JP2000072962A - Polycarbonate resin composition and molded article made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polycarbonate resin compositions excellent in resistance to moist heat in the resin compositions obtained by compounding a polymer alloy of a polycarbonate resin and a styrenic resin with a phosphate ester type flame retardant. SOLUTION: Polycarbonate resin compositions comprise 100 pts.wt. resin composition composed of 40-92 wt.% polycarbonate resin containing not more than 350 ppm chlorine compound in terms of the amount of chlorine atom as component (a), 5-40 wt.% styrenic resin as component (b), and 3-20 wt.% phosphate ester type flame retardant as component (c) with a total amount of components (a), (b) and (c) of 100 wt.%, and 0.1-30 pts.wt. silicate salt based filler as component (d). Molded articles can be obtained by molding these polycarbonate resin compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition having excellent wet heat resistance and a molded product obtained by melt-molding the same.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used industrially because of their excellent mechanical and thermal properties. However, because of poor processability and moldability, many polymer alloys with other thermoplastic resins have been developed,
Among them, a polymer alloy with a styrene resin represented by an ABS resin is widely used in the fields of automobiles, office automation equipment, electronic and electric equipment, and the like. On the other hand, in recent years, there has been a strong demand for resin materials to be used in flame-retardant applications, especially for applications such as OA equipment and home electric appliances. Many studies have been made.

Conventionally, in such polymer alloys, a halogen-based flame retardant having bromo and a flame retardant auxiliary such as antimony trioxide have been generally used in combination. However, bromo is used due to a problem of generating harmful substances during combustion. Investigations on flame retardancy that does not include halogen compounds have become active. For example, a method of blending triphenyl phosphate and polytetrafluoroethylene having a fibril-forming ability into a polymer alloy of a polycarbonate resin and an ABS resin (Japanese Patent Laid-Open No. 2-3)
2154), a method of blending a phosphate-based oligomer which is a condensed phosphate ester (JP-A-2-1152)
No. 62), a method of blending a specific inorganic filler and a specific impact modifier (Japanese Patent Application Laid-Open No. 7-126510) and the like have been proposed. On the other hand, in recent years, from the viewpoints of product safety, reduction of environmental load due to prolonged product life, and guarantee of products by manufacturers, performance retention during long-term use has become extremely important.

However, in a polycarbonate resin composition containing such a phosphate ester flame retardant, the phosphoric acid ester flame retardant incorporated therein is hydrolyzed during long-term use, and the decomposed product is bonded to the carbonate bond of the polycarbonate resin. Hydrolysis is promoted, and for example, there is a problem that impact strength and the like are significantly reduced. That is, in a resin composition in which a phosphate ester-based flame retardant is blended with a polymer alloy of a polycarbonate resin and an ABS resin, it is required to improve wet heat resistance, and the solution has been urgently required.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition comprising a polymer alloy of a polycarbonate resin and a styrene-based resin and a phosphate ester-based flame retardant, the polycarbonate resin composition having excellent wet heat resistance. Is to provide.

The present inventors have made intensive studies to achieve the above object, and as a result, added a specific inorganic filler to a resin composition comprising a specific polycarbonate resin, a styrene resin, and a phosphate ester flame retardant. Thus, the present inventors have found that a polycarbonate resin composition having excellent hydrolysis resistance in long-term use, that is, excellent wet heat resistance, can be obtained, and the present invention has been achieved.

[0007]

According to the present invention, there is provided a polycarbonate resin (a component) containing 40 to 92% by weight of a chlorine compound having a chlorine atom content of 350 ppm or less, and a styrene resin (b component) 5 to 40% by weight. % And a phosphate ester flame retardant (component (c)) in an amount of 3 to 20% by weight, and 100 to 100 parts by weight of a total of 100% by weight of a silicate filler (component (d)) in an amount of 0.1 to 30% by weight. The present invention relates to a polycarbonate resin composition obtained by blending parts, and a molded product obtained by melt-molding the polycarbonate resin composition.

The polycarbonate resin in the component a of the present invention refers to a polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor, that is, an aromatic polycarbonate resin. Typical examples of the dihydric phenol used here include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A),
1,1-bis (4-hydroxyphenyl) ethane, 1,
1-bis (4-hydroxyphenyl) cyclohexane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,
5-dibromophenyl) propane, 2,2-bis (4-
Hydroxy-3-methylphenyl) propane, bis (4
-Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like. Preferred dihydric phenols are 2,2-bis (4-hydroxyphenyl) alkanes, and bisphenol A is particularly preferred. Examples of the carbonate precursor include carbonyl halide, carbonic acid diester, bishaloformate and the like, and specific examples include phosgene, diphenyl carbonate, dibischloroformate of dihydric phenol and the like. In producing the polycarbonate resin by reacting the dihydric phenol and the carbonate precursor, the dihydric phenol may be used alone or in combination of two or more, or even a polycarbonate resin, two or more polycarbonate It may be a mixture of resins.

