JP2000319495A - High-flowability flame-retardant resin composition excellent in discoloration resistance in dark - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition which is excellent in discoloration resistance in dark and is suitable for thin-wall molding by compounding a polycarbonate resin with a copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, a copolymer formed by grafting an aromatic vinyl monomer component onto a rubbery polymer, an organophosphorus flame retardant and an antioxidant. SOLUTION: This composition comprises 50-98 pts.wt. polycarbonate resin, 49-0.1 pt.wt. copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, 1-30 pts.wt. copolymer prepared by grafting at least one monomer selected from among aromatic vinyl monomers, vinyl cyanide monomers and alkyl (meth)acrylates onto a rubbery polymer (the sum of amounts of ingredients described hereinabove being 100 pts.wt.), 5-20 pts.wt. flame retardant comprising 99-93 wt.% organophosphorus compound of formula I and 1-7 wt.% organophosphorus compound of formula II and 0.01-0.8 pt.wt. antioxidant. In the formulas, Ra to Rd are each aryl; (n) is a natural number; X is an aromatic group; Re to Rg are each Ra or the like; and (j) to (m) and (q) to (s) are each 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a mold deposit (MD) which is hardly deteriorated even in high-temperature molding, has excellent resistance to discoloration in a dark place, and is generated in a molding die during molding. The present invention relates to a flame-retardant polycarbonate resin composition having extremely low flowability and high fluidity and high flame retardancy suitable for thin-wall molding.

[0002]

2. Description of the Related Art A resin composition in which an ABS (acrylonitrile / butadiene / styrene) resin and an organic phosphorus flame retardant are blended with polycarbonate (PC) (flame retardant PC / A).
BS alloy) is a non-halogen flame retardant material and has excellent mechanical properties, heat resistance and light resistance, so it is used as a housing material for OA equipment such as electrical products, computers, printers, word processors and copiers. Widely used.

In recent years, there has been a strong demand for lighter and thinner housings for OA equipment, and flame-retardant PC / ABS alloys have excellent fluidity for thin-wall molding and are excellent in thin-walled molded articles. There is a need for the development of materials that exhibit flame retardancy. Techniques relating to a flame-retardant PC / ABS composition in which fluidity, impact resistance and flame retardancy are highly balanced are disclosed in JP-A-6-240127 and JP-A-7-824.
No. 66, JP-A-8-127686, JP-A-8-127686
No. 25366.

[0004] The design of a flame-retardant PC / ABS alloy with high fluidity reduces the molecular weight of the PC in the composition,
In addition, composition compositions having a high composition ratio are becoming mainstream. In addition, a decrease in impact resistance caused by a decrease in the molecular weight of PC is reduced by a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate. A compounding technique is disclosed. Flame retardant PC / A containing PC of low molecular weight as a main component for such high fluidization
In the case of a BS-based alloy, the physical properties may be significantly reduced due to thermal deterioration of the resin component and the rubber component during processing, particularly when molded at a high temperature. In order to obtain a thin-walled molded product, the molding temperature is often set to a high temperature as a method of improving the flowability of the molten resin. However, in the case of a flame-retardant PC / ABS alloy, the physical properties in high-temperature molding are reduced. May limit the forming range.

[0005] For this reason, an antioxidant is blended in order to prevent thermal deterioration of the resin and rubber components. However, when the antioxidant is blended, discoloration of the composition often occurs in a dark place. Since dark discoloration impairs the color tone of the product, improvement thereof is desired. In order to obtain a composition having high fluidity, it is desirable that the organophosphorus flame retardant used has a low viscosity. In particular, when the composition ratio of PC in the composition is high, the viscosity of the organic phosphorus-based flame retardant itself greatly affects the fluidity of the composition. Therefore, in order to obtain a highly fluid composition, the use of a mono-organic phosphorus compound having a lower viscosity than that of the oligomer-type organic phosphorus compound generally has a high improvement effect. However, when a mono-organic phosphorus compound is used as a flame retardant, there is a drawback that a large amount of MD adheres to the mold surface during molding. JP-A-7-82466 and JP-A-8-253
No. 66 discloses a composition in which an oligomeric organic phosphorus compound and a mono-organic phosphorus compound are used in combination as an organic phosphorus-based flame retardant. M sometimes adheres to the mold surface
The amount of D generated is still large, and its improvement is desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention is characterized in that the deterioration of the physical properties is small even in high-temperature molding, the discoloration resistance in a dark place is excellent, and the generation of a mold deposit (MD) generated in a molding die during molding. It is an object of the present invention to provide a flame-retardant polycarbonate-based resin composition having an extremely small amount and having high fluidity and high flame retardancy suitable for thin-wall molding.

[0007]

Means for Solving the Problems The present inventors have used a mono-organic phosphorus compound in an amount of several wt% based on the total amount of an organic phosphorus-based flame retardant mainly composed of an oligomer-type organic phosphorus compound, and further used an antioxidant. By blending the compound, a decrease in physical properties during high-temperature molding is suppressed, and a composition having significantly improved discoloration in a dark place of the composition can be obtained. The amount of MD generated in the molding die is extremely low, and the average degree of condensation N of the oligomeric organic phosphorus compound, which is a flame retardant, is controlled to 1 or more and less than 1.2, resulting in high fluidity. To obtain a flame-retardant PC / ABS alloy having high flame retardancy and the like.

