JPH06240126A - Flame retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, comprising a polycarbonate-based resin, an ABS-based resin, a copolymer containing a specific structural unit, a phosphorus compound, a silicone and/or a fluorine-based resin, excellent in flame retardancy and heat resistance and useful as OA equipment, etc. CONSTITUTION:This resin composition comprises (A) preferably 40-95 pts.wt. polycarbonate-based resin, (B) preferably 4-39 pts.wt. ABS-based resin, (C) preferably 1-36 pts.wt. copolymer containing a structural unit composed of one or more of (meth)acrylic acid, an unsaturated carboxylic acid anhydride-based monomer and an N-substituted maleimide, (D) a phosphorus compound such as trimethyl phosphate in an amount of 5-20 pts.wt. 100 pts.wt. sum total of the components (A) to (C) and (E) a silicone such as polydimethylsiloxane and/or a fluorine-based resin such as polytetrafluoroethylene in an amount of 0.01-5 pts.wt. based on 100 pts.wt. sum total of the components (A) to (C). Furthermore, a salt of a group 2B metal with a carboxylic acid is preferably added to produce this resin composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition. More specifically, polycarbonate resin and acrylonitrile-butadiene-styrene (AB
S) a polymer alloy with a resin, a phosphorus compound and at least one selected from silicone and / or fluorine resins, (meth) acrylic acid, unsaturated carboxylic acid anhydride monomers, and N-substituted maleimides. The present invention relates to a flame-retardant resin composition that exhibits excellent flame retardancy and heat resistance by adding a copolymer containing a structural unit derived from a seed.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used industrially because they have excellent mechanical properties and thermal properties. However, because of the problem of high melt viscosity and poor moldability, many polymer blends with other thermoplastic resins have been developed. Among them, polymer alloys with ABS resins are used in the automotive field, OA equipment field, electronic field, and electronic field. -Widely used in the electric field, etc. On the other hand, in recent years O
There is a strong demand for flame-retardant resin materials to be used, mainly for applications such as A appliances and home appliances, and many flame-retardant resins have been developed and studied in order to meet these demands. Conventionally, chlorine- or bromine-containing compounds, phosphorus compounds, etc. have been mainly used for flame-retarding resin components including polycarbonate-based resins, and in many cases, in addition to these flame-retardants, antimony trioxide, etc. are also used as flame-retardants. It is also used as an auxiliary agent.

[0003]

When a chlorine- or bromine-containing compound is used for flame-retarding a resin containing a polycarbonate resin, the flame-retarding effect is relatively large,
When a fire or incineration process occurs, a toxic or harmful substance is generated, which poses a problem of endangering human life, making emergency or fire extinguishing difficult, or causing environmental pollution. Therefore, it is desired to develop a flame-retardant resin containing no chlorine or bromine-containing compound or containing a small amount of chlorine or bromine-containing compound. When a general phosphoric acid ester is used as a flame retardant among phosphorus compounds, the blending amount becomes large in order to obtain sufficient flame retardancy, so the heat resistance and impact of the obtained flame retardant resin There was a problem such as a decrease in strength. The present invention solves these conventional problems, and an object thereof is to provide a flame-retardant resin composition that retains excellent flame retardancy and has good impact resistance and heat resistance. Especially.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that the heat resistance of a flame-retardant polymer alloy with a polycarbonate resin and an ABS resin using a phosphorus compound as a flame retardant essentially containing no chlorine or bromine. As a result of intensive studies to improve the properties, polymer alloys with polycarbonate resins and ABS resins, phosphorus compounds, silicone and / or fluorine resins, (meth) acrylic acid, unsaturated carboxylic acid anhydrides. The inventors have found that excellent flame retardancy and heat resistance are exhibited by adding a copolymer containing a structural unit derived from at least one selected from a system monomer and an N-substituted maleimide, and have reached the present invention.

