KR100624875B1 - Composition for production flame retardant insulating material of halogen free type with drip resistance properties and flame retardant insulating material of halogen free type using the same - Google Patents

Abstract

The present invention relates to a composition for producing a non-halogen flame retardant insulating material having an improved drip property and a non-halogen flame retardant insulating material using the same. The composition for producing a non-halogen flame retardant insulating material having improved drip characteristics according to the present invention is blended with 40 to 70 wt% of an ethylene-α-olefin copolymer and 30 to 60 wt% of an ethylene copolymer, and has a number average molecular weight ( 100 parts by weight of the base resin having a ratio (Mw / Mn) of the weight average molecular weight (Mw) to Mn) of 5 or less; selected from magnesium hydroxide (Mg (OH) ₂ ) and aluminum hydroxide (Al (OH) ₃ ) 100 to 200 parts by weight of a metal hydroxide-based flame retardant as a single material or a mixture of two; And 1 to 20 parts by weight of a flame retardant aid including 1 to 5 parts by weight of a material based on a substance. According to the present invention, since the halogen element is not included in the composition components used, it can be said to be more environmentally friendly than conventional halogen-based products during combustion, and it can be manufactured while satisfying the conditions required for mechanical properties such as tensile strength or elongation. Ease of processing is secured, and particularly, drip characteristics are suppressed while maintaining flame retardancy.

Drip Properties, Halogen, Blends, Polyethylene, Zinc Borate,

Description

Composition for production flame retardant insulating material of halogen free type with drip resistance properties and flame retardant insulating material of halogen free type using the same}

The present invention relates to a composition for producing a non-halogen flame retardant insulating material with improved drip characteristics and to a non-halogen flame retardant insulating material using the same. The present invention relates to a non-halogen flame retardant insulating material having improved drip characteristics and a non-halogen flame retardant insulating material using the same.

In order to be used as an insulating material for electric wires, a flame retardance of a certain degree or more is required, and a method of using a resin composition containing a halogen element is known that has been developed for the purpose of improving the flame retardancy. On the other hand, in the case of an insulating material manufactured using a resin composition containing a halogen element, it is known to suppress the combustion of materials by generating a non-flammable heavy halogen gas during combustion and forming a solidified ash by reacting with an additive. Therefore, in the case of the insulating material manufactured using a halogen-based resin, flame retardancy is basically retained, and various flame retardants are added for the purpose of further improving flame retardancy. The various flame retardants added in this way do not significantly affect the basic physical properties of the base resin because it is used only a small amount, it does not cause an increase in the viscosity of the insulating material has the advantage of expressing excellent extrusion processability.

As a representative material used as a flame retardant added to the base resin for manufacturing a conventional insulating material, polyvinyl chloride (PVC) may be mentioned, but when the insulating material produced by using the resin composition containing the material is burned, Due to the release of the same toxic gas, it is known to have a harmful effect on the human body and the environment. In connection with this, the development of new materials with relatively low hazards is being progressed along with regulations for environmental protection and interests in the development of environmentally friendly alternative materials.

Inorganic metal hydroxides are used in technologies that are emerging as environmentally friendly flame retardant technologies.In order to improve the flame retardancy, a considerable amount of these materials must be added, but the mechanical properties such as tensile strength and elongation of the manufactured insulation are deteriorated. It is becoming.

On the other hand, resins with high crystallinity, such as polyethylene (PE), which is one of the ethylene copolymers, have low flame retardancy and poor drip characteristics. Thus, by blending different types of resins rather than using them alone to form a base resin, Research has been conducted on how to compensate for the shortcomings, and the metal hydroxide used as the flame retardant is uniformly and tightly combined with the base resin and promotes char formation during combustion to enhance flame retardancy as well as burned ash ( By preventing ash from flowing down (drip characteristics), the contact with air can be alleviated to improve the flame retardancy. Therefore, various methods can be used to eliminate or significantly reduce the drip characteristics. In the related industrial field, the present invention has been devised under such technical background.

The technical problem to be solved by the present invention based on the above-mentioned conventional problems is to compose a composition containing no halogen element in order to solve environmental problems, and to provide mechanical properties and manufacturing requirements for an insulating material such as an insulating coating layer of an electric wire. In order to enhance the ease of processing, particularly to enhance the flame retardancy, and to provide a composition for producing a non-halogen flame retardant insulation material with improved drip properties that can achieve such a technical problem and a non-halogen flame retardant insulation material using the same There is an object of the present invention.