That is, the present invention relates to a copolymer (1) comprising (A) 50 to 98 parts by weight of a polycarbonate resin, (B) an aromatic vinyl monomer component, and (b2) a vinyl cyanide monomer component. At least one of (C) (c1) an aromatic vinyl monomer component, (c2) a vinyl cyanide monomer component, and (c3) an alkyl (meth) acrylate monomer component. Species or two or more species (c
4) Copolymers 1-3 graft-polymerized to rubbery polymer
0 parts by weight, and based on 100 parts by weight of (A), (B) and (C), (D) (d1) one or more oligomers represented by the formula (1) (D2) one or more mono-organic phosphorus compounds represented by formula (2): 1 to 7 wt%
% (However, the sum of (d1) and (d2) is 100 wt%
5-20 organic phosphorus compounds comprising a combination of
Parts by weight, further comprising (E) 0.01 to 0.8 parts by weight of an antioxidant,

[0009]

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[0010]

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[2] The flame-retardant resin composition according to the above [1], wherein (d1) of the component (D) is one or more oligomeric organic phosphorus compounds represented by the formula (3):

[0012]

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[3] Component (A) has a weight average molecular weight of 1
The flame-retardant resin composition according to the above [1] or [2], wherein the weight average molecular weight of the component (B) is 5,000 or more and 5,000 or less, and 5,000 or more, and 5,000 or less. The component (C) comprises (c1) an aromatic vinyl monomer component and (c2) a vinyl cyanide monomer component comprising (c)
4) a copolymer graft-polymerized to a rubbery polymer;
(C3) The above-mentioned [1], wherein the alkyl (meth) acrylate monomer component comprises a combination of a copolymer obtained by graft-polymerizing the (c4) rubbery polymer.
The flame-retardant resin composition according to [2] or [3], wherein the component [d1] has an average degree of condensation N of 1 or more and less than 1.2, [1], [2], [3] and [4] The flame-retardant resin composition according to [1], wherein [6] the component (E) is a phenolic antioxidant having a molecular weight of 500 or more.
The flame-retardant resin composition according to [3], [4] or [5], [7] The above-mentioned [1], [2], [3], [4] or [5] further containing polytetrafluoroethylene. ] And [6].

Hereinafter, the present invention will be described in detail. The polycarbonate resin (A) used in the present invention has the formula (4)
Having a main chain consisting of a repeating unit represented by

[0015]

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(Where Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene,
Examples include pyridylene and those represented by the formula (5). )

[0017]

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(Wherein, Ar ¹ and Ar ² are each an arylene group; for example, a group such as phenylene, naphthylene, biphenylene, pyridylene, etc., and Y is an alkylene group or a substituted alkylene group represented by the formula (6)) Is.)

[0019]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a lower alkyl group, a cycloalkyl group,
An aryl group or an aralkyl group, which may be optionally substituted by a halogen atom or an alkoxy group;
And R ⁵ and R ⁶ are independently selected for each X, and each independently represents a hydrogen atom, or a lower alkyl group or an aryl group, and is optionally substituted with a halogen atom or an alkoxy group. And X represents a carbon atom. ) Further, a divalent aromatic residue represented by the formula (7) may be contained as a copolymer component.

[0021]

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(In the formula, Ar ¹ and Ar ² are the same as in the formula (4).
Z is a mere bond, or -O-, -CO-, -S-,
_{-SO 2 -, - CO 2 -} , - CON (R 1) - (R 1 is as defined in the formula (6)) is a divalent group such as. Examples of these divalent aromatic residues include those represented by formulas (8) and (9).

[0023]

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[0024]

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(Wherein R ⁷ and R ⁸ are each independently
Hydrogen, halogen, C ₁ -C ₁₀ alkyl group, C ₁ -C ₁₀ alkoxy group, C ₁ -C ₁₀ cycloalkyl group or a phenyl group. m and n are integers of 1 to 4; when m is 2 to 4, each R ⁷ may be the same or different; and when n is 2 to 4, each R ⁸ is the same. However, they may be different. Among them, one represented by the formula (10) is a preferable example. In particular, a compound containing 85 mol% or more of a repeating unit in which the compound represented by the formula (10) is Ar is preferable.

[0026]

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The polycarbonate which can be used in the present invention may contain a trivalent or higher aromatic residue as a copolymer component. Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a phenolic hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. The aryl carbonate terminal group is represented by the formula (11), and specific examples include:
For example, equation (12) is given.

[0028]

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(In the formula, Ar ³ is a monovalent aromatic residue, and the aromatic ring may be substituted.)

[0030]

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The alkyl carbonate terminal group has the formula (13)
And a specific example is, for example, the formula (14).

[0032]

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(In the formula, R ⁷ represents a linear or branched alkyl group having 1 to 20 carbon atoms.)

[0034]

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Of these, phenolic hydroxyl groups, phenyl carbonate groups, pt-butylphenyl carbonate groups, p-cumylphenyl carbonate and the like are preferably used. In the present application, the ratio of the phenolic hydroxyl group terminal to the other terminal is not particularly limited, but the phenolic hydroxyl group terminal ratio for all terminals is preferably in the range of 20 to 80 mol%.

The method for measuring the phenolic hydroxyl group terminal amount is as follows.
In general, a method using NMR, a titanium method,
It can be determined by the V or IR method. The weight average molecular weight (Mw) of the polycarbonate resin (A) used in the present invention is usually 15,000 to 50,000,
A range of 15,000 to 25,000 is preferred. It is more preferably from 17,000 to 24,000, still more preferably from 18,000 to 230,000, and particularly preferably from 18,500 to 22,000. 15,0
If it is less than 00, the impact resistance is insufficient.
If it exceeds 00, it will be difficult to obtain a high-flow composition intended for the present invention.

The measurement of the weight average molecular weight (Mw) in the present invention is carried out by using gel permeation chromatography (GPC). The measurement conditions are as follows: tetrahydrofuran is used as a solvent, and polystyrene gel is used.
It is determined from the constitutive curve of the standard monodisperse polystyrene using a reduced molecular weight calibration curve according to the following equation. ^{_{M PC = 0.3591M PS 1.0388 (M}} PC molecular weight of the polycarbonate, M _PS molecular weight of polystyrene) These polycarbonates can be prepared by known methods. Specifically, a known method of reacting an aromatic dihydroxy compound with a carbonate precursor, for example,
Interfacial polymerization method (phosgene method) in which aromatic dihydroxy compound and phosgene react in the presence of sodium hydroxide aqueous solution and methylene chloride solvent, transesterification method in which aromatic dihydroxy compound reacts with diphenyl carbonate (melting method), crystallization carbonate Method for solid-state polymerization of prepolymer (JP-A-1-158033, 1-27142)
6, 3-68627, etc.).

