JPH062851B2 - Flame retardant composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition having excellent flame retardancy. More specifically, the present invention relates to a composition having not only good flame retardancy but also excellent mechanical strength and good light transmission.

[Conventional technology]

In recent years, the demand for flame-retardant compositions has continued to increase, and the performance requirements for flame-retardant compositions have become severe. For example, optical communication cables for communication,
When wiring high-voltage distribution lines to construction sites such as civil engineering and construction, it is conventionally flame-retardant when used for construction obstacle retention covers that are used to protect approaching places such as constructions and trees. Was sufficient for V-2 in the UL-94 standard.
However, recently, due to the fact that they are burned at the above-mentioned approaching points, and melted and dropped, and accidents of ignition frequently occur, highly flame-retardant compositions have been demanded. Further, also for the coating material for optical communication, the demand for flame retardancy is increasing similarly to the above.

[Problems to be Solved by the Invention]

When used for optical communication, the conventional flame retardancy was not necessary, but recently VW-1 of UL-94 method was used.
There is a demand for highly flame-retardant compositions as they have to pass the law. In particular, as an optical communication coating material, polyethylene resin has conventionally been added with flame retardancy to impart flame retardancy, and vinyl chloride resin is flexible by adding a flame retardant or a plasticizer. A product that gives is being developed. However, in any case, the added flame retardant bleeds out (choking) on the surface,
It is pointed out that the translucency is reduced due to the plasticizer bleeding out.
The current situation is that none of these have been satisfactory solutions.

From the above, the present invention does not have these drawbacks (problems), that is, not only is it excellent in flame retardancy, but also there is no decrease in translucency due to bleed-out of the added flame retardant, and tearability Is to obtain a good composition.

[Means and Actions for Solving the Problems]

According to the present invention, these problems include (A) a chlorinated product obtained by reacting only a chlorine-containing polymer with ethylene (hereinafter referred to as "chlorinated ethylene-based polymer"), B) Density is 0.930 g / cm ³ or more and melting point is 112-14
The temperature is 0 ° C., and the melt index [measured according to JIS K210 under the condition of 4; hereinafter referred to as “MI (1)”] is 0.0.
Ethylene polymer having 1 to 100 g / 10 min and having at most 15 alkyl groups having at most 8 carbon atoms as side chains per 1000 carbon atoms in the main chain, (C) Chlorinated The molecular weight obtained by reacting vinyl resin, (D) antimony oxide, (E) aluminum hydroxide and / or magnesium hydroxide and (F) bromine-containing epoxy compound with 1,3,5-tribromophenol is
1,200-6,000 and bromine content 5.0-60% by weight
The composition ratio of the chlorinated ethylene polymer in the polymer substance consisting of the chlorinated ethylene polymer, the ethylene polymer and the vinyl chloride resin is 10 to 75% by weight. The composition ratio of the ethylene-based polymer is 5.0 to 60% by weight, but the composition ratio of the vinyl chloride resin is at least 5.0% by weight, and the composition ratio with respect to 100 parts by weight of these polymer substances is 10% by weight of antimony oxide. 30 parts by weight, and the total amount of aluminum hydroxide and magnesium hydroxide is
10 to 35 parts by weight, and the bromine-containing reaction product is 20 to 50 parts by weight.
The flame-retardant composition is part by weight. Hereinafter, the present invention will be specifically described.

In the present invention, the polymer substance comprises the following chlorinated ethylene polymer, ethylene polymer and vinyl chloride resin.

(A) Chlorinated ethylene-based polymer The chlorinated ethylene-based polymer used in the present invention is a chlorinated product obtained by reacting only a chlorine-containing polymer described below with chlorine.

Examples of the polymer containing ethylene as a main component include ethylene homopolymers, copolymers of ethylene and α-olefins, ethylene-propylene copolymers having a slight amount of crystal components, and at least ethylene and α, β-unsaturation. Examples thereof include a copolymer with dicarboxylic acid or its anhydride.

Ethylene homopolymers and ethylene-α-olefin copolymers shall be homopolymerized with ethylene or copolymerized with ethylene and at most 20% by weight of α-olefin (generally, at most 12 carbon atoms). Is obtained by. Its density is generally 0.910 to 0.970 g / cc. Further, its molecular weight is at least 30,000, and particularly preferably 50,000 to 700,000.