In order to achieve the technical problem to be achieved by the present invention, one of the compositions for preparing a non-halogen-based flame retardant insulation material having improved drip characteristics according to the present invention is 40 to 70 wt% of an ethylene-α-olefin copolymer and 30 to 100 parts by weight of a base resin blended with 60% by weight of an ethylene copolymer and having a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 5 or less; and magnesium hydroxide (Mg ( OH) ₂ ) and aluminum hydroxide (Al (OH) ₃ ) 100 to 200 parts by weight of a metal hydroxide-based flame retardant of a single or a mixture of two selected from one; And 1 to 20 parts by weight of a flame retardant aid including 1 to 5 parts by weight of a material based on a substance.
In order to achieve the technical problem to be achieved by the present invention, another composition of the non-halogen-based flame retardant insulation material with improved drip properties according to the present invention, 40 to 70% by weight of ethylene-α-olefin copolymer and 30 100 to 200 parts by weight of the base resin blended with the ethylene-based copolymer of about 60% by weight; 1 to 20 parts by weight of a flame retardant adjuvant including 1 to 5 parts by weight of a drop-based material; And 1 to 10 parts by weight of a silane coupling agent.

With respect to the content of the ethylene-α-olefin copolymer constituting the base resin, the tensile strength, oil resistance and heat resistance is lowered when the lower limit of the numerical limit is lowered, and the flexibility is exceeded when the upper limit of the numerical limit is exceeded. This lowers and is not preferable. With respect to the content of the ethylene copolymer constituting the base resin, the flexibility falls when the lower limit of the numerical limit is lowered, and when the upper limit of the numerical limit is exceeded, the tensile strength, oil resistance and heat resistance are lowered. Not desirable

Crystalline resins such as polyethylene (PE), which is one of the ethylene copolymers, have low flame retardancy and poor drip characteristics. Therefore, rather than being used alone in forming a base resin, this resin is intended to compensate for these disadvantages. It is preferable to use the ethylene alpha olefin copolymer mixed and blended in the above ratio. The ethylene copolymer is more preferably polymerized using a metallocene catalyst.

It is preferable that ratio (Mw / Mn) of the weight average molecular weight (Mw) with respect to the number average molecular weight (Mn) of the said base resin is 5 or less. The molecular weight distribution ratio (Mw / Mn) as described above affects the physical properties of the product after molding and affects the melt index (MI) during molding. Therefore, when the upper limit of the numerical limit is exceeded, the physical properties are improved. The workability is weakened, which is not preferable. The molecular weight distribution ratio can be controlled by the production process conditions, such as the catalyst used, temperature or pressure.

The metal hydroxide, which is the flame retardant, is preferably one or a mixture of two selected from magnesium hydroxide (Mg (OH) ₂ ) and aluminum hydroxide (Al (OH) ₃ ), and the metal hydroxide, which is a flame retardant, is surfaced with fatty acids or silanes. It is more preferable if it has been processed. With respect to the content of the metal hydroxide, if the lower limit of the numerical limit is less than the flame resistance is lowered, if it exceeds the numerical limit, the mechanical properties, e.g. elongation rate is lowered, which is undesirable.

The composition for producing a non-halogen flame retardant insulation material having improved drip characteristics is preferably made by further comprising 1 to 10 parts by weight of a silane coupling agent. In this case, the silane coupling agent serves to support the resin and the flame retardant to be tightly coupled to each other, it is preferable that the silane-based coupling agent is melt-mixed in the carrier resin during the manufacturing process. On the other hand, with respect to the content of the silane coupling agent, if the lower limit of the numerical limit is less than the cross-linking reaction does not occur sufficiently, mechanical properties such as tensile strength may deteriorate, heat deformation deterioration, extrusion torque When the moldability is increased, the moldability deteriorates, and when the upper limit of the numerical limit is exceeded, the mechanical property and the moldability are hardly improved, and thus, a problem occurs that odor is generated.

The material constituting the flame retardant aids the formation of a char to improve the flame retardancy by forming a solid film during combustion, and to have a low smoke, and in relation to the content, if it is less than the numerical limit If this is lowered and the numerical value is exceeded, the mechanical properties are lowered, which is not preferable. On the other hand, the material based on the flame retardant aid, like the zinc borate-based material, helps to form a char and improves flame retardancy, as well as suppresses a phenomenon that ash flows during combustion of the insulating material. In addition, if the numerical limit is not met, the purpose of the addition cannot be achieved, and if the numerical limit is exceeded, the increase in the price ratio addition effect is relatively weak, and the cause of discoloration is provided. Not desirable

The non-halogen flame retardant insulating material can be manufactured using the composition for preparing non-halogen flame retardant insulating material having improved drip characteristics according to the present invention, and the non-halogen flame retardant insulating material has an elongation of 120% or more, and the tensile strength thereof. The strength is 10 to 20 Mpa, and its oxygen index is characterized by being 28 or more. Elongation and tensile strength are numerical values according to ASTM D412 and oxygen indexes are numerical values according to ASTM D2863.

