KR100730835B1 - Composition for production flame retardant insulating material including micro capsulated flame retardant supplement - Google Patents

Abstract

Provided is a composition for preparing a flame retardant insulating material containing a microcapsulated flame retardant aid by using environmentally friendly materials to improve flame retardancy and workability without the deterioration of mechanical properties. The composition comprises 100 parts by weight of a base resin which comprises 10-90 wt% of an ethylene-vinyl acetate copolymer resin containing 15-22 wt% of vinyl acetate, and 10-90 wt% of an ethylene-vinyl acetate copolymer resin containing 23-27 wt% of vinyl acetate; 5-350 parts by weight of an inorganic flame retardant which is a metal hydroxide surface treated with any one selected from a vinyl silane, a fatty acid and an aminopolysiloxane; 5-80 parts by weight of a microcapsulated flame retardant aid(10) which comprises a center part(12) comprising a red phosphorus microparticle and a capsule wall(14) comprising melamine; and 1-10 parts by weight of a crosslinking aid which is a cyanurate-based material.

Description

Composition for production flame retardant insulating material including a micro-encapsulated flame retardant supplement

The following drawings attached to this specification are illustrative of preferred embodiments of the present invention, and together with the detailed description of the invention to serve to further understand the technical spirit of the present invention, the present invention is a matter described in such drawings It should not be construed as limited to.

1 is a cross-sectional view of a microencapsulated flame retardant adjuvant according to the present invention.

<Description of main parts of drawing>

10 ... Microencapsulated Flame Retardant

12 ... centered 14 ... melamine capsule wall

The present invention relates to a composition for producing a flame retardant insulating material comprising a micro-encapsulated flame retardant aid, a micro-encapsulated flame retardant aid used to express sufficient flame retardancy while maintaining the required mechanical properties, and a method for manufacturing the same and a composition for producing a flame retardant insulating material using the same It is about.

Conventionally, as a method for adding flame retardancy to an insulating material, a method of adding a halogen flame retardant such as bromine is difficult in long-term application due to the recently tightened environmental regulations and the use of bromine flame retardants. have. In order to solve this problem, nitrogen-based flame retardants such as phosphorus and melamine have been used, but this is less efficient than halogen-based flame retardants such as bromine-based flame retardants, smoke is generated more severely, and char is smoothly formed during combustion. It is not made so, causing a dripping phenomenon in which the combustion products melt, there is a problem that the application is not possible depending on the flame retardant test method. On the other hand, metal hydroxide flame retardants such as aluminum hydroxide and magnesium hydroxide, which are widely used to realize flame retardancy in polyolefin resins, have an excellent effect of suppressing char formation and dripping, but aluminum hydroxide has a decomposition temperature higher than the melting point of polyolefin resin. In the case of magnesium hydroxide, hydrolysis occurs in the temperature range of 200 to 250 ° C., which reduces the mechanical properties, and the resulting salt is attached to the metal surface of the processing equipment to prevent damage to the processing equipment. As it is caused, its application is also difficult.

Therefore, in addition to selecting an appropriate base resin, a non-halogen-based metal hydroxide is used as a flame retardant, but researches for adding a flame retardant adjuvant for the purpose of solving the problems of deterioration of mechanical properties and workability due to excessive use of the flame retardant are in progress. Has been. For example, the method of encapsulating the flame retardant disclosed in the Republic of Korea Patent Publication No. 10-2004-83908 and US Patent No. 6,750,282 has been introduced, but the disadvantage that the flame retardancy of the resin constituting the capsule wall is not secured and the polyolefin resin There are limitations in compatibility, so many technical constraints as well as low reproducibility have been known in the use as a composition for producing an actual insulating material.

It has been recognized that the need to solve such a problem, in the related art, in the manufacture of insulating materials, a resin composition that can be used to produce an insulating material that can ensure the stable mechanical properties and manufacturing process efficiency, and can sufficiently express the required flame retardancy Efforts have been made to develop steadily, and the present invention has been devised under this technical background.

