JPS60210665A - Self-extinguishing resin composition - Google Patents

Abstract

PURPOSE:To provide a self-extinguishing resin compsn. having excellent flame retardance (which meets requirements of class V-0 according to UL standard), by blending a thermoplastic resin, a hydrated inorg. filler and a bisphenol A brominated epoxy resin (crosslinked product). CONSTITUTION:100pts.wt. thermoplastic resin (A) (e.g. polyolefin resin, polystyrene or methacrylate resin), 60-250pts.wt. hydrated inorg. filler (B) (e.g. magnesium hydroxide or aluminum hydroxide having a particle size of 0.01-50mu) and 2-10wt% (based on the entire quantity of compsn.) bisphenol A brominated epoxy resin (C) having a bromine content of 16-60wt%, an epoxy equivalent of 200-3,000 and an MW of 400-6,000 or crosslinked product thereof are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a self-extinguishing resin composition having excellent flame retardancy.

[Prior art]

Conventionally, flame-retardant thermoplastic resin compositions have been disclosed, for example, in Japanese Patent Publication No. 57-4665 and Japanese Patent Publication No. 57-108.
No. 98, etc. are known, and are widely used as wire coatings, sheets, molded products, etc.

However, sheets obtained from such conventional compositions,
In the combustion test, the molded products showed insufficient flammability, and had the disadvantage that they were not completely self-extinguishing.

[Purpose of the invention]

An object of the present invention is to eliminate the above-mentioned drawbacks, exhibit a high degree of flame retardancy, and comply with the American UL standard Subject 94. Grade V
The present invention aims to provide a self-extinguishing resin composition that passes -O.

[Structure of the invention]

In order to achieve the above object, the present invention has a primary composition, that is, 6 parts by weight of a hydrous inorganic filler is added to 100 parts by weight of a thermoplastic resin.
0 to 250 parts by weight of a bisphenol A-based brominated epoxy resin or a crosslinked product thereof; The present invention is characterized by a self-extinguishing resin composition containing 2 to 10 weight percent gold relative to the self-extinguishing resin composition.

The thermoplastic resin in the present invention is a well-known thermoplastic resin, and specifically includes polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, poly-4-methylpentene-1, polystyrene, and ABS resin. , styrene resins such as AS resins, polyamide resins, polyester resins, vinyl chloride resins, methacrylic resins, and the like.

These thermoplastic resins can be used by blending them with each other if necessary.

The hydrous inorganic filler in the present invention may be any compound containing bound water or a hydroxyl group capable of thermally decomposing and generating moisture in one molecule.

Specific examples include magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and the like.

~50μ, preferably 0.1~20μ. In addition, these water-containing inorganic fillers are mixed with higher fatty acids and higher fatty acid salts before being mixed with the resin.

Silane coupling agent, titanate surface treatment agent.

It is desirable to use a material coated with a flame retardant aid, and it is particularly desirable to use magnesium hydroxide and/or aluminum hydroxide whose surface is treated with at least one of these.

The bisphenol A thread brominated epoxy resin in the present invention includes a brominated epoxy resin (formula 2) mainly composed of diglycidyl ether of tetrabromobisphenol A (formula 1).

(Formula 1) (Formula 2) Usually, among these bisphenol A-based brominated epoxy resins, those with the largest epoxy equivalent.

For example, those having an epoxy equivalent of 800 or more, more preferably 1200 or more are desirable from the viewpoint of less bleed-out during sheet molding and better crosstalk with the base resin.

A specific commercial product of bisphenol A-based brominated epoxy resin is "Sumi Epoxy'ESB-" manufactured by Sumikagaku Kogyo ■.
440, 400, 500, 700, ``DER-511, 54, 2'' manufactured by Dow Chemical Company, etc., ``1'' manufactured by Shell Chemical Company.
045-B-80”.

-o x-248-B, -80-, etc., as well as "5R-TEA-350,400" manufactured by Itamoto Yakuhin Kogyo @.In addition, from the point of view of sheet formability and @fil fuel reagent bleed-out. It is preferable to use the above-mentioned brominated epoxy resin as a pre- or f-remerized product or a crosslinked product. In the present invention, the crosslinked bisphenol A-based brominated epoxy resin refers to a bisphenol A-based brominated epoxy resin alone or When a mixture of two or more types of bromine with different bromine contents, or when these brominated epoxy resins are contained in a polyolefin resin using a well-known curing agent for epoxy resins, in the crosslinked product of the brominated epoxy resin, part,
The uncrosslinked material 9 may contain, for example, a prepolymer.

Furthermore, it is also possible to use a mixture of a prepolymer and a monomer in the crosslinked brominated epoxy resin.

The curing agent required for the three-dimensional crosslinking of the above-mentioned brominated epoxy resin may be any general curing agent for epoxy resins, and specific examples include ethylenediamine, diethylenetriamine, triethylenetetramine, and metaphenylenediamine l4+. -diaminodiphenylmethane, 4
, 4/-diaminodiphenylsulfone, amine catalysts such as boron trifluoride monoethylamine complex, maleic anhydride,
Acid anhydride catalysts such as phthalic anhydride and methylhimic anhydride.

