromatic polyester resin based on (A) 100 pts.wt. polycarbonate containing a constituting unit derived from a dihydroxy compound expressed by general formula (1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition. More specifically, it is a resin composition comprising a polycarbonate and an aromatic polyester resin containing isosorbide, which is a biomass resource, and is derived from a dihydroxy compound having improved chemical resistance and excellent fluidity, mechanical properties, and heat resistance. Polycarbonate resin composition containing structural units

  Aromatic polycarbonate resin is known as a resin that has the highest impact resistance among engineering plastics and has good mechanical properties, heat resistance, and dimensional accuracy, and is used in various fields by taking advantage of these characteristics. However, it has the disadvantages of chemical resistance, fluidity and moldability. In particular, since chemical resistance is inferior, when it comes into contact with chemicals such as organic solvents, cracks occur and mechanical properties are remarkably deteriorated. In order to improve the chemical resistance of aromatic polycarbonates, as shown in Patent Document 1, alloys with aromatic polyesters such as polyethylene terephthalate have been developed.

  By the way, an aromatic polycarbonate resin and an aromatic polyester resin are generally produced 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 obtain a carbonate polymer by transesterification with diphenyl carbonate using isosorbide as a plant-derived monomer (see, for example, Patent Document 2). However, the obtained carbonate polymer is brown and the mechanical strength is not satisfactory as a molding material. In addition, as a carbonate copolymer of isosorbide and other dihydroxy compounds, a polycarbonate copolymerized with bisphenol A has been proposed (see, for example, Patent Document 2), and further, isosorbide and an aliphatic diol are copolymerized. Thus, attempts have been made to improve the rigidity of homopolycarbonates made of isosorbide (see, for example, Patent Document 4). These were insufficient in mechanical strength and chemical resistance for application to molded products.

  Although carbonate polymers using isosorbide have been proposed in this way, they are still a resin with a comprehensive balance of heat resistance, mechanical strength, chemical resistance, fluidity, etc. for application to molded products. That's not the case. Further, these documents disclose only glass transition temperature and further basic mechanical characteristics, and characteristics such as chemical resistance important for molded article use are not sufficiently disclosed.

A number of polycarbonates obtained by polymerizing 1,4-cyclohexanedimethanol, which is an alicyclic dihydroxy compound, instead of bisphenol A have been proposed (for example, Patent Documents 5 and 6). The molecular weight of these polycarbonates is At most, it is as low as about 4000. Therefore, many have a low glass transition temperature, and the mechanical strength is insufficient as a molding material.
Japanese Patent Publication No. 36-14035 GB1079686 Publication JP-A-56-55425 WO 2004/111106 gazette JP-A-6-145336 Japanese Patent Publication No. 63-12896

  As described above, the aromatic polycarbonate resin that is currently widely used for molded products, and the alloy of aromatic polycarbonate resin and aromatic polyester resin with improved chemical resistance can be used in the construction of a better future society. There is a problem from the viewpoint of oil resource conservation. Accordingly, it was made for the purpose of providing a resin composition having improved mechanical properties and heat resistance, with improved chemical resistance as well as environmental and resource conservation.

  In view of the above problems, the present inventors have intensively studied. As a result, the polycarbonate composed of plant-derived monomer, isosorbide, does not contain an aromatic group as a main component, and the aromatic polyester resin and the molding material. As a result, the chemical resistance and fluidity were improved by alloying the two, and the present invention was completed. Furthermore, it has been found that polycarbonates copolymerized with alicyclic dihydroxy compounds have a good balance between glass transition temperature and impact resistance and have good characteristics even in a wide range of blends with aromatic polyester resins. Is.

That is, the gist of the present invention resides in the following [1] to [8].
At least from 1 to 80 parts by weight of the aromatic polyester resin (B) with respect to 100 parts by weight of the carbonate (co) polymer (A) containing a structural unit derived from the dihydroxy compound represented by the following general formula (1) It exists in the carbonate (co) polymer resin composition containing the structural unit derived from the comprised dihydroxy compound.

