JPH0616918A - Flame retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame retardant resin composition excellent in flame retardancy and impact and heat resistance by blending a resin component containing a polycarbonate-based resin with a phosphorus compound, a metallic carboxylate and a silicone and/or a fluororesin. CONSTITUTION:The flame retardant resin composition comprises 100 pts.wt. thermoplastic resin containing a polycarbonate resin and other resins, e.g. a blend composed of 99-50wt.% polycarbonate-based resin (preferably a halogen- free polycarbonate-based resin) and 1-50wt.% ABS-based resin, (B) preferably 1-30 pts.wt., more preferably 5-20 pts.wt. phosphorus compound such as a phosphoric acid ester, e.g. trimethyl phosphite, (C) preferably 0.0001-l pt.wt., more preferably 0.0001-0.1 pt.wt. salt of a carboxylic acid with a group IIB metal of the periodic table (preferably zinc acetate) and (D) 0.01-5 pts.wt., preferably 0.01-2 pts.wt. silicone (preferably polydimethylsiloxane) and/or fluororesin (preferably polytetrafluoroethylene).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition. More specifically, it relates to a flame-retardant resin composition in which a flame-retardant agent containing a phosphorus compound and a specific carboxylic acid metal salt is mixed with a resin component containing at least a polycarbonate resin as one component.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used industrially because they have excellent mechanical properties and thermal properties. However, since it has a problem of poor moldability, many polymer blends with other thermoplastic resins have been developed. Among them, polystyrene resins, acrylonitrile butadiene styrene (ABS) resins, polyester resins, etc. Polymer alloys are widely used in the fields of automobiles, office automation equipment, electronics and electricity, etc. On the other hand, in recent years, there has been a strong demand for flame-retardant resin materials used mainly for applications such as office automation equipment and home electric appliances, and many flame retardants 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 phosphorus compound is used, the flame retardant effect is relatively lower than that of a chlorine- or bromine-containing compound, so that not only sufficient flame retardancy cannot be obtained, but in order to obtain sufficient flame retardancy, Since the blending amount becomes large, there is a problem that heat resistance and impact strength of the obtained flame-retardant resin are lowered. The present invention solves these conventional problems, and an object thereof is to provide a flame retardant resin composition having excellent flame retardancy, impact resistance and heat resistance.

[0004]

[Means for Solving the Problems] The inventors of the present invention have earnestly studied to improve the flame retardancy of a resin component containing at least a polycarbonate resin as one component by using a flame retardant containing essentially no chlorine or bromine. As a result, the inventors have found that an excellent flame retardant effect is exhibited by using a flame retardant containing a phosphorus compound and a metal salt of a carboxylic acid, and further adding a silicone and / or a fluororesin, and thus the present invention has been achieved. .

That is, the present invention provides (1) a thermoplastic resin containing the following components (A) a polycarbonate resin and a resin other than the polycarbonate resin (B) a phosphorus compound (C) a carboxylic acid and a metal of Group 2B of the periodic table. (D) a flame-retardant resin composition containing a silicone and / or a fluorine-based resin, (2) the composition according to (1) is (A ') a polycarbonate-based resin in an amount of 99 to 50% by weight and an ABS-based resin. 100 parts by weight of polymer blend consisting of 1 to 50% by weight, (B ')
5 to 20 parts by weight of phosphoric acid ester, 0.0001 to 1 part by weight of a salt of (C ′) carboxylic acid and a metal of Group 2B of the periodic table,
(D ′) A flame-retardant resin composition comprising 0.01 to 2 parts by weight of silicone and / or polytetrafluoroethylene.

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 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 having one or more ester oxygen atoms directly bonded to the phosphorus atom is preferably used. 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 is preferably the resin component 10
It is in the range of 1 to 30 parts by weight with respect to 0 parts by weight. More preferably, it is in the range of 1 to 20 parts by weight. If the amount is less than 1 part by weight, a sufficient flame retardant effect cannot be obtained, and if the amount is more than 30 parts by weight, the heat resistance of the resulting composition is deteriorated, and volatile components during molding are increased. Occurs.

