JP2002327108A - Thermoplastic resin composition suitable for blow molding having weld part and the blow molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which has excellent mechanical characteristics such as rigidity, impact strength, weld strength, etc., and excellent blow moldability, comprises an aromatic polycarbonate resin, an aromatic polyester resin and an inorganic filler and is suitable for a blow molding. SOLUTION: This thermoplastic resin composition comprises 100 parts.wt. of the total of (A) 10-95 parts.wt. of the aromatic polycarbonate resin (component A) and (B) 5-90 parts.wt. of the aromatic polyester resin (component B), (C) 1-100 parts.wt. of the inorganic filler (component C) and (E) 0.01-10 parts.wt. of mixed powder (component E) composed of 100 wt.% of the total of 30-70 wt.% of a polymer (component e1) which has 50,000-500,000 weight-average molecular weight calculated by GPC(gel permeation chromatography) measurement and is obtained by polymerizing at least one kind selected from an aromatic vinyl monomer and a vinyl cyanide monomer and 70-30 wt.% of a fluorinated olefinic polymer (component e2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition comprising an aromatic polycarbonate resin and an aromatic polyester resin. More specifically, aromatic polycarbonate resin, aromatic polyester resin, inorganic filler,
And a resin composition comprising a powder mixture of a specific polymer consisting of a monomer selected from an aromatic vinyl monomer and a vinyl cyanide monomer and a fluorinated olefin polymer, and having a weld strength and the like. The present invention relates to a thermoplastic resin composition for hollow molding, which exhibits excellent hollow moldability without a decrease in mechanical strength, and a hollow molded article thereof.

[0002]

2. Description of the Related Art A resin composition comprising an aromatic polycarbonate resin and an aromatic polyester resin has been widely used in various industrial fields because of its excellent mechanical properties, dimensional stability, and chemical resistance. .

[0003] In particular, in order to improve rigidity and coefficient of linear expansion, inorganic fillers such as glass fiber, talc, mica, wollastonite and the like are blended into interior and exterior parts and OA housing materials in the automobile field. In general, a method of blending a rubbery polymer to improve the impact strength has been widely used.

[0004] In recent years, hollow injection molding such as gas injection molding has attracted attention in the automotive field and the OA field for the purpose of weight reduction and cost reduction by shortening the molding cycle. In particular, attention has been paid to the field of automobiles where the demand for weight reduction is strong.

However, a resin composition comprising an aromatic polycarbonate resin and an aromatic polyester resin has a problem in that the range of gas injection conditions is narrow due to a problem relating to rheological properties during hollow injection molding such as gas injection molding. In other words, if the gas hardly enters, or if the gas pressure is set high so as to allow the gas to enter, on the contrary, there are many defects that the gas enters too much and the molded product bursts and leaks outside, and the hollow injection molding stability is reduced. There was a problem of chipping, and as a result, it was difficult to increase the hollow ratio.

In order to solve such a problem, the present applicant has already disclosed in Japanese Patent Application No. 11-289396 that the aromatic polycarbonate resin, the aromatic polyester resin, and the weight average molecular weight calculated from GPC measurement are 2,000,000 to 10,000,000. We have proposed a resin composition consisting of a copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer and another vinyl monomer copolymerizable therewith, if necessary, to solve such problems. You have come to.

However, in the case of a hollow molded article, the following properties may be required in some cases.

(1) High rigidity is required. This is to cover the reduction in wall thickness. For such a demand, a technique such as blending of an inorganic filler can be considered.

(2) Good weld strength is required.
This is because the weld strength of a hollow molded product, particularly a hollow injection molded product, tends to decrease. That is, in a hollow injection-molded product, the collision of the resin in the weld portion tends to be at a low pressure and low temperature as compared with a normal case. On the other hand, when the above-mentioned inorganic filler is blended, such a point tends to be more remarkable. This is due to the fact that the reinforcing effect of the inorganic filler is not substantially obtained in the weld portion.

That is, a resin composition comprising an aromatic polycarbonate resin, an aromatic polyester resin and an inorganic filler capable of achieving good hollow moldability without reducing mechanical strength such as weld strength and impact strength is desired. ing.

Japanese Patent Application Laid-Open No. 2000-256546 discloses a polycarbonate resin, an aromatic polyester resin,
A resin composition comprising an inorganic filler or a rubber-like filler, and a fluorinated olefin polymer having a specific molecular weight is disclosed,
It is described that the composition can provide a good resin composition without generation of jetting or flow mark.

JP-A-2000-290486 discloses a resin composition comprising a polycarbonate resin, a thermoplastic polyester resin, and a powder comprising polytetrafluoroethylene particles of 10 μm or less and an organic polymer. It is described that the composition improves the dispersibility of polytetrafluoroethylene, and gives poor melt appearance and good melt tension with a small amount.

However, in any case, a resin composition comprising an aromatic polycarbonate resin, an aromatic polyester resin, and an inorganic filler capable of achieving good hollow moldability without reducing mechanical strength such as weld strength and impact strength is used. It was not fully disclosed.

[0014]

An object of the present invention is to provide an aromatic polycarbonate resin and an aromatic polyester resin which are excellent in mechanical properties such as rigidity, impact strength and weld strength, and which are also excellent in hollow moldability. An object of the present invention is to provide a thermoplastic resin composition suitable for hollow molding comprising an inorganic filler.

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the aromatic polycarbonate resin, the aromatic polyester resin, and the inorganic filler were further added with an aromatic vinyl monomer and vinyl cyanide. When a specific polymer consisting of monomers selected from monomers and a mixed powder consisting of a fluorinated olefin polymer are blended, there is no decrease in mechanical strength such as weld strength and excellent hollow moldability. And reached the present invention.

[0016]

The present invention provides (A) an aromatic polycarbonate resin (A component) in an amount of 10 to 95 parts by weight,
(C) 1 to 100 parts by weight of an inorganic filler (component (C)) and (E) GPC (gel permeation chromatography) with respect to a total of 100 parts by weight of (B) an aromatic polyester resin (component (B)) of 5 to 90 parts by weight. Graphy) is obtained by polymerizing at least one monomer selected from an aromatic vinyl monomer and a vinyl cyanide monomer having a weight average molecular weight calculated from the measurement of 50,000 to 500,000. 0.01 to 10 parts by weight of a mixed powder (component (E)) consisting of 30 to 70% by weight of the polymer (component (e1)) and 70 to 30% by weight of the fluorinated olefin polymer (component (e2)) The present invention relates to a thermoplastic resin composition comprising:

In the present invention, the component A is preferably 50 to 9
5 parts by weight and the B component is 5 to 50 parts by weight according to the thermoplastic resin composition.

In the present invention, the component E1 preferably has a weight average molecular weight of 5 as calculated from GPC (gel permeation chromatography) measurement.
60 to 80% by weight of an aromatic vinyl monomer having a molecular weight of 000 to 500,000 and 20 to 4% of a vinyl cyanide monomer.
The present invention relates to the thermoplastic resin composition which is a copolymer comprising 0% by weight.