The propylene copolymerization ratio of the ethylene-propylene copolymer having a small amount of crystal components is 15 to 40% by weight, preferably 18 to 40% by weight, and particularly preferably 20 to 38% by weight. When chlorinated with an ethylene-propylene copolymer having a propylene copolymerization ratio of 15% by weight, the obtained chlorinated ethylene-propylene copolymer has poor rubber-like elasticity and is rather plastic-like in the product. Yes, the resulting composition does not exhibit rubber-like properties. On the other hand, when chlorination is performed using an ethylene-propylene copolymer that exceeds 40% by weight, the number of particles of the chlorinated ethylene-propylene copolymer obtained during chlorination becomes large and the reaction system becomes agglomerated. Not preferred because of

The ethylene-propylene copolymer has a melt index [measured according to JIS K7210 under conditions of 14, hereinafter referred to as "MI (1)"] of 0.01 to 5.0 g / 10 minutes,
0.02-5.0g / 10min is desirable, especially 0.05-5.0g /
10 minutes is preferred. If chlorination is carried out using an ethylene-propylene copolymer having MI (1) of less than 0.01 g / 10 min, the processability of the resulting chlorinated ethylene-propylene copolymer will be poor. On the other hand, when chlorination is carried out using an ethylene-propylene copolymer that exceeds 5.0 g / 10 minutes, the reaction efficiency during the production of the chlorinated ethylene-propylene copolymer is poor, and the chlorinated product is severely agglomerated.

Mooney viscosity of the ethylene-propylene copolymer (ML
_{1 + 4} , 100 ° C.) is usually 10 to 180, preferably 10 to 170, and particularly preferably 10 to 150. If an ethylene-propylene copolymer having a Mooney viscosity of less than 10 is chlorinated, the agglomeration of the chlorinated product is severe during the chlorination. On the other hand, when an ethylene-propylene copolymer having a ratio of more than 180 is used, the resulting chlorinated product has excellent mechanical properties, but has poor rubber-like elasticity and is rather plastic-like.

In addition, the ethylene-propylene copolymer is usually a differential scanning calorimeter (DSC)
The melting peak measured at 80 ° C or higher and the crystallinity measured by X-ray is 35% or higher, preferably 80 to 125 ° C, particularly preferably 85 to 125 ° C. The melting peak is 80
If the temperature is lower than 0 ° C, the chlorinated ethylene-propylene copolymer becomes lumpy during production, and a uniform chlorinated product cannot be obtained, which is not preferable.

The crystallinity of the ethylene-propylene copolymer measured by X-ray is 3% or more, preferably 3 to 50%, and more preferably 3 to 45%. If chlorination is carried out using an ethylene-propylene copolymer having a crystallinity of less than 3%, it will be lumpy at the chlorination stage, and similarly a uniform chlorinated product cannot be obtained.

Furthermore, the weight average molecular weight ( _w ) / number average molecular weight ( _n ), which is an index of the molecular weight distribution measured by the ethylene-propylene copolymer gel permeation chromatography (GPC), is 4 or more, preferably 4 to 8. . _w
It is not preferable to use an ethylene-propylene copolymer in which / _n is less than 4 because the resulting chlorinated product has poor processability.

Further, at least a copolymer of ethylene and α, β-unsaturated dicarboxylic acid or an anhydride thereof has ethylene and “α,
β-unsaturated dicarboxylic acid and 1 or its anhydride ”
It may be a copolymer with [hereinafter referred to as "comonomer (1)"], and is composed of "unsaturated carboxylic acid ester, alkoxyalkyl acrylate and vinyl ester as a third copolymerization component in addition to ethylene and comonomer (1). It may be a multi-component copolymer composed of a "monomer having at least one double bond selected from the group" [hereinafter referred to as "comonomer (2)"].

Of the comonomer (1), α, β-unsaturated dicarboxylic acid
The carbon number is usually at most 20, especially 4 to 16
Those are preferable. As a typical example of the dicarboxylic acid,
Maleic acid, fumaric acid, itaconic acid, citraconic acid, 3,
6-Endomethylene-1,2,3,6-tetrahydro-cis-
Talic acid (Nadic acid ) Is given.