The molecular weight of the polycarbonate resin is usually from 10,000 to 40,000, preferably from 12,000 to 30,000, expressed as a viscosity average molecular weight. The viscosity average molecular weight (M) is determined by inserting the specific viscosity (ηsp) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation. ηsp / C = [η] + 0.45 × [η] ² C [η] = 1.23 × 10 ⁻⁴ M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration of 0.7)

An interfacial polymerization method for producing a polycarbonate resin will be briefly described. In the interfacial polymerization method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. As the acid binder, for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. Examples of the molecular weight regulator include alkyl-substituted phenols such as phenol and p-tert-butylphenol and 4- (2 It is desirable to use a terminal stopper such as an aralkyl-substituted phenol such as (-phenylisopropyl) phenol. The reaction temperature is usually 0 to 40 ° C., the reaction time is preferably several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. still,
Not all of the resulting chain ends need have a structure derived from the terminator.

In the transesterification reaction (melting method) using carbonic acid diester as a carbonate precursor, a predetermined ratio of a dihydric phenol component and, if necessary, a branching agent and the like are stirred while heating with the carbonic acid diester in an inert gas atmosphere. This is carried out by a method of distilling off alcohols or phenols produced. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, etc.
The range is from 0 to 300 ° C. The reaction is completed under reduced pressure from the beginning while distilling off alcohol or phenols produced. Also, to promote the reaction,
It is also possible to use catalysts used in transesterification reactions known at present such as alkali metal compounds and nitrogen-containing basic compounds. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate,
Dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned. Of these, diphenyl carbonate is particularly preferred. Adding diphenyl carbonate, methyl (2-phenyloxycarbonyloxy) benzenecarboxylate, or the like as a terminal terminator at an early stage of the reaction or at an intermediate stage of the reaction;
It is also preferable to add various conventionally known catalyst deactivators immediately before the end of the reaction.

The polycarbonate resin as the component a used in the present invention is the above-mentioned polycarbonate resin and a polycarbonate resin containing a chlorine compound of 350 ppm or less in terms of chlorine atom weight. Preferably, it is a polycarbonate resin containing a chlorine compound of 100 ppm or less, particularly preferably 20 ppm or less in terms of chlorine atom weight. 350pp converted to chlorine atomic weight
With a polycarbonate resin containing a chlorine compound exceeding m, it is difficult to improve the wet heat resistance even when the present invention is applied.
As can be seen from the above production method, in the polycarbonate resin, for example, in the case of a solution method, a residual solvent and a modified product thereof, a catalyst, a catalyst deactivator and a modified product thereof,
In addition, chlorine compounds remain due to by-products and the like during the production. The present inventor has found that such residues have an adverse effect on the hydrolysis effect caused by the phosphate ester.

In order to obtain such a low chlorine compound-containing polycarbonate resin, for example, when the polycarbonate resin is treated with acetone, or when the polycarbonate resin powder is pelletized, water is forcibly injected into a vented extruder to remove the resin. It can be obtained by various conventionally known methods such as a method of performing a chlorine compound, a method of precipitating a non-solvent of a polycarbonate resin solution, and a further strengthening of a drying treatment.

Further, an organic solvent solution of the polycarbonate resin is continuously supplied to the container in which the mixture of the polycarbonate resin granules and the hot water is present under stirring, and the solvent is evaporated to obtain the polycarbonate resin. In the method for producing a polycarbonate resin granule from an organic solvent solution, the temperature in the container is set to T _{1 represented} by the following formula.
(° C.) or T ₂ (° C.), stirring speed is 60 to 100 rpm, and stirring capacity is 5 to 10 k.
The production method characterized by w / hr · m ³ is preferred because not only the reduction of residual chlorine compounds but also the production of a polycarbonate resin with less powder, good filterability, and excellent drying properties can be obtained. It can be used. 0.0018 × M ₁ + 37 ≦ T ₁ (° C.) ≦ 0.0018 ×
M ₁ +42 (M ₁ : viscosity average molecular weight 10,000 to 20,000
0) 0.0007 × M ₂ + 59 ≦ T ₂ (° C.) ≦ 0.0007 ×
M ₂ +64 (M ₂ : viscosity average molecular weight 20,000 or more)

Further, in the case of the melt polymerization method, since a solvent component which is a main component of the residual chlorine compound is not used, particularly,
When a non-chlorine compound is used as the catalyst component and the deactivator component, it is possible to obtain a polycarbonate resin that is almost zero.