The technical problem to be achieved by the present invention on the basis of the above-mentioned conventional problems is to use a flame retardant to secure sufficient flame retardancy, to solve the problems of mechanical properties or process efficiency deterioration caused thereby, It is an object of the present invention to provide a composition for producing a flame retardant insulating material comprising a micro-encapsulated flame retardant aid that can achieve the problem.

The composition for producing a flame retardant insulating material provided in the present invention for achieving the technical problem to be achieved by the present invention, characterized in that it comprises a microencapsulated flame retardant aid consisting of a capsule wall made of a melamine surrounding the central portion and made of a particulate. do.

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Hereinafter, specific examples will be described in order to help understanding of the present invention, and it will be described in more detail with reference to the accompanying drawings. 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 fully explain the present invention to those skilled in the art.

1 is a cross-sectional view of a microencapsulated flame retardant adjuvant according to the present invention.

The microencapsulated flame retardant aid 10 is composed of a capsule wall 14 wrapping the central portion 12 and its outer peripheral surface. The central portion 12 is composed of a particle of a flame retardant adjuvant component, the capsule wall 14 is made of melamine.

It is preferable that the microencapsulated flame retardant aid as shown in FIG. 1 be prepared by the following two methods.

The first method for preparing a micro-encapsulated flame retardant aid is a method called in-situ polymerization, which is converted into a prepolymer by controlling the pH of an aqueous solution of melamine, a material constituting the capsule wall (S11). Thereafter, (S12) is prepared by proceeding the process of mixing the prepolymer with the emulsion containing the core material consisting of the enemy. At this time, the parameters related to the various materials used, such as the amount of stabilizer, the concentration of the reactive monomers, and the relative concentrations between the components and the process parameters, such as the stirring speed, the stirring rod and the design of the reaction vessel, are optimized. It is preferable to determine the particle size and distribution of the enemy at and.

On the other hand, the second method for preparing a micro-encapsulated flame retardant aid is a method called spray drying (S21) after mixing the melamine and the core material (S21) capsule wall material, (S22) of the mixture It is prepared by the process of pumping the emulsion phase solution using a spray dryer (spray dryer).

The base resin included in the composition for preparing a flame retardant insulating material provided in the present invention includes 10 to 90 wt% of ethylene vinyl acetate (EVA) having a vinyl acetate content of 15 to 22 wt%; and ethylene having a vinyl acetate content of 23 to 27 wt%. 10 to 90% by weight of vinyl acetate (EVA); blended resin may be used. Regarding the vinyl acetate content contained in each of the ethylene vinyl acetate (EVA) contained in the blended mixed resin, if the lower limit is not reached, the compatibility with the flame retardant is not preferable, and if the upper limit is exceeded, a smoke defect occurs. Not desirable Maintaining the blending ratio in the blended mixed resin is preferable to ensure compatibility of the mixed resin, flame retardancy.

In addition, the base resin included in the composition for preparing a flame retardant insulating material provided in the present invention, 60 to 95% by weight ethylene vinyl acetate copolymer resin having a vinyl acetate content of 23 to 27% by weight; and ethylene vinyl acetate copolymerized with maleic anhydride 5 to 40% by weight of resin; blended resin may be used. With respect to the vinyl acetate content contained in the ethylene vinyl acetate (EVA) contained in the blended mixed resin, when the lower limit is lower, it is not preferable to reduce the compatibility with the flame retardant, and when the upper limit is exceeded, smoke defects occur, which is not preferable. Can not do it. Maintaining the blending ratio in the blended mixed resin is preferable to ensure compatibility of the mixed resin, flame retardancy.

The inorganic flame retardant included in the composition for preparing a flame retardant insulating material provided in the present invention is preferably included in an amount of 5 to 350 parts by weight based on 100 parts by weight of the base resin. The inorganic flame retardant is preferably a metal hydroxide surface-treated as any one selected from vinylsilane, fatty acid, and aminopolysiloxane, and more preferably, the metal hydroxide is any one of metal hydroxide selected from aluminum hydroxide and magnesium hydroxide.