Among the α, β-unsaturated dicarboxylic acid components of the present application, the anhydrides of the α, β-unsaturated dicarboxylic acids are desirable, and maleic anhydride is particularly preferable.

Among the comonomers (2), the unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and particularly preferably 4 to 20 carbon atoms. As a typical example, methyl (meth) acrylate,
Those having good heat stability such as ethyl (meth) acrylate are preferable.

Furthermore, the alkoxyalkyl acrylate usually has at most 20 carbon atoms. Also, the number of carbon atoms in the alkyl group is 1.
To 8 (preferably 1 to 4), and the alkoxy group has 1 to 8 carbons (preferably 1 to 4).
It is desirable to have one). Representative examples of preferred alkoxyalkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate.

The carbon number of vinyl ester is generally at most 20.
(Preferably 4 to 16). Representative examples of suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl piperate, and the like.

In the ethylene-based copolymer of the present invention, the comonomer (1)
The copolymerization ratio is 0.5 to 25 mol%, preferably 1.0 to 25 mol%, and particularly preferably 1.0 to 20 mol%. When an ethylene-based copolymer having a copolymerization ratio of the comonomer (1) of less than 0.1 mol% is used, the effect of the obtained chlorinated product is not exhibited.
On the other hand, an ethylene-based copolymer having a content of more than 25 mol% has a problem in cost and production in industrial production.

In the present invention, the terpolymer composed of ethylene, the comonomer (1) and the comonomer (2) has no blocking during chlorination, and the reaction can be easily carried out. Further, the obtained chlorinated ethylene-based copolymer is not preferable because the copolymer has excellent rubber elasticity and heat resistance.

Further, the copolymerization ratio of the comonomer (2) is generally at most 25 mol% both in terms of production and cost, preferably 0.5 to 25 mol%, particularly preferably 1.0 to 25 mol%. Is.

The melt index of the ethylene-based copolymer [JIS K721
According to 0, the measurement is carried out under the condition of 4, hereinafter referred to as "MI (1)"] is 0.1 to 100 g / 10 minutes, preferably 0.5 to 100 g / 10 minutes, particularly 1.0 to 100 g / 10 minutes. Is preferred. If an ethylene copolymer having an MI (1) of less than 0.1 g / 10 min is used, the resulting chlorinated ethylene copolymer will have poor moldability and kneading properties. On the other hand, if an ethylene-based copolymer exceeding 100 g / 10 minutes is used, the mechanical properties of the resulting chlorinated ethylene-based copolymer will be poor.

The chlorinated ethylene polymer of the present invention can be obtained by chlorinating these polymers. Chlorination can be achieved by applying the method of chlorination in aqueous suspension that is commonly used to produce these chlorinated products.

The chlorine content of the chlorinated ethylene polymer is generally 15 to
45% by weight, preferably 17-45% by weight, especially 20
~ 43 wt% is preferred. When the chlorine content of the chlorinated ethylene-based polymer is less than 15% by weight, the reaction can be performed in the production, but it becomes very difficult in the water washing step during the post-treatment, while when it exceeds 45% by weight, it was obtained. Chlorinated ethylene polymers are hard and not elastomeric.

The Mooney viscosity (ML _{1 + 4} , 100 ° C. is usually 10 to 150, preferably 10 to 130, and particularly preferably 10 to 120 from the viewpoint of moldability and mechanical properties.

(B) Ethylene-based polymer The ethylene-based polymer used in the present invention is obtained by homopolymerizing ethylene or copolymerizing ethylene with an α-olefin (having 3 to 10 carbon atoms). The density of the ethylene polymer is 0.930 g / cm ³
It is above, and 0.930 to 0.975 g / cm ³ is preferable, and especially
0.930 to 0.972 g / cm ³ is suitable. When the density of the ethylene polymer is less than 0.930 g / cm ³ , the tensile strength of the obtained composition is low. The melting point of this ethylene polymer is 112 to 140 ° C, preferably 115 to 140 ° C, and more preferably 117 to 140 ° C. When the melting point of this ethylene polymer is less than 112 ° C., the mechanical strength (particularly tensile strength) of the obtained composition is low. On the other hand, when an ethylene-based polymer having a melting point of higher than 140 ° C. is used, the composition obtained is low in processability, welds are generated in the hinge portion, and cracks easily occur. Furthermore, the MI of the ethylene polymer
(1) is 0.01 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, particularly preferably 5 to 50 g / 10 minutes. When the MI (1) of this ethylene polymer is less than 0.01 / 10 minutes, the moldability of the resulting composition is poor. On the other hand, if it exceeds 100 g / 10 minutes, the composition has good moldability, but a good product cannot be obtained because it does not have appropriate rigidity.

