KR100801823B1 - Flame retardant polypropylene resin composition - Google Patents

Abstract

The present invention relates to a flame-retardant polypropylene resin composition, more specifically, (A) 100 parts by weight of polypropylene, (B) bis (3,5-dibromo, 4-dibromo puroxy phenyl) sulfone as a flame retardant Or 1 to 30 parts by weight of tetrabromo bisphenol A-bis (2,3-dibromo propylether), (C) 1 to 15 parts by weight of antimony trioxide as flame retardant aid, (D) 0.01 to 1 cyclic sodium phosphate as nucleating agent It is related with the flame-retardant polypropylene resin composition characterized by including a weight part and 0.01-1 weight part of hydroxyl amines as (D) antioxidant, Comprising: It is excellent in flame retardance, but rigidity, glossiness, and discoloration resistance by this invention. A flame retardant polypropylene resin composition which does not fall can be provided.

Polypropylene, Flame Retardant, Stiffness, Gloss, Discoloration Resistance

Description

Flame Retardant Polypropylene Resin Composition {FLAME RETARDANT POLYPROPYLENE RESIN COMPOSITION}

The present invention relates to a flame retardant polypropylene resin, more specifically, (A) 100 parts by weight of polypropylene, (B) bis (3,5-dibromo, 4-dibromo furoxy phenyl) sulfone or 1-30 parts by weight of tetrabromo bisphenol A-bis (2,3-dibromo propylether), (C) 1-15 parts by weight of antimony trioxide as flame retardant aid, (D) 0.01-1 weight of cyclic sodium phosphate as nucleating agent And (D) a flame retardant polypropylene resin composition comprising 0.01 to 1 part by weight of hydroxyl amine as an antioxidant.

Polypropylene resin is excellent in impact, stiffness, appearance, and moldability. It is used in various fields such as electric and electronic parts and automobile parts, but it is easy to ignite or ignite, so when used in electrical appliances, ignition caused by electrical troubles, Various proposals have been made regarding flame retardant to prevent combustion or fire. In particular, in the flame retardancy standards of electrical appliances, the UL standard (UL94) of the United States requires a high degree of flame retardancy depending on the product or part, so export products to the United States need to select a material that meets the UL standard. To meet these demands, organic and inorganic flame retardants and flame retardants are used in combination with polypropylene resins, and decabromo diphenyl ether, brominated bisphenol S derivatives, brominated bisphenol derivatives and the like are mainly used as the flame retardants.

In addition, in the case of large electric and electronic parts, high rigidity is required within a range that does not impair fluidity and impact resistance of polypropylene. In general, the method of high rigidity of polypropylene includes a method of high rigidity by fillers such as talc, but in this case, the impact of flame retardant may be impaired depending on the type of flame retardant added as well as deteriorating other properties such as impact and gloss of polypropylene. In some cases. Among the flame retardants, decabromo diphenyl oxide exhibits good flame retardancy even when fillers such as talc are added, but its use is limited in Europe due to the dioxin hazard. Another method of high stiffening of polypropylene is to use high crystalline polypropylene and mix a nucleating agent. However, when a sorbitol-based nucleating agent such as dibenziridine sorbitol and a crystal nucleating agent such as aluminum salt are combined with a flame retardant, the gas is It is easy to occur and easily discolored, and there is a problem that the flame retardant effect is inhibited by the nucleating agent.

In addition, in order to stabilize polypropylene pellets during processing and molding, a hindered phenol-based antioxidant is generally used in combination. However, phenolic chromophores in the manufacture of resin pellets or molding parts are likely to cause discoloration due to quinone formation and reaction with flame retardants. There is a problem.

The present invention is to solve the problems of the prior art as described above, poly (propylene, bis (3,5-dibromo, 4-dibromo furoxy phenyl) sulfone or tetrabromo bisphenol A-bis ( 2,3-dibromo propylether) and the addition of antimony trioxide as flame retardant, cyclic sodium phosphate as nucleating agent, and hydroxyl amine as antioxidant, showing excellent flame retardancy and high rigidity, gloss and resistance. It is an object of the present invention to provide a resin composition in which discoloration is not reduced.

That is, the present invention relates to (A) 100 parts by weight of polypropylene, (B) bis (3,5-dibromo, 4-dibromo furoxy phenyl) sulfone or tetrabromo bisphenol A-bis (2, 3-dibromo propylether) 1 to 30 parts by weight, (C) 1 to 15 parts by weight of antimony trioxide as flame retardant aid, (D) 0.01 to 1 parts by weight of cyclic sodium phosphate as nucleating agent, and (D) hydrate as antioxidant It relates to a flame retardant polypropylene resin composition comprising 0.01 to 1 part by weight of oxyl amine.

Hereinafter, the present invention will be described in more detail.

The polypropylene resin herein is a crystalline polypropylene homopolymer or other alpha such as ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptene, 1-octene and 1-decene Crystalline copolymers of olefins and propylene are used. Particularly for rigidity and high glossiness, polypropylene homopolymers or copolymers having a comonomer component of 10 mol% or less are preferred.

