KR20120090005A - Insulating tube and heat shrinkable tube - Google Patents

Abstract

Provided are non-halogen-based insulated tubes and heat-shrinkable tubes that are compatible with mechanical properties, heat resistance and flame retardancy, and have flame retardancy that can pass the vertical combustion test even if the tube inner diameter is small.
The present invention is an insulated tube obtained by molding a flame-retardant resin composition containing a thermoplastic resin, a polyfunctional monomer, and an organophosphorus flame retardant into a tubular shape, wherein the thermoplastic resin comprises a resin having a carbon-carbon unsaturated bond or a resin having a carbonyl group in its entirety. The organic phosphorus flame retardant is selected from the group consisting of a metal phosphinate salt, a phosphate melamine compound, an ammonium phosphate compound, and a polyphosphazene compound obtained by ring-opening polymerization of cyclophosphazene. It is 1 or more types, content of the said organic phosphorus flame retardant is 5 mass parts-100 mass parts with respect to 100 mass parts of said thermoplastic resins, and content of the said polyfunctional monomer is 1 mass part-20 mass parts with respect to 100 mass parts of said thermoplastic resins. It is about the insulated tube.

Description

Insulation Tube & Heat Shrink Tubing {INSULATING TUBE AND HEAT SHRINKABLE TUBE}

The present invention relates to an insulating tube and a heat shrink tube composed of non-halogen flame retardant materials and having excellent flame retardancy and mechanical properties.

Insulation tubes or heat-shrink tubes used in the field of electronic devices or automobiles require excellent mechanical properties. For example, in the US UL standard widely used in the field of electronic devices, the initial maximum tensile strength is required to be 10.4 MPa or more for a tube or heat-shrink tube insulated from plastic such as polyethylene.

On the other hand, insulated tubes and heat-shrinkable tubes have applications in which high flame retardancy is required. In general, flame retardancy is defined in the automotive field, such as the horizontal flame retardancy test and the gradient combustion test, and in the electronics field, such as the American UL standard vertical combustion test (VW-1 test). Conventionally, as a material which satisfies flame retardancy and mechanical properties, a halogen such as a bromine flame retardant, a chlorine flame retardant, or the like in a soft polyvinyl chloride composition or a polyolefin resin such as polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, etc. The flame retardant resin composition which mixed the system flame retardant was used. However, a flame-retardant material containing such a halogen element is not preferable from the environmental point of view because it generates combustion gas harmful to the human body such as hydrogen halide gas upon incineration.

From these circumstances, the material which mix | blended metal hydroxide type flame retardants, such as aluminum hydroxide and magnesium hydroxide, with polyolefin resin, such as polyethylene, an ethylene- ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer, is put into practical use (for example, patent document 1). . However, in the metal hydroxide flame retardant, it is necessary to add a large amount of metal hydroxide flame retardant in order to obtain flame retardancy enough to pass the UL standard vertical combustion test VW-1, and as a result, the mechanical properties are deteriorated. It was difficult to attain both compatibility.

In order to improve flame retardancy, the material which combined metal hydroxide and red phosphorus is also known. For example, Patent Document 2 describes a shrink tube using a resin composition in which a metal hydroxide, red phosphorus, and molybdenum compound are added to a polyolefin resin.

[Patent Document 1] Japanese Patent Application Laid-Open No. 7-145288 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-72776

In patent document 2, by using red phosphorus together, the addition amount of a metal hydroxide can be reduced, and both flame retardance and a mechanical characteristic become compatible. However, red phosphorus is undesirable from an environmental point of view because toxic phosphines are generated during combustion. There is also a problem that the tube is colored by red phosphorus.

Organic phosphorus flame retardants such as phosphate esters are also known as phosphorus flame retardants, but the flame retardant effect thereof is not sufficient, and satisfactory flame retardancy is not obtained unless added in large quantities. Since phosphate ester has low compatibility with polyolefin resin, so-called bleedout which the phosphate ester rises on the surface of a resin composition will generate | occur | produce when it adds in large quantities.

Flexible Noryl sold by SABIC Innovative Plastics Japan Joint Company (former Nippon GE Plastics) uses a blend of polyphenylene ether and styrene resin or thermoplastic styrene elastomer as base polymer, A phosphorus flame retardant (phosphate ester) is mixed. Since polyphenylene ether is more flame retardant than polyolefin resin, it is possible to reduce the amount of organophosphorus flame retardant added, and in some grades, it is used as an electric wire coating material, but since this composition cannot irradiate crosslinking, it is heat resistant. When this is not enough, when used as a heat shrink tube, a shape cannot be maintained at the time of diameter expansion process or heat shrink characteristic is inadequate.

