JP5049507B2 - Method for producing thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a thermoplastic resin composition containing an inorganic filler and excellent in impact resistance, stiffness, flowability and resident thermal stability. <P>SOLUTION: This thermoplastic resin composition comprises a resin component (component A) of 40-99 pts.wt. consisting of an aromatic polycarbonate resin (component A1) and a thermoplastic polyester resin (component A2), an inorganic filler (component B) of 1-60 pts.wt. and a rubbery polymer (component C) of 0-35 pts.wt., and additionally, based on the total of 100 pts.wt. of the components A, B and C, comprises an alkyl silane compound (component D) of 0.01-3 pts.wt. represented by a specific general formula and a phosphorous compound (component E) of 0.005-1 pts.wt. In the manufacturing method for the resin composition, the aromatic polycarbonate resin (component A1) and the thermoplastic polyester resin (component A2) are melted and kneaded, and then the phosphorous compound (component E) is added thereto to be melted and kneaded. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a method for producing a thermoplastic resin composition containing (mixed) an inorganic filler. Specifically, the present invention relates to a method for producing a thermoplastic resin composition containing an inorganic filler, which is particularly excellent in impact resistance and excellent in rigidity, fluidity, and residence heat stability.

  Aromatic polycarbonate resin is excellent in transparency, impact resistance, heat resistance, dimensional stability, etc. as general-purpose engineering plastics. Due to these excellent characteristics, it is used for electrical / electronic / OA equipment parts, machine parts, vehicle parts, etc. Used in a wide range of fields. Furthermore, a polymer alloy composed of an aromatic polycarbonate resin and a thermoplastic polyester resin has improved the chemical resistance and molding processability, which are the disadvantages of the aromatic polycarbonate resin, while taking advantage of the excellent properties of the aromatic polycarbonate resin. It is a molding material and is used as a resin material for vehicle interior / exterior parts, various housing members, and many other products and parts.

  As a method for improving the rigidity and dimensional stability of a polymer alloy composed of an aromatic polycarbonate resin and a thermoplastic polyester resin, a method of blending an inorganic filler with a base resin is employed. Particularly in fields where a beautiful appearance such as vehicle exterior parts is required, pulverized silicate inorganic materials, synthetic whiskers, and the like are used as the inorganic filler. However, the resin composition containing the inorganic filler has a problem that impact resistance and molding processability (fluidity) are lowered. Furthermore, most of the silicate-based inorganic pulverized materials that give a beautiful appearance are basic, and these basic substances are decomposed by aromatic polycarbonate resin or transesterified between aromatic polycarbonate and thermoplastic polyester resin. There is a drawback that the reaction proceeds excessively and the thermal stability of the residence (during the production of a molded product from the resin material, the resin material is difficult to be discolored while staying in the molding machine cylinder) is significantly reduced. .

  Particularly in recent years, there has been a strong demand for vehicle exterior parts to be thin and highly rigid at the same time, and a material that still exhibits high impact resistance is required even if a large amount of inorganic filler is blended. In addition, there is a strong demand for materials that are excellent in fluidity as the molded products are made thinner and larger. When an inorganic filler is blended with a resin material, fluidity generally decreases, so it is necessary to increase the temperature at the time of molding, and if the molding temperature is increased, a vicious cycle occurs in which the residence heat stability and impact resistance deteriorate, Even when an inorganic filler is blended, there has been a strong demand for a resin composition that exhibits not only rigidity but also excellent fluidity and impact resistance.

  Resin composition consisting of polycarbonate resin, aromatic polyester resin, rubber-like elastic body, surface-treated talc, and / or surface-treated mica as a resin composition having excellent rigidity, impact resistance, and thermal stability A thing is proposed (for example, refer to patent documents 1). Furthermore, as a resin composition excellent in thermal stability and hue, a resin composition comprising a polycarbonate resin, a polyalkylene terephthalate resin, and a neutralized wollastonite has been proposed (for example, see Patent Document 2). However, according to experiments by the present inventors, it has been found that even these resin compositions do not exhibit sufficiently satisfactory characteristics in impact resistance and fluidity.

Moreover, as a resin composition excellent in rigidity, impact resistance, thermal stability, etc., a resin composition comprising an aromatic polycarbonate resin, a styrene resin, an inorganic filler, and a specific alkoxysilane compound (see, for example, Patent Document 3) However, a resin composition composed of an aromatic polycarbonate resin, an alkali metal sulfonate, and a silicate filler surface-treated with a specific silane compound (see, for example, Patent Document 4) has been proposed. In these techniques, there is a description in the above literature that other thermoplastic resins can be blended. Specifically, in Patent Document 3, polyester resin, in Patent Document 4, polyethylene terephthalate, polybutylene terephthalate, etc. It is described that the polyester resin can be used in a small proportion. However, there is no specific description or suggestion regarding the improvement in fluidity that decreases with the blending of inorganic fillers, and all the properties of rigidity, impact resistance, fluidity, and residence heat stability are improved, and the balance of physical properties is improved. There is no disclosure of a resin composition that excels in resistance.

Furthermore, as a resin composition that exhibits extremely good thermal stability in various production environments, an aromatic polycarbonate resin (component a), an aromatic polyester resin (component b), and a basic inorganic filler (component c) On the other hand, a resin composition combining a phosphite stabilizer (component d) having a specific acid value increase value, and an extruder as a kneader when producing this resin composition has at least two supply ports. A method for producing a polycarbonate resin composition (e.g., supplying at least the a component and the d component from a first supply port, and supplying the b component and the c component from at least a supply port after the second supply port (for example, However, according to experiments conducted by the present inventors, it is still difficult to produce a satisfactory resin composition that lacks rigidity and stagnant heat stability. It was bought.
JP-A-8-127711 JP-A-2005-232298 JP 2004-168822 A JP 2005-220216 A JP 2004-359913 A

An object of the present invention is to provide a method for producing a thermoplastic resin composition that eliminates the above-mentioned drawbacks of the prior art and that is particularly excellent in impact resistance. That is, the object of the present invention is as follows.
1. To provide a method for producing a thermoplastic resin composition containing an inorganic filler, which is excellent in impact resistance and rigidity.
2. To provide a method for producing a thermoplastic resin composition containing an inorganic filler, which is excellent in fluidity and residence heat stability.