In the present invention, as the flame retardant, bis (3,5-dibromo, 4-dibromo furoxy phenyl) sulfone or tetrabromo bisphenol A-bis (2,3-dibromo propylether) alone or in combination thereof It can be mixed and used. The blending amount of the flame retardant is 1 to 30 parts by weight and preferably 3 to 20 parts by weight based on 100 parts by weight of polypropylene. If the blending amount is smaller than the lower limit, flame retardancy cannot be obtained. If the blending amount is higher than the upper limit, stable kneading and molding operations are difficult, specific gravity increases, and impact resistance decreases.

In the present invention, antimony trioxide is used as a flame retardant aid. The compounding quantity is 1-15 weight part with respect to 100 weight part of polypropylene, Preferably it is 1-10 weight part. If it is more than the upper limit, the specific gravity increases and the impact resistance is lowered, which is not preferable.

In the present invention, cyclic sodium phosphate is used as the nucleating agent, and preferably, a substance represented by the following Chemical Formula 1 is used. Specific examples of such materials include sodium 2,2′-methylenebis- (4,6-dimethylphenyl) phosphate, sodium 2,2′-methylenebis- (4,6-di-t-butylphenyl) phosphate Etc. The compounding quantity is 0.01-1 weight part with respect to 100 weight part of polypropylene, Preferably it is 0.05-0.5 weight part. If the blending amount is smaller than the lower limit, sufficient rigidity cannot be obtained. If the blending amount is larger than the upper limit, the rigidity no longer improves, which is not preferable.

In said formula, R is a C1-C4 alkyl group.

In the present invention, a hydroxyl amine is used as the antioxidant, and a substance represented by the following Chemical Formula 2 is preferably used. The compounding quantity is 0.01-1 weight part with respect to 100 weight part of polypropylene, Preferably it is 0.05-0.5 weight part. If the blending amount is smaller than the lower limit, sufficient antioxidant effect cannot be obtained, which is not preferable.

The flame retardant polypropylene resin composition of the present invention may be added with known stabilizers, antistatic agents, lubricants, antifreeze agents, colorants, fillers and the like within the range not impairing the effects of the present invention in addition to the above components.

In order to prepare the flame retardant polypropylene resin of the present invention, the mixing method and the mixing order of each component are not limited, and Henschel mixer, a general tumbler mixer, and the like can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.

The flame retardancy evaluation carried out in the present invention was based on performing a vertical combustion (V0) vertical burning test of the "combustibility test of plastic materials for mechanical parts" of UL subject 94 (Underwrites Laboratories Incorporation). The test fraction used was 1/16 inch thick.

The compositions prepared by the present invention were classified as UL94 V0 when the following criteria were met; A set of five specimens of dimensions 127 mm x 12.7 mm x 1.6 mm shall be in direct contact with a flame (19 mm high), each held twice for 10 seconds and then flame burned for at least 10 seconds to ensure no specimens burn. . For 10 sparks applied to each set of five specimens, the total flame burn time shall not exceed 50 seconds. None of the specimens shall be free of spark particles, no flammable or more flammable specimens until clamped, and no flammable specimens lasting more than 30 seconds after the second removal of the test flame.

The classification to UL94 V1 requires that the flame burning time per specimen shall not exceed 30 seconds and that the total flame burning time for 10 flame applications in each set of five specimens shall not exceed 250 seconds. The combustion progress should not last longer than 60 seconds. Other criteria are the same as those mentioned above. Materials with specimens from which spark particles fell while satisfying other criteria for classification of UL94 V1 were classified as UL94 V2.

The stiffness test measured the flexural modulus in accordance with ASTM D790. Using an injection molding machine, the test specimen was prepared 127mm x 12.7mm x 3.2mm specimen and the test speed was 5mm / min.

The gloss test was performed using an injection molding machine to prepare a 130 mm x 120 mm x 2 mm specimen and to evaluate the glossiness of the surface. Glossiness was expressed as good gloss, good gloss, no gloss.

The discoloration resistance test was performed using an injection molding machine, the test specimen was prepared 127mm x 12.7mm x 3.2mm specimen and the color change of the surface was measured. Color change is indicated as ○ no discoloration, △ slightly discoloration, X discoloration.

According to the present invention, the polypropylene, flame retardant, flame retardant aid, nucleating agent, antioxidant, 0.1% calcium stearate as an additive, and 0.1% of IRGAFOS-168 (trade name: Ciba-Geigy Co., Ltd.) antioxidant were charged in a Henschel mixer. It stirred and mixed for 3 minutes. The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame retardancy, rigidity and glossiness. Glossiness was measured.