MEANS TO SOLVE THE PROBLEM The present inventors used what mixed polyphenylene ether, a thermoplastic styrene elastomer, and an olefin resin as a base polymer, and added the organophosphorus flame retardant, a nitrogen flame retardant, and a polyfunctional monomer, and the tube using the same. And a heat shrink tube were developed and filed as Japanese Patent Application No. 2008-100984. This tube is compatible with flame retardancy and mechanical properties, and is excellent in heat resistance and heat deformation resistance by crosslinking the resin.

In general, in an insulating tube and a heat shrink tube, the smaller the diameter (tube inner diameter) becomes, the more severe the condition of flame retardancy is. Also in the tube using the above-mentioned resin composition, when the tube inner diameter was 5 mm or more, it had flame retardance which passed the vertical combustion test, but it turned out that the pass rate of a vertical combustion test becomes low when a tube inner diameter becomes small.

Accordingly, an object of the present invention is to provide a non-halogen-based insulated tube and a heat-shrinkable tube having both flame-retardant properties that are compatible with mechanical properties, heat resistance and flame retardancy, and which can pass the vertical combustion test even if the tube inner diameter is small.

The invention according to claim 1 is an insulating tube obtained by molding a flame-retardant resin composition containing a thermoplastic resin, a polyfunctional monomer, and an organophosphorus flame retardant into a tubular shape, wherein the thermoplastic resin has a resin having a carbon-carbon unsaturated bond or a resin having a carbonyl group. 5 mass% or more with respect to the whole thermoplastic resin, and the said organic phosphorus flame retardant consists of a polyphosphazene compound obtained by ring-opening-polymerizing a phosphinate metal salt, a melamine phosphate compound, an ammonium phosphate compound, and cyclophosphazene. It is 1 or more types chosen from the group, Content of the said phosphorus flame retardant is 5 mass parts-100 mass parts with respect to 100 mass parts of said thermoplastic resins, Content of the said polyfunctional monomer is 1 mass part with respect to 100 mass parts of said thermoplastic resins. It is an insulated tube of ˜20 parts by mass.

Among the organophosphorous flame retardants, flame retardancy can be improved by using at least one selected from the group consisting of metal phosphinates, melamine phosphate compounds, ammonium phosphate compounds, and polyphosphazene compounds obtained by ring-opening polymerization of cyclophosphazenes, The flame retardance which passes a vertical combustion test can be obtained even if a nitrogen flame retardant is not used together.

Although arbitrary things can be selected as a thermoplastic resin, since flame retardance will become inadequate only if it is a resin with low flame retardances, such as polyethylene and a polypropylene, the resin which has a carbon-carbon unsaturated bond or a carbonyl group with a high flame retardancy is a whole thermoplastic resin. It is necessary to contain 5 mass% or more of.

The thermoplastic resin is polyphenylene ether resin, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, styrene thermoplastic elastomer, polystyrene resin, nylon, thermoplastic polyamide elastic It is preferable to contain 5 mass% or more of 1 or more types chosen from the group which consists of a polymer, the polyolefin resin which has a carbon-carbon unsaturated bond, and the polyolefin resin which has a carbonyl group (claim 2). Since these resins are relatively high in flame retardancy, the flame retardancy of the insulating tube can be improved.

The thermoplastic resin is preferably composed of 5% by mass to 80% by mass of polyphenylene ether resin or polystyrene resin, 20% by mass to 95% by mass of styrene thermoplastic elastomer, and 0% by mass to 70% by mass of polyolefin resin. (Claim 3). Polyphenylene ether resin and polystyrene resin are especially excellent in flame retardancy. Styrene-based thermoplastic elastomers are excellent in flexibility and extrusion processability, and have good compatibility with polyphenylene ether resins, so that mechanical properties can be improved. Polyolefin resin is excellent in flexibility, it is possible to improve the mechanical properties and extrusion processability. By mixing these resins in a balanced manner, the mechanical properties and flame retardance of the insulating tube can be improved.

The thermoplastic resin contains 50% by mass to 100% by mass of an ethylene-αolefin copolymer having a carbonyl group, and the ethylene-αolefin copolymer having a carbonyl group has a comonomer content of 9% by mass to 46% by mass and melt flow. It is preferred if the melt flow rate is from 0.3 g / 10 min to 25 g / 10 min (claim 4). Since the ethylene- alpha olefin copolymer which has a carbonyl group is excellent in flame retardancy, and even when used alone, the balance of a characteristic can be balanced, and mixing of a resin composition becomes easy. In addition, melt flow rate (MFR) is the value measured on condition of 190 degreeC and 2.16 kg of loads based on ASTMD1238.

