JPH02284944A - Fire retardant composition - Google Patents

Abstract

PURPOSE:To obtain fire retardant composition comprising chlorinated ethylenic polymer, specific ethylenic polymer, vinyl chloride resin, antimony oxide, Al(OH)3 and/or Mg(OH)2 and specific bromine-containing reaction product. CONSTITUTION:(A) 10-75wt.% chlorinated ethylenic polymer is mixed with (B) 5-60wt.% ethylenic polymer containing <=15 pieces of <=8C alkyl group as side chain per 100 pieces of C atom in main chain and having >=0.93g/cm<3> density, 112-140 deg.C melting point and 0.01-100g/10min melt index and (C) >=5wt.% vinyl chloride resin. Then, 100 pts.wt. resultant polymer mixture is mixed with (D) 10-30 pts.wt. antimony oxide, (E) 10-35 pts.wt. Al(OH)3 and/or Mg(OH)2 and (F) 20-50 pts.wt. reaction product obtained by reacting bromine-containing epoxy-based compound and 1,3,5-tribromophenol having 1200-6000 molecular weight and 5-60wt.% bromine content to afford the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composition with excellent flame retardancy. More specifically, the present invention relates to a composition that not only has good flame retardancy but also excellent mechanical strength and good translucency.

[Prior Art 1] In recent years, the demand for flame-retardant compositions has continued to increase, and the performance requirements for flame-retardant compositions have become more severe. For example, optical communication cables for communications, etc.
When wiring high-voltage power distribution lines to factory sites such as civil engineering and construction, conventionally flame-retardant However, V-2 was sufficient according to the UL-94 standard.

However, recently, highly flame-retardant compositions are desired because of the frequent occurrence of combustion, melting and dripping, and ignition accidents at the above-mentioned close locations. Similarly to the above, there is a strong demand for flame retardancy for coating materials for optical communications.

[Problem to be solved by the invention 1: Conventional flame retardancy was not required when used in optical communications, but recently, VW-1 under UL-94
There is a growing demand for highly flame retardant compositions that have to pass the law. In particular, for optical communication coating materials, conventional polyethylene resins have been added with flame retardants to give them flame retardant properties, and even vinyl chloride resins have been added with flame retardants and plasticizers to make them flexible and flame retardant. A product has been developed that provides this. However, in either case, the added flame retardant may bleed out (chalking) on the surface, or
It has also been pointed out that the translucency decreases due to plasticizer bleed out, and various efforts have been made.
At present, no satisfactory solution has been achieved in either case.

From the above, the present invention does not have these drawbacks (problems) (that is, it not only has excellent flame retardancy but also does not reduce the translucency due to bleed-out of the added flame retardant).
Moreover, the object is to obtain a composition having good tearability.

[Means and effects for solving the problems] According to the present invention, these problems are solved.

fA) A chlorinated product obtained by reacting only chlorine with a polymer whose main component is ethylene (hereinafter referred to as "chlorinated ethylene polymer"), fB) a density of 0.930 g/c or more, melting point is 1
12 to 140°C, and melt index [JT
Measured under conditions 4 according to S210, hereinafter rMNl
) J] is 0. fcl vinyl chloride, an ethylene polymer having a content of 100 g/lO and at most 15 alkyl groups having at most 8 carbon atoms as side chains per 1000 carbon atoms in the main chain. The molecular weight obtained by reacting a bromine-containing epoxy compound with 1.3.5-1-ribromophenol is 1. , 200 to 6.000 and a bromine content of 5.0 to 60% by weight, and a polymer consisting of a chlorinated ethylene polymer, an ethylene polymer, and a vinyl chloride resin. The composition ratio of the chlorinated ethylene polymer in the substance is 10 to 75% by weight, and the composition ratio of the ethylene polymer is 50 to 60% by weight.
However, the composition ratio of vinyl chloride resin is small (both 5,
0% by weight, and 100ffi f of these polymeric substances
The composition ratio of antimony oxide to the fi part is 1 to 3
0 parts by weight, 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. I can do it. The present invention will be explained in detail below.