Other examples include dicyandiamide, imidazole, and polyamide resin. In particular, boron trifluoride monoetheramine complexes are preferred curing agents.

As described above, the resin composition of the present invention is one in which a bisphenol A-based brominated epoxy resin or a crosslinked product thereof is blended together with a water-containing inorganic filler. It is necessary that the resin or its crosslinked product contain bromine in an amount of 2 to 10 parts by weight, preferably 2 to 8 parts by weight.

If this is less than 2 weight ratios, the flame retardance will be insufficient, which is not preferable. On the other hand, if the weight ratio exceeds 10, the brominated epoxy resin or its crosslinked product will bleed out onto the surface of the molded product and smoke will be emitted during combustion, which is not suitable.

Note that the resin composition of the present invention may contain flame retardant aids such as antimony trioxide, other flame retardants, and heat stabilizers as long as they do not impair the purpose of the present invention other than reduction in content.

UV absorbers, plasticizers, lubricants, pigments, antistatic agents.

Additives such as dispersants can be blended.

Next, an example of a method for manufacturing the resin composition of the present invention will be described. A predetermined amount of a water-containing inorganic filler and a bisphenol A-based brominated epoxy resin or crosslinked product thereof are blended into the above thermoplastic resin without stirring, and the mixture is melt-kneaded. In this kneading method, a master hatch may be prepared in advance and then mixed, or the materials may be melt-kneaded all at once.

As the kneading device, any suitable kneading device may be used, such as a panburi mixer, a pressure kneader, a roll mixer, a screw extruder, a twin screw extruder, and the like.

The composition obtained by melt-kneading in this manner is usually processed into a pellet shape using an extruder and provided as a molding resin (usually having a density of 1.0 g/cc or more).

The above-mentioned berets are generally 2 to 6 thighs in diameter.

Although it is often used in a cylindrical shape with a length of about 3 to ID mm, it is not limited to this.

A sheet molded article obtained from the composition of the present invention can also be crosslinked by electron beam irradiation.

It is also possible to mix a chemical crosslinking agent into the composition of the present invention and heat crosslinking after molding.

The composition of the present invention can be used for flame retardant applications such as electrical insulating materials, films, and sheets such as electric wire coating materials, molding materials for cabinets such as radios and televisions, and other electrical equipment, building materials, interior materials, and automobile parts. It can be widely used in fields that require a high degree of flame retardancy, such as materials.

〔Effect of the invention〕

By using a brominated epoxy resin or a crosslinked product thereof as a flame retardant, the composition of the present invention exhibits an effect of accelerating carbonization of the polymer during combustion, which cannot be obtained with other flame retardants, and as a result, no drip phenomenon occurs. Has characteristics. Furthermore, when combined with a water-containing inorganic filler, flammable thermoplastic resin becomes completely self-extinguishing and emits less smoke when burned, so a high degree of flame retardancy is required. It is extremely useful for use as a member.

[Method of measuring characteristics, evaluation criteria]

Note that the measured values of the present invention are based on the following measuring method.

(11 Bromine content) Accurately weigh a small piece cut from a nibles sheet. This sample is decomposed by the flask combustion method, and the absorbed liquid is titrated potentiometrically with a silver nitrate solution using a silver electrode. This titration curve shows the The amount was measured and the content (% by weight) was calculated.

(2) Flame retardancy: US UL standard, Subject
It was measured according to the method of 94.

〔Example〕

Hereinafter, one embodiment of the present invention will be described based on Examples.

Examples 1-5. Comparative Examples 1 to 5 Low density polyethylene (LDPE) as thermoplastic resin
, ethylene-vinyl acetate copolymer (EVA) (vinyl acetate content 26-
6), magnesium hydroxide (Mg(O
H), ) as a flame retardant, bisphenol A-based brominated epoxy resin (TEA-400, 1200, 1500)
and its prepolymer (TE A-400-P-I
Table 1 shows L decabromodiphenyl ether (DBE) respectively.
Blend in the proportions shown and use a pressurized knee gun to
150 x 15
A sheet with a diameter of 0 square and a thickness of 3.2 mm was press-molded.

A test piece with a length of 12 holes and a width of 12.7 mm was cut out from this sheet and its flame retardance was evaluated.

All of Examples 1 to 5il-1' met all the requirements of the present invention, had excellent flame retardancy, and were all V-O.

On the other hand, in Comparative Examples 1 to 4, the amount of water-containing inorganic filler added was small and did not meet the requirements of the present invention. Because it was not included, the evaluation results of flame retardancy were inferior to those of Examples, and were at the level of V-1 and V-2.

Claims (1)

[Claims] (1) A self-extinguishing resin composition comprising 100 parts by weight of a thermoplastic resin, 60 to 250 parts by weight of a water-containing inorganic filler, and a bisphenol A-based brominated epoxy resin or a crosslinked product thereof. and a self-extinguishing resin composition in which the amount of the bisphenol A-based brominated epoxy resin or its crosslinked product is 2 to 10 weight percent gold relative to the self-extinguishing resin composition.