In order to achieve the above object, in the present invention, a resin component comprising a total of 100% by weight of an aromatic polycarbonate resin (A1 component) 10 to 90% by weight and a thermoplastic polyester resin (A2 component) 90 to 10% by weight ( A component) contains 40 to 99 parts by weight of inorganic filler (B component) 1 to 60 parts by weight, rubber polymer (C component) 0 to 35 parts by weight, and total of A component, B component and C component Contains 0.01 to 3 parts by weight of an alkylsilane compound (D component) represented by the following general formula (I) and 0.005 to 1 part by weight of a phosphorus compound (E component) with respect to 100 parts by weight In the method for producing a thermoplastic resin composition,
The inorganic filler (B component) is pre-treated with an alkylsilane compound (D component),
The phosphorus compound (E component) is at least one selected from an organic phosphate compound, an organic phosphite compound, and an organic phosphonite compound,
First, a thermoplastic resin composition characterized in that an aromatic polycarbonate resin (A1 component) and a thermoplastic polyester resin (A2 component) are melt-kneaded , and then a phosphorus compound (E component) is added and melt-kneaded. A method for manufacturing a product is provided.

The thermoplastic resin composition according to the present invention has the following particularly advantageous effects, and its industrial utility value is extremely large.
1. The thermoplastic resin composition obtained by the production method according to the present invention is excellent in impact resistance and rigidity.
2. The thermoplastic resin composition obtained by the production method according to the present invention is excellent in fluidity and residence heat stability.
3. The thermoplastic resin composition obtained by the production method according to the present invention has an excellent balance of rigidity, fluidity, impact resistance and residence heat stability, and also has excellent chemical resistance and appearance.・ Suitable for manufacturing materials such as skin parts and vehicle interior parts.

Hereinafter, the present invention will be described in more detail.
[1] Aromatic polycarbonate resin (A1 component)
In the present invention, the aromatic polycarbonate resin (hereinafter sometimes abbreviated as “A1 component”) includes, for example, an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination therewith. A linear or branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reaction. The manufacturing method of this aromatic polycarbonate resin (A1 component) is not specifically limited, It can manufacture by the method known conventionally. Examples of the production method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  As aromatic dihydroxy compounds used as raw materials, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= Tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy) Phenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-) 3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, , 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2- Bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Bis (hydroxyaryl) alkanes exemplified by the above; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4- Bis (hydroxyaryl) cycloalkanes exemplified by droxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4- Cardio structure-containing bisphenols exemplified by hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′-dihydroxydiphenyl ether, 4,4′- Dihydroxydiaryl ethers exemplified by dihydroxy-3,3′-dimethyldiphenyl ether and the like; exemplified by 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide and the like Dihydroxydiaryl sulfides; 4,4′-dihydroxydiphe Dihydroxydiaryl sulfoxides exemplified by nyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc .; 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3 Examples include dihydroxydiaryl sulfones exemplified by '-dimethyldiphenylsulfone; hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like.

  Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. . These aromatic dihydroxy compounds may be used alone or in combination of two or more.

  Examples of the carbonate precursor to be reacted with the aromatic dihydroxy compound include carbonyl halide, carbonate ester, haloformate and the like. Specific examples include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and dihaloformates of dihydric phenols. These carbonate precursors may also be used alone or in combination of two or more.

  The aromatic polycarbonate resin (component A1) may be a branched aromatic polycarbonate resin that is copolymerized in the presence of a small amount of a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6- Tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1, Polyhydroxy compounds exemplified by 1,1-tri (4-hydroxyphenyl) ethane and the like, or 3,3-bis (4-hydroxyaryl) oxyindole (= isatin bisphenol), 5-chloroisatin, Examples include 5,7-dichloroisatin and 5-bromoisatin, and among these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable. The polyfunctional aromatic compound can be used by replacing a part of the aromatic dihydroxy compound, and the amount used is preferably in the range of 0.01 to 10 mol% with respect to the aromatic dihydroxy compound. The range of .1 to 2 mol% is more preferable.

  Next, the manufacturing method of A1 component is demonstrated. Of the methods for producing the A1 component, the interfacial polymerization method will be described first. The polymerization reaction in this production method is usually carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the pH is usually kept at 9 or higher, and an aromatic dihydroxy compound and, if necessary, a molecular weight modifier (end terminator). In addition, an antioxidant is used for the purpose of preventing oxidation of the aromatic dihydroxy compound, and after reacting with phosgene, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added to perform interfacial polymerization. Thus, polycarbonate can be obtained. The timing for adding the molecular weight regulator to the polymerization system is not particularly limited as long as it is from the time of phosgenation to the time of the start of the polymerization reaction. In addition, reaction temperature is 0-40 degreeC, for example, and reaction time is several minutes (for example, 10 minutes)-several hours (for example, 6 hours), for example.

  Examples of the organic solvent inert to the reaction used in the interfacial polymerization method include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. Etc. Examples of the alkali compound for preparing the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. The addition amount of the molecular weight modifier is preferably 0.5 to 50 mol, more preferably 1 to 30 mol, per 100 mol of the aromatic dihydroxy compound.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine: quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride Etc.

Next, the melt transesterification method will be described. The polymerization reaction in this production method is, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. The carbonic acid diester is preferably diphenyl carbonate or substituted diphenyl carbonate, more preferably diphenyl carbonate.

In this production method, generally, a polycarbonate having a desired molecular weight and a terminal hydroxyl group amount is obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound or adjusting the degree of vacuum during the reaction. Is obtained. As a more aggressive method, it can be adjusted by adding a terminal terminator separately during the reaction. In this case, examples of the terminal terminator include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. The amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone, etc. of the aromatic polycarbonate resin which is the A1 component. Although depending on the application, in order to provide practical physical properties, it is preferably 1000 ppm or less, more preferably 700 ppm or less. Moreover, in the aromatic polycarbonate manufactured by the transesterification method, the amount of terminal hydroxyl groups is preferably 100 ppm or more. By setting it as the amount of such terminal hydroxyl groups, the fall of molecular weight can be suppressed and a color tone can also be made more favorable. Accordingly, it is more preferable to use the carbonic acid diester in an amount of equimolar amount or more, for example, 1.01 to 1.30 mol with respect to 1 mol of the aromatic dihydroxy compound.

  When producing an aromatic polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. As the transesterification catalyst, those conventionally used can be used without particular limitation. Specific examples include alkali metal compounds and / or alkaline earth metal compounds. In addition, 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. As the transesterification reaction using the above raw materials, the reaction is usually carried out at a temperature of 100 to 320 ° C., and finally, melt polycondensation is performed while removing by-products such as aromatic hydroxy compounds under a reduced pressure of 2 mmHg or less. The method of performing reaction is mentioned.

  Although the melt transesterification method can be carried out batchwise or continuously, it is preferably carried out continuously in view of the stability of the resin composition finally obtained. The aromatic polycarbonate resin obtained by the melt transesterification method contains a residual catalyst, and this residual catalyst adversely affects the thermal stability during the molding of the aromatic polycarbonate resin. It is preferable to add an agent. The deactivator is preferably a compound that neutralizes the used catalyst, for example, a sulfur-containing acidic compound or a derivative formed therefrom. The compound that neutralizes such a catalyst is preferably added in the range of 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the alkali metal contained in the used catalyst. In addition, the compound that neutralizes such a catalyst is preferably added in the range of 1 to 100 ppm, more preferably 1 to 20 ppm, based on the aromatic polycarbonate resin.

