JP2000226503A - Resin composition having high flame resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame resistant resin composition excellent in flame resis tance, fluidity and impact resistance, and hardly causing mold deposit generated on a mold for molding when molding the resin by adding a specific organic phosphorus compound to a polycarbonate resin, a copolymer comprising an aromatic vinyl monomer and a vinyl cyanide monomer, or the like. SOLUTION: This composition comprises (A) 100 pts.wt. component consisting of (i) 1-100 pts.wt. polycarbonate resin and (ii) 99-0 pts.wt. copolymer comprising an aromatic vinyl monomer component and a vinyl cyanide monomer component, (B) 0.5-40 pts.wt. copolymer comprising (i) an aromatic vinyl monomer component, (ii) an alkyl (meth)acrylate monomer component and (iii) a gum polymer as constituent components, and (C) 0.1-30 pts.wt. organic phosphorus compound of the formula (X is a divalent or polyvalent organic group; Ra to Rd are each an alkyl, a cycloalkyl or an aryl; and (n) is a natural number).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention is excellent in flame retardancy, excellent in fluidity, impact resistance and coloring, and has very little mold deposit (MD) generated in a molding die during molding. The present invention relates to a polycarbonate resin composition.

[0002]

2. Description of the Related Art A resin composition (flame-retardant PC / ABS alloy) obtained by blending an ABS (acrylonitrile-butadiene-styrene) resin and an organic phosphorus compound in a polycarbonate is a non-halogen-based flame-retardant material, It is widely used as a housing material for OA equipment such as electric appliances, computers, printers, word processors, and copiers because of its excellent mechanical properties and heat resistance.

[0003] The technology relating to this material is disclosed in Japanese Patent Application Laid-Open No. 2-321.
No. 54, JP-A-2-115262,
JP-A-4-285655, JP-A-4-29855
4, JP-A-4-300937, JP-A-6-300937
192553, JP-A-6-228364,
JP-A-6-240127, JP-A-7-11119
JP, JP-A-7-26129, JP-A-7-33
971, JP-A-7-82466, JP-A-7-82466
JP-A-145307, JP-A-7-150028, JP-A-7-199681, JP-A-7-196
872, JP-A-7-196873, JP-A-7-196874, JP-A-7-331045, JP-A-7-331051, JP-A-8-339
7, JP-A-8-34916, JP-A-8-3
4926, JP-A-8-67810, JP-A-8-120169, JP-A-8-127686, JP-A-8-165392, and JP-A-8-225
737, JP-A-8-277344, JP-A-8-208972, JP-A-9-3312,
JP-A-9-48912, JP-A-9-95610, JP-A-9-104811, JP-A-9-12
4920, JP-A-9-143357, JP-A-9-143
JP-A-165518, JP-A-9-176471,
JP-A-9-183893, JP-A-9-18880
No. 8 and JP-A-9-194713.

[0004] In recent years, with the trend toward thinner devices,
There is a demand for the development of a flame-retardant material having high fluidity to reduce the weight and thickness. Attempts to achieve high fluidity in flame-retardant PC / ABS alloy materials, for example, by lowering the molecular weight of polycarbonate or increasing the ratio of ABS or SAN (styrene-acrylonitrile copolymer) to improve fluidity Has been made. However, in such an improved method, dripping is liable to occur in a UL94 combustion test, and it is difficult to obtain good flame retardancy. Further, impact resistance and heat resistance are reduced, and physical properties of the material are reduced. It is difficult to maintain balance.

[0005] In order to comply with the UL94 5VB test, 10 parts by weight or more of an organic phosphorus compound is usually blended with respect to 100 parts by weight of a resin component. In order to improve the flame retardancy of the resin, it is necessary to increase the amount of the organic phosphorus compound.However, since the impact resistance decreases accordingly, it is not easy to improve the flame retardancy and the impact resistance in a well-balanced manner. Absent.

A flame-retardant PC / A using a phosphorus-based flame retardant
In the case of a BS alloy material, a phenomenon in which a phosphorus-based flame retardant or the like adheres to the surface of a mold during molding, that is, a mold deposit (MD) occurs, which may impair productivity. As a technique for improving this, a technique of adding an oligomeric phosphate ester flame retardant is disclosed, but even when an oligomeric phosphate ester is used, it is insufficient for suppressing the MD. However, many improvements are desired.

