KR100586113B1 - High flame retardant and low smoke sheath material composition with excellent thermal stability and cable with sheath formed therefrom - Google Patents

Abstract

The present invention relates to a high flame retardant and low-flammable sheath material composition and a cable having a sheath formed therefrom, wherein the sheath material composition according to the present invention is 100 parts by weight of polyvinyl chloride resin, phosphorus flame-retardant plasticizer 10 to 30 Parts by weight, brominated flame retardant plasticizer 10 to 30 parts by weight, phthalate plasticizer 5 to 20 parts by weight, inorganic hydroxide 30 to 100 parts by weight, ammonium octamolybdate 5 to 40 parts by weight, zinc-molybdate salt complex 5 to 20 Parts by weight, 1 to 10 parts by weight of zinc borate and 1 to 10 parts by weight of antimony trioxide. The sheath formed from the composition according to the present invention not only has excellent mechanical properties such as tensile strength, tensile elongation and flexibility, but also has excellent thermal stability and high flame retardancy and low smoke resistance, so that a plenum-class cable can be manufactured that satisfies the UL910 standard. Can be.

Description

High performance flame retardant, low smoke and thermally stable composition for sheath and a cable having the sheath formed therefrom}

The present invention relates to a high flame retardant and low smoke sheath material composition having excellent thermal stability and to a cable having a sheath formed therefrom.

The main development direction for the conventional cable has been focused on improving the transmission capacity and speed of the cable. However, in recent years, when fires occur in offices or buildings, problems such as toxic gas generation and fire propagation due to cable combustion have been raised, so that the cable has high flame retardancy and low smoke resistance by changing the structure of the cable or changing the material. Efforts to grant continue.

For example, category 5 of unshielded twisted pair (UTP) cables has a flame retardant added to a copper conductor layer insulated with a self-extinguishing fluorine-based resin to satisfy the plenum, the highest flame retardant grade of the cable. It consists of a cable which consists of a flame retardant sheath of polyvinyl chloride, and category 6 has the structure which inserted the cross-shaped cross filler comprised of the fluorine-type resin between conductors. Further, as a material constituting the sheath of an optical cable, an optical cable in which phosphate plasticizer and bromine plasticizer is added alone or in combination thereof to polyvinyl chloride has been developed. However, the phosphate plasticizer has a low smoke characteristics, but the flame retardancy is lowered, while the bromine plasticizer improves the flame retardancy, while releasing toxic gases harmful to the human body during the combustion process has a disadvantage that does not satisfy the low smoke characteristics. In particular, when only phosphate plasticizer and bromine plasticizer are used in combination, the plasticization performance is lowered and thermal stability is weak during processing.

In order to satisfy low smoke and high flame retardancy, inorganic flame retardants such as ammonium octamolybdate (AOM) used as smoke inhibitors in the above-described plasticizers, and aluminum trihydrate (ATH, aluminum) used as smoke inhibitors and flame retardants trihydrate) and magnesium dihydrate (MDH) have been proposed. However, when the ammonium octamolybdate is added to a predetermined content or more, the low smokeability of the cable is improved, but the thermal stability is lowered, so that the carbonization occurs in the material during the cable extrusion process, resulting in a decrease in the physical properties of the cable. In addition, when aluminum trihydrate and magnesium dihydrate are added to a predetermined content or more, low smokeability and flame retardancy are improved, flexibility required for cable installation is reduced, and there is a problem that mechanical properties are lowered by lowering elongation after heating. In addition, it increases the load during machining and increases the frictional heat, which causes a decrease in thermal stability. That is, the aluminum trihydrate must be 150 parts by weight or more and the ammonium octamolybdate must be added at least 30 parts by weight based on 100 parts by weight of the base resin to satisfy the flame retardant and smoke resistance characteristics of UL910 level, but such a content is added. If the above problem occurs.

Therefore, the technical problem to be solved by the present invention is to solve the above problems, not only excellent mechanical properties such as tensile strength, tensile elongation, flexibility, etc., but also excellent in thermal stability and high flame retardancy and low smoke resistance, satisfying UL910 standard. A cable having a sheath material composition from which a cable can be made and a sheath formed therefrom is provided.