As a flame retardant, it is preferable to contain 3 mass parts-100 mass parts of nitrogen-type flame retardants with respect to 100 mass parts of said thermoplastic resins (claim 5). The flame retardant properties can be further improved by using the organophosphorus flame retardant and the nitrogen flame retardant in combination. As the nitrogen-based flame retardant, melamine cyanurate can be preferably used (claim 6).

It is preferable to contain phosphate ester as said organophosphorus flame retardant (claim 7). By using together an organic phosphorus flame retardant which is excellent in flame retardance, such as a phosphinate metal salt, and a phosphate ester, the flame retardance of an insulation tube further improves.

The invention according to claim 8 is the insulating tube according to any one of the above, wherein the tube inner diameter is 5 mm or less. The insulated tube described above is excellent in flame retardancy and can be applied to a product having a tube inner diameter of 5 mm or less. In the case of a heat shrinkable tube, the inner diameter of the tube is the inner diameter after shrinkage.

The invention according to claim 9 is the insulating tube according to any one of the above, which passes the vertical combustion test (VW-1). Moreover, invention of Claim 10 is the insulation tube in any one of said above whose tensile strength in room temperature is 10 Mpa or more.

Invention of Claim 11 irradiates ionizing radiation to the insulating tube in any one of said, expands a diameter under heating, and is made by cooling and fixing. This heat shrink tube has excellent mechanical properties, heat resistance and flame retardancy.

According to the present invention, it is possible to obtain a non-halogen-based insulated tube and a heat-shrinkable tube which can achieve both mechanical properties, heat resistance and flame retardancy, and which can pass the vertical combustion test even if the tube inner diameter is reduced.

(Hand over flame retardant)

The various materials which comprise the insulation tube of this invention are demonstrated. The organophosphorous flame retardant includes at least one member selected from the group consisting of metal phosphinates, melamine phosphate compounds, ammonium phosphate compounds, and polyphosphazene compounds obtained by ring-opening polymerization of cyclophosphazene as essential components. Among these, metal phosphinate salts are preferable because of their excellent flame retardancy.

Phosphate metal salt is a compound represented by following formula (I). In addition, in said formula, R <1>, R <2> is a C1-C6 alkyl group or a C12 or less aryl group, respectively, M is calcium, aluminum, or zinc, and when M = aluminum, it is m = 3 and others In this case m = 2.

Examples of the phosphinic acid metal salt include aluminum salts of organic phosphinic acids such as EXOLIT OP1230, EXOLIT OP1240, EXOLIT OP930, and EXOLIT OP935 manufactured by Clariant Co., Ltd., or blends of aluminum salts of organic phosphinic acids such as EXOLIT OP1312 and melamine polyphosphate. Can be used.

As the melamine phosphate compound, polyphosphoric melamine such as MELAPUR200 manufactured by Chiba Specialty Co., Ltd., polyamine melamine, melamine phosphate, melamine orthophosphate, melamine pyrophosphate or the like can be used.

As the ammonium phosphate compound, ammonium polyphosphate, polyphosphate amide, polyammonium phosphate ammonium, polycarbamic acid or the like can be used.

As a polyphosphazene compound obtained by ring-opening-polymerizing cyclophosphazene, Otsuka Chemical Co., Ltd. SPR-100, SA-100, SR-100, SRS-100, SPB-100L, etc. can be used.

Said organophosphorus flame retardant may be used independently, or may be used in combination of multiple.

Moreover, when phosphate ester is used in combination with said organophosphorus flame retardant, flame retardance can be improved further. Examples of the phosphate esters include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, cresyl 2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate, 1,3-phenylenebis (diphenylphosphate), 1,3-phenylenebis (di-2,6-xylenylphosphate), bisphenol A bis (diphenylphosphate), resorcinolbisdiphenylphosphate, Octyldiphenyl phosphate, diethylene ethyl ester phosphate, dihydroxy propylene butyl ester phosphate, ethylene disodium ester phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butyl Phenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (isopropylphenyl) diphenylphosphate, tris- (isopropylphenyl) phosphate, tris (2-ethylhexyl) foam Phosphate, tris (butoxyethyl) phosphate, trisisobutylphosphate, methylphosphonic acid, methylphosphonic acid dimethyl, methylphosphonic acid diethyl, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methyl-propylphosphonic acid , t-butylphosphonic acid, 2,3-dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, diethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenyl Phosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, alkyl phosphate esters and the like can be used.

