JPH09143359A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin compsn. improved in mold flow and chemical resistance without detriment to its heat resistance by mixing a polycarbonate resin with a polyester resin contg. a layered silicate compd. SOLUTION: This compsn. comprises 30-99wt.% polycarbonate resin and 70-1wt.% mixture comprising a polyester resin (e.g. polyethylene terephthalate) and a layered silicate compd. Pref. examples of the silicate compd. are a smectite clay mineral and Na- and Li-fluoromicas, one contg. org. onium ions intercalated thereinto being also usable. The compd. has an average particle size of 25μm or lower, is contained in an amt. of 0.1-50wt.% (pref. 1-40wt.%) in the mixture, and has a distance between the bottom planes of 30Åor higher. The mixture is prepd. pref. by using a dispersion of the compd. in a glycol, etc., as a material in the polymn. process for producing the polyester resin. The compsn. exhibits good mold flow and does not allow burr to appear.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate-based resin composition, more specifically, a polycarbonate-based resin composition having excellent heat resistance, chemical resistance, etc., improved flowability during molding, and suppressed burr formation. It relates to a resin composition.

[0002]

2. Description of the Related Art Polycarbonate resin is a thermoplastic resin that has excellent heat resistance, impact resistance and toughness.
It is widely used in parts such as automobiles, electricity and electronics.

Among such polycarbonate resins, aromatic polycarbonate resins have a high glass transition temperature and are expected to have high heat resistance, but on the other hand, in order to obtain sufficient fluidity in processing, 300 A relatively high processing temperature of around 0 ° C. is required, and a relatively high injection speed and pressure are required when a molded product is obtained by injection molding or the like. Further, the polycarbonate-based resin has a problem in chemical resistance such as cracking or melting on the surface of the molded product when it comes into contact with various organic solvents, gasoline, etc. In particular, a molded product was obtained by injection molding or the like. In this case, since molding is performed at a relatively high injection speed and pressure, distortion remains in the molded body,
Cracking is remarkable at that portion. Further, the polycarbonate-based resin is not sufficient in terms of weather resistance, such as cracking on the surface of the molded body or discoloration to yellow.

On the other hand, the crystalline thermoplastic polyester resins represented by polyethylene terephthalate and polytetramethylene terephthalate are excellent in mechanical properties, electrical properties, chemical resistance and the like and have a crystal melting point higher than their own. When it is heated to 1, it shows good molding fluidity, and has been widely used as a fiber, a film, a molding material, and the like.

Therefore, in order to solve the above-mentioned problems in polycarbonate resins, Japanese Patent Publication No. 36-1403.
No. 5, Japanese Patent Publication No. 39-20434, Japanese Patent Laid-Open No. 59
JP-A-176345 proposes a technique of adding a polyester resin to improve molding fluidity and chemical resistance.

[0006]

When a polyester resin is added to a polycarbonate resin, the molding fluidity and the chemical resistance are certainly improved, but the heat resistance is inevitably lowered. This is because in the composition, a part of the polycarbonate-based resin and the polyester-based resin react to produce a resin having a relatively low glass transition temperature, or particularly when polyethylene terephthalate is used as the polyester-based resin, It is considered that most of the resin remains amorphous in the composition because the resin has relatively low crystallinity. Further, due to such a phenomenon, chemical resistance is not satisfactory. Also in terms of molding fluidity, when molding a relatively large molded product such as by injection molding, a high injection speed and pressure are still required. Therefore, if the amount of polyester resin added is increased, the heat resistance will decrease. Moreover, a new problem such as the occurrence of burrs occurs on a part of the molded body.

In order to improve the above-mentioned problem of deterioration of heat resistance, even in polycarbonate resins, inorganic fibers such as glass fibers and carbon fibers, glass flakes, glass beads, silica, mica, talc, clay and other inorganic powders. Reinforcing fillers such as bodies or clay minerals have been added. However, although the heat resistance is improved, the strength, toughness, surface properties, etc. may deteriorate due to poor dispersion of the reinforcing filler or poor adhesion between the reinforcing filler and the resin.

