JPH1160829A - Flame-retardant crosslinked olefin resin composition - Google Patents

Abstract

(57) [Problem] To provide a flame-retardant crosslinked olefin resin composition having high flame retardancy, no foaming during processing, and excellent in physical properties such as tensile strength and elongation. A composition comprising a metal hydrate treated or treated with a polyolefin, a silane coupling agent and / or a titanate coupling agent, a silane coupling agent and / or a titanate coupling agent, a crosslinking agent, and a catalyst. A flame-retardant crosslinked olefin resin composition characterized by being crosslinked.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant crosslinked olefin resin composition.

[0002]

2. Description of the Related Art Polyolefin resins are widely used as various insulating materials because of their excellent electrical insulation properties and also excellent workability, water resistance and chemical resistance.
It has the disadvantage of being flammable. In order to solve this drawback, a flame-retardant crosslinked olefin resin composition is known in which a large amount of a metal hydrate is blended into a polyolefin resin and a metal atom and a polymer molecule are crosslinked with a silane coupling agent. In this case, there is a problem that a foaming phenomenon occurs during processing due to a water absorbing action of the metal hydrate, and a large decrease in the strength occurs due to a large amount of the metal hydrate. This is considered to be due to the fact that the interface between the metal hydrate and the polymer is not compatible, and that the water generated during the siloxane condensation (silane crosslinking) between the silane coupling agents attacks the metal hydrate.

[0003]

SUMMARY OF THE INVENTION The present invention provides a flame-retardant crosslinked olefin resin composition having high flame retardancy, no foaming during processing, and excellent physical properties such as tensile strength and elongation. That is the task.

[0004]

SUMMARY OF THE INVENTION The present invention is directed to a metal hydrate, silane coupling agent and / or titanate cup treated or treated with a polyolefin resin, a silane coupling agent and / or a titanate coupling agent. A flame-retardant crosslinked olefin resin composition obtained by crosslinking a composition comprising a ring agent, a crosslinking agent and a catalyst.

[0005] The flame-retardant crosslinked olefin resin composition of the present invention is a metal hydrate, a silane coupling agent and / or a titanate coupling agent which has been treated or treated with a silane coupling agent and / or a titanate coupling agent. , A composition obtained by blending a crosslinking agent and a catalyst with a polyolefin. The metal hydrate used in the present invention is mixed with a silane coupling agent and / or a titanate coupling agent (hereinafter, also collectively referred to simply as a coupling agent) before being mixed with each of the above components. The treated one is preferred, but the blending method may be adjusted so that the metal hydrate is treated with the coupling agent during the blending.

The treatment of a metal hydrate with a coupling agent is as follows:
The silane coupling agent or the titanate coupling agent may be used alone or in combination. The metal hydrate treated or treated with the coupling agent is preferably one obtained by treating or treating 100 parts by weight of the metal hydrate with 0.3 to 30 parts by weight of the coupling agent.

The flame-retardant crosslinked olefin resin composition of the present invention comprises 100 parts by weight of a polyolefin, 80 to 200 parts by weight of a metal hydrate treated with a coupling agent, 0.5 to 20 parts by weight of a coupling agent, It is preferred that the composition comprises 0.5 to 10 parts by weight of a crosslinking agent and 0.5 to 10 parts by weight of a catalyst.

The polyolefin used in the present invention includes ethylene, propylene, butene-1, pentene-
1, hexene-1, heptene-1, 3-methylbutene-
Homopolymers of olefinic hydrocarbon monomers such as 1,4-methylpentene-1 and copolymers of two or more of these monomers, for example, ethylene-propylene copolymer, ethylene-butene-1 copolymer and the like Or copolymers of these olefinic hydrocarbon monomers with a small amount of vinyl ester monomers or (meth) acrylate monomers, for example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate Copolymers, ethylene-vinyl acetate copolymer and the like, and these various polymers alone,
Alternatively, they can be used as a mixture of two or more.

