JPH06287354A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which does not generate a toxic substance such as a hydrogen halide, a phosphorus-contg. gas, or dioxin during burning and which retains the properties of a resin before being blended with a flame retardant. CONSTITUTION:The compsn. comprises 100 pts.wt. resin and 10-300 pts.wt. mixed flame retardant which comprises a mixture of at least one metal salt of a fatty acid with ammonium sulfate in a wt. ratio of the salt to the sulfate of (0.001-0.1):1 and an expandable graphite in a wt. ratio of the mixture to the graphite of (0.1-10):1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition. In particular, the present invention relates to a flame-retardant resin composition that does not generate toxic substances such as hydrogen halide, phosphorus-containing gas, and dioxin during combustion.

[0002]

2. Description of the Related Art In recent years, resins have been used in various fields, but some of them have the drawbacks of being easily ignited and combustible. Has been flame-retarded by various methods. Generally, when a resin is made flame-retardant, it is common to add a flame retardant, and the halogen-based flame retardant is most often used as the flame retardant.

However, although these flame retardants are effective with a small amount of compounding, they have the drawback of generating toxic gases such as hydrogen halides during combustion. In particular, recently, it was reported that dioxins were generated from a resin containing decabromodiphenyl oxide, which is a type of brominated flame retardant. Some places have restrictions in the form of regulations.

Further, phosphorus-based flame retardants typified by red phosphorus, phosphoric acid esters and ammonium polyphosphate must be blended in a larger amount than halogen-based flame retardants in order to make the resin flame-retardant. The toxicity of phosphorus-containing gas generated during combustion is also a problem. On the other hand, moisture-releasing inorganic flame retardants such as magnesium hydroxide and carbonized film-forming flame retardants such as thermally expansive graphite are flame retardants that do not generate toxic gas, but in order to make them flame-retardant. However, there is a problem in that a very large amount of compound must be added and the properties of the resin itself are impaired. Recently, it has been reported that the combination of red phosphorus and heat-expandable graphite has a flame retardant effect with a small amount of compounding. However, they have problems of toxicity of phosphorus-containing gas generated during combustion and handling of red phosphorus. Applications are very limited due to problems.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a flame-retardant resin composition which does not have the problem of generating toxic substances such as hydrogen halide, phosphorus-containing gas and dioxin during combustion, and which does not impair the properties of the resin. To provide things.
The present inventors have conducted intensive research to solve the above problems. As a result, the resin composition obtained by blending the ammonium sulfate mixture obtained by mixing the ammonium sulfate and the fatty acid metal salt with the resin and the thermally expandable graphite has a high degree of flame retardancy, without impairing the properties of the resin, and The inventors have found that there is no problem of generation of toxic substances such as hydrogen halide, phosphorus-containing gas, and dioxin during combustion, and have completed the present invention.

[0006]

Means for Solving the Problems That is, the present invention comprises, based on 100 parts by weight of a resin, A (1) one or more kinds of fatty acid metal salts and (2) ammonium sulfate, and a weight ratio (1 ):
(2) is composed of a mixture of ammonium sulphate of 0.001 to 0.1: 1 and B heat-expandable graphite, and the weight ratio A: B is 0.1 to 0.1.
Provided is a flame retardant resin composition containing 10 to 300 parts by weight of a flame retardant mixture of 10: 1.

The resin used in the present invention is
Either a thermoplastic resin or a thermosetting resin may be used. Specific examples of such resin include polypropylene, polyolefin such as polyethylene, polystyrene,
Styrene resin such as AS resin and ABS resin, polyvinyl resin such as polymethylmethacrylate, polyvinyl acetate, polyvinyl alcohol, ethylene vinyl acetate copolymer, polyamide resin such as nylon 6 and nylon 66, polyethylene terephthalate, polybutylene Thermoplastic resins such as polyester resins such as terephthalate, polycarbonate resins, polyether resins, homopolymers, mixtures or copolymers, or various resins modified with them, and SBR,
Examples thereof include elastic polymers such as NBR, polybutadiene and polyisoprene, and thermosetting resins such as phenol resin, unsaturated polyester, polyurethane and epoxy resin.

As the ammonium sulfate for producing the ammonium sulfate mixture used in the present invention, commercially available products can be used without particular limitation. As the fatty acid metal salt used for producing the ammonium sulfate mixture, known compounds can be used without any limitation. To give a specific example,
It is a metal salt of a saturated or unsaturated fatty acid having a fatty acid group with 6 to 22 carbon atoms, and examples of the metal include aluminum, magnesium, calcium, zinc, sodium, potassium and the like. In particular, the aluminum salts shown below are preferable.

That is, for example, aluminum monocaproate, aluminum dicaproate, aluminum tricaproate, aluminum monocaprylate, aluminum dicaprylate, aluminum tricaprylate, aluminum monocaprate, aluminum dicaprate, aluminum tricaprate, aluminum Monolaurate, aluminum dilaurate, aluminum trilaurate, aluminum monomyristate,
Aluminum Dimyristate, Aluminum Trimyristate, Aluminum Monopalmitate, Aluminum Dipalmitate, Aluminum Tripalmitate, Aluminum Monostearate, Aluminum Distearate, Aluminum Tristearate, Aluminum Monooleate, Aluminum Dioleate, Aluminum Trio Rate, aluminum monoarachidate, aluminum diarachidate, aluminum triarachidate, aluminum monobehenate, aluminum dibehenate, aluminum tribehenate and the like.

The ammonium sulfate mixture useful in the present invention has a weight ratio of ammonium sulfate to fatty acid metal salt of 1 :.
0.001-0.1, preferably 1: 0.005-0.
It is a mixture in the range of 08. When the weight ratio of the both is out of the above range, the miscibility of the both is lowered, which is not preferable. The average particle size of the ammonium sulfate mixture is preferably 75 μm or less.