Content of an organophosphorus flame retardant shall be 5 mass parts-100 mass parts with respect to 100 mass parts of thermoplastic resins. When less than 5 mass parts, flame retardance is inadequate, and when it exceeds 100 mass parts, mechanical property will fall. The organophosphorous flame retardant may be used by treating the surface with melamine, melamine cyanurate, fatty acid, or silane coupling agent. Moreover, you may perform the integral blend which adds a surface treating agent when mixing with a thermoplastic resin instead of surface-treating beforehand.

Arbitrary resin may be used as the thermoplastic resin, but polyphenylene ether resin, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, styrene thermoplastic elastomer, polystyrene resin, It is necessary to contain 5 mass% or more of resin which has carbon-carbon unsaturated bonds, such as nylon, a thermoplastic polyamide elastomer, and polyolefin resin which has a carbon-carbon unsaturated bond, and resin which has a carbonyl group with respect to the whole thermoplastic resin.

Polyphenylene ether is an engineering plastic obtained by oxidatively polymerizing 2, 6- xylenol synthesize | combined using methanol and a phenol as a raw material. Moreover, in order to improve the shaping | molding processability of polyphenylene ether, the material which melt-blended polystyrene, HIPS, styrene butadiene rubber, or these hydrogenated substances to polyphenylene ether is marketed as various modified polyphenylene ether resins. As polyphenylene ether resin used for this invention, any of the above-mentioned polyphenylene ether resin single body and polyphenylene ether resin which melt-blended polystyrene, HIPS, styrene butadiene rubber, or these hydrogenated substances was melted and blended. You can also use it. Moreover, what introduce | transduced carboxylic acid, such as maleic anhydride, can also be mixed suitably and used.

Examples of the polystyrene resin include polystyrene polymerized with styrene, HIPS obtained by dispersing rubber, and the like in which maleic anhydride, an epoxy group, and oxazoline are introduced.

The styrene thermoplastic elastomer is a block copolymer of a polystyrene block and a rubber component block. In the present invention, the styrene-based thermoplastic elastomer is a styrene-ethylene butylene-styrene copolymer, a styrene-ethylene butylene copolymer, a styrene-ethylene-butylene-olefin copolymer, a styrene-isoprene copolymer, a styrene-ethylene-isoprene A copolymer, a styrene isoprene styrene copolymer, a styrene ethylene isoprene styrene copolymer, etc. are mentioned, These hydrogenated polymers, a partially hydrogenated polymer, Furthermore, these maleic anhydride modified products or an epoxy Chemical modified polymers, such as a modified product, can be illustrated, As a styrene butadiene rubber, the copolymer of styrene and butadiene of styrene content of 30 mass%-60 mass%, this hydrogenated polymer, a partial hydrogenated polymer, etc. can be illustrated. And maleic anhydride modified products or epoxy modified products thereof, and in addition to using these alone, You may use combining several types.

Examples of the polyolefin resin include polypropylene (monopolymer, block polymer, random polymer), polypropylene thermoplastic elastomer, reactor type polypropylene thermoplastic elastomer, dynamic crosslinked polypropylene thermoplastic elastomer, polyethylene (high density polyethylene, fabric Linear low density polyethylene, low density polyethylene, ultra low density polyethylene), ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer , Ethylene-propyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene rubber, ethylene acrylic rubber, ethylene-glycidyl methacrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid copolymer Or between molecules of ethylene-acrylic acid copolymer It can be used an ionomer resin, or the like bonded between molecules with metal ions such as sodium or zinc. Moreover, what modified these resin with maleic anhydride etc., and what has an epoxy group, an amino group, and an imide group can also be used.

Among the olefin resins, the ethylene-? Olefin copolymer having a carbonyl group having a comonomer content of 9% by mass to 46% by mass and a melt flow rate of 0.3 g / 10 minutes to 25 g / 10 minutes is particularly excellent in flame retardancy and combustion. It can save time. Flame retardancy improves as the comonomer content increases, but the comonomer content is preferably 9% by mass to 46% by mass in consideration of the balance of flame retardancy and cost.

The thermoplastic polyurethane elastomer is a polymer obtained by block copolymerization of a soft segment made of a polyurethane composed of a condensation polymer of diisocyanate such as tolylene diisocyanate and short chain diol such as polyethylene glycol, and made of a bifunctional polyol or the like. to be. According to the kind of bifunctional polyol of a soft segment, polyether type, adipate type, caprolactone type, polycarbonate type, etc. using polytetramethylene glycol (PTMG) etc. can be used. Among these, it is preferable that hardness is 95 or less in JISA.

As the thermoplastic polyamide elastomer, an amorphous soft segment composed of crystalline hard segments such as 6-nylon, 6,6-nylon, 11-nylon and 12-nylon and polyoxymethylene glycol such as polytetramethylene ether glycol Block copolymers can be used.