Preferred polycarbonate resins include:
A polycarbonate resin containing substantially no chlorine atom, which is produced from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester by a transesterification method, may be mentioned. In the present invention, two or more types of components (A) having different structures and molecular weights can be used in combination.

The proportion of the component (A) for obtaining a resin composition in which fluidity, impact resistance and flame retardancy are balanced at a high level, which is the object of the present invention, is as follows: (A) and (B) 50 parts by weight to 98 parts by weight, preferably 70 to 95 parts by weight, more preferably 75 to 9 parts by weight, based on 100 parts by weight in total of (C).
0 parts by weight. If the amount of the component (A) is less than 50 parts by weight, heat resistance and flame retardancy are insufficient, while if it exceeds 98 parts by weight, fluidity is insufficient.

The component (B) used in the present invention comprises (b)
1) A copolymer containing an aromatic vinyl monomer component and (b2) a vinyl cyanide monomer component. The fluidity of the resin composition can be improved by the component (B). Here, as the aromatic vinyl monomer component (b1), for example, styrene, α-methylstyrene, paramethylstyrene, vinylxylene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like can be mentioned. These are used alone or in combination of two or more. Preferred are styrene and α-methylstyrene.

As the vinyl cyanide monomer component (b2), for example, acrylonitrile, methacrylonitrile and the like can be mentioned. One or more of these are used. The composition ratio of (b1) / (b2) in the copolymer is not particularly limited, but preferably (b1) is 95 to 5
0% by weight, (b2) is 5 to 50% by weight, more preferably (b1) is 92 to 65% by weight, and (b2) is 8 to 50% by weight.
35% by weight.

In the component (B), in addition to the components (b1) and (b2), a monomer copolymerizable with these components may be used within a range not to impair the purpose of the present invention. Can be. Such copolymerizable monomers include,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethyl (meth) acrylate, 2-
Alkyl (meth) acrylate monomer components such as ethylhexyl methacrylate, preferably butyl acrylate,
(Meth) acrylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as maleic anhydride, N
Maleimide monomers such as -phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; and glycidyl group-containing monomers such as glycidyl methacrylate. These monomers may be used alone or in combination of two or more. Can be used.

Preferred examples of the component (B) include styrene-acrylonitrile copolymer resin (SAN) and butyl acrylate-styrene-acrylonitrile copolymer resin (BAAS).
(Preferably the butyl acrylate monomer component is 2 to 20
% By weight) is particularly suitable for improving the flowability of the resin composition.

Examples of the method for producing the component (B) include generally known production methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The weight average molecular weight (Mw) of the component (B) is usually from 30,000 to 250,000, preferably from 50,000 to 150,000,
More preferably, it is 60,000 to 140,000,
It is more preferably from 70,000 to 130,000, particularly preferably from 80,000 to 120,000. If it is less than 30,000, the impact resistance is insufficient, and if it exceeds 250,000, it is difficult to obtain a highly fluid composition.

Component (B) for achieving the object of the present invention
Is from 49 parts by weight to 0.1 part by weight, preferably from 30 parts by weight to 100 parts by weight of the total of (A), (B) and (C).
1 part by weight, more preferably 20 to 3 parts by weight. If the component (B) is less than 0.1 part by weight, the fluidity becomes insufficient,
On the other hand, when it exceeds 49 parts by weight, heat resistance and flame retardancy are insufficient. Component (B) can be used in combination of two or more components (B) having different structures and molecular weights.

Next, the component (C) will be described. (C) is at least one or two of (c1) an aromatic vinyl monomer component, (c2) a vinyl cyanide monomer component, and (c3) an alkyl (meth) acrylate monomer component.
At least one kind is a copolymer obtained by graft-polymerizing the (c4) rubbery polymer. Examples of the (c1) aromatic vinyl monomer component and (c2) vinyl cyanide monomer component include (b1) and (b2) shown in the component (B).

The (c3) alkyl (meth) acrylate monomer components include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylate monomers such as ethyl (meth) acrylate and 2-ethylhexyl methacrylate can be used, and one or more of these are used. Preferred is methyl methacrylate.

As the rubbery polymer (c4), those having a glass transition temperature of 0 ° C. or less can be used. Specifically, polybutadiene, styrene-butadiene copolymer rubber, diene rubber such as acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene propylene rubber, ethylene propylene rubber・ Including block copolymers such as diene terpolymer rubber, styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber and their hydrogenated products, polyorganosiloxane component and polyalkyl (meth) acrylate component Composite rubber (silicone-acrylic composite rubber) or the like can be used. Among these polymers, preferred are polybutadiene, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, polybutyl acrylate, and silicone / acryl composite rubber.

Component (C) is obtained by adding (c1) an aromatic vinyl monomer component, (c2) a vinyl cyanide monomer component, and (c3) an alkyl (meth) to the rubber polymer (c4).
At least one or two or more of the acrylate monomer components may further include, if necessary, (meth) acrylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as maleic anhydride, Bulk polymerization, suspension polymerization, bulk / suspension of one or more maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, and glycidyl group-containing monomer components such as glycidyl methacrylate It is obtained by graft polymerization using a method such as polymerization, solution polymerization or emulsion polymerization, particularly emulsion polymerization.

Here, the amount of the rubbery polymer (c4) used is usually 10 to 95% by weight, preferably 30 to 82% by weight, more preferably 40 to 80% by weight. When a butadiene-based polymer is used, the ratio of the butadiene component of the butadiene-based polymer is preferably 50% by weight or more. If the amount of the rubbery polymer in the component (C) is less than 10% by weight, the effect of improving the impact resistance is low, and
If the content is more than 10% by weight, the dispersion of the component (C) in the composition becomes insufficient, which is not preferable.