Hereinafter, the present invention will be described with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Classification of Example (1-5) and Comparative Example (1-6)

As examples according to the present invention, divisions were set as Examples 1 to 5 (see Table 1 below), and Comparative Examples 1 to 6 (see Table 2 below) were set as divisions for the purpose of comparison.

After blending the compositions according to Examples (1-5) shown in Table 1 below, and mixing in a sheet form on an 8-inch open roll, press-molded at 170 ℃ for 20 minutes, suitable for the measurement or evaluation of each characteristic Insulation specimens were prepared. In Table 1 below, tensile strength, elongation rate and 5% modulus, which are mechanical properties of insulating materials prepared using the compositions shown in Examples (1-5), were measured, respectively, and the aging tensile retention and aging were evaluated for heat resistance. The residual elongation was measured, the oxygen index was measured for the evaluation of flame retardancy, and the hot / set test, the smoke density test and the drip characteristics were evaluated to evaluate the drip property, and the results are shown in Table 1 below.

The tensile strength and the elongation rate were measured while producing a dumbbell-type test piece according to IEC 60811-1-1 from a press sheet having a thickness of 1 mm and proceeding at a speed of 250 nm / min. On the other hand, 5% modulus measured the tensile strength value when the specimen is stretched 5%. The aging tensile elongation and aging elongation residual rate associated with the heat resistance evaluation were evaluated by the residual strength by measuring the tensile strength and elongation after aging for 7 days under air condition of 100 ℃. The flame retardancy was measured by an oxygen index measuring method according to ASTM D2863 from a press sheet having a thickness of 3 mm. The hot / set test was evaluated by IECA T-562 after 15 minutes exposure to 150 ℃ air condition as a tensile test specimen. The said smoke density test calculated | required the maximum value of the smoke density value by ASTM E662 from the press sheet of thickness 2mm, width 75mm, and length 75mm, and rejected when the smoke density was 150 or more, and judged as pass when it is less than 150. In the drip property evaluation, the case where the ash during combustion did not flow down during the smoke density test was judged as a case where the case where the ash flowed down passed.

division Example One 2 3 4 5 Composition EVA 70 LLDPE 60 50 70 70 Ethylene Copolymer 30 40 50 30 30 Flame retardant 120 130 140 80 120 Flame retardant aids (1) 10 10 10 10 10 Flame retardant aids (2) 2 2 2 2 3 Coupling agent 2 2 2 2 2 Antioxidant 2 2 2 2 2 Lubricant 2 2 2 2 2 Properties Tensile Strength (Mpa) 18 15 14 21 17 Elongation (%) 440 400 390 450 350 5% Modulus (Mpa) 5.6 4.5 3.8 3.6 5.5 Aging Residual Rate (%) 104 96 98 98 101 Aging Elongation (%) 97 95 99 94 92 Oxygen Index (%) 33 33 34 30 34 Hot / set experiment 5/0 5/0 5/0 5/0 5/0 Smoke density test pass pass pass pass pass Drip characteristics pass pass pass pass pass

In Table 1, the EVA is ethylene vinyl acetate having a vinyl acetate (VA) content of 17%, the LLDPE is a linear low density polyethylene (molecular weight distribution = 3.5), the ethylene copolymer is an ethylene butene copolymer, As the flame retardant, silane-coated aluminum hydroxide was used, zinc borate was used as the flame retardant aid (1), and phosphorus was used as the flame retardant aid (2), and a vinylsilane-based coupling agent was used as the coupling agent. As the antioxidant, a hindered phenol-based antioxidant was used, and as the lubricant, stearic acid was used.

