JP2001064502A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which yields a molded article having excellent resistance to moist heat and flame resistance. SOLUTION: This resin composition substantially comprises (A) 40-92 wt.% of an aromatic polycarbonate resin, (B) 5-40 wt.% of a styrene-based resin, (C) 3-20 wt.% of a phosphate-based flame retardant and (D) 0.1-30 pts.wt. of a silicate-based filler based on 100 pts.wt. of the total of the components A, B and C, wherein the content of a chlorine compound is 100 ppm or less based on the amount of chlorine atoms.

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 article formed therefrom. More specifically, the present invention relates to a polycarbonate resin composition having excellent wet heat resistance and also excellent flame retardancy, and a molded article formed therefrom.

[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-based resin represented by an ABS resin is widely used in the field of automobiles, OA equipment, electronic and electric equipment, and the like. On the other hand, in recent years, there has been a strong demand for flame-retardant resin molded products to be used, mainly in applications such as OA equipment and home electric appliances. There have been many studies of the conversion.

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 with a polymer alloy of a polycarbonate resin and an ABS resin (Japanese Unexamined Patent Publication No.
No. 32154), a method of blending a phosphate oligomer which is a condensed phosphate ester (JP-A-2-115)
262) and a method of blending a specific inorganic filler and a specific impact modifier (Japanese Patent Application Laid-Open No. 7-126510). On the other hand, in recent years, performance retention during long-term use has become extremely important from the viewpoints of product safety, reduction of environmental load due to prolonged product life, and product guarantee of manufacturers.

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 A first object of the present invention is to provide a resin composition comprising a polymer alloy of a polycarbonate resin and a styrene-based resin and a phosphate ester-based flame retardant. It is to provide a resin composition. A second object of the present invention is to
In a flame-retardant resin composition in which a polymer alloy of a polycarbonate resin and a styrene-based resin is mixed with a polytetrafluoroethylene having a fibril-forming ability as a phosphate ester-based flame retardant and an anti-drip agent, wet heat resistance, impact resistance, An object of the present invention is to provide a polycarbonate resin composition having excellent flame retardancy and coloring properties.

Another object of the present invention is to determine V-0 based on a combustion test according to UL Standard 94V, and to reduce impact strength and molecular weight under a relatively high temperature and high humidity condition. It is to provide a polycarbonate resin molded product.

The present inventors have conducted research to achieve the object of the present invention. As a result, when a phosphate ester-based flame retardant was blended in a polymer alloy of a polycarbonate resin and a styrene-based resin, Polycarbonate resin with excellent flame retardancy and long-term hydrolysis resistance (moisture and heat resistance) by reducing the content of chlorine compounds to a specific amount or less and combining specific types of inorganic fillers The inventors have found that a composition can be obtained, and have reached the present invention.

[0008]

According to the present invention, there are provided (A) an aromatic polycarbonate resin (a component) 40 to 9
2% by weight (B) 5 to 40% by weight of styrene resin (component (b)) (C) 3 to 20% by weight of phosphoric ester-based flame retardant (component (c)) A resin composition substantially consisting of 0.1 to 30 parts by weight of a silicate filler (component (d)) per 100 parts by weight.
The content of chlorine compound in terms of chlorine atomic weight is 100pp
m or less (hereinafter sometimes referred to as “resin composition-I”).

Further, according to the present invention, (A) an aromatic polycarbonate resin (a component) 40 to 9
2% by weight (B) 5 to 40% by weight of styrenic resin (component (b)) (C) 3 to 20% by weight of phosphoric ester-based flame retardant (component (c)) (D) Total of component a, component b and component c 100 0.1 to 30 parts by weight of silicate filler per part by weight (component d) (E) 0.1 to 2 parts by weight of fibril forming ability per 100 parts by weight of the total of components a, b and c And (F) 1 to 10 parts by weight of a (meth) acrylate-based core-shell graft copolymer per 100 parts by weight of the total of the components (a), (b) and (c). f-1 component), which is a more substantial resin composition, wherein the resin composition has a chlorine compound content of not more than 100 ppm in terms of chlorine atom, and is provided as a polycarbonate resin composition (hereinafter, referred to as a polycarbonate resin composition). , This composition "resin Composition-II "). In the present invention, when simply referred to as "resin composition",
The above-mentioned resin compositions -I and -II are collectively referred to.

The present invention provides a composition comprising a polycarbonate resin, a styrene-based resin and a phosphate ester-based flame retardant, wherein the content of a chlorine compound is converted to chlorine atoms by 1%.
By controlling the content to not more than 00 ppm and incorporating a certain amount of a silicate filler, the wet heat resistance (hydrolysis resistance) is improved, and further, a resin composition in which the impact strength over a long period of time is extremely reduced can be obtained. Hereinafter, the polycarbonate resin composition of the present invention will be described more specifically. First, the components constituting the resin composition will be described in detail.

(A) Polycarbonate Resin (Component a) The polycarbonate resin in the component a of the present invention is 2
Polycarbonate resin obtained by reacting a divalent phenol with a carbonate precursor, that is, an aromatic polycarbonate resin. Representative 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, and 1,1-bis ( 4
-Hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) 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, and dibischloroformate of dihydric phenol. In producing the polycarbonate resin by reacting the dihydric phenol with the carbonate precursor, the dihydric phenol may be used alone or in combination of two or more, and the polycarbonate resin is a mixture of two or more polycarbonate resins. There may be.

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 (η _sp ) 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. η _sp /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)

An interfacial polymerization method (solution 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. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction. 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, and the reaction time is 10 minutes to 5 minutes.
Preferably, the pH during the reaction is maintained at 9 or more during the reaction. It is not necessary that all of the resulting molecular chain ends have a structure derived from the terminator.

In the transesterification reaction (melt polymerization method) using a 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 a carbonic acid diester in an inert gas atmosphere. Then, it is carried out by a method of distilling off the alcohol or phenols produced. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 350 ° C. The reaction is completed under reduced pressure from the beginning while distilling off alcohol or phenols produced. In order to promote the reaction, a catalyst used in known transesterification reactions such as an alkali metal compound and a nitrogen-containing basic compound can also be used. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate,
Examples include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and the like. 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 may be one produced by any of the above-mentioned interfacial polymerization method and melt polymerization method. However, the present invention is suitable for using a polycarbonate resin produced by an interfacial polymerization method as the component a. The reason will be described below. As described above, in the polycarbonate resin produced by the interfacial polymerization method, a solvent and a modified product thereof, a catalyst, a catalyst deactivator and a modified product thereof, and a chlorine compound such as a reaction by-product remain in a small amount. ing. This residual chlorine compound is removed to some extent by purification, but slight residual chlorine compound cannot be avoided. The present inventor believes that the presence of a chlorine compound derived mainly from a polycarbonate resin interacts with a phosphate ester (c component) as a flame retardant in the composition to cause hydrolysis of the composition. Was. However, in the present invention, by further blending a silicate filler, even when a chlorine compound is present to some extent due to the polycarbonate resin in which the chlorine compound remains, hydrolysis is significantly suppressed,
This makes it possible to improve the resistance to moist heat. On the other hand, in order to further improve the moist heat resistance, the content of the chlorine compound in the polycarbonate resin as a main component was reduced in order to suppress the content of the chlorine compound in the composition. As a result, the content of the chlorine compound in the resin composition is 100 ppm or less, preferably 90 ppm or less in terms of chlorine atoms,
It has been found that it is particularly preferable that the content be 50 ppm or less.

In the composition of the present invention, the content of the chlorine compound may be kept within the above range, and the chlorine compound is
It may be mixed from any component. However, as described above, the polycarbonate resin (a component) is a component that occupies the main proportion of the resin composition of the present invention, and a chlorine compound remains due to the production method. Those having a low content of chlorine compounds should be used.

The content of the chlorine compound in the polycarbonate resin to be used depends on the proportion of the polycarbonate resin (component (a)) in the composition of the present invention and the content of the chlorine compound in the other components. Converted to 10
0 ppm or less, preferably 90 ppm or less, particularly preferably 20 ppm or less is advantageous.

In order to obtain such a polycarbonate resin containing a low chlorine compound, 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 a conventionally known various method such as a method of performing a chlorine compound, a method of precipitating a non-solvent of a polycarbonate resin solution, and a method of further enhancing a drying treatment.

Further, an organic solvent solution of the polycarbonate resin is continuously supplied to a container containing a mixture of the polycarbonate resin particles and warm water with stirring, and the solvent is evaporated to obtain the polycarbonate resin. In the method for producing polycarbonate resin particles from an organic solvent solution of the above, the temperature in the container is set to T
₁ (° C.) or T ₂ (° C.), stirring speed is 60-100 rpm, and stirring capacity is 5-10 k
The production method characterized by w / hr · m ³ is preferable 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.) ≦ 0.1
0018 × M ₁ +42 (M ₁ : viscosity average molecular weight 10,000 to 20,000) 0.0007 × M ₂ + 59 ≦ T ₂ (° C.) ≦ 0.0007 × M
₂ +64 (M ₂ : viscosity average molecular weight 20,000 or more) The content of chlorine atoms in the polycarbonate resin composition and the like according to the present invention is determined by using a PIX-2000 fully automatic fluorescent X-ray analyzer manufactured by Rikagaku Electric Industry Co., Ltd. This is a value measured by an analytical method using the fluorescent X-ray used.