In the present invention, a particulate graft copolymer obtained by emulsion polymerization can be most preferably used as the component (C). In this case, the average particle size of the graft copolymer is as follows. It is preferably from 0.1 to 1.5 μm, more preferably from 0.15 to 0.8 μm, particularly preferably from 0.2 to 0.6 μm. When the thickness is less than 0.1 μm, the effect of improving the impact resistance of the resin composition is insufficient, and
If it exceeds m, the fluidity and the appearance of the molded article will deteriorate.

Preferred examples of the component (C) according to the present invention include acrylonitrile / butadiene / styrene copolymer, acrylonitrile / ethylene / propylene / styrene copolymer, acrylonitrile / chlorinated polyethylene / styrene copolymer, acrylonitrile / acrylic copolymer Elastic polymer / styrene copolymer. It is more preferable to use a copolymer in which only the alkyl (meth) acrylate monomer component is grafted in order to balance high fluidity and impact resistance at a high level.
3) A copolymer in which methyl methacrylate is grafted as a component is preferred. For example, styrene
A butadiene-methyl methacrylate copolymer or a copolymer in which methyl methacrylate is grafted onto silicon-acrylic rubber can be suitably used. For example, “METABLEN C-MATH” manufactured by Mitsubishi Rayon Co., Ltd.
233A "," METABLEN C-323A ", and" METABLEN S-2001 "(all trade names) are particularly preferably used.

In the resin composition of the present invention, the above component (C)
Can be used alone or in combination of two or more kinds, and the compounding amount is 1 part by weight to 30 parts by weight based on 100 parts by weight of the total of (A), (B) and (C). . Preferably it is 2 to 20 parts by weight, more preferably 3 to 15 parts by weight. If the amount of the component (C) is less than 1 part by weight, there is almost no effect of improving the impact resistance, while if it exceeds 30 parts by weight, the fluidity and rigidity are insufficient.

In particular, in the composition of the present invention, as the component (C), a copolymer obtained by graft-polymerizing an aromatic vinyl monomer component and a vinyl cyanide monomer component onto a rubbery polymer, such as acrylonitrile. A butadiene / styrene copolymer (hereinafter referred to as C (a) component) and a copolymer obtained by graft-polymerizing methyl methacrylate on a rubbery polymer;
For example, by using a styrene-butadiene-methyl methacrylate copolymer or a copolymer obtained by grafting methyl methacrylate onto silicon-acrylic rubber (hereinafter referred to as C (b) component), fluidity and impact resistance are improved. It is suitable for obtaining a resin composition balanced at a high level. In this case, the composition ratio of C (a) and C (b) is not particularly limited, but the C (b) component is preferably 90 to 10% by weight, more preferably the total amount of C (a) and C (b). Is 70 to 20% by weight, more preferably 60 to 3% by weight.
0 wt%.

The component (D) used in the present invention comprises 99 to 93% by weight of one or more oligomeric organic phosphorus compounds represented by the following formula (1) and (d2) a compound represented by the following formula (2). It is an organic phosphorus compound comprising a combination of one or more mono-type organic phosphorus compounds represented by 1 to 7 wt% (provided that the sum of (d1) and (d2) is 100 wt%).

[0056]

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[0057]

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The component (d1) is represented by the formula (1), and the substituents R ^a , R ^b , R ^c , and R ^d in the formula (1) are aryl groups, and one or more hydrogens thereof are substituted. You don't have to. Compounds in which the substituents R ^a , R ^b , R ^c , and R ^d are an alkyl group or a cycloalkyl group have insufficient retention stability of the molten resin in a molding machine during injection molding, resulting in a decrease in physical properties of the resin. Easy to invite. When one or more hydrogens of the substituents R ^a , R ^b , R ^c , and R ^d are substituted, the substituent may be an alkyl group, an alkoxy group, an alkylthio group, a halogen,
Examples include an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group. A group obtained by combining these substituents (for example, an arylalkoxyalkyl group) or these substituents are replaced with an oxygen atom, a sulfur atom, a nitrogen atom A group (for example, an arylsulfonylaryl group or the like) combined by bonding through the above may be used as a substituent. Preferred aryl groups are phenyl, cresyl,
Xylyl group, propylphenyl group and butylphenyl group, and phenyl group is particularly excellent in both fluidity and flame retardancy. Further, the substituents R ^a , R ^b , R ^c , and R ^d may be the same or different.

X in the formula (1) is an aromatic group derived from a dihydric phenol, and catechol,
Resorcinol, hydroquinol, 4-t-butylcatechol, 2-t-butylhydroquinone, bisphenol A, bisphenol S sulfide, bisphenol F,
Bis (4-hydroxyphenyl) sulfone, bis (3
An aromatic group derived from (5dimethyl-4-hydroxyphenyl) sulfone and the like can be mentioned, and in the present invention, the compound represented by the formula (3)

[0060]

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X is a diphenyloldimethylmethane group (an aromatic group derived from bisphenol A)
By using the oligomeric organic phosphorus-based compound, the retention stability can be improved and the generation of MD can be reduced. The oligomeric organic phosphorus compounds represented by the formulas (1) and (3) are usually used as a mixture of compounds having different values of n (n is a natural number) in the formulas (1) and (3). In many cases. The average degree of condensation N is the average value of n. N is calculated by calculating the weight fraction of each component having different n by gel permeation chromatography and calculating the weight average of n. The detector uses an RI detector. However, in the present invention, a component in which n is 0, that is, a compound having only one phosphorus atom in the molecule is excluded from the calculation of N.

