TW201741392A - Flame retardant composition and wire using the same - Google Patents

Abstract

The present disclosure provides a flame retardant composition. The flame retardant composition includes 55 wt% ~ 85 wt% of polyether-based thermoplastic polyurethane, 10 wt% ~ 40 wt% of an organophosphorus flame retardant, 1wt% ~ 10wt% of a first compatibilizer, 1wt% ~ 10wt% of a second compatibilizer and 0.2 wt% ~ 1 wt% of additives, in which the first compatibilizer includes TPO-g-MAH. Accordingly, a wire manufactured by the abovementioned. flame retardant composition is not only anti-dripped but also keeps its mechanical properties and workability.

Description

Flame resistant composition and electronic wire used therewith

The present invention relates to a flame resistant composition, and more particularly to a flame resistant composition containing no halogen element and an electronic wire rod using the same.

With the development of the communication industry, the automotive industry and the power industry, there is an increasing demand for high-temperature resistant electronic wires, such as aviation wires, automotive wires, communication wires, power cables, high-temperature instrument cables, oil rig cables, and many other occasions. High temperature resistant electronic wire is required. In other words, the quality of electronic wire has a great impact on the safety of ultra-high buildings, MRT, shopping malls, office buildings, etc. Once the electronic wire is damaged by fire, the smoke exhaust system and alarm system needed for escape. The notification system, etc. will not function, affecting not only the escape but also the disaster rescue. Therefore, the material used for the electronic wire is particularly resistant to flame resistance in addition to the necessary insulation. In more detail, in terms of flame resistance, the test method may vary depending on the degree of necessity (the intended use thereof) and the like. Therefore, in practice, the aforementioned electron beam has at least a certain flame resistance according to the required degree, for example, by an upright flame test (VW) specified in UL 1581 (reference standard for wires, cables, and flexible cores). -1).

At present, Thermoplastic Polyurethane (TPU) has been widely used in the production of electronic wires, and it is classified into a polyether type and a polyester type by the difference of long-chain diols. The polyester thermoplastic polyurethane elastomer is represented by polycaprolactone (PCL), which has the advantages of good mechanical strength, processing and chemical resistance, but the polyester thermoplastic polyurethane elastomer has poor hydrolysis resistance. . Polyether thermoplastic polyurethane elastomer generally uses polytetrahydrofuran glycol (PTMG) as a soft segment, and its molecular chain is regular and soft, and has good stretchability, low temperature resistance, low hardness and long life. And it has better hydrolysis resistance than polyester-type thermoplastic polyurethane elastomer, which is advantageous for subsequent applications. However, the polyether type thermoplastic polyurethane elastomer has disadvantages in that its mechanical strength and processability are inferior to those of the polyester type thermoplastic polyurethane elastomer, and its burning is dripping, making it difficult to be widely used.

Accordingly, in order to improve the flame resistance of the electron beam, a conventional flame retardant is often added to the prior art, and the conventional flame retardant is a flame retardant containing a halogen atom. However, when a fire occurs, such halogen-containing flame retardants generate a large amount of smoke and toxic corrosive hydrogen halide gas, causing secondary hazards. At present, halogen-free flame retardants have been developed in order to meet the current environmental protection trend, but it is difficult to maintain the original mechanical properties of the above polyether thermoplastic polyurethane elastomer after adding a halogen-free flame retardant, which is why it is difficult to be further applied. .

In view of this, how to develop a polyether-based thermoplastic polyurethane elastomer that combines both flame resistance and mechanical properties is a problem that is currently being overcome.

One embodiment of one aspect of the present invention is to provide a flame resistant composition. The aforementioned flame resistant composition is from 55 to 85 weight percent of the polyether thermoplastic polyurethane elastomer, 10 to 40 weight percent of the organophosphorus flame retardant, and 1 to 10 weight percent of the first compatibilization The agent, 1% by weight to 10% by weight of the second compatibilizer and 0.2% by weight to 1% by weight of the additive, and the aforementioned first compatibilizer comprises a maleic anhydride grafted polyolefin elastomer.

The flame resistant composition according to the above embodiment, wherein the polyether thermoplastic polyurethane elastomer has a Shore hardness value of 85.

A flame resistant composition according to the above embodiment, wherein the aforementioned first compatibilizer may be polyethylene grafted maleic anhydride.

A flame resistant composition according to the above embodiment, wherein the aforementioned second compatibilizer may be a styrene grafted maleic anhydride copolymer.

Based flame resistance of the composition in the above embodiment, wherein the additive comprises an antioxidant and the antioxidant accounting for the total weight content of the flame composition may be a weight percentage of 0.1 to 0.5 weight percent and selected from IRGANOX ^TM 1010, or IRGAFOS ^® 168 .

