KR100200513B1 - Non-halogen flame retardant compound with low smoke generation - Google Patents

Abstract

The present invention provides a resin composition comprising a non-halogen flame retardant resin composition having a composition obtained by mixing an inorganic flame retardant and a flame retardant additive in a polyolefin-based matrix resin, or a phosphorus flame retardant additive comprising an inorganic compound coated with a phenol resin do. The phosphorus flame retarding additive is preferably added in an amount of 0.3-10 parts by weight based on 100 parts by weight of the matrix resin.

According to the present invention, it is possible to obtain a halogen-free flame retardant resin composition which is excellent in mechanical properties and flame retardancy, and which does not generate a toxic gas during combustion,

Description

Low smoke and non-halogen flame retardant resin composition

The present invention relates to a non-halogen flame retardant resin composition which is excellent in mechanical properties and flame retardancy but does not generate a toxic gas during combustion and has a greatly improved ductility.

Most deaths and injuries that occur during a fire are caused by a lot of toxic gases and smoke from the fire, rather than the flame itself, and the failure of the initial escape due to uncertainty of sight. Accordingly, development of a flame retardant resin composition having excellent flame retardancy (smoke resistance) that does not generate toxic gas and / or smoke upon combustion has been desired, as well as a flame retardant property that retards and suppresses the occurrence of fire .

The conventional non-halogen flame retardant resin composition is composed of a matrix resin composed of a polyolefin resin such as polyethylene (PE), ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate copolymer (EEA), aluminum hydroxide, magnesium hydroxide (Metal hydrate), and other flame retarding additives composed of a mixture of carbon black, zinc oxide, titanium dioxide, etc., alone or in a mixture of two or more, and antioxidants and / or processing aids And the like.

It is judged that the above-mentioned malodorization of the metal hydrate is attributed to the number of crystals chemically bonded to metal atoms. This number of crystals is stable at the molding processing temperature of most plastics, and is not released even under prolonged heating. However, at temperatures above the combustion temperature of most plastics, it is pyrolyzed to release crystalline water and absorb thermal energy.

The metal oxide thus formed combines with the carbonized product of the surface of the burning plastic to form a protective film to block the penetration of heat energy and oxygen. At the same time, the water vapor released from the metal oxide oxidizes the flammable gas by the dilution effect of the flammable gas in the vapor phase .

However, such an inorganic flame retardant has a side effect of adversely affecting the processability and the timepiece property of the matrix resin, so that the amount of the inorganic flame retardant is insufficient and the effect of fuming exhibited by the metal hydrate is unsatisfactory.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a flame retardant flame retardant resin composition which reduces the amount of toxic gases generated during combustion, maintains excellent mechanical properties and flame retardancy, To provide a resin composition.

In order to achieve the above object, the present invention provides a non-halogen flame retardant resin composition having a composition in which an inorganic flame retardant and a flame retardant additive are mixed in a matrix resin, Based flame-retardant additive. The present invention also provides a resin composition comprising the phosphorus-based flame retardant additive.

The resin composition of the present invention preferably contains 0.3 to 10 parts by weight of a phosphorus-based flame-retardant auxiliary based on 100 parts by weight of a polyolefin-based resin as a matrix.

Examples of the polyolefin resins usable in the present invention include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer. Any one of the resins alone or a mixture of two or more thereof may be used.

On the other hand, as the inorganic flame retardant used in the resin composition of the present invention, known metal hydrates such as aluminum hydroxide and magnesium hydroxide are used. These hydrates include saturated or unsaturated fatty acids such as stearic acid and oleic acid, silane-based binders, titanate- It is preferable that it is surface-treated with a zirconium-based coupling agent. The metal hydrate used in the present invention preferably has a particle size of 0.5 to 20 mu m and a specific surface area (BET) of 2 to 15 m2 / g. The metal hydrate is preferably added in an amount of about 80-100 parts by weight based on 100 parts by weight of the matrix resin. When the addition amount of the metal hydrate is less than 80 parts by weight, it is difficult to obtain the desired flame retardancy and defoaming property. When the addition amount exceeds 100 parts by weight, the flame retardancy and the improvement of the ductility are not only limited, but also the mechanical properties There is a problem that the workability is lowered.

In addition to the inorganic flame retardant, a flame retardant additive such as carbon black, zinc oxide, and titanium dioxide is also used in the composition of the present invention. Carbon black is generally used as such a flame retarding aid, and carbon black having a particle size of 15-30 mu m and a specific surface area (BET) of 50-300 m < 2 > / g is most preferable. The addition amount of the other flame retarding auxiliary is usually 1 to 20 parts by weight based on 100 parts by weight of the matrix resin.

In addition, various additives such as an antioxidant or a processing aid may be added to the resin composition of the invention in order to improve processing characteristics or mechanical properties. As the antioxidant, known primary and secondary antioxidants may be used singly or in the form of a mixture of two or more kinds. The antioxidant is preferably added in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the polyolefin-based resin.

Examples of the primary antioxidant include 2,6-di-tert-butyl-paracresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'- 3-methyl-6-tert-butylphenol), octadecyl-3- (4-hydroxy- Di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. Examples of the secondary antioxidant include di-lauryl sulfide, di-lauryl thio-di-propionate, and di-stearyl thio-di-propionate.

As the processing aid which can be used in the present invention, stearic acid, zinc stearate, paraffin wax, low molecular weight polyethylene and blue pin oil can be used singly or in the form of a mixture of two or more kinds. The amount of the processing aid to be added is generally about 0.3 to 15 parts by weight per 100 parts by weight of the polyolefin resin.