(B) Styrene resin (component b) The styrene resin used as the component b in the present invention refers to styrene or α-based resin per 100% by weight of the resin.
The ratio obtained from the styrene monomer of methylstyrene or vinyltoluene is 20% by weight or more, preferably 25% by weight.
Refers to a resin containing by weight. Accordingly, examples of the styrene-based resin include homopolymers of such styrene-based monomers or mutual copolymers of these monomers, and copolymers of these styrene-based monomers with vinyl monomers such as acrylonitrile and methyl methacrylate. Further, a diene rubber such as polybutadiene, an ethylene / propylene rubber, an acrylic rubber, a composite rubber having a structure in which a polyorganosiloxane component and a poly (meth) alkyl acrylate component are entangled with each other so that they cannot be separated. Examples of the rubber component include those obtained by graft polymerization of a styrene monomer or a styrene monomer and a 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) and the like, or a mixture thereof. In the copolymer and the mixture, the styrene-based monomer component contains 2% of the styrene-based resin in 100% by weight.
0% by weight or more is contained. As such various polymers, those produced by various polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and bulk suspension polymerization can be used, and even if the copolymerization method is copolymerized in one step, It may be copolymerized in multiple stages.

As the component b of the present invention, among these, polystyrene, impact-resistant polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS)
Resin) is preferable, and ABS resin is most preferable from the viewpoint of impact resistance. 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 as the component (b) of 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, usually forming a mixture with another polymer by-produced during graft polymerization of an AS resin or the like. Is what it is. Further, mixtures of such ABS resins and separately polymerized AS resins are widely used industrially. Such A
As the diene rubber component forming the BS 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 5% in 100% by weight of the ABS resin component.
Preferably it is ~ 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 50% by weight and the aromatic vinyl compound is 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Is 50 to 95% by weight. 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 may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization. It is more preferable in terms of doing. Although the cause has not been fully elucidated, emulsion polymerization,
Whether metal salt components such as emulsifiers used in suspension polymerization directly affect hydrolysis caused by phosphate esters,
Alternatively, it is conceivable that the compound may act on a chlorine compound remaining in the polycarbonate resin composition to affect hydrolysis.

According to the study of the present inventor, when a styrenic resin (in particular, an ABS resin) containing acrylonitrile as a monomer constituent unit as the component b is used, the content of the acrylonitrile monomer remaining in the resin is small. Those have been found to be preferred. That is, it has been found that when the acrylonitrile monomer mainly derived from the component b is contained in the resin composition of the present invention in an amount exceeding 50 ppm, it has an undesirable effect on the wet heat resistance of the resin composition. The reason is not clear,
It is presumed that the acrylonitrile monomer acts on the phosphate ester (c component) or the chlorine compound in the resin to affect the hydrolysis of the polycarbonate resin.

Advantageously, the content of acrylonitrile monomer contained in the resin composition of the present invention is 50 ppm or less, preferably 30 ppm or less, most preferably 20 ppm or less.

In order to reduce the content of the acrylonitrile monomer in the resin composition to the above ratio, a resin having a low acrylonitrile monomer content is used as a styrene resin containing acrylonitrile as a monomer constituent unit (particularly an ABS resin). This is the simplest means. The acrylonitrile monomer content in the component b is
Although mainly depends on the ratio of the component b in the resin composition,
Those satisfying the conditions of usually 200 ppm or less, more preferably 100 ppm or less, and particularly preferably 50 ppm or less are desirable. When the amount of the residual acrylonitrile monomer satisfies these amounts, the acrylonitrile monomer content in the resin composition can be in the above range, and more favorable wet heat resistance can be satisfied. Therefore, a styrene resin (particularly an ABS resin) containing acrylonitrile as a monomer constituent unit is more preferably a styrene resin having an acrylonitrile monomer content of 2%.
It is at most 00 ppm, more preferably at most 100 ppm, particularly preferably at most 50 ppm, and is produced by a bulk polymerization method.

(C) Phosphate Ester Flame Retardant (Component (c)) The resin composition of the present invention contains a phosphate ester flame retardant for the purpose of achieving high flame retardancy without containing a halogen-containing flame retardant. It is blended. The component c may be a phosphate ester flame retardant used as a non-halogen flame retardant for a polycarbonate resin. A preferred phosphate ester flame retardant is represented by the following formula (1).

[0029]

Embedded image

Wherein X represents a residue of an aromatic dihydroxy compound, j, k, l and m each independently represent 0 or 1, n represents 0 or an integer of 1 to 5,
R ₁ , R ₂ , R ₃ and R ₄ each independently represent an aromatic monohydroxy compound residue.

In the above formula (1), j, k, l and m each independently represent 0 or 1.
Preferably, l and m are both 1. N represents 0 or an integer of 1 to 5, and is preferably 0 or an integer of 1 to 3. Particularly preferred is 0 or 1. Usually n is given as the average value in a mixture of n different phosphate esters. Accordingly, n can be represented as an average value of 0 to 5, preferably 0 to 3.
X represents a residue of an aromatic dihydroxy compound, and R ₁ , R ₂ , R ₃ and R ₄ each independently represent a residue of an aromatic monohydroxy compound. Here, the residue means a group obtained by removing two OH groups or one OH group from a dihydroxy compound or a monohydroxy compound, respectively. For example, the residue (X) of bisphenol A is

[0032]

Embedded image It is represented by

Specific examples of X include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl)
Examples include the residues of sulfone, bis (4-hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide, of which the residues of hydroquinone, resorcinol and bisphenol A are preferred. On the other hand, specific examples of R ₁ , R ₂ , R ₃ and R ₄ include the residues of phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol. Of these, phenol, cresol and xylenol Are preferred, and phenol and xylenol residues are particularly preferred.

The phosphate ester flame retardant as the component c is triphenyl phosphate as a monophosphate compound, resorcinol bis (dixylenyl phosphate) as a condensed phosphate ester, and has good flame retardancy and is suitable for molding. Can be preferably used because of its good fluidity.

(D) Silicate Filler (d Component) In the present invention, the silicate filler as the d component is an inorganic filler containing 35% by weight or more of a SiO ₂ component due to its chemical composition, preferably Means an inorganic filler containing at least 40% by weight. Specific examples of such silicate fillers include kaolin, talc, clay, pyrophyllite, mica, montmorillonite, bentonite, wollastonite, sepiolite, zonotolite, natural silica, synthetic silica, various glass fillers, zeolite, and diatomaceous earth. And halloysite, or a mixture thereof.

In particular, in the resin composition of the present invention,
Talc, mica, wollastonite, etc., from the viewpoint that the point of action for suppressing hydrolysis can be increased by finely dispersing the filler, and the reinforcing effect on the resin is also important from the viewpoint of imparting flame retardancy. Or mixtures thereof can be mentioned as preferred fillers. Among them, talc is most preferable.

The mica as the component d is preferably a powder having an average particle diameter 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, etc., and any mica can be used as the mica. Rather, muscovite having a higher SiO ₂ content is preferred. 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. In the present invention, there is a wet pulverization method in which dewatering and drying are performed, and a dry pulverization method is more common at a lower cost, but it is difficult to pulverize mica thinly and finely. It is preferable to use mica manufactured by the following 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 diameter 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, those having a thickness of 0.01 to 1 μm actually measured by observation with an electron microscope can be used. Preferably, the thickness is from 0.03 to 0.3 μm. Further, the mica may be surface-treated with a silane coupling agent or the like, and may be granulated with an epoxy-based, urethane-based, acrylic-based binder, or the like to be granulated. 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 in the market.

The talc as the d component is preferably a 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 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 a high SiO ₂ component amount, the content of Fe ₂ O ₃ as an impurity tends to be relatively small, so that such talc is also advantageous in terms of hue. Also, there is no particular limitation on the production method when such talc is crushed from a rough stone, such as 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 handling properties and the like.Examples of such a production method include a method using deaerated compression, a method using a binder resin and compression, and the like.
In particular, the degassing compression method is preferred because it is simple and does not mix unnecessary binder resin components into the composition of the present invention.

Wollastonite as the d component is a natural white mineral having needle-like crystals mainly composed of calcium silicate, and is substantially represented by the chemical formula CaSiO ₃ , usually about 50% by weight of SiO _2. , CaO contains about 47% by weight, Fe ₂ O ₃ , Al ₂ O _3, etc., and the specific gravity is about 2.
9

The wollastonite has a particle size distribution of 75% or more for 3 μm or more, 5% or less for 10 μm or more, and an aspect ratio L / D (length / diameter) of 3 or more, particularly an L / D of 8 or more. Is preferred. In the particle size distribution, 3% or more is 75% or more, and 10 μm or more is 5% or more.
%, The reinforcing effect is sufficient, the flame retardancy is easily increased, and the resin is finely dispersed in the resin, and the wet heat resistance is also improved. 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, preferably 40 or less are more advantageous. 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.