Further, flame-retardant PC / ABS alloy materials are usually used after being colored with dyes and pigments, and it is desired that the resin has excellent coloring properties. When the base resin is yellowish, the desired color, especially OA equipment, is more light-colored than when it is white, but a large amount of dyes and pigments are required for coloring. Increasing the amount of dyes and pigments not only increases the cost of coloring, but also often results in a reduction in mechanical properties such as elongation of the material after coloring and impact resistance.

As described above, a material having high flame retardancy, high flowability, high impact resistance, high heat resistance, and good coloring properties for safety at the same time. Although there is a strong demand for a material having a low mold deposit (MD), a material in which all of these physical properties are balanced to a satisfactory level has not yet been obtained, and its development has been demanded. .

[0009]

SUMMARY OF THE INVENTION Therefore, the present invention relates to the UL
A polycarbonate resin composition that has passed the 5VB test of No. 94 and has a high level of balance between high fluidity, high impact resistance, high heat resistance, and good colorability, and has extremely low MD during molding. The purpose is to provide things.

[0010]

Means for Solving the Problems When the present inventors use an oligomeric phosphate ester having a specific molecular structure as a flame retardant, an effective flame retardant effect can be obtained with a smaller amount than in the past. I found that. Further, it has been found that the required flame retardancy level can be obtained by blending a small amount of the phosphorus compound, so that the obtained resin composition has good impact resistance. It has also been found that by using a graft rubber containing no vinyl cyanide monomer component in the graft copolymer portion as the rubber component, the fluidity, impact resistance, and colorability of the composition can be simultaneously improved. Furthermore, it has been found that in the present composition, the generation of MD during molding is extremely small. Based on these findings, the present inventors have invented the polycarbonate resin composition of the present invention.

That is, the present invention relates to (A) (A-1) 1 to 100 parts by weight of a polycarbonate resin, (A-2) (a
1) A copolymer containing 99 to 0 parts by weight of an aromatic vinyl monomer component and (a2) a vinyl cyanide monomer component, and (B) (b1 A) an aromatic vinyl monomer component, (b2) an alkyl (meth) acrylate monomer component, and (b3) a rubbery polymer as a component of the copolymer, containing 0.5 to 40 parts by weight of a copolymer. And (C) one or more organic phosphorus-based compounds represented by Chemical Formula 2, based on 100 parts by weight of the total of (A) and (B), 0.1 to 30 parts by weight,

[0012]

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(Where X is a divalent or higher valent organic group, a substituent
R^a, R^b, R^c, R^dAt least one of which is an alkyl group
Or a cycloalkyl group and another substituent R^a,
R^b, R ^c, R^dAt least one of the aryl groups
And n is a natural number. ) Consisting of flame-retardant resin
A composition.

Hereinafter, the present invention will be described in detail. The polycarbonate resin used in the present invention has a main chain composed of a repeating unit represented by the following formula (3).

[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 following chemical formula 4. )

[0017]

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(In the formula, Ar ¹ and Ar ² are each an arylene group. For example, they represent groups such as phenylene, naphthylene, biphenylene, and pyridylene, and Y is an alkylene group or a substituted alkylene group represented by the following formula. .)

[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, and in some cases, a halogen atom or an alkoxy group. May be substituted, k
Is an integer of 3 to 11, and R ⁵ and R ⁶ are independently selected for each X, and each independently represents a hydrogen atom, a lower alkyl group, an aryl group, and optionally a halogen atom, an alkoxy group. X may be substituted, and X represents a carbon atom. In addition, a divalent aromatic residue represented by the following formula 6 may be contained as a copolymer component.

[0021]

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(Wherein, Ar ¹ and Ar ² are the same as in Chemical formula 2. Z
Is a mere bond, or -O-, -CO-, -S-,-
_{SO 2 -, - CO 2 -} , - CON (R 1) - (R 1 is as defined Formula 4) is a divalent group such as. Examples of these divalent aromatic residues include those represented by the following chemical formulas (7) and (8).

[0023]

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[0024]

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(Wherein R ⁷ and R ⁸ are each independently hydrogen, halogen, a C ₁ -C ₁₀ alkyl group, C ₁ -C
_{A 10} alkoxy group, a C ₁ -C ₁₀ cycloalkyl group or a phenyl group. m and n are integers of 1 to 4;
In the case of 4, each R ⁷ may be the same or different, and when n is 2 to 4, each R ⁸ may be the same or different. Among them, one represented by the following formula 9 is a preferable example. In particular, a compound containing 85 mol% or more of a repeating unit represented by the following chemical formula 9 as 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 following formula 10, and specific examples include:
For example, Chemical Formula 11 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 is represented by the following formula:
And specific examples include, for example, Chemical Formula 13 below.