  In the present invention, the molecular weight of the aromatic polycarbonate resin is not particularly limited as long as it can be used as a molding material, and the viscosity average molecular weight [Mv] converted from the solution viscosity is in the range of 10,000 to 50,000. preferable. When the viscosity average molecular weight of the aromatic polycarbonate resin is 10,000 or more, the mechanical strength is improved, and it is more suitable for use in applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is less than 50,000, the decrease in fluidity can be improved, which is preferable from the viewpoint of moldability. A more preferable range of the viscosity average molecular weight is 12,000 to 40,000, and a more preferable range is 14,000 to 30,000. Moreover, the mixture of 2 or more types of aromatic polycarbonate resin from which a viscosity average molecular weight differs may be sufficient. When the mixture is composed of two or more kinds of aromatic polycarbonate resins having different molecular weights, the mixture may contain an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range as long as the molecular weight of the mixture is within the above range.

Here, the viscosity average molecular weight [Mv] means that methylene chloride is used as a solvent, an Ubbelohde viscometer is used, an intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. is measured, and Schnell's viscosity formula is used. That is, it means a value calculated from η = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following formula (A) by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

  The aromatic polycarbonate resin (A1 component) in the present invention may contain an aromatic polycarbonate oligomer in order to improve the appearance of the molded product and the fluidity. The aromatic polycarbonate oligomer has a viscosity average molecular weight [Mv] of preferably 1500 to 9500, more preferably 2000 to 9000. The aromatic polycarbonate oligomer is preferably contained in the range of 30% by weight or less of the A1 component.

  The aromatic polycarbonate resin (A1 component) may be not only a so-called virgin raw material but also an aromatic polycarbonate resin regenerated from a used product, a so-called recycled aromatic polycarbonate resin. Used products include optical recording media such as optical discs, light guide plates, vehicle transparent parts such as automobile window glass, automobile headlamp lenses and windshields, containers such as water bottles, eyeglass lenses, soundproof walls and glass windows, These include building materials such as corrugated plates, and safety equipment such as helmets and bulletproof shields. Further, it may be a non-conforming product, a pulverized product obtained from a sprue, a runner or the like, or a pellet obtained by melting them. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less of the A1 component.

[2] Thermoplastic polyester resin (A2 component)
The thermoplastic polyester resin in the present invention (hereinafter sometimes abbreviated as “A2 component”) comprises a dicarboxylic acid component comprising a dicarboxylic acid or a reactive derivative thereof, and a diol component comprising a diol or an ester derivative thereof. It is a polymer or copolymer that contains the main components and is obtained by a condensation reaction.

  The production of the thermoplastic polyester resin (component A2) is carried out by reacting the dicarboxylic acid component with the diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., according to a conventionally known method. The by-product water or lower alcohol is discharged out of the system. The production method may be a batch type or a continuous type for both the transesterification reaction and the polycondensation reaction, and may be a method in which one is a batch type and the other is a continuous type, and the degree of polymerization is increased by solid phase polymerization. You can also.

  The dicarboxylic acids may be either aromatic dicarboxylic acids or aliphatic dicarboxylic acids, but aromatic dicarboxylic acids are preferred from the viewpoints of heat resistance and dimensional stability. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylether dicarboxylic acid 4,4′-biphenylmethanedicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-ter-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, and the like, and substituted products thereof (for example, 5- Alkyl group substitution products such as methyl isophthalic acid) and reactive derivatives (eg terephthalic acid) Methyl, and alkyl ester derivatives such as diethyl terephthalate), and also like.

  Of these, terephthalic acid, 2,6-naphthalenedicarboxylic acid and their alkyl ester derivatives are more preferred, and terephthalic acid and its alkyl ester derivatives are particularly preferred. These aromatic dicarboxylic acids may be used alone or in combination of two or more, and together with these aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, etc. It can also be used in combination with one or more alicyclic dicarboxylic acids.

  Diols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, triethylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6- Aliphatic diols such as hexanediol, decamethylene glycol, 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, trans- or cis- Alicyclic diols such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol; p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxy Ethyl ether It is and aromatic diols, such as may be substituted versions thereof.

  Of these, ethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are more preferable, and ethylene glycol is particularly preferable from the viewpoints of heat resistance and dimensional stability. These may be used alone or in combination of two or more. In addition, as the diol component, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be used in combination with the diols. You can also.

Moreover, the thermoplastic polyester resin (A2 component) in this invention can also be branched by adding a small amount of branching agents at the time of manufacture of A2 component. If the branching agent is conventionally used at the time of thermoplastic polyester resin manufacture, there will be no restriction | limiting in the kind. Specific examples include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, pentaerythritol and the like.

The thermoplastic polyester resin (component A2) in the present invention may be other polyester resins in addition to the polyester resin. Examples of the other polyester resin include a popivalolactone resin obtained by ring-opening polymerization of lactone, a poly (ε-caprolactone) resin, and a liquid crystal polymer (thermotropic liquid crystal polymer; TLCP) that forms a liquid crystal in a molten state. Specifically, commercially available liquid crystal polyester resin, such as Mitsubishi Engineering Plastics Novacurate, Eastman Kodak X7G, Dartco Xyday, Sumitomo Chemical Econor, Celanese Vectra, etc. Can be mentioned.

Suitable as the thermoplastic polyester resin (component A2) are polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene naphthalate resin (PEN). , Polybutylene naphthalate resin (PBN), poly (1,4-cyclohexanedimethylene terephthalate) resin (PCT), polycyclohexylcyclohexylate (PCC), and the like. Among these, polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), and polybutylene terephthalate resin (PBT) are preferable from the viewpoint of fluidity and impact resistance. Particularly, the content of polyethylene terephthalate resin (PET) is 100 weights of component A2. The amount is preferably 10 parts by weight or more, and more preferably 12 to 50 parts by weight.

  The polyethylene terephthalate resin particularly suitable as the A2 component in the present invention is mainly composed of terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component as a main component, and a saturated polyester polymer or copolymer obtained by a condensation reaction thereof. It is a polymer and is a thermoplastic polyester resin containing ethylene terephthalate units as repeating units, preferably 70 mol% or more, more preferably 80 mol% or more. The polyethylene terephthalate resin contains diethylene glycol which is a side reaction product at the time of polymerization. The amount of diethylene glycol is 0.5 mol% or more in 100 mol% of the total amount of diol components used in the polymerization reaction. Preferably, it is usually 6 mol% or less, and particularly preferably 5 mol% or less.

