JPH05339444A - Polyethylenic resin composition - Google Patents

Abstract

PURPOSE:To provide the polyethylenic resin composition improved in flame retardance substantially without causing deterioration of its characteristics. CONSTITUTION:The polyethylenic resin composition good in flame retardance comprises 95-50wt.% of a modified polyethylene resin obtained by copolymerizing ethylene with an unsaturated compound having an organic carboxylic acid group or organic carboxylic acid ester group, and 5-50wt.% of an alkylphenolic resin not having thermal reactivity.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has a modified polyethylene resin having an organic carboxylic acid group or an organic carboxylic acid ester group showing good compatibility with a phenol resin and an alkyl group showing a good compatibility with polyethylene. The present invention relates to a polyethylene-based resin composition having a non-heat-reactive alkylphenol resin as a main component and obtained by melt-kneading the same and having good flame retardancy.

[0002]

2. Description of the Related Art Polyethylene, which is one of typical polyolefin resins, is inexpensive, transparent, has good impact resistance, has good electrical insulation, is chemically stable, and has low moisture permeability. Since it has many advantages, it has a wide range of uses such as various containers, tableware, toys, daily necessities, kitchen utensils, etc., but has a drawback that it is easily burned. In order to improve this drawback, a method of blending a halogen-based, phosphorus-based or nitrogen-based flame retardant, a so-called addition type flame retardant such as aluminum hydroxide or magnesium hydroxide has been used.
There is a problem that the characteristics of the composition obtained by using these methods are deteriorated. The best flame-retardant method is to make the resin itself flame-retardant. In the case of polyethylene resin, the method of blending halogenated polyethylene has been used, but this method improves the flame-retardant property. Though
There is a problem that a large amount of halogen, which is a problem in environmental destruction, must be used. From the above, it is most preferable that the polyethylene-based resin can be made flame-retardant by the polymer alloy of the polyethylene and the halogen-free flame-retardant resin. However, the polyethylene-based resin has poor compatibility with other resins. Conventionally, flame retardation by such a method has not been found.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyethylene resin having improved flame retardancy with almost no deterioration of properties.

[0004]

[Means for Solving the Problems] The present inventors have paid attention to the fact that a phenol resin has good flame retardancy, and as a result of diligent studies on improving the affinity between a polyethylene resin and a phenol resin, A modified polyethylene resin having an organic carboxylic acid group or an organic carboxylic acid ester group exhibiting good compatibility and a non-thermoreactive alkylphenol resin having an alkyl group exhibiting good compatibility with polyethylene are blended in a predetermined amount, and further melt-kneaded. By doing so, it was found that the effect of improving the flame retardancy of the polyethylene resin can be obtained with almost no deterioration of the characteristics, and the present invention has been completed. That is, the present invention comprises 95 to 50% by weight of a modified polyethylene resin obtained by copolymerizing an unsaturated compound having an organic carboxylic acid group or an organic carboxylic acid ester group and 5 to 50% by weight of a non-thermoreactive alkylphenol resin. Composition 10
The present invention relates to a polyethylene resin composition having good flame retardancy obtained by melt-kneading 0 parts by weight.

The modified polyethylene resin used in the present invention is not particularly limited and is commercially available.
For example, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer and a compound obtained by partially ion-crosslinking them, ethylene / methyl acrylate copolymer,
Examples thereof include ethylene / methyl methacrylate copolymer and ethylene / ethyl acrylate copolymer. These resins may be used alone or in combination of two or more.

The non-thermo-reactive alkylphenol resin used in the present invention is not particularly limited and is commercially available. For example, p-tert. -Butylphenol, p-tert. -Phenols such as octylphenol and p-nonylphenol and formalin are charged into a reaction kettle at a compounding ratio such that the ratio of phenols / formaldehyde is 0.5 to 1.0, and further oxalic acid, hydrochloric acid, sulfuric acid and toluene. After adding a catalyst such as sulfonic acid, heat it and carry out a reflux reaction for an appropriate time, then vacuum dehydration or static dehydration to remove separated water, and further remove remaining water and unreacted phenols. Can be obtained. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components may be used alone or in combination of two or more kinds.

