JP2015089934A - Flame-retardant resin composition, molded product, wire and jacket - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition having excellent flame retardancy even if reducing an amount of use of flame retardant.SOLUTION: A flame-retardant resin composition comprises thermoplastic resin (A), polytetrafluoroethylene (B) and flame retardant (C), with the flame retardant (C) being at least one selected from the group consisting of zinc stannate and zinc borate.

Description

The present invention relates to a flame retardant resin composition, a molded article, an electric wire, and a jacket.

The flame retardant resin composition has been conventionally used in applications requiring flame retardancy, homes, offices, factories, and the like. In thermoplastic resin molded products, for example, electric appliances and OA equipment, many of the thermoplastic resins are flammable. Therefore, a device for improving the flame retardancy of the resin molded products is required. In addition, the resin itself may be flame retardant, such as a self-extinguishing polyvinyl chloride (PVC) resin, and depending on the application, a flammable plasticizer may be added. Flame resistance may not be sufficient. For this reason, it is common to add a flame retardant to a thermoplastic resin.

Patent Document 1 discloses a coating material made of a polyvinyl chloride composition in which 0.5 to 5 parts by weight of polytetrafluoroethylene powder is added to 100 parts by weight of polyvinyl chloride. The weight average molecular weight of the polytetrafluoroethylene powder is in the range of 10,000 to 100,000, and it is described that polytetrafluoroethylene powder having a low molecular weight is used. In the examples, 10 parts by weight of antimony trioxide is further added to 100 parts by weight of polyvinyl chloride.

Antimony trioxide is widely used as a flame retardant for thermoplastic resins such as PVC. However, since antimony trioxide is a rare metal compound and its country of origin is limited, there are concerns that it may become difficult to obtain or increase in price due to changes in social conditions. In addition, since antimony trioxide has a large specific gravity, it tends to cause poor blending and poor dispersion as the amount added increases, and the quality tends to vary. There is also a problem that it is likely to occur. Furthermore, reduction of the amount of antimony trioxide used and antimony free are also demanded from the problem of fuming, the influence on the environment, and troublesome handling.

Under such circumstances, the use of a flame retardant other than antimony trioxide has also been studied. Patent Document 2 discloses that 100 parts by weight of a vinyl chloride polymer, 1 to 20 parts by weight of zinc hydroxystannate and zinc borate. A flame-retardant low-smoke vinyl chloride resin composition characterized by containing 5 to 30 parts by weight is described.

Patent Document 3 discloses a flame-retardant soft vinyl chloride compound comprising 100 parts by weight of a vinyl chloride resin, 40 to 60 parts by weight of a plasticizer, 3 to 10 parts by weight of a stabilizer, and 20 to 100 parts by weight of a flame retardant. A low smoke and low toxicity flame retardant vinyl chloride compound characterized in that the flame retardant contains 2 to 10 parts by weight of zinc stannate is described.

JP-A-6-313147 Japanese Patent Laid-Open No. 11-80474 Japanese Patent Laid-Open No. 7-278386

However, in the inventions described in Patent Documents 2 and 3, since the amount of the flame retardant added is large, there is a problem that the molten resin flows down and drops at the time of combustion, affects physical properties, and costs increase. It is necessary to reduce the amount used.

This invention is made | formed in view of the said present condition, and even if it reduces the usage-amount of a flame retardant, it aims at providing the flame retardant resin composition which is excellent in a flame retardance.

In the resin composition containing a thermoplastic resin, the present inventor has excellent flame retardancy even if the amount of the flame retardant used is reduced by using a specific flame retardant together with polytetrafluoroethylene. We found what could be achieved and reached the present invention.

That is, the present invention contains a thermoplastic resin (A), polytetrafluoroethylene (B) and a flame retardant (C), and the flame retardant (C) is selected from the group consisting of zinc stannate and zinc borate. It is a flame retardant resin composition characterized by being at least one kind.

In the flame-retardant resin composition of the present invention, the polytetrafluoroethylene (B) is 0.01 to 5 parts by weight and the flame retardant (C) is 100 parts by weight of the thermoplastic resin (A). It is preferable that it is 0.001-20 weight part.

