JPH064728B2 - Self-extinguishing resin composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a self-extinguishing resin composition having excellent flame retardancy.

[Prior art]

Conventionally, as a flame-retardant thermoplastic resin composition, for example, Japanese Patent Publication No. 57-4665 and Japanese Patent Publication No. 57-108.
No. 98, etc. are known and are widely used as electric wire coating materials, sheets, molded products and the like.

However, sheets obtained from such conventional compositions,
In the combustion test, the molded products, etc. had a defect that the flame retardancy was still insufficient and they were not completely self-extinguishing.

[Object of the Invention]

It is an object of the present invention to provide a self-extinguishing resin composition which overcomes the above-mentioned drawbacks, exhibits a high degree of flame retardancy, and passes the UL standard Subgect 94, grade V-0.

[Structure of Invention]

In order to achieve the above object, the present invention has the following constitution: 100 parts by weight of ethylene or propylene resin, 60 to 250 parts by weight of filler made of magnesium hydroxide or aluminum hydroxide, and bisphenol A.
A self-extinguishing resin composition comprising a cross-linked product of a system-based brominated epoxy resin, wherein the amount of the cross-linked product of the bisphenol A-based brominated epoxy resin is 2 with respect to the composition. It is characterized by a self-extinguishing resin composition containing 10 to 10% by weight.

Ethylene-based or propylene-based resin in the present invention,
A well-known ethylene-based or propylene-based resin, specifically, a homopolymer such as polyethylene or polypropylene, a copolymer such as an ethylene-vinyl acetate copolymer, an ethylene-propylene copolymer, or a mixture thereof. .

These ethylene-based or propylene-based resins may be blended with each other if necessary.

The filler composed of magnesium hydroxide or aluminum hydroxide in the present invention is a necessary condition that it is a compound containing a bound hydroxyl group in the molecule which can generate bound water or thermal decomposition to generate water. Specific examples thereof include magnesium hydroxide, aluminum hydroxide, a mixture of both, or a compound obtained by adding other inorganic compound such as hydroxide inorganic compound or water of crystallization, for example, basic magnesium carbonate.

The particle size of the filler made of magnesium hydroxide or aluminum hydroxide is generally 0.01 to 50 μ, preferably from the viewpoint of filter clogging during molding and dispersibility.
It is preferably 0.1 to 20 μm. In addition, these fillers made of magnesium hydroxide or aluminum hydroxide, prior to mixing with the resin, higher fatty acid, higher fatty acid salt, silane coupling agent, titanate surface treatment agent,
It is desirable to use those which have been coated with a flame retardant aid or the like, and it is particularly desirable to use magnesium hydroxide and / or aluminum hydroxide whose surface is treated with at least one of these.

Examples of the bisphenol A-based brominated epoxy resin in the present invention include a diglycidyl ether of Tetonoraprom bisphenol A (formula 1) or a brominated epoxy resin mainly composed of this (formula 2).

(Equation 1) (Formula 2) Usually, these bisphenol A-based brominated epoxy resins have a bromine content of 16 to 60% by weight and an epoxy equivalent of 2
Those having a molecular weight of 00 to 3000 and a molecular weight of 656 to 6000 can be used.

Among these, those with a large epoxy equivalent, for example,
Epoxy equivalent of 800 or more, more preferably 1
A crosslinked product obtained from a resin having a viscosity of 200 or more is desirable because it has less bleed-out during sheet molding and improves kneading properties with the base resin.

"Sumiepoxy" ESB manufactured by Sumitomo Chemical Co., Ltd. as a specific commercial product of bisphenol A-based brominated epoxy resin
-340,400,500,700 and "DER-511,542" manufactured by Dow Chemical Company, "1 manufactured by Ciel Chemical Company"
045-B-80 ″, DX-248-B-80 ″, etc., and “SR-TBA-350” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.
400 "etc.

From the standpoints of sheet formability and bleed-out of flame retardant, it is necessary to use a prepolymerized brominated epoxy resin as a crosslinked product.

The term "bisphenol A-based brominated epoxy resin cross-linked product" as used in the present invention means a bisphenol A-based brominated epoxy resin alone or a mixture of two or more kinds having different bromine contents, or a well-known epoxy for these brominated epoxy resins. It is insoluble and infusible by three-dimensional crosslinking with a resin curing agent.

However, when the above-mentioned crosslinked product is contained in the polyolefin resin of the present invention as a flame retardant, even if a part of the crosslinked product of the brominated epoxy resin contains an uncrosslinked product, for example, a prepolymer. I don't care.

Further, it is also possible to use a mixture of a brominated epoxy resin crosslinked product with a prepolymer and a monomer.

The curing agent required for three-dimensional crosslinking of the brominated epoxy resin may be any curing agent for general epoxy resins, and specific examples include ethylenediamine, diethylenetriamine, triethylenetetramine, metaphenylenediamine, 4 , 4'-diaminodiphenylmethane, 4,
There are amine catalysts such as 4'-diaminodiphenyl sulfone, boron trifluoride monoethylamine complex, etc., acid anhydride catalysts such as maleic anhydride, phthalic anhydride, methylhymic anhydride, etc., and other dicyandiamide, imidazole, polyamide resin, etc. . In particular, boron trifluoride monoethylamine complex is a preferred curing agent.