In the present invention, the content of chlorine atoms in the polycarbonate resin is determined by the value of PI manufactured by RIKEN ELECTRIC INDUSTRIES, LTD.
It is a value measured by an analysis method using fluorescent X-rays using an X-2000 fully automatic fluorescent X-ray analyzer.

The styrene resin used as the component b in the present invention is a resin containing styrene or a styrene derivative such as α-methylstyrene or vinyltoluene in an amount of 20% by weight or more based on 100% by weight of the styrene resin. . Accordingly, as the styrene resin, homopolymers or copolymers of such styrene derivatives, copolymers of these monomers with vinyl monomers such as acrylonitrile and methyl methacrylate, and diene rubbers such as polybutadiene, ethylene Styrene and / or styrene derivatives in rubber components such as propylene rubber, acrylic rubber, and composite rubber having a structure in which polyorganosiloxane component and poly (meth) alkyl acrylate component are entangled with each other so that they cannot be separated. Or those obtained by graft-polymerizing styrene and / or a styrene derivative and another vinyl monomer. Specific examples of these styrene resins include polystyrene, high impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene. Styrene copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acryl rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber
Styrene copolymer (AES resin), acrylonitrile
Chlorinated polyethylene / styrene copolymer (ACS resin)
And the like, or a mixture thereof. In the copolymer and the mixture, the styrene-based derivative component is contained in an amount of 20% by weight or more in 100% by weight of the styrene-based resin. Such various polymers, bulk polymerization, suspension polymerization, emulsion polymerization, those produced by various polymerization methods such as bulk suspension polymerization can be used, and even if the copolymerization method is copolymerized in one step, Copolymerization may be carried out in multiple stages.

In the present invention, among these, polystyrene, impact-resistant polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin) are preferable. In view of the above, an ABS resin is most preferable. Further, among these, those produced by the bulk polymerization method can be preferably used in that the wet heat resistance can be further improved. These b-components can be used alone or in combination of two or more.

The ABS resin referred to in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and is usually produced as a by-product during the graft polymerization of an AS resin or the like. To form a mixture with other polymers. Further AB
A mixture of S resin and separately polymerized AS resin is widely used industrially. As the diene rubber component forming the ABS resin, for example, a rubber having a glass transition point of 10 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and the ratio thereof is 100% by weight of the ABS resin component. It is preferably from 5 to 75% by weight. Examples of the vinyl cyanide compound grafted to the diene rubber component include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound grafted to the diene rubber component include styrene and α-methylstyrene. And nucleus-substituted styrene. The content ratio of the vinyl cyanide compound and the aromatic vinyl compound is such that the vinyl cyanide compound is 5 to 5% by weight based on the total amount of the vinyl cyanide compound and the aromatic vinyl compound.
50% by weight and 95 to 50% by weight of the aromatic vinyl compound. Further, methyl acrylate, methyl methacrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used, but their content should be 15% by weight or less in the component b.

The ABS resin of the present invention may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization. As described above, the ABS resin produced by the bulk polymerization method has poor wet heat resistance. This is more preferable in that it is further improved. Although the cause has not been clarified sufficiently, emulsion polymerization, metal salt components such as emulsifiers used in suspension polymerization,
It is conceivable that it directly affects the hydrolysis caused by the phosphate ester or acts on the chlorine compound remaining in the polycarbonate resin to influence the hydrolysis.

Further, the ABS resin preferably satisfies the condition that the amount of acrylonitrile monomer remaining in the ABS resin is 200 ppm or less, more preferably 100 ppm or less, particularly preferably 50 ppm or less. When the amount of the residual acrylonitrile monomer satisfies these amounts, better moisture and heat resistance can be satisfied. When the amount of the acrylonitrile monomer is less than 5 ppm, the wet heat resistance is not significantly improved, but the economic disadvantage due to an increase in the number of steps for reducing the amount of the monomer is increased. It is.

The phosphate ester flame retardant used as the component c in the present invention is represented by the following formula (I).