The resin composition I of the present invention contains four essential components a, b, c and d. The mixing ratio of these essential components in the resin composition-I will be described. The mixing ratio of the components a, b and c in the resin composition is represented based on the total weight of the three components. The component a is 4 per 100% by weight of the total of the three components.
0 to 92% by weight, b component is 5 to 40% by weight, c component is 3%
-20% by weight. Component a is less than 40% by weight or b
When the amount of the component exceeds 40% by weight, heat resistance (particularly, deflection temperature under load) and mechanical strength are reduced. Also,
Component a exceeds 92% by weight or component b is 5% by weight
If it is less than 3, the fluidity is reduced and the moldability is reduced. Further, if the amount of the component c is less than 3% by weight, sufficient flame retardancy cannot be obtained. . The preferable mixing ratio of the component a, the component b and the component c is 50 to 88% by weight of the component a, 7 to 35% by weight of the component b and 5 to 15% by weight of the component c.

In the present invention, the proportion of the component d is 0.1 per 100 parts by weight of the total of the components a, b and c.
To 30 parts by weight, preferably 0.5 to 20 parts by weight. If the proportion of the d component is less than 0.1 part by weight,
There is no effect of improving the moist heat resistance. When the amount exceeds 30 parts by weight, the effect on the moist heat resistance is saturated, but the impact strength is lowered and the surface appearance of the obtained molded product is unfavorably deteriorated.

The resin composition I of the present invention may further contain polytetrafluoroethylene (component e) having a fibril-forming ability 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 a fibril-forming ability has a drip-preventing performance at the time of a combustion test of a test piece in a vertical burning test of UL standard. It is commercially available as Teflon 6J from Fluorochemicals Co., Ltd. or as polyflon from Daikin Chemical Industries, Ltd. and can be easily obtained. The compounding amount of polytetrafluoroethylene having a fibril-forming ability is the above-mentioned component a, component b and c
The amount is preferably 0.1 to 2 parts by weight based on 100 parts by weight of the total of the three components. If the amount is less than 0.1 part by weight, it is difficult to obtain sufficient melting drop prevention performance, and if it exceeds 2 parts by weight, the appearance is deteriorated. The proportion of the component e is particularly preferably 0.1 to 1 part by weight.

As such polytetrafluoroethylene, in addition to the usual solid form, aqueous emulsion and dispersion forms can also be used. However, since the dispersant component tends to have an adverse effect on wet heat resistance, it is particularly preferable to use a solid state. Those can be preferably used. In addition, polytetrafluoroethylene having such fibril-forming ability improves dispersibility in a resin, and in order to obtain better appearance and mechanical properties, an emulsion of polytetrafluoroethylene and an emulsion of a vinyl polymer are used. Aggregated mixtures can also be mentioned as a preferred form.

Here, as the vinyl polymer, polypropylene, polyethylene, polystyrene, HIPS, AS
Resin, ABS resin, MBS resin, MABS resin, AAS
Resin, polymethyl (meth) acrylate, a block copolymer composed of styrene and butadiene and a hydrogenated copolymer thereof, a block copolymer composed of styrene and isoprene, and a hydrogenated copolymer thereof, an acrylonitrile-butadiene copolymer, Ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, ethylene and α-olefin copolymer, ethylene-unsaturated carboxylic acid such as ethylene-butyl acrylate Copolymers with esters, acrylate-butadiene copolymers such as butyl acrylate-butadiene, rubbery polymers such as polyalkyl (meth) acrylates, composite rubbers containing polyorganosiloxanes and polyalkyl (meth) acrylates, Or even That the composite rubber styrene, acrylonitrile, a vinyl monomer of polyalkyl methacrylate and the like and a copolymer obtained by grafting.

Among these, from the viewpoint of compatibility with the component b, composite rubbers containing polystyrene, HIPS, ABS resin, AAS resin, polymethyl methacrylate, polyorganosiloxane and polyalkyl (meth) acrylate, and such composite rubbers A copolymer obtained by grafting a vinyl-based monomer such as styrene, acrylonitrile, or polyalkyl methacrylate is more preferable, and a polymer of the same type as the component b is more preferably used.

In order to prepare such an agglomerated mixture, an aqueous emulsion of the component (b) having an average particle size of 0.01 to 1 μm, particularly 0.05 to 0.5 μm, is prepared by adding an average particle size of 0.0 to 0.5 μm.
It is mixed with an aqueous emulsion of polytetrafluoroethylene having a size of 5 to 10 μm, in particular 0.05 to 1.0 μm.
Such an emulsion of polytetrafluoroethylene,
It is obtained by polymerizing polytetrafluoroethylene by emulsion polymerization using a fluorinated surfactant. In addition,
At the time of such emulsion polymerization, another copolymerization component such as hexafluoropropylene is added to 10% of the whole polytetrafluoroethylene.
It is also possible to copolymerize at less than weight%.

When obtaining such an agglomerated mixture, a suitable polytetrafluoroethylene emulsion usually has a solids content of 40 to 70% by weight, especially 50 to 65% by weight, and the styrene-based component b The resin emulsion used has a solid content of 25 to 60% by weight, particularly 30 to 45% by weight. Further, the proportion of polytetrafluoroethylene in the aggregated mixture is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, based on 100% by weight of the total with the vinyl polymer used in the aggregated mixture. After mixing the above-mentioned emulsions, stirring, mixing, throwing into hot water in which a metal salt such as calcium chloride, magnesium sulfate or the like is dissolved, salting out, and coagulation to separate and collect the emulsion, are preferred. Other examples include a method of recovering the stirred mixed emulsion by a method such as spray drying and freeze drying.

Various forms of agglomerated mixtures of polytetrafluoroethylene emulsions having a fibril-forming ability and vinyl polymer emulsions can be used. For example, a vinyl-based emulsion may be formed around polytetrafluoroethylene particles. Examples include a form in which a polymer is surrounded, a form in which a polytetrafluoroethylene is surrounded around a vinyl-based polymer, and a form in which several particles are aggregated with respect to one particle.

Further, a mixture in which the same or another type of vinyl monomer is graft-polymerized on the outer layer of the aggregated mixture can also be used. As such a vinyl monomer,
Styrene, α-methylstyrene, methyl methacrylate,
Cyclohexyl acrylate, dodecyl methacrylate, dodecyl acrylate, acrylonitrile, acrylic acid-2
-Ethylhexyl can be mentioned preferably, and these can be used alone or copolymerized.

As a commercially available coagulated mixture of the above-mentioned polytetrafluoroethylene emulsion having a fibril-forming ability and an emulsion of a vinyl polymer, methabrene “A3000” may be mentioned as a representative example from Mitsubishi Rayon Co., Ltd. It can be mentioned as a preferred form of the component e of the present invention.

The resin composition I of the present invention may contain a rubbery polymer (component f) for the purpose of improving the impact resistance, especially at low temperatures. Such rubbery polymers include:
Examples include (meth) acrylate-based core-shell graft copolymers, polyurethane-based elastomers, and polyester-based elastomers. Resin composition-
When the rubbery polymer (component f) is further blended with I, the ratio is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, per 100 parts by weight of the total of the components a, b and c. preferable.

As described above, the rubbery polymer as the component f includes a (meth) acrylate-based core-shell graft copolymer (component f-1), a polyurethane-based elastomer (component f-2) and A polyester-based elastomer (f-3 component) can be mentioned as a typical example.

The (meth) acrylic acid ester-based core-shell graft copolymer (component (f-1)) has 2 carbon atoms.
Alkyl (meth) acrylate and optionally copolymerizable vinyl monomer in a core with a copolymer or mixture with a rubbery alkyl (meth) acrylate polymer having an alkyl group of from 8 to 8 and a diene rubbery polymer A core-shell polymer in which a shell obtained by polymerizing a body is formed, and a multi-stage core-shell polymer in the same manner can also be used. Also, a core composed solely of a diene rubbery polymer can be used. Such a (meth) acrylate core-shell graft polymer is available from Kureha Chemical Industry Co., Ltd.
Resins available under the trade names "HIA-15" and "HIA-28" from Kureha Chemical Industry Co., Ltd. Name "PARALOID EXL-2
602 ".

Further, as the f-1 component, the composite rubber having a structure in which the polyorganosiloxane component and the poly (meth) alkyl acrylate component are entangled with each other so as not to be separable is added to the alkyl (meth) acrylate and optionally the co-polymer. A polymer obtained by graft polymerization of a polymerizable vinyl monomer (hereinafter referred to as an IPN-type polymer) can also be used. Such an IPN-type polymer is commercially available from Mitsubishi Rayon Co., Ltd. under the trade name "METABLEN S-2001", and is easily available. The f-1 component will be described in further detail later.

As other examples of the rubbery polymer (component f), a polyurethane elastomer (component f-2) includes:
It is obtained by the reaction of an organic polyisocyanate, a polyol, and a chain extender having 2 to 3 functional groups and a molecular weight of 50 to 400, and various known thermoplastic polyurethane elastomers can be used. Such a thermoplastic polyurethane elastomer is easily available, for example, “Kuramilon U” (trade name) manufactured by Kuraray Co., Ltd.

As a polyester elastomer (f-3 component) as still another example of the rubbery polymer (f component), a bifunctional carboxylic acid component, an alkylene glycol component, and a polyalkylene glycol component are polycondensed. And various known thermoplastic polyester elastomers 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.