The flame retardant auxiliary agent included in the composition for preparing a flame retardant insulating material provided in the present invention is preferably included in an amount of 5 to 80 parts by weight based on 100 parts by weight of the basic resin. Regarding the numerical range of the content of the flame retardant auxiliary agent, if it is lower than the lower limit, it is not preferable because it hardly contributes to the improvement of flame retardancy, and if the upper limit is exceeded, it may cause deterioration of physical properties in compatibility with the resin.

The crosslinking aid included in the composition for preparing a flame retardant insulating material provided in the present invention is preferably included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the base resin. In relation to the numerical range of the content of the crosslinking aid, if the lower limit is reached, the crosslinking reaction does not occur properly, the crosslinking degree is lowered, and the heat resistance is poor. If the upper limit is exceeded, the radical formation that participates in the crosslinking reaction is excessively excessive. Although the degree of crosslinking of the material is high, the molecular weight is lowered, which may lower the physical properties and heat resistance, which is not preferable. The crosslinking aid is preferably a cyanurate-based substance.

The composition for producing a flame retardant insulating material provided in the present invention may further include any one or two or more materials selected from antioxidants, lubricants and processing aids. Any one component selected from the antioxidant, lubricant and processing aid is preferably included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the base resin.

Regarding the numerical range of the amount of the antioxidant, if it is lower than the lower limit, it is difficult to achieve the effect of antioxidant for the purpose of addition, and if it exceeds the upper limit, it is uneconomical without increasing the proportional effect to the excess amount. It is not preferable because of the problem of or the problem of inhibiting compatibility with other materials. As the antioxidant, any one selected from thioester-based and phenol-based antioxidants or a mixture thereof is preferable.

Lubricant refers to one of the additives added in order to improve the fluidity of the resin, to prevent sticking to the processing machine or to improve the releasability in the mold when molding the resin. The effect of the lubricant is divided into internal lubrication and external lubrication depending on the compatibility of the lubricant with the resin. Both parts of the compatibility are related to the lubricant molecular chain length and the polarity. For example, those having polar groups such as carboxyl groups, ester bonds or hydroxyl groups (fatty acid derivatives, alcohols) have good compatibility with resins and have a plasticizing action. Used as internal lubricant. On the other hand, long-chain hydrocarbon-based ones (paraffins and waxes) without polar groups are used as external lubricants having a slip effect due to their low compatibility with resins. In fact, many lubricants with both internal and external lubrication are being manufactured, but they are not universal for any application or processing. Therefore, it is important to select a suitable lubricant according to resin, plasticizer, molding method and the like. Regarding the numerical range for the content of the type of the body, if the lower limit is not reached, it is difficult to achieve the purpose of the addition as described above, and if the upper limit is exceeded, it is not preferable to express low tensile strength. As the lubricant, any one selected from amide or polyolefin wax or a mixture thereof may be used.

Processing aids are materials added for the purpose of improving the physical properties such as the color of the product, the surface state, the tear strength at the time of heat addition by a small amount of addition, and representative examples thereof are acrylic modifiers. Regarding the numerical range of the amount of the processing aid, if the lower limit is not reached, the effect of reducing load during the processing does not occur, so that the purpose of the addition cannot be sufficiently achieved, and if the upper limit is exceeded, the partially added portion It is undesirable to diffuse onto the surface of the finished product, causing poor appearance.