As a polyfunctional monomer, a monoacrylate type, a diacrylate type, a triacrylate type, a monomethacrylate type, a dimethacrylate type, a trimethacrylate type, a triallyl isocyanurate type, a triallyl cyanurate The monomer which has several carbon-carbon double bond in a molecule | numerator, such as a rate system, can be used. Content of a polyfunctional monomer shall be 1 mass part-20 mass parts with respect to 100 mass parts of thermoplastic resins. If it is less than 1 mass part, a crosslinking effect will not be acquired and heat deformation resistance and heat resistance will fall. On the other hand, if it exceeds 20 parts by mass, flame retardancy deteriorates because unreacted monomers remain.

You may add antioxidant, a lubricating agent, a processing stabilizer, a coloring agent, a foaming agent, a reinforcing agent, a filler, a granule, a metal deactivator, a silane coupling agent, etc., in the range which does not impair flame retardance, heat resistance deformation, and a mechanical property. Metal hydroxides, such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide, or nitrogen-based flame retardants, such as melamine and melamine cyanurate, may be added.

In particular, when nitrogen-based flame retardants such as melamine and melamine cyanurate are used in combination, the flame retardancy is further improved, which is preferable. The content of the nitrogen-based flame retardant is 3 parts by mass to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When it is less than 3 parts by mass, the effect of improving flame retardancy is less. Moreover, when it exceeds 100 mass parts, mechanical property will fall. Since the organophosphorous flame retardant selected from the group consisting of metal phosphate salts, melamine phosphate compounds, ammonium phosphate compounds, and polyphosphazene compounds obtained by ring-opening polymerization of cyclophosphazene has a plasticizing effect, even when nitrogen-based flame retardants are used in combination Flexibility is not degraded.

The above components are mixed in predetermined amounts and mixed using known mixers such as a single screw extrusion mixer, an open roll mixer, a pressurized kneader, a Banbury mixer, a twin screw mixer, and the like. Among these, a biaxial mixer is preferable at the point of kneading | mixing property and productivity. The mixed resin composition can be molded into a tubular shape using a melt extruder, an injection molding machine or the like to obtain an insulating tube.

As the insulating tube, the extrusion molded product may be used as it is, but the mechanical properties (tensile strength, elongation, etc.), heat resistance, and heat deformation resistance can be improved by crosslinking the resin by irradiating ionizing radiation. Examples of the ionizing radiation source include accelerated electron beams, gamma rays, X-rays, α-rays, ultraviolet rays, and the like. However, acceleration electron beams are most preferable from the viewpoint of industrial use such as ease of using a source, transmission thickness of ionizing radiation, and speed of crosslinking treatment. Available.

The heat-shrink tube of this invention cools and fixes the insulation tube which irradiated the ionizing radiation, after expanding the diameter under heating. Specifically, the tube-shaped molded article irradiated with ionizing radiation is expanded to a predetermined outer diameter by a method such as introducing compressed air into the tube while heated to a temperature above the glass transition point or melting point of the base polymer, and then cooled and shaped. By fixing the heat shrink tube can be obtained. The diameter expansion is preferably about 2 to 4 times the original tube inner diameter.

Since the heat shrink tube of this invention is excellent in heat resistance, when it heats about glass transition point or melting | fusing point again, it can shrink | contract to the original shape, without melting. Accordingly, the packaged object can be tightly packaged by heat treatment at 100 ° C to 250 ° C in a state where unpackaged products such as electronic components and cables to be protected and packaged are inserted into the tube. The tube contracted by the heat shrink treatment has the same mechanical properties as the tube before the diameter expansion treatment.

Example

Next, the present invention will be described in more detail based on examples. The examples do not limit the scope of the invention. In addition, "part" in a table means a "mass part" unless there is a notice.

First, the method of measurement evaluation performed in the following example is demonstrated.

(Mechanical characteristics)

The tube was subjected to a tensile test (tensile velocity = 500 mm / min, distance between mark lines = 20 mm), and tensile strength (MPa) and tensile elongation at break (%) were measured on each of three samples, and their average values were measured. Was obtained. Tensile strength of 10.4 MPa or more and 150% of tensile elongation at break set it as the pass level.

(Heat shock test)

The tube was heated for 4 hours in a gear oven set at 250 ° C., and then taken out. If there was no change in appearance, the pass level was OK.

(Heat resistance)

After leaving a tube for 168 hours (7 days) in the gear oven set to 158 degreeC, a tension test is performed similarly to mechanical property evaluation. The tensile strength after the heat treatment was 7.3 MPa or more and the tensile elongation at break 100% or more was set as the pass level.