Further, in the present invention, preferably, the C component is at least one selected from talc and wollastonite.
The present invention relates to the above thermoplastic resin composition which is a kind of inorganic filler.

Further, the present invention preferably further comprises (D) a rubbery polymer (D) based on 100 parts by weight of the total of the components A and B.
Component) in an amount of 0.5 to 50 parts by weight.

Further, the present invention provides a resin composition having a weld strength retention (X) when molded by ordinary injection molding.
1) is 60% or more, and the hollow ratio is 5 to 5 by the hollow injection molding method.
The present invention relates to the thermoplastic resin composition having a weld strength retention (X2) of 50% or more when molded to 30%.

Further, the present invention relates to a hollow molded article having a weld portion formed from the thermoplastic resin composition by a hollow injection molding method.

The details of the present invention will be described below.

The aromatic polycarbonate resin as the component A of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of dihydric phenols include:
2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4
-Hydroxyphenyl) -3-methylbutane, 9,9-
Bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene. In particular, a homopolymer of bisphenol A can be mentioned. Such an aromatic polycarbonate resin is preferable in that it has excellent impact resistance.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate and the like are used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

In producing the polycarbonate resin by reacting the dihydric phenol with the carbonate precursor by an interfacial polycondensation method or a melt transesterification method, if necessary, a catalyst, a terminal stopper and a dihydric phenol are oxidized. For example, an antioxidant or the like may be used to prevent the oxidation.
Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.

When a polyfunctional compound producing a branched polycarbonate resin is contained, such a proportion is preferably 0.001 to 1 mol%, preferably 0.1 to 1 mol%, based on the total amount of the aromatic polycarbonate.
005 to 0.5 mol%, particularly preferably 0.01 to 0.
3 mol%. In particular, in the case of the melt transesterification method,
Although a branched structure may occur as a side reaction, the amount of such a branched structure in the total amount of the aromatic polycarbonate,
0.001 to 1 mol%, preferably 0.005 to 0.5
Mole%, particularly preferably 0.01 to 0.3 mol% is preferred. The ratio is ¹ H-NM
It can be calculated by R measurement.

Further, a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid may be used. Examples of the aliphatic difunctional carboxylic acid include an aliphatic difunctional carboxylic acid having 8 to 20, preferably 10 to 12 carbon atoms. Such an aliphatic bifunctional carboxylic acid may be linear, branched or cyclic. Aliphatic bifunctional carboxylic acids are α, ω
-Dicarboxylic acids are preferred. Preferred examples of the aliphatic difunctional carboxylic acid include straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decane diacid), dodecane diacid, tetradecandioic acid, octadecandioic acid, and eicosane diacid.

Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane unit can be used.

Aromatic polycarbonate resins include the above-mentioned various polycarbonate resins having different dihydric phenols, polycarbonate resins containing branching components, various polyester carbonates, and various types of aromatic polycarbonate resins such as polycarbonate-polyorganosiloxane copolymers. It may be a mixture of more than one species. Further, a mixture of two or more kinds of various kinds such as a polycarbonate resin having a different production method and a polycarbonate resin having a different terminal stopper may be used.

In the polymerization reaction of the aromatic polycarbonate resin, the reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amine compounds such as pyridine. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Specific examples of monofunctional phenols include, for example, phenol, p-tert.
-Butylphenol, p-cumylphenol and isooctylphenol. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was adjusted to 1.33 × 10 ³ to 1
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Catalysts such as alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide, and nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine can be used. Further, alkoxides of alkali (earth) metals, alkali (earth)
Catalysts usually used for esterification reactions and transesterification reactions of metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds and the like can be used. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts to be used is preferably 1 × 10 ⁻⁸ to 1 × 1 with ^respect to 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 0 ^-3 equivalents, more preferably 1 × 10 ^{-7 to} 5 × 10 ^-4 equivalents.

In the reaction by the melt transesterification method, in order to reduce the number of phenolic terminal groups, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenyl are used later or after completion of the polycondensation reaction. Compounds such as phenyl carbonate can be added.

In the melt transesterification method, it is preferable to use a deactivator for neutralizing the activity of the catalyst. The amount of such a deactivator is 0.5 to 1 mol of the remaining catalyst.
It is preferable to use 50 moles. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm, based on the polycarbonate resin after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, the strength and the like will be reduced, and if it is more than 50,000, the moldability will be reduced. 10,000
~ 50,000, preferably 15,000 to 4
More preferably, it is more preferably 2,000.
It is between 000 and 35,000. In this case, it is naturally possible to mix with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range.

In particular, a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight of more than 50,000 shows good properties in hollow moldability. Therefore, the use of such an aromatic polycarbonate resin mixture can be mentioned as one of the preferred embodiments of the present invention.

More preferably, the viscosity average molecular weight is 80,0
It is a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight of 100,000 or more, more preferably a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight of 100,000 or more. That is, those which can observe the molecular weight distribution of two or more peaks by a measuring method such as GPC (gel permeation chromatography) can be preferably used.

The viscosity-average molecular weight referred to in the present invention is determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. Viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling of methylene chloride, t is the number of seconds of falling of the sample solution] The obtained specific viscosity is inserted by the following equation to obtain the viscosity average. Molecular weight M
Ask for. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The aromatic polyester resin as the component B in the present invention refers to a polymer or copolymer obtained by a condensation reaction comprising an aromatic dicarboxylic acid or its reactive inducer and a diol or its ester derivative as main components. It is united.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferably used.

The aromatic dicarboxylic acids may be used as a mixture of two or more kinds. If the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol which is a component of the aromatic polyester of the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl -1,3-propanediol, aliphatic diols such as diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and fragrances such as 2,2-bis (β-hydroxyethoxyphenyl) propane Ring-containing diols and the like, and mixtures thereof, and the like. If the amount is further small, one or more long-chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be copolymerized.

The aromatic polyester of the present invention can be branched by introducing a small amount of a branching agent.
The type of the branching agent is not limited, and examples thereof include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene -1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, and the like,
Copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like. Among them, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and mixtures thereof, which are well balanced in mechanical properties and the like, can be preferably used.

The structure of the terminal group of the obtained aromatic polyester resin is not particularly limited, and the case where the ratio of the hydroxyl group and the carboxyl group in the terminal group is substantially the same as that of the aromatic polyester resin is large. You may. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

The terminal group structure of the aromatic polyester resin used in the present invention is not particularly limited. In the case where the ratio of the hydroxyl group and the carboxyl group in the terminal group is almost the same, one of them is large. It may be. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

The method for producing the aromatic polyester resin used in the present invention is as follows, according to a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., while heating while heating the dicarboxylic acid component and the diol component. And the water or lower alcohol produced as a by-product is discharged out of the system. For example, examples of the germanium-based polymerization catalyst include oxides, hydroxides, halides, alcoholates, and phenolates of germanium, and more specifically, germanium dioxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, And antimony trioxide.