  The second gist lies in the resin composition according to claim 1, wherein the carbonate (co) polymer (A) has a glass transition temperature of 90 ° C. or higher.

  The third gist is that the carbonate (co) polymer (A) includes a structural unit derived from the dihydroxy compound represented by the formula (1) and a structural unit derived from the alicyclic dihydroxy compound. The resin composition according to any one of claims 1 and 2, wherein the resin composition comprises a coalescence.

  The fourth gist lies in a carbonate (co) polymer resin composition containing a structural unit derived from a dihydroxy compound, wherein the aromatic polyester resin (B) is a polybutylene terephthalate resin.

The fifth gist is a carbonate containing a structural unit derived from a dihydroxy compound, characterized in that 0.01 to 1 part by weight of (C) an organophosphorus compound is further blended with 100 parts by weight of the resin composition. It exists in the (co) polymer resin composition.

  The polycarbonate resin composition containing the structural unit derived from the dihydroxy compound of the present invention is a resin composition comprising a polycarbonate composed of isosorbide and an aromatic polyester resin excellent in mechanical strength, impact strength, heat resistance, surface hardness, weather resistance, etc. Polycarbonate composed of isosorbide is derived from biomass resources such as plants, and even in the construction of a better future society, it is possible to improve the environment and resource conservation as much as possible from the viewpoint of environment and petroleum resource conservation. In addition, the improvement in chemical resistance and fluidity of the polycarbonate is extremely useful for various industrial applications such as the automobile field, OA equipment field, and electronic / electric equipment field.

  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 polycarbonate of the present invention comprises a structural unit derived from a dihydroxy compound represented by the following general formula (1), and a part of the dihydroxy compound is replaced with another type of dihydroxy compound. It may be a compound, for example, a copolymer derived from a structural unit derived from an aliphatic or aromatic dihydroxy compound, or a copolymerized structural unit such as polyalkylene glycol.

  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, 2- Examples thereof include ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like.

  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 dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol 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, it is difficult to obtain a molding material having sufficient mechanical properties. Moreover, it is generally difficult to obtain a polycarbonate resin having a single dihydroxy compound represented by the general formula (1) having a high molecular weight. 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, but the polycarbonate of the present invention is different from the types of dihydroxy compounds and alicyclic dihydroxy compounds represented by the general formula (1). By adjusting the blending ratio, 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.

  The polymerization degree of the polycarbonate of the present invention is such that a mixed solution of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 is used as a solvent, and the polycarbonate copolymer concentration is 1.00 g / dl. As a reduced viscosity (hereinafter simply referred to as “reduced viscosity of carbonate (co) polymer”) measured at a temperature of 30.0 ° C. ± 0.1 ° C., adjusted to 0.40 dl / g or more, particularly 0 The degree of polymerization is preferably 40 dl / g or more and 2.0 dl / g or less. If the reduced viscosity of this polycarbonate is extremely low, the mechanical strength of the molded product 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 0.90 to 1.10, more preferably 0.94 to 1.04, relative to the dihydroxy compound. When this molar ratio is less than 0.90, 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 greater than 1.10, the ester is esterified under the same conditions. The rate of the exchange reaction is reduced, making it difficult to produce a polycarbonate having a desired molecular weight, and the amount of residual carbonic diester in the produced polycarbonate is increased. It is not preferable because it causes odor.

  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 copolymer having a sufficiently increased degree of polymerization is obtained. Arbitrariness.

  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 carbonate (co) polymer of the present invention can be blended with an antioxidant generally known for the purpose of preventing oxidation.

  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) Aromatic polyester resin As (B) aromatic polyester resin used by this invention, well-known aromatic polyester resin can be used widely. The aromatic polyester resin may be used alone or in combination of two or more. The aromatic polyester resin is preferably an aromatic polyester resin composed of a dicarboxylic acid or a derivative thereof and a diol.