[0008]

Means for Solving the Problems The inventors of the present invention have improved the above-mentioned problems and, as a result of diligent studies on a polycarbonate resin composition having less heat resistance, chemical resistance, molding fluidity and less burr, polyester By using a polyester resin containing a layered silicate compound as a part or all of the resin, it is found that heat resistance is maintained, chemical resistance is further improved, and moldability is also improved. The present invention has been reached.

That is, the first aspect of the present invention is to provide a polycarbonate resin composition comprising (A) a polycarbonate resin and (B) a layered silicate compound-containing polyester resin,
A second aspect of the present invention includes a polycarbonate resin composition comprising (A) a polycarbonate resin, (B) a layered silicate compound-containing polyester resin, and (C) a polyester resin not containing a layered silicate compound, respectively. To do.

The (A) polycarbonate resin used in the present invention is a thermoplastic polycarbonate resin, which is an aromatic polycarbonate resin produced mainly by reacting a dihydric phenol compound with phosgene or a carbonic acid diester.

Examples of the dihydric phenol compound constituting the polycarbonate resin include 2,2-bis (4-
Hydroxyphenyl) propane (bisphenol A),
Bis (4-hydroxyphenyl) methane, 1,1-bis (4′-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC), bis ( 4-
Hydroxyphenyl) cyclohexylmethane, 2,2-
Bis (4'-hydroxy-3,5'-dibromophenyl) propane, bis (4-hydroxy-3,5-diculuruphenyl) methane, bis (4-hydroxy-3,5-)
Dimethylphenyl) methane, 2,2-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) propane,
1,1-bis (4'-hydroxyphenyl) -1-phenylethane, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, Examples thereof include bis (4-hydroxy-3,5-dimethylphenyl) sulfone, 4,4′-dihydroxybenzophenone and bis (4-hydroxyphenyl) sulfide. Further, in order to enhance flame retardancy, a polymer in which a phosphorus compound is copolymerized or end-capped can be used, and in order to enhance weather resistance, a polymer obtained by copolymerizing a dihydric phenol having a benzotriazole group. Can also be used. These phenols are used alone or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin is preferably 10,000 or more, more preferably 15,000 to 45,000, further preferably 18,000.
３５35,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength of the obtained resin composition is lowered, which is not preferable. The polycarbonate resins may be used alone or in combination of two or more having different compositions or components and / or different molecular weights. The weight ratio of the (A) polycarbonate resin in the polycarbonate resin composition of the present invention is preferably 30 to 99% by weight, more preferably 35 to 95% by weight, and further preferably 40 to 90% by weight. If it is less than 30% by weight, the heat resistance is insufficient, and if it is 99% by weight or more, the molding fluidity tends to decrease.

The polyester resin in the (B) layered silicate compound-containing polyester resin used in the present invention uses terephthalic acid or a derivative thereof capable of forming an ester as an acid component and has 2 to 10 carbon atoms as a glycol component. A polyester resin obtained by using a derivative having a glycol or its ester forming ability,
Specific examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, etc. These may be used alone or in combination of two or more.

Known components that can be copolymerized can be used in the polyester resin as long as the characteristics of the composition are not impaired. As the component, a divalent or more aromatic carboxylic acid having 8 to 22 carbon atoms, a divalent or more aliphatic carboxylic acid having 4 to 12 carbon atoms, and further a divalent or more alicyclic carboxylic acid having 8 to 15 carbon atoms. Carboxylic acids such as acids and ester-forming derivatives thereof, aliphatic compounds having 3 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms, which are in the molecule Examples thereof include compounds having two or more hydroxyl groups, and ester-forming derivatives thereof.

Specifically, as carboxylic acids, other than terephthalic acid, for example, isophthalic acid, naphthalene dicarboxylic acid, bis (p-carboxyphenyl) methaneanthracene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2 -Bis (phenoxy) ethane-4,4'-
Dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, decahydronaphthalenedicarboxylic acid Examples of the hydroxyl group-containing compounds include decanodiol, neopentyl glycol, and cyclohexanedimethanol in addition to ethylene glycol, propylene glycol, butanediol, and hexanediol. , Cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, etc. Objects or derivatives having an ester-forming ability and the like.

Further, oxy acids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid, and ester-forming derivatives thereof, cyclic esters such as ε-caprolactone, etc. can also be used. Further, a polyalkylene glycol unit such as polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymer polyethylene glycol, polytetramethylene glycol, etc. is incorporated into the polymer chain. It is also possible to use a partially copolymerized product.