In the present invention, compounds such as manganese, zinc, calcium, and magnesium used in a transesterification reaction which is a prior stage of a conventionally known polycondensation can be used together. Alternatively, it is possible to deactivate such a catalyst with a phosphorous acid compound or the like to perform polycondensation.

The method for producing the aromatic polyester can be any of a batch system and a continuous polymerization system.

The aromatic polyester resin has an intrinsic viscosity of 0.4 to 1.5 as measured at 35 ° C. using o-chlorophenol as a solvent.
1.2 is preferred, and 0.6-1.15 is more preferred.

As the inorganic filler of the component C in the present invention, glass fiber (chopped strand), carbon fiber,
Fibrous filler such as metal-coated carbon fiber, metal fiber, wollastonite, zonotolite, potassium titanate whisker, aluminum borate whisker, basic magnesium sulfate whisker, plate-like filling such as talc, mica, glass flake, graphite flake Agent, short glass fiber (milled fiber), short carbon fiber, glass beads, glass balloon, silica particles, titania particles, alumina particles,
Examples include particulate fillers such as kaolin, clay, calcium carbonate, and titanium oxide.

In particular, the C component is preferably at least one inorganic filler selected from talc and wollastonite from the viewpoint of improvement in rigidity and weld strength retention.

The inorganic filler may have been subjected to a surface treatment with various surface treatment agents such as a silane coupling agent and polymethyl hydrogen siloxane.

The talc of the present invention is a scale-like particle having a layered structure, is a hydrated magnesium silicate in chemical composition, and generally has a chemical formula of 4SiO ₂ · 3MgO · 2H _2.
O, usually 56-65% by weight of SiO ₂ , MgO
And is configured to 28 to 35 wt%, from H ₂ O about 5 wt%. 0.03 of Fe ₂ O ₃ as another minor component
１．２1.2% by weight, Al ₂ O ₃ is 0.05-1.5% by weight,
CaO is 0.05 to 1.2 wt%, K ₂ O is 0.2 wt% or less, Na ₂ O are contained, such as 0.2 wt% or less, a specific gravity of about 2.7.

There is no particular limitation on the production method for pulverizing such talc from raw ore, and there are no particular restrictions on the axial flow mill method, annular mill method, roll mill method, ball mill method, jet mill method, and container rotary compression shearing mill method. Etc. can be used. Further, the talc after the pulverization is subjected to a classification treatment by various classifiers, and one having a uniform particle size distribution is preferable. There are no particular restrictions on classifiers. Impactor type inertial classifiers (variable impactors, etc.), Coanda effect type inertial classifiers (elbow jet, etc.), centrifugal classifiers (multi-stage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator,
And a super separator).

Further, such talc is preferably in an agglomerated state in terms of handleability and the like. Examples of such a production method include a deaeration compression method and a compression method using a binder resin. The method is preferred in that the method is simple and unnecessary binder resin components are not mixed into the composition of the present invention.

The wollastonite of the present invention can be obtained by pulverizing and classifying wollastonite from a natural white mineral having acicular crystals whose main component is calcium silicate. Due to such a crystal structure, a crushed mineral also has a fibrous form. In the present invention, naturally synthesized wollastonite can also be used. These wollastonite are substantially represented by the chemical formula CaO.SiO ₂ ,
It contains about 50% by weight of iO ₂ , about 47% by weight of CaO, and other impurities such as Fe ₂ O ₃ , Al ₂ O ₃ , CaCO ₃ , and the specific gravity thereof is known to be about 2.9. .

Examples of the wollastonite pulverizer include a high-speed rotation mill, a ball mill, a medium stirring mill, and a jet mill. Among them, a jet mill is preferable. Further, examples of the jet mill system include an air current suction system, a nozzle suction system, a collision body collision system, an opposed jet collision system, and a combined type. Among them, a pulverizer of an opposed jet collision system is preferable.

It is preferable that the pulverized wollastonite is classified by using various classifiers in the same manner as in the case of the talc to remove a component having a long fiber length and obtain a desired wollastonite.

Further, as a preferred embodiment of the wollastonite of the present invention, the wollastonite having a loss on ignition of 1.7% by weight or less shown below can be mentioned. Such a loss on ignition is more preferably 1.5% by weight or less, and further preferably 1.2% by weight or less. The lower limit is about 0.4%. Wollastonite that satisfies the condition of loss on ignition has few breaks and is excellent in reinforcing performance.

In order to reduce the ignition loss of wollastonite, wollastonite which has been treated at 110 ° C. for 6 hours in order to remove water and then allowed to cool to room temperature in a desiccator (containing a desiccant) is prepared. Such wollastonite is converted to TGA (The
rmgravimetric Analysis: 1,300 at 10 ° C./min with a measuring machine
The temperature is continuously raised to 0 ° C., and the weight loss value at the time when the temperature reaches 1,300 ° C. is calculated to be the ignition loss.

As the rubbery polymer of the component D in the present invention, a rubber component having a glass transition temperature of 10 ° C. or less, an aromatic vinyl, a vinyl cyanide, an acrylic acid ester, a methacrylic acid ester, and copolymerizable with them. And a graft copolymer obtained by copolymerizing one or more monomers selected from various vinyl monomers.

Further, a block copolymer of such a rubber component and the above monomer may also be used. Specific examples of the block copolymer include styrene / ethylene propylene / styrene elastomer (hydrogenated styrene / isoprene / styrene elastomer) and hydrogenated styrene / butadiene / styrene.
Examples include thermoplastic elastomers such as styrene elastomers.

It is also possible to use various elastic polymers known as other thermoplastic elastomers, for example, polyurethane elastomers, polyester elastomers, polyetheramide elastomers and the like.

The rubber component having a glass transition temperature of 10 ° C. or lower includes butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, acryl-silicon composite rubber, isobutylene-silicon composite rubber, isoprene rubber, styrene-butadiene rubber. , Chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber,
Examples thereof include fluororubbers and those obtained by adding hydrogen to the unsaturated bond portions thereof.

Among them, an elastic polymer containing a rubber component having a glass transition temperature of -10 ° C. or lower, more preferably -30 ° C. or lower is preferable, and particularly, butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, and acrylic-silicon composite rubber An elastic polymer using is preferred. The composite rubber refers to a rubber obtained by copolymerizing two types of rubber components or a rubber obtained by polymerizing so as to have an IPN structure entangled with each other so as not to be separated. The acrylic rubber component may be composed of two or more monomer components.

Examples of the aromatic vinyl monomer copolymerized with the rubber component include styrene, α-methylstyrene, 4-methylstyrene and 3,5-diethylstyrene, with styrene being preferred. As the vinyl cyanide monomer, acrylonitrile, methacrylonitrile,
Ethacrylonitrile can be mentioned, among which acrylonitrile is preferable. As the acrylate monomer and methacrylate monomer copolymerized with the rubber component,
Methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, and the like,
Among them, ethyl acrylate and methyl methacrylate are preferred.