This ethylene-based polymer is essentially 1000 carbon atoms in the main chain.
Each has at most 15 carbons and at most 15 side chains (short chain branches). The “essentially” in the ethylene-based polymer of the present invention is composed of the above short-chain branch, and also includes those having an extremely small number of side chains having 11 or more carbon atoms.

The α-olefin used for producing the ethylene-based polymer is generally an α-olefin having at most 12 (preferably 8 or less) carbon atoms, and representative examples are propylene, butene-1, and hexene-. 1,4-methylpentene-
1 and octene-1. The copolymerization ratio of α-olefin in this copolymer is usually at most 5% by weight.

(C) Vinyl chloride resin Furthermore, the vinyl chloride resin used in the present invention is
It is a vinyl chloride homopolymer and a copolymer with vinyl chloride and a compound having at least one double bond capable of copolymerizing with vinyl chloride at most 50% by weight (preferably 45% by weight or less). The polymerization degree of this vinyl chloride resin is usually 600
-3500, especially 800-3200 are preferred. As a typical example of the compound having at least one double bond,
Vinylidene chloride, ethylene, propylene, vinyl acetate,
Mention may be made of acrylic acid and methacrylic acid and their esters, maleic acid and their esters and acrylonitrile. These vinyl chloride resins are obtained by homopolymerizing or copolymerizing vinyl chloride alone or vinyl chloride and the above vinyl compound in the presence of a free radical catalyst, and the production method thereof is widely used and is widely used. It has been used throughout.

(D) Antimony oxide 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 above "Handbook, Rubber / Plastic Compounding Chemicals" and the like.

(E) Aluminum Hydroxide and Magnesium Hydroxide Furthermore, the aluminum hydroxide used in the present invention has a Na ₂ O content of 0.35 wt% or less, a particle surface of a silicon compound of 200 ppm or more (SiO ₂ equivalent) and 50 ppm or more ( Heat-resistant aluminum hydroxide and magnesium hydroxide having adsorbed a compound of an alkaline earth metal (as oxide) are preferably used. The average particle size of these aluminum hydroxides and magnesium hydroxides is 0.5 to 3.0 μm (desirably 0.5 to 2.0 μm) in terms of mixability and moldability and the mechanical strength of the resulting composition.

(F) Bromine-containing reaction product Further, the representative bromine-containing reaction product used in the present invention is a bromine-containing epoxy compound represented by the formula (I).
It is obtained by reacting with 1,3,5-tribromophenol and is represented by the formula (II) as a main component. As a result, the terminal epoxy groups of the bromine-containing epoxy compound represented by the formula (I) react, and the residual epoxy groups account for at most 15% of the initial epoxy amount.

[In the formulas (I) 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, and i is 1 to 4. The bromine-containing epoxy compound represented by the formula (I) contains 4,4′-dioxydiphenylpropane (bisphenol A) containing at least one bromine atom and epichlorohydrin in the same manner as a general ether type epoxy resin. It can also be manufactured by a method. Further, it can be produced by reacting an bromine-free ether type epoxy resin with bromine.

The bromine-containing reaction product has a molecular weight of 1,200 to 6,000,
Particularly, 1,400 to 5,000 are preferable. The bromine content is 5.0 to 60% by weight, and particularly preferably 10 to 60% by weight.

(G) Composition ratio In producing the flame-retardant composition of the present invention, the composition ratio of the chlorinated ethylene polymer in the polymer substance is 10 to 75.
%, Preferably 15 to 75% by weight, particularly preferably 20 to 75% by weight. If the composition ratio of the chlorinated ethylene polymer in the polymer substance is less than 10% by weight, a composition having good flame retardancy cannot be obtained. On the other hand, when it exceeds 75% by weight, a composition having good flame retardancy can be obtained. However, a good molded product cannot be obtained because of poor moldability and processability.