The carboxylic acid metal salt used in the present invention is
The carboxylic acid component is represented by the general formula R (COOH) n (where R represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, n represents an integer of 1 or more), and the metal component is a periodic Table 2 is a salt of a carboxylic acid and a metal, which is a Group B metal. In this carboxylic acid metal salt, a free carboxyl group may be present, and a salt containing no halogen component 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. Examples thereof include acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, methacrylic acid, crotonic acid, oleic acid, fumaric acid, maleic acid, benzoic acid, phthalic acid and cinnamic acid. 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 blending amount of these metal salts is not particularly limited, but is preferably 0.000 per 100 parts by weight of the resin component.
It is in the range of 1 to 1 part by weight. More preferably 0.000
It is in the range of 1 to 0.1 parts 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, the fluororesin and silicone used in the present invention are phosphorus compounds and carboxylic acids.
Both of them work effectively in combination with the group B metal salt.

[0011] 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 fluororesin 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 fluorine resin used in the present invention is 100 parts by weight of the resin component.
It is in the range of 0.01 to 5 parts by weight. If the amount of silicone and / or fluororesin is 0.01 parts by weight or less, a sufficient drip preventing effect cannot be obtained, and if it exceeds 5 parts by weight, the blended resin composition has a poor appearance of the molded product and an increase in melt viscosity. In some cases, such a defective phenomenon may occur.

As the resin other than the polycarbonate resin used in the present invention, any thermoplastic resin can be effectively used without any particular limitation. Typical examples of them are polystyrene resin (PS, HIPS), acrylonitrile-styrene resin (SAN), acrylonitrile-butadiene-styrene resin (ABS), polyester resin (PBT, PET). , (Modified) polyethylene, (modified) polypropylene, (modified)
Ethylene / propylene copolymer resin, polyphenylene ether, polyamide resin, polyacetal, polymethylmethacrylate, styrene / maleic anhydride copolymer resin,
Examples thereof include styrene / N-phenylmaleimide / maleic anhydride copolymer resin, styrene / N-phenylmaleimide / acrylonitrile copolymer resin, styrene / N-phenylmaleimide copolymer resin, and the like. These resins are used in combination of two or more kinds. It is also possible to use. Next, some of these will be described in more detail.

The polystyrene-based resin used in the present invention is a polymer obtained by polymerizing an unsaturated monomer containing an aromatic vinyl-based monomer, and further, the polymer is a rubbery polymer. It also includes a polymer modified by coalescence. Examples of the aromatic vinyl-based monomer used as the unsaturated monomer include styrene, α-methylstyrene, nuclear methyl-substituted styrene, t-butylstyrene, hydroxystyrene and halostyrene. Furthermore, together with these monomers, (meth) acrylic acid, (meth)
One or more kinds of monomers selected from acrylic acid ester, maleimide-based monomer, unsaturated dicarboxylic acid anhydride-based monomer and the like can be used. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like. Examples of the maleimide-based monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide. Examples of unsaturated dicarboxylic acid anhydride-based monomers include maleic anhydride. The method for producing the polystyrene resin is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. The polystyrene-based resin preferably used in the present invention is polystyrene, styrene / methyl methacrylate copolymer, styrene / methacrylic acid copolymer, styrene / maleic anhydride copolymer and rubber modified products thereof.

