KR20090127577A - Halogen free retardant thermoplastic polyurethane compound and a tube for wire protecting using the same - Google Patents

Abstract

PURPOSE: A halogen free retardant thermoplastic polyurethane compound is provided to minimize mechanical and physical properties of a thermoplastic polyurethane resin, and to prevent the generation of harmful materials and dripping phenomenon. CONSTITUTION: A halogen free retardant thermoplastic polyurethane compound comprises a thermoplastic polyurethane resin 100.0 parts by weight, a phosphate flame retardant 50-140 parts by weight, and an anti-drip agent 0.5-5 parts by weight. The anti-drip agent is at least one selected from nanoclay and fluorinated resin. The composition comprises further a flame-retarding aid -10 parts by weight and an antioxidant 0.1-3 parts by weight.

Description

Halogen-free retardant thermoplastic polyurethane compound and a tube for wire protecting using the same}

The present invention relates to a non-halogen flame-retardant thermoplastic polyurethane resin composition and a wiring protection tube using the same, and more particularly, to a thermoplastic polyurethane resin having flexibility and heat resistance without adding a phosphorus-based flame retardant containing no halogen element, without deteriorating physical properties. The present invention relates to a non-halogen flame-retardant thermoplastic polyurethane resin composition capable of adding a flame retardant and adding a drip preventing agent to prevent a melt of the thermoplastic polyurethane resin, and a tube for wiring protection using the same.

In general, many electric wires are entangled like spider webs in electronic devices, automobiles, machines, etc. These wires are excellent in heat resistance and flame retardant, and need to be flexible because they need to be fitted to the internal structure of the device. In addition, sharp components inside the appliance shall not generate dust or burrs due to surface scratching during installation.

1 is a view showing an internal wiring protection tube used in a typical LCD TV.

Referring to FIG. 1, a tube 200 is used to protect a power line 100 connecting a main board and a back light unit (BLU) inside an LCD TV. The inside of the device has a sharp press, which may damage the wire sheath during the installation of the power cable, which may cause the wire to break. In such a case, there is a high possibility of a fire caused by a short circuit or an abnormality in the LCD TV itself.

In addition, in the case of electronic component parts, it is easy to be exposed to high temperature due to the nature of the use environment. Therefore, do not use materials that are damaged or generate flames when an internal fire occurs.

Conventionally, polyvinyl chloride (PVC) material containing a Group 7B (halogen group) element on the chemical periodic table has been used in order to satisfy such requirements, but these halogen flame retardants have recently been regulated by environmental regulations of developed countries such as the European Union and the United States. Among them, the use of flame retardants containing chlorine, bromine and the like is excluded.

The use of chlorine or bromine-based compounds has the advantages of excellent flame retardancy, low cost, and easy processing, but upon combustion, dioxin, a carcinogen, is emitted and corrosive gas is released.

Halogen-containing resins are used with halogen flame retardants and metal hydroxides, antimony trioxide, and the like to release inert gases during combustion, enabling the material to exhibit high flame retardancy. In addition, since halogen-containing polymer resins are basically flame retardant, by adding a small amount and an appropriate amount of flame retardant, it is possible to secure general properties required for the flame-retardant tube material while maintaining flame retardancy, and has excellent extrusion processability.

PVC resins containing chlorine, which is a halogen group element, generally include a material called plasticizer, which is used to provide flexibility, which is known to be an environmental hormone-inducing substance and its use is regulated.

In addition, in the case of using a general polyolefin-based tube, there is a possibility that a serious error in the inside of the device by generating a dust or burrs due to the lack of flexibility and surface scratches occur.

And in order to secure flame retardancy with polyolefin, an excessive flame retardant filler should be used. Such flame retardant fillers degrade mechanical properties and flexibility, have a high risk of surface scratching, and a tube made of silicone undergoes a crosslinking process for recycling. This is impossible and expensive.

On the other hand, the thermoplastic polyurethane resin has excellent mechanical properties and elasticity, and is easy to mold the product has been used in various industrial fields. However, thermoplastic polyurethane resins have poor flame retardancy, and their use has been limited. Therefore, methods for imparting flame retardancy to such thermoplastic polyurethane resins have been developed. To this end, methods for adding a flame retardant to thermoplastic polyurethane resins are mainly used.