In the present invention, the polymeric substance consists of the following chlorinated ethylene polymer, ethylene polymer, and vinyl chloride resin.

fA) Chlorinated ethylene polymer The chlorinated ethylene polymer used in the present invention is a chlorinated product obtained by reacting only chlorine with a polymer whose main component is ethylene, which will be described later.

Examples of the polymer containing ethylene as a main component include ethylene homopolymer, copolymer of ethylene and a-olefin, ethylene-propylene copolymer having a slight crystal content, and at least ethylene and α,β-unpolymers. Examples include copolymers with saturated dicarboxylic acids or their anhydrides.

Ethylene homopolymers and copolymers of ethylene and α-olefins are prepared by homopolymerizing ethylene or copolymerizing ethylene with at most 20% by weight of α-olefins (generally, 12 carbon atoms). Its density is generally 0.910 to 0.9.
70 g/cc. Further, its molecular weight is at least 30,000, preferably 50,000 to 700,000.

Further, the copolymerization ratio of propylene in the ethylene-propylene copolymer having a slight crystal content is 15 to 40% by weight, preferably 18 to 40% by weight, and particularly preferably 20 to 38% by weight. When an ethylene-propylene copolymer with a propylene copolymerization ratio of 15% by weight is used for chlorination, the resulting chlorinated ethylene-propylene copolymer has poor rubber-like elasticity and is rather plastic-like in the product. , the resulting composition does not exhibit rubbery properties. On the other hand, when chlorinating using an ethylene-propylene copolymer exceeding 40% by weight, the number of particles of the chlorinated ethylene-propylene copolymer obtained during chlorination increases, resulting in lump-like formation in one reaction system. Unfavorable for becoming.

In addition, the melt index of the ethylene-propylene copolymer [measured according to JIS 721O under conditions of 14, hereinafter referred to as rMI11)J] is B, old ~ 5, Og/
10 minutes, preferably 0-02 to 5.0 g/10 minutes, particularly preferably 0.05 to 5.0 g/10 minutes. If an ethylene-propylene copolymer with an M I +11 of less than 0.01 g/10 min is used for chlorination, the processability of the resulting chlorinated ethylene-propylene copolymer is good (no, on the other hand, 5. When chlorinating using an ethylene-propylene copolymer exceeding 0 g/10 minutes, the reaction efficiency during production of the chlorinated ethylene-propylene copolymer is poor, and moreover, the chlorinated product is agglomerated.

Mooney viscosity (M
L,..., 100℃) is usually 10 to 180,
lO~170 is preferable, and lO~150 is particularly suitable. If an ethylene-propylene copolymer having a Mooney viscosity of less than 10 is chlorinated, the chlorinated product will be agglomerated severely during chlorination. On the other hand, when an ethylene-propylene copolymer with a molecular weight exceeding 180 is used, the resulting chlorinated product has excellent mechanical properties, but has poor rubber-like elasticity and is rather plastic-like.

Note that the ethylene-propylene copolymer is usually measured using a differential scanning calorimeter (Differential Scanning Calorimeter).
g or more, preferably from 80 to 125°C, particularly from 85 to 125°C.
125°C is preferred. If the melting peak is below 80°C, the chlorinated ethylene-propylene copolymer becomes lumpy during production, making it impossible to obtain a uniform chlorinated product, which is not preferable.

In addition, the ethylene-propylene copolymer has a crystallinity of 3% or more as measured by X-rays, preferably 3 to 50%,
Particularly suitable is 3 to 45%. This crystallinity is 3%
If the ethylene-propylene copolymer is used for chlorination, it will become lumpy during the chlorination step, and a homogeneous chlorinated product will not be obtained.

Furthermore, the ethylene-propylene copolymer has a discretionary average molecular weight (U = )/number average molecular weight (M.), which is an index of molecular weight distribution measured by gel permeation chromatography (GPC), of 4 or more, 4 to 8 are preferred.

If an ethylene-propylene copolymer with M, /M, of less than 4 is used, it is not preferable because the processability of the resulting chlorinated product is poor.