The copolymerization amount of the above components is generally 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less. Furthermore, due to the balance between mechanical properties and moldability, ethylene terephthalate and / or
Alternatively, a polyester resin containing a tetramethylene terephthalate unit as a main component is preferable.

Intrinsic viscosity of the polyester resin [phenol: 1,1,2,2-tetrachloroethane = 1: 1
(Weight ratio) measured at 25 ° C. using a mixed solvent] is preferably 0.35 or more, more preferably 0.4 to
2.0, and more preferably 0.45 to 1.5.
When the intrinsic viscosity is less than 0.35, heat resistance and chemical resistance are deteriorated, and burrs may occur during molding by injection molding, which is not preferable. The polyester resins may be used alone or in combination of two or more having different compositions or copolymerization components and / or having different intrinsic viscosities.

The layered silicate compound used in the polyester resin containing the layered silicate compound is a compound having a structure in which phases mainly composed of silicate are laminated in a layered manner, and is an octahedron containing Al, Mg, Li and the like. Seat structure 2
A 2: 1 type sandwiching a single SiO ₄ tetrahedral sheet structure is preferable, and specific examples thereof include montmorillonite, hectorite, fluorohectorite, saponite,
Smectite-based clay minerals such as beidellite and stevensite, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine-mica, synthetic mica such as Li-type tetrasilicon-fluorine mica, vermiculite, fluorovermiculite, and halosite. It may be natural or synthetic.

Among them, smectite clay minerals such as montmorillonite and hectorite, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica and Li type tetrasilicon fluorine mica are preferable, and especially Na type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica is preferred.

Further, these layered silicate compounds are
It may be an intercalated organic onium ion represented by ⁺ -RY. Here, X ⁺ is an ammonium ion, a pyridinium ion, a phosphonium ion, a sulfonium ion, or the like, R is an organic group such as an alkyl group, a phenyl group, or an alkylene group, and Y is a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group, a nitro group. ,
It represents a sulfone group or a derivative thereof. The average particle size of the layered silicate compound is preferably 25 μm or less, more preferably 20 μm or less. Average particle size is 25μ
When it exceeds m, toughness and surface property are deteriorated, which is not preferable.

These layered silicate compounds may be used alone or in combination of two or more, and the ratio thereof is 0.1 in 100% by weight of the (B) layered silicate compound-containing polyester resin.
Is preferably 50% by weight, more preferably 0.3 to 45%.
%, More preferably 1 to 40% by weight. 0.
If it is less than 1% by weight, the effect of improving the heat resistance, fluidity and chemical resistance of the polycarbonate resin composition will be small, and if it exceeds 50% by weight, the production of the layered silicate compound-containing polyester resin becomes difficult. Therefore, it is not preferable.

It is preferable that a part and / or all of the layered silicate compounds in the polycarbonate resin composition of the present invention have a bottom spacing of 30 Å or more. The bottom surface spacing here is the thickness of the unit layer in the layer stacking direction in the crystal structure of the layered silicate compound,
From the diffraction angle of the diffraction line in the X-ray diffraction measurement,
It is determined by the condition of g. The bottom distance and X-ray diffraction measurement of the layered silicate compound are described in, for example, "Clay Handbook" (edited by The Clay Society of Japan: Gihodo Publishing). In addition, in order to measure the X-ray diffraction of the layered silicate compound in the composition, the composition is molded into a flat plate shape by, for example, injection molding or press molding, and then the surface is polished into a flat shape to prepare a sample. Can be measured. further,
In the composition of the present invention, it is preferable that the diffraction intensity of the diffraction line derived from the bottom surface spacing in X-ray diffraction measurement satisfies the following formula. 0.2 ≦ {I (≧ 30Å) / [I (≧ 30Å) + I (<
30 Å))]} where I (≧ 30 Å) is the diffraction intensity of the diffraction line corresponding to the bottom spacing of 30 Å or more, and I (<30 Å) is the bottom spacing of 30 Å
It is the diffraction intensity of the diffraction line corresponding to less than.