  As the dicarboxylic acid or derivative thereof, aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and aliphatic dicarboxylic acid, and esters of these lower alkyls or glycols are preferred, and aromatic dicarboxylic acids or their lower alkyls (for example, C1-4) or an ester of glycol is more preferable, and terephthalic acid or a lower alkyl ester thereof is more preferable.

  Aromatic dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxy. Preferred examples include ethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid and 2,6-naphthalenedicarboxylic acid. Preferred examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Preferred examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. These dicarboxylic acids or derivatives thereof may be used alone or in combination of two or more.

  As the diol, an aliphatic diol, an alicyclic diol, and an aromatic diol are preferable. The aliphatic diol is preferably an aliphatic diol having 2 to 20 carbon atoms, such as ethylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, Preferable examples include polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 1,8-octanediol. The alicyclic diol is preferably an alicyclic diol having 2 to 20 carbon atoms, such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol and 1,4-cyclohexane. A preferred example is dimethylol. The aromatic diol is preferably an aromatic diol having 6 to 14 carbon atoms, such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane and bis (4- Hydroxyphenyl) sulfone can be mentioned as a preferred example. These diols may be used alone or in combination of two or more.

  The aromatic polyester resin used in the present invention may have a hydroxycarboxylic acid, a monofunctional component, and / or a trifunctional or higher polyfunctional component. Preferable examples of the hydroxycarboxylic acid include lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid and p-β-hydroxyethoxybenzoic acid. Preferred examples of the monofunctional component include alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid and benzoylbenzoic acid. Preferred examples of the trifunctional or higher functional component include tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, and pentaerythritol.

  (B) As aromatic polyester resin, aromatic polyester resin, such as polybutylene terephthalate resin (PBT resin), polyethylene terephthalate resin (PET resin), polyethylene naphthalate resin (PEN resin), is preferable, and PBT resin is more preferable. PBT resin is preferably a polybutylene terephthalate homopolymer having terephthalic acid as the only dicarboxylic acid unit and 1,4-butanediol as the only diol unit, from the viewpoint of heat resistance, but from the viewpoint of ease of workability, etc. The copolymer obtained by copolymerizing other monomer components such as isophthalic acid is also used. In the present invention, the PBT resin means that terephthalic acid accounts for 50 mol% or more of the total dicarboxylic acid component, and 1,4-butanediol accounts for 50 mol% or more of the total diol. The PBT resin further preferably has a terephthalic acid ratio in the dicarboxylic acid unit of 70 mol% or more, more preferably 90 mol% or more. Moreover, 70 mol% or more is preferable and the ratio of 1, 4- butanediol in a diol unit has more preferable 90 mol% or more. Use of such a PBT resin is preferred because mechanical properties and heat resistance tend to be further improved.

  The intrinsic viscosity of the PBT resin in the present invention is preferably 0.5 to 3.0 dl / g as measured at 30 ° C. in a mixed solvent of 1: 1 (weight ratio) of tetrachloroethane and phenol, and 0.5 to 1 0.5 dl / g is more preferable, and 0.6 to 1.3 dl / g is even more preferable. By setting the intrinsic viscosity to 0.5 or more, the mechanical properties are more effectively exhibited, and by setting the intrinsic viscosity to 3.0 or less, the molding process becomes easier. Further, two or more intrinsic viscosity PBT resins may be used in combination.

  When manufacturing an aromatic polyester resin, a well-known method can be employ | adopted widely. For example, in the case of a PBT resin composed of a terephthalic acid component and a 1,4-butanediol component, either a direct polymerization method or a transesterification method can be employed. The direct polymerization method is, for example, a method in which terephthalic acid and 1,4-butanediol are directly esterified, and water is generated in the initial esterification reaction. The transesterification method is a method using, for example, dimethyl terephthalate as a main raw material, and alcohol is generated by an initial transesterification reaction. The direct esterification reaction is preferable from the viewpoint of raw material costs.