[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 used in the present invention is:
Generally, the weight average molecular weight is preferably in the range of 5,000 to 50,000, more preferably 10,000.
~ 40,000, more preferably 15,000
~ 30,000, particularly preferably 18,000 ~
25,000. If it is less than 5,000, the impact resistance is insufficient, and if it exceeds 50,000, the fluidity is insufficient, which is not preferable.

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, component (A) may optionally include (A-2) (a
The copolymer may contain 1) an aromatic vinyl monomer component and (a2) a vinyl cyanide monomer component. (A
-2) The blending of the component is preferable because the fluidity of the resin composition can be improved.

Here, the (a1) aromatic vinyl monomer component includes, for example, styrene, α-methylstyrene, paramethylstyrene, vinylxylene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like. These may be used alone or in combination of two or more. Preferred are styrene and α-methylstyrene.

The vinyl cyanide monomer component (a2) includes, for example, acrylonitrile, methacrylonitrile, etc., and one or more of these are used. The composition ratio of (a1) / (a2) in the copolymer is not particularly limited, but preferably (a1) is 95 to 5
0% by weight, (a2) is 5 to 50% by weight, and more preferably, (a1) is 92 to 65% by weight, and (a2) is 8 to 50% by weight.
35% by weight.

In (A-2), in addition to the above-mentioned components (a1) and (a2), monomers copolymerizable with these components are used within a range not to impair the purpose of the present invention. be able to. 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 copolymer (A-2) that can be used in the present invention include styrene-acrylonitrile copolymer resin (SAN) and butyl acrylate-styrene-acrylonitrile copolymer resin (BAAS). BAAS (preferably 2 to 20% by weight of a butyl acrylate monomer component in the copolymer) is particularly suitable for improving the flowability while maintaining the impact resistance of the resin composition.

Examples of the method for producing the copolymer (A-2) include generally known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Component (A)
The ratio of (A-1) and (A-2) in the above is determined according to the required mechanical strength, rigidity, moldability and heat resistance. Component (A-2) is 80 to 5 parts by weight with respect to 95 parts by weight,
More preferably, component (A-2) is 70 to 10 parts by weight based on 30 to 90 parts by weight of component (A-1). Further, a blend of the component (A-1) and the component (A-2) comprises one or more components (A-1) and one or more components (A-2). Blends can be used in the required composition ratio.

Next, the component (B) will be described. (B) is a copolymer containing (b1) an aromatic vinyl monomer component, (b2) an alkyl (meth) acrylate monomer component, and (b3) a rubbery polymer as constituent components of the copolymer. . In the present invention, by using a graft rubber containing no vinyl cyanide monomer component in the vinyl monomer component to be grafted on the rubber polymer as the component (B), the fluidity and the resistance of the resin composition are improved. The balance of impact properties can be maintained at a high level, and the color tone of the resin can be greatly improved to provide a resin composition having excellent coloring properties.

(B1) The aromatic vinyl monomer component includes (a1) shown in (A-2) of the above-mentioned component (A). In addition, (b2) alkyl (meth) acrylate monomer components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethyl (meth) acrylate.
Alkyl (meth) acrylate monomers such as acrylate and 2-ethylhexyl methacrylate can be exemplified. Further, as the rubbery polymer (b3), any one having a glass transition temperature of 0 ° C. or lower 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 Block copolymers such as diene terpolymer rubber, styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber, and hydrogenated products thereof can be used. Among these polymers, preferred are polybutadiene, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, polybutyl acrylate, and the like.

Component (B) is added to the above rubbery polymer by adding (b)
1) Aromatic vinyl monomer component, (b2) alkyl (meth) acrylate monomer component, and, if necessary, (meth) acrylic acids such as acrylic acid and methacrylic acid, and α and β such as maleic anhydride. -One or more of a maleimide-based monomer such as unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, or a glycidyl group-containing monomer component such as glycidyl methacrylate is subjected to bulk polymerization and suspension. It is obtained by graft polymerization by a method such as polymerization, bulk / suspension polymerization, solution polymerization or emulsion polymerization, particularly emulsion polymerization.