[0023]

Embedded image

(Where X in the above formula is hydroquinone,
Derived from resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide J, k, l, and m are each independently 0 or 1, n is an integer of 0 to 5,
Alternatively, in the case of a blend of phosphate esters having different numbers of n, the average value is 0 to 5, and R ₁ , R ₂ , R ₃ , and R ₄ are each independently phenol, cresol, xylenol,
It is derived from isopropylphenol, butylphenol and p-cumylphenol. )

Among them, X in the above formula preferably includes those derived from hydroquinone, resorcinol and bisphenol A, wherein j, k, l and m are each 1 and n is 0 to 3. Is an integer or an average of 0 to 3 for a blend of n different phosphate esters, wherein R ₁ , R ₂ , R ₃ , and R ₄ are each phenol,
It is derived from cresol and xylenol.

More preferably, X is derived from resorcinol, j, k, l, m are each 1, n is 0 or 1, and R ₁ , R ₂ , R ₃ ,
And R ₄ are each independently derived from phenol or xylenol.

Among such phosphate ester flame retardants,
Triphenyl phosphate as the monophosphate compound and resorcinol bis (dixylenyl phosphate) as the condensed phosphate ester can be preferably used because of their good flame retardancy and good fluidity during molding.

In the present invention, the silicate-based filler used as the component d means that the SiO ₂ component is 35% due to its chemical composition.
Inorganic filler containing at least 40% by weight, preferably 40% by weight
It refers to the inorganic filler contained above. Such silicate-based fillers include kaolin, talc, clay, pyrophyllite, mica, montmorillonite, bentonite, wollastonite, sepiolite, zonotolite, natural silica, synthetic silica, various glass fillers, zeolites, diatomaceous earth, halloysite And the like.

Among them, in the present invention, it is possible to increase the number of action points for suppressing the hydrolysis by finely dispersing such a filler, and that the reinforcing effect on the resin is also important from the viewpoint of imparting flame retardancy. In terms of talc, mica,
Wollastonite can be mentioned as a preferred filler. Among them, talc is most preferable.

The mica used in the present invention is preferably in the form of a powder having an average particle size of 1 to 80 μm from the viewpoint of securing the reinforcing effect. Mica is a crushed silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, artificial mica and the like, and any mica can be used as the mica of the present invention. In particular, phlogopite, biotite and phlogopite
Preference is given to muscovite having a higher SiO ₂ content than to artificial mica in which the H groups have been replaced by F atoms. The pulverization method for producing mica includes a dry pulverization method in which raw mica is pulverized by a dry pulverizer and a coarse pulverization of mica ore in a dry pulverizer, and then adding water to a wet pulverizer in a slurry state. There is a wet pulverization method that performs main pulverization, then dewaters and dries,
The dry grinding method is generally used at a lower cost, but it is difficult to grind the mica thinly and finely. Therefore, in the present invention, it is preferable to use mica produced by a wet grinding method.

The average particle size of mica is from 1 to 80 as measured by a microtrack laser diffraction method.
μm can be preferably used. More preferably, the average particle size is 2 to 50 μm. In the case of 1 to 80 μm, a good effect on the flame retardancy is obtained, and the condition for fine dispersion in the resin is satisfied, so that the wet heat resistance can be maintained well.

As for the thickness of mica, one having a thickness actually measured by observation with an electron microscope of 0.01 to 1 μm can be used. Preferably, the thickness is 0.03-0.3 μm.
Further, such mica may be surface-treated with a silane coupling agent or the like, and may be granulated with a binder such as an epoxy-based, urethane-based, or acrylic-based binder to form granules. Specific examples of mica include mica powder (mica powder) A-41, A-21, and A-11 manufactured by Yamaguchi Mica Industrial Co., Ltd., and these are easily available on the market.

The talc used in the present invention is preferably in the form of powder having an average particle size of 0.5 to 20 μm from the viewpoint of securing rigidity. Since talc is thicker than mica, it is preferable that talc has a smaller particle size in order to have the same dispersion in the resin. Here, the average particle size of talc means a value measured by a microtrack laser diffraction method.

The talc of the present invention is not particularly limited to the place of production, but more preferably, the talc has a higher SiO ₂ component, for example, 60% by weight or more. In the case of such an SiO ₂ component amount, the content of Fe ₂ O ₃ which is an impurity tends to be relatively large, and therefore, such talc is also advantageous in terms of hue. There is no particular limitation on the production method for grinding such talc from rough stones, and examples thereof include an axial flow mill method, an annular mill method, a roll mill method, a ball mill method, a jet mill method, and a container rotating compression shearing mill method. Can be used. Further, such talc is preferably in an agglomerated state in terms of its handleability and the like.
There is a method of compressing using a binder resin, and the like, and a method of degassing and compressing is particularly preferable because a simple and unnecessary binder resin component is not mixed into the composition of the present invention.