In order to achieve the above technical problem, the present invention provides 100 parts by weight of a polyvinyl chloride resin, 10 to 30 parts by weight of a phosphorus flame retardant plasticizer, 10 to 30 parts by weight of a brominated flame retardant plasticizer, 5 to 20 parts by weight of a phthalate plasticizer, and an inorganic hydroxide of 30 to High flame retardant and low smoke sheath comprising 100 parts by weight, 5 to 40 parts by weight of ammonium octamolybdate, 5 to 20 parts by weight of zinc-molybdate salt complex, 1 to 10 parts by weight of zinc borate and 1 to 10 parts by weight of antimony trioxide Provide a material composition.

In the highly flame-retardant and low-flammable sheath material composition according to the present invention, the phosphorus flame-retardant plasticizer can be used alone or in combination of phosphorus plasticizers of phosphorus phosphate-based, alkyldiphenyl ester / phosphate having 12 to 16 carbon atoms. As the brominated flame retardant plasticizer, brominated dioctyl phthalate and tetrabromophthalate ester may be used alone or in combination thereof, and the phthalate plasticizer may include butyloctyl phthalate, diisodecyl phthalate and diisononyl phthalate. It may be used alone or in combination thereof.

Sheaths formed using the sheath material compositions described above can be used to make highly flame retardant and low-flammable cables.

Hereinafter will be described in detail with respect to the high flame retardant and low fume sheath material composition according to the present invention.

In the highly flame-retardant and low-flammable sheath material composition of the present invention, it is preferable to use a polyvinyl chloride resin which is a base resin having a polymerization degree of 800 to 2,000.

Three kinds of plasticizers were mixed and used in the highly flame retardant and low-flammable sheath material composition of the present invention.

Phosphorus flame retardant plasticizer was added 10 to 30 parts by weight based on 100 parts by weight of polyvinyl chloride. As the phosphorus flame retardant plasticizer, it is preferable to use phosphorus phosphate-based plasticizer, alkyl diphenyl ester / phosphate mixture having 12 to 16 carbon atoms alone or in combination thereof, and isodecyl as phosphorus phosphate-based plasticizer. Isodecyl diphenyl phosphate, alkyl aryl phosphate, octyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate and the like. If the content of the phosphorus flame retardant plasticizer is less than 10 parts by weight, the plasticizing effect is lowered, and the workability is not good, and high flame retardancy to pass the plenum flame retardant test cannot be obtained. In addition, if the content exceeds 30 parts by weight, there is a problem that the heat resistance is lowered.

The brominated flame retardant plasticizer was added in an amount of 10 to 30 parts by weight based on 100 parts by weight of polyvinyl chloride. Brominated flame retardant plasticizers are preferably brominated dioctyl phthalate or tetrabromophthalate esters alone or in combination. If the content is less than 10 parts by weight, phosphorus flame retardant The synergistic effect of the flame retardant with the plasticizer is insignificant, and if it exceeds 30 parts by weight, the smokeability increases, so that the effect of low smokeability is difficult to be expected.

In addition, the phthalate plasticizer was added 5 to 20 parts by weight based on 100 parts by weight of polyvinyl chloride. As the phthalate plasticizer, it is preferable to use butyloctyl phthalate, diisodecyl phthalate, diisononyl phthalate alone or in combination thereof. If the content is less than 5 parts by weight, the plasticizing effect and thermal stability are lowered. When the weight part is exceeded, the flame retardancy and the low smokeability deteriorate.

In addition, the highly flame retardant and low smoke sheath material composition of the present invention contains 30 to 100 parts by weight of inorganic hydroxide. As the inorganic hydroxide, aluminum trioxide, magnesium hydroxide, huntite, magnesium hydrate, or the like is preferably used alone or in combination thereof. If the content is less than 30 parts by weight, it is difficult to obtain high flame retardancy and is more than 100 parts by weight. Filling and workability are inferior, thermal stability falls and mechanical properties fall.

In addition, the highly flame retardant and low-flammable sheath material composition of the present invention includes 5 to 20 parts by weight of zinc-molybdate salt composite and 1 to 10 parts by weight of zinc borate, and within this range, an increase in flame retardant effect is achieved without deterioration of mechanical properties. You can expect

On the other hand, the highly flame retardant and low smoke sheath material composition of the present invention contains 5 to 40 parts by weight of ammonium octamolybdate (AOM) as a smoke inhibitor. If the content is less than 5 parts by weight, it is difficult to expect a low smoke-retardant smoke density suppression effect and a flame retardant synergistic effect. If the content exceeds 40 parts by weight, the mechanical properties and thermal stability is lowered.