Furthermore, at least a copolymer of ethylene and an α,β-unsaturated dicarboxylic acid or anhydride thereof is a copolymer of ethylene and [α,β-unsaturated dicarboxylic acid or anhydride thereof.
β-unsaturated dicarboxylic acid and/or its anhydride”
[hereinafter referred to as "comonomer (1)"]] In addition to ethylene and comonomer + 1), as a third copolymer component "unsaturated carboxylic acid ester, alkoxyalkyl acrylate, late, and vinyl ester" may be used. A multi-component copolymer having at least one double bond selected from the group consisting of a comonomer (hereinafter referred to as comonomer (2) J) may also be used.

Of the comonomers +11, the α,β-unsaturated dicarboxylic acid usually has at least 20 carbon atoms, especially 4 to 1 carbon atoms.
Six pieces are preferred. Typical examples of the dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, 53,6-nindomethylene-1,2,3,6-titrahydrosis-phthalic acid (nadic acid 2).

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

Among the comonomers (2), the unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and 4 to 20 carbon atoms are particularly preferred. Representative examples include methyl (meth)acrylate, ethyl (meth)acrylate, Those with good thermal stability are preferred.

Further, the number of carbon atoms in the alkoxyalkyl acrylate is the usual amount (both are 20).Also, it is preferable that the alkyl group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), and the alkoxy group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). The number is 1 to 8 (preferably 1 to 8)
4) is desirable. Representative examples of preferred alkoxyalkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate.

Furthermore, the number of carbon atoms in vinyl ester is generally at most 2.
The number is 0 (preferably 4 to 16). Representative examples of suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl bivalate, and the like.

In the ethylene copolymer of the present invention, comonomer +1
The copolymerization ratio of 1 is 0.5 to 25 mol%, and 1.0 to 25 mol%.
25 mol% is preferred, particularly 1.0 to 20 mol%. The copolymerization ratio of comonomer (1) is 0.1 mol%
If less than 20% of the ethylene copolymer is used, the effect of the resulting chlorinated product will not be exhibited.

On the other hand, an ethylene copolymer containing more than 25 mol % poses problems in terms of cost and production when industrially produced.

In the present invention, the terpolymer consisting of ethylene, comonomer fi+, and comonomer (2) is free from blocking during chlorination, and the reaction can be easily carried out. Furthermore, the resulting chlorinated ethylene copolymer is not preferred because it has excellent rubber elasticity and heat resistance.

In addition, the copolymerization ratio of the comonomer (2) is generally at most 25 mol% from the viewpoint of production and cost, and is 0.5% by mole.
~25 mol% is preferable, especially 1.0~25 mol%.
Mol% is preferred.

The melt index of the ethylene copolymer [JIS
Measured under 4 conditions according to K7210, hereinafter rMNl
) J] is 0.1 to 100 g/10 min, and 0
．． 5 to too g/IQ is preferable, especially 1.
0 to 100 g/10 minutes is suitable. M! +1
If an ethylene copolymer containing less than 0.1 g/10 min of ethylene is used, the resulting chlorinated ethylene copolymer will have good moldability and crosstalk (no crosstalk). If a chlorinated ethylene-based copolymer is used, the resulting chlorinated ethylene-based copolymer has poor mechanical properties.

The chlorinated ethylene polymer of the present invention can be obtained by chlorinating these polymers. Chlorination can be achieved by applying the methods of chlorination in aqueous suspension that are commonly practiced for producing these chlorinated products.

The chlorine content of the chlorinated ethylene polymer is generally 15
-45% by weight, preferably 17-45% by weight, particularly preferably 20-43% by weight. If the chlorine content of the chlorinated ethylene polymer is less than 15% by weight, the reaction can be carried out during production, but it will be extremely difficult to perform the water washing process during post-treatment. The chlorinated ethylene polymer is hard and not elastomer-like.