The wollastonite in the present invention is a natural white mineral having needle-like crystals mainly composed of calcium silicate, and is substantially represented by the chemical formula CaSiO ₃ ,
It contains about 50% by weight of iO ₂ , about 47% by weight of CaO, Fe ₂ O ₃ , Al ₂ O _3, etc., and has a specific gravity of about 2.9.
It is.

In the wollastonite used in the present invention, 3 μm or more in the particle size distribution is 75% or more,
Those having 0% or more and 5% or less and having an aspect ratio L / D of 3 or more, particularly L / D of 8 or more are preferable. When the particle size distribution is 75% or more for 3 μm or more and 5% or less for 10 μm or more, the reinforcing effect is sufficient, the flame retardancy is easily increased, and the finely dispersed in the resin, and the moist heat resistance is also improved. is there. In particular, when the aspect ratio is 8 or more, the reinforcing effect is sufficient, which is preferable. However, considering the working environment, those having an aspect ratio of 50 or less are more preferable. The wollastonite may be subjected to a surface treatment with a normal surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent.

Next, the mixing ratio of each component in the resin composition of the present invention will be described. The mixing ratio of the components a to c in the resin composition is represented based on the total weight of the three components.
The component a is 40 to 92% by weight, the component b is 5 to 40% by weight, and the component c is 3 to 20% by weight per 100% by weight of the total of the three.
It is. When the component a is less than 40% by weight or the component b exceeds 40% by weight, heat resistance (particularly, deflection temperature under load) and mechanical strength are reduced. Further, the a component is 92
If the content is more than 5% by weight or the content of the component (b) is less than 5% by weight, the fluidity is reduced and the moldability is reduced.
Further, if the component c is less than 3% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 20% by weight, mechanical strength and heat resistance (particularly, deflection temperature under load) are remarkably reduced, and wet heat resistance is also significantly reduced. .

In the present invention, the compounding ratio of the component d is in the range of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight per 100 parts by weight of the total of the components a to c. When the compounding ratio of the d component is less than 0.1 part by weight, there is no effect of improving the moist heat resistance, and when it exceeds 30 parts by weight, the effect on the moist heat resistance is saturated, but the impact strength is reduced or the molded article obtained Is not preferred because the surface appearance of the film deteriorates.

In the composition of the present invention, polytetrafluoroethylene having a fibril forming ability can be used in order to further improve the flame retardancy. Polytetrafluoroethylene having a fibril-forming ability is classified into type 3 in the ASTM standard. Polytetrafluoroethylene having fibril-forming ability is UL
Polytetrafluoroethylene having a fibril-forming ability and having a fibril-forming ability in a standard vertical combustion test during a combustion test of a test piece is, for example, Teflon 6J from DuPont-Mitsui Fluorochemicals Co., Ltd. or Daikin It is commercially available from Chemical Industry Co., Ltd. as Polyflon and can be easily obtained. The compounding amount of polytetrafluoroethylene having a fibril-forming ability is the above-mentioned a.
0.1 to 100 parts by weight of the total of the three components of the component to the component c.
Preferred is 1 to 1 part by weight. If the amount is less than 0.1 part by weight, it is difficult to obtain sufficient performance to prevent melt dripping, and if it exceeds 1 part by weight, the appearance is deteriorated.

The polytetrafluoroethylene having a fibril-forming ability can be used in either solid state or dispersion form in which it is dispersed and mixed in a dispersion medium. In particular, a solid-state material can be preferably used because it is liable to adversely affect the surface.

The resin composition of the present invention may be used in addition to the above-mentioned styrene resin, particularly for the purpose of improving the low-temperature impact characteristics.
A rubbery polymer can be blended. Examples of such rubbery polymers include acrylate-based core-shell graft copolymers, polyurethane-based elastomers, polyester-based elastomers, and the like.

Examples of the acrylate-based core-shell graft copolymer include a copolymer or a mixture of a rubbery alkyl (meth) acrylate polymer having a C2-8 alkyl group and a diene rubbery polymer. In the core of
A core-shell type polymer having a shell formed by polymerizing an alkyl (meth) acrylate and optionally a copolymerizable vinyl monomer, and a similar multi-stage core-shell type polymer can also be used. Also, a core composed solely of a diene rubbery polymer can be used. As such acrylate core-shell graft polymers, trade names “HIA-15” and “HIA” from Kureha Chemical Industry Co., Ltd.
-28 ", and a resin consisting solely of a diene-based rubbery polymer as a core is commercially available from Kureha Chemical Industry Co., Ltd. under the trade name" PARALOID EXL-2602 ". Resin.