The conjugated diene monomer other than butadiene which can be used as the rubber component of the present invention includes isoprene,
Examples thereof include 1,3-heptadiene and 2,3-dimethylbutadiene. In addition, as the acrylate monomer that can be used as the rubber component, n-butyl acrylate,
Examples include ethyl acrylate and 2-ethylhexyl acrylate, and examples of the methacrylate monomer include hexyl methacrylate and 2-ethylhexyl methacrylate. Among them, n-butyl acrylate and 2-ethylhexyl acrylate are preferable.

The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or lower may be prepared by any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. May be a single-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer of only a graft component produced as a by-product at the time of production. Examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-step swelling polymerization method. In the suspension polymerization method, a method in which an aqueous phase and a monomer phase are separately held, and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the number of revolutions of the disperser. In the method, a method may be employed in which the monomer phase is supplied to an aqueous liquid having dispersibility by passing it through a small-diameter orifice having a diameter of several to several tens of μm or a porous filter to control the particle size.

When at least one of the above monomers is copolymerized with the rubber component, the rubber component is at least 10% by weight, preferably at least 25% by weight, based on 100% by weight of the total amount of the rubbery polymer. More preferably 50 to 8
0% by weight.

Such rubbery polymers are commercially available and can be easily obtained. For example, as a rubber component having a glass transition temperature of 10 ° C. or less, those mainly composed of butadiene rubber, acrylic rubber or butadiene-acryl composite rubber include Kaneace B series of Kanebuchi Chemical Industry Co., Ltd. and Mitsubishi Rayon Co., Ltd. METABLEN C series,
W series, EX series of Kureha Chemical Industry Co., Ltd., H
The IA series, the BTA series, the KCA series, and the UCL Modifier resin series of Ube Sycon Co., Ltd. are listed. Mitsubishi Rayon (Acrylic-silicon composite rubber as a rubber component having a glass transition temperature of 10 ° C. or less is mainly used) METABLEN S-2001
Alternatively, one sold under the trade name SRK-200 may be mentioned.

The component E in the present invention is composed of an aromatic vinyl monomer and a vinyl cyanide monomer having a weight average molecular weight of 50,000 to 500,000 calculated by GPC (gel permeation chromatography) measurement. From a total of 30 to 70% by weight of a polymer (component (e1)) obtained by polymerizing at least one selected monomer and 70 to 30% by weight of a fluorinated olefin polymer (component (e2)), Mixed powder.

As the aromatic vinyl monomer and vinyl cyanide monomer, monomers similar to those copolymerized with the rubber component in the rubbery polymer of the above-mentioned D component can be used.

The weight average molecular weight of the component e1 used in the component E of the present invention is calculated by GPC measurement using a calibration curve with a standard polystyrene resin. The weight average molecular weight is preferably 50,000 to 500,000, Is 7
0000-450,000, more preferably 80,0
00 to 400,000. Weight average molecular weight of 50,
If it is less than 000, the weld strength and impact properties are not sufficiently improved, and if it exceeds 500,000, the dispersibility of the fluorinated olefin polymer as the e2 component is undesirably reduced.

Further, the component E according to the present invention is characterized in that the ratio of the component e1 to the component e2 is 30 to 70% by weight of the component e1 and the component e2
It is composed of a total of 100% by weight of 70 to 30% by weight of the components. Preferably, it is composed of 40 to 60% by weight of the e1 component and 60 to 40% by weight of the e2 component. If the content of the component e2 is less than 30% by weight and the content of the component e1 is more than 70% by weight, the effect of improving the hollow moldability is low. If the E component is filled at a high level, the weld strength and the impact resistance may decrease. On the other hand, when the e1 component is less than 30% by weight and the e2 component exceeds 70% by weight, the dispersibility of the fluorinated olefin polymer as the e2 component is reduced, and the effects of improving hollow moldability, weld strength and the like are reduced. Therefore, it is not preferable.

As the e1 component, a copolymer of styrene and acrylonitrile (hereinafter referred to as an AS polymer) can be preferably used. Among them, styrene 60-80% by weight,
Preferably 65-78% by weight, and acrylonitrile 20
A consisting of ４０40% by weight, preferably 22-35% by weight
S polymers can be preferably used.

On the other hand, in the present invention, examples of the fluorinated olefin polymer of component e2 in component E include polytetrafluoroethylene, tetrafluoroethylene-fluoroalkylvinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer. Copolymers, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-fluoroalkylvinyl ether copolymers, among which polytetrafluoroethylene can be preferably used.

The molecular weight of the e2 component is preferably in the range of 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of number average molecular weight. The number average molecular weight is determined from the standard specific gravity.

The mixed powder of the component E of the present invention is produced, for example, by the following method using an aqueous dispersion of a fluorinated olefin polymer having an average particle diameter of 0.05 to 1.0 μm. be able to.

(1) A method in which an aqueous dispersion of the e2 component and an aqueous dispersion or solution of the e1 component are mixed to obtain a coaggregated mixture.
Such a method is described in JP-A-60-258263. (2) A method of mixing an aqueous dispersion of the e2 component with solid e1 particles and removing the dispersion medium by heat of mixing or other methods. This method is described in Japanese Patent Application Laid-Open No. 4-27.
No. 2957, for example. (3) A method in which the medium is simultaneously removed from a mixture of the aqueous dispersion of the e2 component and the solution of the e1 component. Such a method is described in JP-A-08-188653 and the like.
(4) A method of mixing an aqueous dispersion of the e2 component and a monomer constituting the e1 component, and polymerizing the monomer. Such a method is described in JP-A-9-95583 and the like. (5) A method in which the aqueous dispersion of the e2 component and the aqueous dispersion of the e1 component are mixed, and then a monomer constituting an additional e2 component is mixed in the mixed dispersion to polymerize. Such a method is disclosed in JP-A-11-29679 and JP-A-11-29679.
000-290486. Among these, the methods (4) and (5) are preferable, and the E component obtained by the method (4) is particularly preferable.

Examples of the aqueous dispersion of the above-mentioned e2 component include Fluon AD manufactured by Asahi Glass Fluoropolymer.
-1, AD-936, polyflon D manufactured by Daikin Industries, Ltd.
-1, D-2, Teflon 30J manufactured by DuPont-Mitsui Fluorochemicals, and the like.

The size of the mixed powder of the component E obtained by the above method or the like is preferably 80 μm or less, more preferably 70 μm or less in average particle diameter. On the other hand, the lower limit is preferably 5 μm or more. The average particle size is a weight average particle size obtained by diluting an aqueous dispersion of the component E with water and measuring the resulting solution by a dynamic light scattering method (temperature: 25 ° C., scattering angle: 90 °).

As described above, according to the present invention, a specific E
By blending the components, the A component, the B component of the present invention,
And C component, more preferably in a thermoplastic resin composition containing the D component, without reducing the mechanical strength,
The hollow formability can be improved. Here, the composition ratio of the components A to E will be described.