In addition, Mooney viscosity (M L , , 100°C
) is usually 10-150 from the point of formability and mechanical properties.
10 to 130 is preferable, and 10 to 120 is particularly preferable.

fIll Ethylene Polymer The ethylene polymer used in the present invention is obtained by homopolymerizing ethylene or copolymerizing ethylene and α-olefin (3 to 10 carbon atoms). The density of the ethylene polymer is 0.930
g/c rd or more, 0,930~0.975
g/crn' is preferred, especially 0.930 to 0.972
g/crn' is preferred. If the density of the ethylene polymer is less than 0.930 g/cr11', the tensile strength of the resulting composition will be low, and the melting point of the ethylene polymer will be 112 to 14 Q'C, 115 to 14
A temperature of 0°C is desirable, and a temperature of 117 to 140°C is particularly suitable. If the melting point of this ethylene polymer is less than 112°C,
The mechanical strength (especially tensile strength) of the resulting composition is low. On the other hand, if an ethylene polymer with a melting point exceeding 140°C is used, the processability of the resulting composition will be low and welds may form in the hinge part. The ethylene polymer has a M I +11 of 0. Old~1
00 g/10 minutes, preferably 0.1 to 50 g/710 minutes, particularly preferably 5 to 50 g/10 minutes.

Ml+11 of this ethylene polymer is 0.01g/IQ
If it is less than 1 minute, the moldability of the resulting composition will be poor. on the other hand,
If it exceeds 100 g/10 minutes, the moldability of the composition is good, but a good product cannot be obtained due to lack of appropriate rigidity.

This ethylene polymer essentially consists of carbon in the main chain "Essentially" in the ethylene polymer of the present invention consists of the above-mentioned short chain branches, and an extremely small number of carbon atoms (11). Also included are those having more than one side chain.

In the a-olefin used for producing the ethylene polymer, -H has at most 12 carbon atoms (preferably 8 carbon atoms).
Typical examples are propylene, butene-1, hexene-1, 4-methylpentene-1, and
1 and octene-1. The copolymerization ratio of α-olefin in this copolymer is 5% by weight.

fcl vinyl chloride resin Furthermore, the vinyl chloride resin used in the present invention is
Vinyl chloride homopolymer and vinyl chloride and at most 50
It is a copolymer with a compound having at least one copolymerizable double bond with vinyl chloride in an amount by weight (preferably 45% by weight or less). The degree of polymerization of this vinyl chloride resin is usually 600 to 3,500, particularly preferably 8(+(1 to 3,200). Typical examples of compounds having at least one double bond include vinylidene chloride, ethylene, propylene, Examples include vinyl acetate, acrylic acid and methacrylic acid and their esters, maleic acid and their esters, and acrylonitrile.These vinyl chloride resins are prepared by combining vinyl chloride alone or vinyl chloride and the vinyl compound in the presence of a free radical catalyst. It is obtained by homopolymerization or copolymerization, and its manufacturing method is widely used and used in many fields.

fD) 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-mentioned "Handbook, Rubber/Plastic Compounded Chemicals."

fEl aluminum hydroxide and magnesium hydroxide Furthermore, the aluminum hydroxide used in the present invention has a Na20 content of 0.35% or less and a silicon compound on the particle surface of 200 ppm or more (silicon compound in place of Sty2 and 50 ppm or more). Heat-resistant aluminum hydroxide and magnesium hydroxide that have adsorbed alkaline earth metal compounds (in terms of oxides) are preferably used. The mechanical strength of the composition is usually 0.5 to 3.0 μm (preferably 0.5 to 2.0 μm).
0 μm).

fFl Bromine-containing reaction product A typical example of the bromine-containing reaction product used in the present invention is the reaction of the bromine-containing epoxy compound represented by formula (I) with 1.3.5-) ribromophenol. It is obtained by (■) as the main component.
It is shown by the formula. As a result, the terminal epoxy group of the bromine-containing epoxy compound represented by formula (I) reacts, and the remaining epoxy group is larger than the initial epoxy amount (both are 15%).

(Left below) The bromine-containing epoxy compound represented by the formula (1) is a general ether-type compound of 4,4°-dioxydiphenylpropane (bisphenol A) and epichlorohydrin, each containing a small number of bromine atoms. It can also be produced in the same manner as epoxy resins.Also, it can be produced by reacting bromine-free ether type epoxy resin with bromine.

The bromine-containing reaction product has a molecular weight of 1.200 to 6.00.
0 Te, preferably 1.400 to 5,000, and the bromine content is 5.0 to 60% by weight,
Particularly desirable is 10 to 60% by weight.

