JP3132121B2 - Flame-retardant resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having not only good flame retardancy but also excellent mechanical strength and good bleeding property, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers (hereinafter referred to as T
PE) has been developed and used in various fields such as automotive parts, electric cables and adhesives. As the field of use expands, there is a recent demand for TPE with flame retardancy.

[0003]

However, in the conventional flame retarding method by adding a flame retardant, not only the flame retardant or other additives bleed out to the surface of the molded article to significantly impair the appearance, but also the bleed There was a problem that flexibility was increased by out.

The present invention has been made in view of such circumstances, and has as its object to provide a thermoplastic elastomer composition free from bleed-out due to flame retardancy.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by blending a specific flame-retardant composition, and based on this finding, the present invention has been achieved. The invention has been completed.

That is, the present invention relates to (A) a thermoplastic elastomer, (B) a chlorinated ethylene polymer, (C) an ethylene polymer, (D) antimony oxide, (E) aluminum hydroxide and / or hydroxide. The molecular weight obtained by reacting magnesium and (F) a bromine-containing epoxy compound with 1,3,5-tribromophenol is from 1,200 to 6,000, and the bromine content is from 5.0 to 5.0. 60% by weight of a bromine-containing reaction product, wherein the composition ratio of the component (A) in the composition is 80 to 98% by weight, and (B) and (C)
The proportion of the component (B) in the total amount of the components is 10 to 75.
% By weight and based on the total amount of 100 parts by weight,
A flame-retardant resin composition comprising 10 to 30 parts by weight of component (D), 10 to 35 parts by weight of component (E) and 20 to 50 parts by weight of component (F); The method for producing a flame-retardant resin composition according to claim 1, characterized in that the components (B) to (F) except for (A) are mixed in advance and then the component (A) is mixed. Hereinafter, the present invention will be described in detail.

(A) Thermoplastic Elastomer (TPE) The TPE used in the present invention is a polymer material which exhibits rubber-like elasticity at normal temperature but is plasticized and moldable at high temperature.
The TPE can be molded with a normal plastic molding machine, and does not require a long vulcanization step such as rubber.
A material having sufficient strength without a reinforcing material and having a wide range of physical properties from a soft rubber to a plastic region can be obtained. In addition, TPE is structurally composed of a soft segment (hereinafter, referred to as SS) and a hard segment (hereinafter, HS).
), And is generally HS
Depending on the type, styrene, olefin, polyvinyl chloride, urethane, polyester, polyamide,
Fluorine and chlorinated polyethylene have been developed.

As typical examples, styrene-based TPE (trade name: Califlex TR, Clayton G) composed of polystyrene for SS and polybutadiene for SS, polypropylene for HS for ethylene and propylene copolymer or ethylene-propylene for SS -An olefin-based TPE comprising a diene copolymer (trade names: Santoprene, Mirastomer, Thermolan, Sumitomo TPE, Oriflex, etc.), gel PV instead of HC and SS block copolymer
C or polyvinyl chloride-based TPE in which plasticized products of high degree of polymerization or modified products of nitrile rubber are mainstream
(Product name: Sumiflex, Sumikon, Denka Romer G, Denka LCS, Elastor, Sunplane, Aron Erasroma, Eraslit, Elastdal, Vanex, Dominus, Shin-Etsu EZ800 series, etc.), polyurethane from HS to polyol or polyester from SS to SS Polyurethane TPE (trade name: Elastolane,
Polyester TPE (commodity) such as paraprene, pandex, bamboo lac, rezzamine, peresene, desmopan, europolymer, hyprene, iron rubber), polybutylene terephthalate for HS and polytetramethylene glycol for SS. Name: Pelprene, Hytrel, Lowmod, etc.), HS
Nylon oligomers such as nylon 6,66,610,612,11,12, etc., and polyamide-based TPEs (polyamide oligomers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.) in SS. (Relax, Pebax, etc.), fluorinated TPE consisting of fluorinated resin molecules in HS and fluorinated rubber molecules in SS (trade name: Daquel Thermoplastic, etc.), and HS
Chlorinated polyethylene TPE consisting of block chlorinated polyethylene and random chlorinated polyethylene for SS
(Product name: Eraslen, Daisolak, Hostalet,
Tyrin etc.). Of these TPEs, styrene, olefin, polyvinyl chloride, polyester, chlorinated polyethylene and polyamide are preferably used.