In addition, the highly flame retardant and low-flammable sheath material composition of the present invention contains 1 to 10 parts by weight of antimony trioxide as a flame retardant aid. If the content is less than 1 part by weight can not be expected to increase the flame retardancy, if the content exceeds 10 parts by weight shows a high smoke density value.

As described above, the sheath formed of a material consisting of the composition and the composition ratio according to the present invention is excellent in thermal stability and exhibits high flame retardancy and low smoke resistance, and thus can be used to manufacture a plenum-class cable that satisfies the UL910 standard. Mechanical properties such as strength, tensile elongation and flexibility are also excellent.

Hereinafter, examples will be described in detail to help understand the present invention. However, embodiments according to the present invention can be modified in many different forms, the scope of the invention should not be construed as limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Examples 1-5

It was kneaded in an open roll with the components and the composition ratio as described in Table 1, and then molded at 170 ℃ for 10 minutes to prepare a specimen.

Ingredients (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Polyvinyl chloride resin 100 100 100 100 100 Isodecyldiphenyl phosphate 30 30 20 20 - Alkyldiphenyl Ester / Phosphate Mixtures - - - - 10 Bromine plasticizer 10 20 10 20 30 Phthalate plasticizer 5 15 10 5 10 Antimony trioxide 5 5 5 5 5 Aluminum trihydrate 50 50 70 50 50 Ammonium octamolybdate 10 10 10 20 30 Zinc-Molybdate Complex 5 5 5 5 5 Zinc borate 5 5 5 5 5 Paraffin wax 0.5 0.5 0.5 0.5 0.5 Phenolic Antioxidants 0.5 0.5 0.5 0.5 0.5 TLS Lead Stabilizer 5 5 5 5 5

Comparative Examples 1 to 6

Specimens were prepared in the same manner as in Example except that the ingredients and contents according to Table 2 were changed.

Ingredients (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Polyvinyl chloride resin 100 100 100 100 100 100 Isodecyldiphenyl phosphate 30 30 - 30 30 30 Bromine plasticizer 20 - - 20 20 20 Phthalate plasticizer - 20 50 10 10 10 Antimony trioxide 5 5 5 5 5 5 Aluminum trihydrate 50 50 50 120 50 50 Ammonium octamolybdate 20 20 20 20 4 20 Zinc-Molybdate Complex 5 5 5 5 5 - Zinc borate 5 5 5 5 5 5 Paraffin wax 0.5 0.5 0.5 0.5 0.5 0.5 Phenolic Antioxidants 0.5 0.5 0.5 0.5 0.5 0.5 TLS Lead Stabilizer 5 5 5 5 5 5

In Tables 1 and 2, brominated flame retardant plasticizers were brominated dioctyl phthalate, and phthalate plasticizers were diisodecyl phthalate (DIDP), and the composition ratio unit is parts by weight.

Physical properties of the samples prepared according to the above Examples and Comparative Examples were measured and shown in Table 3 below.

THE (total heat evolved)

Combustion experiments were performed on cone calorimeters in accordance with ASTM 1356-90. After a certain size of specimen (100 × 100 × 3mm) was placed horizontally under the cone-shaped heater, a constant amount of heat (70 kW / m 2) was applied to measure the amount of heat released during combustion of the material. It has been empirically deduced that in order to have a flame retardancy of UL910 level, the value of THE should be less than about 25 MJ / m 2 when applying a heat of 70 kW / m 2.

TSR (total smoke released)

Smoke density was measured in the same manner as in THE. It has been empirically derived to have a low TSR value of about 700 or less when applying 70 kW / m2 of heat to have a low smokeability of UL910 level.

Room temperature characteristics

Tensile strength and elongation were measured according to ASTM D638.

Thermal stability

About 5 mg of the specimen was placed in a glass test tube, and then the upper part was blocked with indicator paper and the time was measured when the color of the indicator paper was changed due to pyrolysis of the sheath material while maintaining 200 ° C.