According to the study of the present inventor, further studies on the improvement of the physical properties of the above-mentioned resin composition-I were carried out. As a result, the resin composition containing a component, b component, c component and d component as essential components A composition in which polytetrafluoroethylene (component (e)) having a fibril-forming ability and a (meth) acrylate-based core-shell graft copolymer (component (f-1)) having a specific ratio are further blended with product-I. Have been found to have even better properties.

Thus, according to the present invention, the following resin composition-II is provided. (A) Aromatic polycarbonate resin (a component) 40 to 9
2% by weight (B) 5 to 40% by weight of styrenic resin (component (b)) (C) 3 to 20% by weight of phosphoric ester flame retardant (component (c)) (D) Total of component a, component b and component c 100 0.1 to 30 parts by weight of silicate filler (d component) per part by weight (E) 0.1 to 2 parts by weight of fibril forming ability per 100 parts by weight of the total of component a, component b and component c And (F) 1 to 10 parts by weight of a (meth) acrylate-based core-shell graft copolymer per 100 parts by weight of the total of the components (a), (b) and (c). f-1 component), which is a more substantial resin composition, wherein the resin composition has a chlorine compound content of 100 ppm or less in terms of chlorine atoms.

The resin composition-II of the present invention is characterized in that the above-described resin composition-I further comprises an e component and a specific f component as essential components. Thus, in the resin composition-II, the component a, the component b, the component c, and the component d are substantially the same as the resin composition-I and are used in the same ratio. The e component is the resin composition
The compounds described as optional components of I are used in the same proportions. In the resin composition-II, a (meth) acrylate-based core which is one kind of a rubbery polymer (component (f))
The shell graft copolymer (component f-1) is used as an essential component. The f-1 component is used in an amount of 0.1 to 10 parts by weight, preferably 2 to 8 parts by weight, per 100 parts by weight of the total of the components a, b and c.

Next, the f-1 component will be described in detail.
The (meth) acrylate-based core-shell graft copolymer (component (f-1)) refers to one containing an acrylate or a methacrylate as an essential component of the core or the shell.

The form of the core of the (meth) acrylic ester-based core-shell graft copolymer may be one in which the core component is composed of a homopolymer of one kind of monomer, or two or more kinds of monomers. A structure composed of a polymer and a structure in which two or more homopolymers and copolymers are intertwined with each other, a so-called IPN (Inter-Penetrating-Net)
work), and any form can be used.

The proportion of the core in the (meth) acrylate-based core-shell graft copolymer, that is, the proportion of the rubber component, must be 30% by weight or more, preferably 40% by weight or more, particularly preferably 40% by weight or more. It is preferably at least 50% by weight. On the other hand, the upper limit is 95% by weight or less, preferably 90% by weight or less, particularly preferably 85% by weight or less. The portion other than the core ratio constitutes the shell.

The average particle diameter of the core is 0.08.
It is preferably in the range of ~ 0.6 µm. If the average particle size is less than 0.08 μm, the improvement in impact resistance is insufficient, and if it exceeds 0.6 μm, the appearance of the surface of the molded product is deteriorated. On the other hand, the shell form of the (meth) acrylate-based core-shell graft copolymer may be one in which a homopolymer of one type of monomer is graft-polymerized, and two or more types of monomers are simultaneously graft-copolymerized. In addition to those described above, those obtained by multistage grafting in which graft polymerization of one or more kinds of monomers is performed in multiple stages can be mentioned, and any form can be used.

The (meth) acrylic acid ester-based core-shell graft copolymer as the component f-1 can be combined with any of the above-mentioned forms of the core and the shell. Such cores include acrylic rubber, butadiene rubber, isoprene rubber, styrene-
Butadiene rubber, butyl rubber, ethylene-propylene-
Diene rubber, chloroprene rubber, nitrile rubber, silicone rubber, epichlorohydrin rubber and the like can be used. Among such rubber components, butadiene rubber, isoprene rubber, styrene-butadiene rubber, and acrylic rubber are preferable in terms of impact resistance, and butadiene rubber is particularly preferable.

Further, acrylate, methacrylate, butadiene, isoprene, isobutylene, ethylene, propylene, α-olefin, ethylidene norbornene, dicyclopentadiene and styrene
Copolymer rubbers with more than one type of monomer can be used as the core. This copolymer rubber has impact resistance, flame retardancy,
The copolymer rubber component can be preferably used in view of better balance of wet heat resistance and the like, and from such a viewpoint, among such copolymer rubber components, acrylate and / or methacrylate and butadiene, isoprene, isobutylene, ethylene, propylene, α-olefin From ethylene, ethylidene norbornene, dicyclopentadiene and styrene
A copolymer rubber with at least one kind of monomer is preferable, and a copolymer of acrylate and / or methacrylate with butadiene and / or isoprene is particularly preferable, and acrylate and / or isoprene are particularly preferable.
Alternatively, it is a copolymer of methacrylate and butadiene.

Further, a silicone rubber component and any one of a rubber component selected from an acrylic rubber component, a butadiene rubber component, an isoprene rubber component, an isobutylene rubber component, an ethylene-propylene-diene rubber component, and a copolymerization component of these components are used. IPN rubber having a structure entangled with each other so that it cannot be separated from each other can be used. Such an IPN rubber is excellent in flame retardancy by containing a silicone rubber component, and also excellent in impact resistance and the like due to its entangled structure with other rubber components. Such IP
Among N rubbers, IPN comprising a silicone rubber component, an acrylic rubber component and / or an isobutylene rubber component
Rubber is preferable, and more preferably, IPN rubber having a structure in which the silicone rubber component and the acrylic rubber component are entangled with each other so that they cannot be separated.

On the other hand, as the monomer component forming the shell, one or more selected from acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds and vinyl cyanide compounds, and copolymerizable with them. Other monomers can be used. Here, other copolymerizable monomers include maleic anhydride, maleimide, N-
Methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like can be mentioned.

The acrylic or methacrylic ester used for the acrylic rubber, copolymer rubber, or IPN rubber in the core of the (meth) acrylic ester-based core-shell graft copolymer of the f-1 component is carbon Those having a number of 2 to 12 alkyl groups are preferred. Specifically, examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. Among them, n-butyl acrylate, 2-ethylhexyl Acrylates are preferred. Examples of the methacrylate include hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate.

Examples of the organosiloxane used for the silicone rubber and the IPN rubber in the core of the (meth) acrylate-based core-shell graft copolymer of the f-1 component include various cyclic members having three or more ring members. And preferably used are 3- to 6-membered rings. For example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like, These can be used alone or 2
Used as a mixture of more than one species.

The acrylate or methacrylate in the shell of the (meth) acrylate-based core-shell graft copolymer of the f-1 component includes:
Those having an alkyl group having 1 to 8 carbon atoms are preferred. Specifically, examples of the acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, hydroxyethyl acrylate, cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate, and examples of the methacrylate include methyl methacrylate. , Ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like. Of these, methyl methacrylate is more preferred.

Examples of the aromatic vinyl compound in the shell of the (meth) acrylate-based core-shell graft copolymer of the f-1 component include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene and the like. Among them, styrene is preferable. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, among which acrylonitrile is preferable.

In the (meth) acrylate-based core-shell graft copolymer of the component f-1, it is possible to use a crosslinking monomer or a graft-crosslinking agent in the core or shell. In the case where the component is not contained, it is more preferably used.

Examples of the crosslinkable monomer corresponding to the acrylate or methacrylate include aromatic divinyl compounds such as divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
Examples thereof include 1,4-butylene glycol dimethacrylate and allyl methacrylate. Among them, allyl methacrylate and ethylene glycol dimethacrylate are preferable. Examples of the graft crosslinking agent corresponding to an acrylic ester or a methacrylic ester include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like.

Examples of the crosslinking monomer corresponding to the organosiloxane include trifunctional or tetrafunctional silane compounds, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-silane. Propoxysilane and tetrabutoxysilane are used. Particularly, a tetrafunctional crosslinking monomer is preferable, and among them, tetraethoxysilane is particularly preferable. As the graft-linking agent corresponding to the organosiloxane, a compound capable of forming units represented by the following formulas (2), (3) and (4) is used.

[0079]

Embedded image (In each formula, R ¹ is a methyl group, an ethyl group, a propyl group or a phenyl group, R ² is a hydrogen atom or a methyl group, n is 0,
1 or 2, p represents the number of 1-6. )

Acryloyloxysiloxane or methacryloyloxysiloxane capable of forming the unit of the formula (2) has a high grafting efficiency, so that an effective graft chain can be formed and is advantageous in terms of exhibiting impact resistance. Note that methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the formula (2). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.
Examples include methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and δ-methacryloyloxybutyldiethoxymethylsilane. F-
Among the (meth) acrylate-based core-shell graft copolymers as one component, the following graft copolymers are more preferred.