  In addition, the aromatic polyester resin may be produced by either a batch method or a continuous method with respect to the raw material supply or the polymer discharge form. Further, the initial esterification reaction or transesterification reaction is performed in a continuous operation, and the subsequent polycondensation is performed in a batch operation, or conversely, the initial esterification reaction or transesterification reaction is performed in a batch operation, followed by There is also a method of performing polycondensation in a continuous operation.

  The polybutylene terephthalate resin used in the present invention preferably has a terminal carboxyl group concentration of 80 eq / ton or less, 60 eq / ton or less, and further 40 eq / ton or less. In the present invention, the terminal carboxyl group concentration was measured by dissolving 0.5 g of polyalkylene terephthalate in 25 mL of benzyl alcohol and titrating using a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. As a method for adjusting the terminal carboxyl group concentration, a method for adjusting polymerization conditions such as a raw material charging ratio at the time of polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, and the like can be appropriately applied. A method for obtaining polybutylene terephthalate having a terminal carboxyl group concentration as defined in the present invention is not particularly limited. For example, melt polycondensation of terephthalic acid and 1,4-butanediol has a relatively small molecular weight. Polybutylene terephthalate having an intrinsic viscosity of 0.1 to 0.9 can be produced, and then obtained by solid phase polycondensation until the desired molecular weight is obtained. A lower terminal carboxyl group is preferable in terms of long-term heat aging resistance, hydrolysis resistance, and low transesterification reactivity, but it also affects the productivity of the resin. Is about 10 eq / ton.

  The polybutylene terephthalate resin used in the present invention more preferably has a titanium content of more than 10 ppm and not more than 80 ppm as titanium atoms. Titanium is usually derived from a polymerization catalyst of polybutylene terephthalate, but even if the amount of titanium is less than 10 ppm or more than 80 ppm, long-term heat aging and hydrolysis resistance, which are important characteristics in the information equipment and automobile fields, are present. descend. The reason for this is not clear, but it is considered that the decomposition of polybutylene terephthalate at high temperatures is accelerated and the long-term resistance is lowered when the titanium content derived from the catalyst is large. The polybutylene terephthalate having a titanium content defined in the present invention is, for example, added to terephthalic acid and 1,4-butanediol in an amount of 10 to 80 ppm as titanium atoms with respect to the theoretical yield of polybutylene terephthalate as a catalyst. Then, an ester exchange reaction is carried out at a normal pressure in the temperature range of 180 to 240 ° C to obtain an oligomer, which can be obtained by proceeding polycondensation at 230 to 270 ° C under reduced pressure.

  Furthermore, the polybutylene terephthalate resin used in the present invention contains (a) a titanium compound and (b) a Group 1 metal compound and / or a Group 2 metal compound, and (a) the content of the titanium compound is a titanium atom. It is most preferably 10 ppm to 80 ppm in terms of conversion, and (b) the content of the Group 1 metal compound and / or the Group 2 metal compound is most preferably 1 ppm to 50 ppm in terms of the metal atom.

  The polybutylene terephthalate resin used in the present invention is a polycondensation of an oligomer obtained by an esterification reaction (or transesterification reaction) between 1,4-butanediol and terephthalic acid (or dialkyl terephthalate). As a catalyst (polycondensation catalyst) used in this polycondensation, by using (a) a titanium compound and (b) a group 1 metal compound and / or a group 2 metal compound, (a ) And (b) are preferable because the dispersibility of the metal compound can be improved.

