JPH01242645A - Flame-retarding olefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which does not produce any noxious halogenous gases, by mixing a mixture of an olefin resin with a silane graftomer prepared by grafting a silane onto an olefin resin with a hydrated metal compound and a specified polymer. CONSTITUTION:100 pts.wt. mixture of at least one resin selected from among an ethylene/alpha-olefin copolymer, an ethylene/ethyl acrylate copolymer resin and an ethylene/-methyl methacrylate copolymer resin with a silane graftomer obtained by grafting an organosilane onto an olefin resin by a well-known process is mixed with 0.1-30 pts.wt. PE, ethylene/vinyl acetate copolymer resin or maleic acid (anhydride) derivative of an ethylene/alpha-olefin copolymer, 0.1-30 pts.wt. methyl methacrylate/maleic anhydride copolymer and a modified silicone product obtained by grafting a reactive polyorganosiloxane onto a thermoplastic resin and 50-300 pts.wt. hydrated metal compound of an initial decomposition temperature in the range of 150-450 deg.C (e.g., Al2O3.3H2O).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a flame-retardant material that does not generate any harmful and corrosive halogen gas even when burned due to a fire, and is particularly intended for application to electric wires and cables. This invention relates to an olefin resin composition.

[Conventional technology]

Conventionally, flame retardancy was achieved by adding halogen compounds and antimony dioxide to polyolefins to impart flame retardancy to polyolefin compositions, which are often used as insulating materials for electric wires, cables, and other electrical appliances. However, these compositions are halogen compositions and generate halogen gas when burned, which is harmful to the human body and corrodes metals, so they are not preferred. <There wasn't. In addition, due to the large amount of smoke and poor visibility, evacuation of people and firefighting activities in the event of a fire were severely restricted.

In particular, recently there has been a strong demand for not generating such halogen-based gases from the standpoint of safety. In light of this situation, inorganic flame retardants, which are hydrated metal compounds with very little smoke generation and toxicity, have been attracting attention.

In recent years, magnesium hydroxide,
It is a resin composite filled with a large amount of aluminum hydroxide, etc., but the magnesium hydroxide reacts with moisture and carbon dioxide in the air. Crystal white matter forms.

(2) Magnesium hydroxide and aluminum hydroxide have extremely poor chemical resistance to acids and alkalis, and are easily dissolved and eluted from the surface of the resin composition. In particular, it is significantly eluted even by weak acids with a pH of about 2, which tends to cause surface deterioration.

■The surface is easily damaged because it is filled with a large amount of inorganic filler.

■The surface turns white or buckles when bent.

These problems caused a delay in the practical application of electric wires and cables.

However, in connection with the present invention, a patent application filed in 1983 has already been filed. -1290
64 and Japanese Patent Application No. 61-1.38316, the silane graftomer does not require any help from a catalyst to promote crosslinking, and the hydroxyl groups on the surface of the hydrated metal compound (
OH group) and the silanol group (')S of the silane graftomer
Due to the influence of the slight moisture on the surface of the hydrated metal compound and the hydrated metal compound similar to the organometallic compound catalyst, a condensation reaction occurs due to hydrolysis in the environment of frictional heat generated during crosstalk, and the i-OH) becomes strong. siloxane bond (-3i -0-Mm
On; M metal) is formed. At this time, no catalyst or the like is required at all.

For this strong connection, the above-mentioned patent application No. 61-129064
No. 61-138316 specifies that it has excellent shape retention at high temperatures, prevents dripping during combustion, and is effective in improving bending whitening and abrasion resistance as mechanical properties.

In addition, the Examples also describe improvements in mechanical properties, surface properties, thermal properties including thermal deformation, and combustion properties including oxygen index.

Traditionally, polyethylene, polypropylene, ethylene-
With a skeleton of liquid hydrocarbons such as vinyl acetate copolymer resin (hereinafter referred to as EVA), ethylene-ethyl acrylate copolymer resin (hereinafter referred to as EEA), copolymer of ethylene and α-olefin, and liquid polybutadiene. There is a modified unsaturated dicarboxylic acid obtained by reacting maleic anhydride with a radical generator such as peroxide, and many of these are sold in Japan.