Further, a composite rubber having a structure in which the polyorganosiloxane component and the poly (meth) alkyl acrylate component are entangled with each other so as to be inseparable from each other is added to an alkyl (meth) acrylate and optionally a copolymerizable vinyl monomer. A polymer obtained by graft polymerization of a monomer (hereinafter referred to as an IPN-type polymer) can also be used. As such an IPN-type polymer, “METABLEN S-2” is available from Mitsubishi Rayon Co., Ltd.
001 "and is easily available.

The thermoplastic polyurethane elastomer which can be used in the present invention includes an organic polyisocyanate, a polyol and two or three functional groups having a molecular weight of 50 or less.
~ 400 chain extenders are obtained,
Various currently known thermoplastic polyurethane elastomers can be used. As such a thermoplastic polyurethane elastomer, for example, "Kuramilon U" manufactured by Kuraray Co., Ltd.
(Product name) etc. can be easily obtained.

The thermoplastic polyester elastomer which can be used in the present invention is obtained by polycondensing a bifunctional carboxylic acid component, an alkylene glycol component and a polyalkylene glycol component. Can be used. Such thermoplastic polyester elastomers are easily available, for example, "Pelprene" (trade name) manufactured by Toyobo Co., Ltd. and "Nouvellen" (trade name) manufactured by Teijin Limited.

The resin composition of the present invention can be produced by mixing the above components with a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, and an extruder. Further, other thermoplastic resins such as polyester, polyamide, and polyphenylene ether may be mixed within a range not to impair the object of the present invention, and if necessary, various additives in an amount in which the effect is exhibited, for example, stable additives. Agents, release agents, antistatic agents, ultraviolet absorbers, dyes and pigments, and the like.

Examples of the heat stabilizer include phosphoric acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, which are conventionally known as heat stabilizers for aromatic polycarbonates. Specifically, trisnonylphenyl Phosphite, trimethyl phosphate, tris (2,4-di-t
Preferred are tert-butylphenyl) phosphite and dimethyl benzenephosphonate. These heat stabilizers may be used alone or in combination of two or more.

As the heat stabilizer of the present invention, in addition to the above, it is also preferable to add a hindered phenol compound or a sulfur compound generally known as an antioxidant. Such a compound is particularly preferable in that the thermal stability of the styrenic resin is maintained and the thermal decomposition of the resin is suppressed. Specific examples of such a compound include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-tert-butylphenol), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-4-methylphenol, 2,4-di- tert-amyl-6- [1- (3,5-di-tert-amyl-2)
-Hydroxyphenyl) ethyl] phenyl acrylate, pentaerythrityltetrakis (3-laurylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, Stearyl-3,3'-thiodipropionate and the like can be mentioned.

The resin composition thus obtained is extruded,
It can be easily molded by injection molding, compression molding, etc.
Also, it can be applied to blow molding, vacuum molding and the like. Especially UL
It is most suitable as a material for electrical and electronic parts that require 94V-0 and exterior use of OA.

[0050]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. The parts in the examples are parts by weight, and the evaluation was made by the following method.

(1) Moisture / heat resistance -1: 1/8 "Izod impact test piece was subjected to notch cutting treatment, and then subjected to an environmental tester (Platinum Subzero Lucifer manufactured by Tabai Espec Co., Ltd.).
After treatment under the conditions of 5 ° C. and 85% RH for 500 hours, A
Izod notched impact resistance values were measured according to STM D256, and compared with Izod notched impact resistance values before wet heat treatment.

(2) Moisture and heat resistance-2: The apparent viscosity average molecular weight of the test piece after the wet heat treatment of (1) was measured by the same method as that for measuring the molecular weight of the aromatic polycarbonate resin. That is, after dissolving the test piece in methylene chloride, the insoluble content was removed by filtration, and the specific viscosity of the solution obtained as a solution was measured in the same manner as the viscosity average molecular weight measurement of the polycarbonate resin described in the text, and the same calculation formula was used. Was used to calculate the value of the apparent viscosity average molecular weight.

(3) Flame retardancy: A combustion test was conducted at a thickness of 1.6 mm according to UL standard 94V.