(B) Chlorinated ethylene-based polymer The chlorinated ethylene-based polymer used in the present invention is a chlorinated product obtained by reacting chlorine with a polymer containing ethylene as a main component described below. Examples of the polymer containing ethylene as a main component include an ethylene homopolymer, a copolymer of ethylene and an α-olefin, an ethylene-propylene copolymer having a small amount of crystal, and at least ethylene and an α, β-unsaturated. Copolymers with dicarboxylic acids or their anhydrides are exemplified.

[0010] Ethylene homopolymer and ethylene and α-
The copolymer with olefin is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 20% by weight of an α-olefin (generally having 3 to 12 carbon atoms). Its density is generally 0.910
0.970 g / cc. Further, its molecular weight is at least 30,000, and particularly preferably 50,000 to 700,000.

In addition, ethylene having a slight crystal fraction
The propylene copolymerization ratio of the propylene copolymer is usually 1
5 to 40% by weight, preferably 18 to 40% by weight,
Particularly, 20 to 38% by weight is suitable. When the copolymerization ratio of propylene is 15% by weight, the obtained chlorinated ethylene-propylene copolymer has poor rubber-like elasticity, and is rather plastic-like in the product. On the other hand, when the content exceeds 40% by weight, particles of the chlorinated ethylene-propylene copolymer obtained during chlorination become large, and are not preferable because they are aggregated in the reaction system.

Further, the melt index of the ethylene-propylene copolymer (according to JIS K7210,
The condition (measured at 14; hereinafter referred to as “MI (1)”) is usually 0.01 to 5.0 g / 10 min, and 0.02 to 5.0 g.
/ 10 minutes is desirable, and especially 0.05 to 5.0 g / 10 minutes is suitable. With an ethylene-propylene copolymer having an MI (1) of less than 0.01 g / 10 minutes, the resulting chlorinated ethylene-propylene copolymer has poor processability. on the other hand,
If it exceeds 5.0 g / 10 minutes, the reaction efficiency in chlorination is poor, and the chlorinated products are agglomerated.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the ethylene-propylene copolymer is usually from 10 to 180, preferably from 10 to 170, particularly preferably from 10 to 150. In ethylene-propylene copolymers having a Mooney viscosity of less than 10, chlorinated products agglomerated during chlorination. On the other hand, if it exceeds 180, rubber-like elasticity is poor,
Rather, it is plastic-like.

Incidentally, the ethylene-propylene copolymer is usually used as a differential scanning calorimeter (Differential).
(Scanning Colorimeter, DSC)
The melting peak measured at 80 ° C. or higher is usually
125 ° C is preferable, and particularly preferably 85 to 125 ° C. If the melting peak is lower than 80 ° C., the chlorination reaction is not preferable because it becomes a lump during the chlorination reaction and a uniform chlorinated product cannot be obtained.

[0015] The ethylene-propylene copolymer usually has a crystallinity of 3% or more as measured by X-ray.
0% is desirable, and 3 to 45% is particularly preferable. If the degree of crystallinity is less than 3%, the chlorination stage will result in a lump,
Similarly, a uniform chlorinated product cannot be obtained.

Further, the ethylene-propylene copolymer is subjected to gel permeation chromatography (GPC).
Polymerization average molecular weight (M
w) / number average molecular weight (Mn) is usually 4 or more;
To 8 are preferred. If Mw / Mn is less than 4, the resulting chlorinated product is not preferred because of poor processability.

Further, at least a copolymer of ethylene and an α, β-unsaturated dicarboxylic acid or an anhydride thereof may be a copolymer of ethylene and “α, β-unsaturated dicarboxylic acid and / or an anhydride thereof” (hereinafter referred to as “comonomer (1) ))), And in addition to ethylene and the comonomer (1), at least one selected from the group consisting of unsaturated carboxylic acid esters, alkoxyalkyl acrylates and vinyl esters as the third copolymerization component (Hereinafter, referred to as “comonomer (2)”).