In addition, many findings have been published regarding the use of these materials to impart adhesion to other resins and metal inorganic powders, and a large number of related patent applications have been filed. For example, Japanese Patent Publication No. 82-5788, Japanese Patent Publication No. 62-913
Publication No. 5 is mentioned.

Also, JP-A-62-10151, JP-A-62-1
As seen in Japanese Patent No. 1745, there is also an example in which maleic anhydride is added to a copolymer of ethylene and α-olefin using peroxide or the like to improve the heat resistance and mechanical strength of the composition. These methods simply add a polar group of maleic anhydride to a non-polar resin to increase its affinity with the filler and ultimately improve its mechanical strength and heat resistance. Focusing on hydrated metal compounds, water-mediated bonding,
In other words, the siloxane bond of the silane graftomer is not intended for bonding by forming a complex salt based on the reaction of dicarboxylic anhydride derivatives.

[Problem to be solved by the invention]

In order to solve the above-mentioned problems, the present inventors have already developed a flame-retardant composition consisting of an olefin resin, a silane graft tomer of the olefin resin grafted with silane in advance, a hydrated metal compound, and a dicarboxylic acid derivative or dicarboxylic acid anhydride derivative. We proposed an olefin resin composition (patent application 1986).
-45200), the present invention addresses surface deterioration and chemical resistance of these resin compositions that occur during various environmental tests or during actual use due to the inclusion of a hydrated metal compound as a flame retardant. The object of the present invention is to provide a flame-retardant resin composition that prevents significant deterioration and further improves surface scratches, surface scratches and buckling when bent.

[Means to solve the problem]

The flame-retardant resin composition of the present invention is a composition consisting of the following components (a) to (f), in which (a)→-(b) 100%
(e) is 0.1 to 30 parts by weight, (d) is 0.1 to 30 parts by weight, (e) is 0.1 to 30 parts by weight, and (f) is 50 to 30 parts by weight. It is characterized by containing 1 part of ftff.

(a) a copolymer of ethylene and α-1st nophine,
One or more resins selected from EEA or ethylene-methyl methacrylate copolymer resin (hereinafter referred to as T'EMMA) (b) A silane graft tomer (e) of the first nophine resin grafted with silane in advance ) Polyethylene, EVA or ethylene-α
-Maleic acid derivative or maleic anhydride derivative of olefin copolymer (d) Ethylene-ethyl acrylate-71 twin acid anhydride copolymer or ethylene-methyl methacrylate-
Maleic anhydride copolymer (e) Silicone modified product obtained by graft polymerizing a reactive polyorganosiloxane to a thermoplastic resin (f) Hydrated metal compound In the present invention, as an olefin resin to be used after silane grafting Examples include low density polyethylene, medium density polyethylene, high density polyethylene, copolymers of ethylene and α-olefin, EVA, EEA, EMMA, ethylene propylene rubber, ethylene propylene diene rubber, and the like.

Examples of α-olefins in the copolymer of ethylene and α-olefin used in components (a), (b), and (e) include polypropylene of 03 to c12, butene-1, pentene-1, hexene-1, heptene-1,
octene-11,4methylpentene-1,4methylhexene-],]4-4-dimethylpentene-1nonene-1
, decene-1, undecene-1 and dodecene-1. Particularly desirable are butene-1, pentene-1, hexene-1, and heptene-1,4 methylpentene-1.

The silane graftomer used in the present invention has the general formula RR' S i Y 2 '(R
is a monovalent olefinically unsaturated hydrocarbon group, Y is a hydrolyzable organic group, and R' is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon or the same as Y). It is obtained by reacting in the presence of radical-generating compounds. This is published in Japanese Patent Publication No. 57-24373, Japanese Patent Publication No. 48-1711, and Japanese Patent Publication No. 50-2
This method uses the known method disclosed in Publication No. 4342, etc., and specifically uses polyolefin resin as a base, vinyltrimethoxysilane, etc., and DCP (dicumyl peroxide), which has a strong polymerization initiating effect. Obtained by using oxides in combination.

