JP3379847B2 - Flame retardant resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant styrene resin. More specifically, the present invention relates to a resin composition having a high degree of flame retardancy, in which no corrosive gas or toxic gas is generated during the thermal decomposition of the composition, and the physical properties are not deteriorated. Heretofore, as a method of imparting flame retardancy to a styrene resin, a halogen-based flame retardant represented by decabromodiphenyl ether has been filled. However, halogen-based flame retardants have the disadvantage that corrosive or toxic gases are generated during processing or combustion. In recent years, with increasing interest in environmental issues, a method of solving these drawbacks is to make styrene resin flame-retardant without using halogen. However, in general, it was necessary to fill a styrene resin material with a large amount of additives until the flame resistance of UL 94V-O level was obtained. Filling such a large amount of additives causes a problem that the physical properties of the material are deteriorated. SUMMARY OF THE INVENTION [0004] The present invention is directed to a process which does not generate corrosive or toxic gas during processing or combustion.
An object of the present invention is to provide a flame-retardant resin composition having excellent flame retardancy, a small decrease in physical properties, and containing no halogen. Means for Solving the Problems The present inventors have made intensive studies and found that a specific organic phosphorus compound, a carbonization-promoting additive and a silicone oil were added to a styrenic resin to obtain a composition. The present inventors have found a flame-retardant resin composition which does not generate corrosive gas or toxic gas at the time of thermal decomposition of a substance and does not deteriorate physical properties, and have completed the present invention. That is, the present invention relates to (a) a styrene resin 100
(B) 10 to 50 parts by weight of an organic phosphorus compound represented by the following general formula (I) based on parts by weight: (C) 5 to 30 parts by weight of a carbonization promoting additive and (d)
The present invention relates to a flame-retardant resin composition containing 0.1 to 20 parts by weight of silicone oil. The styrene resin as the component (a) of the present invention includes a homopolymer or a copolymer of styrene or a styrene derivative such as α-methylstyrene or vinyltoluene;
Copolymers of these monomers with vinyl monomers such as acrylonitrile and methyl methacrylate, diene rubbers such as polybutadiene, ethylene propylene rubbers,
It is obtained by graft-polymerizing styrene or a styrene derivative and another vinyl monomer to an acrylic rubber or the like, and examples thereof include polystyrene, high-impact polystyrene, AS resin, ABS resin, AAS resin, and AES resin. The organic phosphorus compound as the component (b) of the present invention is represented by the following general formula (I). The organic phosphorus compound of the general formula (I) is a compound synthesized from pentaerythritol, phosphorus oxychloride, and melamine. [0011] [0012] The carbonization-promoting additive which is the component (c) of the present invention means an additive which forms a char (carbonaceous substance) when subjected to a condition exposed to a flame. For example, salts with polyvalent polynuclear phenols, for example novolaks and substances which form their multiply charged ions, for example alkaline earth metals, zinc, aluminum and iron. Or a combination of novolak and relatively basic materials capable of forming metal salts with novolak under conditions of exposure to flame, such as oxides of magnesium, calcium, zinc, aluminum, iron, manganese, zirconium and tin, Hydroxides, carbonates, phosphates, borates and silicates. Particularly useful are boron oxide, borates of non-basic oxides (eg, zinc, iron, aluminum, manganese, copper and lead), and melamine borate, and boron oxide (or boric acid) in novolak (novolak borate). Acid ester). Other carbonization promoting additives include crude phenolic resin, phenolic resin cross-linked or elongated by epoxy resin, pentaerythritol, dipentaerythritol, tripentaerythritol, dipentaerythritol benzoate,
Tripentaerythritol benzoate, phosphate and phosphonate. The silicone oil as the component (d) of the present invention is a general term for a wide range of polysiloxane materials. Typically effective silicones are silicone fluids or gums such as: That is, typically, R ₃ SiO _0.5 , R ₂ SiO, R ¹ SiO _1.5 , R ¹ R ₂ SiO _0.5 , RR ¹ Si
An organopolysiloxane polymer composed of chemically linked siloxy units selected from the group consisting of O, (R ¹ ) ₂ SiO, RSiO _1.5 and SiO ₂ and mixtures thereof. Here, each R independently represents a saturated or unsaturated monovalent hydrocarbon group, and R ¹
Represents a group such as R 1 or a group selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxy group, an aryl group, a vinyl group, an allyl group, and the like.