The ratio of the (B) layered silicate compound-containing polyester resin in the polycarbonate resin composition of the present invention is preferably 70 to 1% by weight, more preferably 65 to 65% by weight.
It is 5% by weight, more preferably 60 to 10% by weight. If it is less than 1% by weight, the effect of improving chemical resistance and molding fluidity is insufficient, and if it exceeds 70% by weight, the inherent properties of the polycarbonate resin, particularly heat resistance, are unfavorably deteriorated.

As a method for producing the polyester resin composition containing the layered silicate compound (B), there is a method of melt-kneading the polyester resin and the layered silicate compound using a general extruder. For the purpose of improving the dispersibility of the compound, the adhesiveness with the resin, etc., a part or all of the layered silicate compound is dispersed in glycol constituting the polyester or a derivative thereof having an ester forming ability, and the polyester is dispersed in the glycol. It is preferable to add the layered silicate compound to the polyester resin to obtain a layered silicate compound-containing polyester resin, and then melt-knead the layered silicate compound if necessary.

The method for obtaining the polyester resin containing the layered silicate compound by polymerization is not particularly limited, and a polycondensation method for obtaining an ordinary polyester can be used as it is. For example, after a layered silicate compound dispersed in a starting material of a polyester resin and / or a polyester resin and a glycol or a derivative thereof having an ester-forming ability is added in a pressure vessel and mixed by stirring, or a mixture thereof is prepared. Add to a pressure vessel, heat, then 133 Pa (1
Torr) A method of melt polycondensation under reduced pressure, a polyester resin heated and melted is continuously supplied to a horizontal or vertical continuous reactor whose pressure is reduced to 133 Pa or less, and glycol or its ester is formed. A method of continuously adding a layered silicate compound dispersed in a derivative having an ability during the supply of a reactor and / or a polyester resin to continuously obtain a polymer, and after melt polycondensation by the method as described above. Further, a method of solid phase polymerization and the like can be mentioned. When obtaining the layered silicate compound-containing polyester resin, it is preferable to add one or more stabilizers such as a phenolic antioxidant, a phosphorus compound and a sulfur antioxidant.

If desired, the polycarbonate resin composition of the present invention may further contain (C) a polyester resin containing no layered silicate compound.
Examples of the polyester resin not containing the layered silicate compound include the same polyester resins as those exemplified as the layered silicate compound-containing polyester resin. In particular, in order to obtain a sufficient modifying effect, it is preferable that the main components of the polyester resins used for both are the same.

The amount of the (C) polyester resin not containing the layered silicate compound is 80 based on 100 parts by weight of a composition comprising (A) the polycarbonate resin and (B) the layered silicate compound-containing polyester resin. Up to 75 parts by weight, preferably up to 75 parts by weight, more preferably 6
It is up to 0 parts by weight. When it exceeds 80 parts by weight, heat resistance and the like are deteriorated.

If desired, an impact resistance improver can be added to the polycarbonate resin composition of the present invention. As an impact resistance improver, the glass transition temperature is 0 ° C.
Below, more preferably, a rubber-like elastic body at -15 ° C or lower, such as polybutadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NB
R), butyl acrylate-butadiene rubber, styrene-butadiene-styrene rubber (SBS) and other diene rubbers, polybutyl acrylate and other acrylic rubbers, ethylene-propylene-non-conjugated diene rubber (EPDM) and other polyolefin rubbers, silicone A system rubber or the like can be used. Each of the rubber-like elastic bodies is single or 2
Used in combination of more than one species.

Further, a reinforcing filler may be further added to the polycarbonate resin composition of the present invention, if necessary. As the reinforcing filler, known and conventional ones can be used as they are. For example, glass fiber, carbon fiber, potassium titanate fiber, glass beads, glass flakes, calcium silicate, calcium carbonate, calcium sulfate, magnesium silicate, barium sulfate, talc, kaolin, mica, clay and the like, these alone or. Used in combination of two or more.

When a fibrous reinforcing agent such as glass fiber or carbon fiber is used as the reinforcing filler, chopped strand glass fibers treated with a sizing agent are preferably used from the viewpoint of workability. Further, in order to enhance the adhesiveness between the resin and the fibrous reinforcing agent, it is preferable that the surface of the fibrous reinforcing agent is treated with a coupling agent, and a binder may be used. As the coupling agent,
For example, alkoxysilane compounds such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane are preferably used, and as the binder, for example, epoxy resin, urethane resin and the like are preferably used.
It is not limited to these.