In the polyethylene resin composition of the present invention, the modified polyethylene resin and the non-thermoreactive alkylphenol resin are 95: 5 to 50: 50% by weight, preferably 8%.
0:20 to 60: 40% by weight, more preferably 75: 2
It is compounded in the range of 5 to 65: 35% by weight. When the blending ratio of the modified polyethylene resin is less than 50% by weight, properties such as tensile strength and impact resistance are deteriorated, and when the blending ratio of the non-heat-reactive alkylphenol resin is less than 5% by weight, flame retardancy The improvement effect is insufficient. Thus, the polyethylene-based resin composition of the present invention has an effect of improving flame retardancy without causing deterioration of the characteristics of the polyethylene-based resin, which is because it has good compatibility with polyethylene. The alkyl groups of phenolic resins and the organic carboxylic acid groups or organic carboxylic acid ester groups of modified polyethylene resins that have good compatibility with phenolic resins improve the compatibility of polyethylene-based resins with phenol-based resins and create a microphase-separated structure. It is thought that it is possible to take it.

The polyethylene resin composition of the present invention comprises
Further, depending on the use and purpose, other compounding agents, for example, talc, mica, calcium carbonate, inorganic fillers such as wollastonite, coupling agents or reinforcing agents such as glass fibers and carbon fibers, flame retardants, flame retardants, etc. A combustion aid, an antistatic agent, a stabilizer, a pigment, a release agent, an impact resistance improving agent such as an elastomer, and the like can be added. As a method for producing the polyethylene resin composition of the present invention, a conventionally known method can be applied, and the raw materials of the thermoplastic resin composition of the present invention are collectively or divided and sufficiently mixed with a Henschel mixer. Further, it can be obtained by a method of melt-kneading and kneading with a biaxial kneader, or by melt-kneading with a pressure kneader, a Banbury mixer or the like.

[0009]

【Example】

<< Example 1 >> 90 parts by weight of ethylene-methyl methacrylate copolymer (Acrylift RWH202 manufactured by Sumitomo Chemical Co., Ltd.) and a novolac-type paraoctylphenol resin (Sumitomo Dures Co., Ltd.) as the non-thermoreactive alkylphenol (a). 10 parts by weight of light resin RPR-19900) was put into a pressure kneader and the temperature was adjusted to 2 at 190 to 200 ° C.
The mixture was melt-kneaded for 0 to 30 minutes, formed into a sheet with a roll, cooled to room temperature, and pelletized with a sheet pelletizer to obtain a polyolefin resin composition. Thereafter, injection molding was performed, and the obtained test pieces were evaluated for tensile strength, tensile elongation, Izod impact strength, and oxygen index. The evaluation results are shown in Table 1. << Example 2 >> Ethylene-methacrylic acid copolymer (Mitsui
DuPont Poly Chemical Co., Ltd. Nucrel R 0903
HC) 70 parts by weight and a novolak-type paranonylphenol resin as a non-thermo-reactive alkylphenol (b) (Sumilite Resin R PR-5 manufactured by Sumitomo Dures Co., Ltd.)
3362) The mixture preblended with 30 parts by weight was melt-kneaded in the same manner as in Example 1 and, after molding, its characteristics were evaluated. The evaluation results are shown in Table 1. << Example 3 >> Ethylene-methacrylic acid copolymer (Mitsui
DuPont Poly Chemical Co., Ltd. Nucrel R 0903
HC) 60 parts by weight and a novolac-type paraoctylphenol resin as a non-thermoreactive alkylphenol (a) (Sumilite Resin R PR-1 manufactured by Sumitomo Dures Co., Ltd.)
9900) 20 parts by weight and a novolak-type paranonylphenol resin as a non-heat-reactive alkylphenol (b) (Sumilite Resin R PR-5 manufactured by Sumitomo Dures Co., Ltd.)
3362) The mixture preblended with 20 parts by weight was melt-kneaded in the same manner as in Example 1, and after molding, its characteristics were evaluated. The evaluation results are also shown in Table 1. << Example 4 >> 35 parts by weight of ethylene-methyl methacrylate copolymer (Acrylift RWH202 manufactured by Sumitomo Chemical Co., Ltd.) and ethylene-methacrylic acid copolymer (Nucrel R 0903H manufactured by Mitsui DuPont Polychemical Co., Ltd.)
C) 35 parts by weight and a novolac-type paranonylphenol resin as a non-thermo-reactive alkylphenol (b) (Sumilite Resin R PR-1 manufactured by Sumitomo Dures Co.
9900) 30 parts by weight of the pre-blended mixture was melt-kneaded in the same manner as in Example 1 and, after molding, its characteristics were evaluated. The evaluation results are also shown in Table 1.