With respect to the same evaluation item as the physical property evaluation item in each embodiment as shown in Table 1, and proceeded in the same manner for Comparative Examples 1 to 6, the results are shown in Table 2 below.

division Comparative example One 2 3 4 5 6 Composition EVA 30 100 50 70 LLDPE 100 Ethylene Copolymer 50 30 HDPE 100 Flame retardant 120 160 100 220 50 50 Flame Retardant 10 0 10 10 5 5 Antioxidant 2 2 2 2 2 2 Lubricant 2 2 2 2 2 2 Properties Tensile Strength (Mpa) 11 9.4 12.1 7.3 16 18 Elongation (%) 340 210 320 200 350 650 5% Modulus (Mpa) 2.5 4.5 7.8 3.6 4.5 9.5 Aging Residual Rate (%) 80 96 96 87 101 97 Aging Elongation (%) 77 95 94 83 92 92 Oxygen Index (%) 28 29 28 30 25 22 Hot / set experiment 5/0 5/0 80/30 5/0 5/0 65/25 Smoke density test fail fail fail fail fail fail Drip characteristics fail fail fail fail fail fail

In Table 1, the EVA is ethylene vinyl acetate having a vinyl acetate (VA) content of 28%, the LLDPE is a linear low density polyethylene (molecular weight distribution = 3.5), the ethylene copolymer is an ethylene butene copolymer, The HDPE is a high density polyethylene (molecular weight distribution = 10), the silane-coated aluminum hydroxide was used as the flame retardant, the zinc borate was used as the flame retardant aid, the hindered phenol-based antioxidant as the antioxidant Stearic acid was used as a lubricant.

As can be confirmed by comparing the physical properties of Examples (1-5) and Comparative Examples (1-6) according to Tables 1 and 2, various mechanical in Examples (1-5) according to the present invention It can be seen that the properties, heat resistance, flame retardancy, etc. have superior physical properties than the comparative examples (1-6), in particular, hot / set (hot / set) experiments, smoke density test and drip characteristics showed better results. .

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention in detail to those skilled in the art and are not intended to limit the scope of the present invention as defined in the claims or the claims.

According to the present invention, since the halogen element is not included in the composition components used, it can be said to be more environmentally friendly than conventional halogen-based products during combustion, and it can be manufactured while satisfying the conditions required for mechanical properties such as tensile strength or elongation. Ease of processing is secured, and in particular, the drip property is suppressed, so that the flame retardancy is particularly enhanced.

Claims (7)

Blended from 40 to 70% by weight of ethylene-α-olefin copolymer with 30 to 60% by weight of ethylene copolymer, the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) 100 parts by weight of a base resin of 5 or less; 100 to 200 parts by weight of a metal hydroxide flame retardant; And 1 to 20 parts by weight of the flame retardant aid including 1 to 5 parts by weight of the material based; The metal hydroxide-based material, which is the flame retardant, is a non-halogen-based flame retardant having improved drip characteristics, characterized in that a single substance or a mixture of two selected from magnesium hydroxide (Mg (OH) ₂ ) and aluminum hydroxide (Al (OH) ₃ ). Insulation material composition. The method of claim 1, Metal hydroxide-based material selected as the flame retardant is a composition for producing a non-halogen flame retardant insulation material improved drip properties, characterized in that the surface treatment is made of fatty acids or silane. 100 parts by weight of the base resin blended with 40 to 70% by weight of the ethylene-α-olefin copolymer and 30 to 60% by weight of the ethylene copolymer; 100 to 200 parts by weight of a metal hydroxide flame retardant; 1 to 20 parts by weight of a flame retardant adjuvant including 1 to 5 parts by weight of a drop-based material; And 1 to 10 parts by weight of a silane coupling agent; composition for producing a non-halogen flame-retardant insulation material improved drip properties characterized in that it comprises a. The method of claim 3, A ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the base resin is 5 or less composition for producing a non-halogen flame retardant insulation improved drip characteristics. The method of claim 3, The metal hydroxide-based material, which is the flame retardant, is a non-halogen-based flame retardant having improved drip characteristics, characterized in that a single substance or a mixture of two selected from magnesium hydroxide (Mg (OH) ₂ ) and aluminum hydroxide (Al (OH) ₃ ). Insulation material composition. The method of claim 5, The metal hydroxide-based material selected as the flame retardant is a composition for producing a non-halogen flame retardant insulating material having improved drip property, characterized in that the surface treatment is made of fatty acids or silanes. In non-halogen flame retardant insulating material, A non-halogen flame retardant insulating material having improved drip properties according to any one of claims 1 to 6 is prepared using a composition for manufacturing, the elongation is more than 120%, the tensile strength is 10 to 20Mpa, Non-halogen flame retardant insulation material with improved drip characteristics, characterized in that the oxygen index is 28 or more.