(Flame retardant)

The VW-1 vertical combustion test described in UL standard 224 was performed with five samples. When repeated 15 seconds of ignition for each sample 5 times, it is extinguished within 60 seconds, and the cotton wool on the bottom is not burned down by the combustion drops, and the kraft paper attached to the upper part of the sample is burned. Or not pressed was the pass. When even one point among five points of samples did not become a pass level, it was set as rejection. In addition, for some samples, the combustion time (the time from the end of ignition to the digestion) was measured.

(Heat resistance deformation)

It carried out according to JIS C3005. Into the tube, a metal rod having the same diameter as the tube inner diameter (inner diameter before the diameter expansion treatment in the case of the heat shrink tube) was inserted, and placed in a thermostat set at 140 ° C. for preheating for 1 hour. Thereafter, a jig having a diameter of 9.5 mm was pressed on the tube to carry a load of 500 g. The thickness of the tube layer after leaving for one hour in a 140 degreeC thermostat in the state which applied the load was measured, and the residual ratio with respect to the thickness before deformation was computed. If the residual rate is 50% or more, it is the pass level. In addition, when evaluating the heat shrink tube which performed diameter expansion-heat-shrink processing, after inserting a metal rod into the heat shrink tube which expanded the diameter, it evaluated using what integrated the metal and the tube by heat-shrinking the tube.

(Examples 1-7, 17-26)

Each material was mix | blended in the ratio shown in Table 1, Table 2, and 0.5 part of oleic acid amide and pentaerythritol- tetrakis [3- (3,5-di-t- butyl- 4-hydroxy] with respect to 100 parts of base polymers Phenyl) propionate] was added and kneaded with a twin screw mixer set at a die temperature of 280 ° C. The strand of the resulting kneaded product was pelletized with a pelletizer, and then the inner diameter was 0.8 mm at an extrusion temperature of 230 ° C. using a melt extruder (45 mmΦ, L / D ratio = 24, compression ratio 2.5, full flight type). And tubular molded articles having a thickness of 0.25 mm were obtained. The tubular molded article was irradiated with 250 kGy of an electron beam having an acceleration voltage of 2 MeV, and a series of evaluations were performed on the obtained insulating tube.

(Examples 8-16, 27)

Using the resin composition of the mixing | blending shown in Table 3-Table 7, the insulating tube irradiated with the electron beam was produced like the above. In addition, the inner diameter and thickness of the tube were described in the table. The insulation tube is left to stand in a thermostat set at 160 ° C. for 3 minutes to preheat, and then compressed air is introduced into the tube to expand the diameter until it reaches an internal diameter of 2.5 times the extruded inner diameter. After the heat shrink tube was produced, a series of evaluations were performed. The above result is shown to Tables 1-7.

(* 1) Asahi Kasei Chemicals Corporation gyrone WH100

(* 2) Asahi Kasei Chemicals Co., Ltd. product theory X9102

(* 3) PS Japan Corporation HH102

(* 4) Styrene-ethylene butylene-styrene copolymer: Asahi Kasei Chemicals Co., Ltd. Tuftec H1041 (30 wt% of styrene)

(* 5) Styrene, ethylene, butylene, olefin crystal block polymer: JSR Corporation Dynaron 4600P (20 wt% styrene)

(* 6) Ethylene-ethyl acrylate: Nippon Polyethylene Co., Ltd. make REXPEARL A1150 (15% EA)

(* 7) Ultra low density polyethylene: Doug Chemical Nippon Engage 8150 (MFR=0.5@190°C×2.16 kg, density 0.868 g? Cm3)

(* 8) Phosphate metal salt: Exolit OP930 manufactured by Clariant

(* 9) Melamine polyphosphate: Melapur200 manufactured by Chiba Specialty Co., Ltd.

(* 10) Polyphosphazene: Otsuka Kagaku Co., Ltd. SPS-100

(* 11) Condensation phosphate ester: Daihachi Kagaku Kogyo Co., Ltd. product PX-200 (9.0% of phosphorus)

(* 12) Trimethylolpropane trimethacrylate: NK ester TMPT manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.

(* 13) Styrene-ethylene butylene-styrene copolymer: Asahi Kasei Chemicals Toughtech H1041 (styrene amount 30 wt%)

(* 14) Random Copolymer Thermoplastic Polyester Elastomer: GriltexD 1652E GF (melting point 85 ° C) manufactured by EMS Chemie Co., Ltd.