The proportions of the components A and B used in the present invention are 10 to 95 parts by weight of the component A and 5 to 90 parts by weight of the component B based on 100 parts by weight of the total of the components A and B. In addition, in such a total of 100 parts by weight, the component A is 5
The amount is preferably 0 to 95 parts by weight, more preferably 60 to 90 parts by weight, and still more preferably 60 to 80 parts by weight. On the other hand, the component B is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, and more preferably 20 to 4 parts by weight in the total 100 parts by weight.
0 parts by weight is more preferred.

For 100 parts by weight of the total of the components A and B, 50 to 95 parts by weight of the component A and 5 to 50 parts by weight of the component B
In the case of parts by weight, good and well-balanced properties can be obtained in any of impact strength, dimensional accuracy, chemical resistance, and moldability.

The component C of the present invention is used in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, and still more preferably 100 parts by weight of the total of the components A and B. 5 to 30 parts by weight. If the component C exceeds 100 parts by weight, the moldability in injection molding is poor, and control of gas injection tends to be difficult. In addition, the appearance is deteriorated and the strength is deteriorated, which is not preferable.

The component D used in the present invention is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, further preferably 2 to 30 parts by weight, based on 100 parts by weight of the total of the components A and B. Preferably, 2 to 15 parts by weight are particularly preferred. If the D component exceeds 50 parts by weight, the heat resistance and the rigidity are undesirably greatly reduced.

The component E used in the present invention is 0.01 to 10 parts by weight based on 100 parts by weight of the total of the component A and the component B.
Preferably 0.1 to 7 parts by weight, more preferably 0.5 to
5 parts by weight. If the component E is less than 0.01 part by weight, the effect of improving the hollow moldability is insufficient, and if it exceeds 10 parts by weight, the moldability and weld strength are undesirably reduced.

The thermoplastic resin composition of the present invention can achieve the following characteristics by adopting the above constitution. That is, according to the present invention, when the resin composition is molded by ordinary injection molding without hollow injection molding, the weld strength retention (X1) is 60% or more, and the hollow ratio is 5 to 5 by hollow injection molding. A thermoplastic resin composition having a weld strength retention (X2) of 50% or more when molded to 30% is provided. More preferably, X1
Is provided, and X2 is 60% or more. On the other hand,
X1 is 100%, and X2 is 95%.

Here, the weld strength holding ratios X1 and X2 are calculated by the following equations (1) and (2). X1 = 100 × Y1 / Y3 (1) X2 = 100 × Y2 / Y3 (2)

Here, Y1 is the tensile strength of the molded product obtained by injection molding without hollow molding, Y2 is the tensile strength of the molded product obtained by injection molding without hollow molding, and Y3 is no weld. It is the tensile strength of the molded article in the case. The unit is MPa.

More specifically, such characteristics can be confirmed using a TYPE I test piece conforming to ASTM D-638. That is, ASTM D-63
A test piece having a TYPE I test piece shape conforming to No. 8 and provided with gates at both ends in the length direction and having a weld portion at the center is prepared. When a test piece having such a weld portion is prepared by ordinary injection molding (without hollow molding), the tensile strength of the test piece is defined as Y1. When a test piece having such a weld portion is prepared by hollow injection molding, the tensile strength of the test piece is defined as Y2. In addition, the tensile strength of a test piece of TYPE I based on ASTM D-638 and having no gate obtained by providing a gate at one end in the length direction of the test piece is defined as Y3.

Further, as the molding conditions of the test piece, for example, in the case of ordinary injection molding (without hollow molding), the molding temperature is 250 to 290 ° C., the mold temperature is 60 to 90 ° C., the injection pressure is 60 to 120 MPa, The pressure range is 60 to 120 MPa, and the dwell time is 5 to 15 seconds. In the case of hollow injection molding, a molding temperature of 250 to 290 ° C. and a mold temperature of 60 to
90 ° C., injection pressure of 60 to 120 MPa, delay time (time from the end of injection to start of gas injection) of 0 to 5 seconds, gas pressure of 5 to 20 MPa, and gas pressure holding time of 5 to 15 seconds. A test piece having a hollow ratio of 5 to 30%, preferably 10 to 25% is used. In addition, in the case of ordinary injection molding and hollow injection molding, it is necessary to predry the pellets of the resin composition of the present invention at 110 ° C. for 6 hours before molding. In molding under such conditions, the thermoplastic resin composition of the present invention has good properties that can satisfy the above formulas (1) and (2).

In the hollow injection molding of the present invention, various media such as gas or liquid are injected into a molten resin. Preferably, gas injection molding (gas is used as a medium), which is generally widely known, is used. This is called a molding method. In general, such a method is such that after a molten resin is filled in a mold, an inert gas is pressed into an inside of a molded article until the resin is cooled and solidified from an injection port or another blowing port, and then cooled and solidified. How to The inert gas to be injected is not particularly limited as long as it is a gas having no reactivity with the resin at the time of molding and at the time of using the molded article, and specific examples include nitrogen and air.

Further, the thermoplastic resin composition obtained in the present invention is suitable for hollow molding.
It is suitable for blow molding, injection blow molding, gas injection molding and the like. Above all, it is very useful in hollow injection molding such as gas injection molding. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerless can be manufactured. Further, in the case of the hollow injection molding in the present invention, ultra high speed injection molding, injection compression molding, injection press molding, insert molding, local high temperature mold molding (including heat insulating mold molding), sandwich molding, two-color molding, etc. Can be combined with other molding methods.

Among them, a method of locally increasing the mold cavity surface temperature to improve the transferability, such as local high-temperature mold molding, is useful. This is because gas injection molding generally improves the appearance of sink marks and the like as compared with ordinary injection molding, but tends to reduce mold transferability.

The thermoplastic resin composition of the present invention satisfies not only good hollow moldability but also good mechanical properties such as good impact strength and weld strength in the hollow injection molding method. Therefore, according to the present invention, there is provided a hollow molded article having a weld portion formed by using a hollow injection molding method excellent in these properties.

Specific examples of such molded articles include vehicle interior parts and vehicle exterior parts.
Such a field is a field in which weight reduction is particularly required. Interior parts for vehicles include center panel, instrument panel, dashboard, inner door handle,
Examples include a display housing for a rear board, a car navigation system, a car television, and the like.

As exterior parts for vehicles, outer door handles, fender panels, door panels, spoilers,
Garnish, pillar cover, front grille, rear body panel, motorbike cowl, truck bed cover, etc.

Among these, the inner door handle and the outer door handle, which are particularly thick members and require high strength, are preferable.

In addition, cameras, digital cameras, video movies, telescopes, binoculars, mobile phones, personal digital assistants,
Portable notebook computers, portable tape recorders,
Portable optical disc players, portable navigation devices, watches, notebook computers, personal computers, CRT displays, printers, copiers, drive devices for recording media (CD, DVD, etc.), scanners, various parts used in facsimile machines, etc. be able to.