Example (1-3) and Comparative example (1-4)

As shown in Table 1 below, the respective compositions according to the divided Examples (1 to 3) and Comparative Examples (1 to 4) were prepared. Thereafter, the composition having a composition as shown in Table 1 was kneaded at 130 ° C. for 10 minutes using a roll mill, and then pressed at 170 ° C. for 20 minutes to prepare a specimen, and evaluated required physical properties.

division Example (1-3) Comparative example (1-4) One 2 3 One 2 3 4 Resin A 50 60 40 50 60 40 60 Resin B 40 30 50 40 30 50 30 Resin C 10 10 10 10 10 10 10 Inorganic flame retardant A 150 - - 150 - - - Inorganic flame retardant B - 200 200 - 200 200 200 Flame Retardant A 10 10 5 - - - - Flame Retardant Supplement B - - - 10 10 5 - Flame retardant auxiliary C - - - - - - 10 Lubricant and processing aid 4 4 4 4 4 4 4 Antioxidant 3 3 3 3 3 3 3 Crosslinking aid 3 3 3 3 3 3 3

In Table 1, 'resin A' represents an ethylene vinyl acetate copolymer resin having a vinyl acetate content of 19% by weight, 'resin B' represents an ethylene vinyl acetate copolymer resin having a vinyl acetate content of 25% by weight, and 'resin C' 'Represents ethylene vinyl acetate copolymer resin into which maleic anhydride is introduced,' inorganic flame retardant A 'represents aluminum hydroxide surface-treated with vinyl silane,' inorganic flame retardant B 'represents magnesium hydroxide surface-treated with a polymer,' Flame retardant A 'represents the microencapsulated enemy with melamine,' flame retardant auxiliary B 'represents the enemy,' flame retardant auxiliary C 'represents the urea formaldehyde microencapsulated enemy. On the other hand, in Table 1, the lubricant and the processing aid was used a low molecular weight polyethylene wax, the antioxidant was used a phenolic material, the crosslinking aid was used a cyanurate-based material.

The specimens prepared from each composition according to Table 1 were measured at room temperature as mechanical properties, tensile strength and elongation were measured, flame retardancy and processability were evaluated, and flame retardancy was evaluated separately on the tube. Table 2 shows each.

At room temperature, the tensile strength and the elongation were measured according to the UL224 standard, and the tensile strength was 1.06 kgf / mm 2 or more and the elongation was 200% or more. The flame retardancy of the specimens was carried out according to the UL94 V0 standard, 1.5 mm and 1.0 mm thick specimens were evaluated. On the other hand, in order to evaluate the flame retardancy on the tube, a heat shrinkable tube having an outer diameter of 10 mm and a thickness of 1 mm was manufactured. The tube thus manufactured was subjected to the evaluation of VW-1, which is a vertical flame retardant test of UL224, and compared with the results of the evaluation of UL94 V0, which is an evaluation on a specimen. Finally, processability was measured using a Hakeke mixer, a small laboratory mixer.

division Example (1-3) Comparative example (1-4) One 2 3 One 2 3 4 Room temperature characteristics Tensile strength (kgf / ㎡) 1.72 1.56 1.45 1.52 0.78 1.21 0.82 Elongation (%) 256 420 385 85 243 265 78 Flame retardant (UL94 V0) 1.5 mm pass pass pass pass pass pass 1.0 mm pass pass pass leaving out pass leaving out Flame retardant (UL224 VW-1) pass pass pass leaving out leaving out leaving out leaving out Machining Load (Nm) 56 60 64 45 51 52 38

As can be seen from Table 2, Comparative Examples 2 and 4 in the tensile strength of one of the room temperature characteristics do not meet the required standard value, Comparative Examples 1 and 4 in the elongation rate of the other one of the room temperature characteristics are required reference value Is not falling short. Comparative Example 4 was evaluated as undesirable in flame retardancy evaluation (UL94 V0) for 1.5 mm thick specimens and Comparative Examples 1, 3 and 4 were evaluated as undesirable in flame retardancy evaluation (UL94 V0) for 1.0 mm thick specimens It became. In the flame retardancy evaluation (UL224 VW-1) on the tube, all of the comparative examples (1 to 4) were evaluated as undesirable. With regard to the processing loads discussed last, in Examples 1 to 3, the processing load was measured to be 56 N · m, and all of the workability was evaluated to be good. On the contrary, in all cases of Comparative Examples (1 to 4), Compared with the examples, the lower processing load is measured, and the workability is also relatively poor.