In the present invention, the average value N (average degree of condensation) of n is usually 1 or more and 5 or less, and it is particularly preferable that N is 1 or more and less than 1.2. The smaller the N, the better the compatibility with the resin, the better the fluidity, and the higher the flame retardancy. In particular, N = 1
Is particularly excellent in the balance between flame retardancy and fluidity in the resin composition. As a method for obtaining an oligomeric organophosphorus compound in which N is 1 or more and less than 1.2 in the oligomeric organophosphorus compound according to the present invention, for example, [a] phosphorus oxyhalide is added to phenol or 2,6. -Reacting an aromatic monohydroxy compound such as xylenol under a Lewis acid catalyst to obtain a diaryl phosphorohalide in advance and subsequently adding an aromatic dihydroxy compound such as bisphenol A, hydroquinone, resorcinol (a dihydric phenol) Compound) in the presence of a Lewis acid catalyst. [A] An aromatic dihydroxy compound is reacted with a large excess thereof (about 4 times molar equivalent or more) of phosphorus oxyhalide under a Lewis acid catalyst, and then the excess phosphorus oxyhalide is completely removed by heating under reduced pressure. And then reacting the reaction product with an aromatic monohydroxy compound in the presence of a Lewis acid catalyst. And the like.

The component (d2) is represented by the formula (2). In the mono-organic phosphorus compound represented by the formula (2), the substituents R ^e , R ^f and R ^g are each independently represented by the formula (1) )), And the aromatic groups derived from dihydric phenols, in addition to those represented by the substituents R ^a , R ^b , R ^c and R ^d . Specific preferred examples of the mono-organic phosphorus compound include triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, trixylenyl phosphate, and xylenyl phenyl phosphate. Triphenyl phosphate is particularly preferred.

The component (d2) has an effect of suppressing discoloration in a dark place of the composition, and 1 to 7% by weight based on the total amount of the component (D).
Preferably 1.5-6.5 wt%, more preferably 2
-6 wt%. If the amount is less than 1 wt%, the effect of suppressing discoloration in a dark place is insufficient, while if it exceeds 7 wt%, the amount of MD generated increases. Further, the component (d2) improves the shear sensitivity of the composition (the susceptibility of a decrease in the viscosity of the molten resin to an increase in the shear rate), and improves the fluidity in a high shear rate region required for injection molding. And has the effect of improving thin-wall moldability.

As the component (d2), a predetermined amount is blended and melt kneading is carried out. Alternatively, the by-produced mono-organic phosphorus compound contained in the oligomer-type organic phosphorus compound may be used as it is. In the case of using the above method [A] as a method for producing an oligomeric organic phosphorus compound, the content of a mono-organic phosphorus compound by-produced can be controlled by the production conditions.

The content of the organic phosphorus compound (D) in the composition is 5 to 20 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). If it is less than 5 parts by weight, the flame retardant effect is insufficient. On the other hand, if it exceeds 20 parts by weight, the impact resistance and heat resistance of the resin composition decrease. Preferably 8 to
The range is 17 parts by weight, and a particularly preferred range is 10 to 10 parts by weight.
It is in the range of 15 parts by weight.

Further, it is effective and preferable to use an anti-dripping agent in combination with the component (D). Examples of the anti-dripping agent include perfluoroalkane polymers such as polytetrafluoroethylene, silicone rubber, polycarbonate / diorganosiloxane copolymer, siloxane polyetherimide, liquid crystal polymer, and the aforementioned silicone / acryl composite rubber. Particularly preferred is polytetrafluoroethylene, which is preferably in the range of 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, when the total of components (A) to (C) is 100 parts by weight. Department. If the amount is less than 0.01 part by weight, the effect of preventing dripping during combustion is insufficient, and high flame retardancy cannot be obtained. Also, 3
When the amount is more than the weight part, the moldability and rigidity are reduced.

Further, in combination with the component (D), other flame retardants other than the component (D), for example, nitrogen-containing organic compounds such as melamine, inorganic compounds such as magnesium hydroxide and aluminum hydroxide, antimony oxide, oxides Metal oxides such as bismuth, zinc oxide and tin oxide, red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, inorganic phosphorous compounds such as phosphoric anhydride, expanded graphite, silica, silica-based A glass melt or the like may be contained within a range not contrary to the gist of the present invention.

The component (E) used in the resin composition of the present invention is an antioxidant. By adding the component (E), the processing stability of the resin composition can be increased and the heat deterioration can be suppressed. it can. Further, physical properties can be maintained even in high-temperature molding. Examples of the antioxidant include a phenolic antioxidant having a molecular weight of 500 or more, a thioether-based antioxidant, and a phosphite-based antioxidant, and a phenol-based antioxidant is particularly preferable.

As the phenolic antioxidant, a hindered phenolic compound having a molecular weight of 500 or more, which shields the nature of the OH group of the phenolic compound, is preferred.
-Octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] , Pentaerythritol tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferred.

Examples of the thioether antioxidants include dialkyl-3,3'-thiodipropionate, tetrakis [methylene-3- (alkylthio) propionate] methane, and bis [2-methyl-4- (3-alkyl-thiopropionyl). Oxy) -5-tert-butylphenyl] sulfide is preferred. As the phosphite-based antioxidant, tris (2,4-di-tert-butylphenyl) phosphite and those having a pentaerythritol skeleton in the molecule are preferable, and di (2,4-di-tert-butylphenyl) pentaerythritol di-phosphite is particularly preferable. Phosphite and bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite are preferred.

The component (E) is used in an amount of 0.01 to 0.8 part by weight, preferably 0.05 to 0.7 part by weight, based on 100 parts by weight of the total of the components (A), (B) and (C). Parts, more preferably 0.1 to 0.6 parts by weight. If the amount is less than 0.01 part by weight, no effect is obtained. If the amount is more than 0.8 part by weight, the composition is not preferable because yellowing occurs and the amount of MD increases. Component (E) can be used as a single component or as a combination of two or more components.

The resin composition of the present invention may contain glass fibers, glass flakes, or the like for the purpose of modifying the resin composition.
Inorganic fillers such as glass beads, calcium carbonate, talc and mica, and reinforcing agents such as carbon fiber and charcoal can be added. The preferable addition amount is 0.01 to 60 parts by weight, more preferably 5 to 55 parts by weight, based on 100 parts by weight in total of (A) to (C).