Further, the composition ratio of the ethylene-based polymer in the polymer substance is 5.0 to 60% by weight, preferably 5.0 to 55% by weight,
Especially, 5.0 to 50% by weight is preferable. When the composition ratio of the ethylene polymer in the polymer substance is less than 5.0% by weight, a composition having excellent mechanical strength (particularly tensile strength) cannot be obtained. On the other hand, if it exceeds 60% by weight,
A highly flame-retardant composition cannot be obtained.

Further, the composition ratio of the vinyl chloride resin in the polymer substance is at least 5.0% by weight, preferably 5.0 to 30% by weight, and particularly preferably 5.0 to 25% by weight. If the composition ratio of the vinyl chloride resin in the polymer substance is less than 5.0% by weight, not only a composition having excellent flexibility cannot be obtained, but there is also a problem in flame retardancy.

The composition ratio of antimony oxide to 100 parts by weight of these polymer substances is 10 to 30 parts by weight, preferably 10 to 27 parts by weight, and particularly preferably 10 to 25 parts by weight. If the composition ratio of antimony oxide to 100 parts by weight of these polymer substances is less than 10 parts by weight, there is a problem in flame retardancy of the obtained composition. On the other hand, if it exceeds 30 parts by weight, there is a problem in bleeding property.

Further, the composition ratio of aluminum hydroxide and magnesium hydroxide to 100 parts by weight of the polymer substance is 10 to 35 parts by weight, preferably 12 to 35 parts by weight, and particularly preferably 15 to 35 parts by weight. If the composition ratio of aluminum hydroxide and magnesium hydroxide is less than 10 parts by weight with respect to 100 parts by weight of the polymer substance, the flame retardancy is not good. On the other hand, if it exceeds 35 parts by weight, the moldability is poor.

The composition ratio of the bromine-containing product to 100 parts by weight of the polymer is 20 to 50 parts by weight, preferably 20 to 45 parts by weight, more preferably 25 to 45 parts by weight, and especially 25 to 45 parts by weight.
Weight parts are preferred. If the composition ratio of the bromine-containing reaction product to 100 parts by weight of the polymer 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, the bromine-containing product bleeds from the molded product.

(H) Mixing method, molding method, etc. Although the composition of the present invention can be obtained by uniformly blending the above substances, oxygen, light, ozone and Stabilizers against heat, lubricants, colorants, organic peroxides (as cross-linked products), cross-linking accelerators, cross-linking promoters, tackifiers, plasticizers, shatterers, softeners,
Additives such as slip agents, flame retardants and antistatic agents may be added depending on the intended use of the composition.

To obtain the composition of the present invention, a mixing method generally used in the rubber industry and the plastics industry may be applied. Examples of the mixing method include a dry blending method using a mixer such as a Henschel mixer, and a melt kneading method using a mixer such as a kneader, Banbury, roll mill and extruder. Before mixing, a more uniform mixture (composition) can be obtained by dry-blending in advance and further melt-kneading the obtained mixture.

The composition thus obtained is molded into a product having a desired shape by molding methods such as extrusion molding, injection molding, compression molding, transfer molding and stamp molding which are generally carried out in the rubber and plastic industries. .

[Examples and Comparative Examples]

Hereinafter, the present invention will be described in more detail with reference to Examples.

In Examples and Comparative Examples, tensile strength (hereinafter referred to as “T
_B )) and elongation (hereinafter referred to as “E _B ”)
It was measured using a Tensilon tester according to TM D790. In addition, the flame retardance test complies with UL standard 1581 and is VW
-1 (Vertical Wire) Flame Test was performed. Furthermore, the oxygen index test measured the oxygen index according to JIS K7201. In the wet heat test, the temperature of the sample was 85 ° C., the humidity was 95%, and the sample was left for 15 days in a thermostatic chamber to visually observe whether or not there was bleeding from the surface of the sample. .

The chlorinated ethylene polymers, ethylene polymers, vinyl chloride resins, antimony oxide, aluminum hydroxide, magnesium hydroxide and bromine-containing reaction products used in Examples and Comparative Examples are shown below in terms of physical properties and the like. Show.