Through the above results, all of the examples (1 to 3) according to the present invention meet all the standard values required for room temperature properties, and are excellent in flame retardancy for specimens and flame retardancy for tubes, and also excellent in workability. It can be seen that the present invention sufficiently achieves the object.

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 used to limit the scope of the present invention as defined in the meaning or claims.

According to the present invention, an eco-friendly material is used because it does not contain a halogen-based component, and it is preferable, and it solves the problem of deterioration of physical properties due to the added flame retardant to improve the flame retardancy, maintains high flame retardancy sufficiently and improves processability. It can be provided with a composition for the production of an insulating material, it is easy to manufacture the insulating material manufactured using such a composition, there is an advantage that can ensure sufficient flame retardancy in the event of a fire.

Claims (12)

10 to 90% by weight of ethylene vinyl acetate copolymer resin having a vinyl acetate content of 15 to 22% by weight, and 23 to 27% by weight of vinyl acetate content To 100 parts by weight of a basic resin which is a mixed resin blended with 10 to 90% by weight of ethylene vinyl acetate copolymer resin, 5 to 350 parts by weight of an inorganic flame retardant which is a metal hydroxide surface-treated as a material selected from vinylsilane, fatty acid and aminopolysiloxane; 5 to 80 parts by weight of a microencapsulated material consisting of a capsule wall made of melamine surrounding the center and made of particulates; And 1 to 10 parts by weight of the crosslinking aid, which is a cyanurate-based material; composition for producing a flame-retardant insulating material, characterized in that it comprises a. The method of claim 1, The metal hydroxide used as the inorganic flame retardant is a composition for producing a flame retardant insulating material, characterized in that the material of any one selected from aluminum hydroxide and magnesium hydroxide. The method according to claim 1 or 2, The composition for producing a flame retardant insulating material, 0.5 to 10 parts by weight of antioxidant based on 100 parts by weight of the base resin; 0.5 to 10 parts by weight of lubricant based on 100 parts by weight of the base resin; And 0.5 to 10 parts by weight of a processing aid based on 100 parts by weight of the basic resin; The composition for producing a flame retardant insulating material, characterized in that it further comprises any one selected from materials or two or more materials. The method of claim 3, The antioxidant is a composition for producing a flame retardant insulating material, characterized in that any one or a mixture of two or more selected from thioester-based and phenolic antioxidants. 60 to 95% by weight of ethylene vinyl acetate copolymer resin having a vinyl acetate content of 23 to 27% by weight, and 100 parts by weight of a basic resin which is a mixed resin blended with 5 to 40% by weight of ethylene vinyl acetate copolymer resin into which maleic anhydride is introduced. about, 5 to 350 parts by weight of an inorganic flame retardant which is a metal hydroxide surface-treated as a material selected from vinylsilane, fatty acid and aminopolysiloxane; 5 to 80 parts by weight of a microencapsulated material consisting of a capsule wall made of melamine surrounding the center and made of particulates; And 1 to 10 parts by weight of the crosslinking aid, which is a cyanurate-based material; composition for producing a flame-retardant insulating material, characterized in that it comprises a. The method of claim 5, The metal hydroxide used as the inorganic flame retardant is a composition for producing a flame retardant insulating material, characterized in that the material of any one selected from aluminum hydroxide and magnesium hydroxide. The method according to claim 5 or 6, The composition for producing a flame retardant insulating material, 0.5 to 10 parts by weight of antioxidant based on 100 parts by weight of the base resin; 0.5 to 10 parts by weight of lubricant based on 100 parts by weight of the base resin; And 0.5 to 10 parts by weight of a processing aid based on 100 parts by weight of the basic resin; The composition for producing a flame retardant insulating material, characterized in that it further comprises any one selected from materials or two or more materials. The method of claim 7, wherein The antioxidant is a composition for producing a flame retardant insulating material, characterized in that any one or a mixture of two or more selected from thioester-based and phenolic antioxidants. delete delete delete delete

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