A flame-resistant composition according to the above embodiment, wherein the aforementioned additive comprises a processing oil, and the aforementioned processing oil may be contained in an amount of from 0.1% by weight to 0.5% by weight based on the total weight of the flame-resistant composition and may be selected from eucalyptus oil or white oil.

A flame-resistant composition according to the above embodiment, wherein the flame-retardant composition has an elongation at break when the test piece is made into a test piece having a thickness of 2 mm The rate is greater than or equal to 400% and less than or equal to 650%.

A flame-resistant composition according to the above embodiment, wherein when the aforementioned flame-retardant composition is formed into a test piece having a thickness of 2 mm, the tensile strength is greater than or equal to 14 MPa and less than or equal to 20 MPa.

Another embodiment of one aspect of the present invention is to provide a flame resistant composition. The aforementioned flame resistant composition is composed of 55 to 85 weight percent of the polyether thermoplastic polyurethane elastomer, 10 to 40 weight percent of the organophosphorus flame retardant, and 1 to 10 weight percent of the maleic anhydride. The polyolefin elastomer is composed of 0.2% by weight to 1% by weight of the additive.

An embodiment of another aspect of the present invention provides an electronic wire for use in an electronic device, wherein the electronic wire comprises an insulating layer made of the flame resistant composition.

Thereby, the electronic wire material produced by the flame-retardant composition provided by the present invention can maintain good mechanical properties and workability in addition to being resistant to dripping.

The Summary of the Invention is intended to provide a simplified summary of the present disclosure in order to provide a basic understanding of the disclosure. This Summary is not an extensive overview of the disclosure, and is not intended to be an

The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood. 1 is a view showing a case where a commercially available flame-retardant composition of Comparative Example 1 was subjected to UL-94 combustion test; and FIG. 2 is a view showing a test piece obtained by the flame-retardant composition of Example 3 of the present invention by UL- 94 situation after the burning test.

The various embodiments of the invention are discussed in more detail below. However, this embodiment can be applied to various inventive concepts and can be embodied in various specific ranges. The specific embodiments are for illustrative purposes only and are not limited by the scope of the disclosure.

The present invention is directed to providing a flame resistant composition having two embodiments: one of which is a polyether thermoplastic polyurethane elastomer, an organophosphorus flame retardant, a first compatibilizer, a second compatibilizer, and an additive. The composition is composed of a polyether thermoplastic polyurethane elastomer, an organophosphorus flame retardant, a first compatibilizer, and an additive. That is to say, the flame resistant composition of the present invention may or may not contain the second compatibilizer, and the purpose of adding the second compatibilizer and the achievable effects thereof will be described in detail later, and will not be described herein. . Further, the polyether thermoplastic polyurethane elastomer is a main body of the flame resistant composition, and the content of the total weight of the flame resistant composition is specifically 55 to 85 weight percent, and the Shore hardness value may be 85. However, the invention is not intended to be limited thereto.

Next, the purpose of adding an organophosphorus flame retardant is to cause strong dehydration of the organic phosphorus after thermal decomposition, which can rapidly carbonize the polymer to form a dense carbon layer, which can effectively block the transmission of heat and heat, and make the material and the conductor It is isolated from the flame and prevents the flame from continuing to spread, achieving a flame retardant effect. Specifically, the flame retardant composition of the present invention contains 10% by weight to 40% by weight of the organophosphorus-based flame retardant, and more specifically, the aforementioned organophosphorus-based flame retardant may be a phosphorus-nitrogen flame retardant, such as none The halogen flame retardant JLH-W666 is a high performance phosphorus-nitrogen organic flame retardant, and it is a triazinetrione compound or a triazine triamine compound, but the invention is not limited thereto.

The first compatibilizer can make the polyether thermoplastic polyurethane elastomer compatible with the organophosphorus flame retardant, and even if the organophosphorus flame retardant can be effectively dispersed in the polyether thermoplastic polyurethane elastomer, It interacts with it when it is thermally decomposed to produce a dense carbon layer that resists dripping. Specifically, the flame resistant composition of the present invention comprises 1% by weight to 10% by weight of the first compatibilizer, and the first compatibilizer is a modified thermoplastic polyolefin material such as maleic anhydride grafted polyolefin. Elastomer, and the aforementioned maleic anhydride grafted polyolefin elastomer can be selected from polyethylene grafted maleic anhydride (PE-g-MAH), ethylene-vinyl acetate copolymer grafted maleic anhydride (EVA-g-MAH) Polypropylene grafted maleic anhydride (PP-g-MA) or polystyrene grafted maleic anhydride (PS-g-MAH). Further, the first compatibilizer may be used singly or in combination of one or more of the foregoing.