Further, if necessary, other additives such as a lubricant, an antistatic agent, an ultraviolet absorber, a coloring agent, titanium oxide, a surface modifier, a dispersant, a plasticizer and the like can be added. The method for producing the resin composition in the present invention is not particularly limited, and the resin composition can be produced by a usual method, for example, melt blending by extrusion kneading.
Further, the molding method of a molded article made of these thermoplastic resin compositions includes extrusion molding, compression molding, injection molding, gas assist molding and the like, and is not particularly limited.

[0075]

The present invention will be described in detail with reference to the following examples. The materials used are shown below. 1. (A) Component (Polycarbonate: PC) Bisphenol A-based polycarbonate having a Mw of 20,600 produced from bisphenol A and diphenyl carbonate by a melt transesterification method and having a hydroxy group terminal amount of 33%. (B) Component (acrylonitrile / styrene copolymer: SAN) 25.0 wt% of acrylonitrile unit, 75.
Acrylonitrile / styrene copolymer (butyl acrylate / acrylonitrile / styrene copolymer: BAAS) consisting of 0 wt% and Mw of 140,000 butyl acrylate unit 10.0 w
2. A butyl acrylate / acrylonitrile / styrene copolymer having a Mw of 110,000, which is composed of at%, acrylonitrile unit 27.0 wt%, and styrene unit 63.0 wt%. (C) Component (Acrylonitrile / Butadiene / Styrene Copolymer Rubber: ABS) Powdered ABS resin having a mesh residue of less than 90% (manufactured by Mitsubishi Rayon Co., Ltd., trade name RC) (Methyl methacrylate / styrene) -Butadiene copolymer rubber: MBS) Methyl methacrylate grafted styrene / butadiene rubber (Metrene C-233A (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) whose outermost layer is coated with methyl methacrylate) (Methyl methacrylate grafted silicone acrylic rubber: Silicone rubber composite rubber) Composite rubber (manufactured by Mitsubishi Rayon Co., Ltd.) in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component whose outermost layers are coated with methyl methacrylate have a mutual intrusion network structure. METABLEN S-20 1) 4. (D) Component (Organic phosphorus compound (D1)) Organophosphorus compound obtained by the method of Reference Example 1 below. (Reference Example 1) Bisphenol A (30 liter container) equipped with an agitator, a condenser, and a heating jacket (1 molar equivalent) to phosphorus oxychloride (4
Molar equivalent) and magnesium chloride (0.025 molar equivalent)
, And the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorus oxychloride was removed from the obtained reaction mixture under reduced pressure at 120 ° C. and 20 mmHg for 4 hours.
Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the reaction was completed at 150 ° C. for 8 hours to complete the reaction. After completion of the reaction, residual phenol was removed from the reaction mixture.
After removing the product under reduced pressure at 0 ° C. and 20 mmHg for 2 hours, washing and drying the obtained product, the remaining phenol was completely removed by a thin film distillation method, and the oligomer represented by the following formula (15) was obtained. An organic phosphorus compound was obtained. The average degree of condensation N and the content (wt%) of the mono-organic phosphorus compound in the product were determined by GPC measurement to be 1.14 and 1.5 wt%, respectively.

[0076]

Embedded image

(Organic phosphorus compound (D2)) Referential Example 2 below
(Reference Example 2) Phosphorus oxychloride (1.5 mole equivalent) and magnesium chloride (0.025 mole) were used in the autoclave used in Example 1 with respect to bisphenol A (1 mole equivalent) in the autoclave used in Example 1. (Molar equivalent), and the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorus oxychloride was removed from the obtained reaction mixture under reduced pressure at 120 ° C. and 30 mmHg for 2 hours. Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the reaction was completed at 150 ° C. for 8 hours to complete the reaction. After completion of the reaction, the remaining phenol was removed from the reaction mixture under reduced pressure at 170 ° C. and 20 mmHg for 3 hours, and the obtained product was washed and dried. Then, the remaining phenol was completely removed by a thin film distillation method. An oligomeric organic phosphorus compound represented by the formula (15) was obtained. The average degree of condensation N of the obtained organic phosphorus compound and the content (wt%) of the mono-based organic phosphorus compound in the product were 2.12 and 3.5 wt%, respectively. (Organic phosphorus compound (D3)) Product name PX-200 manufactured by Daihachi Chemical Industry Co., Ltd. The average condensation degree N is 1.00, and the content of the monophosphorus compound is 0.4 wt%. Oligomeric organophosphorus compounds

[0078]

Embedded image

(Organic phosphorus compound (D4)) Triphenyl phosphate (TPP) manufactured by Daihachi Chemical Industry Co., Ltd. (Organic phosphorus compound (D5)) Product name CR733S manufactured by Daihachi Chemical Co., Ltd. 1.4. Oligomeric organophosphorus compound represented by the following formula (17) having a content of mono-based organophosphorus compound of 4.8 wt%

[0080]

Embedded image

(Organic phosphorus compound (D6)) The average degree of condensation N is 1.12, and the content of the mono organic phosphorus compound is 3.5.
wt% of an oligomeric organophosphorus compound represented by the following formula (18):

[0082]