As a preferred graft copolymer core, (i) a rubber composed of 60 to 100% by weight of butadiene and 0 to 40% by weight of styrene in total of 100% by weight, (ii) 60 to 90% by weight of an acrylate ester and 10 to 10% by weight of butadiene. A copolymer rubber composed of 100% by weight of a total of 40% by weight, or (iii) a polymer component 5 composed of 5-95% by weight of an organosiloxane polymer component and an acrylate and / or methacrylate.
９５95% by weight of a composite rubber having a structure entangled with each other so as to be inseparable, and a total of 100% by weight of 40 to 90% by weight of a composite rubber, and acrylic acid ester, methacrylic acid ester as a shell, (Meth) acrylic acid ester-based core-shell graft copolymer comprising 10 to 60% by weight of a polymer or copolymer comprising one or more monomers selected from aromatic vinyl compounds and vinyl cyanide compounds Polymer. In the “preferred graft copolymer”, the following graft copolymers (1) to (3) are particularly preferred embodiments.

Graft copolymer (1) As a core, (i) 40 to 90% by weight of a rubber composed of 100 to 100% by weight of butadiene and 60 to 40% by weight of styrene, and methacrylic acid ester as a shell are essential. One or more monomers 10 selected from aromatic vinyl compounds, acrylic acid esters and vinyl cyanide compounds, if necessary.
〜60% by weight of a copolymer graft-polymerized by a method such as bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization, particularly emulsion polymerization (hereinafter referred to as “graft copolymer (1)”). May be called).

The proportion of the core of the graft copolymer (1) is
60 to 85% by weight is more preferable, and further preferably 6 to 85% by weight.
5 to 80% by weight. The proportion of such a core is 60 to 85
In the case of weight%, it is possible to achieve both improved impact resistance and better flame retardancy. Butadiene rubber is more preferred as the core.

As the shell, a total of 10 to 100% by weight of methacrylic acid ester and 0 to 70% by weight of aromatic vinyl compound and / or acrylic acid ester is used.
A polymer or copolymer consisting of 0% by weight is preferable,
As the methacrylate, methyl methacrylate is preferred. Particularly preferably methyl methacrylate 60-
It is a polymer or copolymer composed of 100% by weight and 10 to 40% by weight of an acrylate such as ethyl acrylate.

Therefore, it is particularly preferable that the graft copolymer (1) has a total amount of 100% by weight of the copolymer.
A polymer or copolymer consisting of 65 to 80% by weight of butadiene rubber as a core and 60 to 100% by weight of methyl methacrylate and 0 to 40% by weight of an acrylate such as ethyl acrylate in 100% by weight of the total amount of the shell as a shell. It is a graft copolymer consisting of 20 to 35% by weight.

The graft copolymer (1) has a butadiene rubber component having a high effect of improving impact resistance as a main component of the core, and is therefore advantageous for improving impact resistance. Therefore, when a condensed phosphate ester whose impact resistance is slightly reduced is used, that is, when n is not 0 as an average value in the above formula (1), preferably when n is 0.5 to 3, it is used in combination. Is preferred.

Graft Copolymer (2) Acrylic ester, based on 40 to 90% by weight of copolymer rubber consisting of 60 to 90% by weight of acrylate ester and 10 to 40% by weight of butadiene in total,
The shell comprises 10 to 60% by weight of one or more selected from methacrylic acid esters, aromatic vinyl compounds, and vinyl cyanide compounds grafted by one or two or more stages of graft polymerization. A copolymer composed of a total of 100% by weight of the shell (hereinafter sometimes referred to as "graft copolymer (2)"). More preferably, the core has 50 to 75% by weight and the shell has 25 to 50% by weight.
% By weight, more preferably 5% by weight.
0 to 70% by weight and 30 to 50% by weight of the shell.

The ratio of acrylate to butadiene in the core is such that 60 to 80% by weight of acrylate and 2% by weight of butadiene in 100% by weight of the total amount of the core.
0 to 40% by weight is more preferred. The core may be copolymerized with another copolymerizable monomer, preferably methacrylate or aromatic vinyl, in a range of 20% by weight or less based on 100% by weight of the total core. .

The graft copolymer (2) has weather resistance,
Resin with excellent balance of properties such as flame retardancy, impact resistance, weather resistance, and colorability, because the core contains a well-balanced acrylic ester component with good flame retardancy and a butadiene component with excellent impact resistance. It is possible to obtain a composition.

As the acrylate ester used for the core of the graft copolymer (2), n-butyl acrylate and 2-ethylhexyl acrylate are preferably used, and 2-ethylhexyl acrylate is particularly preferable.
As the methacrylate used for the shell, methyl methacrylate is particularly preferred. Further, the average particle size of the core of the graft copolymer (2) is 0.08.
~ 0.25 µm, more preferably 0.13 µm
０0.20 μm.

The shell in the graft copolymer (2) is a polymer or copolymer composed of one or more selected from aromatic vinyl compounds, vinyl cyanide compounds, methacrylic esters and acrylic esters. However, particularly, those containing an aromatic vinyl compound and a methacrylic acid ester are preferable in order to take advantage of the excellent characteristics of the above-mentioned cores, and it is particularly preferable to contain a methacrylic acid ester.

Here, the ratio of each monomer in the shell of the graft copolymer (2) is 100% of the total amount of the shell.
The methacrylic acid ester content is preferably 45 to 80% by weight, more preferably 55 to 70% by weight. Therefore, the content of the aromatic vinyl compound and other components is preferably 20 to 55% by weight, more preferably 30 to 55% by weight.
~ 45% by weight. Further, when a vinyl cyanide compound or an acrylate ester is contained, the proportion thereof is 20 to 20% by weight in total with the aromatic vinyl compound.
It is preferably 35% by weight, more preferably 22 to 30% by weight. As such another component, a vinyl cyanide compound is more preferable.

Further, as the shell of the graft copolymer (2) of the present invention, the shell of the graft copolymer comprises two-stage graft polymerization, and the first-stage graft component comprises an aromatic vinyl compound and a methacrylic acid ester. Or a mixture of an aromatic vinyl compound, a vinyl cyanide compound and a methacrylic acid ester, and the second-stage graft component is composed of a methacrylic acid ester, and Total 1
40 to 75% by weight of the first stage graft component in 00% by weight
And those having a second stage graft component of 25 to 60% by weight can be preferably used. Furthermore, the first-stage graft component contained 42 to 70% by weight and the second-stage graft component contained 3 to 3% by weight.
More preferably, the amount is 0 to 58% by weight.

Further, the graft copolymer (2) of the present invention
When polymerizing the core of the copolymer and the shell at each stage, a crosslinkable monomer and, if necessary, a graft crosslinking agent can also be used. These ratios are as follows: for polymerization of the core, 0.01 to 3% by weight based on 100% by weight of the total amount of monomers used for polymerization of the core, It is 0.01 to 2% by weight in the total 100% by weight of the monomer. Further, as the graft copolymer (2), those which have been subjected to a treatment for improving blocking resistance for the purpose of eliminating poor dispersion during the production of the resin composition of the present invention can be used. Can take.

Examples of such a method include a method of spray-drying a latex of a graft copolymer and spheroidizing the powder, a method of adjusting salting-out conditions of the copolymer latex, and a method of adding an additive such as a lubricant. Can be Further, a monomer 51 forming a hard polymer is formed in 5 to 49% by weight of the elastic base polymer.
A method in which 0.1 to 25 parts by weight of a powdery property-improving graft copolymer obtained by graft polymerization of about 95% by weight to 95% by weight is blended with 100 parts by weight of the graft copolymer (2) in a slurry state. . Here, the elastic backbone polymer refers to a polymer or copolymer of a monomer used for the core of the graft copolymer (2), and the monomer forming the hard polymer is a graft copolymer ( The monomer used in the shell of 2).

Alternatively, a method of adding an emulsion of a hard inelastic polymer to a coagulated slurry of the graft copolymer (2) may be used. Here, the hard inelastic polymer is a polymer obtained by polymerizing one or more monomers selected from an aromatic vinyl compound, a vinyl cyanide compound, and a methacrylic acid ester, and in particular, 80% by weight of methyl methacrylate. Those described above are preferred.

Among the above treatments for improving the anti-blocking property, the method of blending the graft copolymer (2) in the slurry state with the powder property-improving graft copolymer or the rigid inelastic polymer is simple and effective. This is preferable in that blocking resistance can be achieved. The method for improving the blocking resistance by adding a powder property improving graft copolymer or a hard inelastic polymer is described in the graft copolymer (2) of the present invention.
Is performed within the range of each component amount in the above.

Particularly preferred graft copolymers (2) include, when the total of the core and the shell is 100% by weight, 60-80% by weight of acrylate ester and 20-4% of butadiene.
A mixture of an aromatic vinyl compound and a methacrylic acid ester, and if necessary, a mixture of a vinyl cyanide compound and 50% to 70% by weight of a rubber latex core containing 100% by weight in total of 0% by weight was mixed in two stages. 30 to 50% by weight of a shell grafted by graft polymerization, wherein the methacrylic acid ester is 55 to 70% by weight in 100% by weight of the shell, and when the vinyl cyanide compound is further contained, the vinyl cyanide compound is used. 22-3 in a total of 100% by weight with an aromatic vinyl compound
0% by weight, and the first graft component is any one of a mixture of an aromatic vinyl compound and a methacrylic acid ester, or a mixture of an aromatic vinyl compound, a vinyl cyanide compound and a methacrylic acid ester. The graft component is composed of a methacrylic ester, and in a total of 100% by weight of the shell component,
Those in which the first graft component is 42 to 70% by weight and the second graft component is 30 to 58% by weight. Specific examples of the graft copolymer (2) include trade names “HIA-15” and “HIA-2” from Kureha Chemical Industry Co., Ltd.
8 "and" HIA-28S ".