That is, the present invention provides (1) the following components (A) polycarbonate resin (B) ABS resin (C) (meth) acrylic acid, unsaturated carboxylic acid anhydride monomer, N-substituted maleimide A flame-retardant resin composition containing a copolymer (D) a phosphorus compound (E) a silicone and / or a fluorine-based resin, containing a structural unit derived from at least one selected from the group consisting of (2) Periodic Table 1A and 2A. The flame-retardant resin composition according to (1), further containing a salt of at least one metal selected from Group 8 and 2B metals, (3) The composition according to (1), (A ′) 95 to 50 parts by weight of polycarbonate resin, 4 to 49 parts by weight of ABS resin, styrene-maleic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid copolymer,
One or more copolymers 1 to 46 selected from styrene-N-phenylmaleimide copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, styrene-N-phenylmaleimide-maleic anhydride copolymer
100 parts by weight of polymer blend,
From 5 to 20 parts by weight of (B ') phosphate ester, 0.0001 to 1 part by weight of a salt of (C') carboxylic acid and a metal of Group B of the periodic table, (D ') from silicone and / or polytetrafluoroethylene The present invention relates to a flame-retardant resin composition containing 0.01 to 2 parts by weight of at least one selected.

The polycarbonate resin used in the present invention is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method.
Typical examples of the dihydric phenol are 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1.
-Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4- Examples thereof include hydroxyphenyl) sulfide and bis (4-hydroxyphenyl) sulfone. A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane-based one, and more preferably one containing bisphenol A as a main raw material. Further, as the carbonate precursor, carbonyl halide,
Examples thereof include carbonyl ester and haloformate, and specifically, phosgene, diphenyl carbonate, dimethyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof. In producing a polycarbonate resin, one or more of these dihydric phenols can be used. The polycarbonate resins thus obtained may be used in combination of two or more. In the present invention, a halogen-free polycarbonate is preferably used. The amount of the polycarbonate resin used in the present invention is preferably 50 to 95 parts by weight, more preferably 40 to 95 parts by weight.

The ABS resin used in the present invention is a graft polymer obtained by graft-polymerizing a vinyl monomer containing an aromatic vinyl monomer to a rubber-like polymer, and further, It also includes a blend of a polymer obtained by polymerizing a vinyl-based monomer containing an aromatic vinyl-based monomer and the graft polymer. The graft polymer is a rubber-like polymer having a glass transition temperature of 10 ° C. or lower, and one or more monomers selected from aromatic vinyl-based monomers, (meth) acrylonitrile, (meth) acrylic acid ester, and the like. Is obtained by graft polymerization. Aromatic vinyl monomers include styrene and α
-Methylstyrene, nuclear methyl-substituted styrene, t-butylstyrene, hydroxystyrene, halostyrene and the like. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate,
Examples thereof include ethyl methacrylate. These monomers can be used in combination of two or more kinds. Monomers preferably used in the graft polymer used in the present invention are styrene, acrylonitrile and / or methyl methacrylate. The method for producing the graft polymer is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. Examples of the rubber-like polymer used for the graft polymer include polybutadiene, butadiene-styrene copolymer, butadiene-styrene block copolymer, hydrogenated butadiene-styrene block copolymer, butadiene-acrylonitrile copolymer, and acrylic type. Rubber, ethylene-propylene (diene component) copolymer, isobutylene-isoprene copolymer,
Examples thereof include styrene-isoprene block copolymers, hydrogenated styrene-isoprene block copolymers, polyurethane rubbers, polyamide rubbers, and silicone rubbers. In the present invention, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, silicone rubber, etc. are preferably used.

As the polymer to be blended with the graft polymer, a polymer obtained by polymerizing the monomers used in the above graft polymer can be used. Polymers preferably used are α-methylstyrene / acrylonitrile copolymer, styrene / acrylonitrile copolymer, α
-Methylstyrene / methyl methacrylate copolymer, styrene / methyl methacrylate copolymer and the like. These polymers may be used alone or in combination of two or more. The method for producing these polymers is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. The amount of the ABS resin used in the present invention is preferably 4 to 49 parts by weight, more preferably 4 to 39 parts by weight.

