JP2007070586A - Granular flame retarder composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bromine-based flame retarder composition that does not raise problems of deteriorating working circumstance by its scattering and of giving an adverse effect on workers, that allows the pneumatic transportation to a mixer by pipeline and the automatic measuring and feeding, and that can be produced by a simpler process than a process using a masterbatich, further hardly raises a problem of discoloration, so called burning, in a process molding together with a thermoplastic resin. <P>SOLUTION: The granular flame retarder composition comprises a 100 pts.wt. bromine-based flame retarder, an 1-10 pts.wt. ethylene-vinyl acetate copolymer, an 0.5-3.0 pts.wt. acrylic resin, a 0.1-1.0 pt.wt. fatty acid amide, and at least 0.1 pt.wt. tin compound, and optionally a pigment of not more than 5 pts.wt. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a granular flame retardant composition which is added to a thermoplastic resin at the molding step and flame-retards the thermoplastic resin.

  As a method for making a thermoplastic resin flame retardant, a method in which a brominated flame retardant is additionally added to the resin in a molding process such as resin extrusion, extrusion foaming, injection molding, blow molding or the like is performed. As a method for this additional addition, a bromine-based flame retardant powder is directly mixed with the resin, and a master flame retardant master batch that is pre-kneaded with the bromine-based flame retardant at a high concentration into the resin to be mixed with the resin. A batch system etc. can be mentioned.

  The method of mixing the brominated flame retardant powder directly into the resin has the problem that the working environment deteriorates due to the scattering of the powder during measurement, preparation and mixing, resulting in adverse effects on the health of the worker. It is gradually decreasing. On the other hand, the masterbatch system has become mainstream because it can prevent scattering by pelletization and can also transfer the resin air in the pipe to the mixer.

However, this masterbatch method involves mixing bromine-based flame retardant and resin, heating and kneading using an extruder, cooling, cutting into pellets, and completing the pellets with the same particle size using a sorter. Requires a simple manufacturing process. As a result, there is a problem that this method is not economical.
JP 2004-95963 A (Claim 12, paragraph 0035)

Problems to be solved by the invention

  The present invention does not cause the problem of deterioration of the work environment due to scattering or the like, or adverse effects on the health of the worker, and on the other hand, air transfer in pipes to the mixer, automatic weighing, and automatic feed are possible. It is an object of the present invention to provide a brominated flame retardant composition that can be produced by a simpler process and is less likely to cause discoloration, that is, so-called burns, during molding with a thermoplastic resin.

Means for solving the problem

  As a result of intensive studies to solve the above problems, the present inventors have found that a granular flame retardant composition in which a bromine-based flame retardant is combined with an ethylene vinyl acetate copolymer, an acrylic resin, a fatty acid amide, a tin compound in a specific ratio The present inventors have found that the above problems can be solved by a product, and have completed the present invention.

  That is, the present invention relates to a brominated flame retardant and 1 to 10 parts by weight of an ethylene vinyl acetate copolymer, 0.5 to 3.0 parts by weight of an acrylic resin, and 100% by weight of the brominated flame retardant. The present invention provides a granular flame retardant composition comprising 0.1 to 1.0 part by weight of an amide and 0.1 part by weight or more of a tin compound (claim 1).

  The granular flame retardant composition of the present invention can be combined with a pigment in a specific ratio, if necessary, in addition to the above essential components. That is, the present invention provides the above-mentioned granular flame retardant composition, further comprising 5 parts by weight or less of the pigment with respect to 100 parts by weight of the brominated flame retardant (claim). Item 2).

The invention's effect

  Since the granular flame retardant composition of the present invention is produced by mixing and granulating the above-mentioned components, it can be produced by a much simpler process than the master batch and is excellent in economic efficiency. On the other hand, the strength of the granular flame retardant composition of the present invention is large and is not easily destroyed, so there is no dust scattering at the time of weighing, charging and mixing. The problem of adverse effects is suppressed. Moreover, since the strength as a grain is large, it is possible to perform air transfer, automatic weighing, and automatic feed in the pipe to the mixer. The granular flame retardant composition of the present invention is further characterized in that resin discoloration (discoloration) is less likely to occur during molding with a thermoplastic resin.

  Next, the form for implementing this invention is demonstrated in detail.