(* 15) Thermoplastic polyurethane elastomer: Resamine PL201 (ether based)

(* 16) Thermoplastic polyamide elastomer: Pebax2533 (melting point 134 ° C) manufactured by Alchema

(* 17) Ethylene-methylacrylate: Elvaloy AC1125 manufactured by Dupont (25% MA, MFR=0.5@190°C*2.16 kg comonomer content 25% by mass)

(* 18) Ultra low density polyethylene: Doga Chemical Nippon Engage 8150 (MFR=0.5@190°C*2.16 kg, density = 0.868 g / cm3)

(* 19) Phosphate metal salt: Clariant Co., Ltd. Exolit OP935 (OP930 fine particle type)

(* 20) Polyphosphazene: Otsuka Kagaku SPB-100L

(* 21) Ultra low density polyethylene: Doug Chemical Nippon Engage 8411 (MFR=18@190°C×2.16 kg, density 0.880 g? Cm 3)

(* 22) Sanko Co., Ltd. cyclic organic phosphorus flame retardant HCA-HQ-HS

(* 23) Chiba Specialty Co., Ltd. Melapur MC15

(* 24) Condensation phosphate ester: Daihachi Kagaku Kogyo Co., Ltd. product PX-110 (phosphorus 7.8%)

(* 25) Melamine cyanurate: Nissan Chemical Co., Ltd. MC6000

Insulation tubes and heat-shrink tubes of Examples 1 to 38 were all clear of flame retardancy, and mechanical properties, heat shock, heat resistance, and heat deformation were also pass levels.

In particular, Example 1 using a polyphenylene ether, a styrene-based thermoplastic elastomer, and an ethylene-? Olefin copolymer (polyolefin-based resin) having a carbonyl group as the thermoplastic resin had a short burning time of 19 seconds, and was particularly excellent in flame retardancy. Further, Examples 1, 17 and 21 to 25 each containing 50 parts by mass or more of an ethylene-α olefin copolymer having a carbonyl group had a combustion time of 30 seconds or less and were excellent in flame retardancy. In particular, the mixing | blending of Example 24 was able to balance a characteristic with only one type of resin. When there are many kinds of resins to mix, it is necessary to apply shear stress at the time of mixing in order to increase the compatibility of the resins, and the cost of mixing increases, but when one type of resin is used, the mixing is easy and the cost decreases. Ganda has the advantage.

(Comparative Examples 1 to 26)

In the same manner as in Examples 1 to 26, an insulation tube and a heat shrink tube were produced using the resin composition shown in Table 8, and a series of evaluations were performed. The results are shown in Tables 8 to 10.

In Comparative Examples 11 and 19 which are heat-shrinkable tubes using the resin composition of the combination of the comparative example 1 and the comparative example 1, since content of the organophosphorus flame retardant (metal phosphate salt) was 105 mass parts with respect to 100 mass parts of thermoplastic resins, Heat shock, heat resistance, and heat deformation were inferior. On the contrary, in Comparative Examples 12 and 20 which are heat shrink tubes using the resin compositions of Comparative Examples 2, 9, 10 and Comparative Example 2, the content of the organophosphorus flame retardant was small, and the flame retardancy was failed.

Comparative Examples 3 to 5 and Comparative Examples 13 to 15 and 21 to 25, which are heat-shrinkable tubes using these resin compositions, ring-opened phosphinate metal salts, melamine phosphate compounds, ammonium phosphate compounds, and cyclophosphazene which are highly flame retardant organophosphorus flame retardants. It did not contain the polyphosphazene compound obtained by superposition | polymerization, and flame-retardance was disqualified on the conditions whose internal diameter is 2.5 mm-0.8 mm. Moreover, even if it is a combination of these, when internal diameter is large, it is thought that it is possible to show flame retardance.

In Comparative Example 6 and Comparative Examples 16 and 24 which are heat-shrink tubes using this resin composition, content of resin which has a carbon-carbon unsaturated bond or resin which has a carbonyl group in a thermoplastic resin was less than 5 mass%, and the flame retardance failed.

Comparative Example 7 and Comparative Examples 17 and 25, which are heat-shrinkable tubes using the resin composition, had a low elongation and failed flame retardance because the content of the polyfunctional monomer was 22 parts by mass with respect to 100 parts by mass of the thermoplastic resin and was more than 20 parts by mass. It was. Since Comparative Example 18 and Comparative Examples 18 and 26 which are heat shrink tubes using this resin composition do not contain a polyfunctional monomer, they resulted in inferior heat resistance, heat shock, and heat deformation.