In order to make the polycarbonate resin composition of the present invention a composition having higher performance, a phenolic antioxidant, a thioether antioxidant, an amine antioxidant,
It is preferable to use a heat stabilizer such as a phosphorus-based antioxidant alone or in combination of two or more kinds. In addition, if necessary, generally well known stabilizers, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, plasticizers, organic or inorganic nucleating agents, crystallization accelerators, flame retardants, flame retardant aids. Agents, pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, antibacterial agents,
One or more kinds of additives such as a polyfunctional compound and a reaction catalyst thereof can be added.

Further, any other thermoplastic or thermosetting resin such as another saturated or unsaturated polyester resin or polyester carbonate resin may be used as long as the mechanical properties and moldability are not impaired. , Liquid crystal polyester resin, polyolefin resin, polyamide resin, rubber polymer reinforced styrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, polyarylate resin, etc. alone or 2 You may add in combination of 1 or more types.

The polycarbonate resin composition of the present invention can be obtained by mixing and melting the components (A), (B) and (C), the compounding agent and the like by an arbitrary method. It is not limited. For example, it can be produced by melt-kneading using a single-screw extruder, a twin-screw extruder, a kneader or the like.

The molding method of the composition produced by the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, sheet molding, and rolls. Molding, press molding,
Lamination molding, film molding by melt casting method, spinning,
A molding method such as the above can be applied.

[0036]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the following description, unless otherwise specified.
"Parts" means parts by weight and "%" means% by weight. In addition,
The resin composition was evaluated by the following methods.

Evaluation Method After drying the obtained resin composition at 120 ° C. for 5 hours or more, a cylinder temperature of 280 was measured using a 75t injection molding machine.
Injection molding at ℃, mold temperature 70 ℃, thickness 1/4 inch bar (width 12mm, length 127mm), and AST
The dumbbell of No. M1 was obtained and the following evaluations were performed.

Heat resistance: Using a 1/4 inch bar, AST
According to MD-648, the deflection temperature under load was measured at a load of 1.82 MPa to evaluate heat resistance.

Chemical resistance: 1% ASTM No. 1 dumbbell
Bending strain was applied and the absorbent cotton soaked with gasoline was placed on the strained part. After 1 hour, the absorbent cotton was removed, and the maximum length of the generated cracks was measured with a caliper to evaluate the chemical resistance. The larger the crack length, the poorer the chemical resistance. Since the width of the strained part of the dumbbell used is 12 mm,
The maximum value is 12.

Bottom interval: A test piece was prepared by polishing the surface of ASTM No. 1 dumbbell, and 2θ = 0.2 ° to 16 ° using an X-ray generator (RU-200B manufactured by Rigaku Denki Co., Ltd.). X-ray diffraction measurement is performed, and Bragg is measured from the peak position.
The bottom surface distance was obtained under the diffraction conditions of, and the intensity ratio was calculated from the diffraction intensity using the following formula. X-ray diffraction intensity ratio = {I [≧ 30Å] / [I (≧ 30Å)
+ I (<30Å)]} where I (≧ 30Å) is the diffraction intensity of the diffraction line corresponding to the bottom spacing of 30Å or more, and I (<30Å) is the bottom spacing of 30Å
The diffraction intensity of the diffraction line corresponding to less than.

Flowability: After drying the obtained resin composition at 120 ° C. for 5 hours or more, using a capillograph, a cavity temperature of 280 ° C., a preheating time of 5 minutes, a shear rate of 12
The melt viscosity was measured at 20 / sec to evaluate the fluidity.

Burr generation evaluation: 12
After drying at 0 ° C for 5 hours or more, injection molding is performed at a cylinder temperature of 290 ° C and a mold temperature of 70 ° C using a 150t injection molding machine, and a container having a thickness of 4 mm, a length of 300 mm, a width of 200 mm, and a depth of 50 mm. Whether or not burrs were generated when a shaped article was formed was evaluated.