((A) chlorinated ethylene polymer)

As a chlorinated ethylene polymer, the density is 0.940 g / cm ³
The chlorine content obtained by chlorinating the polyethylene (average molecular weight of about 200,000) by the aqueous suspension method is 3
0.3% by weight chlorinated polyethylene [density 1.10 g / cm ³ ,
Mooney viscosity (ML _{1 + 4} , (120 ° C)) 82.5, amorphous, hereinafter referred to as "chlorinated product (1)" and density 0.930 g / cm
^The chlorine content obtained by chlorinating polyethylene of ³ (average molecular weight about 150,000) by the aqueous suspension method is
Chlorinated polyethylene of 30.1% by weight [density 1.13 g / c
m ³ , Mooney viscosity (ML _{1 + 4} , 120 ° C)) 107.0, crystallinity, hereinafter referred to as "chlorinated compound (2)", MI (1) 100 g / 1
By chlorinating the ethylene-methyl methacrylate-maleic anhydride terpolymer of 0 minutes (copolymerization ratio of methyl methacrylate 18.5 mol%, copolymerization ratio of maleic anhydride 1.5 mol%) by an aqueous suspension method The obtained chlorinated ethylene copolymer [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 ( ML
_{1 + 4} , 100 ° C) is 115, and the propylene copolymerization ratio is 2
Mooney viscosity (ML _{1 +} 4,120) obtained by chlorinating an ethylene-propylene copolymer (melting point: 120 ° C.) having a MI (1) of 2% by weight and an MI (1) of 1.0 g / 10 min.
Propylene copolymer [chlorine content 30.5 wt%, amorphous, hereinafter referred to as "chlorinated product (4)"] - ° C.) is 42, and chlorinated density of 1.09 g / cm ³ Ethylene It was

[(B) ethylene polymer]

Also, as an ethylene polymer, the density is 0.955 g / cm ³
And high density polyethylene (hereinafter referred to as "HDPE") having MI (1) of 20 g / 10 min.

[(C) Polyvinyl chloride resin] Furthermore, as a polyvinyl chloride resin, the average degree of polymerization is about 65.
A vinyl chloride homopolymer of 0 (hereinafter referred to as "PVC") was used.

[(D) Antimony oxide]

As antimony oxide, antimony trioxide having an average particle size of 1 μm (hereinafter referred to as “Sb ₂ O ₃ ”) was used.

[(E) Aluminum hydroxide and magnesium hydroxide]

Furthermore, as aluminum hydroxide, manufactured by the Bayer method, the content of impurities fixed in the crystal is 0.25 wt% as Na ₂ O conversion, 0.008 wt% as SiO ₂ conversion and 0.005 wt% as CaO conversion. Heat-resistant aluminum hydroxide that adsorbs 1620 ppm of silicon, 370 ppm of calcium and 290 ppm of magnesium to aluminum hydroxide [thermal decomposition temperature 206 ° C, average particle size 1.7 μm, hereinafter referred to as “Al (OH) ₃ ”. ] Was used. Also, as magnesium hydroxide, the average particle size is 1.5 μm and the apparent specific gravity is 0.58 g.
/ Cm ³ and specific surface area (measured by BET method) of 8 m ² /
Magnesium hydroxide (trade name: Kismer 5B, manufactured by Kyowa Chemical Industry Co., Ltd., hereinafter referred to as “Mg (OH) ₂ ”) was used.

[(F) Bromine-containing material]