  The intrinsic viscosity of the thermoplastic polyester resin (component A2) is preferably in the range of 0.4 to 1.5 dl / g. When the intrinsic viscosity is less than 0.4, the impact resistance of the resulting resin composition is lowered, and when it exceeds 1.5, the fluidity is lowered. A more preferable range of the intrinsic viscosity is 0.5 to 1.3 dl / g. Here, the intrinsic viscosity means a value measured at a temperature of 30 ° C. in a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio). The amount of terminal carboxyl groups of the thermoplastic polyester resin is preferably in the range of 5 to 50 μeq / g. When the terminal carboxyl group amount is less than 5 μeq / g, the heat resistance and impact resistance of the resulting resin composition are likely to decrease, and when it exceeds 50 μeq / g, the heat and moisture resistance and thermal stability are likely to be insufficient. Neither is preferred. A more preferable range of the intrinsic viscosity is 10 to 30 μeq / g.

  The thermoplastic polyester resin (component A2) in the present invention may be not only a so-called virgin raw material but also a thermoplastic polyester resin regenerated from a used product, a so-called recycled thermoplastic polyester resin. Spent products include mainly containers, films, sheets, fibers, etc., but more preferable are containers such as PET bottles. The recycled thermoplastic polyester resin may be a non-conforming product, a pulverized product obtained from a sprue, a runner or the like, or a pellet obtained by melting them.

[3] Inorganic filler (component B)
The inorganic filler in the present invention (hereinafter sometimes abbreviated as “B component”) is a solid inorganic compound. The solid form (appearance) is arbitrary, and may be any of, for example, a spherical shape, a plate shape, a needle shape, a fiber shape, and an indeterminate shape. The spherical shape includes not only a spherical shape but also an elliptical cross section or a substantially oval shape to some extent. Preferably, the aspect ratio (the longest diameter of the spherical body / the minimum diameter of the spherical body) ) Is in the range of 0.5 to 2, and a value close to 1 is preferable. The plate-like form is one having an aspect ratio (the length of the longest side of the plate-like surface of the plate-like powder / the thickness of the plate-like body) in the range of 2 to 100. What has an acicular shape means that the length is 100 μm or less and the aspect ratio (particle length / particle diameter) is in the range of 2-20. The thing of fibrous form shows what exceeds 100 micrometers in length. The form (appearance) of the inorganic filler can be easily determined by an electron micrograph or the like. In order to improve the dimensional stability and rigidity of the finally obtained resin composition, the form is preferably plate-like, needle-like or fibrous.

  Specific examples of the plate-like inorganic filler include magnesium silicate such as talc, kaolinite, clay, mica, graphite, sericite, montmorillonite, plate-like calcium carbonate, plate-like alumina, glass flake and the like. Specific examples of the acicular inorganic filler include calcium silicates such as wollastonite, moss heidi, zonotlite, calcium titanate, aluminum borate, acicular calcium carbonate, acicular titanium oxide, and tetrapot type zinc oxide. Examples of the fibrous inorganic filler include glass fiber, carbon fiber, metal fiber, mineral fiber, and ceramic whisker.

When the inorganic filler (component B) is a plate-like or needle-like inorganic filler, the average particle diameter may be appropriately selected and determined according to the physical properties to be imparted to the molded product. Is selected within the range. If the average particle size is too small, the reinforcing effect tends to be insufficient, while if too large, the product appearance tends to be adversely affected, and the impact resistance may be insufficient. The average particle diameter is preferably in the range of 0.3 to 15 μm, particularly preferably in the range of 0.5 to 10 μm. Here the average particle diameter refers to the D ₅₀ as measured in the liquid phase precipitation method using X-ray transmission. An apparatus that can perform such measurement includes a Sedigraph particle size analyzer (manufactured by Micromeritics Instruments, model: model 5100).

Moreover, when an inorganic filler (B component) is a fibrous inorganic filler, the average fiber diameter can be suitably selected in the range of 1-20 micrometers according to the physical property which should be provided to a molded article. If the fiber diameter is less than 1 μm, the reinforcing effect is insufficient, and if it exceeds 15 μm, the product appearance is adversely affected. A more preferable range of the fiber diameter is 2 to 17 μm, and particularly preferable is 3 to 15 μm. In addition, the fiber diameter of a fibrous filler can be easily measured with an electron micrograph.

Of the inorganic fillers (component B), a silicate compound is preferable from the viewpoint of the balance of rigidity, fluidity, impact resistance, and product appearance of the finally obtained resin composition. The silicate compound is composed of at least a metal oxide component and a SiO ₂ component, and the chemical structure can be any of the silicate compounds that can be taken, such as orthosilicate, disilicate, cyclic silicate, chain silicate, layered silicate, etc. It may be the structure. Moreover, the silicate compound in the present invention exhibits a crystalline state, and the form of crystals may be appropriately selected from forms such as fibers and plates. Furthermore, the silicate compound may be a natural mineral or an artificial synthetic product. As the artificial compound, those obtained by various known production methods can be used as they are. The silicate compound can also be used by adjusting to a desired particle size and fiber length by pulverization and classification.

As a preferable silicate compound as the component B, a compound represented by the following general formula, that is, xMO · ySiO ₂ · zH ₂ O is preferable. In this general formula, x and y represent natural numbers, z represents an integer of 0 or more, MO represents a metal oxide component, and may be a plurality of metal oxide components. Examples of the metal M in the metal oxide MO include potassium, sodium, lithium, barium, calcium, zinc, manganese, iron, cobalt, magnesium, zirconium, aluminum, and titanium. Preferred as the metal oxide MO is one that substantially contains either CaO or MgO.

  Specific examples of the silicate compound preferable as the component B include wollastonite, talc, mica, zonotlite, sepiolite, attabulgite, kaolinite, montmorillonite, bentonite, smectite and the like. Wollastonite, talc and mica are preferred from the viewpoint of rigidity, impact resistance and appearance of the finally obtained resin composition, and wollastonite is particularly preferred from the viewpoint of improving impact resistance.

Wollastonite preferable as the component B is a white mineral having needle-like crystals, and the chemical formula is represented by CaO · SiO ₂ . Usually, it contains about 50% by weight of SiO ₂ , about 46% by weight of CaO, other Fe ₂ O ₃ , Al ₂ O _{3 and the} like, and the specific gravity is 2.9. Examples of such wollastonite include those commercially available as PH330 and PH450 from Kawatetsu Mining Co., Ltd., Nigros 4 and Nigros 5 from Nico Minerals, SH1250 and SH1800 from Kinsei Matech, and the like. Those having an aspect ratio of 3 or more are preferred. A particularly suitable wollastonite may contain Fe ₂ O ₃ derived from a raw material mineral, and the amount thereof is 0% in the wollastonite from the viewpoint of improving the impact resistance of the finally obtained resin composition. It is preferable to include the resin in the range of 0.5 to 1% by weight, particularly 0.51 to 1% by weight.