The number average molecular weight, melt index (MI) and the like of the polyolefin used in the present invention are selected according to the use of the composition of the present invention. Among the polyolefins, polyethylene is preferable, and examples thereof include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE), and LDPE and LLDPE are particularly preferable.

The metal hydrate used in the present invention includes:
Magnesium hydroxide, aluminum hydroxide, zirconium hydroxide and the like are preferred.

As the silane coupling agent used in the present invention, conventionally known silane coupling agents can be used, but vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, normal hexyltrimethoxysilane and the like are preferable.

As the titanate coupling agent used in the present invention, conventionally known ones can be used, but isopropyl triisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate and the like are preferable.

Examples of the crosslinking agent for promoting crosslinking between the polyolefin and the coupling agent used in the present invention include, for example,
Examples thereof include dicumyl peroxide, benzoyl peroxide, and azo compounds. Of these, dicumyl peroxide is preferable.

The catalyst used in the present invention catalyzes the siloxane condensation of at least the coupling agent, or further comprises a metaloxysiloxane bond between the metal atom of the metal hydrate and the coupling agent, or the coupling agent of the coupling agent. There is no particular limitation as long as it catalyzes the crosslinking between the functional groups and the polyolefin molecules. For example, dibutyltin dilaurate, dibutyltin diacetate and the like are preferable.

In the present invention, the above-mentioned siloxane condensation or metaloxysiloxane bond is caused, and at the same time, the polyolefin molecule is crosslinked with the functional group of the metal hydrate-coupled coupling agent or a single coupling agent. The molecules and the metal hydrate are compatible with each other, the dispersion state is extremely improved, and the metal hydrate is not directly affected by moisture due to the metaloxysiloxane bond, and can suppress the foaming phenomenon, and have physical properties. And a flame-retardant crosslinked olefin resin composition excellent in the above.

The method for producing the flame-retardant crosslinked olefin resin composition of the present invention is not particularly limited, and examples thereof include the following method. A method in which a polyolefin and a metal hydrate treated with a coupling agent are mixed to produce a flame-retardant mixture, which is then impregnated with a coupling agent, a crosslinking agent, and a catalyst, and then processed by extrusion or the like. A method in which a flame-retardant mixture composed of components excluding a catalyst is prepared and a catalyst-containing master batch is added during extrusion molding. A method of extruding all components at once. In the above-mentioned and flame-retardant mixtures, siloxane condensation or metaloxysiloxane bonding occurs due to the presence of water before extrusion molding. In such a case, conditions such as the method of contact with water and temperature are appropriately selected, and the siloxane The conditions for the condensation or the metaloxysiloxane bond and the crosslinking reaction between the polyolefin molecule and the functional group of the coupling agent can be appropriately adjusted by the temperature, extrusion pressure and the like during extrusion molding. In the above, the metal hydrate needs to be treated with a coupling agent before at least all the components are blended as described above. In addition, moisture, temperature, extrusion molding conditions, and the like can be appropriately adjusted according to the above.

Other additives to the composition include a red phosphorus-based flame retardant (which may be coated with a phenolic resin), a filler, a whitening inhibitor, an antioxidant, a lubricant, a pigment, and a neutralizing agent. And an ultraviolet absorber. These are used within a range that does not impair the physical properties of the base material.

[0018]

Hereinafter, specific examples of the present invention will be described.
The present invention is not limited to this. Examples 1 to 8 and Comparative Examples 1 to 4 The olefin resin composition obtained by mixing, dispersing, and kneading the components shown in Table 1 was used at a temperature of 190 ° C. × 30 rpm and an outer diameter of 5 mm in a 20 mmφ test extruder. Were extruded with a round die to obtain samples of various flame-retardant crosslinked olefin resin compositions. However, in Comparative Examples 1 to 4, magnesium hydroxide or aluminum hydroxide was not treated with silane coupling agent I beforehand, but all components were simultaneously compounded.