(G1 composition ratio In producing the flame retardant composition of the present invention, the composition ratio of tm and tetraethylene polymer in the polymer substance is
0 to 75% by weight, preferably 15 to 75% by weight,
In particular, 20 to 75% by weight is suitable. If the composition ratio of the chlorinated ethylene polymer in the polymer substance is less than 10% by weight, a composition with good flame retardancy cannot be obtained.
On the other hand, if it exceeds 75% by weight,! A composition with good flammability can be obtained.

However, good molded products cannot be obtained due to poor moldability and processability.

Further, the composition ratio of the ethylene polymer in the polymer substance is 5.0 to 60% by weight, preferably 5.0 to 55% by weight, and particularly preferably 5.0 to 50% by weight.

The composition ratio of ethylene polymer in the polymer material is 5
If it is less than 0% by weight, a composition with excellent mechanical strength (especially tensile strength) cannot be obtained, while 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 polymeric substance is at least 5.0% by weight, preferably 5.0 to 30% by weight, and particularly preferably 5.0 to 25% by weight.

The composition ratio of vinyl chloride resin in the polymer material is 5.
If the amount is less than 0% by weight, not only will it be impossible to obtain a composition with excellent flexibility, but there will also be problems in terms of flame retardancy.

Furthermore, the composition ratio of antimony oxide to 100 parts by weight of these polymeric substances is 10 to 30 parts by weight, and 10 to 30 parts by weight.
27 parts by weight is desirable, and 10 to 25 parts by weight is particularly preferred. If the composition ratio of antimony oxide to 100 parts by weight of these polymeric substances is less than 10 parts by weight, there is a problem in terms of flame retardancy of the resulting composition. On the other hand, 30
If it exceeds parts by weight, there is a problem in terms of bleedability.

Furthermore, the composition ratio of aluminum hydroxide and magnesium hydroxide to 100 parts by weight of the polymeric substance is 10 to 3.
5 parts by weight, preferably 12 to 35 parts by weight, especially 1
5 to 35 parts by weight is preferred. If the total composition ratio of aluminum hydroxide and magnesium hydroxide to 100 parts by weight of the polymeric substance is less than 10 parts by weight, the flame retardant property will not be good.

On the other hand, if it exceeds 35 parts by weight, moldability is poor.

Further, the composition ratio of the bromine-containing reaction product to 100 parts by weight of the polymeric substance is 20 to 50 parts by weight, and 20 to 45 parts by weight.
Parts by weight are preferred, especially 25 to 45 parts by weight, especially 25 to 45 parts by weight.

If the composition ratio of the bromine-containing reaction product to 100 parts by weight of the polymeric substance is less than 20 parts by weight, a composition with excellent fl flammability cannot be obtained; on the other hand, if it exceeds 50 parts by weight, the bromine-containing reaction product The object bleeds from the molded object.

Although the composition of the present invention can be obtained by uniformly blending the above-mentioned substances (old mixing method, molding method, etc.), oxygen, light, ozone and heat stabilizers, lubricants, colorants,
Contains additives such as organic peroxides (as crosslinkers), crosslinking accelerators, crosslinking accelerators, tackifiers, plasticizers, shirt removers, softeners, slip agents, flame retardants and antistatic agents. It may be added depending on the intended use of the product.

In order to obtain the composition of the present invention, mixing methods commonly used in the rubber and plastics industries may be applied, including tri-blending using a mixer such as a Henschel mixer, and Nigoo and Banbury roll mills. and a method of melt-kneading using a mixer such as an extruder. When mixing, a more uniform mixture (composition) can be obtained by tri-blending in advance and further melt-kneading the resulting 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 commonly practiced in the rubber and plastic industries. .

[Examples and Comparative Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in Examples and Comparative Examples, tensile strength (hereinafter "T
The elongation rate (hereinafter referred to as rE, J) was measured according to ASTM 0790 using a Tensilon tester. In addition, the flame retardancy test was conducted using VW-1 (Vertical Wire) in accordance with UL standard 1581.
Flame Te5t was performed. Furthermore, the oxygen index test was carried out in accordance with JIS 7201. In addition, in the thermal test, the temperature was 85°C and the humidity was 95°C.
The specimen was left in a constant temperature chamber for 15 days and visually observed to see if there was any bleeding from the surface of the specimen.