Preferred talc B component, a hydrated magnesium silicate having a layered structure, the chemical formula is represented by _{4SiO 2 · 3MgO · H 2 O} , typically, a SiO ₂ 58 to 66 wt%, 28 to 35 weight MgO %, H ₂ O about 5% by weight. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, and the specific gravity is about 2.7. The average particle diameter of talc is preferably in the range of 0.3 to 15 μm, more preferably 0.5 to 10 μm.

Preferred mica as the component B is a pulverized silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite {mascobite, chemical formula: K (AlSi ₃ O ₁₀ ) (OH) ₂ Al ₄ (OH) ₂ (AlSi ₃ O ₁₀ ) K}, phlogopite {phlogopite, chemical formula: K (AlSi ₃ O ₁₀₎ ) (OH) ₂ Mg ₆ (OH) ₂ (AlSi ₃ O ₁₀ ) K}, biotite {biotite, chemical formula: K (AlSi ₃ O ₁₀ ) (OH) ₂ (Mg, Fe) ₆ (OH) ₂ ( AlSi ₃ O ₁₀ ) K}, artificial mica {fluorine phlogopite, chemical formula: K (AlSi ₃ O ₁₀ ) (OH) ₂ F ₂ Mg ₆ F ₂ (AlSi ₃ O ₁₀ ) K}, and the like. Any mica can be used in the present invention, but muscovite is preferred among them. The mica may be pulverized by either dry pulverization method or wet pulverization method. As a result, the reinforcing effect of the resin composition becomes higher, which is preferable.

[4] Rubber polymer (component C)
The thermoplastic resin composition obtained by the production method according to the present invention is further abbreviated as a rubbery polymer (hereinafter referred to as “C component”) for the purpose of improving mechanical properties such as impact resistance of the resin composition. In some cases). In the present invention, the rubbery polymer (component C) is a homopolymer of a monomer for producing a rubbery polymer having a glass transition temperature of 0 ° C. or lower, particularly −20 ° C. or lower. A copolymer (copolymer) obtained by copolymerizing a monomer for producing a polymer with another monomer copolymerizable therewith, and a graft copolymer obtained by grafting another polymerizable monomer to a rubbery polymer. Also includes polymers.

  Rubber polymers (component C) include polybutadiene, diene copolymers (butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, acrylic monomer-butadiene copolymer, etc.), polyisoprene, ethylene And α-olefin (ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, etc.), copolymer of ethylene and unsaturated carboxylic acid, copolymer of ethylene and unsaturated carboxylic acid ester Polymer, copolymer of ethylene and aliphatic vinyl compound, terpolymer (EPDM) of ethylene, propylene and non-conjugated diene, acrylic rubber {polybutyl acrylate, poly (2-ethylhexyl acrylate), butyl acrylate 2- Ethylhexyl acrylate copolymer}, silicone rubber {Polymer Organosiloxane rubbers, polyorganosiloxane rubber and a polyalkyl (meth) consisting of acrylate rubber-IPN composite rubber like} and the like.

Other copolymerizable monomers that can be copolymerized with the monomer that forms the rubber polymer include vinyl aromatic compounds (styrene, α-methylstyrene, etc.), vinyl cyanide compounds (acrylonitrile, meta Acrylonitrile, etc.), epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate, maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, maleic acid, phthalic acid, itaconic acid, etc. Mention may be made of α, β-unsaturated carboxylic acid compounds and their anhydrides, such as maleic anhydride. These monomers may be used alone or in combination of two or more. Further, the following rubbery polymer, that is, a copolymer of ethylene and an aliphatic vinyl compound may be mentioned. The rubber polymer (C component) can be used alone or in combination of two or more.

  In order to improve the impact resistance of the thermoplastic resin composition obtained by the production method according to the present invention, the rubber polymer of component C is preferably a core / shell type graft copolymer. The core / shell type graft copolymer has a rubber polymer as a core, and a shell layer formed by copolymerizing a polymerizable monomer component with a graph is formed on the surface thereof. A thing of structure. Examples of rubbery polymers suitable as the core layer include butadiene-containing rubber, butyl acrylate-containing rubber, and silicone rubber. Examples of the monomer for forming the shell layer include acrylic acid esters, methacrylic acid esters, and aromatic vinyl compounds. The shell layer-forming monomer may be used alone or in combination of two or more.

  Specific examples of the core / shell type graft copolymer as rubbery polymerization (component C) include methyl methacrylate / butadiene / styrene polymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene polymer (MABS resin). , Methyl methacrylate / butadiene polymer (MB resin), methyl methacrylate / acrylic rubber polymer (MA resin), methyl methacrylate / acrylic / butadiene rubber copolymer, methyl methacrylate / acrylic / butadiene rubber / styrene copolymer, methyl methacrylate -(Acrylic / silicone IPN (interpenetrating polymer network) rubber) polymer and the like can be mentioned, and a rubbery polymer containing no styrene component is preferred from the viewpoint of impact resistance. Such a core / shell type graft copolymer may be used alone or in combination of two or more.

[5] Alkylsilane compound (component D)
The alkylsilane compound (hereinafter sometimes abbreviated as “D component”) in the present invention is an alkylsilane compound represented by the general formula (I). In the general formula (I), R ¹ is an alkyl group having 4 to 30 carbon atoms, and when R ¹ is an alkyl group having 4 or less carbon atoms, the impact resistance of the resin composition finally obtained is In addition, the flowability and residence heat stability are not sufficient, and an alkyl group having 30 or more carbon atoms is not preferable because the resin composition does not have sufficient impact resistance, fluidity and residence heat stability. R ¹ is more preferably an alkyl group having 7 to 25 carbon atoms, and particularly preferably an alkyl group having 9 to 23 carbon atoms. R ¹ may have any structure such as linear, branched, and cyclic, but is more preferably linear or branched, and even more preferably linear. A linear alkyl group is preferred because it imparts excellent thermal stability to the resin composition.

On the other hand, in the general formula (I), OR ² reacts with water to form a silanol group and binds to an OH group on the surface of the inorganic filler (component B). R ² is an alkyl group having 1 to 4 carbon atoms. Unfavorable in the alkyl group carbon atoms R ² is more than 4, poor in reactivity with the OH groups of the inorganic filler (B component) surface, since the impact resistance of the finally obtained resin composition is not sufficient . R ² is more preferably a methyl group or an ethyl group, which may be the same or different. In addition, when there are a plurality of R ¹ and / or R ² , R ¹ and R ² may be the same or different. A particularly suitable alkylsilane compound (component D) is an alkylsilane compound represented by the following general formula (II).

  Examples of suitable alkylsilane compounds (component D) include heptylmethyldimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, decylmethyldimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, and the like. The methoxy group of the alkylsilane compound may be substituted with an ethoxy group.