As described above, the resin composition of the present invention contains a cross-linked product of a bisphenol A-based brominated epoxy resin together with a filler made of magnesium hydroxide or aluminum hydroxide. Bromine in the crosslinked product of the A-based brominated epoxy resin is 2 to 10
It is necessary that the content be wt%, preferably 2 to 8 wt%.

If it is less than 2% by weight, the flame retardance is insufficient, which is not preferable. On the other hand, if it exceeds 10% by weight, bleeding out of the cross-linked product of the brominated epoxy resin on the surface of the molded article and smoke generation during combustion become severe, which is not preferable.

In addition to the above components, the resin composition of the present invention is a flame retardant aid such as antimony trioxide, other flame retardants, heat stabilizers, ultraviolet absorbers, plasticizers, etc., as long as the object of the present invention is not impaired. Additives such as agents, lubricants, pigments, antistatic agents, and dispersants can be added.

Next, an example of the method for producing the resin composition of the present invention will be described. First, a predetermined amount of a filler made of magnesium hydroxide or aluminum hydroxide and a cross-linked product of a bisphenol A-based brominated epoxy resin is mixed with the above ethylene-based or propylene-based resin, and melt-kneaded. In this kneading method, the masterbatch may be manufactured in advance and then mixed, or the melt kneading may be performed all at once.

As the kneading device, a known device such as Banbury mixer, pressure kneader, roll mixing, single-screw extruder, twin-screw extruder can be used.

The composition thus obtained by melt-kneading is usually processed into pellets by an extruder and provided as a molding resin (usually having a density of 1.0 g / cc or more).

The above pellets generally have a diameter of 2 to 6 mm and a length of 3 to
It is often used in a cylindrical shape of about 10 mm, but is not limited to these.

The sheet molded article obtained from the composition of the present invention can be irradiated with an electron beam to be crosslinked.

Further, a chemical crosslinking agent may be added to the composition of the present invention, and the composition may be molded and then heat-crosslinked.

INDUSTRIAL APPLICABILITY The composition of the present invention is used for electric insulation materials such as electric wire coating materials, films, sheets, and molding materials for cabinets such as radios and televisions and other electric devices, building materials, interior materials, flame retardants such as automobile parts. It can be widely used in fields such as materials where high flame retardancy is required.

〔The invention's effect〕

The composition of the present invention uses a cross-linked product of a brominated epoxy resin as a flame retardant, and exhibits a carbonization-promoting action of a polymer which cannot be obtained by other flame retardants at the time of combustion, resulting in no drip phenomenon. Have. In addition, when used in combination with a filler made of magnesium hydroxide or aluminum hydroxide, it has the characteristics that the flammable ethylene-based or propylene-based resin is completely self-extinguishing and emits less smoke during combustion. , It is extremely useful for parts that require high flame retardancy.

[Characteristic measuring method, evaluation criteria]

 The measured value of the present invention is based on the following measuring method.

(1) Bromine content: A small piece cut from a press sheet is precisely weighed. This sample is decomposed by the flask combustion method, and the absorption liquid is subjected to potentiometric titration with a silver nitrate solution using a silver electrode. The bromine content was calculated from this titration curve to calculate the content (% by weight).

(2) Flame retardancy: Measured according to the method of US UL standard, Subgect 94.

〔Example〕

An embodiment of the present invention will be described below based on examples.

Examples 1-2 and Comparative Examples 1-8 As ethylene-based or propylene-based resins, low density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EV
A) (26% vinyl acetate content), polypropylene (PP) 1
Magnesium hydroxide (Mg (OH) ₂ ) is used as a filler composed of magnesium hydroxide or aluminum hydroxide per 100 parts by weight, and a cross-linked product of bisphenol A-based brominated epoxy resin (TBA-400, 1200,
1500) and its prepolymer (TBA-400-P
-1) and decabromodiphenyl ether (DBE) were blended in the proportions shown in Table 1 and melt-kneaded at 140 to 150 ° C using a pressure kneader to obtain 150 x 1
A 50-mm square sheet having a thickness of 3.2 mm was press-molded. A test piece having a length of 127 mm and a width of 12.7 mm was cut out from this sheet to evaluate the flame retardancy.

Since all of Examples 1 and 2 satisfied all the requirements of the present invention, they were excellent in flame retardancy and were all V-0.

On the other hand, in Comparative Examples 1 to 3, since the addition amount of the filler made of magnesium hydroxide or aluminum hydroxide is small and does not satisfy the requirements of the present invention, Comparative Examples 4 and 5 are bisphenol A-based brominated epoxy resins. Since the crosslinked product was not contained, the flame retardancy evaluation results were inferior to those of the examples, and the levels were V-1 and V-2.

In Comparative Examples 6, 7, and 8, since the bisphenol A-based brominated epoxy resin is a prepolymer, the UL94 vertical test certainly gives V-0, but the drip phenomenon is recognized. It does not have sufficient flame retardancy.

Claims (1)

[Claims] 1. An ethylene-based or propylene-based resin 100
A self-extinguishing resin composition comprising 60 parts by weight to 250 parts by weight of a filler made of magnesium hydroxide or aluminum hydroxide, and a cross-linked product of a bisphenol A-based brominated epoxy resin. A self-extinguishing resin composition comprising a cross-linked product of a bisphenol A-based brominated epoxy resin in an amount of 2 to 10% by weight based on the self-extinguishing resin composition.