The amount of silane graftomer in 100 parts of resin,
The amount is preferably 2% by weight or more, and if it is less than this, the shape retention property at high temperatures and the effect of preventing dripping during combustion will be small.

The degree of crosslinking of the silane graftomer is preferably 20% to 80% by weight in terms of xylene-insoluble residue and gel fraction. If the gel fraction is less than 20% by weight, the effect of maintaining shape at high temperatures and preventing sagging during combustion will be weak, and if the gel fraction is more than 80% by weight, moldability will be poor.

Regarding the addition amount of maleic acid derivative or maleic anhydride derivative of polyethylene, EVA or ethylene-α-olefin copolymer and 12, if it is less than 0.1 part by weight, the effect is weak;
If it exceeds 0 parts by weight, the bonding caused by the reaction with the hydrated metal compound will be too strong, resulting in poor extrusion processability and poor appearance during extrusion processing.

The addition amount of ethylene-ethyl acrylate-maleic anhydride copolymer or ethylene-methyl methacrylate-maleic anhydride is less than 0.1 m; the effect is weak;
If it exceeds 30 parts, the extrusion processability will be poor and the heat exchangeability will be poor.

In the present invention, the thermoplastic resin to which the reactive polyorganosiloxane is graft-polymerized includes polyethylene, polypropylene, a copolymer of ethylene and α-olefin, and EVASEEA.

Examples include polyolefin resins such as EMM A, polystyrene, acrylonitrile-butadiene-styrene copolymer resins, and the like.

If the amount of modified silicone is less than 0.1 part by weight, the effect will be weak, and if it exceeds 30 parts by weight, it will not show any significant effect exceeding the improvement effect shown by the present invention, and the product will be expensive, so it is not practical. Not.

The hydrated metal compound used in the present invention has a decomposition initiation temperature in the range of 150 to 450°C and has the general formula Mien ・XH2O (wherein N1
is a metal, nl, n is an integer of 1 or more determined by the valence of the metal, and X is a number indicating 3H-bonded water), or a double salt containing the compound. AI 0 -3H20; or AI
(OH) 3) Magnesium hydroxide (MgO.HO; or M g (OH) 2 ), calcium hydroxide (c
aO=HO or Ca(OH) 2 ), barium hydroxide (BaO11HO or B, a O-9H20), zirconium oxide hydrate (ZrOφn H20), tin oxide hydrate (SnO H2O), basic magnesium carbonate (
3Mg CO-Mg (OH) 2 ・3H20), hydrotano isite (6M g OA, 9 0-HO)
, Dortnight (N a C03・A I7 0 −
n H20), borax (N a 20 ・B O-5
HO), zinc borate (ZnB407'2ZnO), etc. If the amount added is less than 50 parts by weight, the desired flame retardant effect will not be achieved, and if it is more than 300 parts by weight, mechanical properties such as tensile strength will be poor, and extrusion processability will be poor.

As other additives, the flame retardant composition of the present invention may optionally contain commonly used additives such as antioxidants, neutralizers,
Ultraviolet absorbers, antistatic agents, pigments, dispersants, lubricants, thickeners, foaming agents, metal deterioration inhibitors, fungicides, fluidity regulators, etc., as well as phosphorus and phosphine derivative flame retardants, and other inorganic fillers. , a crosslinking agent, a crosslinking aid, or other synthetic resin may also be included. It is also possible to carry out crosslinking by electron beam irradiation.

As for the production method, (a) Copolymer of ethylene and α-olefin, E
One or more resins selected from EA or EMMA (b) Silane graftomer of olefin resin to which silane has been grafted in advance (e) Malein of polyethylene, EVA or ethylene-α-olefin copolymer Acid derivative or maleic anhydride derivative (d) Ethylene-ethyl acrylate-maleic anhydride copolymer or ethylene-methyl methacrylate-maleic anhydride copolymer (c) A reactive polyorganosiloxane is graft-polymerized onto a thermoplastic resin. Among the hydrated metal compounds of the silicone modified product (f) obtained, (1) (a), (b), (e), (d), (e), (
Method (II) of manufacturing by bulk kneading (') (c) when preparing the silane graftomer of (b)
.