The fi types and physical properties of the chlorinated ethylene polymer, ethylene polymer, vinyl chloride resin, antimony oxide, aluminum hydroxide, magnesium hydroxide, and bromine-containing reaction product used in the Examples and Comparative Examples are as follows. Shown below.

[(A) Chlorinated ethylene polymer] As a chlorinated ethylene polymer, the density is 0.940 g/
crrr? Chlorinated polyethylene with a chlorine content of 30.3% by weight [density
1.10g/crr? , Mooney viscosity (MLl+4, (
120℃)) 82.5, non-quality, hereinafter referred to as “chlorinated product (
1)" and the density is 0.930 g/c rn
Chlorinated polyethylene with a chlorine content of 30.1% by weight [density 1.1
3g/crn', Mooney viscosity, (ML,
, 4, 120°C) R07, [l, crystalline, hereinafter referred to as "chlorinated product (2)"], M I (11 is 100
g/10 minutes, an ethylene-methyl methacrylate-maleic anhydride ternary copolymer (copolymerization ratio of methyl methacrylate: 18.5 mol%, copolymerization ratio of maleic anhydride: 1.5 mol%) was subjected to an aqueous suspension method. A chlorinated ethylene comonomer obtained by chlorination with [
Chlorine content: 30.1% by weight, Mooney viscosity (ML,...
, 100℃) 28, non-quality, hereinafter "chlorinated substance (3)"
] and Mooney viscosity (ML,..., 100℃
) is 115, the copolymerization ratio of propylene is 22% by weight, and M I il+ is 1.0 g/Io min. Obtained by chlorinating an ethylene-propylene copolymer (melting point 120 ° C.) Mooney viscosity (ML,
□, 120℃) is 42, and the density is 1.09g
/crr? A chlorinated ethylene-propylene copolymer [chlorine content: 30.5% by weight, non-quality, hereinafter referred to as "chlorinated product 14"] was used.

[(B) Ethylene polymer] Also, as an ethylene polymer, the density is 0.955 g.
/crr? High-density polyethylene (hereinafter referred to as rHD PEJ) having a MN21 of 20 g/lo was used.

[(C) Polyvinyl chloride resin] Furthermore, as a polyvinyl chloride resin, the average degree of polymerization is about 6.
50 vinyl chloride homopolymer (hereinafter referred to as rPVCJ) was used.

[(D) Antimony Oxide] Antimony trioxide (hereinafter referred to as rsb, 0.J) having an average particle size of 1 μm was used as antimony oxide.

[(E) Aluminum hydroxide and magnesium hydroxide] Furthermore, aluminum hydroxide is produced by the Bayer method, and the content of impurities fixed in the crystal is Na1
0.25% by weight in terms of O, 0.25% in terms of Sin,
008% by weight and 0.005% by weight in terms of CaO
1620pp+ for aluminum hydroxide containing
m silicon, 370 ppm calcium and 290 p
Heat-resistant aluminum hydroxide adsorbed with p+o magnesium [thermal decomposition temperature 206℃, average particle size 1.7μem
, hereinafter referred to as r Al fOHl s J].

In addition, as magnesium hydroxide, the average particle size is 1.5μ
Magnesium hydroxide with an apparent specific gravity of 0.58 g/cm' and a specific surface area (measured by the BET method) of 8rn''7g [manufactured by Kyowa Kagaku Kogyo Co., Ltd., trade name: Kismer 5]
B. 1, hereinafter referred to as rMg(OH1,J), was used.

[(F) Bromine-containing substance] Among the bromine-containing substances, as a bromine-containing reaction product,
Both are bromine-containing reaction products in which R9 is a hydrogen atom and R2 is a methyl group in the above formula (II) [average molecular weight approximately 2,000, bromine content 56% by weight, hereinafter referred to as "bromine (A)"] A bromine-containing reaction product [hereinafter referred to as bromine (B)] having a bromine content of 55% by weight and an average molecular weight of about 3.600 was used. For comparison, decabromodiphenyl ether [hereinafter referred to as [bromine (C)]] was used.

