JPH10176095A - Flame resistant styrenic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a styrenic resin composition having high flame resistance without causing dripping of thermally degraded molten material when burning. SOLUTION: This styrene resin composition includes (a) 10-40wt.% organic halogen-based compound as a flame retardant, (b) 2-10 pts.wt. ammonium polyphosphate-based compound and/or phosphate of a triazine compound and (c) 0.05-8 pts.wt. of a agent for preventing dripping (polytetrafluoroethylene or a chlorinated polyethylene) in 100 pts.wt. styrenic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having no dripping of a pyrolysis melt during combustion and having high flame retardancy.

[0002]

2. Description of the Related Art In recent years, the fields of use of plastics materials have become increasingly diverse. Among them, styrene-based thermoplastic resins such as high-impact polystyrene, ABS resin, etc. are used in a very large number of fields as automobile parts, electric equipment, office equipment, and various other molded products due to their excellent impact resistance, moldability, and dimensional stability. Used in

On the other hand, with the expansion of such uses,
Due to safety concerns, flame retardant materials have been required to have high flame retardancy. Conventionally, a halogen-containing compound or the like is mainly used for flame retardation of a styrene resin, and a method in which antimony trioxide or the like is further added as a flame retardant auxiliary in addition to the flame retardant additive. Has been adopted.
Although these methods provide excellent flame retardancy, antimony trioxide is designated as a deleterious substance, and there is a concern that it may affect the human body. Therefore, there is a need to develop or reduce the amount of antimony trioxide substitute. Zirconium oxide, bismuth oxide, zinc borate, titanium oxide and the like have been tried as flame retardant aids, but all have a smaller effect than antimony trioxide. If you try to achieve the same level of flame retardancy as using antimony trioxide,
A large amount of zirconium oxide, bismuth oxide, zinc borate, titanium oxide, etc. must be added, and as a result, the moldability and physical property balance of the resulting flame-retardant resin composition are significantly impaired, and the product cost increases significantly. I do. Attempts have also been made to use antimony trioxide and nickel oxide in combination to reduce the amount of antimony trioxide used (JP-A-51-80347), but all have found satisfactory methods. Not. Also, if the amount of the halogen-based flame retardant is significantly increased, the amount of antimony trioxide used can be reduced. However, this method also significantly impairs the balance of physical properties of the resin and significantly increases the product cost.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which does not use antimony trioxide at all, does not cause dripping of a pyrolysis melt during combustion, and has high flame retardancy. It is.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and as a result, based on 100 parts by weight of a styrene-based thermoplastic resin, (a) an organic halogen-based compound 10 as a flame retardant. To 40 parts by weight, (b) 2 to 10 parts by weight of a phosphate of an ammonium polyphosphate-based compound and / or a triazine compound as a flame retardant aid, and (c) 0.05 to 8 parts by weight of a melt dripping inhibitor. By doing
A resin composition having no dripping of the pyrolysis melt during combustion and having high flame retardancy while maintaining the excellent properties of the styrenic resin has been achieved.

The composition of the present invention has no dripping during thermal decomposition and has excellent flame retardancy. It is further surprising that high flame retardancy can be obtained without using antimony trioxide by using an organic halogen compound and a phosphate of an ammonium polyphosphate compound and / or a triazine compound in combination with a melt drip inhibitor. It was done.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The styrene resin used in the present invention is a homopolymer or a copolymer of a styrene monomer, or a copolymer of these monomers and another vinyl monomer. . In addition, styrene monomers and / or
Alternatively, those obtained by graft polymerization of other vinyl monomers are also included.

The above-mentioned styrene monomer includes styrene,
It is a generic term for α-methylstyrene and styrene derivatives in which the hydrogen atom of the benzene nucleus is substituted with a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl or hydroxyalkyl group. Such styrene monomers include styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene,
and p-tert-butylstyrene. Also,
Representative examples of the other vinyl monomers described above include (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid-2-
(Meth) acrylic acid such as ethylhexyl or (meth) acrylic acid-β-hydroxyethyl and their various esters, or vinyl acetate, vinyl chloride, vinylidene chloride, vinylpyrrolidone, (meth) acrylamide, dimethyl (meth) acrylamide, Examples include maleic anhydride, itaconic anhydride or maleimide, vinyl ketones or vinyl ethers.