However, in order to minimize the deterioration of physical properties such as elongation at break, rebound modulus, elastic modulus and abrasion of the thermoplastic polyurethane resin by adding a flame retardant, it is preferable to add a minimum amount of flame retardant, but in this case, there is a problem that the flame retardancy is deteriorated, It is also a problem that additional accidents may occur due to the phenomenon that it decomposes during the time and becomes a low molecular weight molten material and dripping.

Therefore, in order to solve the above problems, the present invention provides a flame retardant by adding a non-halogen phosphorus flame retardant to the thermoplastic polyurethane resin, and at the same time prevents the occurrence of harmful substances in the event of a fire, and adds a drip prevention agent to the dripping It is an object of the present invention to provide a non-halogen flame-retardant thermoplastic polyurethane resin composition which prevents the phenomenon, but does not lower the mechanical and physical properties of the thermoplastic polyurethane resin, and a wiring protection tube using the same.

The flame-retardant non-halogen thermoplastic polyurethane resin composition according to the present invention comprises 100 parts by weight of a thermoplastic polyurethane resin; 50 to 140 parts by weight of a phosphorous flame retardant; And 0.5 to 5 parts by weight of the anti-drip agent.

In addition, the wiring protection tube using the non-halogen flame-retardant thermoplastic polyurethane resin composition according to the present invention, 100 parts by weight of the thermoplastic polyurethane resin; 50 to 140 parts by weight of a phosphorous flame retardant; And 0.5 to 5 parts by weight of the anti-drip agent; a non-halogen flame-retardant thermoplastic polyuretan resin composition containing a wiring protection tube.

The non-halogen flame-retardant thermoplastic polyurethane resin composition and the wiring protection tube using the same according to the present invention are added to the thermoplastic polyurethane resin by adding a phosphorus-based flame retardant and a anti-drip agent which is a non-halogen substance, thereby reducing the mechanical and physical properties of the thermoplastic polyurethane resin. Minimizing the amount of water and preventing the occurrence of dripping phenomenon that causes harmful substances or melts in the event of a fire, it is possible to respond to more stringent environmental regulations.

EMBODIMENT OF THE INVENTION Hereinafter, although the Example of this invention is described in detail, this invention is not limited to a following example, unless the summary is exceeded.

The present invention uses a non-halogen flame-retardant phosphorus compound and a anti-drip agent in the thermoplastic polyurethane resin to minimize the deterioration of mechanical properties, to prevent the generation of harmful substances during combustion and to prevent melting non-halogen flame-retardant thermoplastic poly It relates to a urethane resin composition and a tube for wiring protection using the same.

Thermoplastic Polyurethane (TPU) resin used in the present invention is excellent in flexibility, heat resistance and abrasion resistance, and is a non-toxic plastic material having excellent heat resistance, impact resistance, cold resistance, durability, and the like compared to polyvinyl chloride (PVC). .

Since the thermoplastic polyurethane resin has hygroscopicity to absorb moisture and may cause problems such as deterioration of physical properties and bubbles during molding and processing, it is dried for 4 to 5 hours at 80 ° C to 120 ° C before molding. It is desirable to carry out a pretreatment process to remove the moisture contained.

In order to impart flame retardancy to 100 parts by weight of the pretreated thermoplastic polyurethane resin, a non-halogen flame retardant is added to prevent dripping.

Non-halogen flame retardants include metal inorganic hydroxide flame retardants, phosphorus flame retardants, melamine flame retardants, boric acid flame retardants and silicone flame retardants, etc. In the present invention, the phosphorus flame retardant is used in an amount of 50 to 140 parts by weight.