Production Example 1: Production of Layered Silicate Compound Sodium silicate fluoride (Na ₂ SiF ₆ ) was added to talc 20 times.
% Mixture was heated in an electric furnace for 1 hour to obtain sodium fluorine mica. As a result of the X-ray diffraction measurement of the obtained sodium fluorine mica, a diffraction peak was observed at 2θ = 7.1 °, which corresponds to a bottom spacing of 12Å. Similarly, lithium fluoride mica was obtained from talc and lithium silicofluoride (Li ₂ SiF ₆ ).

Production Example 2: Production of Layered Silicate Compound In 4.8 liters of water, No. 3 water glass (SiO ₂ 28%, N ₂
a ₂ O 9%) 1032 g was dissolved and 95% sulfuric acid 194
g was added with stirring to obtain a silicate solution. Subsequently, 1.2 liters of water was added to MgCl ₂ . 6H ₂ O (purity 98%)
672 g was dissolved and this was added to the silicate solution to obtain a mixed solution. The mixed solution was added with 2N sodium hydroxide solution 4.2.
The reaction product was obtained by adding to liter with stirring. The reaction product was filtered and washed with water, and 0.24 liter of water and Li (O 2
H) .H ₂ O 17.4 g of a solution was added. After heating at 250 ° C. for 3 hours in a pressure vessel, the reaction product was taken out by cooling and dried to obtain a synthetic smectite. As a result of X-ray diffraction measurement of the obtained synthetic smectite, the bottom surface spacing was about 13Å. 12 g of the synthetic smectite was dispersed in 0.6 liter of water, to which 22 g of methyldiethyl polypropylene glycol (molecular weight 1450) / ammonium chloride dissolved in 0.4 liter of water was added, and the mixture was stirred at room temperature for 2 hours. It was After solid-liquid separation, it was washed and further dried to obtain an organic onium ion composite synthetic smectite. As a result of X-ray diffraction measurement, the bottom distance is about 45Å
Met.

Production Example 3: Production of Layered Silicate Compound-Containing Polyester Resin (a) A dimethyl terephthalate 20 was placed in a pressure vessel (capacity 7 liters: made by Nippon Pressure Glass) equipped with a distilling tube and a stirrer.
Production Example 1 in advance to 00 g and 1280 g of ethylene glycol
115 g of sodium fluorine mica obtained in 1. and 7.5 g of a hindered phenol-based stabilizer were dispersed using a homogenizer, left for 24 hours, added, and heated to 200 ° C. with stirring under a nitrogen stream. After the methanol was distilled off, the temperature was raised to 285 ° C., the pressure was reduced to 133 Pa or less, the mixture was stirred for 2 hours, and the reaction was terminated to obtain a layered silicate compound-containing polyester resin (a). Obtained resin (a)
The intrinsic viscosity of polyethylene terephthalate alone was 0.65.

Production Example 4: Production of Layered Silicate Compound-Containing Polyester Resin (b) Polyethylene terephthalate (intrinsic viscosity 0.6) was placed in a pressure vessel (capacity 7 liters: made by Nippon Pressure Glass) equipped with a distilling tube and a stirrer. ) 2000 g, ethylene glycol 1
600 g of sodium fluorine mica previously obtained in Production Example 1 and a hindered phenolic stabilizer (Adeka Stab AO-60: Asahi Denka Co., Ltd.) were dispersed in 000 g using a homogenizer, and the mixture was allowed to stand for 24 hours. While stirring, the temperature was raised to 285 ° C. and the mixture was melted and mixed. 2
After reaching 85 ° C., the pressure was reduced to 133 Pa or less and the mixture was stirred for 2 hours to complete the reaction, and a layered silicate compound-containing polyester resin (b) was obtained.

Production Example 5: Production of Layered Silicate Compound-Containing Polyester Resin (c) Polyethylene terephthalate to 3000 g, ethylene glycol to 600 g, and sodium fluorine mica 60.
A layered silicate compound-containing polyester resin (c) was obtained in the same manner as in Production Example 4 except that 0 g was changed to 90 g of lithium fluorine mica.