The timing for using these polycondensation catalysts is arbitrary, and specific examples of the method of use include the following methods (1) to (4). Hereinafter, (a) a titanium compound may be referred to as a titanium catalyst, and (b) a group 1 metal compound and a group 2 metal compound may be referred to as a group 1 metal catalyst and a group 2 metal catalyst, respectively.
(1) A method of using both (a) and (b) in the esterification reaction (or transesterification reaction) and bringing them into the polycondensation reaction.
(2) A method in which a part of both (a) and (b) is used in the esterification reaction (or transesterification reaction) and added at the start of the polycondensation reaction or during the reaction.
(3) A method in which one of the catalysts (a) and (b) is used in the esterification reaction (or transesterification reaction), and the other is added at the start of the polycondensation reaction or during the reaction.
(4) A method in which neither (a) nor (b) is used in the esterification reaction (or transesterification reaction), and both are added at the start of the polycondensation reaction.

  The (a) titanium compound used in the present invention is not particularly limited. Specifically, for example, inorganic titanium compounds such as titanium oxide and titanium tetrachloride; titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate And the like; and titanium phenolates such as tetraphenyl titanate; Of these, titanium alcoholates are preferable, tetraalkyl titanates are more preferable, and tetrabutyl titanate is particularly preferable.

  The (b) Group 1 metal compound and / or Group 2 metal compound used in the present invention is not particularly limited. Specifically, for example, the Group 1 metal compound may be hydroxylated with lithium, sodium, potassium, rubidium, or cesium. Compounds; oxides; alcoholates; various organic acid salts such as acetates, phosphates, carbonates, etc., and examples of group 2 metal compounds include beryllium, magnesium, calcium, strontium, Various compounds such as barium hydroxides; oxides; alcoholates; various organic acid salts such as acetates, phosphates and carbonates; These may be used alone or in combination.

  Among them, lithium, sodium, potassium, magnesium, calcium, and other compounds are preferable from the viewpoints of handling and availability, and catalytic effect, and lithium or magnesium compounds that are excellent in catalytic effect and color tone are preferable, especially magnesium compounds. Is preferred. Specific examples of the magnesium compound include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate. Of these, organic acid salts are preferable, and magnesium acetate is particularly preferable.

  In the polybutylene terephthalate resin used in the present invention, the content of the (a) titanium compound is 10 ppm or more and 80 ppm or less in terms of titanium atoms. When there is too much content of this titanium compound, the color tone and hydrolysis resistance of PBT may fall, and the solution haze and foreign material by deactivation of a titanium catalyst may increase. On the other hand, if the amount is too small, the polymerizability of the PBT is lowered. Therefore, the content of the (a) titanium compound is preferably 70 ppm or less, particularly 60 ppm or less, more preferably 50 ppm or less, and particularly preferably 40 ppm or less, and the lower limit thereof is 15 ppm or more, especially 20 ppm or more, and particularly preferably 30 ppm or more. .

  In the PBT used in the present invention, the content of the (b) Group 1 metal compound and / or Group 2 metal compound is 1 ppm or more and 50 ppm or less in terms of each metal atom. When there is too much content of this group 1 metal compound and / or a group 2 metal compound, the hydrolysis resistance of the resin molded product of this invention may fall. On the other hand, even if the amount is too small, the surface appearance of the molded product may deteriorate. Therefore, the content of (b) Group 1 metal compound and / or Group 2 metal compound is 40 ppm or less, preferably 30 ppm or less, more preferably 20 ppm or less, particularly preferably 15 ppm or less, and the lower limit thereof is 3 ppm or more, especially 5 ppm or more. In particular, it is preferably 10 ppm or more.

  The metal content such as titanium atom can be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) after recovering the metal in the polymer by a method such as wet ashing.

  Examples of the PBT polycondensation catalyst used in the present invention include (a) titanium compounds and (b) Group 1 metal compounds and / or Group 2 metal compounds as described above. Examples of other polycondensation catalysts include: Tin and its compound are mentioned. Tin is usually used as a tin compound, specifically, for example, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, Triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid, etc. Can be mentioned.