(Examples 39 to 45)

Each material was mix | blended in the ratio shown in Table 11, and 0.5 part of oleic acid amide and pentaerythritol- tetrakis [3- (3,5-di-t- butyl- 4-hydroxyphenyl) pro with respect to 100 parts of base polymers Cypionate] 3 parts by mass was added and kneaded with a twin screw mixer set at a die temperature of 280 ° C. The strand of the resulting kneaded product was pelletized with a pelletizer, and then a melt diameter extruder (45 mmΦ, L / D ratio = 24, compression ratio 2.5, full flight type) was used at an extrusion temperature of 230 deg. A tubular molded article of mm was obtained. The tubular molded article was irradiated with 250 kGy of an electron beam having an acceleration voltage of 2 MeV, and a series of evaluations were performed on the obtained insulating tube.

(Examples 46-49)

Using the resin composition of the mixing | blending shown in Table 12, the insulating tube irradiated with the electron beam was produced like the above. In addition, the inner diameter and thickness of the tube were described in the table. The insulation tube is left to stand in a thermostat set at 160 ° C. for 3 minutes to preheat, and then compressed air is introduced into the tube to expand the diameter until it reaches an internal diameter of 2.5 times the extruded inner diameter. After the heat shrink tube was produced, a series of evaluations were performed.

Insulation tubes and heat-shrink tubes of Examples 39 to 49 were all pass levels in flame retardancy, mechanical properties, heat shock, heat resistance, and heat deformation. Moreover, in Example 39, Example 40, and Examples 43-45 which used the nitrogen type flame retardant, the combustion time was short as 30 second or less, and the flame retardance improved.

As described above, according to the present invention, there is no problem of generation of hydrogen halide gas during combustion, and excellent in mechanical strength (elongation, tensile strength), heat resistance, heat deformation resistance, and excellent flame resistance even when the inner diameter is small The heat shrink tube can be obtained. The insulation tube and the heat shrink tube can be used for the protection of internal wiring and components of consumer electronic devices such as electronic devices, OA devices, audio, video, DVD, Blu-ray, vehicles, ships, and the like.

Claims (11)

An insulated tube formed into a tubular shape of a flame retardant resin composition containing a thermoplastic resin, a polyfunctional monomer, and an organophosphorus flame retardant,
The said thermoplastic resin contains 5 mass% or more of resin which has a carbon-carbon unsaturated bond or resin which has a carbonyl group with respect to the whole thermoplastic resin,
The organophosphorus flame retardant is at least one selected from the group consisting of metal phosphinates, melamine phosphate compounds, ammonium phosphate compounds, and polyphosphazene compounds obtained by ring-opening polymerization of cyclophosphazene,
The insulation tube whose content of the said organophosphorus flame retardant is 5 mass parts-100 mass parts with respect to 100 mass parts of said thermoplastic resins, and whose content of the said polyfunctional monomer is 1 mass part-20 mass parts with respect to 100 mass parts of said thermoplastic resins. The method of claim 1, wherein the thermoplastic resin is polyphenylene ether resin, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, styrene thermoplastic elastomer, polystyrene resin, nylon And an insulating tube containing 5% by mass or more of at least one member selected from the group consisting of a thermoplastic polyamide elastomer, a polyolefin resin having a carbon-carbon unsaturated bond, and a polyolefin resin having a carbonyl group. The said thermoplastic resin is 5 mass%-80 mass% of polyphenylene ether resin or polystyrene resin, 20 mass%-95 mass% of styrene thermoplastic elastomer, 0 mass of polyolefin resins. Insulation tube containing% to 70% by mass. The said thermoplastic resin contains 50 mass%-100 mass% of the ethylene- alpha olefin copolymer which has a carbonyl group, The ethylene- alpha olefin copolymer which has the carbonyl group has a comonomer content of Claim 1 or 2 A flame-retardant resin composition having a mass% to 46 mass% and a melt flow rate of 0.3 g / 10 min to 25 g / 10 min. The flame-retardant resin composition according to any one of claims 1 to 4, further comprising 3 parts by mass to 100 parts by mass of a nitrogen-based flame retardant based on 100 parts by mass of the thermoplastic resin. The flame retardant resin composition according to claim 5, wherein the nitrogen-based flame retardant is melamine cyanurate. The insulation tube according to any one of claims 1 to 6, further comprising a phosphate ester as the organophosphorus flame retardant. The insulated tube according to any one of claims 1 to 7, wherein the inner diameter of the tube is 5 mm or less. Insulation tube of any one of Claims 1-8 which passes the vertical combustion test (VW-1) prescribed | regulated by UL standard. The insulated tube according to any one of claims 1 to 9, wherein the tensile strength at room temperature is 10 MPa or more. The heat shrink tube which irradiates ionizing radiation to the insulating tube in any one of Claims 1-10, expands a diameter under heating, and cools and fixes it.