[6] Surface treatment In the method for producing a thermoplastic resin composition according to the present invention, from the viewpoint of impact resistance, fluidity, and residence heat stability of the resin composition, the inorganic filler (B component) is changed to A component (resin component). It is preferable to perform surface treatment with an alkylsilane compound (component D) in advance before blending. As the surface treatment method, for example, (1) using various mixers such as a Henschel mixer, a ball mill, an atomizer colloid mill, a Banbury mixer, and the like, while stirring the inorganic filler (component B), the alkylsilane compound (component D) ) Spraying and dropping, (2) a method of wetting the inorganic filler (component B) with the alkylsilane compound (component D), and (3) immersing the inorganic filler (component B) in the alkylsilane compound (component D) Method, etc. The D component can be diluted with water or a solvent before the D component and the B component are mixed and contacted by the methods (1) to (3). Examples of the solvent include organic solvents, water / organic solvent mixtures, and the like. After mixing and contacting the D component and the B component, stirring and mixing is preferably continued until the temperature reaches 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. The stirring and mixing time is selected in the range of 15 minutes to 1.5 hours depending on the mixer used. By stirring and mixing, the surface of the B component is coated with the D component, reacted, and the solvent is scattered (volatilized).

  When diluting the D component with water when surface-treating the B component, the D component and water are premixed in the presence of the acid component, and the alkoxy group of the alkylsilane compound (D component) is hydrolyzed to produce a silanol group. It is preferable to make it. As the acid component, various conventionally known acids such as lactic acid and acetic acid can be used. The amount is preferably such that the pH of the aqueous solution is about 2 to 6, and is selected in the range of 0.05 to 2% by weight with respect to water.

  Organic solvents that can be used when the B component is surface-treated with the D component include alcohol solvents such as methanol, ethanol, and isopropanol, hydrocarbon solvents such as toluene, hexane, and heptane, and ethers such as dioxane and tetrahydrofuran (THF). Examples of the solvent include ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl isobutyl ketone (MIBK) and acetone, and halogenated hydrocarbon solvents such as methylene chloride and chloroform. Further, when the alkylsilane compound is a solid or viscous liquid at room temperature, it can be handled by heating and dissolving it as necessary to reduce the viscosity.

  The amount of the alkylsilane compound (component D) during the surface treatment is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the inorganic filler (component B). If the amount of component D is less than 0.05 parts by weight, the impact resistance, fluidity and residence heat stability of the finally obtained resin composition will not be sufficient. And stability of residence heat are not sufficient, and neither is preferable. A more preferred amount of component D is 0.1 to 10 parts by weight, and particularly preferred is 0.2 to 5 parts by weight.

[7] Phosphorus compounds (component E)
The phosphorus compound in the present invention (hereinafter sometimes abbreviated as “E component”) improves the residence thermal stability of the finally obtained thermoplastic resin composition, and generates gas, discoloration, and mechanical properties. It functions to prevent a decrease in strength. Examples of the phosphorus compound (component E) include various phosphorus compounds conventionally known as resin additives, such as organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds. The organic phosphate compound is a compound represented by the following general formula (III), the organic phosphite compound is a compound represented by the following general formula (IV), and the organic phosphonite compound is represented by the following general formula ( Compounds represented by V) are preferred. The phosphorus compound (E component) can be used alone or in combination of two or more.

In the general formula (III), R ¹ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 2 to 25 carbon atoms. It is. m is preferably 1 or 2. Specific examples of the alkyl group having 1 to 30 carbon atoms include octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, triacontyl and the like. .

Specific examples of the organic phosphite compound represented by the general formula (IV) include tris (2,4-di-t-butylphenyl) phosphite and bis (2,4-di-t-butylphenyl) pentaerythritol. -Di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphos Phyto, 4-4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5 t-butylphenyl) butane, tris (mixed mono and dinonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4′-isopropyl Denbis (phenyl-dialkylphosphite) and the like, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, And bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite.

Specific examples of the organic phosphonite compound represented by the general formula (V) include tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphonite. As the phosphorus compound (E component), an organic phosphate compound represented by the above general formula (III) is particularly preferable.

  In the aromatic polycarbonate-thermoplastic polyester resin composition produced by the method of the present invention, the content ratio of the A component to the E component constituting the aromatic polycarbonate resin (A1 component) is 10 to 90% by weight, 40 to 99 parts by weight of a resin component (component A) composed of 90 to 10% by weight of a plastic polyester resin (component A2), (B) 1 to 60 parts by weight of an inorganic filler (component B), and rubber weight The alkylsilane compound (D component) represented by the general formula (I) is contained in an amount of 0. 30 to 30 parts by weight of the coalescence (C component) and 100 parts by weight of the total of the A component, the B component, and the C component. In addition, the phosphorous compound (E component) is contained in an amount of 0.005 to 1 part by weight with respect to a total of 100 parts by weight of the A component, the B component and the C component.

  The content ratio of the A1 component and the A2 component is selected in the range of 10 to 90% by weight of the A1 component in the total of 100% by weight of the A1 component and the A2 component. If the A1 component is less than 10% by weight, the impact resistance of the finally obtained resin composition is not sufficient, and the resin composition is more than 90 parts by weight, inferior in fluidity, chemical resistance and residence heat stability. Neither is preferred. The above range is preferably 30 to 90% by weight, more preferably 50 to 85% by weight, particularly preferably 55 to 80% by weight, and the A2 component is 90 to 10% by weight, preferably 10 to 70% by weight, and more. Preferably it is 15-50 weight%, Most preferably, it is 20-45 weight%.

  The B component is selected in the range of 1 to 60 parts by weight with respect to 100 parts by weight of the total of the A component, the B component, and the C component. When the component B is less than 1 part by weight, the rigidity of the finally obtained resin composition is insufficient, and when it exceeds 60 parts by weight, the balance between rigidity and impact resistance and fluidity of the resin composition is also inferior. Absent. The amount of component B is preferably 2 to 55 parts by weight, more preferably 5 to 50 parts by weight. Moreover, the quantity of C component is chosen in the range of 0-35 weight part, A preferable quantity is 1-30 weight part, A more preferable quantity is 2-25 weight part.

  The D component is selected in the range of 0.01 to 3 parts by weight with respect to 100 parts by weight of the total of the A component, the B component, and the C component. If the D component is less than 0.01 part by weight, the impact resistance and fluidity of the finally obtained resin composition are not sufficient, and even if the D component exceeds 3 parts by weight, the impact resistance and retention of the resin composition are not sufficient. Thermal stability deteriorates, and neither is preferable. A preferred amount of component D is 0.03 to 2.5 parts by weight, and a more preferred amount is 0.05 to 2 parts by weight.

The E component is selected in the range of 0.005 to 1 part by weight with respect to 100 parts by weight of the total of the A component, the B component, and the C component. If the E component is less than 0.005 parts by weight, the finally obtained resin composition has insufficient thermal stability and residence heat stability, and even if the E component exceeds 1 part by weight, the thermal stability of the resin composition. It is not preferable because it may cause a deterioration of the stability of residence heat and adversely affect other performances. A preferable amount of the E component is 0.01 to 0.7 parts by weight, and a more preferable amount is 0.03 to 0.5 parts by weight.

