JPS61213239A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition exhibiting excellent flame-retardance and high mechanical strength, etc., and free from generation of smoke and toxic gas even in a flame, by compounding a specific EVA with hydrated magnesia, red phosphorus, a hindered phenol antioxidant and an organic peroxide. CONSTITUTION:(A) 100pts.(wt.) of an ethylene-vinyl acetate copolymer having a melt index of 1-5 and a vinyl acetate content of 10-25wt% is compounded with (B) 50-250pts. of hydrated magnesia, (C) 3-50pts. of red phosphorus, (D) 0.1-10pts. of a hindered phenol antioxidant and (E) 0.5-10pts. of an organic peroxide. The component B is preferably the one having a specific surface area of 3-15m<2>/g by BET method and having a content of particles of >=5mu in diameter of 0% by the particle size distribution by Lusex method. The component C is a red phosphorus coated on the surface with a thermosetting resin having a red phosphorus content of >=80%.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a flame-retardant resin composition, and more particularly to a flame-retardant resin composition for electrical insulation having excellent heat resistance.

BACKGROUND ART As flame retardant resin compositions, halogen-containing polymers or non-halogen polymers containing '111m halogen flame retardants are known. However, although all products obtained using such flame-retardant resin compositions self-extinguish when kept away from flames, they do not last long when exposed to high-temperature flames, such as during a fire. There were drawbacks such as combustion continuing until the end of the process, producing smoke, thermal decomposition producing highly corrosive and toxic acid gas, and resin melting and flowing.

Purpose of the Invention The present invention is halogen-free, flame retardant, heat resistant,
The purpose of the present invention is to provide a flame-retardant resin composition that has excellent mechanical strength, electrical properties, aging resistance, and especially heat resistance.

The constitution of the invention, that is, the present invention consists of 100 parts by weight of an ethylene-vinyl acetate copolymer having a melt index of 1 to 5 and a vinyl acetate content of 10 to 25% by weight, and 50 to 25 parts by weight of hydrated magnesia.
0 parts by weight, 3 to 50 parts by weight of red phosphorus, 0.1 to 5 parts by weight of a hindered phephenol anti-aging agent, and 0.5 to 10 parts by weight (6) parts of organic peroxide. Pertains to flame-retardant resin composite acid compounds.

The ethylene-vinyl acetate copolymer used as the base polymer in the present invention has a melt index (Ml) of 1.
~5, an ethylene-vinyl acetate copolymer having a vinyl acetate-containing layer of 10 to 25% by weight. As a specific example, for example, ethylene-vinyl acetate copolymer [evatate H2O11
, manufactured by Sumitomo Chemical Co., Ltd.], Ml is 1.5, vinyl acetate content is 2
0% by weight ethylene-vinyl acetate copolymer (Evatate H2O31, Sumitomo Chemical Co., Ltd. 11J), ethylene-vinyl acetate copolymer with MI of 2.0 and vinyl acetate content of 15% by weight (NUC8450, manufactured by Nippon Unicar Co., Ltd.) , Ml is 2.
Examples include ethylene-vinyl acetate copolymer (Yukalon V505, manufactured by Mitsubishi Yuka Co., Ltd.) having a vinyl acetate content of 20% by weight.

In the present invention, the above-mentioned ethylene-vinyl acetate copolymer may be used alone or in a mixture (blend) of two or more thereof. The above copolymer is crosslinked. The crosslinking method in this case is to add an organic peroxide to the copolymer and heat-treat it to crosslink it.