Here, the amount of the rubbery polymer used is usually 1
0 to 85% by weight, preferably 30 to 82% by weight, and more preferably 40 to 80% by weight. When a butadiene-based polymer is used as the rubbery polymer, the ratio of the butadiene component of the butadiene-based polymer is 50%. % By weight or more is preferred. If the amount of the rubbery polymer in the component (B) is less than 10% by weight, the impact resistance of a molded article obtained from the obtained polycarbonate composition is low, and if it exceeds 85% by weight, the fluidity of the obtained composition decreases. Not preferred.

The composition ratio of (b1) / (b2) is not particularly limited, and each component is blended according to the use. In the present invention, a particulate graft copolymer obtained by emulsion polymerization can be most preferably used as the component (B). In this case, the average particle size of the graft copolymer is 0.1. ~ 1.5 µm is preferred. If it is less than 0.1 μm, the impact resistance of the resin composition will be reduced, and if it exceeds 1.5 μm, the appearance of the molded product will be poor.

As the component (B) according to the present invention, MB
S resin (styrene / butadiene / methyl methacrylate resin) can be suitably used. For example, “METABLEN MBS C223A” (trade name) from Mitsubishi Rayon Co., Ltd.
Those commercially available as are particularly preferably used. In the resin composition of the present invention, the above-mentioned component (B) can be used alone or as a mixture of two or more. The compounding amount is 0.5 to 100 parts by weight of component (A). It is 40 parts by weight, preferably 0.5 to 30 parts by weight. Component (B)
If it is less than the above range, the impact resistance becomes insufficient, and if it is more than the above range, the fluidity and rigidity decrease.

The component (C) used in the present invention is an organic phosphorus compound represented by the following chemical formula (14).

[0051]

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(Where X is a divalent or higher valent organic group, a substituent
R^a, R^b, R^c, R^dAt least one of which is an alkyl group
Or a cycloalkyl group and another substituent R^a,
R^b, R ^c, R^dAt least one of the aryl groups
And n is a natural number. The component (C) is a compound represented by the formula^a, R^b, R^c, R^d
At least one of which is an alkyl group or a cycloalkyl
Group, and another substituent R^a, R^b, R^c, R^dOut of
At least one is selected from aryl groups. Archi
As a cycloalkyl group or a cycloalkyl group,
Alkyl groups or cycloalkyl groups having 5 to 6 carbon atoms are preferred.
Particularly preferably, an alkyl group having 1 to 4 carbon atoms or
Is a cyclohexyl group. The smaller the carbon number, the more organic
Low content due to high phosphorus content
High flame retardant effect is obtained.

The alkyl group, cycloalkyl group or aryl group of the substituents R ^a , R ^b , R ^c and R ^d may or may not be substituted with one or more hydrogen atoms. When substituted, the substituent includes an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group,
A group obtained by combining these substituents (eg, an arylalkoxyalkyl group) or a group obtained by combining these substituents by an oxygen atom, a sulfur atom, a nitrogen atom, or the like (eg, aryl A sulfonylaryl group) may be used as a substituent. Particularly preferred aryl groups are phenyl, cresyl, xylyl, propylphenyl, and butylphenyl.

The component (C) used in the present invention is a compound in which, in the substituents R ^a , R ^b , R ^c and R ^d in Chemical formula ¹ , an alkyl group (or a cycloalkyl group) and an aryl group are simultaneously contained. There is a characteristic. In Chemical Formula 1,
When all of the substituents R ^a , R ^b , R ^c , and R ^d are an alkyl group or a cycloalkyl group, the compound (C) has insufficient heat stability and is not suitable for preparing a resin composition. Decomposition occurs during melt kneading, and MD tends to occur during molding. On the other hand, when all are aryl groups, the thermal stability is improved, but the flame retardancy is insufficient. In the compound (C) used in the present invention, the substituent R
By simultaneously introducing an alkyl group (or a cycloalkyl group) and an aryl group in ^a , R ^b , R ^c , and R ^d ,
Its thermal decomposition is controlled. That is, (C) has a suitable thermal stability that is not easily decomposed by melt-kneading, but exhibits a high flame-retardant action during combustion.
It is considered that this effect is due to the decomposition rate of the resin and the decomposition rate of the flame retardant during combustion approaching each other. In order to suppress the generation of MD and obtain an effective flame retardant action, the ratio of the number of alkyl groups and / or cycloalkyl groups to the total number of substituents R ^a , R ^b , R ^c , and R ^d in Chemical formula 1 Is from 0.2 to
0.8, more preferably 0.4 to
0.6.