It is preferable that the flame retardant resin composition of the present invention does not substantially contain antimony trioxide.

The thermoplastic resin (A) is preferably at least one resin selected from the group consisting of polyvinyl chloride resins, polyolefin resins, nylon resins and polyester resins.

The flame retardant resin composition of the present invention preferably contains 30 to 70 parts by weight of the plasticizer (D) with respect to 100 parts by weight of the thermoplastic resin (A).

The thermoplastic resin (A) is preferably a polyvinyl chloride resin.

The flame retardant (C) is preferably 5 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A).

This invention is also a molded article, an electric wire, or a jacket obtained by shape | molding the said flame-retardant resin composition.

By having the said structure, the flame-retardant resin composition of this invention has the outstanding flame retardance even if it reduces the usage-amount of a flame retardant. The flame retardant resin composition of the present invention is also excellent in shape retention and mechanical properties.

The flame retardant resin composition of the present invention contains a thermoplastic resin (A).

The thermoplastic resin (A) is not particularly limited, but a polyolefin resin (polyethylene resin, polypropylene resin, polymethylpentene resin, etc.), polyvinyl chloride resin, polystyrene resin (polystyrene, AS, ABS, etc.) ), Polycarbonate (PC) resins (PC, PC / ABS and other PC alloy resins), polyamide resins (nylon, semi-aromatic polyamide, etc.), polyester resins (polybutylene terephthalate, polyethylene terephthalate, etc.), acrylic Resin (polymethyl methacrylate, polyacrylonitrile, etc.), polyacetal, polyether ether ketone, modified polyphenylene ether, polyarylene sulfide resin, polysulfone resin, and other various polymer alloys.
Since the effect of improving flame retardancy due to the addition of PTFE (B) is remarkably exhibited, the thermoplastic resin (A) includes a polyvinyl chloride resin, a polyolefin resin (particularly, a polyethylene resin or a polypropylene resin). Resin), a nylon resin, a polyester resin, and a polycarbonate resin, and is preferably at least one resin selected from the group consisting of polycarbonate resins. More preferably, it is at least one resin selected from the group consisting of polyvinyl chloride resins, polyolefin resins, nylon resins and polyester resins, and more preferably from polyolefin resins and polyvinyl chloride resins. It is at least one resin selected from the group consisting of, and particularly preferred is a polyvinyl chloride resin.
Particularly in the case of polyvinyl chloride, the flame retardant usually used is antimony trioxide, which is a deleterious substance. Therefore, it is preferable in terms of handling and environment that it can be reduced.

The polyvinyl chloride resin may be a vinyl chloride homopolymer or a copolymer composed of vinyl chloride and another comonomer.
Examples of the other comonomer include α-olefins such as ethylene and propylene; vinyl compounds such as vinyl acetate, acrylate esters, alkyl vinyl ethers, vinyl bromide, vinyl fluoride, styrene, and acrylonitrile; vinylidene chloride and the like. And vinylidene compounds.
The polyvinyl chloride resin preferably has a degree of polymerization of 400 to 3000, and more preferably 800 to 1700. When the degree of polymerization is in the above range, the flame retardant resin composition of the present invention is more excellent in flexibility.

The flame retardant resin composition of the present invention contains polytetrafluoroethylene (hereinafter also referred to as “PTFE”) (B). The content of PTFE (B) is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). If the PTFE (B) is too small, the desired flame retardancy cannot be obtained. If there is too much PTFE (B), there is a risk of poor PTFE dispersion. The lower limit of the content of PTFE (B) is more preferably 0.05 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), still more preferably 0.1 parts by weight, Part by weight is particularly preferred. The upper limit of the content of PTFE (B) is more preferably 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), still more preferably 1 part by weight, and 0.7 parts by weight. It is particularly preferred.