As a method for producing the above ammonium sulfate mixture, known methods can be used without any limitation.
It is preferable that the ammonium sulfate and the fatty acid metal salt are premixed and then pulverized. In addition, as a preferable crushing method,
A method using a crusher having a grinding effect can be mentioned. In the present invention, known thermally expandable graphite can be used without any limitation.

The weight ratio of the above ammonium sulfate mixture to the thermally expandable graphite is 0.1 to 10: 1, preferably 0.1.
It is in the range of 5-8: 1. When the weight ratio of the both is out of the above range, the flame retardancy of the obtained resin composition decreases. The blending amount of the flame retardant mixture obtained by mixing the ammonium sulfate mixture and the heat-expandable graphite is 10 to 300 parts by weight, preferably 20 to 250 parts by weight, based on 100 parts by weight of the resin. If the blending amount of the flame retardant mixture is less than the above lower limit value, sufficient flame retardancy cannot be obtained. On the other hand, when the amount is more than the above upper limit, the flame retardant effect is not further improved and the physical properties are deteriorated, which is not preferable.

In addition to the above-mentioned components, the flame-retardant resin composition of the present invention contains, if necessary, conventionally known stabilizers, colorants, antistatic agents, lubricants, cores, etc. Agents, anti-blooming agents, fillers and the like may be added. The mixing order, mixing method, etc. of each component when preparing the flame-retardant resin composition of the present invention is not particularly limited, and generally, a tumbler type blender, a V-type blender, a Henschel mixer, a ribbon mixer, etc. are used by a conventional method. Done.

[0014]

FUNCTION AND EFFECT The flame-retardant resin composition of the present invention is UL
According to the 94 standard (combustion test method standard for plastic materials), it has a high level of flame retardancy of V-0, and there is no problem of generation of toxic substances such as hydrogen halide, phosphorus-containing gas and dioxin during combustion. . The reason why the ammonium sulfate mixture and the heat-expandable graphite exhibit a high degree of flame retardancy due to a synergistic effect is not clear, but the formation of a coating film by the ammonium sulfate mixture during combustion is promoted by the heat-expandable graphite, and the heat-expandable graphite It is presumed that a high degree of flame retardancy is exhibited because the coating becomes strong due to the expansion of the.

[0015]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The symbols used in Examples and Comparative Examples are as follows. 1. Resin A: Propylene homopolymer (Tokuyama Polypro PN240,
Tokuyama Soda Co., Ltd. B: Ethylene-propylene block copolymer (Tokuyama Polypro PN670, Tokuyama Soda Co., Ltd.) C: Low density polyethylene (M420, Mitsubishi Kasei Co., Ltd.) D: High density polyethylene (TVO70H, Mitsubishi Kasei Kogyo Co., Ltd. E: Polymethylmethacrylate (Acrypet MD, Mitsubishi Rayon Co., Ltd.) F: Polystyrene (Stylon 666, Asahi Kasei Co., Ltd.)
G): ethylene vinyl acetate copolymer (Evaflex P-280
5, manufactured by Mitsui Polychemical Co., Ltd. H: Ethylene-ethyl acrylate copolymer (WN-9)
30, manufactured by Nippon Unicar Co., Ltd. I: High-impact polystyrene (Stylon 492,
Asahi Kasei Co., Ltd. J: ABS resin (Clara Stick K-3272M, Sumitomo Nogatac Co., Ltd.) 2. Ammonium sulfate Ammonium sulfate 3. 3. Fatty acid metal salt L: Aluminum tristearate M: Aluminum monocaproate N: Aluminum dibehenate P: Magnesium distearate Q: Calcium distearate R: Zinc distearate 4. Thermally Expandable Graphite Thermally Expandable Graphite (Exp Graphite CA-60, manufactured by Chuo Kasei Co., Ltd.) Examples and Comparative Examples Compositions were prepared and tested as follows.

(1) Mixing of Ammonium Sulfate Mixture Ammonium sulfate and a fatty acid metal salt were mixed in the mixing ratios shown in Table 1 and pulverized using a pulverizer. The average particle size of the obtained ammonium sulfate mixture was 18 μm. (2) Premixing 100 parts by weight of the resin shown in Table 2 was mixed with the flame retardant mixture and premixed with a Henschel mixer.

(3) Pelletization The above mixture was pelletized using a 50 mmφ extruder. (4) Preparation of test piece Using the above pellet, a combustion test piece was prepared with a 2oz injection molding machine. (5) Combustion test The combustibility classification was judged by the combustion test based on UL standard Sb94. The test was conducted with the thickness of the test piece being 1/8 inch.

[0018]

[Table 1]

[0019]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yutaka Nabara 1-3-3-3 Yamashiro-cho, Yao-shi, Osaka (72) Inventor Hitoshi Inada 1-1 1-1 Mikage-cho, Tokuyama-shi, Yamaguchi Prefecture Tokuyama Soda Co., Ltd. (72) Inventor Katsushi Hashizume 1-1, Mikagecho, Tokuyama City, Yamaguchi Prefecture Tokuyama Soda Co., Ltd.

Claims (1)

[Claims] 1. A weight ratio of (1): A (1) consisting of one or more kinds of fatty acid metal salts and (2) ammonium sulfate to 100 parts by weight of the resin.
(2) is composed of a mixture of ammonium sulphate of 0.001 to 0.1: 1 and B heat-expandable graphite, and the weight ratio A: B is 0.1 to 0.1.
A flame retardant resin composition comprising 10 to 300 parts by weight of a flame retardant mixture of 10: 1.