The performance of the obtained sample was evaluated as follows, and the results are shown in Table 1. Degree of crosslinking (%): JIS C 3005, Item 27 Solvent: xylene, immersion conditions: 110 ° C x 24 h Heat deformation (%): JIS C 3005, Item 25 Heating temperature: 120 ° C, Load: 9.8 N Oxygen index: JIS K 7201. Tensile strength / elongation: According to JIS C 300518. Presence / absence of foaming during processing: The sample was cut, and the presence / absence of foaming was confirmed.

[0020]

[Table 1]

1: LDPE: W-1010 (manufactured by JPO) 2: LLDPE: 0134N (manufactured by Idemitsu) 3: Magnesium hydroxide: Kisuma 5 (manufactured by Kyowa Chemical) 4: Aluminum hydroxide: Heidilite 42 (Showa) 5: Magnesium hydroxide after treatment: Kisuma 5 + vinyltrimethoxysilane (5 parts by weight based on 100 parts by weight of magnesium hydroxide) 6: Aluminum hydroxide after treatment: Heidilite 42 + vinyltrimethoxysilane (water) 7: Magnesium hydroxide after treatment II: Kisuma 5 + isopropyl triisostearoyl titanate (5 parts by weight based on 100 parts by weight of magnesium hydroxide) 8: Silane coupling agent I: vinyltrimethoxysilane (SZ6300, manufactured by Toray Industries, Inc.) 9: silane Coupling agent II: normal hexyl trimethoxysilane (AY43-206M, manufactured by Toray Industries, Inc.) 10: titanate coupling agent: isopropyl triisostearoyl titanate (KR-TTS, manufactured by Ajinomoto Co.) 11: crosslinking agent: dicumyl peroxide ( 12: Catalyst: dibutyltin dilaurate (manufactured by Asahi Kasei Corporation, B
T-11)

Looking at the performance of each sample on the basis of the target values of the samples shown in Table 1, the comparative example in which the metal hydrate treated with the coupling agent was not used showed foaming during processing and tensile strength. It is understood that the flame retardancy tends to be inferior to that of the present invention. On the other hand, it can be seen that the examples of the present invention satisfy all the performances of the evaluation items.

[0023]

The present invention relates to a metal hydrate treated or treated with a polyolefin, a silane coupling agent and / or a titanate coupling agent, a silane coupling agent and / or a titanate coupling agent, a crosslinking agent and A crosslinked olefin resin composition having excellent physical properties such as flame retardancy, tensile strength, and elongation can be obtained by easily crosslinking a composition comprising a catalyst by extrusion molding or the like.

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Claims (4)

[Claims] 1. A composition comprising a metal hydrate treated or treated with a polyolefin, a silane coupling agent and / or a titanate coupling agent, a silane coupling agent and / or a titanate coupling agent, a crosslinking agent and a catalyst. A flame-retardant crosslinked olefin resin composition obtained by crosslinking a product. 2. 100 parts by weight of polyolefin, 80 to 200 parts by weight of metal hydrate treated with a silane coupling agent and / or a titanate coupling agent, 0.5 to 50 parts by weight of a silane coupling agent and / or a titanate coupling agent The flame-retardant crosslinked olefin resin composition according to claim 1, comprising 20 parts by weight, 0.5 to 10 parts by weight of a crosslinking agent and 0.5 to 10 parts by weight of a catalyst. 3. A metal hydrate treated or treated with a silane coupling agent and / or a titanate coupling agent, wherein 100 parts by weight of the metal hydrate is a silane coupling agent and / or a titanate coupling agent. .
3. The flame-retardant crosslinked olefin resin composition according to claim 1, which is treated or treated with 3 to 30 parts by weight. 4. Polyethylene; magnesium hydroxide and / or aluminum hydroxide treated with vinyltrimethoxysilane or isopropyltriisostearoyl titanate; and vinyltrimethoxysilane, normal hexyltrimethoxysilane and isopropyltriisostearoyl titanate. The flame-retardant crosslinked olefin resin composition according to any one of claims 1 to 3, comprising at least one kind; dicumyl peroxide; and dibutyltin dilaurate.