Example 1-13, Comparative Example 1-12 Chlorinated ethylene polymers (hereinafter referred to as "chlorinated products") whose types and amounts are shown in Table 1, and whose amounts are shown in Table 1. The types of HDPE and PvC1 are shown in Table 1 [30 parts by weight of aluminum hydroxide or magnesium hydroxide (hereinafter referred to as "hydroxide") (however, in Comparative Example 6, neither was blended), 40 parts by weight of the bromine-containing substances whose types are shown in Table 1 (but not included in Comparative Example 7), 20 parts by weight of Sb, 0. (However, it was not blended in Comparative Example 5) and 4.0 parts by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., trade name Alcamicer IW, average particle size 1.
5 μl as a stabilizer), 0.5 parts by weight of magnesium stearate (as a lubricant), 2.0 parts by weight of oleamide (as a lubricant), 0.5 parts by weight of hindered bisphenol containing sulfur (as a lubricant). ° as an oxidizing agent
) and 1.0 parts by weight of furnace black (manufactured by Showa Cabot Co., Ltd., trade name: Show Black N-330, average particle size: 40 nm, HAF, as a coloring agent) in a kneader whose tank temperature was preset at 160°C. Each mixture was kneaded for 20 minutes using a mixer. A sheet was manufactured from each of the obtained mixtures using an oven roll previously set at 120°C. Each of the sheets thus obtained was cut into pellets of 311,111 squares using a sheet cutter. Some of the pellets produced in this way are pressed to a pressure of 200 kg/c rr using a press set at a temperature of 180°C. (gauge pressure) for 5 minutes to produce a sheet with a thickness of 2 mm+, and produce samples for tensile strength (T6) and elongation (E, ) measurements and oxygen index tests.

Also, using an extrusion molding machine, the temperature of cylinder 1 was set to 13
The temperature of cylinder 2 was set to 140°C, the temperature of cylinder 3 was set to 150°C, and the temperature of the head was set to 150°C, and each strand with a diameter of 1 mm in width was created. A flame retardancy test and a thermal test were conducted on each strand.

In all Examples and Comparative Examples 4 and 11, all flame retardancy tests were passed. However, Comparative Examples 1 to 3, Comparative Examples 5 to 1O, and Comparative Example 12 all failed. Further, in all Examples and Comparative Examples 1.2.5 to 7 and 12, no bleeding was observed in the thermal test. However, in Comparative Examples 3.4 and 8 to 11, bleeding occurred in all of them.

Additionally, tensile strength and elongation measurements and oxygen index tests were performed. The results are shown in Table 2.

(The following are blank spaces) Table (Part 1) (Part 2) From the above results, the flame retardant composition of the present invention not only has extremely excellent flame retardancy, but also has good mechanical strength. It is clear that it also has excellent heat and humidity properties.

[Effects of the Invention 1 The flame retardant composition of the present invention exhibits the following effects↑1.

11fi’! Excellent heat resistance.

2) Good moldability.

3) Excellent cold resistance.

4) Good thermal expansion properties.

5) Excellent volume resistivity.

6) Good oxygen index properties.

The flame retardant composition of the present invention can be used in a wide variety of ways to achieve the above-mentioned effects. Typical uses are shown below.

fll Coating materials for fibers for optical communications (2) Coating materials for furnace wires for automobiles (3) Clamp covers and polyethylene pipes for fields that require high flame retardancy (4) Flame-retardant sheets for automobile interiors masterbatch etc.

Claims (1)

[Scope of Claims] (A) A chlorinated product obtained by reacting only chlorine with a polymer whose main component is ethylene, (B) a density of 0
．． 930g/cm^3 or more, melting point 112-14
0°C and a melt index of 0.01 to 10
0 g/10 min, and the number of alkyl groups having at most 8 carbon atoms as side chains per 1000 carbon atoms in the main chain is at most 15, (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, 200 to 6,000 and the bromine content is 5.0 to 60% by weight. The composition ratio of the compound is 10 to 75% by weight, the composition ratio of the ethylene 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 these The composition ratio for 100 parts by weight of the polymeric substance is 10 to 30 parts by weight of antimony oxide, 10 to 35 parts by weight of aluminum hydroxide and magnesium hydroxide, and 20 to 35 parts by weight of the bromine-containing reaction product. 50 parts by weight of a flame retardant composition.