It is necessary to incorporate hydrated magnesia as a flame retardant into the composition of the present invention. As the hydrated magnesia used in the present invention, a wide variety of conventionally known magnesias can be used, such as MQO.mH20 (m represents 1.5 to 2.5). Among the above hydrated magnesias, those with a specific surface area of 3 to 15 m'/a by the BET method and a particle size distribution of 5 μ or more by the Luzex method are 0.
% is preferred. Specific examples include Kiss 75B, Kisuma 5A, Kiss 75E (all manufactured by Kyowa Chemical Industry Co., Ltd.), etc. In the present invention, such hydrated magnesia is usually used as the ethylene-vinyl acetate copolymer 100.
50 to 250 parts by weight (hereinafter simply referred to as "parts")
parts, preferably 70 to 200 parts, more preferably 90 to 200 parts
It is recommended to mix 150 parts. If the amount of hydrated magnesia exceeds 250 parts, a drawback arises in that the mechanical properties of the resulting composition deteriorate. Furthermore, when the amount of hydrated magnesia is less than 50 parts, the resultant composition has M1! The disadvantage is that the performance is reduced.

In the present invention, it is essential to incorporate red phosphorus into the composition of the present invention as a flame retardant aid. As the red phosphorus, conventionally commercially available ones can be widely used. For example, red phosphorus has a red phosphorus content of 80% or more, a loss on drying of 0.8% or less, and 7
It is preferable that the 4-mesh sieve residue is 7% or less. It is also preferable that the surface of the red phosphorus is coated with a thermosetting resin such as phenol-formalin resin. Specific examples include No Bullet #120, No Bullet #1
20uF (all manufactured by Rin Kagaku Kogyo Co., Ltd.), and the like.

In the present invention, the amount of such red phosphorus is usually 3 to 50 parts, preferably 5 to 50 parts, per 100 parts of the ethylene-vinyl acetate copolymer.
The amount is preferably 30 parts, more preferably 5 to 10 parts.

If the amount exceeds 50 parts, a drawback arises in that the mechanical properties and aging properties of the resulting composition deteriorate. On the other hand, if the amount of red phosphorus blended is less than 3 parts, there will be a drawback that the additive effect of red phosphorus will not be observed.

In the composition of the present invention, it is necessary to incorporate a hindered phephenol anti-aging agent. As the hindered phephenol anti-aging agent, a wide range of conventionally known anti-aging agents can be used, such as tetrakis (methylene-3-(3
, 5-di-tert-butyl-4-hydroxyphenol) propionate comethane [Irganox 1010
．． (manufactured by Ciba Geigy), 2,2-thio[diethyl-bis-3-(3,5-di-tert-butyl-4-human-oxyphenol)propionate] (Irganox 1035, manufactured by Ciba Geigy), 4. 4'-thiobis(3-methyl-6-tert-butylphenol)
[Santonox, manufactured by Monsanto], 4,4'-methylene-bis(3,5-di-tert-butylphenol) [Ionox 22o.

Manufactured by Fu IC1 Co., Ltd.].

In the present invention, the hindered phephenol anti-aging agent is usually used in an amount of 0.1 to 10 parts, preferably 0.3 to 5 parts, and more preferably 0.3 parts to 100 parts of the ethylene-vinyl acetate copolymer. It is recommended to mix up to 3 parts. If the blending amount exceeds 10 parts, disadvantages such as plate-out of the anti-aging agent will occur. On the other hand, if the amount of the hindered phenol anti-aging agent is less than 0.1 part,
The anti-aging effect cannot be expressed.

In the present invention, it is essential to blend an organic peroxide into the composition of the present invention. As the organic peroxide, a wide variety of conventionally known ones can be used, such as dicumyl peroxide [Bark Mill-01 manufactured by NOF Corporation L2.5-
Dimethyl-2,5-di(tert-butylperoxy)
Hexane [Barhexa 25B1 manufactured by NOF Corporation], α, α
'-bis(tert-butylperoxy-m-isopropylbenzene [perbutyl P1 manufactured by NOF Corporation], ter
Examples include t-7 chillumyl peroxide (manufactured by Kayabutyl C1 Chemical Nouri Co., Ltd.).