The copolymer (C) used in the present invention is
An unsaturated monomer containing at least one selected from (meth) acrylic acid, an unsaturated carboxylic acid anhydride-based monomer, and an N-substituted maleimide is used together with another copolymerizable unsaturated monomer. It is a copolymer obtained by polymerization and further includes a polymer obtained by modifying the polymer with a rubbery polymer. As (meth) acrylic acid,
Acrylic acid, methacrylic acid, unsaturated carboxylic acid anhydride-based monomers include maleic anhydride, and N-substituted maleimide-based monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, and N-propyl. Maleimide,
Examples thereof include N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (alkyl-substituted phenyl) maleimide and N- (hydroxyl-substituted phenyl) maleimide. The other copolymerizable unsaturated monomer is not particularly limited as long as it is a copolymerizable unsaturated monomer, but it is preferably an aromatic vinyl monomer or a (meth) acrylic acid monomer. Body, an unsaturated monomer containing at least one selected from vinyl cyanide-based monomers is used. As the aromatic vinyl-based monomer, styrene, α-methylstyrene, nuclear methyl-substituted styrene, t-butylstyrene,
Hydroxystyrene etc. are mentioned. Examples of the (meth) acrylic acid ester-based monomer include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and examples of the vinyl cyanide-based monomer include acrylonitrile and methacrylonitrile. The method for producing the copolymer (C) is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. The copolymer (C) preferably used in the present invention is
Styrene / methacrylic acid copolymer, styrene-maleic anhydride copolymer, α-methylstyrene / acrylonitrile / N-phenylmaleimide copolymer, styrene / acrylonitrile / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / Maleic anhydride copolymers and rubber modified products thereof. These copolymers may be used alone or in combination of two or more. The amount of the copolymer (C) used in the present invention is preferably 1 to 46 parts by weight, more preferably 1 to 36 parts by weight.

The phosphorus compound used in the present invention is not particularly limited as long as it is a compound having a phosphorus atom, but an organic phosphorus compound represented by the general formula (I) is preferably used. In the formula, R ₁ , R ₂ and R ₃ each independently represent a C _{1 to} C ₈ alkyl group or a C _{6 to} C ₂₀ aryl group optionally substituted with alkyl, and n is 0 or 1. Examples of these phosphorus compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixyl phosphate. Nylphosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate , Di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate, di Chiruhosufeto, monobutyl phosphate, di -2
-Ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and condensates thereof and the like. To be

Examples of the phosphite include trimethylphosphite, triethylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tributoxyethylphosphite, trioleylphosphite, triphenylphosphite, tricresylphosphite. Fight, trixylenylphosphite, tris (isopropylphenyl) phosphite, trisnonylphenylphosphite, tris (o-phenylphenyl) phosphite, tris (p-phenylphenyl) phosphite, trinaphthylphosphite, cresyldiphenyl Phosphite, xylenyl diphenyl phosphite, diphenyl (2-ethylhexyl) phosphite, di (isopropylphenyl) phenyl phosphite, o-phenylphenyl dicresi Phosphite, dibutyl phosphite, monobutyl phosphite, di-2-ethylhexyl phosphite, monoisodecyl phosphites and condensates thereof and the like. Examples of phosphorus compounds other than these include triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, and diethyl phenylphosphonate. These phosphorus compounds may be used alone or in combination of two or more. The blending amount of these phosphorus compounds is not particularly limited, but preferably (A),
1 to 30 per 100 parts by weight of the total of the components (B) and (C)
The range is parts by weight. More preferably, it is in the range of 5 to 20 parts by weight. If the amount is less than 1 part by weight, a sufficient flame retarding effect cannot be obtained, and if the amount is more than 30 parts by weight, the heat resistance of the resulting composition is remarkably lowered, and volatile components increase during molding. Cause

The metal salt used in the present invention is not particularly limited, but as the acid component, sulfuric acid, sulfurous acid, sulfonic acid, carboxylic acid, etc. are preferably used, and more preferably carboxylic acid is used. As the metal component, preferably, metals of Group 1A, Group 2A, Group 8 and Group 2B of the periodic table are used,
More preferably, a Group 2B metal of the periodic table is used. The carboxylic acid metal salt has a carboxylic acid component represented by the general formula R (COO
H) n (wherein R represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms or a derivative thereof, and n represents an integer of 1 or more). In this carboxylic acid metal salt, a free carboxyl group may be present, and a salt containing no halogen is preferable. Examples of preferred carboxylic acid components include formic acid, acetic acid, propionic acid, butyric acid, valeric acid,
Hexanoic acid, octanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, Examples thereof include methacrylic acid, crotonic acid, oleic acid, fumaric acid, maleic acid, benzoic acid, phthalic acid and cinnamic acid. A preferred metal component in combination with a carboxylic acid is a metal of Group 2B of the Periodic Table. Periodic table 2B
Zn, Cd as the metal component preferably used in the group I metal
And Zn is more preferably used. These metal salts composed of a carboxylic acid component and a metal component can be arbitrarily combined, and further, these metal salts can be used alone or in combination of two or more kinds. In the present invention, preferably zinc formate, zinc acetate, zinc propionate, zinc stearate,
Zinc butyrate, zinc valerate, zinc hexanoate, zinc benzoate and the like are used, and zinc acetate is more preferably used.
The amount of these metal salts blended is not particularly limited, but is preferably in the range of 0.0001 to 1 part by weight, and more preferably 100 parts by weight of the components (A), (B) and (C). It is in the range of 0.0001 to 0.1 part by weight. If the amount is smaller than this, a sufficient flame retarding effect cannot be obtained, and if the amount is larger than this, there are problems such as acceleration of decomposition of the polycarbonate resin. The phenomenon that the molten resin that burns when the resin burns drops is not a preferable phenomenon for disaster prevention. For the purpose of preventing such resin dripping, both the fluororesin and silicone used in the present invention effectively act.