  In the thermoplastic resin composition produced by the production method of the present invention, in addition to the above components A to E, other resins (F) and various kinds of resins can be used as long as the purpose of the present invention is not impaired. A resin additive (G) can be blended. Examples of other resins (F) include polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. , Phenol resin, epoxy resin and the like. In addition, as the resin additive (G), an antioxidant, a release agent, a dye / pigment, a heat stabilizer, a weather resistance improver, an antistatic agent, an antifogging agent, a lubricant / antiblocking agent, a fluidity improver, Plasticizers, dispersants, antibacterial agents and the like can be mentioned. These can be used alone or in combination of two or more.

To produce a resin composition by the method according to the present invention, in the first step, an aromatic polycarbonate resin (A1 component) and a thermoplastic polyester resin (A2 component) are melt-kneaded to obtain a resin component (A component). The method of preparing and adding a phosphorus compound (E component) to the resin component (A component) in a molten state in the second step is adopted. B component, C component, D component and components other than components A to E added as necessary can be added in any of the first step and the second step, but the resin composition finally obtained In order to improve the physical properties such as impact resistance and improve the residence heat stability, it is preferable to add the B component and the D component in the second step. The first step and the second step can be performed in separate melt kneaders, but are preferably performed in the same melt kneader. Examples of the melt kneader include a Banbury mixer, a heating roll, a Brabender, a single screw extruder, a twin screw extruder, and a kneader. Among these, a single screw extruder, a twin screw extruder, and the like are preferable.

When the first step and the second step are performed by the same extruder, the extruder is provided with at least two supply ports, and first, the A1 component and the A2 component are supplied from the first supply port (main feed). It is preferable to perform melt-kneading and then melt-kneading by supplying (side-feeding) at least E component from a supply port after the second supply port. The cylinder set temperature and melt kneading time (residence time) of the extruder in the first step and the second step vary depending on the ratio of the A1 component and the A2 component, the amount of the B component, and the like, but usually in the range of 260 to 320 ° C. Preferably, it is selected in the range of 270 to 310 ° C., and the melting time (residence time) is usually selected in the range of 0.5 to 20 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes.

  The thermoplastic resin composition obtained by the production method according to the present invention is used as a resin material for production (molding) of various products (molded products). As a molding method, a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation. Specifically, general injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, rapid heating molds Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method Etc.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these ranges. In the following examples and comparative examples, the blending amount means parts by weight.

The constituent components of the resin compositions used in the examples and comparative examples have the following characteristics.
<A1 component>
(1) PC-1: Bisphenol A type aromatic polycarbonate (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-3000FN, viscosity average molecular weight 22500).
(2) PC-2: Bisphenol A type aromatic polycarbonate (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon E-2000FN, viscosity average molecular weight 28000).

<A2 component>
(3) PBT-1: polybutylene terephthalate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Nova Duran 5020, intrinsic viscosity 1.20 dl / g). Here, the intrinsic viscosity of the A2 component was measured at a temperature of 30 ° C. by dissolving at a concentration of 1% by weight in a 1: 1 (weight ratio) mixed solution of phenol and tetrachloroethane.
(4) PBT-2: Polybutylene terephthalate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Nova Duran 5008, intrinsic viscosity 0.85 dl / g).
(5) PET-1: Polyethylene terephthalate resin (manufactured by Mitsubishi Chemical Corporation, trade name: Novapex GG500, intrinsic viscosity 0.76 dl / g).

<B component>
(6) B-1: Wollastonite (manufactured by Nico Minerals, trade name: Nigros 4, average particle size 3.4 μm, Fe ₂ O ₃ content 0.77% by weight).
(7) B-2: Wollastonite (manufactured by Nico Minerals, trade name: Nigros 8, average particle size 7.3 μm, Fe ₂ O ₃ content 0.77 wt%).

<C component>
(8) C-1: Core / shell type graft copolymer made of polybutadiene (core layer) / alkyl acrylate / alkyl methacrylate copolymer (shell layer) (Rohm and Haas Japan, product) Name: EXL2603).

<D component>
(9) D-1: Decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., brand name: KBM3103).
(10) D-2: Octadecyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., brand name: LS6970).

<B component / D component (surface treated product)>
(11) BD-1: A mixed aqueous solution is prepared by adding and stirring 1000 g of the above D-1 to 1500 g of deionized water lactic acid (manufactured by Shonan Wako Pure Chemicals, reagent) aqueous solution (lactic acid concentration 0.3 wt%). did. Next, 100 kg of the B-1 was charged into a 300 L Henschel mixer (super mixer, Z-3SP), and the mixed aqueous solution of D-1 was added over several minutes while pre-stirring at 400 rpm. Subsequently, stirring and mixing were continued while stirring and mixing at 750 rpm until the internal temperature reached 120 ° C., and surface-treated BD-1 was obtained.

(12) BD-2: A mixed aqueous solution in the same procedure as in the preparation example of (11) BD-1, except that the amount of D-1 in the preparation example of (11) BD-1 was changed to 750 g. Was added and stirring was continued to obtain a surface-treated BD-2.
(13) BD-3: Mixed aqueous solution in the same procedure as in the preparation example of (11) BD-1, except that in the preparation example of (11) BD-1, the amount of D-1 was changed to 500 g Was added and stirring was continued to obtain a surface-treated BD-3.
(14) BD-4: Mixed aqueous solution in the same procedure as in the preparation example of (11) BD-1 except that D-1 was changed to D-2 in the preparation example of (11) BD-1 above. Was added and stirring was continued to obtain a surface-treated BD-4.
(15) BD-5: Mixed aqueous solution in the same procedure as in the preparation example of (11) BD-1 except that B-1 was changed to B-2 in the preparation example of (11) BD-1 above. Was added and stirring was continued to obtain a surface-treated BD-5.

<E component>
(16) E-1: Phosphorus compound (Asahi) represented by the following chemical formula, that is, O = P (OH) _{n ′} (OC ₁₈ H ₃₇ ) _{3-n ′} (where n ′ is a mixture of 1 and 2) Denka Kogyo Co., Ltd., trade name: ADK STAB AX-71).
(17) E-2: The following chemical formula, P- {O-φ (t-Bu) -t-Bu} ₃ (Adeka Stub 2112 manufactured by Asahi Denka Kogyo Co., Ltd.). In this chemical formula, φ represents a benzene ring.