In the present invention, such an organic peroxide is usually blended in an amount of 0.5 to 10 parts, preferably 1 to 5 parts, and more preferably 1 to 3 parts per 100 parts of the ethylene-vinyl acetate copolymer. If the amount exceeds 10 parts, excessive crosslinking will occur, resulting in a disadvantage that the mechanical properties of the resulting composition will deteriorate.

On the other hand, if the amount is less than 0.5 part, there will be a drawback that a preferable crosslinked state cannot be obtained.

A coupling agent may be added to the composition of the present invention. As the coupling agent, a wide variety of conventionally known coupling agents can be used, and examples include monoalkoxy type, neoalkoxy type, coordination type, chelate type titanate coupling agents and silane coupling agents. Among the titanate coupling agents mentioned above, those containing phosphorus are preferred. This phosphorus-containing coordination type titanate coupling agent has the general formula %) [wherein R represents an alkyl group having 3 to 12 carbon atoms.

R' represents an alkyl group having 1 to 18 carbon atoms. Preferred examples include organic titanates represented by the following. Specific examples include tetraisoprovir di(dioctyl phosphite) titanate (KR-41B, manufactured by Kenrich),
Tetraoctyl di(ditridecyl phosphite) titanate (KR-46B, manufactured by the same company), tetraisoprovir di(dilauryl phosphite) titanate (KR-36)
01 manufactured by the same company] tetra(2,2-diallyloxymethyl-1-butoxy) di(di-tridecyl) phosphite titanate (KR-55, manufactured by the same company), isoprobil tris(dioctylpyrophosphate) titanate (KR
FM i
K can do it.

The chelate type titanate coupling agent has the general formula [wherein R represents an alkyl group having 1 to 18 carbon atoms, an aryl group, an acyl group, or a sulfonyl residue]. X is > CH2
or >C-0. ] Preferred are organic titanates represented by the following, specifically diisostearoyloxyacetate titanate (KR-101, manufactured by Kenrich),
Isostearoyl methacryloxyacetate titanate (KR-106, manufactured by the same company), isostearoyl acrylic, oxyacetate titanate (KR-11O8,
Di(dioctyl phosphate)oxyacetate titanate (KR-1128, manufactured by the same company), 4-
Aminobenzenesulfonyldodecylbenzenesulfonyloxyacetate titanate (KR-1263, manufactured by the same company), dimethacryloxyacetate titanate (KR
-133C8, manufactured by the same company], dicumylferrate oxyacetate titanate (KR-1348, manufactured by the same company)
, 4-aminobenzoylisostearoyloxyacetate titanate (KR-13788, manufactured by the same company), di(
Dioctyl pyrophosphate) oxyacetate titanate (KR-1388, manufactured by the same company), diacryloxyacetate titanate (KR-139C8, manufactured by the same company), di(dioctyl, butyl pyrophosphate) oxyacetate titanate (KR-158FS, manufactured by the same company) ], diisostearoyl ethylene titanate (KR-2
01, manufactured by the same company), di(dioctyl phosphate) ethylene titanate (KR-212, manufactured by the same company), 4-aminobenzenesulfonyldodecylbenzenesulfonyl ethylene titanate (KR-2268, manufactured by the same company), dimethacrylic ethylene ditanate (KR-233, manufactured by the same company)
, di(dioctylpyrophosphate) ethylene titanate (KR-2388, manufactured by the same company), dianthranyl ethylene titanate (KR-252, manufactured by the same company), di(butyl, methylpyrophosphate) ethylene titanate (KR-262ES, manufactured by the same company) For example,

As the silane coupling agent, trialkoxysilane having a carbon-carbon double bond or an epoxy group is preferable, and specifically, vinyl-tris(β-methoxyethoxysilane) (A172, manufactured by Nippon Unicar Co., Ltd.), γ-methacrylate Roxypropyltrimethoxysilane (A174.,
(manufactured by Nippon Unicar), β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A186, manufactured by Nippon Unicar), γ-glycidyloxypropyltrimethoxysilane (SH6040, manufactured by Toray Silicone), etc. .