Reference Example 1 Production of Polycarbonate Resin (1) A 500 L horizontal shaft having an organic solvent supply port for polycarbonate, a hot water supply port, a steam introduction port, an exhaust port for vaporized organic solvent, and an overflow discharge port A stirrer having a ribbon shape as a stirring blade was attached to a biaxial container of a rotary mixer. The container was charged with 50 g of polycarbonate resin particles having an average particle diameter of 7 mm and 250 g of water. When the temperature in the container reached 77 ° C. while stirring at a stirring speed of 80 rpm, the average molecular weight was 22,000.
A methylene chloride solution having a polycarbonate resin concentration of 16% by weight, which was 0, was supplied at a rate of 10 kg / min, and hot water was supplied at a rate of 10 kg / min. During the supply, the amount of hot water in the container / polycarbonate resin powder (volume ratio) was maintained at about 5, and the temperature in the container was 2.7 kg / cm.
The temperature of 77 ° C. was maintained by heating the steam inlet and the jacket using the steam of No. ² . The stirring capacity is 6 kw / hr.
M was ³ . After the start of the supply, the level of the slurry in the container was increased, and the generated polycarbonate resin powder and hot water were discharged from a discharge port provided at an upper portion in the container. At this time, the residence time of the polycarbonate resin particles was 1 hour.

Next, a sample was taken after the granules were discharged and the properties of the granules were stabilized. The polycarbonate resin particles and warm water discharged from the outlet were then centrifuged with a vertical centrifuge (manufactured by Kokusan) at a centrifugal force of 1500 G, and the polycarbonate resin particles were separated by filtration.
The separated polycarbonate resin granules were pulverized by a pulverizer to an average particle size of 2 mm, and heated at 140 ° C. by a hot air drier.
Drying was performed for 4 hours. The viscosity average molecular weight of the obtained polycarbonate resin was 22,000, the bulk density was 0.3 g / cm ³ , and the chlorine atom weight was 5 ppm. The polycarbonate resin obtained here is called PC-1.

Reference Example 2 Production of Polycarbonate Resin (2) Production was carried out in the same manner as in Reference Example 1, except that the temperature in the container was changed to 70 ° C. The viscosity average molecular weight of the obtained polycarbonate resin was 22,000, the bulk density was 0.4 g / cm ³ , and the chlorine atom weight was 50 ppm. The polycarbonate resin obtained here is called PC-2.

Reference Example 3 Production of Polycarbonate Resin (3) Production was carried out in the same manner as in Reference Example 1, except that the temperature in the container was changed to 50 ° C. The viscosity average molecular weight of the obtained polycarbonate resin was 22,000, the bulk density was 0.65 g / cm ³ , and the chlorine atom weight was 370 ppm. The polycarbonate resin obtained here is called PC-3.

[Examples 1 to 10, Comparative Examples 1 to 4] After mixing the components shown in Tables 1 and 2 in a V-type blender based on the amounts shown in the tables, vented twin-screw extrusion with a diameter of 30 mmφ was performed. The mixture was pelletized at a cylinder temperature of 240 ° C. using a machine [TEX30XSST manufactured by Japan Steel Works, Ltd.]. After drying the pellets at 100 ° C. for 5 hours, an injection molding machine [FANU
C-T-150D], cylinder temperature 250 ° C,
Various test pieces were prepared at a mold temperature of 70 ° C. and evaluated. The evaluation results are shown in Tables 1 and 2. In addition, the symbol which shows each component of Table 1 and Table 2 is as follows.

(Component a) PC-1: Polycarbonate resin produced in Reference Example 1 above PC-2: Polycarbonate resin produced in Reference Example 2 above (other than Component a) PC-3: Production in Reference Example 3 above Polycarbonate resin

(B component) ABS-1: After being produced by a bulk polymerization method, a polymer was obtained from a separation and recovery device comprising a multitubular heat exchanger and a decompression chamber.
After that, ABS resin which is granulated into pellets by a multi-stage vent type twin screw extruder. The composition of the ABS resin is 15% by weight of acrylonitrile, 20% by weight of butadiene, and 65% by weight of styrene. The weight average molecular weight of a free acrylonitrile-styrene polymer is 90,000 (standard polystyrene conversion by GPC), and the graft ratio is 55%. The average rubber particle size determined by observation with an electron microscope is 0.80 μm;
The BS resin was dissolved in chloroform, and the amount of residual acrylonitrile monomer measured by liquid chromatography was 250 ppm.

ABS-2: ABS-1 obtained above
Was put into a stainless steel container equipped with a stirring blade, and 7 times (weight ratio) of methanol was added thereto, followed by stirring and washing for 1 hour. Thereafter, vacuum drying was performed at 60 ° C. for 12 hours.
The residual acrylonitrile monomer amount in the ABS resin was 80 ppm.

ABS-3: The ABS-1 obtained above was washed with methanol for 2 hours three times in the same manner as ABS-2, and then vacuum dried at 60 ° C. for 12 hours. The residual acrylonitrile monomer amount in the ABS resin was 20 ppm.