Graft copolymer (3) A structure in which 5 to 95% by weight of an organosiloxane polymer component and 5 to 95% by weight of a polymer component composed of an acrylate and / or a methacrylate are entangled with each other so that they cannot be separated. And a core of 40 to 90% by weight of a composite rubber having a total of 100% by weight, and one or two selected from acrylates, methacrylates, aromatic vinyl compounds, and vinyl cyanide compounds.
Polymer or copolymer composed of at least one kind of monomer 10
A graft copolymer comprising 60% by weight of a shell (hereinafter sometimes referred to as "graft copolymer (3)").

The preferred ratio of the organosiloxane polymer component to the acrylate and / or methacrylate ester polymer component in the core is such that the organosiloxane polymer component is 5 to 5% by weight of the total of these components.
70% by weight, more preferably 6 to 60% by weight, even more preferably 7 to 50% by weight, and acrylates and / or methacrylates are preferably 30 to 70% by weight.
It is 95% by weight, more preferably 40 to 94% by weight, still more preferably 50 to 93% by weight.

The ratio of the composite rubber serving as the core in the graft copolymer (3) is such that the total amount of the copolymer is 10%.
The content is preferably 60 to 90% by weight, more preferably 60 to 85% by weight in 0% by weight. When the content is 60 to 90% by weight, it is possible to achieve both improved impact resistance and better flame retardancy. The average particle size of the composite rubber is 0.08 to 0.6 μm.
m, more preferably 0.1 to 0.4 μm.

In order to produce such a composite rubber of the graft copolymer (3), an emulsion polymerization method is most suitable. First, an organosiloxane polymer latex is prepared, and then an acrylate monomer and / or It is preferred that the methacrylic acid ester monomer is impregnated into the rubber particles of the organosiloxane polymer latex before the monomer is polymerized.

The organosiloxane polymer component constituting the composite rubber can be adjusted by emulsion polymerization using the following organosiloxane and a crosslinking monomer corresponding to the above-mentioned organosiloxane. A graft crosslinking agent corresponding to the organosiloxane may be used in combination. Examples of the organosiloxane include various cyclic members having three or more membered rings, and preferably a three- to six-membered ring. For example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like, These may be used alone or in combination of two or more. These are used in an amount of 50% by weight or more, preferably 70% by weight or more, in the polyorganosiloxane rubber component.

As the crosslinkable monomer, a tetrafunctional one is particularly preferred, and tetraethoxysilane is particularly preferred. The amount of the crosslinkable monomer used in the organosiloxane polymer component of the composite rubber in the graft copolymer (3) was 0.1% in 100% by weight of the organosiloxane polymer component.
It is 1 to 30% by weight, preferably 0.5 to 10% by weight. As the graft-crosslinking agent, the above-mentioned ones can be used, but the amount is 0 to 10% by weight in the organosiloxane polymer component.

For the production of such an organosiloxane polymer latex, for example, the methods described in US Pat. Nos. 2,891,920 and 3,294,725 can be used. For example, an organosiloxane and a mixed solution of a corresponding crosslinkable monomer and, if desired, a corresponding graft-linking agent are mixed with water using a homogenizer or the like, for example, in the presence of a sulfonic acid emulsifier such as an alkylbenzenesulfonic acid or an alkylsulfonic acid. It is preferable to produce by a method of shear mixing. Alkyl benzene sulfonic acid is preferred because it acts as an emulsifier for the organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use a metal salt of an alkyl benzene sulfonic acid, a metal salt of an alkyl sulfonic acid or the like in combination, since this is effective for stably maintaining the polymer during graft polymerization.

Next, in order to produce a polymer comprising acrylate and / or methacrylate constituting the composite rubber, sodium hydroxide, potassium hydroxide,
The above-mentioned acrylate and / or methacrylate, a crosslinkable monomer, and a graft crosslinking agent are added to the organosiloxane polymer latex neutralized by the addition of an aqueous alkali solution such as sodium carbonate to form an organosiloxane polymer. After impregnating the rubber particles, the reaction is carried out by the action of a usual radical polymerization initiator. Here, the total amount of the crosslinkable monomer and the graft-linking agent corresponding to the acrylate ester and the like is 0.1 to 20% by weight in 100% by weight of the polymer composed of the acrylate and / or methacrylate, Preferably it is 0.5 to 10% by weight.

As the polymerization proceeds, a crosslinked network of a polymer composed of an acrylate ester and / or a methacrylic ester is formed in the crosslinked network of the organosiloxane polymer rubber. A latex of a composite rubber with a polymer comprising an acid ester and / or a methacrylic ester is obtained.

In this composite rubber, the main skeleton of the organosiloxane polymer has a repeating unit of dimethylsiloxane, and the main skeleton of the polymer composed of an acrylic ester and / or a methacrylic ester has a repeating unit of n-butyl acrylate. The composite rubber having is preferably used.

The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer, and can be a polymer comprising an organosiloxane polymer component and an acrylate and / or methacrylate. Since the components are tightly entangled with each other, they cannot be extracted and separated with ordinary organic solvents such as acetone and toluene. The gel content measured by extracting the composite rubber with toluene at 90 ° C. for 12 hours is 80% by weight or more. Examples of the vinyl monomer to be graft-polymerized to such a composite rubber include the above-mentioned aromatic vinyl compound, methacrylic acid ester, acrylic acid ester, vinyl cyanide compound and the like, and these may be used alone or in combination of two or more. Can be

The graft copolymer (3) is obtained by adding the above-mentioned vinyl monomer to a composite rubber latex and polymerizing it in one step or in multiple steps by a radical polymerization technique to obtain a latex such as calcium chloride or magnesium sulfate. Is poured into hot water in which the metal salt is dissolved, and salted out and coagulated to be separated and recovered.

Preferred graft copolymers (3) include organosiloxane polymer components 7 to 50 as a core.
60% to 85% by weight of a composite rubber having a structure in which 50% by weight and an acrylic ester and / or a methacrylic acid ester are intertwined with each other so that they cannot be separated, and the total is 100% by weight. One or two selected from acid esters, methacrylic esters, aromatic vinyl compounds and vinyl cyanide compounds
Polymer or copolymer composed of at least three kinds of monomers 15 to
It is composed of a total of 100% by weight of 40% by weight.

The (meth) acrylic core-shell graft polymer as the f-1 component of the present invention comprises a methacrylic acid ester, an acrylic acid ester, an aromatic vinyl compound, a cyanide, which constitutes the graft polymer and the shell component. One or more monomers 70 selected from vinyl compounds
To 100% by weight and other monomers copolymerizable therewith
It may be a mixture with a polymer or copolymer obtained by polymerizing 30% by weight. Such a polymer and copolymer component may be included separately as a free polymer and / or copolymer generated in the course of graft polymerization, or may be separately mixed.

Among the preferred graft copolymers and the graft copolymers (1) to (3) described above, the graft copolymer (2) has a flame-retardant effect and coloring property as compared with other graft copolymers. Both sides are excellent. The flame retardant effect and the colorability are more remarkable when the proportion of the phosphoric ester-based flame retardant of the component c is relatively small.

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, polyester, polyamide, other thermoplastic resins such as polyphenylene ether may be mixed as long as the object of the present invention is not impaired,
It is also possible to incorporate a polyorganosiloxane flame retardant.

Further, as long as the objects of the present invention are not impaired, stabilizers (for example, phosphate esters and phosphites), antioxidants (for example, hindered phenol compounds), light stabilizers (For example, benzotriazole-based compounds, hindered amine-based compounds, benzophenone-based compounds), coloring agents, foaming agents, antistatic agents, and the like, may be blended with various generally-mixed additives.
These may be used alone or in the form of master pellets of various resins.

Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, which are known as heat stabilizers for aromatic polycarbonate resins. Phyto, tris nonylphenyl phosphite, tris (2,4-di-t
tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl Diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,
Phosphite compounds such as 6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite; Phosphorus such as tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. As an acid ester compound and other phosphorus-based heat stabilizers, tetrakis (2,4-di-ter
t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite,
Tetrakis (2,4-di-tert-butylphenyl)
-3,3'-biphenylenediphosphonite, bis (2,4
-Di-tert-butylphenyl) -4-biphenylenediphosphonite and the like. Of these, trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) Phosphite, triphenyl phosphate, trimethyl phosphate tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite is preferred. These heat stabilizers may be used alone or in combination of two or more.

As the heat stabilizer of the present invention, a hindered phenol compound or a sulfur compound, which is generally known as an antioxidant, is preferably blended in addition to the above. 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, and 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.
It is particularly suitable for injection molding. Also, it can be applied to blow molding, vacuum molding and the like. In particular, it is most suitable as a material for electrical and electronic parts that require UL94V-0 and exterior use of OA.