[0013] There is no particular limitation as long as it has an O) n-skeleton. Examples of the silicone used in the present invention include polydimethylsiloxane, polymethylphenylsiloxane, amino-modified silicone, mercapto-modified silicone, and epoxy-modified silicone. These may be used alone or in combination of two or more. Furthermore, these silicones can be used in a wide range of molecular weights of several hundreds to several millions, and their forms are oily, varnish-like,
It may be in the form of gum, resin or the like. In the present invention, polydimethylsiloxane is preferably used.

Examples of the fluorine-based resin used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoride. Examples thereof include ethylene-ethylene copolymers, polytrifluoroethylene chloride, and polyvinylidene fluoride. These may be used alone or in combination of two or more.
The fluorinated resin may be in any form such as emulsion, suspension, microfibril, powder and granule. In the present invention, polytetrafluoroethylene is preferably used. The amount of silicone and / or fluororesin used in the present invention is in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). The amount of silicone and / or fluorine resin is 0.01
If it is less than 5 parts by weight, a sufficient anti-dripping effect cannot be obtained, and if it exceeds 5 parts by weight, the blended resin composition may cause defects such as poor appearance of the molded product and increase in melt viscosity.

In the present invention, if desired, it is also possible to mix a thermoplastic resin other than those shown in the claims in an amount within a range that does not impair the flame retardancy. Typical examples of them are polystyrene resins (PS, HI
PS), polyester resins (PBT, PET), (modified) polyethylene, (modified) polypropylene, (modified) ethylene / propylene copolymer resin, polyphenylene ether, polyamide resin, polyacetal, polymethyl methacrylate, etc. Can be mentioned. These resins can be used in combination of two or more kinds.

The flame-retardant resin composition of the present invention does not use a compound containing bromine or chlorine as a flame-retardant component,
Although it exhibits an excellent flame retardant effect, a commonly used known flame retardant additive may be used in combination. Further, known flame retardant additives may be used in combination. The flame retardant additive is not particularly limited as long as it has a flame retardant effect, and includes red phosphorus, chlorine or bromine containing compounds, antimony compounds, nitrogen compounds, thermally expansive graphite, metal oxides, metal hydroxides. Flame retardant additives such as compounds, polynuclear substituted hydroxystyrenes, guanamine resins, phenol resins, melamine resins and urea resins can be used. These flame retardant additives may be used alone or in combination of two or more.

There is no particular limitation on the method for mixing the resin and the flame retardant, and any means can be adopted as long as they can be mixed uniformly. For example, mixing, kneading, and the like using various mixing machines such as an extruder, a Henschel mixer, a Banbury mixer, a kneader, and a heating roll can be appropriately adopted. At this time, if necessary, various fillers, additives and the like can be blended in an amount such that the effect is exhibited within a range that does not impair the flame retardancy. Examples thereof include glass fibers, asbestos, carbon fibers, aromatic polyamide fibers, potassium titanate whisker fibers, metal fibers, ceramic fibers, fibrous fillers such as boron whisker fibers, mica, silica,
Fillers such as talc, clay, calcium carbonate, glass beads, glass balloons, glass flakes, mold release agents, lubricants, plasticizers, ultraviolet absorbers, light stabilizers, antioxidants, heat stabilizers, anti-aging agents, Examples include additives such as dyeing agents (face). Further, an impact strength improving material for improving the properties of the polymer blend, a compatibilizing component and the like can be added.