Next, in order to impart better physical properties to the article to be subsequently applied, the flame resistant composition of the present invention may be added with a second compatibilizer, and the compatibilizing effect of the second compatibilizer is produced by mixing the copolymer. In particular, at least two of the components participating in the copolymerization have a reactive group, and the reaction rates between the functional groups carried by the two components are fast, such as the reaction type of a carboxyl group and an amino group, and an anhydride. The type of reaction with an amino group or the type of reaction of an oxy group with an amino group or a carboxyl group, In addition to improving the dispersibility of the material, it can also form a bridge with the aforementioned polymer to further enhance the mechanical strength of the material. Specifically, the flame resistant composition of the present invention may comprise from 1% by weight to 10% by weight of the second compatibilizer, and the second compatibilizer may be a styrene-grafted maleic anhydride copolymer (Sg-MAH), However, the invention is not intended to be limited thereto.

Further, the flame resistant composition of the present invention further contains from 0.2% by weight to 1% by weight of the additive. In detail, the aforementioned additive may contain an antioxidant, and the content of the aforementioned antioxidant in the total weight of the flame resistant composition is specifically 0.1% by weight to 0.5% by weight. More particularly, the antioxidant is tetrakis (methylene (3,5-di - tertiary butyl-4-hydroxyhydrocinnamate)) methane (trade name: IRGANOX ^TM 1010) or tris - (2, 4-Di-t-butylphenyl)phosphite (trade name: IRGAFOS ^® 168). Furthermore, the aforementioned additive may further comprise a processing oil, and the processing oil may comprise from 0.1% by weight to 0.5% by weight based on the total weight of the flame-retardant composition of the present invention and may be selected from the group consisting of eucalyptus oil or white oil, but in the present invention The added antioxidant and processing oil are not intended to be limited to any of the foregoing embodiments.

The components of the flame-retardant composition provided by the present invention have been roughly described as above. Although the method for preparing the flame-resistant composition is not described below, the preparation method can be combined with, but not limited to, a twin-screw extrusion. It is carried out by machine, but the invention is not intended to be limited thereto. First, each of the above components is weighed and mixed in a uniform ratio, and then melt-kneaded and granulated by a twin-screw extruder through a feeder. Specifically, the granulation temperature condition of the foregoing twin-screw extruder may be, but is not limited to, a conveying section of 170 ° C to 180 ° C, a melting section of 230 ° C to 200 ° C, a mixing section of 200 ° C to 180 ° C, and an exhaust section of 200 ° C. To 180 °C, vacuum section 190 ° C, delivery section and die 190 ° C to 180 ° C, and its rotation speed is 200 rpm to 300 rpm.

Accordingly, the present invention further provides an electronic wire which is used in an electronic device, and the electronic wire comprises an insulating layer made of the flame resistant composition.

Hereinafter, specific examples 1 to 4 and comparative examples 1 to 2 will be further described in detail. When the insulating layer of the electronic wire is produced by using the flame-retardant composition provided by the present invention, the electronic wires can be made resistant to dripping. It also maintains good mechanical properties and processability.

It should be noted that Comparative Example 1 is a commercially available flame resistant composition, that is, a polyether thermoplastic polyurethane elastomer to which a flame retardant is conventionally added. In the first embodiment to the fourth embodiment and the comparative example 2, the particles obtained by the above-mentioned preparation method of the flame-retardant composition were first dried in an oven at 80 ° C for 2 hours to be dried, and then formed by an injection molding machine. Standard test pieces of millimeters for physical property testing. And the first compatibilizer used in the flame retardancy compositions of Examples 1 to 4 and Comparative Example 2 is polyethylene grafted maleic anhydride, and the second compatibilizer is styrene grafted maleic anhydride, but The invention is not limited thereto.

The tensile strength and elongation at break of the test piece were tested in accordance with the method specified in ASTM D638, and the units were in parts per million (MPa) and percentage (%). As for the flame resistance, the fire test and evaluation are carried out in accordance with the UL-94 standard. Specifically, the test piece is fixed at one end and horizontally held so that the gas burner flame is flame-contacted to its free end for 30 seconds. When the test piece continues to burn after leaving the flame, the burning speed is measured. Burning speed is no more than 76.2 mm per minute, or the flame is in the slave When the end of the test piece reached a point of 102 mm, when the combustion was stopped, it was evaluated as equivalent to "HB", and this was the lowest level. Further, similarly to the test piece, the gas burner flame was subjected to a flame test for 10 times by flame contact with the lower end of the test piece held vertically. When the average burning time (seconds) of five sheets at the time of the test was 50 seconds or less, the evaluation was equivalent to "V0". The second is whether the test piece can pass the test after the VW-1 burning test in accordance with UL1581 section 1080. Finally, the test results of Examples 1 to 4 and Comparative Example 2 are organized as shown in Table 1.