The ABS resin used in the present invention is a graft polymer obtained by graft-polymerizing a vinyl-based monomer containing an aromatic vinyl-based monomer to a rubber-like polymer. 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 an aromatic vinyl monomer and (meth) acrylonitrile, (meth) acrylic acid ester, maleimide monomer, unsaturated dicarboxylic acid. It can be obtained by graft-polymerizing at least one monomer selected from anhydrous monomers and the like. As the aromatic vinyl-based monomer, styrene,
Examples include α-methylstyrene, nuclear methyl-substituted styrene, t-butylstyrene, hydroxystyrene, and halostyrene. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like. As the maleimide-based monomer, maleimide, N-methylmaleimide,
N-ethylmaleimide, N-propylmaleimide, N-
Hexyl maleimide, N-cyclohexyl maleimide,
N-phenyl maleimide etc. are mentioned. Examples of unsaturated dicarboxylic acid anhydride-based monomers include maleic anhydride. 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, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, polyurethane rubber, polyamide rubber, silicone rubber, etc. Is mentioned. In the present invention, preferably,
Polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, silicone rubber and the like are 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 / methylmethacrylate copolymer, styrene / methylmethacrylate copolymer, α-methylstyrene / acrylonitrile / N-phenylmaleimide copolymer, styrene / acrylonitrile / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / maleic anhydride 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.

When a polymer blend of a polycarbonate-based resin and a resin other than the polycarbonate-based resin is used in the present invention, the compounding ratio is 50/50 to 9: polycarbonate-based resin / resin other than the polycarbonate-based resin.
The range of 9/1 (weight ratio) is preferable, and 6 is more preferable.
It is in the range of 0/40 to 95/5 (weight ratio). When the proportion of the resin other than the polycarbonate resin exceeds 50 weight ratio, the flame retardant resin may have impaired properties such as flame retardancy, mechanical properties and thermal properties. The flame-retardant resin composition of the present invention exhibits an excellent flame-retardant effect without using a compound containing bromine or chlorine as a flame-retardant component. Additives can also be used together. 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. Only one of these flame retardant additives may be used, or 2
It is also possible to use a combination of two or more species.

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.

[0020]

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 11 and Comparative Examples 1 to 9 The components shown in Table 1 were mixed at a compounding ratio shown in the table with a Henschel mixer, and then a 30 mmφ twin-screw extruder (PCM-30, manufactured by Ikegai Tekko KK) was used. The mixture was melt-kneaded and extruded at 250 to 280 ° C., and pelletized by 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. In the UL combustion test, a 127 mm × 12.7 mm × 1.6 mm combustion test piece was produced from the obtained pellets by injection molding, and the flame retardancy of the resin composition was measured by subject 94 of Underwriters Laboratory, Inc., USA. (UL-94) It measured according to the vertical combustion test. The Izod impact strength was measured according to JIS K7110 by producing a notched test piece having a width of 3.2 mm. The deflection temperature under load was measured according to the method A of JIS K7207.

The symbols in the table are as follows. PC: Polycarbonate resin, (Mitsubishi Kasei Kogyo novarex 7030PJ) ABS: ABS resin, (Denki Kagaku Kogyo GR)
-3000) TPP: cresyl diphenyl phosphate, (Daihachi Chemical Industry Co., Ltd. TPP) PDMS: polydimethylsiloxane, (Toshiba Silicone Co., Ltd. TSF451-1000) PTFE: polytetrafluoroethylene, (Mitsui DuPont Fluorochemicals) Teflon 6J Co., Ltd. Izod: Izod impact strength (JIS K7110)
HDT: Deflection temperature under load (based on JIS K7207)

[0022]

[Table 1]

[0023]

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 (2)

[Claims] 1. A flame-retardant resin composition comprising the following components. (A) Thermoplastic resin containing polycarbonate-based resin and resin other than polycarbonate-based resin (B) Phosphorus compound (C) Salt of carboxylic acid and metal of Group 2B of the periodic table (D) Silicone and / or fluorine-based resin 2. The composition according to claim 1, wherein 100 parts by weight of a polymer blend comprising (A ′) a polycarbonate resin (99 to 50% by weight) and an ABS resin (1 to 50% by weight), and (B ′) a phosphoric ester 5 ˜20 parts by weight, a salt of (C ′) carboxylic acid and a metal of Group 2B of the Periodic Table 0.0001 to 1
A flame-retardant resin composition comprising 0.01 parts by weight of (D ′) silicone and / or 0.01 to 2 parts by weight of polytetrafluoroethylene.