Embedded image

5. (E) Component (phenolic antioxidant (E1)) IRGANOX 10 manufactured by Ciba Specialty Chemicals
76n-octadecyl-3- (3 ', 5'-ditertiarybutyl-4'-hydroxyphenyl) propionate (phosphite-based antioxidant (E2)) Ciba Specialty Chemicals Co., Ltd. IRGAFOS 1
68 Tris (2,4-di-tert-butylphenyl)
Phosphite 6. Other components (Fluorine-based resin: PTFE) Product name: Teflon 3 manufactured by Mitsui Dupont Fluorochemicals
0J Polytetrafluoroethylene Aqueous Dispersion Each test in Examples and Comparative Examples was performed by the following methods. (1) Flame retardancy test The obtained pellets were dried, and the cylinder temperature was 240 ° C.
Molding was performed with an injection molding machine (Autoshot 50D, manufactured by FANUC) set at a mold temperature of 65 ° C. to prepare a test piece shaped body for a combustion test. The flame retardancy was evaluated based on the UL94 standard vertical combustion test (UL94). (2) Measured at 220 ° C. under a load of 10 kg according to MFR ASTM D1238. (Unit: g / 10 min) (3) Izod impact test Measured with a 1/8 inch notch according to ASTM D256. (Unit: kgf · cm / cm) (4) Evaluation of mold deposit (MD) Injection pressure was 905 kgf / cm ² using an injection molding machine (NIIGATA CN75) set at a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. Under the conditions of a time of 3 seconds, a cooling time of 1.2 seconds, a pause time of 2 seconds, and a molding cycle of 8.3 seconds, a molded body having a test piece weight of 4 g was continuously molded.
The surface state of the mold after 00, 1,000, and 2,000 shots was visually observed. ：: No MD was observed at 1,000 shots. Δ: MD is observed in 500 shots or less. X: MD is observed in 100 shots or less. (5) Evaluation of discoloration in dark place A flat plate test piece (50 mm × 90 mm × 3 mm (thickness)) was prepared at a cylinder temperature of 260 ° C. and a mold temperature of 65 ° C.
Xenon lamp irradiation for 24 hours at 60 ° C.
The molded body was allowed to stand in a dark place at 0 ° C. for 3 days, and the yellowing degree of the molded body was visually observed. ：: Yellowing is hardly observed. Δ: Slight yellowing is observed. ×: Clear yellowing is observed.

[0084]

Examples 1 to 4 and Comparative Examples 1 and 2 The resin compositions were blended with the compositions (parts by weight) listed in Table 1 and a twin screw extruder (ZSK-25, ZSK-25,
(W & P), and a flame retardant was injected with a pump from the middle of the extruder and granulated to obtain pellets of the resin composition.

The obtained pellets were dried, and the cylinder temperature was set to 240 ° C., 250 ° C., 260 ° C., 270 ° C., 2
The temperature was set to 80 ° C., the mold temperature was set to 65 ° C., and molding was performed using an injection molding machine (Autoshot 50D, manufactured by FANUC).
The impact resistance was evaluated. A flame retardancy test was also performed at the same time. Table 1 shows the results. The results of Example 1 and Comparative Example 1 are as follows:
This shows that the composition of the present invention can maintain impact resistance even when molding at a high temperature of 260 ° C to 270 ° C. In Comparative Example 2, the amount of the antioxidant was out of the range of the present invention, and yellowing in a dark place was observed.

[0086]

Examples 5 to 9 and Comparative Examples 3 and 4 The resin compositions were blended in the compositions (parts by weight) shown in Table 2, and pellets of the resin compositions were obtained in the same manner as in Example 1. The obtained pellets were dried, and the cylinder set temperature was 260 ° C. and the mold temperature was 6 ° C.
The temperature was set at 5 ° C., the product was molded by an injection molding machine, and various evaluations were performed.

Table 2 shows the results. It can be seen that all of Examples 5 to 9 are excellent in fluidity, impact resistance, flame retardancy, low MD, and dark place discoloration resistance. In Comparative Example 3, yellowing in a dark place was observed. In Comparative Example 4, MD was remarkable.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

Industrial Applicability According to the present invention, even when molding at a high temperature, there is little deterioration in physical properties, furthermore, it has excellent resistance to discoloration in a dark place, and a mold deposit (M) generated in a molding die during molding.
It is possible to provide a flame-retardant polycarbonate-based resin composition having an extremely small amount of D) and having high fluidity and high flame retardancy suitable for thin-wall molding.

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

[Procedure amendment]

[Submission date] May 28, 1999 (1999.5.2
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction contents]

[0075]

The present invention will be described in detail with reference to the following examples. The materials used are shown below. 1. (A) Component (Polycarbonate: PC) Bisphenol A-based polycarbonate having a Mw of 20,600 produced from bisphenol A and diphenyl carbonate by a melt transesterification method and having a hydroxy group terminal amount of 33%. (B) Component (acrylonitrile / styrene copolymer: SAN) 25.0 wt% of acrylonitrile unit, 75.
Acrylonitrile / styrene copolymer (butyl acrylate / acrylonitrile / styrene copolymer: BAAS) consisting of 0 wt% and Mw of 140,000 butyl acrylate unit 10.0 w
2. A butyl acrylate / acrylonitrile / styrene copolymer having a Mw of 110,000, which is composed of at%, acrylonitrile unit 27.0 wt%, and styrene unit 63.0 wt%. (C) Component (Acrylonitrile / Butadiene / Styrene Copolymer Rubber: ABS) Powdered ABS resin having a mesh residue of less than 90% (manufactured by Mitsubishi Rayon Co., Ltd., trade name RC) (Methyl methacrylate / styrene) -Butadiene copolymer rubber: MBS) Methyl methacrylate grafted styrene / butadiene rubber (Metrene C-233A (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) whose outermost layer is coated with methyl methacrylate) (Methyl methacrylate grafted silicone acrylic rubber: Silicone rubber composite rubber) Composite rubber (manufactured by Mitsubishi Rayon Co., Ltd.) in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component whose outermost layers are coated with methyl methacrylate have a mutual intrusion network structure. METABLEN S-20 1) 4. (D) Component (Organic phosphorus compound (D1)) Organophosphorus compound obtained by the method of Reference Example 1 below (Reference Example 1) Bisphenol A (30 liter container) equipped with a stirrer, a condenser, and a heating jacket 1 molar equivalent) to phosphorus oxychloride ( 5
Molar equivalent) and magnesium chloride (0.025 molar equivalent)
, And the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorous oxychloride was obtained from the resulting reaction mixture.
It was removed under reduced pressure at 160 ° C. and 1 mmHg for 4 hours. Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the reaction was completed at 150 ° C. for 8 hours to complete the reaction. After completion of the reaction, residual phenol was removed from the reaction mixture.
After removing the product under reduced pressure at 0 ° C. and 20 mmHg for 3 hours, washing and drying the obtained product, the remaining phenol was completely removed by a thin-film distillation method, and the oligomer represented by the following formula (15) An organic phosphorus compound was obtained. The average degree of condensation N and the content (wt%) of the mono-organic phosphorus compound in the product were determined by GPC measurement.
1.12 and 0.8 wt%.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Change