In the thermoplastic resin composition of the present invention, various heat stabilizers are preferably used in order to suppress thermal deterioration during molding. Such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and specifically, triphenyl phosphite,
Tris (nonylphenyl) phosphite, tris (2,
4-di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite Phyte, monodecyldiphenyl phosphite,
Monooctyldiphenyl phosphite, bis (2,6-
Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6- Di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl Phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphonic acid Tetrakis (2,4-di-t-
Butylphenyl), dimethyl benzenephosphonate, diethylbenzenebenzene, dipropylbenzenephosphonate and the like. These heat stabilizers may be used alone or in combination of two or more. The amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 1 part by weight based on 100 parts by weight of the total of the component A and the component B.
0.5 parts by weight is more preferable, and 0.001 to 0.1 parts by weight is further preferable.

The thermoplastic resin composition of the present invention may contain an antioxidant generally known for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, tetrakis (4,4′-biphenylenediphosphosphinate) (2,4-di-t-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {-2,4,8,10
-Tetraoxaspiro (5,5) undecane and the like. The compounding amount of these antioxidants is preferably 0.0001 to 0.05 parts by weight based on 100 parts by weight of the total of the component A and the component B.

Further, the thermoplastic resin composition of the present invention may contain, or preferably contains, a breaking inhibitor for suppressing breaking or cracking of the inorganic filler.

As such a breaking inhibitor, a component which is slippery with respect to the aromatic polycarbonate resin as the component A and the aromatic polyester resin as the component B is used for coating the circumference of the wollastonite particles with the breaking inhibitor. Examples include those containing a functional group having reactivity or affinity with wollastonite particles. By having such a structure, during melting and mixing of the components of the resin composition of the present invention, such a fold inhibitor does not bind or adhere to the resin component, while binding or adheres to the wollastonite particles. As a result, the surface of the wollastonite particles is coated with the lubricant.

Examples of the component having a slipperiness in the aromatic polycarbonate resin include higher fatty acid esters, higher fatty acid amides, polyolefin components, polyorganosiloxane components, fluorine-substituted polyolefin components, alkyl ether components, and fluorine-substituted polyalkyl ether components. Among them, a polyolefin wax component, a silicone oil and a fluorine oil component are preferable.

On the other hand, functional groups having reactivity or affinity with wollastonite particles include carboxyl groups,
Cyclic imino ether group such as ester group, amide group, amino group, epoxy group, thioester group, 2-oxazoline group, succinic anhydride-2-yl group, succinic anhydride-2,
Examples thereof include carboxylic anhydride groups such as a 3-diyl group. Particularly preferred are those having no decomposing action on the aromatic polycarbonate resin, such as a carboxyl group, an epoxy group, and a carboxylic anhydride group, and particularly preferably a copolymer of maleic anhydride.

The method of bonding the lubricant with various functional groups includes (1) a method of reacting the lubricant with the compound having the above functional group and a functional group reactive with the lubricant, and (2) a method of synthesizing the lubricant during the synthesis of the lubricant. (3) a method of mixing and reacting a lubricant, a compound having a functional group, and a radical generator under heating, and (4)
Modification by thermal oxidation can be mentioned, and any method can be used.

Preferred examples of such a breaking inhibitor include:
Olefin waxes containing carboxyl groups and / or carboxylic anhydride groups can be mentioned. Preferably, maleic acid and / or maleic anhydride are copolymerized, and the copolymerized copolymer contains a carboxyl group and / or a carboxylic anhydride group at a high concentration and stably.

The carboxyl group or carboxylic anhydride group may be bonded to any part of the olefin wax, and the concentration thereof is not particularly limited, but is preferably in the range of 0.1 to 6 meq / g per gram of the olefin wax. It is preferable because the breaking of wollastonite particles can be efficiently improved, and the range is more preferably 0.5 to 4 meq / g. Here, 1 eq (1 equivalent) means that, in the case of a carboxyl group, 1 mol of a carboxyl group is present, and in the case of a carboxylic anhydride group, 0.5 mol of a carboxylic anhydride group is present. To do. It is preferable that other functional groups are contained to the same extent as in the case of a carboxyl group.

The molecular weight of the olefin wax containing a carboxyl group and / or a carboxylic anhydride group is from 1,000 to 20,000, preferably from 3,000 to 15,000, in terms of weight average molecular weight. Such a molecular weight is a value in terms of polystyrene using a calibration straight line obtained from standard polystyrene in GPC measurement.

Further, as a suitable folding inhibitor in the present invention, a copolymer of an α-olefin and maleic anhydride can be mentioned. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having an average carbon number of 10 to 60 can be preferably mentioned. More preferably, the α-olefin has an average carbon number of 16 to 60, and more preferably 25 to 55.

Commercially available olefin waxes include, for example, Diacarna PA30 and PA30M (manufactured by Mitsubishi Chemical; trade name), 2203 of high wax acid treatment type.
A, 1105A (Mitsui Chemicals; trade name) and the like. Particularly, diamond carna PA30 and PA30M are preferable. These are used alone or as a mixture of two or more.

Other examples of the fold inhibitor include polyorganosiloxanes containing at least one functional group selected from a carboxyl group, a carboxylic anhydride group and an epoxy group.

On the other hand, the same effect can be achieved by previously treating the surface of the inorganic filler with a lubricant. In this case, a lubricant having no reactive functional group may be used. As the lubricant, those described above can be used. The inorganic filler surface-treated in advance with a lubricant can be obtained, for example, by mixing the inorganic filler in a solution state or an aqueous dispersion state with the inorganic filler by a mixer or the like, and then performing a drying treatment or the like.

[0120] The composition ratio of the breaking inhibitor is 0.02 to 5 based on 100 parts by weight of the total of the component A and the component B.
Parts by weight are preferred. If it exceeds 5 parts by weight, delamination may occur.

In order to further improve the releasability from the mold at the time of melt molding, a releasing agent may be added to the thermoplastic resin composition of the present invention within a range not to impair the object of the present invention. It is. Examples of such release agents include olefin waxes, silicone oils, organopolysiloxanes, higher fatty acid esters of monohydric or polyhydric alcohols, paraffin wax, beeswax and the like. The amount of the release agent is 0.1% based on 100 parts by weight of the total of the component A and the component B.
It is preferably from 1 to 2 parts by weight.

A light stabilizer can be added to the thermoplastic resin composition for hollow molding of the present invention as long as the object of the present invention is not impaired. Such light stabilizers include, for example, 2
-(2'-hydroxy-5'-t-octylphenyl)
Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2- Hydroxy-
3,5-bis (α, α-dimethylbenzyl) phenyl]
-2H-benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl),
2,2′-p-phenylenebis (1,3-benzoxazin-4-one) and the like. The compounding amount of such a light stabilizer is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the total of the component A and the component B.

The thermoplastic resin composition for hollow molding of the present invention may contain an antistatic agent as long as the object of the present invention is not impaired. Examples of such antistatic agents include polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate,
Examples include dodecylbenzenesulfonic acid phosphonium salt, maleic anhydride monoglyceride, and maleic anhydride diglyceride.