Among the comonomers (1), the α, β-unsaturated dicarboxylic acid usually has at most 20 carbon atoms, preferably 4 to 16 carbon atoms. Representative examples of the dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, 3,6-endomethylene-1,2,2
3,6-tetrahydro-cis-phthalic acid.
Among the α, β-unsaturated dicarboxylic acid components of the present invention, the anhydride of the α, β-unsaturated dicarboxylic acid is preferable, and maleic anhydride is particularly preferable.

Among the comonomers (2), the unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, especially 4 to 4 carbon atoms.
Twenty are preferred. As a typical example, those having good thermal stability such as methyl (meth) acrylate and ethyl (meth) acrylate are preferable. Furthermore, the alkoxyalkyl acrylate usually has at most 20 carbon atoms. The alkyl group has 1 to 8 carbon atoms (preferably,
1 to 4), more preferably 1 to 8 (preferably 1 to 4) alkoxy groups. Representative examples of preferred alkoxyalkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate, and butoxyethyl acrylate.

The vinyl ester generally has at most 20 (preferably 4 to 16) carbon atoms. Representative examples of suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pipeparate and the like.

In the ethylene copolymer used in the present invention, the copolymerization ratio of the comonomer (1) is usually 0.5 to 2
5 mol%, preferably 1.0 to 25 mol%, and particularly preferably 1.0 to 20 mol%. If the copolymerization ratio of the comonomer (1) is less than 0.1 mol%, the effect of the obtained chlorinated product will not be exhibited. On the other hand, if it exceeds 25 mol%, there is a problem in cost and production in industrial production.

In the present invention, the terpolymer composed of ethylene, comonomer (1) and comonomer (2) has no blocking during chlorination, and the reaction can be easily carried out. Further, the obtained chlorinated ethylene copolymer has excellent rubber elasticity and heat resistance.

The copolymerization ratio of the comonomer (2) is generally at most 25 mol% from the viewpoint of production and cost, and is preferably 0.5 to 25 mol%, more preferably 1.0 to 25 mol%. Those having 25 mol% are preferred.

Melt index of the ethylene copolymer (measured under condition 4 in accordance with JIS K7210)
Hereinafter, “MI (2)”) is usually 0.1 to 100 g /
The duration is 10 minutes, preferably 0.5 to 100 g / 10 minutes, particularly preferably 1.0 to 100 g / 10 minutes.
If the MI (2) is less than 0.1 g / 10 minutes, the moldability and kneading properties of the obtained chlorinated ethylene copolymer are not good. on the other hand,
If it exceeds 100 g / 10 minutes, the mechanical properties of the chlorinated ethylene copolymer obtained are not good.

The chlorinated ethylene polymer of the present invention can be obtained by chlorinating these polymers. The chlorination can be achieved by applying a chlorination method in an aqueous suspension commonly performed for producing these chlorinated products.

The chlorine content of the chlorinated ethylene polymer is generally 15 to 45% by weight, preferably 17 to 45% by weight, and more preferably 20 to 43% by weight. If the chlorine content of the chlorinated ethylene-based polymer is less than 15% by weight, a reaction can be performed in the production, but it becomes very difficult in the water washing step during post-treatment. On the other hand, when the content exceeds 45% by weight, the obtained chlorinated ethylene-based polymer is hard and not elastomer-like.

The Mooney viscosity (ML _{1 + 4} , 100
° C) is usually 10 to 15 from the viewpoint of moldability and mechanical properties.
0, preferably 10 to 130, particularly preferably 10 to 120
Is preferred.