PTFE (B) preferably has a standard specific gravity (SSG) of 2.130 to 2.230. By using PTFE having SSG in the above range, the amount of the flame retardant (C) described later can be further reduced. When standard specific gravity exceeds 2.230, there exists a possibility that a flame retardance may be inferior.
The standard specific gravity (SSG) of PTFE (B) is more preferably 2.150-2.220. If the standard specific gravity is too large, the flame retardancy may be inferior or the dispersibility to the resin may be inferior. If it is too small, the flame retardancy may not be sufficiently exhibited.
SSG is a value obtained by a method based on ASTM D-4895-89. The SSG cannot be measured if the molecular weight of PTFE is too small. For example, low molecular weight PTFE having a weight average molecular weight of 100,000 or less cannot measure SSG.

PTFE (B) has non-melt processability and may be a tetrafluoroethylene (TFE) homopolymer, or a TFE unit based on TFE and a monomer other than TFE (hereinafter referred to as “modified monomer”). And a modified monomer unit based on the above).
In the modified PTFE, the modified monomer unit is preferably 0.001 to 1.0% by weight of the total monomer units. More preferably, it is 0.01 to 0.50% by weight. More preferably, it is 0.02 to 0.30% by weight.

The modifying monomer is not particularly limited as long as it can be copolymerized with TFE. For example, perfluoroolefin such as hexafluoropropylene [HFP]; chlorofluoroolefin such as chlorotrifluoroethylene [CTFE]; Examples thereof include hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; fluoroalkyl vinyl ether; fluoroalkylethylene; ethylene; fluorine-containing vinyl ether having a nitrile group. Moreover, the modified | denatured monomer to be used may be 1 type, and multiple types may be sufficient as it.

（式中、ｍは、０又は１〜４の整数を表す。）で表される基であるもの、Ｒｆ^１が下記式：

（式中、ｎは、１〜４の整数を表す。）で表される基であるもの等が挙げられる。
上記フルオロアルキルエチレンとしては特に限定されず、（パーフルオロアルキル）エチレンが好ましく、例えば、（パーフルオロブチル）エチレン（ＰＦＢＥ）、（パーフルオロヘキシル）エチレン等が挙げられる。 It does not specifically limit as said fluoroalkyl vinyl ether, For example, following General formula (1)
CF ₂ = CF-ORf ¹ (1)
(Wherein Rf ¹ represents a perfluoro organic group), and the like. In the present specification, the “perfluoro organic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoro organic group may have ether oxygen.
Examples of the fluoroalkyl vinyl ethers such as, in the above general formula (1), Rf ¹ is mentioned fluoromonomer is representative of the perfluoroalkyl group having 1 to 10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.
Examples of the perfluoroalkyl group in the fluoroalkyl vinyl ether include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Purpleo (propyl vinyl ether) [PPVE], in which the fluoroalkyl group is a perfluoropropyl group, is preferred.
Examples of the fluoroalkyl vinyl ether, further, in the above general formula (1), intended Rf ¹ is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, Rf ¹ is represented by the following formula:

(Wherein m represents an integer of 0 or 1 to 4), Rf ¹ is a group represented by the following formula:

(In the formula, n represents an integer of 1 to 4).
The fluoroalkylethylene is not particularly limited, and (perfluoroalkyl) ethylene is preferable, and examples thereof include (perfluorobutyl) ethylene (PFBE) and (perfluorohexyl) ethylene.

PTFE (B) preferably has an apparent density of 0.2 to 1.0 g / ml. More preferably, it is 0.25 to 0.95 g / ml. If the apparent density is too small, the handleability of the powder may be lowered, and if it is too large, the dispersibility for the resin may be deteriorated. The apparent density is a value measured according to JIS K6892.

PTFE (B) preferably has an average particle diameter of 1 to 1000 μm. More preferably, it is 100-700 micrometers. If the average particle size is too small, the proportion of the fine powder increases, which may cause problems such as fluttering and adhesion, and if it is too large, the dispersibility to the resin may be inferior. The average particle diameter is a value measured according to JIS K6891.