The thermoplastic resin composition of the present invention may contain other resins as long as the effects of the present invention are not impaired. As other resins, for example, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyethylene, polyolefin resin such as polypropylene, polystyrene, acrylonitrile-styrene copolymer and the like Styrene resin, polymethacrylate resin, phenol resin,
Examples of the resin include an epoxy resin.

Further, the thermoplastic resin composition of the present invention comprises
As long as the effects of the present invention are not impaired, other additives may be included. Other various additives include, for example, flame retardants (halogen-based, phosphate-based,
Metal salts, red phosphorus, silicones, metal hydrates, etc., including anti-drip agents), lubricants, coloring agents (organic dyes, organic pigments, inorganic pigments, etc.), fluorescent brighteners, phosphorescent pigments, Examples include fluorescent dyes, flow modifiers, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers, and photochromic agents.

For producing the thermoplastic resin composition of the present invention, any method is employed. For example, A component, B component,
There can be mentioned a method in which the component C and the component E, and optionally other components are premixed, then melt-kneaded and pelletized. Examples of the premixing means include a V-type blender, a Henschel mixer, a mechanochemical device, and an extruder. In the pre-mixing, granulation can also be carried out by an extrusion granulator or a briquetting machine, if necessary. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vented twin-screw extruder, and pelletized by a device such as a pelletizer.

In addition, there is also a method in which the components A, B, C and E, and optionally other components are independently supplied to a melt kneader represented by a twin screw extruder without premixing. Can be taken. A component, B component, C component
After the components and the E component, and optionally some of the other components are premixed, a method in which the remaining components are independently supplied to a melt kneader may be used. Premixing means and granulation are the same as described above. Preferably, melt kneading by a twin-screw extruder is used. In this case, it is preferable that the component B and the component C are supplied from a second supply port in the middle of the extruder and kneaded.

When the components to be mixed are in a liquid state, a so-called liquid injection device or a liquid addition device can be used for supply to the melt kneader.

Further, when producing the thermoplastic resin composition of the present invention, it is preferable that the components A and B contain a small amount of water before the melt-kneading. Therefore, it is preferable to melt-knead the dried A component or B component by various methods such as hot air drying, electromagnetic wave drying, and vacuum drying. On the other hand, it is preferable that the suction of the vent during the melt-kneading be performed without increasing the degree of vacuum so much. More preferably, the method is performed in a state close to the atmospheric pressure. Further, a method of discharging volatile components out of the system while circulating nitrogen gas or the like can be used.

[0130]

The present invention will be further described with reference to the following examples.

(Examples 1 to 13 and Comparative Examples 1 to 11)
Each of the components shown in Tables 1 and 2 was added at the mixing ratio shown in the table to 1
A component and D component which were dried with hot air at 20 ° C. for 5 hours, E
Component and further, distearyl pentaerythritol diphosphite (a product of Asahi Denka Kogyo KK)
0.1 parts by weight of EP-8) and 0.05 parts by weight of trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.) (both phosphorus-based stabilizers are 90 parts by weight of polycarbonate powder of the A component and the stabilizers) 10 parts by weight were used in a dry-blended form with a supermixer) and 0.3 parts by weight of a breaking inhibitor (manufactured by Mitsubishi Chemical; Diacarna PA-30M) were uniformly mixed with a Nauta mixer, and then vented to a diameter of 30 mm. Twin screw extruder (Nippon Steel Works; TEX30SST)
The mixture was charged from the last first charging port, passed through a kneading zone composed of a kneading disk, and then dried at 120 ° C. for 5 hours. From the second inlet of the side feed section, use a measuring device (manufactured by Kubota; CWF)
It was charged so as to have the ratios shown in Tables 1 and 2, and pelletized at a cylinder temperature of 270 ° C. This pellet is
After drying at 20 ° C. for 5 hours, the weld strength and impact strength are measured by an injection molding machine (FANUC; T-150D).
Each test piece was molded at a cylinder temperature of 270 ° C. and a mold temperature of 90 ° C., and the evaluation results were implemented. Regarding the hollow moldability, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .; ULT)
RA220) at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., the door handle simulated molded product shown in FIG. 1 was molded and evaluated. In addition, the gas control at the time of hollow injection molding was implemented using (Battenfeld; AIRMOLD).

The evaluation methods described in Tables 1 and 2 and symbols indicating each component are as follows. (I) Evaluation of weld strength retention rate and impact strength (1) Weld strength retention rate: Using test pieces for measuring tensile strength of TYPE I described in ASTM D638, gates were formed at both ends in the longitudinal direction of the test pieces. Then, a molded product in which a weld was formed at the center was prepared by two types of molding methods, a normal injection molding method and a hollow injection molding method. AS of such a test piece
Tensile strength (Y1, and Y1) according to TM D-638
2) was measured. In addition, in accordance with ASTM D638,
The tensile strength (Y3) of a normal test piece without a weld was also measured, and the retention of the weld strength was calculated according to the equations (1) and (2) described in the text.

The molding conditions for each test piece were as follows. Molding condition of tensile test piece for Y1 measurement Cylinder temperature: 270 ° C., mold temperature: 90 ° C., injection pressure: 100 MPa, holding pressure condition: 80 MPa × 10 seconds Molding condition of tensile test piece for Y2 measurement Cylinder temperature: 270 ° C, mold temperature: 90 ° C, injection pressure: 100 MPa, delay time: 1 second, gas injection condition: 1
8 MPa × 10 seconds, hollow ratio: about 16%. (The gas was injected from the gate opening of the resin.) Molding condition of tensile test piece for Y3 measurement Cylinder temperature: 270 ° C., mold temperature: 90 ° C., injection pressure: 100 MPa, holding pressure condition: 80 MPa × 10 Second

(2) Impact strength: Measured at a thickness of 1/8 ″ in accordance with ASTM D256. (II) Evaluation of hollow moldability The handle-molded simulated molded article shown in FIG.
Measurement and observation of the average value and variation of the hollow ratio and the presence or absence of sink marks according to the following formulas (3) and (4) in a 50-shot hollow molded product obtained by gas injection molding.
And appearance observations were made. The gas injection molding conditions were as follows: cylinder temperature 260 ° C., mold temperature 80 ° C., injection pressure 100 MPa, delay time 1 second,
Gas injection molding was performed at a gas pressure of 2 to 8 MPa and a gas injection time of 5 seconds. In order to calculate the hollow ratio, a molded product to which a holding pressure of 75 MPa × 10 seconds was applied instead of gas injection was prepared as a normal molded product. (3) Hollow ratio (%): The hollow ratio was calculated from the following equation (3).

[0135]

(Equation 1)

[0136] Those in which gas penetration into the molded product during 50 shots, that is, gas intrusion to the hole of the molded product main body or the discarded mold part, were recognized as "x".

(4) Variation (%): Variation was calculated from the following equation (4). In addition, a gas through the molded product during 50 shots, that is, a hole in the molded product main body or gas intrusion to the discarded mold part was recognized was indicated by “x”.