In the above formula, X is a divalent or higher valent organic group, and the divalent or higher valent organic group may be an alkylene group which may or may not be substituted, and preferably a phenylene group, a polynuclear phenol such as Bisphenols (shown in Chemical Formula 5) are mentioned, and the relative positions of two or more free valences are arbitrary. Preferred examples include hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane (bisphenol A), dihydroxydiphenyl, p, p′-dihydroxydiphenylsulfone, dihydroxynaphthalene, and the like. Particularly preferred are diphenylol. Dimethylmethane (bisphenol A).

Component (C) is usually a mixture of compounds having different values of n and different alkyl or cycloalkyl group, aryl group ratios in Chemical Formula 1.
In the case of a mixture of compounds having different values of n, the weight average value of n is generally an average value of 1 to 5. According to our research analysis, the smaller the weight average of n, the higher the compatibility with the resin and the flame retardancy. Among them, the compound of n = 1 is preferable because the balance between the flame retardancy and the mechanical properties of the resin composition is particularly excellent. Accordingly, in the component (C), the proportion of the compound represented by n = 1 is preferably 50% by weight or more, and the weight average value of n is preferably in the range of 1 to 3, and represented by n = 1. It is particularly preferred that the proportion occupied by the compound is 60% by weight or more of the component (C) and the weight average value of n is in the range of 1-2.

The compound of the component (C) of the present invention is, for example,
Phosphorus halide compounds such as phosphorus oxyhalide or derivatives thereof; dihydric phenol compounds such as bisphenol A, hydroquinone and resorcinol; phenol compounds such as 2,6-xylenol and phenol; and methyl alcohol, ethyl alcohol and isopropyl alcohol An alkyl alcohol such as butyl alcohol and cyclohexanol or a cycloalkyl alcohol compound can be synthesized as a raw material.

The condensation degree n of the component (C), the composition of the substituents, and the identification of the components were determined by gel permeation chromatography (GPC), liquid chromatography (LC), and liquid chromatography / mass spectrum (LC / M
S). The content of component (C) is determined according to the required level of flame retardancy.
It is necessary that the amount is 0.1 to 30 parts by weight based on part by weight of the component (A). If the amount is less than 0.1 part by weight, the required flame retardant effect is not exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin will be reduced. It is preferably in the range of 0.5 to 20 parts by weight, and particularly preferably in the range of 5 to 18 parts by weight.

The resin composition of the present invention comprises a compound in which all of R ^a , R ^b , R ^c , and R ^d in Chemical formula 1 are only an alkyl group or a cycloalkyl group, or only an aryl group, a trialkyl phosphate, and a trialkyl phosphate. Organic phosphorus-based compounds other than the component (C) such as allyl phosphate (hereinafter, collectively referred to as component (D)) may be contained within a range not inconsistent with the gist of the present invention. Usually, the content of the component (D) is 30% by weight or less per compound based on the total amount of the components (C) and (D), and 40% by weight or less as a whole of the component (D). When the component (D) is contained in excess of the above values, it becomes difficult to maintain a good balance of flame retardancy, heat resistance, fluidity, and MD of the resin composition.

Further, it is effective and preferable to use an anti-dripping agent in combination with the component (C). Examples of the anti-dripping agent include perfluoroalkane polymers such as polytetrafluoroethylene, silicone rubber, polycarbonate / diorganosiloxane copolymer, siloxane polyetherimide, liquid crystal polymer, and silicone acrylic composite rubber. Particularly preferred is polytetrafluoroethylene, and it is preferably in the range of 0.01 to 3 parts by weight, and more preferably 0.05 to 2 parts by weight, when component (A) is 100 parts by weight. 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. On the other hand, when the amount exceeds 3 parts by weight, the formability and rigidity are reduced.

Further, in combination with component (C), other flame retardants other than (C), 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 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. A 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 of the total of (A) and (B).