ABS-4: polybutadiene latex 1
Emulsion graft polymerization was carried out at a ratio of 0 parts by weight (solid content), 34.8 parts by weight of styrene, and 5.2 parts by weight of acrylonitrile. The obtained graft copolymer was coagulated with dilute sulfuric acid, washed and filtered, and then dried under vacuum at 60 ° C. for 12 hours. The composition of the ABS resin is 69.5% by weight of acrylonitrile,
20% by weight of butadiene and 10.5% by weight of styrene, free acrylonitrile-styrene polymer having a weight average molecular weight of 120,000 (in terms of standard polystyrene by GPC), graft ratio of 50%, average rubber determined by electron microscopic observation The particle size was 0.40 μm, and the residual acrylonitrile monomer amount measured by liquid chromatography was 50 ppm.

(Component c) FR-1: triphenyl phosphate [Daichi Chemical Co., Ltd.
TPP] FR-2: Resorcinol bis (dixylenyl phosphate) [Daichi Chemical FP-500]

(D component) Talc: Talc [Talc P-3 manufactured by Nippon Talc Co., Ltd., average particle diameter: about 3 μm] Mica: Mica powder [A-41 manufactured by Mika Yamaguchi Co., Ltd.]
Average particle diameter: about 40 μm] WSN: Wollastonite [Kinsei Matek Co., Ltd. W
IC10, average diameter D = 4.5 μm, aspect ratio L / D
= 8]

(Filler other than component d) CF; carbon fiber [Vesfight manufactured by Toho Rayon Co., Ltd.]
HTA-C6-U, PAN system, urethane focusing, diameter 7μ
m]

(Others) PTFE: Polytetrafluoroethylene [F-201L manufactured by Daikin Industries, Ltd.] Rubber: Multistage graft copolymer of methyl methacrylate / 2-ethylhexyl acrylate / butadiene / styrene (styrene content: 15% by weight) %)
[HIA-15 manufactured by Kureha Chemical Industry Co., Ltd.]

[0068]

[Table 1]

[0069]

[Table 2]

As is clear from this table, from the comparison between Examples 1 and 5 and Comparative Example 1, when the specific polycarbonate resin of the present invention was not used, the apparent molecular weight was reduced by wet heat treatment, It can be seen that the impact value is greatly reduced. Also, from Comparative Examples 2 and 4, even when the specific polycarbonate resin of the present invention was used, when the silicate-based filler was not blended, and when other fillers were blended, the apparent heat treatment by wet heat treatment was performed. It can be seen that a decrease in molecular weight and a significant decrease in impact resistance cannot be suppressed. Further, from Comparative Example 3, it can be seen that such a decrease in properties during wet heat is a specific phenomenon when a phosphate ester-based flame retardant is added.

[0071]

Industrial Applicability The polycarbonate resin composition of the present invention is excellent in flame retardancy, impact strength and heat and humidity resistance, and is therefore extremely useful for various industrial uses such as OA equipment and electric and electronic equipment.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 9, 1998 (1998.12.
9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction contents]

(Component c) FR-1: triphenyl phosphate [Daichi Chemical Co., Ltd.
TPP] FR-2: Resorcinol bis (dixylenyl phosphate) [ ADK STAB FP-50 manufactured by Asahi Denka Kogyo Co., Ltd.]
0]

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F071 AA12X AA22 AA22X AA34X AA50 AA77 AB26 AC15 AE07 AE17 AF43 AF47 AG02 BA01 BB05 4J002 BC032 BC042 BC062 BN072 BN102 BN122 BN142 BN152 BN162 CG001 DJ071 017 FD136 GC00 GQ00

Claims (4)

[Claims] 1. A polycarbonate resin containing a chlorine compound of 350 ppm or less in terms of chlorine atom weight (a component) 40 to 92% by weight, a styrene resin (b component) 5 to 5%.
40% by weight, phosphate ester flame retardant (component c) 3 to 2
0% by weight, total 100% by weight of the resin composition 100
Silicate-based filler (d component) 0.1 to parts by weight
A polycarbonate resin composition comprising 30 parts by weight. 2. The polycarbonate resin composition according to claim 1, wherein the component d is at least one selected from the group consisting of talc, mica and wollastonite. 3. The component b is a thermoplastic graft copolymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and the graft copolymer is produced by a bulk polymerization method. 3. The polycarbonate resin composition according to claim 1, wherein the amount of acrylonitrile monomer remaining in the component b is 200 ppm or less. 4. 4. A molded article obtained by melt-molding the polycarbonate resin composition according to claim 1.