  However, since tin and a tin compound deteriorate the color tone of PBT, it is preferable that the content of the tin compound in the PBT used in the present invention is low, and it is preferable not to include it. Specifically, it is usually preferable that the content of the tin compound is 200 ppm or less, particularly 100 ppm or less, more preferably 10 ppm or less in terms of tin atoms.

  In the production of PBT used in the present invention, in addition to the titanium catalyst, group 1 metal catalyst and group 2 metal catalyst, antimony compounds such as antimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; manganese Reaction assistants such as compounds; zinc compounds; zirconium compounds; cobalt compounds; phosphorous compounds such as orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, and their esters and metal salts;

  The resin composition of the present invention is composed of at least 1 to 80 parts by weight of (B) aromatic polyester resin, preferably 3 to 60 parts by weight, and more preferably 100 parts by weight of (A) polycarbonate. Is 5 to 50 parts by weight. When the content of the component (B) is more than 80 parts by weight, the effect on resource / environmental conservation, which is an important target of the present invention, is small, the shrinkage rate is large, and the resin composition is greatly different from the characteristics of polycarbonate. Become. On the other hand, when the content of the component (A) is less than 1 part by weight, the effect of improving chemical resistance and fluidity is not sufficient.

  Even if the polycarbonate of the present invention does not contain an aromatic group, it has unexpectedly good compatibility with the aromatic polyester resin, and almost no defects associated with poor compatibility such as peeling and pearl luster are recognized. However, in order to further improve, a compatibilizer may be added. Examples of the compatibilizer include an epoxy compound, an epoxy-modified styrene elastomer and a styrene-maleic anhydride copolymer.

(C) Organophosphorus compound When mixing with the above-mentioned polycarbonate aromatic polyester resin, an organophosphorus compound can be blended in order to control the transesterification reaction and easily maintain heat resistance. Examples of the organic phosphorus compound include an organic phosphate compound, an organic phosphite compound, an organic phosphonite compound, and the like. The organic phosphorus compound can be used in combination with the heat stabilizer of the polycarbonate, and is preferably an organic phosphate compound.

  The organic phosphate compound is preferably a long-chain dialkyl acid phosphate compound represented by the formula (3).

(In the formula, R ¹ and R ² each represent an alkyl group having 8 to 30 carbon atoms.)
Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group, etc. are mentioned. Specific examples of the long-chain dialkyl acid phosphate compound include dioctyl phosphate, di (2-ethylhexyl) phosphate, diisooctyl phosphate, dinonyl phosphate, diisononyl phosphate, didecyl phosphate, diisodecyl phosphate, dilauryl phosphate, ditridecyl phosphate, Examples thereof include diisotridecyl phosphate, dimyristyl phosphate, dipalmityl phosphate, distearyl phosphate, dieicosyl phosphate, and ditriacontyl phosphate. Preferably, distearyl phosphate, dipalmityl phosphate, dimyristyl phosphate are selected.

  The compounding amount of the organic phosphorus compound is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, more preferably 100 parts by weight of the total amount of the component (A) and the component (B). 0.07 to 0.4 parts by weight. When the blending amount is less than 0.01 part by weight, the effect of improving the heat stability and heat retention stability of the material inherent to the organic phosphorus compound is not exhibited. Moreover, when a compounding quantity exceeds 1 weight part, it will have a bad influence on performances other than heat stability and residence stability. Moreover, you may use an organic phosphorus compound in combination of 1 type, or 2 or more types.

  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 amount of the stabilizer to be blended is preferably 0.01 to 2 parts by weight with respect to parts by weight of the polycarbonate as 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 amount of the inorganic filler 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) aromatic polyester resin. 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 ordinary injection molding, extrusion molding, blow molding, and compression molding, and is particularly suitable for injection molding methods. . The resin temperature of the injection molding is 230 to 270 ° C. Further, in the case of a large molded product, the residence time becomes long in the injection molding machine. Therefore, it is preferable for suppressing the transesterification reaction between the polycarbonate and the aromatic polyester resin. Is 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 addition, the part in an Example means a weight part.