Comparative Example 1 Ethylene-methyl methacrylate copolymer (Sumitomo Chemical Co., Ltd. Acryft RWH20
2) 40 parts by weight and a novolac-type paraoctylphenol resin as a non-thermo-reactive alkylphenol (a) (Sumilite Resin RPR-19 manufactured by Sumitomo Dures Co., Ltd.)
900) 60 parts by weight of the pre-blended mixture was melt-kneaded in the same manner as in Example 1 and, after molding, its characteristics were evaluated. The evaluation results are also shown in Table 2. << Comparative Example 2 >> Ethylene-methacrylic acid copolymer (Mitsui
DuPont Poly Chemical Co., Ltd. Nucrel R 0903
HC) 97 parts by weight and a novolac-type paranonylphenol resin as a non-thermo-reactive alkylphenol (b) (Sumilite Resin R PR-5 manufactured by Sumitomo Dures Co., Ltd.)
3362) The mixture pre-blended with 3 parts by weight was melt-kneaded in the same manner as in Example 1 and, after molding, its characteristics were evaluated. The evaluation results are also shown in Table 2. << Comparative Example 3 >> 70 parts by weight of ethylene-methyl methacrylate copolymer (Sumitomo Chemical Co., Ltd. Acrylift R WH202) and novolac-type phenol resin (Sumitomo Dures Co., Ltd. Sumilite Resin R PR-51470) 30
The mixture preblended with the compounding of parts by weight was melt-kneaded in the same manner as in Example 1, and the characteristics of the mixture were evaluated after molding. The evaluation results are also shown in Table 2. << Comparative Examples 4 to 5 >> Single units of ethylene-methacrylic acid copolymer and ethylene-methyl methacrylate copolymer were melt-kneaded in the same manner as in Example 1, and the characteristics were evaluated after molding. The evaluation results are also shown in Table 2.

[0011]

[0012]

* 1 Compatibility: The state of the sheet surface after melt-kneading was visually observed and evaluated. ◯: Good compatibility and transparent Δ: Compatible but opaque ×: Not compatible * 2 Tensile strength: Measured according to ASTM D-638. * 3 Izod impact strength: Measured according to the method described in ASTM D256 for a notched test piece having a 1/2 "width. * 4 Oxygen index: Measured according to the method described in ASTM D-2863.

[0014]

As is apparent from Tables 1 to 3, the polyethylene resin composition of the present invention is a novel material having significantly improved flame retardancy while maintaining the characteristics of polyethylene.

Claims (1)

[Claims] 1. A modified polyethylene resin obtained by copolymerizing an unsaturated compound having an organic carboxylic acid group or an organic carboxylic acid ester group in an amount of 95 to 50% by weight and a non-thermoreactive alkylphenol resin in an amount of 5 to 50% by weight. A polyethylene resin composition having good flame retardancy, which is characterized in that