  Examples of the brominated flame retardant which is an essential component of the granular flame retardant composition of the present invention include hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBA), TBA-epoxy oligomer / polymer, TBA-carbonate oligomer, decabromo. Diphenyl oxide, ethylenebis (tetrabromophthalimide), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, tris (2,3-dibromopropyl) isocyanurate, hexabromobenzene, tetrabromophthalic anhydride Is exemplified.

  The granular flame retardant composition of the present invention contains, in addition to the brominated flame retardant, an ethylene vinyl acetate copolymer (EVA), an acrylic resin, a fatty acid amide, and a tin compound as essential components.

  There is no particular limitation on the ratio of ethylene to vinyl acetate in the ethylene vinyl acetate copolymer used in the present invention, and any ethylene vinyl acetate copolymer can be used, and among them, the vinyl acetate content is 20%. The above is preferable.

  The addition amount of EVA is in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the brominated flame retardant. Preferably it is the range of 2-8 weight part. If the added amount is less than 1 part by weight, it is difficult to form a granular product because there is no substance to be a binder. On the other hand, if it exceeds 10 parts by weight, the particles are sticky and welded at the time of granular molding, and the size is moderate. It becomes difficult to form a granular product.

  Examples of the acrylic resin used in the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, acrylic Examples thereof include copolymers such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and methyl methacrylate-butadiene-styrene copolymer (MBS).

  The amount of the acrylic resin added is in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the brominated flame retardant. Preferably it is the range of 1.0-2.0 weight part. If the addition amount is less than 0.5 parts by weight or more than 3 parts by weight, the proper kneading state is not achieved, and thus the granular product is liable to collapse and stickiness and the like occur, and it is difficult to control to an appropriate state.

  Examples of fatty acid amides used in the present invention include erucic acid amide, oleic acid amide, stearic acid amide, behenic acid amide, N, N′-ethylenebis (stearamide), N, N′-methylenebis (stearamide). The

  The amount of fatty acid amide added is in the range of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the brominated flame retardant. Preferably it is the range of 0.3-0.8 weight part. When the addition amount is less than 0.1 part by weight, the mixed state is not constant, and when it exceeds 1 part by weight, the slipperiness becomes excessive and the strength of the granular product decreases.

  Examples of the tin compound used in the present invention include butyltin oxide, octyltin oxide and derivatives thereof, specifically, butyltin malate polymer, butyltin mercapto polymer, octyltin malate polymer, and octyltin mercapto polymer.

  The addition amount of the tin compound is 0.1 parts by weight or more with respect to 100 parts by weight of the brominated flame retardant. If the amount is less than 0.1 parts by weight, the occurrence of burns increases during resin molding.

  The particulate flame retardant composition of the present invention can contain a pigment in addition to the essential components. That is, a pigment is added when coloring is required. There is no particular limitation on the pigment that can be added. For example, inorganic pigments such as titanium oxide, zinc white, lead white, zinc dust, bengara, cadmium yellow, yellow lead, chromium oxide green, cobalt green, ultramarine blue, cobalt blue, phthalocyanine pigment, azo pigment, nitroso pigment, nitro pigment And basic dye-based lakes and acidic dye-based lakes.

  The addition amount of the pigment is 5.0 parts by weight or less with respect to 100 parts by weight of the brominated flame retardant.

  The granular flame retardant composition of the present invention can be produced by mixing and extruding the above components. For extrusion granulation, a screw-type extrusion granulator, a roll-type extrusion granulator, a blade-type extrusion granulator, a tablet-type extrusion granulator, a briquette-type extrusion granulator, or the like is preferably used. The size of the granular product varies depending on processing conditions and the like and is not particularly limited. However, considering the ease of transportation and storage, a diameter of about 1 to 5 mm is desirable.

  The granular flame retardant composition of the present invention, in addition to the above-mentioned essential components and pigments added as necessary, further, conventionally known organic flame retardants such as chlorine-based flame retardants, phosphorus-based flame retardants, Inorganic flame retardants such as antimony trioxide and magnesium hydroxide, metal soap, lubricant, natural wax, hydrocarbon wax, antistatic agent, antioxidant, UV absorber, hindered amine light stabilizer, foaming agent, foaming aid Agents, fillers and the like may be added as necessary.

  Here, examples of the lubricant include fatty acid esters such as glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, ethylene glycol fatty acid ester, propylene glycol fatty acid ester, and higher alcohol fatty acid ester.

  Examples of the metal soap include calcium stearate, zinc stearate, magnesium stearate, barium stearate, and aluminum stearate.