Further, typical examples of the rubbery substance include polybutadiene rubber, styrene / butadiene copolymer rubber, styrene / butadiene / styrene block copolymer rubber, ethylene / propylene terpolymer rubber, and butadiene / acrylonitrile copolymer. Conjugated 1,3-diene-based monomers such as isoprene or chloroprene, including polymerized rubber, butyl rubber, acrylic rubber, styrene / isobutylene / butadiene copolymer rubber, or isoprene / acrylate copolymer rubber, There are rubbers and the like obtained by using them, and these are used alone or in combination of two or more.

As the organic halogen compound used in the present invention, those usually used in this field can be used without limitation. Examples thereof include tetrabromobisphenol A and tetrabromobisphenol A.
Carbonate oligomer, tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer, tetrabromobisphenol A Tetrabromobisphenol A derivatives such as bisphenol A diglycidyl ether and tribromophenol adduct, decabromodiphenyl ether, octabromodiphenyl ether, ethylene bistetrabromophthalimide, ethylenebisdibromonorbornanedicarboximide, hexabromocyclododecane, 1,2- Bis (pentabromophenyl) ethane,
Brominated aromatic compounds such as 2,3-dibromopropylpentabromophenyl ether, bis (2,4,6-tribromophenoxy) ethane, chlorinated paraffin, chlorinated naphthalene, perchlorocyclopentadecane, chlorinated aromatic And chlorinated alicyclic compounds. Among them, tetrabromobisphenol A and brominated bisphenol type epoxy compounds are preferably used. These compounds achieve their purpose by using one or more of them. The compounding ratio of the halogen compound to 100 parts by weight of the styrene resin is 10 to 40.
When the amount is less than 10 parts by weight, the flame retardancy is not sufficient. When the amount exceeds 40 parts by weight, the flame retardancy naturally increases, but on the contrary, the various physical properties are reduced, and it is suitable from the viewpoint of economy. Not.

The ammonium polyphosphate compound as the component (b) used in the present invention is a flame retardant auxiliary containing ammonium polyphosphate as a main component. As a typical example, there is one obtained by treating ammonium polyphosphate with a melamine resin or the like to make it hardly soluble in water. For example, the following are commercially available. Taien S (made by Taihei Chemicals KK), Smithef P, Smithef PM (all made by Sumitomo Chemical KK) Exolit462
(Manufactured by Hoechst), AMGARD MC (manufactured by Albright and Wilson), Terra-ju C60, Terra-ju C70 (all manufactured by Chisso KK).

[0012] Further, a flame retardant effect improved by adding another auxiliary component to ammonium polyphosphate can be used. For example, Exolit VP IF is a commercially available product.
R-23 (manufactured by Hoechst), SPINFLAM MF8
0 / PP, SPINFLAM MF82 / PP, SPI
NFLAM MF82 / PS (all manufactured by Montecatini Co., Ltd.) and the like.

The phosphate of a triazine compound used in the present invention includes a compound having a triazine skeleton, for example, a phosphate such as melamine, benzoguanamine, methylguanamine and the like. These ammonium polyphosphate-based compounds and phosphate salts of triazine compounds can be used alone or as a mixture of two or more.

Further, (c) used in the present invention
As the melt drip inhibitor of the component, those usually used in this field can be used without limitation, and examples thereof include polytetrafluoroethylene, chlorinated polyethylene, and molybdenum compound. These can be used alone or as a mixture of two or more.

Although the composition of the flame-retardant styrenic resin composition of the present invention is slightly different depending on each component, generally, 100 parts by weight of the styrenic resin is added to the organic halogen-based compound 10 to 10 parts by weight.
40 parts by weight, ammonium polyphosphate compound and / or
Alternatively, it is 2 to 10 parts by weight of a phosphate salt of a triazine compound and 0.05 to 8 parts by weight of an anti-dripping agent.

An ammonium polyphosphate compound and / or
If the amount of the phosphate of the triazine compound is less than 2 parts by weight, the flame retardancy is insufficient, and if it exceeds 10 parts by weight, the physical properties are undesirably deteriorated.

If the amount of the anti-dripping agent is less than 0.05 part by weight, the flame retardancy is insufficient, and if it exceeds 8 parts by weight, the physical properties are deteriorated, which is not preferable from the economical point of view.