(d) Adding one or more of (e) to Pelle.
Method (iii) of producing a sotho-like silane graft tomer and then kneading it with the remaining components (a), (b), (e), (
Any of the following manufacturing methods may be used: d) , (e) , and (d) Select any component from D, knead it in advance, and then knead it with the remaining components.

In addition, compared to conventional technology, the combustion suppression effect is completely different from the combustion suppression effect of carbon powder, and the combustion suppression effect is maintained regardless of the addition of various pigments in order to make identification easier according to 1. Coloring can be freely done depending on the purpose.

〔Example〕

This will be explained below by giving examples.

EXAMPLE First, a polyolefin resin was prepared according to the formulation shown in Table 1 according to the procedure I-'. Dicumyl peroxide (DCP) is dissolved in vinylmethoxysilane, and two types of low-crystalline polyethylene (1) and (2) are used.
The mixtures were mixed and stirred as shown in Table 1, and extruded using a single-screw 50 mmφ extruder at an extrusion temperature of 150 to 200°C to obtain pellet-shaped silane graftomer resins A and B. Resin A,
Each of B was hermetically sealed in an aluminum laminate bag, stored in a state where external moisture was blocked, and dispensed as needed for use.

/' / 7・' / Table 1 Production of silane-grafted resin (silane graft tomer) (1) Softlex (ethylene-α-olefin copolymer) manufactured by Nippon Petrochemical (2) ■ Hon Petrochemical ■ Manufactured by Rexron (EEA) *Xylene! Insoluble residue after immersion at 20°C for 20 hours (w
tP6) Next, as shown in Table 2, various components were mixed all at once in a container, kneaded with a Pan Bali roll, and granulated.

The obtained composition was again roll-pressed to prepare various test pieces for measurement. Using this test piece, we evaluated the degree of surface whitening due to magnesium carbonate formation, weight change when immersed in 10% sulfuric acid and 3% caustic soda aqueous solution, surface scratch resistance, flame retardant properties based on bending whitening property and oxygen index. I did it. In addition, a tube with an outer diameter of 20 mmφ, an inner diameter of 18n+iφ, and a thickness of 1 am was extruded using an extruder.
Extrusion processability and buckling using this extruded tube were evaluated.

As a result, as seen in the examples shown in Table 2, the composition of the present invention showed significant improvements in the degree of whitening, chemical resistance to sulfuric acid and caustic soda, surface scratches, surface whitening during bending, and buckling. I understand that.

(3) Manufactured by Sumitomo Chemical Co., Ltd., EMMA (4) Manufactured by Sumitomo Chemical Co., Ltd., low-density polyethylene 1-non (5)
Maleic anhydride grafted polyolefin MFR manufactured by Mitsui Petrochemical Industries ■! , 3. Density 0.94. Ethylene-α-olefin copolymer base (6) Made by Nippon Petrochemical ■, anhydrous 71 twin acid grafted polyolefin MFRO, 3, density 0°92. Ethylene-α-olefin copolymer base (7) manufactured by Sumitomo Chemical ■, ethylene-methyl methacrylate-maleic anhydride copolymer (8) manufactured by Dow Corning ■, low-density polyethylene-based silicone modified silicone content 40 wt% (9) Manufactured by Showa Denko ■, product name Hisilite H42M (1
0) Kyowa Chemical ■, trade name Kisuma 5B (11) Sanyo Chemical Industries ■, Sunwax 171P 1.0 Ciba Geigy Chuo Co., Ltd. 1 Irganox 10780.3 Sumitomo Chemical ■, Sumilizer WXRO, 3 (12) Pigment
For black: VALCAN 9A-323,0 (13
) 5emX 5evnX in 1g of distilled water 1. Immerse a W-thick BUNOS sheet and pour 100ml of carbon dioxide gas into it.
48 hours after the injection, the degree of whitening (formation of magnesium carbonate crystals) was visually observed.