Properties Example Comparative example One 2 3 4 5 One 2 3 4 5 6 THE (MJ / ㎡) 23 24 21 22 21 22 28 35 19 23 29 TSR 650 680 620 680 670 650 900 1500 550 1200 900 Tensile strength (kgf / ㎡) 1.90 1.78 1.71 1.83 1.75 1.87 1.95 2.0 1.45 1.85 1.83 Elongation (%) 190 220 170 202 198 220 210 225 140 200 195 Thermal stability (sec) 3200 3800 3650 3350 3350 1350 3800 4200 3600 3520 3550 Cable flexibility good good good good good good good good Bad good good UL910 evaluation result (smoke density) pass pass pass pass pass pass - fail - - - UL910 evaluation result (flame length) pass pass pass pass pass pass - fail - - -

Referring to Table 3, the measurement results for the specimens of Examples 1 to 5 were all satisfactory. On the other hand, the specimen of Comparative Example 1 without the addition of a phthalate-based plasticizer was passed the UL910 standard but very poor in thermal stability, and the specimen of Comparative Example 2 without the addition of the bromine-based plasticizer showed high values of THE and TSR. In addition, the specimen of Comparative Example 3, in which only a phthalate-based plasticizer was added as the plasticizer, also had a high THE and TSR value and failed the UL910 standard. The specimen of Comparative Example 4, in which an excessive amount of aluminum trihydrate was added, was excellent in flame retardancy and low smoke resistance, but was inferior in flexibility, and inferior in tensile strength and elongation. The specimen of Comparative Example 5, in which the addition of too small ammonium octamolybdate, had a high TSR value, and the specimen of Comparative Example 6, in which the zinc-molybdate complex was not added, had a high THE and TSR value.

As described above, the sheath formed of a material consisting of the composition and the composition ratio according to the present invention is excellent in thermal stability and exhibits high flame retardancy and low smoke resistance, and thus can be used to manufacture a plenum-class cable that satisfies the UL910 standard. Mechanical properties such as strength, tensile elongation and flexibility are also excellent.

Claims (6)

100 parts by weight of polyvinyl chloride resin, 10 to 30 parts by weight of phosphorus flame retardant plasticizer, 10 to 30 parts by weight of brominated flame retardant plasticizer, butyloctyl phthalate, diisodecyl phthalate, diisononyl phthalate and mixtures thereof 5 to 20 parts by weight of one phthalate plasticizer, 30 to 100 parts by weight of inorganic hydroxide, 5 to 40 parts by weight of ammonium octamolybdate, 5 to 20 parts by weight of zinc-molybdate salt composite, 1 to 10 parts by weight of zinc borate and A high flame retardant and low smoke sheath material composition comprising 1 to 10 parts by weight of antimony trioxide. According to claim 1, wherein the flame-retardant plasticizer is a high flame retardant, characterized in that any one selected from the group consisting of phosphorus plasticizer of phosphorus phosphate-based, alkyl diphenyl ester / phosphoric acid mixture having 12 to 16 carbon atoms and mixtures thereof And low smoked sheath material compositions. The flame retardant and low-flammability sheath material composition of claim 1, wherein the bromine-based flame retardant plasticizer is any one selected from the group consisting of brominated dioctyl phthalate, tetrabromophthalate ester, and mixtures thereof. delete The highly flame retardant and low-flammable sheath material composition according to claim 1, wherein the inorganic hydroxide is any one selected from the group consisting of aluminum trioxide, magnesium hydroxide, humite, magnesium hydrate, and mixtures thereof. 100 parts by weight of polyvinyl chloride resin, 10 to 30 parts by weight of phosphorus flame retardant plasticizer, 10 to 30 parts by weight of brominated flame retardant plasticizer, butyloctyl phthalate, diisodecyl phthalate, diisononyl phthalate and mixtures thereof 5 to 20 parts by weight of one phthalate plasticizer, 30 to 100 parts by weight of inorganic hydroxide, 5 to 40 parts by weight of ammonium octamolybdate, 5 to 20 parts by weight of zinc-molybdate salt composite, 1 to 10 parts by weight of zinc borate and A cable having a high flame retardant and low smoke sheath formed from a composition comprising 1 to 10 parts by weight of antimony trioxide.