(C) Ethylene Polymer The ethylene polymer used in the present invention is obtained by homopolymerizing ethylene or copolymerizing ethylene and an α-olefin. The density of the ethylene-based polymer is usually 0.900 g / cm ³ or more, preferably 0.905~0.975g / cm ^3, it is preferred particularly 0.910~0.972g / cm ^3. When the density of the ethylene polymer is less than 0.900 g / cm ³ , the resulting composition has low tensile strength. The melting point of this ethylene polymer is usually 103 to 140 ° C.
05-140 ° C is desirable, especially 107-140 ° C
Is preferred. The melting point of this ethylene polymer is 103 ° C.
Below, the mechanical strength (particularly, tensile strength) of the obtained composition is low. On the other hand, when the melting point exceeds 140 ° C., the composition obtained has low workability, and a weld is generated at the hinge portion, and cracks are easily formed. Further, MI (1) of the ethylene polymer is usually 0.01 to 100 g / 10 minutes,
0.1 to 50 g / 10 min is preferable, and especially 5 to 50 g / 10 min.
Minutes are preferred. If the MI (1) of this ethylene polymer is less than 0.01 g / 10 minutes, the moldability of the resulting composition will be poor. On the other hand, if it exceeds 100 g / 10 minutes, a good product cannot be obtained because there is no appropriate rigidity.

Α used in the production of the ethylene polymer
-Olefin is generally an α-olefin having 3 to 10 (preferably 3 to 8) carbon atoms, and typical examples include propylene, butene-1, hexene-1, 4-methylpentene-1 and octene. -1. The copolymerization ratio of the α-olefin in this copolymer is usually at most 40% by weight, preferably 5 to 25% by weight.

(D) Antimony Oxide The antimony oxide used in the present invention is generally used as a flame retardant aid for the halogen-containing organic compound. Representative examples include antimony trioxide and antimony pentoxide.

These halogen-containing organic compounds and antimony oxide are well-known from the aforementioned "Handbook, Rubber / Plastic Compounding Chemicals" and the like.

(E) Aluminum hydroxide and magnesium hydroxide Further, the aluminum hydroxide used in the present invention has a Na ₂ O content of 0.35% by weight or less and a particle surface of 200 ppm or more (in terms of SiO ₂ ) of silicon. Heat-resistant aluminum hydroxide and magnesium hydroxide adsorbing a compound and a compound of 50 ppm or more (in terms of oxide) of an alkaline earth metal are preferably used. The average particle size of these aluminum hydroxide and magnesium hydroxide is generally 0.5 to 3.0 μm (preferably 0.5 to 2.0 μm).
).

(F) Bromine-containing reaction product A typical example of the bromine-containing reaction product used in the present invention is a bromine-containing epoxy compound represented by the formula (I) and 1,3,5-tribromophenol. Are obtained by reacting with each other, and are represented by the formula (II) as a main component. As a result, the terminal epoxy group of the bromine-containing epoxy compound represented by the formula (I) reacts,
The residual epoxy group is at most 1 in the initial epoxy amount.
5%.

[0034]

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[0035]

Embedded image

(In the formulas (1) and (II), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom or a methyl group; m is 0 or an integer of 1 to 7;
Is 1-4. )

The bromine-containing epoxy compound represented by the formula (1) is 4,4 'containing at least one bromine atom.
-Dioxydiphenylpropane (bisphenol A) and epichlorohydrin can be produced in the same manner as a general ether type epoxy resin. It can also be produced by reacting bromine with an ether type epoxy resin containing no bromine.

The bromine-containing reaction product has a molecular weight of 1,20.
0 to 6,000, and particularly preferably 1,400 to 5,000. Further, the bromine content is 5,000 to 60% by weight, and particularly preferably 10 to 60% by weight.

(G) Composition Ratio The composition ratio of the thermoplastic elastomer (A) in the flame-retardant composition of the present invention is 80 to 98% by weight, and 80 to 9% by weight.
7% by weight is preferred, and 82-95% by weight is particularly preferred. When the proportion of the component (A) is less than 80% by weight, the mechanical strength is poor. On the other hand, when the content exceeds 98% by weight, the flame retardancy decreases, which is not preferable.

In the flame-retardant resin composition of the present invention, the composition ratio of the component (B) in the polymer substance comprising the chlorinated ethylene polymer (B) and the ethylene polymer (C) is 10 to 10. 75% by weight, preferably 15 to 75% by weight, particularly preferably 20 to 75% by weight. If the composition ratio of the component (B) in the polymer substance is less than 10% by weight, a composition having good flame retardancy cannot be obtained. On the other hand, if it exceeds 75% by weight, moldability and workability are poor.

Further, the composition ratio of other components to 100 parts by weight of the polymer substance is as follows.