[Correction contents]

(Organic phosphorus compound (D2)) Referential Example 2 below
(Reference Example 2) Phosphorus oxychloride (1.5 mole equivalent) and magnesium chloride (0.025 mole) were used in the autoclave used in Example 1 with respect to bisphenol A (1 mole equivalent) in the autoclave used in Example 1. (Molar equivalent), and the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorus oxychloride was removed from the obtained reaction mixture under reduced pressure at 120 ° C. and 30 mmHg for 2 hours. Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the reaction was completed at 150 ° C. for 8 hours to complete the reaction. After completion of the reaction, the remaining phenol was removed from the reaction mixture under reduced pressure at 170 ° C. and 20 mmHg for 3 hours, and the obtained product was washed and dried. Then, the remaining phenol was completely removed by a thin film distillation method. An oligomeric organic phosphorus compound represented by the formula (15) was obtained. The average degree of condensation N of the obtained organic phosphorus compound and the content (wt%) of the mono-based organic phosphorus compound in the product were 2.12 and 3.5 wt%, respectively. (Organic phosphorus compound (D3)) Product name PX-200 manufactured by Daihachi Chemical Industry Co., Ltd. The average condensation degree N is 1.00, and the content of the monophosphorus compound is
3.2 wt% of an oligomeric organic phosphorus compound represented by the following formula (16):

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0084]

Examples 1 to 4, Comparative Examples 1, 2, and 3
And a twin screw extruder (ZSK-2) with a cylinder temperature set at 250 ° C.
5, manufactured by W & P Co.), and a flame retardant was injected with a pump from the middle of the extruder and granulated to obtain pellets of the resin composition.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction contents]

The obtained pellets were dried, and the cylinder temperature was set to 240 ° C., 250 ° C., 260 ° C., 270 ° C., 2
The temperature was set to 80 ° C., the mold temperature was set to 65 ° C., and molding was performed using an injection molding machine (Autoshot 50D, manufactured by FANUC).
The impact resistance was evaluated. A flame retardancy test was also performed at the same time. Table 1 shows the results. The results of Example 1 and Comparative Example 1 are as follows:
This shows that the composition of the present invention can maintain impact resistance even when molding at a high temperature of 260 ° C to 270 ° C. In Comparative Example 2, the amount of the antioxidant was out of the range of the present invention, and yellowing in a dark place was observed. Comparative Example 3 shows dark yellowing
Was .

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 008

[Correction method] Change

[Correction contents]

[0086]

Examples 5 to 9 and Comparative Example 4 The resin compositions were blended in the compositions (parts by weight) shown in Table 2, and pellets of the resin compositions were obtained in the same manner as in Example 1. The obtained pellets are dried, the cylinder-set temperature is 260 ° C., the mold temperature is 65 ° C.
, And molded by an injection molding machine, and various evaluations were made.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0087

[Correction method] Change

[Correction contents]

Table 2 shows the results. It can be seen that all of Examples 5 to 9 are excellent in fluidity, impact resistance, flame retardancy, low MD, and dark place discoloration resistance. Comparative Example 4 has no MD
It was remarkable.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction contents]

[0089]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) (C08L 69/00 25:12 51:04 27:18) F term (reference) 4J002 BC062 BD154 BN153 BN163 CG021 CG031 EJ067 EV047 EW046 EW067 FD010 FD077 GQ00 4J026 AA17 AA68 AA69 AA71 AB44 AC10 AC11 AC12 AC32 BA05 BA27 BA31 DB02 DB03 DB04 DB05 DB08 FA04 GA09

Claims (7)

[Claims] 1. A polycarbonate resin (A) 50 to 98
Parts by weight, (B) an aromatic vinyl monomer component, and (b2)
Copolymer containing vinyl cyanide monomer component 49-0.1
Parts by weight, (C) (c1) an aromatic vinyl monomer component, (c
2) at least one of a vinyl cyanide monomer component and (c3) an alkyl (meth) acrylate monomer component
The seed or two or more kinds include (c4) 1 to 30 parts by weight of a copolymer obtained by graft polymerization to a rubbery polymer, and based on a total of 100 parts by weight of (A), (B) and (C). , (D) (d1) 99 to 93 wt% of one or more oligomeric organophosphorus compounds represented by the formula (1)
And (d2) 1 to 7 wt% of one or more mono-based organic phosphorus compounds represented by the formula (2) (provided that (d1)
5-20 parts by weight of an organic phosphorus compound comprising the combination of (E)
A flame-retardant resin composition comprising 0.01 to 0.8 parts by weight of an antioxidant. Embedded image Embedded image 2. The flame-retardant resin composition according to claim 1, wherein (d1) of component (D) is one or more oligomeric organic phosphorus compounds represented by formula (3). Embedded image 3. The weight average molecular weight of component (A) is 15.0.
3. The flame-retardant resin composition according to claim 1, wherein the weight-average molecular weight of the component (B) is from 50,000 to 150,000. 4. A copolymer obtained by graft-polymerizing (c) a component (c1) an aromatic vinyl monomer component and (c2) a vinyl cyanide monomer component onto (c4) a rubbery polymer; 4. The flame-retardant resin according to claim 1, wherein the (c3) alkyl (meth) acrylate monomer component comprises a combination of (c4) a copolymer graft-polymerized with a rubber polymer. Composition. 5. The flame-retardant resin composition according to claim 1, wherein the average degree of condensation N of the component (d1) is 1 or more and less than 1.2. 6. The flame-retardant resin composition according to claim 1, wherein component (E) is a phenolic antioxidant having a molecular weight of 500 or more. 7. The flame-retardant resin composition according to claim 1, further comprising polytetrafluoroethylene.