PTFE (B) may have a core-shell structure in addition to a single component resin.
The core-shell structure is a conventionally known structure, and is a structure of primary particles in an aqueous dispersion that can be produced by the method described in US Pat. No. 6,841,594. For example, first, tetrafluoroethylene [TFE] and optionally modified monomers are polymerized to produce a core portion (TFE homopolymer or modified PTFE), and then TFE and optionally modified monomers are polymerized to form a shell portion. It can be obtained by producing (TFE homopolymer or modified PTFE).

As PTFE (B) having the above core-shell structure, a monomer composition (TFE and, if necessary, a modified monomer) for producing a core part, and a monomer composition (TFE, and the like) for producing a shell part Examples of emulsions that can be obtained by emulsion polymerization of a modified monomer) if necessary. Emulsion polymerization can be performed by a conventionally known method. As said modified monomer, the thing similar to the modified monomer mentioned above can be used.

As PTFE (B) which has the said core-shell structure, both a core part and a shell part may consist of polytetrafluoroethylene (TFE homopolymer or modified PTFE), and a shell part consists of resin other than PTFE. It may be.
Examples of resins other than PTFE include polystyrene and poly (α-alkylstyrene) (for example, poly-α-methylstyrene, poly-α-ethylstyrene, poly-α-propylstyrene, poly-α-butylstyrene). , Poly-p-methylstyrene, halogenated polystyrene, acrylic polymer (eg, polyacrylonitrile, polymethacrylonitrile, etc.), poly (alkyl acrylate) (eg, poly (methyl acrylate), poly (ethyl acrylate), poly ( Propyl acrylate), poly (butyl acrylate), etc.), poly (alkyl methacrylate) (eg, poly (methyl methacrylate), poly (ethyl methacrylate), poly (propyl methacrylate), poly (butyl methacrylate), etc.), polybutadiene, vinyl Examples thereof include poly (vinyl acetate), poly (vinyl chloride), poly (vinylidene chloride), poly (vinylidene fluoride), poly (vinyl alcohol), and the like, and mixtures thereof.
The shell portion may be a copolymer, such as styrene, alkyl acrylate, alkyl methacrylate, or vinyl chloride, and another monomer such as acrylonitrile, methacrylonitrile, alkyl methacrylate, alkyl acrylate, and the like. And graft polymers such as polybutadiene, polychloroprene or styrene-butadiene copolymers such as acrylonitrile-butadiene copolymer rubber, alkyl acrylate rubber, styrene-butadiene rubber, EPDM rubber or silicone rubber. be able to.
When the shell part of PTFE (B) consists of resin other than PTFE, it is preferable that a core part is 0.1-80 mass%, and 1-70 mass% is more preferable.

In the flame-retardant resin composition of the present invention, the resin components are preferably only the thermoplastic resin (A) and PTFE (B).

The flame retardant resin composition of the present invention contains a flame retardant (C). The flame retardant (C) is at least one selected from the group consisting of zinc stannate and zinc borate. Zinc stannate is a compound represented by ZnSnO ₃ , and zinc borate is a compound represented by 2ZnO · 3B ₂ O ₃ · 3.5H ₂ O.

It is preferable that content of a flame retardant (C) is 0.001-20 weight part with respect to 100 weight part of thermoplastic resins (A). If the amount of the flame retardant (C) is too small, the flame retardant effect tends to be insufficient. If the amount is too large, it is not economical and the mechanical properties of the resin composition tend to be lowered. The lower limit of the content of the flame retardant (C) is more preferably 0.5 parts by weight, still more preferably 0.6 parts by weight, with respect to 100 parts by weight of the thermoplastic resin (A). 8 parts by weight is particularly preferred. The upper limit of the content of the flame retardant (C) is preferably 10 parts by weight, more preferably 7 parts by weight, and more preferably 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). Further preferred.
Moreover, since the flame retardant resin composition of the present invention contains PTFE (B), excellent flame retardancy can be obtained even if the amount of the flame retardant (C) is reduced. For example, even if it is 5 parts by weight or less and further 4 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A), excellent flame retardancy is obtained.
Moreover, when there is little addition amount of a flame retardant (C), it also has the effect that the amount of smoke generation can be reduced. The effect that the amount of smoke generation can be reduced is more conspicuous with the addition amount of less than 4 parts by weight, further 2 parts by weight or less, and particularly less than 2 parts by weight.