[Example 1 to Example 11, Comparative Example 1 to Comparative Example 15] and Comparative Example 2
[Preparation of resin composition]
A1 component, A2 component, B component, and C component were weighed at the ratios (unit: parts by weight) shown in Table-1, Table-2, and Table-3, and uniformly mixed by a tumbler mixer to obtain a mixture. The obtained mixture was extruded under the conditions of a cylinder temperature of 270 ° C. and a screw speed of 250 rpm using a twin-screw extruder (manufactured by Nippon Steel Works, model: TEX30XCT, L / D = 42, barrel number 12). It was fed (main feed) from the barrel 1 of the machine and melt-kneaded . Then, in the middle of the melt-kneading , B component or B component / D component (surface treated product) and E component are mixed into a small amount of A1 component from barrel 7 on the downstream side of barrel 1, and Table-1, The ratios (unit: parts by weight) shown in Table-2 and Table-3 were fed in the middle (side feed), and then melt-kneaded to prepare resin composition pellets.

[Preparation of test piece]
The obtained pellets were dried for 4 hours or longer by a hot air dryer set at a temperature of 120 ° C., and then an injection molding machine (manufactured by Meiki Seisakusho, model: M150AII-SJ) was used. A test piece conforming to the ASTM test was molded under the conditions of a temperature of 80 ° C. and a molding cycle of 55 seconds.

[Evaluation methods]
(1) Fluidity (Q value) (unit: × 10 ⁻² cc / s): Using a Koka type flow tester (manufactured by Shimadzu Corporation) under the conditions of a temperature of 280 ° C. and a load of 160 kgf / cm ² , About the dried pellet-shaped resin composition, the outflow amount Q value per unit time was measured. The orifice used here has a diameter of 1 mm and a length of 10 mm. It means that it is excellent in fluidity | liquidity, so that Q value is high.
(2) Rigidity (flexural modulus) (unit: MPa): Based on ASTM D790, the flexural modulus was measured at a temperature of 23 ° C. for a test piece having a thickness of 6.4 mm. It means that rigidity is excellent, so that a numerical value is large.
(3) Impact resistance (Izod impact strength) (unit: J / m): In accordance with ASTM D256, for a test piece with a thickness of 3.2 mm, an eye dot impact strength (unit: 23 ° C.). J / m) was measured. The larger the value, the better the impact resistance.
(4) Stability thermal stability: When molding a test piece conforming to the above ASTM test, the residence time was formed as 1 cycle 5 minutes, and the surface appearance of each test piece after the fifth shot was visually observed. evaluated. On the surface of the test piece, the case where no rough skin due to silver streak was observed was judged as “◎”, and the case where rough skin due to silver streak was observed was judged as “x”.

From Tables 1 to 3, the following becomes clear.
1. The resin compositions of Examples 1 to 11 produced by the production method according to the present invention are excellent in fluidity, impact resistance and thermal stability (see Examples 1 to 11).
2. On the other hand, the resin compositions of Comparative Examples 1 to 11 in which a phosphorus compound (E component) was added before the resin composition started melting (added at barrel 1 of the extruder = main addition) Compared to that of the example added after melting the product (added at the barrel 7 of the extruder = side addition), the fluidity and rigidity are not changed, but the impact resistance is significantly inferior (Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, and so on)
3. A resin composition containing an inorganic filler (B component) that is not surface-treated with an alkylsilane compound (D component) represented by the general formula (I) flows regardless of the addition time of the phosphorus compound (E component). Inferior in property and impact resistance (Example 1 to Example 6, Comparative Example 1 to Comparative Example 6, Comparative Example 12 to Comparative Example 13 group reference, Example 8, Comparative Example 14 to Comparative Example 15 group reference, Example 10, see groups of Comparative Examples 16 to 17).

  The present invention is as described above in detail, and the thermoplastic resin composition obtained by the production method of the present invention is used as a resin material for production (molding) of various products (molded products). As a molding method, a conventionally known molding method for molding a molded product from a thermoplastic resin material can be applied without limitation. Specifically, general injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, rapid heating molds Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method Etc.

Various products (molded products) include electrical / electronic equipment parts, OA equipment, machine parts, vehicle exterior / skin parts, vehicle interior parts, building components, various containers, leisure goods / miscellaneous goods, mobile phones, etc. A housing etc. are mentioned. Vehicle exterior / skin parts include outer door handle, bumper, fender, door panel, trunk lid, front panel, rear panel, roof panel, bonnet, pillar, side molding, garnish, wheel cap, hood bulge, fuel lid, various spoilers. Motorbike cowl. Examples of vehicle interior parts include an inner door handle, a center panel, an instrument panel, a console box, a luggage floor board, and a display housing for car navigation.

Claims (8)

Inorganic with respect to 40 to 99 parts by weight of resin component (component A) consisting of 10 to 90% by weight of aromatic polycarbonate resin (component A1) and 90 to 10% by weight of thermoplastic polyester resin (component A2) It contains 1 to 60 parts by weight of filler (B component) and 0 to 35 parts by weight of rubbery polymer (C component), and the following general formula (I) with respect to a total of 100 parts by weight of component A, component B and component C In a method for producing a thermoplastic resin composition containing 0.01 to 3 parts by weight of an alkylsilane compound (D component) represented by (II) and 0.005 to 1 part by weight of a phosphorus compound (E component),
The inorganic filler (B component) is pre-treated with an alkylsilane compound (D component),
The phosphorus compound (E component) is at least one selected from an organic phosphate compound, an organic phosphite compound, and an organic phosphonite compound,
First, a thermoplastic resin composition characterized in that an aromatic polycarbonate resin (A1 component) and a thermoplastic polyester resin (A2 component) are melt-kneaded , and then a phosphorus compound (E component) is added and melt-kneaded. Manufacturing method.

  The resin component (A component) is composed of 50 to 85% by weight of an aromatic polycarbonate resin (A1 component) and 50 to 15% by weight (total 100% by weight) of a thermoplastic polyester resin (A2 component). Item 2. A method for producing a thermoplastic resin composition according to Item 1.   The manufacturing method of the thermoplastic resin composition of Claim 1 or Claim 2 which contains 10 weight part or more of polyethylene terephthalate resin as A2 component in 100 weight part of thermoplastic polyester resins (A2 component).   The manufacturing method of the thermoplastic resin composition as described in any one of Claim 1 thru | or 3 whose inorganic filler (B component) is a silicate compound. The method for producing a thermoplastic resin composition according to any one of claims 1 to 4, wherein the alkylsilane compound (component D) is an alkylsilane compound represented by the following general formula (II).

  The method for producing a thermoplastic resin composition according to claim 1, wherein the inorganic filler (B component) is surface-treated in advance with an alkylsilane compound (D component) diluted with water or an organic solvent.   The content of the rubber polymer (component C) in a total of 100 parts by weight of the component A, the component B and the component C is 1 to 30 parts by weight. A method for producing a thermoplastic resin composition.   The method for producing a thermoplastic resin composition according to any one of claims 1 to 7, wherein the Izod impact strength is 90 J / m or more.