Phosphorus-based flame retardants satisfy the two aspects of low toxicity and flame retardancy, and are in the spotlight as alternatives to halogen-based flame retardants.In addition to the demand for recycled products, it is easy to incinerate and recycle, is safe, and has excellent smoke stability in case of fire. Phosphorus-based flame retardants used in the present invention include triphenyl phosphate, triaryl phosphate, aromatic phosphate esters, 2-ethylhexyldiphenyl phosphate, nitrogen-polyporous, TCP, cresylphenyl phosphate, resoldiphenyl phosphate, chloroethyl phosphate At least one of tris-β-chlorpropyl phosphate, trisdichloropropyl phosphate, aromatic condensed phosphate esters, polyphosphates and reds can be used. If a low flame retardant is added to the thermoplastic polyurethane resin, the flame retardant property is lowered, and if the flame retardant is added to a large amount, the flame retardant is added to optimize the flame retardancy and the material properties.

As the anti-drip agent, nanoclay or fluororesin may be used alone, but two anti-drip agents may be used together. In the present invention, the anti-drip agent is used in an amount of 0.5 to 5 parts by weight.

An antioxidant may be added to impart heat resistance thereto. As the antioxidant, a hindered phenol-based antioxidant or a thio compound-based antioxidant may be used alone, or two antioxidants may be used together. In the present invention, the antioxidant is used in an amount of 0.1 to 3 parts by weight.

In addition, a flame retardant aid that can reduce the smoke generation while improving the flame retardant properties of the flame retardant may be used, a silicon compound or a boron compound may be used alone or in combination, the flame retardant aid in the present invention is used in an amount of 1 to 10 parts by weight do.

The non-halogen flame-retardant polyurethane resin composition according to the present invention may further include at least one additive selected from the group consisting of a light stabilizer, a lubricant, a reinforcing agent, a pigment, a colorant, and a plasticizer, in addition to the above materials. Such additives may be used within the range of not impairing the physical properties of the non-halogen flame-retardant polyurethane resin composition according to the present invention.

The non-halogen flame-retardant polyurethane resin composition according to the present invention can be produced into a product of a desired shape by melt-kneading the above-mentioned materials and extrusion molding. The extrusion process proceeds in the order of drying of raw materials, addition, extrusion, cooling, and winding.

In addition, the wire protection tube according to the present invention can be produced through a known extrusion molding method according to the desired tube size using a tube-shaped mold in a single screw extruder.

The following [Table 1] shows the physical property test results of the mixture according to the composition.

 division Comparative example Example One 2 3 4 5 6 One 2        Furtherance PVC 100 PP 100 100 EVA 100 Silicon rubber 100 TPU 100 100 100 Plasticizer 20 Antioxidant 3 3 3 3 3 3 Inorganic flame retardant 150 150 Phosphorus Flame Retardant 150 120 120 Flame Retardant 10 10 10 10 Anti-drip 3 Heat stabilizer One Silica filler 80 Platinum Flame Retardant One    Properties Room temperature characteristics Tensile Strength (kg / ㎡) 1.32 1.42 1.36 1.28 0.6 2.5 1.42 1.37 Elongation (%) 300 250 220 200 150 500 350 300 Thermal properties Tensile residual rate 90 95 95 60 95 95 95 95 Elongation 60 85 80 55 90 90 90 90 Hardness Shore a 80 98 98 95 80 75 80 82 Scratch resistance Sandpaper (200) NO YES YES YES YES YES NO NO Halogen Detection XRF Chlorine detection Not detected Not detected Not detected Not detected Not detected Not detected Not detected Flame retardant UL94 vertical flame test V0 V2 V2 fail V0 fail V0 V0 Whether drip pass fail fail fail pass fail pass pass

* Tensile residual rate, elongated residual rate:

Tensile Strength and Elongation at Normal Temperature / Tensile Strength and Elongation after Aging × 100

* Sandpaper (200): paper used for product polishing, the larger the number, the smaller the surface roughness.

(Comparative Example 1)

Comparative Example 1 was kneaded in an open roll for 10 minutes using 20 parts by weight of a plasticizer and 100 parts by weight of polyvinyl chloride (PVC) and 1 part by weight of a heat stabilizer, and then molded to a test specimen at 170 ° C. for 5 minutes. After sufficient stabilization, physical properties and flame retardancy were measured according to the measuring method described below, and the results are shown in Table 1 above. Plasticizers are used to impart soft performance to PVC.