In addition, the formic acid content of isosorbide used in the following Production Examples 1 to 5 was 5 ppm. The formic acid contained in isosorbide was quantified by the following method.
<Quantification of formic acid>
The amount of formic acid contained in isosorbide was measured by ion chromatography. 0.5 g of isosorbide was precisely weighed and collected in a 50 ml volumetric flask, and the volume was adjusted with pure water. An aqueous sodium formate solution was used as the standard sample, and the peak having the same retention time as that of the standard sample was formic acid.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As measurement columns, AG-15 was used as a guard column manufactured by Dionex, and AS-15 was used as a separation column. The measurement sample was injected into a 100 μl sample loop, and 10 mM NaOH was used as an eluent, and the measurement was performed at a flow rate of 1.2 ml / min and a thermostat temperature of 35 ° C. A membrane suppressor was used as the suppressor, and a 12.5 mM-H2SO4 aqueous solution 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 Corporation, hereinafter abbreviated as “DPC”) 59.2 parts by weight (0.752 mol), and catalyst, Cesium carbonate (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 as a first step of the reaction in a nitrogen atmosphere The heating bath temperature 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 following methods (1) and (2), respectively. 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 cesium 2.19 * 10 <^-4> weight part (1.82 * 10 <^-6> mol). The properties (reduced viscosity, glass transition temperature) of the obtained polycarbonate were measured according to the following methods (1) and (2), respectively. The results are shown in Table 1. The polycarbonate obtained in this production example was designated as “ISOB-PC2”.

[Production Example 3]
In Production Example 1, 15.7 parts by weight (0.288 mol) of isosorbide, 25.8 parts by weight (0.480 mol) of 1,4-CHDM, 58.6 parts by weight (0.734 mol) of DPC, and as a catalyst, It implemented similarly except having changed into 2.18 * 10 <^-4> weight part (1.80 * 10 <^-6> mol) of cesium carbonate. The properties (reduced viscosity, glass transition temperature) of the obtained polycarbonate were measured according to the following methods (1) and (2), respectively. The results 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 properties (reduced viscosity, glass transition temperature) of the obtained polycarbonate were measured according to the following methods (1) and (2), respectively. The results are shown in Table 1. The polycarbonate obtained in this production example was designated as “ISOB-PC4”.

[Production Example 5]
Production Example 1, isosorbide 40.1 parts by weight (0.581 mol), DPC59.9 parts by weight (0.592 mol, as a catalyst, 2.23 × ^{10 -4} parts by weight of cesium carbonate (1.45 × 10 ^- was changed to ⁶ mol), was carried out in the same manner. the properties of the resulting polycarbonate (reduced viscosity, glass transition temperature), the following respective (1) was measured according to the method of (2). results Table 1 The polycarbonate obtained in this production example was designated as “ISOB-PC5”.

[Polycarbonate evaluation method]
(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. .

(B) Aromatic polyester resin In the following examples, the following were used as the (B) aromatic polyester resin.
-Polybutylene terephthalate resin: Mitsubishi Engineering Plastics Co., Ltd. Trade name NOVADURAN 5010 Intrinsic viscosity = 1.1, terminal carboxyl group amount = 35 eq / ton (hereinafter abbreviated as “PBT”)
Moreover, the following organic phosphoric acid ester was used as the organic phosphoric acid compound.
Distearyl phosphate: Asahi Denka Co., Ltd., trade name AX-71

[Evaluation items and methods]
(3) Fluidity Evaluation The Archimedean spiral length of a 6 mm diameter semicircular flow path was measured by an injection molding machine (IS150 manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 250 ° C., a mold temperature of 40 ° C., and an injection pressure of 98.1 MPa.