It is preferable that the flame retardant resin composition of the present invention does not substantially contain antimony trioxide. The flame retardant resin composition of the present invention contains at least one selected from the group consisting of zinc stannate and zinc borate as the flame retardant (C), and thus has been conventionally used as a flame retardant. Even if it does not contain antimony, it exhibits excellent flame retardancy.
“Containing substantially no antimony trioxide” means that the content of antimony trioxide is 1 part by weight or less with respect to 100 parts by weight of the thermoplastic resin (A). More preferably 0.5 parts by weight or less, still more preferably 0.3 parts by weight or less, particularly preferably 0.0001 parts by weight or less, most preferably 0 parts by weight, that is, containing antimony trioxide at all. It is not.

The flame retardant resin composition of the present invention may contain a plasticizer (D). Conventionally, when processing a thermoplastic resin such as a polyvinyl chloride resin, a plasticizer has been added in order to improve processability and flexibility, but this reduces the flame retardancy of the resin. However, the flame retardant resin composition of the present invention has excellent flame retardancy even if it contains a plasticizer.

As a plasticizer (D), the compound generally used as a plasticizer is employable. For example, phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl lauryl phthalate, fatty acid esters such as tributyl citrate, dioctyl adipate, dioctyl sebacate, tricresyl phosphate, trioctyl phosphate, etc. And phosphoric acid esters, alkyl epoxy stearates, epoxy compounds such as epoxidized soybean oil, and chlorinated paraffins. Among these, phthalic acid esters, fatty acid esters, and epoxy compounds that are flammable are preferable. The flame retardant resin composition of the present invention has excellent flame retardancy even if it contains such a flame retardant plasticizer.

The content of the plasticizer (D) is preferably 30 to 70 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). By setting it as 30 weight part or more, the flame-retardant resin composition which is further excellent in a softness | flexibility is obtained. Moreover, when it exceeds 70 weight part, there exists a possibility that the mechanical physical property of a thermoplastic resin (A) may fall. The lower limit of the content of the plasticizer (D) is more preferably 32 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), still more preferably 35 parts by weight, and 40 parts by weight. Is particularly preferred. The upper limit of the content of the plasticizer (D) is preferably 68 parts by weight, more preferably 65 parts by weight, and 60 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). Further preferred.

The total content of the thermoplastic resin (A), PTFE (B), flame retardant (C) and plasticizer (D) in the flame retardant resin composition of the present invention is 100 parts by weight of the flame retardant resin composition. It is preferable that it is 50-100 weight part at the point which the effect of this invention is exhibited more notably. The lower limit of the total content is more preferably 60 parts by weight and even more preferably 70 parts by weight with respect to 100 parts by weight of the flame retardant resin composition. The upper limit of the total content is more preferably 95 parts by weight with respect to 100 parts by weight of the flame retardant resin composition, and still more preferably 90 parts by weight.

In addition to the thermoplastic resin (A), PTFE (B), flame retardant (C) and plasticizer (D), the flame retardant resin composition of the present invention includes known additives such as calcium carbonate and silica. Fillers such as mica, talc, clay, bentonite, graphite, titanium oxide, alumina, molybdenum disulfide, barium sulfate, hollow glass, wood powder;
Thermal stabilizers such as barium stearate, zinc stearate, calcium stearate, dialkyltin laurate, dialkyltin maleate, dialkyltin mercaptite; UV absorbers, antioxidants, antistatic agents, light stabilizers, pigments, Lubricants, molding aids, glass fibers, carbon fibers and the like can be added as necessary.
What is necessary is just to use the said additive in the range which does not prevent the effect of this invention.