(Comparative Example 2)

100 parts of polypropylene (PP), 3 parts by weight of antioxidant, 150 parts by weight of inorganic flame retardant, and 10 parts by weight of flame retardant aid were kneaded for 10 minutes on an open roll, and then molded for test specimens at 170 ° C. for 5 minutes. After sufficient stabilization, physical properties and flame retardance were measured according to the measuring method described below, and the results are shown in [Table 1].

(Comparative Example 3)

Using 100 parts by weight of polypropylene (PP), 3 parts by weight of antioxidant, 150 parts by weight of phosphorus-based flame retardant, and 10 parts by weight of flame retardant aid, kneading for 10 minutes on an open roll, and then molded at 170 ° C. for 5 minutes for test specimens. After stabilization, physical properties and flame retardance were measured according to the measuring method described below, and the results are shown in Table 1 above.

(Comparative Example 4)

Using 100 parts by weight of ethylene vinyl acetate (EVA), 3 parts by weight of antioxidant, 150 parts by weight of inorganic flame retardant and 10 parts by weight of flame retardant, kneaded for 10 minutes on an open roll, and then tested for 5 minutes at 170 ° C. After molding in accordance with the present invention and sufficiently stabilized, physical properties and flame retardance were measured according to the measuring method described below, and the results are shown in [Table 1].

(Comparative Example 5)

100 parts by weight of silicon rubber, 3 parts by weight of antioxidant, 80 parts by weight of silica filler, and 1 part by weight of platinum-based flame retardant were kneaded in an open roll for 10 minutes, and then molded for test specimens at 170 ° C. for 5 minutes. After sufficient stabilization, physical properties and flame retardance were measured according to the measuring method described below, and the results are shown in [Table 1].

(Comparative Example 6)

Using 100 parts by weight of thermoplastic polyurethane (TPU) using 3 parts by weight of antioxidant, kneaded in an open roll for 10 minutes, molded at 170 ° C. for 5 minutes and sufficiently stabilized, followed by physical stabilization according to the measuring method described below. The characteristics and flame retardancy were measured and the results are shown in [Table 1].

(Example 1)

Using 100 parts by weight of thermoplastic polyurethane (TPU) 120 parts by weight of a phosphorous flame retardant, kneading for 10 minutes on an open roll, and then molded for 5 minutes at 170 ℃ for test specimens, and then sufficiently stabilized and physically prepared according to the measurement method described below. The characteristics and flame retardancy were measured and the results are shown in [Table 1].

(Example 2)

After kneading for 10 minutes on an open roll using 100 parts by weight of thermoplastic polyurethane (TPU) 120 parts by weight of phosphorus flame retardant, 120 parts by weight of phosphorus flame retardant, 3 parts by weight of antioxidant, 10 parts by weight of flame retardant aid and 3 parts by weight of drip inhibitor. After molding for 5 minutes at 170 ℃ test specimens, and after sufficiently stabilized in accordance with the measuring method described below to measure the physical properties and flame retardancy is shown in the results [Table 1].

The following characteristics were evaluated using test specimens formed using the materials described above.

(Property evaluation)

Tensile strength and elongation were tested according to ASTM D638, and heat resistance was evaluated by varying the tensile strength and elongation rate by putting tensile specimens for 7 weeks in an oven at 136 ° C. Scratch resistance was evaluated by measuring the occurrence of scratches and the occurrence of branches when scratched using sandpaper. In addition, the use of halogen was evaluated by elemental analysis with an XRF tester, and the flexibility was evaluated by measuring the hardness of the specimen.

(Flame retardancy evaluation)

The flame retardancy of the non-halogen flame-retardant thermoplastic polyurethane resin composition according to the present invention was evaluated based on the criterion described in Table 2 below through UL94 "20 mm vertical burning test".

UL94-V0 UL94-V1 UL94-V2 T1 and T2 of each specimen Within 10 seconds each Within 30 seconds each Within 30 seconds each Sum of post-fire extinguishing times for five specimens (T1 + T2) Within 50 seconds Within 250 seconds Within 250 seconds T2 + T3 on each specimen Within 30 seconds Within 60 seconds Within 60 seconds Whether the specimen burned Not burn down Not burn down Not burn down Cotton burning under the specimen (dripping) Not to burn Not to burn Combustion

The test specimen is manufactured in 125mm × 13mm × 2mm (length, width, thickness), and the burner that burns the specimen generates methane gas with a calorific value of 37MJ / ㎥ and a flame height of 20mm using methane gas as a raw material. Let's do it.