Further, if necessary, ordinary additives such as heat stabilizers, antioxidants, lubricants, antistatic agents, ultraviolet absorbers, coloring agents, titanium oxide, surface modifiers, dispersants, plasticizers, etc. Can be added. As a heat stabilizer,
There are a thioether-based heat stabilizer, a phosphite-based heat stabilizer, a phenol-based heat stabilizer having a molecular weight of 5,000 or more, and the like.
3,3′-thiodipropionate, tetrakis [methylene-3- (alkylthio) propionate] methane, and bis [2-methyl-4- (3-alkyl-thiopropionyloxy) -5-tert-butylphenyl] sulfide are preferred. As the phosphite-based heat stabilizer, those having a pentaerythritol skeleton in the molecule are preferable, and di (2,4-di-tert-butylphenyl) is particularly preferable.
Pentaerythritol diphosphite, bis (2,6-
Ditertiary butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and a hindered phenolic compound having a molecular weight of 500 or more, in which the properties of the -OH group of the phenolic compound are shielded, is particularly preferred as the phenolic stabilizer. -Octadecyl-3-
(3 ', 5'-Ditert-butyl-4'-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-
4-hydroxyphenyl) propionate] is preferred.

The method for producing the resin composition of 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 molded articles made of these thermoplastic resin compositions includes extrusion molding, compression molding, injection molding,
There is gas assist molding or the like, and there is no particular limitation.

[0065]

The present invention will be described in detail with reference to the following examples. The materials used are shown below. 1. (A-1) Component (Polycarbonate: PC) Bisphenol A-based polycarbonate Mw = 20,500 hydroxy group terminal amount = 35% produced by melt transesterification from bisphenol A and diphenyl carbonate. (A-2) Component (Acrylonitrile / styrene copolymer: SAN) 25.0 wt% of acrylonitrile unit, 75.
Acrylonitrile / styrene copolymer consisting of 0 wt% (butyl acrylate / acrylonitrile / styrene copolymer: BAAS) butyl acrylate unit 10.0 w
2. A butyl acrylate / acrylonitrile / styrene copolymer composed of t%, acrylonitrile unit 27.0 wt%, and styrene unit 63.0 wt% (B) Component (styrene / butadiene / alkyl methacrylate copolymer: MBS) MBS (trade name METABLEN C223A) manufactured by Mitsubishi Rayon Co., Ltd. (C) Component (Organic phosphorus compound (C1)) An organic phosphorus compound represented by the formula 1, wherein X is a diphenyloldimethylmethane group, and the substituents R ^a , R ^b , R ^c , ^Rd is ^composed of a methyl group and a phenyl group, the ratio of the number of methyl groups to the total number of substituents R is 0.5, and the average value of the number of repetitions n is 1.15. (Organic phosphorus compound (C2)) An organic phosphorus compound represented by the formula 1, wherein X is a diphenyloldimethylmethane group, and the substituents R ^a , R ^b , R ^c and R ^d are all A compound consisting of a methyl group and having an average number of repetitions n of 1.2. (Organic phosphorus compound (C3)) Phenyl bisphenol A polyphosphate (trade name CR, manufactured by Daihachi Chemical Co., Ltd.)
741) (Organic phosphorus compound (C4)) Phenylresorcinol polyphosphate (trade name CR73) manufactured by Daihachi Chemical Co., Ltd.
3S) 5. Other components (acrylonitrile-butadiene-styrene copolymer:
ABS) Mitsubishi Rayon Co., Ltd. ABS (brand name R)
C) A powdery resin having a mesh residue of less than 90% (fluorine resin: PTFE) Polytetrafluoroethylene (trade name: Teflon 30J) aqueous PTFE dispersion manufactured by Du Pont-Mitsui Fluorochemicals

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Examples 1 to 4 and Comparative Examples 1 to 4 The resin compositions were blended in the composition (parts by weight) shown 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. (1) Flame retardancy test The obtained pellets were dried, and the cylinder temperature was 260 ° C.
Molding was performed using an injection molding machine (Autoshot 50D, manufactured by FANUC) set at a mold temperature of 65 ° C. to prepare a test piece shaped molded body (thickness 1/10 inch) for a combustion test. Flame retardancy evaluation was performed based on the UL94 standard vertical combustion test (UL94-5VB), and the average quenching time (unit: seconds) performed on five test pieces was evaluated. (2) Measured at 220 ° C. and under a load of 5 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. The test piece was molded by an injection molding machine set at a cylinder temperature of 260 ° C. and a mold temperature of 65 ° C. (unit:
kgf · cm / cm) (4) Heat deformation temperature measurement (HDT) 1/8 inch, load 1 according to ASTM D648
It was measured at 8.6 kgf / cm ² . (5) Mold Deposit (MD) Evaluation Using an injection molding machine (NIIGATA CN75) set at a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C., an injection pressure of 905 kgf / cm ² , an injection time of 3 seconds, Under a condition of 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, and the mold surface state after 200 shots was visually observed. ：: MD generation is extremely small. X: MD is generated frequently. (6) Colorability of composition 0.5 parts by weight of titanium oxide is blended with 100 parts by weight of the obtained pellets, kneaded at a cylinder temperature of 240 ° C with a 50 mm single screw extruder, and white colored of the resin composition by visual observation. The sex was examined. ：: excellent white coloring. X: White coloring property is slightly inferior.