[0138]

(Equation 2)

(5) Sink: Sink was visually judged based on the following criteria. ○: No sink marks were generated in all of the 50 shot hollow molded articles. ×: Some molded articles suffered sink marks due to almost no gas penetration during 50 shots.

(6) Appearance of molded article: The appearance of the simulated handle article was visually judged. The judgment was made as follows. ：: No defective appearance due to jetting and butting ×: Poor appearance due to jetting and butting

(III) Each component (A component; aromatic polycarbonate resin) PC: bisphenol A type polycarbonate powder obtained by phosgene method (manufactured by Teijin Chemicals Limited; Panlite L-1250WQ, viscosity average molecular weight 25, 000)

(Component B; aromatic polyester resin) PBT-1: polybutylene terephthalate resin (manufactured by Teijin; TRB-H, intrinsic viscosity 1.07) PBT-2: polybutylene terephthalate resin (manufactured by Changchun Manufactured Resin Co., Ltd .; 1100) -211S, intrinsic viscosity 1.
08) PET: polyethylene terephthalate resin (manufactured by Teijin; TR-8580, intrinsic viscosity 0.8)

(Component C; inorganic filler) WSN-1: Wollastonite (NYCO; NYG
LOS4) WSN-2: Wollastonite (manufactured by Kawairon Mining; PH-
450) Talc: Talc (manufactured by Hayashi Kasei; HST 0.8) GF: glass fiber (manufactured by Nitto Bo; 3PE-948)

(Component D; rubber-like filler) S2001: A rubbery polymer obtained by copolymerizing methyl methacrylate with a composite rubber polymer having a structure in which a polyorganosiloxane rubber and an acrylate rubber are intertwined (manufactured by Mitsubishi Rayon; Metablen) S2001) EXL: rubbery polymer obtained by copolymerizing butadiene rubber with methyl methacrylate (Kureha Chemical Industry; Paraloid EXL2602) W450: butyl acrylate and acrylic acid 2-
Copolymer of methyl methacrylate grafted on a rubber component consisting of ethylhexyl (Mitsubrene W-450A, manufactured by Mitsubishi Rayon)

(E component; mixed powder) PTFE-1: polytetrafluoroethylene 50% by weight
And the weight average molecular weight calculated by GPC measurement is 33.
Styrene-acrylonitrile copolymer 50
Wt% mixed powder (manufactured by GE Specialty Chemicals; Blendex 449, average particle size of powder: 40 μm)

(Others) PTFE-2: 20% by weight of polytetrafluoroethylene
Of methacrylate and 80% by weight of an acrylic resin composed of methyl methacrylate and an acrylate polymer component (manufactured by Mitsubishi Rayon; Metablen A-3000) PTFE-3: polytetrafluoroethylene (manufactured by Daikin Industries; POLYFLON MPA FA500)

[0147]

[Table 1]

[0148]

[Table 2]

[0149]

As is apparent from Examples 1 to 13, the thermoplastic resin composition of the present invention has a higher weldability during normal molding and hollow molding than Comparative Examples 1 to 11 containing no specific E component. It is excellent in hollow injection moldability as well as being excellent in hollow injection moldability, and more specifically, is excellent in appearance, mechanical properties such as sink marks and impact strength, and chemical resistance, and is widely useful for industrial applications.

[Brief description of the drawings]

FIG. 1-A is a side view of a model mock-up of a handle with a throwaway mold used for evaluation. 1-B: A top view as viewed from the cavity side of the simulated molded product with a handle with throwaway cavities used for evaluation.

[Description of Signs] 1 Main body of simulated handle 2 Width of simulated handle (25 mm) 3 Length of simulated handle (160 mm) 4 Gate part of simulated handle (width 5 mm, thickness 2.5 mm) 5 Gate part of the dumping mold part (width 25mm, thickness 1m
m, length 2mm) 6 Discarded mold part (width 30mm, thickness 20mm, length 3)
0) 7 Thickness of the handle simulated molded product (15mm) 8 Gas inlet (5mm inner diameter) 9 Handle latch section (length 30mm, width 10mm, thickness 6mm, oval hole in the center, with weld)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // B29K 25:00 B29K 25:00 27:12 27:12 67:00 67:00 69:00 69: 00 105: 16 105: 16 F term (reference) 4F071 AA10 AA22X AA26 AA34X AA43 AA50 AB00 AB30 AE17 AF14Y AH07 AH11 AH17 BB05 BC04 4F206 AA24 AA28 AB11 AG07 AH17 AM36 JA05 JF01 JF21 4J002 BC06BNBN 145 BP 145 CF005 CF04X CF05X CF06X CF07X CF08X CF09X CF10X CF13X CG01W CG04W CK025 CL075 DA016 DA026 DA066 DE136 DE146 DE186 DE236 DG046 DJ006 DJ016 DJ036 DJ046 DJ056 DK006 DL006 FA016 FA046 FA066 FA086 FA106 FB076 FD016 GC00 GM00GM

Claims (7)

[Claims] (A) An aromatic polycarbonate resin (A)
(C) 1 to 100 parts by weight of (C) an inorganic filler (Component C), based on a total of 100 parts by weight of (Component) 10 to 95 parts by weight and (B) an aromatic polyester resin (Component B) 5 to 90 parts by weight. E) The weight average molecular weight calculated from GPC (gel permeation chromatography) measurement is 50,0
A polymer (e1 component) obtained by polymerizing at least one monomer selected from aromatic vinyl monomers and vinyl cyanide monomers having a molecular weight of from 00 to 500,000 (component e1);
% By weight and fluorinated olefin polymer (e2 component) 70
To 30% by weight (100% by weight)
Component) A thermoplastic resin composition comprising 0.01 to 10 parts by weight. 2. The component A is 50 to 95 parts by weight,
The thermoplastic resin composition according to claim 1, wherein the component B is 5 to 50 parts by weight. 3. The method according to claim 1, wherein the e1 component is GPC.
(Gel permeation chromatography) The weight average molecular weight calculated from the measurement is from 50,000 to 500,000.
3. The thermoplastic resin composition according to claim 1, which is a copolymer comprising 60 to 80% by weight of an aromatic vinyl monomer and 00 to 40% by weight of a vinyl cyanide monomer. 4. The thermoplastic resin composition according to claim 1, wherein the C component is at least one inorganic filler selected from talc and wollastonite. 5. The rubber polymer (D) is added in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the total of the components A and B.
The thermoplastic resin composition according to any one of claims 1 to 4, comprising parts by weight. 6. The resin composition is adjusted so that the weld strength retention (X1) when molded by ordinary injection molding is 60% or more and the hollow ratio is 5 to 30% by hollow injection molding. Weld strength retention (X2) of 50 when molded
% Of the thermoplastic resin composition according to any one of claims 1 to 5. 7. A hollow molded article having a weld portion formed from the thermoplastic resin composition according to claim 1 by a hollow injection molding method.