In addition, the above-mentioned organopolysiloxane is approximately 6% at 25 ° C.
It has a viscosity of 00-300,000,000 centipoise. Preferred silicone oils are approximately 90,000-150,00 at 25 ° C.
Polydimethylsiloxane having a viscosity of 0 centipoise. In the resin composition of the present invention, the amount of the organic phosphorus compound as the component (b) is 10 to 50 parts by weight based on 100 parts by weight of the styrene resin as the component (a). If the amount is less than 10 parts by weight, the flame retardant effect is not sufficient,
Exceeding the parts by weight impairs the mechanical properties of the composition, lowers the impact strength, and also lowers the electrical properties, which is not preferred. Preferably it is 20 to 40 parts by weight. The compounding amount of the carbonization promoting additive of the component (c) is 5 to 30 parts by weight, preferably 10 to 20 parts by weight based on 100 parts by weight of the styrene resin of the component (a).
Used by weight. If the amount of the carbonization promoting additive is less than 5 parts by weight, sufficient flame retardancy cannot be exhibited. On the other hand, if it exceeds 30 parts by weight, there is a problem in terms of impact resistance. The amount of the silicone oil as the component (d) is 0.1 to 20 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the styrene resin as the component (a). The amount of silicone oil
If the amount is less than 0.1 part by weight, the flame-retardant effect is not sufficient.
Exceeding parts by weight impairs the mechanical properties of the composition and increases the cost. The resin composition of the present invention can be obtained by blending these components in predetermined amounts, and the production method thereof may be in accordance with a conventional method. For example, (a) to (d) are prepared by premixing each component with a mixer such as a Henschel mixer, a tumbler blender, a kneader, and then kneading with an extruder, or melt-kneading with a heating roll or a Banbury mixer. I do. In this case, if necessary, various additives generally compounded in the styrene resin, for example, fillers, lubricants, reinforcing agents, stabilizers, light stabilizers, ultraviolet absorbers, plasticizers, antistatic agents, A hue improver or the like may be added. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples. The flame-retardant styrenic resin compositions of the following Examples and Comparative Examples were evaluated in the following manner. (1) Impact Strength The impact strength was measured using a 1/4 inch thick test piece according to ASTM D256, using the notched Izod impact strength as a scale. (2) Flame Retardancy As an evaluation scale of flame retardancy, a test piece (bar sample) having a thickness of 3 mm in accordance with the vertical flammability test (94V-O) specified in UL94 of the US UL standard is used. evaluated. (3) Bleeding property It is visually determined whether there is any material (such as an additive) that seeps out on the surface of the molded product. Examples 1-2 and Comparative Examples 1-6 High impact polystyrene (HIP) was used as the styrene resin.
S), an organic phosphorus compound represented by the following formula as an organic phosphorus compound, pentaerythritol as a carbonization promoting additive,
Polydimethylsiloxane having a viscosity of 90,000 centipoise at 25 ° C. as an organopolysiloxane was mixed in a tumbler blender in a combination and ratio as shown in Table 1, and then melt-kneaded with an extruder to obtain a pellet-shaped resin composition. . Next, test pieces for general physical properties were prepared using an injection molding machine (cylinder temperature 200 ° C., mold temperature 50 ° C.), and physical properties were measured according to a standard method. Table 1 shows the results. Embedded image [Table 1] By combining the organic phosphorus compound represented by the general formula (I) with the carbonization promoting additive and the silicone oil, no corrosive or toxic gas is generated at the time of processing or burning, and an excellent A styrene-based resin composition having flame retardancy, little decrease in physical properties, and containing no halogen can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-168659 (JP, A) JP-A-55-86828 (JP, A) JP-A-6-248160 (JP, A) JP-A-7-28 90147 (JP, A) U.S. Patent 4,336,184 (US, A) U.S. Patent 4,338,245 (US, A) U.S. Patent 4,338,246 (US, A) U.S. Patent 4,425,972 (US, A) (58) Fields studied (Int. Cl. ⁷⁾ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 CA (STN)

Claims (1)

(57) [Claims] [Claim 1] (a) 100 parts by weight of a styrene resin, (b) an organic phosphorus compound represented by the following general formula (I):
50 parts by weight, A flame retardant resin composition comprising (c) 5 to 30 parts by weight of a carbonization promoting additive and (d) 0.1 to 20 parts by weight of a silicone oil.