(D) The composition ratio of antimony oxide is 10 to 10.
The amount is 30 parts by weight, preferably 10 to 27 parts by weight, particularly preferably 10 to 25 parts by weight. If the composition ratio of the component (D) is less than 10 parts by weight, there is a problem in the flame retardancy of the obtained composition. On the other hand, if it exceeds 30 parts by weight,
There is a problem in bleeding.

The composition ratio of (E) aluminum hydroxide and magnesium hydroxide is 1 as the total amount thereof.
0 to 35 parts by weight, preferably 12 to 35 parts by weight,
Particularly, 15 to 35 parts by weight is suitable.

When the amount of the component (E) is less than 10 parts by weight, the flame-retardant property is not good. On the other hand, if it exceeds 35 parts by weight, moldability is not good. Furthermore, the composition ratio of the bromine-containing reaction product (F) is 20 to 50 parts by weight, preferably 20 to 45 parts by weight, and particularly preferably 25 to 45 parts by weight.

When the composition ratio of the component (F) is less than 20 parts by weight, a composition having excellent flame retardancy cannot be obtained. On the other hand, if it exceeds 50 parts by weight, it bleeds from the molded product.

(H) Method for Producing the Composition In order to produce the flame-retardant resin composition of the present invention, the components (B) to (F), excluding the component (A), are mixed in advance. Finally, it is necessary to mix the component (A). (A)
Mixing the components before that is not preferred because the strength, flame retardancy and bleed resistance are reduced.

In addition to the above components, stabilizers for oxygen, light, ozone and heat, lubricants, coloring agents, organic peroxides (as a crosslinked product), and crosslinks commonly used in the rubber and plastic industries. Additives such as an accelerator, a cross-linking accelerator, a tackifier, a plasticizer and an antistatic agent may be added according to the intended use of the composition, but all of them are added before mixing the component (A). There is a need.

Examples of the mixing method include a method of dry blending using a mixer such as a Henschel mixer and a method of melt-kneading using a mixer such as a kneader, a Banbury, a roll mill and an extruder. During mixing, dry blending is performed in advance, and the resulting mixture is further melt-kneaded to obtain a more uniform mixture (composition).

The composition thus obtained is formed into a product having a desired shape by a molding method such as extrusion molding, injection molding, compression molding, transfer molding and stamp molding which is generally performed in the rubber and plastic industries. Molded.

[0050]

The present invention will be described in more detail with reference to the following examples. The tensile strength (hereinafter referred to as “T _B ”) and elongation (hereinafter referred to as “E _B ”) were measured using a Tensilon tester according to ASTM D790. In addition, the flame retardancy test is based on the FMVSS (Frame Motor vehicle) of the United States as a flame retardant regulation for automotive materials.
A frame test was performed in accordance with the “e safety standard” 302. Furthermore, the oxygen index test is based on JIS
The oxygen index was measured according to K7201. In the wet heat test, the specimen was left in a thermo-hygrostat at a temperature of 85 ° C. and a humidity of 95% for 15 days, and whether or not there was bleed from the surface of the sample was visually observed. .

The types and properties of the thermoplastic elastomer, chlorinated ethylene polymer, ethylene polymer, antimony oxide, aluminum hydroxide, magnesium hydroxide and the reaction product containing bromine used are shown below.

[(A) Thermoplastic Elastomer] Clayton G (manufactured by Shell Chemical Co., Ltd., hereinafter referred to as TPS) as a polystyrene-based TPE, and Mylastomer (manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as TPO-1) as an olefin-based TPE; Perprene (manufactured by Toyobo Co., Ltd .; hereinafter referred to as TPR) was used as a polyester-based TPE, and Bevacs (manufactured by Toray Industries, hereinafter referred to as TPA) was used as a polyamide-based TPE.