The distance between one end of the test specimen and the end of the burner is set to 10 mm, and each specimen is burned twice for 10 seconds.

Measure extinguishing time after first combustion (T1 sec) and measure extinguishing time after second combustion (T2 sec). In addition, it measures the time (T3 seconds) that the flame disappears after the second combustion and the flameless combustion (no flame, but glowing red like charcoal) lasts. The criteria for determining V0, V2 and V3 for each test specimen are given in Table 2 above.

(Experiment result)

Referring back to [Table 1], (Comparative Example 1) is excellent in all physical properties and flame retardancy like general PVC, but chlorine, that is, halogen components are detected and unsuitable for use, (Comparative Example 2) and (Comparative Example 3) The flame retardant was added to the polypropylene resin, but the addition of the flame retardant significantly reduced the flexibility and a problem that the scratch occurs on the surface.

In addition, (Comparative Example 4) used magnesium hydroxide alone as a flame retardant in ethylene vinyl acetate, it was burned to satisfy the flame retardant performance on the finished product, (Comparative Example 5) is filled with silica and siliconized platinum flame retardant The flame retardancy, flexibility, scratch resistance and heat resistance required for the addition were excellent, but the tensile strength and elongation at room temperature are lower than those of other comparative examples, and foreign matter such as branching is attached to the surface due to the electrostatic properties of silicon and it is relatively expensive. There is this.

In Comparative Example 6, the thermoplastic polyurethane was used as in the present invention. However, only the antioxidant was added to the thermoplastic polyurethane, and thus the flame retardant was not significantly added.

On the other hand, (Example 1) is to add a flame retardant to the thermoplastic polyurethane resin to impart flame retardancy to the physical properties of the thermoplastic polyurethane resin, as well as excellent UL94-V0 grade of heat resistance, flexibility and scratch resistance Flame retardant performance was shown.

In addition, (Example 2) was added to the anti-drip agent to complement the characteristics that the thermoplastic polyurethane resin is melted during combustion, the flame retardant synergistic effect was further promoted and the carbonized ash after combustion also shows a solidified shape and UL94-V0 grade Showed excellent flame retardant performance.

From these results, it can be seen that the non-halogen flame-retardant polyurethane resin composition according to the present invention can satisfy the flame-retardant performance without deteriorating physical properties such as heat resistance, flexibility and scratch resistance.

In addition, it will be obvious that the wiring protection tube made of the non-halogen flame-retardant polyurethane resin composition described above also has the same performance.

As described above, in the detailed description of the present invention, specific embodiments have been described, but various modifications are possible without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the claims below and equivalents thereof.

1 is a view showing an internal wiring protection tube used in a typical LCD TV.

<Description of main parts of drawing>

100: power line 200: tube

Claims (6)

Per 100 parts by weight of thermoplastic polyurethane resin, 50 to 140 parts by weight of a phosphorous flame retardant; And 0.5 to 5 parts by weight of the anti-drip agent; A non-halogen thermoplastic polyurethane resin composition, characterized by comprising a. The method of claim 1, The drip inhibitor, A non-halogen thermoplastic polyurethane resin composition, characterized in that at least one of nanoclay and fluorine resin. The method of claim 1, The composition, A non-halogen thermoplastic polyurethane resin composition further comprising 1 to 10 parts by weight of a flame retardant and 0.1 to 3 parts by weight of an antioxidant. The method of claim 3, wherein The flame retardant aid, A non-halogen thermoplastic polyurethane resin composition, characterized in that at least one of a silicone compound and a boron compound. The method of claim 3, wherein The antioxidant, A non-halogen thermoplastic polyurethane resin composition, characterized in that it is at least one of a hindered phenol-based antioxidant and a thio compound-based antioxidant. A wiring protection tube comprising the non-halogen thermoplastic polyurethane resin composition according to any one of claims 1 to 5.

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