The preferred range in terms of flame retardancy, physical properties, economy and the like is that the organic halogen compound is 15 to 35 parts by weight, the ammonium polyphosphate compound and / or the triazine compound is 100 parts by weight of the thermoplastic resin. The phosphate is 3 to 8 parts by weight, and the amount of the anti-dripping agent is 0.1 to 5 parts by weight.

In addition, glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium whisker, carbon fiber, fibrous reinforcing agent such as asbestos, talc, calcium carbonate, etc. , Mica, clay, titanium oxide, aluminum oxide,
Granular reinforcing materials such as glass flakes, glass beads, milled fibers, metal flakes, and metal powders may be mixed.

The thermoplastic resin composition of the present invention may further contain one or more additives such as a heat stabilizer, an oxidation stabilizer, a light stabilizer, a lubricant, a pigment, and a plasticizer. The method for producing the thermoplastic resin composition of the present invention is not particularly limited, but is preferably an extruder, a kneader,
A known melt kneading method such as a Banbury mixer is preferably used.

[0021]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

All of the addition ratios in the examples and comparative examples indicate parts by weight. In the present invention, the flammability was evaluated based on Subject 94 (abbreviated as UL-94) standardized by Underwriters Laboratories (UL) in the United States based on a length of 5 inches, a width of 1/2 inch, and a thickness of 5 inches. The test was performed using a 1/12 inch test piece.

Examples 1-2 ABS resin (Sebian-V320, Daicel Chemical KK)
), Tetrabromobisphenol A (BA59P, G
LC), ammonium polyphosphate-based compound (Sumisafe P, manufactured by Sumitomo Chemical KK), and polytetrafluoroethylene (Teflon 6J, manufactured by DuPont-Mitsui Fluorochemical KK) in the blending ratio shown in Table 1. The mixture was pelletized with an extruder having a cylinder temperature of 200 ° C. to obtain a styrene resin composition. Further, a test piece was prepared by an injection molding machine at a cylinder temperature of 200 ° C.

Example 3 A test was conducted in the same manner as in Examples 1 and 2, except that chlorinated polyethylene (Daisolak G235, manufactured by Osaka Soda KK) was used instead of polytetrafluoroethylene. Example 4 Examples 1 and 2 except that chlorinated polyethylene was further used.
The test was performed in the same manner as in the above. Example 5 A test was performed in the same manner as in Examples 1 and 2, except that melamine phosphate (MPP-A, manufactured by KK Sanwa Chemical) was used instead of the ammonium polyphosphate compound.

Example 6 A styrene resin was replaced by a HIPS resin (Daicel Styrol R).
63, manufactured by Daicel Chemical Ltd. KK), and brominated bisphenol-type epoxy resin (Plasam EC)
Examples 1 to 10 except that D. Nippon Ink KK) was used.
The test was performed in the same manner as in Example 2.

Comparative Example 1 A test was conducted in the same manner as in Examples 1 and 2, except that the ammonium polyphosphate compound and polytetrafluoroethylene were not used.

Comparative Example 2 Example 1 except that no polytetrafluoroethylene was used.
The test was performed in the same manner as in the above.

Comparative Example 3 A test was conducted in the same manner as in Examples 1 and 2, except that no ammonium polyphosphate compound was used.

Comparative Example 4 A test was conducted in the same manner as in Example 5 except that the ammonium polyphosphate compound and polytetrafluoroethylene were not used.

Comparative Example 5 Example 5 except that no polytetrafluoroethylene was used.
The test was performed in the same manner as in the above.

[0031]

[Table 1]

[0032]

According to the present invention, in a styrene-based thermoplastic resin composition, an organic halogen-based compound is a phosphate of an ammonium polyphosphate-based compound and / or a triazine-based compound;
By using the anti-dripping agent in combination, a thermoplastic resin composition having high flame retardancy was obtained without losing the original properties of the resin.

Claims (3)

[Claims] 1. 100 parts by weight of a styrene resin (a) 10 to 40 parts by weight of an organic halogen compound (b) 2 to 10 parts by weight of a phosphate of an ammonium polyphosphate compound and / or a triazine compound (c) A flame-retardant styrenic resin composition comprising 0.05 to 8 parts by weight of a dripping inhibitor. 2. The flame-retardant styrene resin composition according to claim 1, wherein (c) the anti-dripping agent is polytetrafluoroethylene. 3. The flame-retardant styrenic resin composition according to claim 1, wherein (c) the anti-dripping agent is chlorinated polyethylene.