On the other hand, as the phosphorus-based flame retarding auxiliary agent which is a feature of the present invention, a phosphorus flame retarding agent coated with a phenolic resin or the like is used.

As the phosphorus flame retarding auxiliary, a composition containing pure or more than 5% can be used. Also, in the present invention, an organic compound coated with phenol resin or the like may be used. When such a resin-coated base compound is used, safety in handling during resin kneading is excellent.

When the added resin is burned, the resin in the resin is oxidized to be phosphorus oxide, and the carbonization of the resin is accelerated by the catalytic action. That is, it increases the amount of water vapor in the thermally decomposed product, and reduces char and combustible gas, thereby exhibiting a flame retarding effect. On the other hand, the resulting phosphorus oxide is converted to methacrylic acid, which is a condensation product of phosphoric acid, to form a coating film. The film-forming polymethacrylic acid is a high-viscosity, nonvolatile protective film layer, and thus acts as a barrier to oxygen. This also has the effect of suppressing the after glow of the produced combustible carbonized layer. That is, in the present invention, the phosphorus-based flame retarding additive exerts an effect of promoting the carbonization of the resin together with an oxygen-blocking effect by the formation of a film, and exhibits excellent flame retarding properties as well as fuming resistance due to synergy with conventional inorganic flame retardants.

In the present invention, the addition amount of the phosphorus-based flame retarding additive is preferably 0.3-10 parts by weight per 100 parts by weight of the matrix resin. When the addition amount is less than 0.3 part by weight, it is difficult to obtain a desired flame retardant effect. When the addition amount is more than 10 parts by weight, the final flame retardancy and the electrical properties of the final resin composition are remarkably lowered.

Examples and Comparative Examples of the present invention will be described below. However, these examples are presented only for the purpose of facilitating understanding of the present invention, and the present invention is not limited by these examples.

[Example 1]

100 parts by weight of magnesium hydroxide (KISUMA 5, manufactured by Kyoe Kogyo Kagaku Kogyo Co., Ltd.) surface-treated with stearic acid was added to 100 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 19% and MI of 0.6 g / 2 parts by weight of pure black, 2 parts by weight of carbon black (HI-BLACK 40B1, manufactured by LG Material Co., Ltd.), 3 parts by weight of paraffin wax and 2 parts by weight of Irganox 1010 manufactured by Ciba-Geigy Co., Were mixed by a known method to prepare a press sheet test piece.

The tensile strength at break, tensile strength at break, elongation at break, flame retardancy and smoke density were measured using the test pieces, and the results are shown in Table 1 below.

[Comparative Example 1]

The tensile strength at break, elongation at break, flame retardancy and smoke density of the test pieces were measured in the same manner as in Example 1 except that no pure additive was added, Respectively.

[Example 2]

The tensile strength at break, elongation at break, flame retardancy and smoke density were measured for the test pieces by preparing the test pieces in the same manner as in Example 1 except that the amount of pure added was changed to 0.3 parts by weight. The results are shown in Table 1 below.

[Example 3]

The tensile strength at break, elongation at break, flame retardancy and smoke density were measured for the test pieces by preparing the test pieces in the same manner as in Example 1 except that the amount of pure added was changed to 5 parts by weight. The results are shown in Table 1 below.

[Example 4]

The test pieces were prepared in the same manner as in Example 1 except that the amount of pure water was changed to 10 parts by weight. The tensile strength at break, tensile strength at break, flame retardancy and smoke density were measured The results are shown in Table 1 below.

[Example 5]

A test piece was prepared in the same manner as in Example 4 except that a commercial human composition (RINKA FR120, manufactured by Japan Kagaku Kogyo K.K.) coated with a resin was used instead of pure The breaking point tensile strength, breaking point elongation, flame retardancy and smoke density of the test pieces were measured, and the results are shown in Table 1 below.

[Comparative Example 2]

The test pieces were prepared in the same manner as in Example 1 except that the addition amount of pure water was changed to 0.1 part by weight. The tensile strength at break point, elongation at break point, flame retardancy and smoke density were measured The results are shown in Table 1 below.

[Comparative Example 3]

The tensile strength at break, elongation at break, flame retardancy and smoke density were measured for the test pieces by preparing the test pieces in the same manner as in Example 1, except that the addition amount of pure water was changed to 12 parts by weight. The results are shown in Table 1 below.

As is confirmed by comparing the physical properties of Examples 1 to 4 and Comparative Example 1, when a composition which is pure or coated with a phenol resin or contains at least 5% of these is added, it is possible to obtain a resin composition having excellent flame retardancy and low- It can be understood that a resin composition is obtained.

As can be seen from the results of Comparative Examples 2 and 3, when the addition amount is less than 0.3 part by weight, the desired flame retardant effect can not be obtained. When the addition amount exceeds 10 parts by weight, It can be seen that the electrical properties are significantly lowered.

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Tensile strength at break: Measured according to ASTM D638

Breaking point elongation: measured according to ASTM D638

Flammability: Measurement according to ASTM D2863

Smoke density: Measured according to ASTM E662 (non-flammable condition), and when the smoke density was 100 or lower, it was evaluated as low smoke ductility.

According to the present invention, it is possible to obtain a halogen-free flame retardant resin composition which is excellent in mechanical properties and flame retardancy, and which does not generate a toxic gas during combustion,

Claims (1)

A flame retardant resin composition comprising a polyolefin matrix resin and an inorganic flame retardant, a flame retardant additive and a phosphorus flame retardant additive mixed with the polyolefin matrix resin, wherein the flame retardant additive is phosphorous-based or is coated with a phenol resin, And 0.3-10 parts by weight based on 100 parts by weight of the matrix resin.