The flame retardant resin composition of the present invention can be produced by blending the above-described components by a known method, but the blending order, blending in a powder state or blending in a dispersion state, or blending machine The types and combinations thereof may be according to known manufacturing methods.
For example, the thermoplastic resin (A), PTFE (B), flame retardant (C) and plasticizer (D), and various additives as required can be produced by mixing them into a mixer.
As other mixing methods, single and twin screw extruders, open rolls, kneaders, Banbury mixers, and the like can also be used.

The flame-retardant resin composition of the present invention can be molded by any known method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc. Can be processed and used.
Molded products include injection-molded products, extrusion-molded products, blow-molded products, various films such as uniaxial stretching and biaxial stretching, sheets, electric wires (coating materials for electric wires), jackets, unstretched yarns, drawn yarns, and super-stretched products. It can be used as various fibers such as yarn.

The flame-retardant resin composition of the present invention can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, daily life goods and sanitary goods.
Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Car exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings and internal parts, Printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording medium (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internal parts And electrical / electronic parts such as facsimile housings and internal parts, parabolic antennas, and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts such as electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Transformer members, coil bobbins, electric wires, cables, jackets and other electrical and electronic parts, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, hot water Scarecrow parts, roof panels, heat insulating walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building components, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other fishery related parts, vegetation nets, Vegetation mats, grass protection bags, grass protection nets, curing sheets, slope protection sheets, fly ash press sheets, drain sheets, water retention sheets, sludge / sludge dewatering bags, concrete formwork and other civil engineering related members, gears, screws, springs , Bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, cable ties, clips, fans, guts, pipes, cleaning jigs, motor parts, mechanical parts such as microscopes, binoculars, cameras, watches, Multi film, tunnel film, bird protection sheet, vegetation protection nonwoven fabric, seedling pot, vegetation pile, seed string tape, germination sheet, house lining sheet Agricultural products such as agricultural bi-fasteners, slow-release fertilizers, root-proof sheets, garden nets, insect nets, juvenile tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage prevention nets, incentive strings, windbreak nets, etc. Sanitary products such as materials, disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes, non-woven fabrics for medical use (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressing materials, scratch tape dressings, labeling material Cloth, surgical sutures, fracture reinforcement, medical supplies such as medical films, toilet seats, calendars, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches Containers, tableware such as containers, tanks, baskets, hot fill containers, containers for microwave ovens, cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverages Bottles, cups, candy packaging, shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, electrical / electronic components Containers and packaging such as wrapping films, natural fiber composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, etc., curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki Hot melt binders such as interior goods, carrier tapes, print laminates, heat sensitive stencil printing films, release films, porous films, container bags, credit cards, cash cards, ID cards, IC cards, paper, leather, non-woven fabrics, etc. , Magnetic material, zinc sulfide, electrode Powder binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage ditch filter, Useful as clear file, coating agent, adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc. .

The flame-retardant resin composition of the present invention is particularly useful as a material for electric wires and jackets because it is excellent in flame retardancy and is flexible and excellent in mechanical strength.
The electric wire may be made of, for example, a metal core wire and a coating material obtained by molding the flame retardant resin composition on the core wire, or the metal core wire and the core wire are covered. And a jacket obtained by molding the flame retardant resin composition.
The jacket is a tube-shaped molded body that houses a core wire and a covering material thereof.

Since the electric wire and jacket of this invention are obtained by shape | molding the said flame-retardant resin composition, they have the outstanding flame retardance. Moreover, it is excellent in mechanical strength.

As a method for molding the flame retardant resin composition, a known molding method can be employed, and for example, extrusion molding is preferably used. The extrusion temperature may be appropriately set depending on the type of the thermoplastic resin (A) to be used, but is usually 120 to 400 ° C, and preferably 150 to 250 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