In the present invention, such a coupling agent is usually used in an amount of 0.1 to 5 parts per 100 parts of the ethylene-vinyl acetate copolymer.
Preferably it is 0.3 to 3 parts, more preferably 3 to 2 parts of O8. If the amount of the coupling agent exceeds 5 parts, it is not preferable because the mechanical properties of the resulting composition tend to deteriorate. Further, if the amount of the coupling agent is less than 0.1 part, the effect of the addition of the coupling agent will not be exhibited, which is not preferable.

In addition to the above-mentioned various components, various known additives may be added to the composition of the present invention. Examples of such additives include naphthenic process oils, aromatic process oils, phthalate esters, plasticizers such as trimeric acid esters, phthalates, lead compounds such as dibasic lead sulfate, dioctyltin dilaurate, etc. Stabilizers such as organotin compounds and organozinc compounds, Mistron paper talc, clay, calcium carbonate, magnesium carbonate, carbon black,
Fillers such as silica and barium sulfate, pigments such as chrome yellow, phthalocyanine blue, and titanium white, lubricants such as refined stone powder, stearic acid, and oleic acid, waxes, paraffins, low-molecular-weight roboryolefins, higher fatty acids or their esters, etc. Examples include processing aids and the like. The amounts of these various additives can be varied widely. Although it can be determined as appropriate from within the range, 5 to 50 parts of plasticizer, 0.1 to 5 parts of stabilizer, and 10 to 200 parts of filler per 1100 parts of degeneracy of the five components that are usually essential components. , 0.1 to 5 parts of pigment, 0.1 part of lubricant
~5 parts, and 0.2 to 10 parts of processing aids.

The composition of the present invention can be obtained by suitably blending predetermined amounts of the above-mentioned various components and uniformly mixing them using a Banbury mixer, Henschel mixer, etc. according to a conventionally known method. Although all of the above components can be mixed at the same time, it is better to add the coupling agent at the same time as the filler is added. In addition, in a polymer blend system, it is preferable to mix the polymer uniformly first and then mix the other components.

When using the composition of the present invention, various conventionally known molding methods can be widely adopted. For example, the composition of the present invention is kneaded using a mixing machine such as a roll kneader, and then this is mixed according to the purpose. It may be molded into various shapes.

Because the composition of the present invention is halogen-free, it will not emit smoke or generate corrosive gas or acidic gas due to thermal decomposition even if it is left in a high-temperature flame such as during a fire. Moreover, it has excellent flame retardancy, heat resistance, mechanical strength, electrical properties, aging resistance, etc.

Therefore, the composition of the present invention is suitable as a coating material for building materials, pipes, hoses, sheets, seat covers, wall materials, electric wires and cables (internal insulators, external sheaths, etc.), and the like.

EXAMPLES Examples will be given below to explain the present invention in more detail.

The characteristics of each sample were tested using the following method.

<Flame retardancy test> The composition of the present invention was mixed with two rolls at 160°C for 20 minutes and then press-molded at 170°C for 30 minutes to create a sheet sample with a thickness of 3nv+.
7201 (oxygen index method) to determine the oxygen index (LOI) and evaluate the flame retardancy.

<Mechanical properties> Examine each property using the following method for the same sample sheet as above.

(1) 100% modulus (kQ/mm2) AST
According to MD882.

(2) 200% modulus (k (1/ mmm2) AS
According to T 0882.

(3) Tensile strength (kMmm2) According to ASTM D882.

(4) Elongation (%) According to ASTM D882.

Gel fraction (%)> For the same sample sheet used in the above flame retardancy test,
Measured according to STM D2765.

<Electrical properties (room temperature)> The composition of the present invention was mixed with two rolls at 160°C for 20 minutes, and then press-molded at 170°C for 30 minutes to create a sheet sample with a thickness of 1 am.
2123, ρ(ohm-cm) is determined.