First, please refer to FIG. 1 and FIG. 2, and FIG. 1 shows the situation after the UL-94 combustion test of the commercially available flame-retardant composition of Comparative Example 1, Fig. 2 is a view showing a state in which a test piece obtained by the flame-retardant composition of Example 3 of the present invention was subjected to UL-94 burning test. As shown in FIGS. 1 and 2, the carbon layer and the anti-drip effect of the test piece prepared by the flame-retardant composition of Example 3 of the present invention after UL-94 burning test, and Comparative Example 1 There are significant differences in the commercially available flame resistant compositions.

Next, referring to Table 1, it can be seen from Example 1 and Comparative Example 2 that when the first compatibilizer is not added to the flame resistant composition, the test piece is evaluated as the minimum flame resistance rating HB after the UL-94 burning test. It is not possible to pass the UL1581 VW-1 combustion test, so it is known that the addition of the first compatibilizer does contribute to the improvement of flame resistance.

Further, as described above, the polyether thermoplastic polyurethane elastomer lowers its physical properties such as mechanical properties and tensile properties after the addition of the halogen-free flame retardant. At this time, it can be seen from Example 2 to Example 4 of Table 1 that when the second compatibilizer is added to the flame resistant composition, the tensile strength of the whole material can be improved, and the second strength is added by 3 wt%. The best effect is achieved with compatibilizers. At the same time, the elongation at break of the material itself was also reduced from 647% (Example 1) without the addition of the second compatibilizer to 541% when the 3% by weight was added (Example 3), even when 6 was added. The weight percentage of the second compatibilizer is further reduced to 485% (Example 4), so the overall tensile resistance of the material also increases as the content of the second compatibilizer increases, and Examples 2 to 4 The test pieces are both highly efficient and flame resistant.

In summary, the present invention provides a flame resistant composition, and the use of the flame resistant composition as an insulating layer of an electron wire not only enables the electron beam to have high flame resistance and drip resistance, but also maintains good mechanical properties. with Processability.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

Claims (10)

A flame resistant composition comprising: 55% by weight to 855% by weight of a polyether thermoplastic polyurethane elastomer; 10% by weight to 40% by weight of an organophosphorus flame retardant; 1% by weight to 10 a first percentage by weight of the first compatibilizer, and the first compatibilizer comprises a maleic anhydride grafted polyolefin elastomer; from 1% by weight to 10% by weight of the second compatibilizer; and from 0.2% by weight to 1% by weight additive. The flame resistant composition according to claim 1, wherein the polyether thermoplastic polyurethane elastomer has a Shore hardness value of 85. The flame resistant composition of claim 1, wherein the first compatibilizer is polyethylene grafted maleic anhydride. The flame resistant composition of claim 1, wherein the second compatibilizer is a styrene grafted maleic anhydride copolymer. The flame-retardant composition of claim 1, wherein the additive comprises an antioxidant, and the antioxidant comprises 0.1% by weight to 0.5% by weight based on the total weight of the flame-resistant composition and is selectable from IRGANOX ^TM 1010 or IRGAFOS ^® 168. The flame-retardant composition according to claim 1, wherein the additive comprises a processing oil, and the processing oil accounts for 0.1% by weight to 0.5% by weight based on the total weight of the flame-resistant composition, and is selected from the group consisting of eucalyptus oil Or white oil. The flame-retardant composition according to claim 1, wherein when the flame-retardant composition is formed into a test piece having a thickness of 2 mm, the elongation at break is greater than or equal to 400% and less than or equal to 650%. The flame-retardant composition according to claim 1, wherein when the flame-retardant composition is formed into a test piece having a thickness of 2 mm, the tensile strength is greater than or equal to 14 MPa and less than or equal to 20 million Pa. An electronic wire which is used in an electronic device, and the electronic wire comprises an insulating layer produced by the flame-retardant composition according to any one of claims 1 to 8. A flame resistant composition comprising: 55 to 85 weight percent of a polyether thermoplastic polyurethane elastomer; 10% by weight to 40% by weight of the organophosphorus flame retardant; 1% by weight to 10% by weight of the maleic anhydride grafted polyolefin elastomer; and 0.2% by weight to 1% by weight of the additive.