Production Example 6: Production of Layered Silicate Compound-Containing Polyester Resin (d) Polyethylene terephthalate (Intrinsic Viscosity 0.8) 300
To 0 g, 300 g of the organic onium ion composite synthetic smectite produced in Production Example 2 and 9 g of a hindered phenolic stabilizer were dry blended, supplied to a hopper of a twin-screw extruder and melt-mixed at a cylinder temperature of 200 ° C. to form a layered silicic acid. A salt compound-containing polyester resin (d) was obtained.

Example 1 Polycarbonate (PC) resin (Taflon A-220
0: manufactured by Idemitsu Petrochemical Co., Ltd.) and 100 parts of a mixture consisting of 30% of the layered silicate compound-containing polyester resin obtained in Production Example 2, and a phosphorus stabilizer (Adeka Stab PE).
(P-36: Asahi Denka Co., Ltd.) 0.3 part was dry blended, supplied to a hopper of a twin-screw extruder and melt-kneaded at a cylinder temperature of 260 ° C. to obtain a resin composition. As a result of X-ray diffraction measurement of the resin composition, diffraction peaks were found at 2θ = 6.7 ° and 0.5 °, which corresponded to the bottom spacing of 13Å and 177Å, respectively, and the intensity ratio thereof was 0.63. It was Table 1 shows the evaluation results.

Examples 2 to 5 Resin compositions were obtained in the same manner as in Example 1 except that the compositions and ratios shown in Table 1 were changed. However, polyethylene terephthalate (PET) having an intrinsic viscosity of 0.6 was used. Table 1 shows the evaluation results.

[0051]

[Table 1]

Comparative Examples 1 to 5 Melt kneading was carried out using a twin-screw extruder with the compositions and ratios shown in Table 2 to obtain resin compositions. Table 2 shows the evaluation results.

[0053]

[Table 2] * 1: No good molded product was obtained. * 2: Added by extrusion kneading.

As is clear from the results shown in Tables 1 and 2, it can be seen that all the resin compositions of the present invention are excellent in heat resistance, chemical resistance and fluidity and have no burrs.

[005]

As described above, the polycarbonate resin composition of the present invention has a good balance of heat resistance, chemical resistance, and fluidity, and since it does not cause burrs, it greatly enhances productivity. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08K 7/00 KKF C08K 7/00 KKF KKN KKN C08L 67/02 LPE C08L 67/02 LPE

Claims (9)

[Claims] 1. A polycarbonate-based resin (A) and (B)
A polycarbonate resin composition comprising a layered silicate compound-containing polyester resin. 2. The (A) polycarbonate resin is 30 to
The polycarbonate resin composition according to claim 1, wherein the polyester resin containing the layered silicate compound (B) is 99% by weight and 70 to 1% by weight. 3. A polycarbonate resin (A) and (B)
A polycarbonate resin composition comprising a layered silicate compound-containing polyester resin and (C) a layered silicate compound-free polyester resin. 4. The (A) polycarbonate resin is 30 to
99% by weight, (B) the layered silicate compound-containing polyester resin is 70 to 1% by weight, and (C) the layered silicate compound-free polyester resin is (A) +
The polycarbonate resin composition according to claim 3, which is 0 to 80 parts by weight with respect to 100 parts by weight of (B). 5. The layered silicate compound in the component (B) is an organic onium ion composite layered silicate compound.
4. The polycarbonate resin composition according to any one of 4 above. 6. The bottom spacing of part or all of the layered silicate compound in the composition is 30 Å or more.
The polycarbonate resin composition according to any one of items 1 to 5. 7. The polycarbonate resin composition according to any one of 1 to 6, wherein a diffraction intensity of a diffraction line derived from a bottom surface distance in X-ray diffraction measurement satisfies the following formula. 0.2 ≦ {I (≧ 30Å) / [I (≧ 30Å) + I (<
30 Å)]} where I (≧ 30 Å) is the diffraction intensity of the diffraction line corresponding to the bottom spacing of 30 Å or more, and I (<30 Å) is the diffraction intensity of the diffraction line corresponding to the bottom spacing of less than 30 Å. 8. The layered silicate compound is sodium fluorine mica and / or lithium fluorine mica.
7. The polycarbonate resin composition according to any one of 7 above. 9. The polycarbonate resin composition according to claim 1, wherein the content of the layered silicate compound in the component (B) is 0.1 to 50% by weight.