[(B) Chlorinated ethylene polymer] Polyethylene having a density of 0.940 g / cm ³ (average molecular weight of about 2
Chlorinated polyethylene having a chlorine content of 30.3% by weight [density 1.
10 g / cm ³ , Mooney viscosity (ML _{1 + 4} , 120 ° C)
82.5, amorphous, hereinafter referred to as “chlorinated product (1)”] and chlorine-containing polyethylene obtained by chlorinating polyethylene (average molecular weight: about 150,000) having a density of 0.930 g / cm ³ by an aqueous suspension method. Chlorinated polyethylene having an amount of 30.1% by weight [density 1.13 g / cm ³ , Mooney viscosity (ML
_{1 + 4} , 120 ° C.) 107.0, crystalline, hereinafter referred to as “chlorinated product (2)”], ethylene-methyl methacrylate-maleic anhydride terpolymer having MI (1) of 100 g / 10 min ( Methyl methacrylate copolymerization ratio 18.5
Mol%, a copolymerization ratio of maleic anhydride 1.5 mol%) obtained by chlorinating the copolymer by an aqueous suspension method [chlorine content 30.1% by weight,
Mooney viscosity (ML _{1 + 4} , 100 ° C.) 28, amorphous, hereinafter referred to as “chlorinated product (3)”] and Mooney viscosity (M
L _{1 + 4} , 100 ° C.) is 115, the copolymerization ratio of propylene is 22% by weight, and MI (1) is 1.0 g.
/ 10 minutes ethylene-propylene copolymer (melting point 12
0 ° C.) has a Mooney viscosity (ML _{1 + 4} , 120 ° C.) of 42 and a density of 1.
A chlorinated ethylene-propylene copolymer having a chlorine content of 30.5% by weight and being amorphous, hereinafter referred to as "chlorinated product (4)" having a content of 09 g / cm < ³ > was used.

[(C) Ethylene Polymer] The density is 0.955 g / cm ³ and the MI (2) is 20 g.
High-density polyethylene (hereinafter referred to as “HDPE”) having a length of / 10 minutes was used.

[(D) Antimony oxide] Antimony trioxide having an average particle diameter of 1 μm (hereinafter referred to as “Sb ₂ O ₃ ”)
Was used.

[(E) Aluminum Hydroxide and Magnesium Hydroxide] Further, aluminum hydroxide was produced by the Bayer method, and the content of impurities fixed in the crystal was 0.25% by weight in terms of Na ₂ O. , SiO ₂
Heat-resistant aluminum hydroxide obtained by adsorbing 1620 ppm of silicon, 370 ppm of calcium and 290 ppm of magnesium to aluminum hydroxide containing 0.008% by weight as conversion and 0.005% by weight as CaO conversion [pyrolysis temperature 206 ° C, average particle size 1.7
μm, hereinafter referred to as “Al (OH) ₃ ”]. Also, as magnesium hydroxide, the average particle size is 0.5 μm
, Apparent specific gravity is 0.58 g / cm ³ , and specific surface area (B
Magnesium hydroxide measured by the ET method) is 8m ² / g [manufactured by Kyowa Chemical Industry Co., Ltd., product name KISUMA -5B, hereinafter referred to as "M
g (OH) ₂ "].

[(F) Bromine-containing product] Among the bromine-containing products, any of the above-mentioned (II) as a bromine-containing reaction product
In the formula, a bromine-containing reaction product in which R ₁ is a hydrogen atom and R ₂ is a methyl group [average molecular weight: about 2,000,
56% by weight bromine content, hereinafter referred to as "bromine (A)"]
And a bromine-containing reaction product having a bromine content of 55% by weight and an average molecular weight of about 3,600 [hereinafter referred to as "bromine (B)"]. For comparison, decabromodiphenyl ether [hereinafter referred to as "bromide (C)"] was used.

Examples 1 to 13 and Comparative Examples 1 to 12 Chlorinated ethylene polymers (hereinafter referred to as "chlorinated products"), whose types and amounts are shown in Table 1, HDPE, Sb
4.0 parts by weight of hydrotalcite (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) as a substance containing ₂ O ₃ , aluminum hydroxide and / or magnesium hydroxide (hereinafter referred to as “hydroxide”) and bromine, and other additives Alcamaiser
1 W, average particle size 1.5 μm, as stabilizer), 0.5 parts by weight of magnesium stearate (as lubricant)
0 parts by weight of oleic amide (as lubricant), 0.5
A hindered bisphenol (as an antioxidant) containing parts by weight of sulfur was kneaded for 20 minutes using a kneader kneader in which the tank temperature was previously set to 160 ° C. A sheet was manufactured from each of the obtained mixtures using an oven roll set at 120 ° C. in advance. Each sheet thus obtained was used to produce pellets of 2 mm square using a sheet cutter cutting machine. The pellets produced in this manner (hereinafter referred to as “chlorinated compound”) were used.