(4) Evaluation of chemical resistance Using a custom scientific minimax injection molding machine “CS-183MMX”, injection molding is performed at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and the length of the parallel part. A tensile test piece having a diameter of 9 mm and a parallel part diameter of 1.5 mm was collected.
The tensile test piece was immersed in methyl alcohol at room temperature for 30 days and in toluene for 1 day, and the tensile tester “CS-183TE type” manufactured by Custom Scientific Co., Ltd. was used for the test piece before and after the immersion. A tensile test was performed under the conditions of a tensile speed of 1 cm / min, the tensile strength was measured, the retention rate was calculated, and the chemical resistance was evaluated. The higher the value, the better the chemical resistance.

(5) Impact strength evaluation Using a custom scientific minimax injection molding machine “CS-183MMX”, a temperature of 240 to 300 ° C., a length of 31.5 mm, a width of 6.2 mm, A rod-shaped test piece having 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”.

(6) Thermal deformation temperature evaluation 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.

[Examples 1-6 and Comparative Examples 1-5]
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, (B) aromatic polyester, and organophosphorus compound were uniformly mixed in a tumbler mixer, then fed from the barrel 1 and melt mixed to prepare a composition. Evaluation of said (3)-(6) 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. The results are shown in Table 2.

From the above results, the following is found.
The polycarbonate used in the compositions of the present invention in Examples 1 to 6 has no color unevenness such as pearly luster despite having no aromatic group, and has sufficient compatibility as a molding material. And compared with Comparative Examples 1-5 which does not mix | blend aromatic polyester resin, fluidity | liquidity is improved and chemical resistance is improved. The composition of Example 2 in which the organophosphorus compound was blended indicates that the chemical resistance is improved as compared with Example 1 and has good compatibility.

  The resin composition of the present invention comprising a polycarbonate containing isosorbide has improved chemical resistance and fluidity than the polycarbonate polymer itself containing isosorbide, and in particular, a constitutional unit derived from a dihydroxy compound and an alicyclic dihydroxy compound. The thermoplastic resin composition using the polycarbonate containing the unit is a resin composition excellent in mechanical strength, impact strength, heat resistance, surface hardness, weathering discoloration, etc., and at the same time, the polycarbonate containing isosorbide is a biomass resource such as a plant. In terms of environmental and petroleum resource conservation, it has become possible to improve the environment and resource conservation even a little in the construction of a better future society. The improved chemical resistance makes it extremely useful for various industrial applications such as the automotive field, OA equipment field, and electronic / electrical equipment field, and the improved fluidity makes it particularly useful for exterior materials in the automotive field. It is also suitable for applications that require relatively large molded products such as interior material applications and electronic equipment casings.

Claims (8)

(A) A resin composition obtained by blending 1 to 80 parts by weight of (B) an aromatic polyester resin with respect to 100 parts by weight of a polycarbonate containing a structural unit derived from a dihydroxy compound represented by the following general formula (1) object.

  The resin composition according to claim 1, wherein the glass transition temperature of the (A) polycarbonate is 90 ° C. or higher.   The resin composition according to claim 1 or 2, wherein the (A) polycarbonate further contains a structural unit derived from an alicyclic dihydroxy compound.   The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the formula (1) and the structural unit derived from the alicyclic dihydroxy compound contained in the polycarbonate (A) is 100: 0 to 45:55. The resin composition according to claim 3, wherein the resin composition falls within the range.   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 contained in the polycarbonate (A) is 90:10 to 50:50. The resin composition according to claim 3, wherein the resin composition falls within the range.   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 contained in the polycarbonate (A) is 85:15 to 65:35. The resin composition according to claim 3, wherein the resin composition falls within the range.   The resin composition according to any one of claims 1 to 6, wherein the aromatic polyester resin (B) is a polybutylene terephthalate resin.   The resin composition formed by mix | blending 0.01-1 weight part of (C) organophosphorus compound with respect to 100 weight part of resin compositions in any one of Claims 1-7.