In particular, the molded article formed from the polycarbonate resin composition of the present invention uses a phosphate ester-based flame retardant and has a V rating based on a combustion test according to UL standard 94V.
The determination of −0 is achieved. In addition, it is possible to obtain a molded article having good heat and moisture resistance and having a very small decrease in impact resistance over a long period of time. More specifically, a phosphate ester flame retardant was used to achieve a V-0 determination, and the impact resistance was maintained when stored for 500 hours in an environment of a temperature of 65 ° C. and a relative humidity of 85%. A molded article having a ratio of not less than 50% and an apparent retention of molecular weight of not less than 80% is achieved. Particularly, a molded article having an impact resistance retention of 50% or more and an apparent molecular weight retention of 80% or more when stored for 1,000 hours in an environment of a temperature of 65 ° C and a relative humidity of 85% is obtained. It is also suitable as a material for electrical and electronic parts that require moisture-heat resistance or a long-term life of a product, and for OA exterior applications.

[0120]

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

(1) Moisture and heat resistance -1: 1/8 "Izod impact test piece was notched and cut with an environmental tester (Platinum Subzero Lucifer manufactured by Tabai Espec Corp.).
After treatment at 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. In addition, the retention ratio represents the ratio of the value after the wet heat treatment to the value before the wet heat treatment in%.

(2) Moist 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 in 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. In addition, the retention ratio represents the ratio of the value after the wet heat treatment to the value before the wet heat treatment in%.

(3) Flame retardancy: A combustion test was conducted at a thickness of 1.6 mm according to UL standard 94V. (4) Impact resistance: Izod notched impact resistance was measured according to ASTM D256.

I. Description of Constituent Components I- (1) Component a (Polycarbonate resin) Reference Example 1 (Production of polycarbonate resin PC-1) Organic solvent supply port, hot water supply port, steam introduction port, exhaust port for vaporized organic solvent and overflow of polycarbonate A stirrer having a ribbon-shaped shape as a stirring blade was mounted on a biaxial container of a 500 L effective internal volume rotary shaft mixer equipped with a mold discharge port. 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 22,22.
A methylene chloride solution having a concentration of 16% by weight of a polycarbonate resin having a concentration of 000 was supplied at a rate of 10 kg / min, and warm 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) is about 5
And the temperature inside the container is 2.7 kg / pressure.
The temperature was maintained at 77 ° C. by heating the steam inlet and the jacket using cm ² of steam. The stirring capacity is 6 kw /
hr · m ³ . After the start of the supply, the level of the slurry in the container was increased, and the generated polycarbonate resin particles and hot water were discharged from a discharge port provided in an upper portion of 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 1,500 G, and the polycarbonate resin particles were separated by filtration. The separated polycarbonate resin particles were pulverized by a pulverizer to an average particle diameter of 2 mm, and then pulverized by a hot air drier.
Drying was performed at 4 ° C. 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 (Polycarbonate resin PC-2)
Production was carried out in the same manner as in Reference Example 1 except that the temperature in the container was set to 70 ° C. and the production method described in Reference Example 1. 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 (Polycarbonate resin PC-3)
Production) Production was carried out in the same manner as in Reference Example 1 except that the temperature in the container was set to 50 ° C. and the production method described in Reference Example 1. The viscosity average molecular weight of the polycarbonate resin thus obtained 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.

I- (2) Component b (Styrene-based resin) Reference Example 4 (Preparation of ABS-1) After polymerizing by the bulk polymerization method, the polymer was separated from the separation and recovery device comprising a multitubular heat exchanger and a decompression chamber. ABS resin which was obtained and then pelletized by a multi-stage vent type twin screw extruder.
The composition of the ABS resin was 15% by weight of acrylonitrile, 20% by weight of butadiene, and 65% by weight of styrene. The weight average molecular weight of the free acrylonitrile-styrene polymer was 90,000 (standard polystyrene conversion by GPC), and the graft ratio was 55%. The average rubber particle size determined by observation with an electron microscope was 0.80 μm, and the amount of residual acrylonitrile monomer measured by liquid chromatography after dissolving ABS resin in chloroform was 25.
It was 0 ppm. This ABS resin is called ABS-1.

Reference Example 5 (Preparation of ABS-2) The ABS-1 obtained in Reference Example 4 was charged into a stainless steel container equipped with stirring blades, and 7 times (weight ratio) of methanol was added thereto. In addition, washing with stirring was performed 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. This ABS resin is called ABS-2.

Reference Example 6 (Preparation of ABS-3) Washing of ABS-1 obtained in Reference Example 4 with methanol for 2 hours was repeated three times in the same manner as for ABS-2. And vacuum drying for 12 hours. The residual acrylonitrile monomer content in the ABS resin is 20
ppm. This ABS resin is called ABS-3.

Reference Example 7 (Preparation of ABS-4) Emulsion graft polymerization was carried out at a ratio of 10 parts by weight of polybutadiene latex (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 such ABS resin is 69.5% by weight of styrene, 20% by weight of butadiene, and 10.5% by weight of acrylonitrile, and free acrylonitrile-
The weight average molecular weight of the styrene polymer is 120,000 (G
Standard polystyrene conversion by PC), graft ratio 50
%, The average rubber particle size determined by observation with an electron microscope is 0.40 μm, and the amount of residual acrylonitrile monomer measured by liquid chromatography is 50 ppm.
Met. This ABS resin is referred to as ABS-4.

I- (3) c component (phosphate ester flame retardant) FR-1: triphenyl phosphate (TPP manufactured by Daihachi Chemical Industry Co., Ltd.) FR-2: resorcinol bis (dixylenyl phosphate) (Asahi ADK STAB FP-50 manufactured by Denka Kogyo Co., Ltd.
0)

I- (4) d component (silicate filler) Talc-1: Talc (Talc P- manufactured by Nippon Talc Co., Ltd.)
3, average particle diameter about 3 μm) Talc-2: talc (HST 0.8 made by Hayashi Kasei Co., Ltd., average particle diameter about 5 μm) WSN-1: wollastonite (Kinsei Matech Co., Ltd.)
WIC10, average fiber diameter 4.5 μm, aspect ratio L
/ D = 8) WSN-2: Wollastonite (Tomo Kogyo Co., Ltd. Psycatek NN-4, average fiber diameter 1.5 μm, aspect ratio L)
/ D = 20) Mica: Mica powder (A-41, manufactured by Mika Yamaguchi Corporation)
(Average particle diameter: about 40 μm) (Filler other than the d component) CF: carbon fiber (Vesfight manufactured by Toho Rayon Co., Ltd.)
HTA-C6-U, PAN system, urethane focusing, diameter 7μ
m)

I- (5) e component (polytetrafluoroethylene) PTFE: polytetrafluoroethylene (F-201L manufactured by Daikin Industries, Ltd.)

I- (6) Component f (rubber polymer) Rubber-1: Multistage graft copolymer of methyl methacrylate, 2-ethylhexyl acrylate, butadiene, and styrene (styrene content: 15% by weight) (Kureha Chemical Co., Ltd.) Industrial Co., Ltd.
Rubber-2: Butadiene-based impact modifier (EXL2602 manufactured by Kureha Chemical Industry Co., Ltd.) Rubber-3: Acrylic-silicon-based impact modifier (Mitsubishi Rayon Co., Ltd. S-2001)

Examples 1 to 16 and Comparative Examples 1 to 4 Based on the components and amounts shown in Tables 1 and 2 below, they were mixed in a V-type blender, and then a vented twin-screw extruder having a diameter of 30 mmφ (( TEX30XSS manufactured by Japan Steel Works, Ltd.
T) pelletized at a cylinder temperature of 240 ° C.
After drying the pellets at 100 ° C. for 5 hours, various test pieces were prepared and evaluated at a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. using an injection molding machine (T-150D manufactured by FANUC Co., Ltd.). The evaluation results are shown in Tables 1 and 2.

[0137]

[Table 1]

[0138]

[Table 2]

[0139]

[Table 3]

[0140]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 21/00 C08L 21/00 25/04 25/04 25/12 25/12 25/16 25/16 27 / 18 27/18 51/04 51/04 55/02 55/02 67/00 67/00 F term (reference) 4F071 AA12 AA22 AA27 AA31 AA34 AA43 AA50 AA53 AA67 AA75 AA77 AB26 AB30 AC15 AE07 AF23 AF47 AF57 AH05 AH12 AH16 BB05 BC04 BC10 4J002 AC004 BC022 BC032 BC062 BC072 BC082 BC092 BD153 BN062 BN124 BN134 BN152 BN174 BN214 BN224 CF004 CG001 CG021 CK024 DJ007 DJ017 DJ037 DJ047 DJ057 DK007 EW046 FB097 FB167 FD017 FD060 060

Claims (39)