  The granular flame retardant composition of the present invention is added to a thermoplastic resin to make the thermoplastic resin flame retardant. The addition is usually performed at a molding processing stage such as extrusion molding of thermoplastic resin, extrusion foam molding, injection molding, blow molding or the like. The kind of thermoplastic resin to which the granular flame retardant composition of the present invention is added is not particularly limited, and examples thereof include the resins shown below.

(1) Polyethylene, for example, high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (L-LDPE),
(2) polypropylene (PP),
(3) methylpentene polymer,
(4) Ethylene-vinyl acetate copolymer (EVA)
(5) Polystyrene (PS), high impact polystyrene (HI-PS),
(6) AS resin,
(7) ABS resin,
(8) MBS resin,
(8) Methacrylic resin (PMMA),
(9) Polyurethane (PU),
(10) Polycarbonate (PC),
(11) Polybutylene terephthalate (PBT), polyethylene terephthalate (PET),
(12) Polyamide resin,
(13) Polyacetal The granular flame retardant composition of the present invention can also be used for a mixture obtained by blending these resins.

  The amount of addition of the particulate flame retardant composition of the present invention to the thermoplastic resin is not particularly limited, and is appropriately adjusted according to the required level of flame retardancy. Generally, 1-10 weight part is preferable with respect to 100 weight part of thermoplastic resins.

EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited by an Example.
Examples 1-4 and Comparative Examples 1-15

  HBCD (FR-1206ILM manufactured by DSB) is used as a brominated flame retardant, and EVA (Sumitomo RB-11 manufactured by Sumitomo Chemical Co., Ltd.) and acrylic resin (Metablene L-manufactured by Mitsubishi Rayon Co., Ltd.) in the ratios shown in Tables 1 and 2 1000), oleic acid amide and dibutyltin maleate (KS-100A manufactured by Kyodo Yakuhin Co., Ltd.) are added and mixed with a super mixer (manufactured by Kawata Co., Ltd.). Granulated flame retardant composition was obtained. The granulation conditions were a material temperature of 120 ° C. and a screen mesh of 3 mm.

Granular formability The granular flame retardant composition thus obtained was visually observed to determine whether the shape and size thereof were uniform, and the granular formability was evaluated based on the following criteria. The results are shown in Tables 1 and 2.

○: Molded product is a glossy columnar shape or a deformed product and does not collapse even when pressed by hand. Δ: Molded product is apparently solidified, but collapsed when pressed by hand. Status. Or the molded product is too soft and sticky

Dust generation at the time of destruction The obtained granular flame retardant composition was crushed with a press, the degree of generation of dust at that time was visually observed, and the generation of dust at the time of destruction was evaluated based on the following criteria. The results are shown in Tables 1 and 2.

◎: Molded product is deformed but dust is not generated ○: Powder of 1 mm or less is 30% or less when pulverized Δ: Generation rate of 1 mm or less is 30 to 70%
×: The incidence of 1 mm or less is 70% or more

Residual coloring during injection molding Polystyrene resin (polystyrene G757X manufactured by Nippon Polystyrene Co.) and granular flame retardant composition are mixed at a ratio of 100: 2 and molded into pellets using an injection molding machine (cylinder temperature 190 ° C, nozzle temperature 200) C., dwell time 15 minutes), and the degree of coloring of the finished test piece was visually compared with the degree of coloration of the sample molded under the same conditions except that the dwell time was 2 minutes. The degree of burn occurrence was evaluated based on the following criteria. The results are shown in Tables 1 and 2.

○: not much different from the sample with a residence time of 2 minutes Δ: colored yellow or red compared to the sample with a residence time of 2 minutes ×: discolored from brown to black compared with the sample with a residence time of 2 minutes

  As shown in Tables 1 and 2, the granular flame retardant composition comprising the composition of the present invention is excellent in granular formability, no dust generation at breakage, and little coloration (discoloration) at molding. Have good performance.

Claims (2)

  1 to 10 parts by weight of ethylene vinyl acetate copolymer, 0.5 to 3.0 parts by weight of acrylic resin, 0.1 to 0.1 part of fatty acid amide with respect to 100 parts by weight of brominated flame retardant and brominated flame retardant A granular flame retardant composition comprising 1.0 part by weight and 0.1 part by weight or more of a tin compound.   The granular flame retardant composition according to claim 1, further comprising 5 parts by weight or less of pigment based on 100 parts by weight of the brominated flame retardant.