Table 1 shows the results. In all of Examples 1 to 4, excellent characteristics are obtained in a well-balanced manner with respect to flame retardancy, fluidity, impact resistance, heat resistance, colorability, and MD generation state. Further, an effective flame retardant effect is obtained with a small amount of an organic phosphorus compound. On the other hand, as compared with the Examples, Comparative Example 1 was inferior in impact resistance and coloring, Comparative Example 2 was inferior in flame retardancy, Comparative Example 3 was inferior in flame retardancy, and Comparative Example No. 4 is inferior in heat resistance and generation of MD is observed.

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[Table 1]

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As described above, according to the present invention, a polycarbonate-based resin composition having improved flame retardancy, fluidity, impact resistance, and colorability at the same time, and having very little MD during molding. Can be provided.

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[Procedure amendment]

[Submission date] April 6, 1999 (1999.4.6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

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[Claims]

Embedded image(Where X is a divalent or higher valent organic group, a substituent R^a, R^b, R
^c, R^dAt least one of which is an alkyl group or a cyclo
From the alkyl group, the other substituent R^a, R^b, R ^c, R^d
At least one is selected from aryl groups;
Is a natural number. )

[Procedure amendment 2]

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[Procedure amendment 3]

[Document name to be amended] Statement

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[Table 1]

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J002 BC01X BC06X BC07X BC08X BC09X BD154 BG044 BG10X BN06X BN10X BN12X BN14X BN16X CF184 CG01W CG02W CG024 CG03W CM044 CP034 CP174 CQ01G FD 050 FD 010 FD 010 FD 010 FD

Claims (6)

[Claims] (A) (A-1) Polycarbonate resin
1 to 100 parts by weight, (A-2) (a1) aromatic vinyl simple
Monomer component and (a2) a vinyl cyanide monomer component
99 to 0 parts by weight of the copolymer, and (A) 100 parts by weight
(B) (b1) aromatic vinyl monomer component
(B2) alkyl (meth) acrylate monomer component
And (b3) the rubbery polymer with the constituent components of the copolymer.
Containing from 0.5 to 40 parts by weight of a copolymer,
(C) to 100 parts by weight in total of (A) and (B)
One or more organophosphorus compounds represented by 1
A flame-retardant resin composition comprising 1 to 30 parts by weight. Embedded image(Where X is a divalent or higher valent organic group, a substituent R^a, R^b, R
^c, R^dAt least one of which is an alkyl group or a cyclo
From the alkyl group, the other substituent R^a, R^b, R ^c, R^d
At least one is selected from aryl groups;
Is a natural number. ) 2. In the formula (1), the ratio of the number of alkyl groups and / or cycloalkyl groups to the total number of R ^a , R ^b , R ^c and R ^d is 0.2 to 0.8. The flame-retardant resin composition according to the above. 3. In the formula (1), the ratio of the number of alkyl groups and / or cycloalkyl groups to the total number of R ^a , R ^b , R ^c and R ^d is from 0.4 to 0.6. The flame-retardant resin composition according to the above. 4. A mixture of two or more kinds of organophosphorus compounds having different values of n, wherein the proportion of the compound represented by n = 1 is 50% by weight or more, and the weight average of n is 4. The flame-retardant resin composition according to claim 1, wherein the value is in the range of 1 to 3. 5. 5. The component (C) according to claim 1, wherein the proportion of the organic phosphorus compound represented by n = 1 is 60% by weight or more, and the weight average value of n is in the range of 1-2. The flame-retardant resin composition according to the above. 6. The flame-retardant resin composition according to claim 1, wherein in the formula (1), X is diphenyloldimethylmethane.