[Claims] (A) Aromatic polycarbonate resin (Component a) 40 to 92% by weight (B) Styrene resin (Component (b)) 5 to 40% by weight (C) Phosphate ester flame retardant (Component (c)) (D) a resin composition consisting essentially of 0.1 to 30 parts by weight of a silicate filler (component (d)) per 100 parts by weight of the total of component (a), component (b) and component (c). The resin composition comprises:
The content of chlorine compound in terms of chlorine atomic weight is 100pp
m or less. 2. The resin composition according to claim 1, wherein the component a is an aromatic polycarbonate resin obtained by an interfacial polymerization method. 3. The component (b) is a styrene-based resin containing acrylonitrile as a monomer constituent unit, and the resin composition has an acrylonitrile monomer content of 50%.
The resin composition according to claim 1, wherein the amount is not more than ppm. 4. The resin composition according to claim 1, wherein the component b is a styrene-based resin in which the styrene-based monomer unit is 20% by weight or more in all the monomer constituent units. 5. The resin composition according to claim 4, wherein the styrene monomer unit is a styrene unit, an α-methylstyrene unit or a vinyl toluene unit. 6. The component b is polystyrene, high impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), or acrylonitrile / butadiene / styrene copolymer (ABS resin).
The resin composition as described in the above. 7. The component (b) is an acrylonitrile-butadiene-styrene copolymer (ABS resin).
The resin composition as described in the above. 8. The component (b) is an acrylonitrile-butadiene-styrene copolymer (A) obtained by a bulk polymerization method.
(BS resin). 9. The resin composition according to claim 1, wherein the component c is a phosphate ester-based flame retardant represented by the following formula (1). Embedded image Wherein X represents an aromatic dihydroxy compound residue,
j, k, l, and m each independently represent 0 or 1, n represents 0 or an integer of 1 to 5, R ₁ , R ₂ , R
₃ and R ₄ each independently represent an aromatic monohydroxy compound residue. 10. The resin composition according to claim 1, wherein the d component is a silicate filler containing 35% by weight or more of a SiO ₂ component. 11. The resin composition according to claim 1, wherein the component d is talc, mica or wollastonite. 12. Component a is 50 to 88% by weight, component b is 7 to 35% by weight, component c is 5 to 15% by weight, and component d is 100 parts by weight of the total of components a, b and c. 2. The resin composition according to claim 1, consisting essentially of 0.5 to 20 parts by weight. 13. The resin composition according to claim 1, wherein the content of the chlorine compound is 90 ppm or less based on the resin composition in terms of chlorine atoms. 14. The resin composition according to claim 3, wherein the content of the acrylonitrile monomer is 40 ppm or less based on the resin composition. 15. The composition according to claim 1, further comprising 0.1 to 2 parts by weight of polytetrafluoroethylene (component e) having a fibril-forming ability per 100 parts by weight of the total of the components a, b and c. Resin composition. 16. A rubbery polymer (component (f))
per 100 parts by weight of the total of the components a, b and c,
The resin composition according to claim 1, which is contained in an amount of 1 to 10 parts by weight. 17. The resin composition according to claim 16, wherein the rubbery polymer (component (f)) is a (meth) acrylate-based core-shell graft copolymer, a polyurethane-based elastomer or a polyester-based elastomer. 18. The resin composition according to claim 16, wherein the rubbery polymer (component f) is a (meth) acrylate-based core-shell graft copolymer. 19. (A) Aromatic polycarbonate resin (component a) 40 to 92% by weight (B) Styrene resin (component b) 5 to 40% by weight (C) Phosphate ester-based flame retardant (component c) 3 (D) 0.1 to 30 parts by weight of a silicate filler per 100 parts by weight of the total of the components a, b and c (component d) (E) Components a, b and c Of polytetrafluoroethylene (component (e)) having a fibril-forming ability of 0.1 to 2 parts by weight per 100 parts by weight of the total of (A), (b) and (c) Part by weight of a (meth) acrylate-based core-shell graft copolymer (component (f-1)), which is a resin composition which is substantially composed of a chlorine compound in terms of chlorine atom. Content is 100 ppm or less Polycarbonate resin composition. 20. The resin composition according to claim 19, wherein the component a is an aromatic polycarbonate resin obtained by an interfacial polymerization method. 21. The b component is a styrene-based resin containing acrylonitrile as a monomer constituent unit,
The resin composition according to claim 19, wherein the resin composition has an acrylonitrile monomer content of 50 ppm or less. 22. The component (b) in all monomer structural units,
20. The resin composition according to claim 19, wherein the styrene-based monomer unit is a styrene-based resin in an amount of 20% by weight or more. 23. The resin composition according to claim 22, wherein the styrene monomer unit is a styrene unit, an α-methylstyrene unit or a vinyl toluene unit. 24. The method according to claim 19, wherein the component b is polystyrene, high impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), or acrylonitrile / butadiene / styrene copolymer (ABS resin). Resin composition. 25. The resin composition according to claim 19, wherein the component b is an acrylonitrile-butadiene-styrene copolymer (ABS resin). 26. The resin composition according to claim 19, wherein the component b is an acrylonitrile-butadiene-styrene copolymer (ABS resin) obtained by a bulk polymerization method. 27. The resin composition according to claim 19, wherein said component c is a phosphate ester flame retardant represented by the following formula (1). Embedded image Wherein X represents an aromatic dihydroxy compound residue,
j, k, l, and m each independently represent 0 or 1, n represents 0 or an integer of 1 to 5, R ₁ , R ₂ , R
₃ and R ₄ each independently represent an aromatic monohydroxy compound residue. 28. The resin composition according to claim 19, wherein the d component is a silicate filler containing 35% by weight or more of a SiO ₂ component. 29. The resin composition according to claim 19, wherein the component d is talc, mica or wollastonite. 30. The f-1 component is a (meth) acrylate-based core-shell graft copolymer, and a total of 100% by weight of (i) 60 to 100% by weight of butadiene and 0 to 40% by weight of styrene as a core. % Rubber,
(Ii) a copolymer rubber comprising a total of 100% by weight of 60 to 90% by weight of an acrylate ester and 10 to 40% by weight of butadiene, or (iii) 5 to 95% by weight of an organosiloxane polymer component and an acrylate and / or
Or a polymer component 5 to 9 comprising a methacrylic acid ester
5 to 40% by weight of any rubber selected from composite rubbers having a structure of being intertwined with each other so that 5% by weight is inseparable and having a total of 100% by weight; 2. A polymer or copolymer comprising 10 to 60% by weight of one or more monomers selected from methacrylates, aromatic vinyl compounds and vinyl cyanide compounds.
10. The resin composition according to item 9. 31. The f-1 component is a (meth) acrylate-based core-shell graft copolymer, 60 to 90% by weight of an acrylate and 10 to 10% of a butadiene.
40% by weight of a total of 100% by weight of a copolymer rubber 4
One or two or more selected from acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds and vinyl cyanide compounds are graft-polymerized in one or two or more stages to a core of 0 to 90% by weight. The resin composition according to claim 19, comprising 10 to 60% by weight of the grafted shell, and a total of 100% by weight of the core and the shell. 32. The component f-1 is a (meth) acrylate-based core-shell graft copolymer, and the acrylate 60 is contained in 100% by weight of the total of the core and the shell.
Core 5 comprising a rubber latex containing a total of 100% by weight of .about.80% by weight and 20-40% by weight of butadiene.
30 to 50% by weight of a shell obtained by grafting a mixture of an aromatic vinyl compound, a methacrylic acid ester, and, if necessary, a vinyl cyanide compound, by two-stage graft polymerization with respect to 0 to 70% by weight, The methacrylic acid ester in 100% by weight of the shell is 55%.
To 70% by weight, and when the composition further contains a vinyl cyanide compound, the vinyl cyanide compound is 22 to 30% by weight based on a total of 100% by weight of the aromatic vinyl compound and the first graft component is an aromatic vinyl compound. A mixture of a compound and a methacrylate, or an aromatic vinyl compound, a mixture of a vinyl cyanide compound and a methacrylate, and the second graft component is a mixture of a methacrylate, and Out of a total of 100% by weight of the shell component, 42 to 70% by weight of the first graft component and 3
The resin composition according to claim 19, which is 0 to 58% by weight. 33. The f-1 component is a (meth) acrylate-based core-shell graft copolymer, wherein 7 to 50% by weight of an organosiloxane polymer component is used as a core, and an acrylate and / or methacrylate is used. A composite rubber having a structure entangled with each other so that 50 to 93% by weight cannot be separated, a total of 60 to 85% by weight of a composite rubber having a total of 100% by weight, an acrylate ester as a shell,
20. A polymer or copolymer comprising one or two or more monomers selected from methacrylic acid esters, aromatic vinyl compounds and vinyl cyanide compounds, comprising a total of 15 to 40% by weight, a total of 100% by weight. 3. The resin composition according to item 1. 34. Component a is 50 to 88% by weight, component b is 7 to 35% by weight, component c is 5 to 15% by weight, component a, b
The component d is 0.5 to 20 parts by weight, the component e is 0.1 to 1 part by weight, and f is 100 parts by weight of the total of the component and the component c.
20. The resin composition according to claim 19, wherein the -1 component consists essentially of 2 to 8 parts by weight. 35. The resin composition according to claim 19, wherein the content of the chlorine compound is 90 ppm or less based on the resin composition in terms of chlorine atoms. 36. The resin composition according to claim 21, wherein the content of the acrylonitrile monomer is 40 ppm or less based on the resin composition. 37. A molded article formed from the resin composition according to claim 1 or 19. 38. The molded article according to claim 37, which has a judgment of V-0 based on a combustion test according to UL standard 94V. 39. An impact value retention rate of 50 hours when kept for 500 hours in an environment of a temperature of 65 ° C. and a relative temperature of 85%.
38. The molded article according to claim 37, which has an apparent molecular weight retention of 80% or more.