(14) Measurement of weight change due to 10 wt% sulfuric acid immersion 50
℃ x 7 days Test piece shape JIS No. 3 dumbbell used 1m + m thickness (15
) Weight change measurement due to 3wt% caustic soda immersion 50
℃X7G Test piece shape JIS No. 3 dumbbell used 1 ■ Thickness (16) Pencil HB hardness, visual judgment by scratching (17) 2 mm
mm-t 180 degree bending whitening visual test (1g) JI
(19) Outer diameter 20mmφ, inner diameter 18mmφ, thickness 1nlI by S K7201
A test sample was prepared by inserting a separately prepared electric wire (single copper wire with a conductor diameter of 1 mmφ coated with a soft vinyl chloride composition with a hardness (JIS A) of 80 to a thickness of 8 cm) into an extruded tube with a length of 300 mm. When this was bent along a mantle with an outer diameter of 100 mmφ, the degree of wrinkles was visually determined.

(20) 50+ll+sφ single screw extruder 150-1
80-170-180℃L/D 25. Compression ratio 3.
5. Tube extrusion outer diameter: 20 mm φ, inner diameter: 18 mm φ Evaluation: Excellent, Good, Fair, and Unsatisfactory, and those up to the acceptable level were considered to be passed.

〔Effect of the invention〕

When the composition of the present invention is molded, (1) the silane graftomer does not require any help from a catalyst to promote crosslinking, and the hydroxyl group (OH group) on the surface of the hydrated metal compound and the silanol group of the silane graftomer ('>5l-OH) is a condensation reaction due to hydrolysis in the environment due to the frictional heat generated during kneading due to the influence of a small amount of water on the surface of the hydrated metal compound and a hydrated metal compound similar to an organometallic compound catalyst. A strong siloxane bond (-5i -0
-MmOn; M metal) is formed.

At this time, no catalyst or the like is required at all.

(2) The maleic acid derivative or maleic anhydride derivative of polyethylene, EVA or ethylene-α-olefin copolymer which is the component (e) and the ethylene-ethyl acrylate-71 twin acid anhydride copolymer which is the component (d) &
The ethylene-methyl methacrylate-maleic anhydride copolymer reacts with the metal ion of the hydrated metal compound to form a complex salt.

A remarkable effect is shown by using the component (e) and the component (d) together.

(3) The modified silicone contributes to improving the wear resistance and moldability of the composition.

As described above, the siloxane bond between the silane graftomer and the hydrated metal compound and the bond formed by the complex salt formation between the maleic acid derivative or maleic anhydride derivative and the hydrated metal compound, which are the components (e) and (d), are confirmed. Due to the synergistic effect and the effect of the silicone modified product, surface deterioration, decrease in chemical resistance, surface scratches, surface whitening and buckling during bending of the flame retardant resin composition are significantly improved.

One procedural amendment (JI (voluntary) June 23, 1986

Claims (1)

[Scope of Claims] A composition comprising the following components (a) to (f),
(c) from 0.1 to 100 parts by weight of (a) + (b)
30 parts by weight, (d) 0.1 to 30 parts by weight, (e) 0
．． A flame-retardant olefin resin composition characterized by containing 1 to 30 parts by weight and 50 to 300 parts by weight of (f). (a) One or more resins selected from a copolymer of ethylene and α-olefin, an ethylene-ethyl acrylate copolymer resin, or an ethylene-methyl methacrylate copolymer resin (b) Silane grafted in advance Silane graft tomer of olefin resin (c) Maleic acid derivative or maleic anhydride derivative of polyethylene, ethylene-vinyl acetate copolymer resin or ethylene-α-olefin copolymer (d) Ethylene-ethyl acrylate-maleic anhydride copolymer (e) Silicone modified product obtained by graft polymerizing a reactive polyorganosiloxane to a thermoplastic resin (f) Hydrated metal compound