[0018]

The following examples are provided to further illustrate the present invention, but these examples are not intended to limit the invention in any way. Examples 1 to 8 and Comparative Examples 1 to 5 The components shown in Table 1 were mixed at a compounding ratio in the table with a Henschel mixer, and then a 30 mmφ twin-screw extruder (Ikegai Tekko KK, P
CM-30), melt kneading and extruding at 280 ° C.,
Pelletized with a pelletizer. Based on the pellets thus obtained, the UL combustion test, Izod impact strength and deflection temperature under load were measured. The results are shown in Table 1.
UL flammability test was conducted by injection molding from the obtained pellets.
A 27 mm x 12.7 mm x 1.6 mm combustion test piece was prepared to measure the flame retardancy of the resin composition by subject 94 (UL-9 of Underwriters Laboratory, Inc., USA).
4) Measured according to the vertical burning test. For Izod impact strength, a notched test piece with a width of 3.2 mm was prepared, and J
It was measured according to IS K-7110. The deflection temperature under load was measured according to the method A of JIS K7207.

The polymers and flame retardant components used in Table 1 are as follows. (A) Polycarbonate (Novarex 7030PJ manufactured by Mitsubishi Kasei Co., Ltd.) (B-1) 60% by weight of styrene / acrylonitrile mixture (weight ratio 75/25) is converted into 40% by weight of polybutadiene rubber having an average particle size of 0.3 μm. Graft polymer grafted by emulsion polymerization (B-2) Styrene / acrylonitrile (weight ratio 75 /
25) Copolymer obtained by suspension polymerization of the mixture (C-1) Copolymer obtained by solution polymerization of a styrene / N-phenylmaleimide / maleic anhydride (weight ratio 49/48/3) mixture C-2) Copolymer obtained by suspension polymerization of styrene / acrylonitrile / N-phenylmaleimide (weight ratio 65/25/10) (C-3) Styrene / acrylonitrile / methacrylic acid (weight ratio 65/25 / Copolymer obtained by emulsion polymerization of (10) (D) Triphenyl phosphate (TPP manufactured by Daihachi Chemical Industry Co., Ltd.) (E-1) Polytetrafluoroethylene (Teflon Mitsui DuPont Fluorochemical Co., Ltd.) 6J) (E-2) Polydimethylsiloxane (Toshiba Silicone Co., Ltd. TSF451-1000) (F-1) Zinc acetate (Wako Pure Chemical Industries, Ltd. reagent) (F-2) Sodium sulfate (wa Pure Chemical Industries Co., Ltd. reagent) (F-3) sodium benzene sulfonate (manufactured by Wako Pure Chemical Industries, Ltd. reagent)

[0020]

[Table 1]

[0021]

According to the present invention, there is provided a flame-retardant resin composition having excellent flame retardancy, impact resistance and heat resistance, which is used for electronic and electric products, office automation equipment and the like, and materials for various parts. Can be suitably used as.

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Claims (3)

[Claims] 1. A flame-retardant resin composition comprising the following components. (A) Polycarbonate-based resin (B) Acrylonitrile-butadiene-styrene-based resin (C) Structure derived from at least one selected from (meth) acrylic acid, unsaturated carboxylic acid anhydride-based monomer, and N-substituted maleimide Copolymer Containing Unit (D) Phosphorus Compound (E) Silicone and / or Fluorine Resin 2. The flame-retardant resin composition according to claim 1, further comprising a salt of at least one metal selected from metals of Group 1A, 2A, 8 and 2B of the periodic table. 3. The composition according to claim 1, wherein (A ′) a polycarbonate resin (95 to 50 parts by weight), an acrylonitrile-butadiene-styrene resin (4 to 49 parts by weight),
Styrene-maleic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid copolymer, styrene-N-phenylmaleimide copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, styrene-N- 100 parts by weight of a polymer blend consisting of 1 to 46 parts by weight of one or more copolymers selected from phenylmaleimide-maleic anhydride copolymer, 5 to 20 parts by weight of (B ') phosphate ester, and (C') carvone. Acid and Periodic Table 2
A flame-retardant resin composition comprising 0.0001 to 1 part by weight of a salt with a Group B metal and 0.01 to 2 parts by weight of (D ') silicone and / or polytetrafluoroethylene.