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

Examples 1 to 13 and Comparative Examples 1 to 12 Chlorinated ethylene-based polymers whose types and amounts are shown in Table 1 (hereinafter referred to as “chlorinated products”), and Table 1 shows the amounts. 30 parts by weight of HDPE and PVC, which are shown in Table 1 and "aluminum hydroxide or magnesium hydroxide (hereinafter referred to as" hydroxide "), but not mixed in Comparative Example 6" , 40 parts by weight of a bromine-containing substance whose type is shown in Table 1 (however, in Comparative Example 7
No compound), 20 parts by weight of Sb ₂ O ₃ (however, Comparative Example 5
4.0 parts by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., trade name)
Alkamycer 1 W, average particle size 1.5 μm, as stabilizer), 0.5 parts by weight of magnesium stearate (as lubricant), 2.0 parts by weight of amide oleate (as lubricant), 0.5 parts by weight of hindered bisphenol containing sulfur ( (As an antioxidant) and 1.0 part by weight of Furnace Black (Showa Cabot Co., trade name Show Black N-330, average particle size 40 nm, HAF, as a colorant) are kneader-kneaded with the chamber temperature set at 160 ° C in advance. Each was kneaded for 20 minutes using a machine. A sheet was manufactured from each of the obtained mixtures by using an oven roll set at 120 ° C. in advance. Using each sheet thus obtained, a 3 mm square pellet was manufactured using a sheet cutter cutting machine. A part of the pellets thus produced was pressed under a condition of a pressure of 200 kg / cm ² (gauge pressure) using a press set at a temperature of 180 ° C.
A sheet having a thickness of 2 mm was formed by pressing for 1 minute, and a sample for tensile strength (T _B ) and elongation (E _B ) measurement and an oxygen index test was manufactured.

Also, use an extruder to increase the temperature of cylinder 1 to 130
℃, the temperature of the cylinder 2 is 140 ℃, the temperature of the cylinder 3 is 150 ℃ and the temperature of the head is 150 ℃, the diameter is 1
Each strand of mm width was created. A flame retardancy test and a wet heat test were performed on each strand. In all Examples and Comparative Examples 4 and 11, the flame retardancy test passed. However, in Comparative Examples 1 to 3, Comparative Examples 5 to 10 and Comparative Example 12, all failed. Further, in all Examples and Comparative Examples 1, 2, 5 to 7 and 12, no bleed could be recognized in the wet heat test. However, Comparative Examples 3, 4 and 8 to 1
In No. 1, all bleeding occurred.

Further, tensile strength and elongation were measured and an oxygen index test was performed. The results are shown in Table 2.

From the above results, it is clear that the flame-retardant composition of the present invention not only has extremely excellent flame retardancy, but also has good mechanical strength and excellent wet heat resistance.

〔The invention's effect〕

 The flame-retardant composition of the present invention exhibits the following effects.

(1) Excellent heat resistance.

(2) Good moldability.

(3) Excellent cold resistance.

(4) Good thermal expansion property.

(5) It has excellent volume resistivity.

(6) The oxygen index property is good.

The flame-retardant composition of the present invention can be used in various fields in order to exert the above effects. Typical uses are shown below.

(1) Fiber coating material for optical communication (2) Furnace wire coating material for automobiles (3) Clamp covers and plastic pipes for fields requiring high flame retardancy (4) Difficulty for automobile interiors Master batch of fuel sheet, etc.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08L 23/08 LCJ 7107-4J 27/06 LEP 9166-4J LEQ 9166-4J 71/10 LQJ 9167-4J LQK 9167 -4J // C08G 65/40 NQV 9167-4J (C08K 13/02 3:22 5:06 5:15)

Claims (1)

[Claims] 1. A chlorinated compound obtained by reacting only chlorine with a polymer containing ethylene as a main component, and (B) having a density of 0.930 g / cm ³ or more and a melting point of 112 to 140.
℃ and melt index 0.01 to 100g / 10
And an ethylene polymer having at most 15 alkyl groups having at most 8 carbon atoms as side chains per 1000 carbon atoms in the main chain, (C) vinyl chloride resin, (D) ) Antimony oxide, (E) aluminum hydroxide and / or magnesium hydroxide and (F) a bromine-containing epoxy compound and 1,3,5-tribromophenol having a molecular weight of 1,3
Composition ratio of chlorinated compounds in polymer materials consisting of chlorinated products, ethylene-based polymers and vinyl chloride resins, which consist of bromine-containing reaction products with a bromine content of 200 to 6,000 and a bromine content of 5.0 to 60% by weight. Is 10 to 75% by weight, the composition ratio of the ethylene-based polymer is 5.0 to 60% by weight, but the composition ratio of the vinyl chloride resin is at least 5.0% by weight.
The composition ratio with respect to parts by weight is 10 to 30 parts by weight of antimony oxide, 10 to 35 parts by weight of aluminum hydroxide and magnesium hydroxide in total, and 20 to 50 parts by weight of bromine-containing reaction product. A flame retardant composition.