The compounding agents described in the following Examples, Comparative Examples and Tables 1 and 2 are as follows.
PVC (manufactured by Kaneka Corporation, polyvinyl chloride resin, degree of polymerization 1300)
Plasticizer (manufactured by J Plus Co., Ltd., dioctyl phthalate (DOP))
Bulking agent (filler) (manufactured by Shiraishi Kogyo Co., Ltd., heavy calcium carbonate)
Thermal stabilizer (manufactured by NI Chemtech Co., Ltd., ND-876)
Zinc stannate (flame retardant, manufactured by Mizusawa Chemical Co., Ltd.)
Zinc borate (flame retardant, manufactured by Mizusawa Chemical Co., Ltd.)
PTFE (Anti-drip agent, manufactured by Daikin Industries, Ltd., SSG = 2.175)

Example 1
100 parts by weight of polyvinyl chloride resin, 40 parts by weight of dioctyl phthalate, 25 parts by weight of heavy calcium carbonate, and 5 parts by weight of heat stabilizer are put in a high-speed mixer (100 L), respectively. It mixed until it heated up to 100 degreeC.
1 part by weight of zinc stannate and 0.5 part by weight of PTFE were added to this mixture, and tumbling mixed in the bag. The obtained mixture was kneaded at 150 ° C. for 10 minutes using a biaxial open roll (manufactured by Osaka Roll Machinery Co., Ltd., 8φTR) to form a sheet.
The obtained sheet was formed into a 150 mm × 150 mm × 1 mm sheet using a heat press, and a UL-94V test piece (125 mm × 13 mm × 1 mm) and a tensile test piece (ASTM D638 V) were formed from this sheet. 5 dumbbells) were cut out.
The obtained test piece for UL-94V was evaluated for combustibility according to the UL-94V test method using a combustion test apparatus (No. 252-UL94 Flammability Tester, manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The results are shown in Table 1.
The shape retention effect was evaluated visually during the UL-94V test. The evaluation results are ◯ when the combustion carbonized layer is held in a state of covering the unburned part, Δ when the crack is generated in the combustion carbonized layer and the molten resin protrudes outside the carbonized layer, and the drip of the molten resin is The case where it occurred was marked with x. The results are shown in Table 1.
Moreover, the tensile test and evaluation were performed according to ASTMD638 using the obtained test piece for a tensile test using the autograph (Shimadzu Corp. make, AGS-J 5kN). The results are shown in Table 1.

Examples 2-8 and Comparative Examples 1-4
A resin composition was prepared in the same manner as in Example 1 except that the compounding agent and the compounding amount were changed as shown in Table 1 or 2, and similarly UL-94 combustion test evaluation, evaluation of shape retention effect, and tension. Test evaluation was performed.
The results are shown in Table 1 or 2.

Since the flame-retardant resin composition of the present invention can obtain a molded article having excellent flame retardancy, it can be used in various applications where flame retardancy is required. Among them, it is particularly suitable as a material for electric wires and jackets.

Claims (10)

Containing thermoplastic resin (A), polytetrafluoroethylene (B) and flame retardant (C),
The flame retardant resin composition is characterized in that the flame retardant (C) is at least one selected from the group consisting of zinc stannate and zinc borate. The polytetrafluoroethylene (B) is 0.01 to 5 parts by weight and the flame retardant (C) is 0.001 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). Flame retardant resin composition. The flame-retardant resin composition according to claim 1 or 2, substantially free of antimony trioxide. The flame retardant according to claim 1, 2 or 3, wherein the thermoplastic resin (A) is at least one resin selected from the group consisting of polyvinyl chloride resin, polyolefin resin, nylon resin and polyester resin. Resin composition. The flame-retardant resin composition according to claim 1, 2, 3 or 4, comprising 30 to 70 parts by weight of the plasticizer (D) with respect to 100 parts by weight of the thermoplastic resin (A). The flame retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyvinyl chloride resin. The flame retardant resin composition according to claim 1, 2, 3, 4, 5 or 6, wherein the flame retardant (C) is 5 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A). A molded article obtained by molding the flame retardant resin composition according to claim 1, 2, 3, 4, 5, 6 or 7. The electric wire obtained by shape | molding the flame-retardant resin composition of Claim 1, 2, 3, 4, 5, 6 or 7. The jacket obtained by shape | molding the flame-retardant resin composition of Claim 1, 2, 3, 4, 5, 6 or 7.