<Aging characteristics> For the same sample sheet used in the above electrical test, AS
Residual tensile strength after 4 days of aging at 150°C according to TM D573
Calculate the rate (%) and remaining elongation rate (%).

Example 1 A composition of the present invention was obtained by mixing predetermined ff1 (parts by weight) of each component shown in Table 1 below using the method described above. In addition, sheets of each composition were created by molding or mold-crosslinking the above compositions under a pressure condition of 50 to 150K (1/C-2) using a hot press.The conditions for molding or mold-crosslinking in this case were ,
As mentioned above.

Table 1 1 2345678 Base polymer A-1100---50505050 A-2-100---50--- A-3--100--5g + -〇-11,
0--1, 0--0, 50, 50-2------1,
01,0 D-3-1,01,0---- F-1-1---- F-2---1-1-0,5 F-3------- 10,5 F-41211, 51211 F-5---1-11 The symbols for the 8 components in Table 1 indicate the following.

Base polymer> A-1... Ethylene vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Evatate H2O11, VA content -15 wt%, M
I=3.0) A-2...Ethylene vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Evatate H2O31, vA content -20wt%, M
l-1,5) A-3...Ethylene vinyl acetate copolymer manufactured by Nippon Unicar Co., Ltd., NUC8450, VA content -15wt%, Ml
-2,0) A-4... Ethylene vinyl acetate copolymer (manufactured by Mitsubishi Yuka Co., Ltd., Yucalon v505, VAAl120wt%, M[-
2,0) <Female flame agent> B-1...Mg (OH)2 (manufactured by Kyowa Kagaku Kogyo Co., Ltd., Kiss 75B) <Flame retardant aid> C-1... Red phosphorus (manufactured by Rin Kagaku Co., Ltd., Tubaret #<Anti-aging agent> D-1... Irganox 1010 (manufactured by Ciba Geigy) D-2... Irganox 1035 (manufactured by Ciba Geigy) D-3... Yoshinox SR (manufactured by Yoshitomi Pharmaceutical) 0- 4
...Tsukurak N5-6 (manufactured by Ohmukai Shinko Co., Ltd.) Organic peroxide> E-1 ... Dicumyl peroxide (manufactured by Nihon Yushi Co., Ltd.) Additive> F-1 ... Seenox 4128 (Shiraishi Co., Ltd.) F-2... Kenreact KR-98 (manufactured by Kenrich) F-3... Kenreact KR-268 (manufactured by Kenrich) F-4... Stearic acid F-5... Stearic acid The properties of molded sheet samples of the compositions of the present invention obtained using each of the above-mentioned types of zinc are shown in Table 2 below.

Table 2 Setup No.

Gender 1 2345678 Difficulty (LOI 30.331.632,533,13
5,436,335,535.4 Mechanical properties (1), 0.570.61 0.66 0
．． 83 0,62 0,71 0.72 0.76 (3
) 1,94 1.93 1,96 2,0
5 1,84 1,74 1,72 1,76 Geno rate % 88 84 g2 81 81
83 84 86x10150.360.46
0,44 0.51 0,42 2.9 0,6 0
．． 54 Aging characteristics 150℃, 4-day tensile strength retention 88 86 90 92
96% 91 93 Growth rate 84
86 82 90 91 87 92 88 From Table 2 above, the sheet obtained using the composition of the present invention is as follows:
It is found that it has particularly excellent properties in terms of flame retardancy, mechanical properties and aging properties.

(that's all)

Claims (1)

[Claims] (1) 100 parts by weight of an ethylene-vinyl acetate copolymer having a melt index of 1 to 5 and a vinyl acetate content of 10 to 25% by weight, 50 to 250 parts by weight of hydrated magnesia,
3 to 50 parts by weight of red phosphorus, 0.1 to 10 parts by weight of hindered phephenol anti-aging agent, and 0 parts by weight of organic peroxide.
．． A flame-retardant resin composition containing 5 to 10 parts by weight.