After dry blending the thermoplastic elastomers and the various chlorinated compounds whose types and amounts are shown in Tables 2 and 3, the cylinder 1 was heated to 130 ° C. using a 50 mmφ twin screw extruder. 2 temperature 150 ° C, cylinder 3 temperature 150 ° C, cylinder 4 temperature 170 ° C, adapter temperature 150
Each strand having a diameter of 1 mm was prepared at a temperature of 150 ° C., a head temperature of 150 ° C., and a rotation speed of 40 rpm. Using a press machine set to a temperature of 170 ° C. for each strand, the pressure was 200 kg / cm ² (gauge pressure).
Pressed for 2 minutes to form a sheet having a thickness of 2 mm. Also, as Comparative Example 12, after dry blending 85 parts by weight of TPO-2, 5 parts by weight of chlorinated product (1) and 3.3 parts by weight of HDPE, Sb ₂ O was used in the same manner as that used for the chlorinated compound. ₃ 1.7 parts by weight, Mg (OH)
₂ 1.7 parts by weight, 3.3 parts by weight of bromide (A) and other additives used in Examples were mixed, extruded into a strand, and a 2 mm sheet was prepared with a press. Each sheet was measured for tensile strength (T _B ) and elongation (E _B ) and subjected to an oxygen index test. The results are shown in Tables 2 and 3.

Further, a sheet having a thickness of 1 mm was prepared by using a press machine set at a temperature of 170 ° C. for 5 minutes under the condition of a pressure of 200 kg / cm ² (gauge pressure). Each sheet was subjected to a flame retardancy (FMVSS) and wet heat test. The results are shown in Tables 2 and 3.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

From the above results, it can be seen that the flame-retardant resin composition of the present invention has not only excellent flame retardancy, but also good mechanical strength and excellent bleeding properties. Is obvious. In addition, the flame-retardant resin composition of the present invention exhibits the following effects. (1) Excellent heat resistance. (2) Good moldability. (3) Excellent cold resistance. (4) Good thermal expansion properties. (5) It has excellent volume specific resistance. (6) Good oxygen index. The flame-retardant resin composition of the present invention can be used in various fields to exhibit the above effects. Representative applications are shown below. (1) Flame retardant sheet for automobile interior. (2) Curtain sheets in fields where high flame retardancy is required. (3) Furnace wires for vehicles and wires for vehicles.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 23:28 23:02 63:00) (72) Inventor Hiromi Hayashi 1-13-9 Shiba-Daimon, Minato-ku, Tokyo Showa Denko shares In-company (56) References JP-A-1-240571 (JP, A) JP-A-4-13749 (JP, A) JP-A-62-207357 (JP, A) JP-A-1-287150 (JP, A) JP-A-2-284944 (JP, A) JP-A-3-199251 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 21/00 C08J 3/20 C08K 3 / 20 C08K 3/22 C08L 23/28 C08L 23/02 C08L 63/00

Claims (2)

(57) [Claims] 1. A thermoplastic elastomer, (B) a chlorinated ethylene polymer, (C) an ethylene polymer,
The molecular weight obtained by reacting (D) antimony oxide, (E) aluminum hydroxide and / or magnesium hydroxide, and (F) a bromine-containing epoxy compound with 1,3,5-tribromophenol is 1,3. 2
And the bromine content is from 5.0 to 6,000.
0% by weight of a bromine-containing reaction product, wherein the component (A) accounts for 80% by weight of the composition.
To 98% by weight, and the proportion of the component (B) in the total amount of the components (B) and (C) is 10 to 75% by weight. 10
A flame-retardant resin composition, which comprises 30 to 30 parts by weight, 10 to 35 parts by weight of the component (E) and 20 to 50 parts by weight of the component (F). 2. The flame-retardant resin composition according to claim 1, wherein the components (B) to (F) excluding the component (A) are mixed in advance, and then the component (A) is mixed. Method.