Example 1

100 parts by weight of a crystalline polypropylene homopolymer having a melt flow index (2.16 kg, 230 ° C.) of 12 g / 10 min as a polypropylene resin, bis (3,5-dibromo, 4-dibromo furoxy phenyl) as a flame retardant 12 parts by weight of sulfone (NONEN-52, trade name), antimony trioxide (Sb203 (trade name) 6 parts by weight, flame retardant aid, sodium 2,2′-methylene bis- (4,6-di-t-butylphenyl) as a nucleus agent) 0.2 parts by weight of phosphate (NA-11, trade name), 0.1 parts by weight of hydroxyl amine as an antioxidant, and 0.1 parts by weight of calcium stearate and antioxidant IRGAFOS-168 (trade name) The mixture was then charged to a Henschel mixer and stirred and mixed for 3 minutes, and the resulting mixture was melted and extruded at 190 ° C. using a twin-screw agitator having a diameter of 30 mm to obtain pellets. Dry the mold, and use an injection molding machine where the cylinder's maximum temperature is fixed at 200 ° C. To prepare the test piece was measured for flame retardancy, flexural modulus, gloss and the discoloration resistance. The results are shown in Table 1.

Example 2

It carried out similarly to Example 1 except having used 12 weight part of tetrabromo bisphenol A-bis (2, 3- dibromo propylether) (PE-68, brand name) as a flame retardant. The results are shown in Table 1.

Examples 3 to 5 and Comparative Examples 1 to 7

It carried out similarly to Example 1 except having changed the kind and compounding quantity of a flame retardant and a flame retardant aid as shown in Table 1. The results are shown in Table 1.

As shown in Table 1, bis (3,5-dibromo, 4-dibromo puroxy phenyl) sulfone or tetrabromo bisphenol A was used as a flame retardant for the resin compositions of Examples 1 to 5 and Comparative Examples 1 to 7. It can be seen that the high flame retardancy, rigidity, glossiness and discoloration resistance can be obtained when antimony trioxide is mixed with bis (2,3-dibromo propylether) and a flame retardant aid.

Examples 6-7 and Comparative Examples 8-12

It carried out similarly to Example 1 except having changed the kind and compounding quantity of a nucleating agent as shown in Table 2. The results are shown in Table 2.

Table 2 shows excellent stiffness, glossiness, and discoloration resistance when sodium 2,2`-methylenebis- (4,6-di-t-butylphenyl) phosphate (NA-11, trade name) is added as a nucleating agent. It can be seen.

Examples 8-10 and Comparative Examples 13-15

It carried out similarly to Example 1 except having changed the kind and compounding quantity of antioxidant as shown in Table 2. The results are shown in Table 2.

In Table 2, it can be seen that when the hydroxyl amine (FS301, trade name) is added as an antioxidant, excellent stiffness, glossiness, and discoloration resistance are shown.

Examples 11-13

It carried out similarly to Example 1 except having changed the kind of polypropylene as shown in Table 2. The results are shown in Table 2.

Composition evaluation division (A) (B) (C) (D) (E) Flame retardant Flexural modulus Luster Discoloration (A) 1 (A) 2 (B) 1 (B) 2 (B) 3 (D) 1 (D) 2 (D) 3 (E) 1 (E) 2 (E) 3 Example 1 100 12 6 0.2 0.1 V0 22,500 ○ ○ Example 2 100 12 6 0.2 0.1 V0 21,000 ○ ○ Example 3 100 6 6 6 0.2 0.1 V0 22,000 ○ ○ Example 4 100 15 6 0.2 0.1 V0 23,500 ○ ○ Example 5 100 3 One 0.2 0.1 V2 19,800 ○ ○ Comparative Example 1 100 One One 0.2 0.1 HB 19,500 ○ ○ Comparative Example 2 100 12 0.2 0.1 HB 22,000 ○ ○ Comparative Example 3 100 12 0.2 0.1 HB 19,500 ○ ○ Comparative Example 4 100 20 6 0.2 0.1 V1 24,000 X ○ Comparative Example 5 100 6 0.2 0.1 HB 19,500 ○ ○ Comparative Example 6 100 0.2 0.1 HB 19,000 ○ ○ Comparative Example 7 100 40 6 0.2 0.1 Molding impossible

Composition evaluation division (A) (B) (C) (D) (E) Flame retardant Flexural modulus Luster Discoloration (A) 1 (A) 2 (B) 1 (B) 2 (B) 3 (D) 1 (D) 2 (D) 3 (E) 1 (E) 2 (E) 3 Example 6 100 12 6 0.05 0.1 V0 18,000 ○ ○ Example 7 100 12 6 0.5 0.1 V0 24,500 ○ ○ Comparative Example 8 100 12 6 3 0.1 V0 25,000 △ △ Comparative Example 9 100 0.2 0.1 HB 19,000 ○ ○ Comparative Example 10 100 12 6 0.1 V0 16,000 ○ ○ Comparative Example 11 100 12 6 0.2 0.1 V0 20,500 △ △ Comparative Example 12 100 12 6 0.2 0.1 V0 21,000 △ △ Example 8 100 12 6 0.2 0.03 V0 22,000 ○ ○ Example 9 100 12 6 0.2 0.05 V0 22,200 ○ ○ Example 10 100 12 6 0.2 0.5 V0 22,500 ○ ○ Comparative Example 13 100 12 6 0.2 3 V0 22,000 ○ △ Comparative Example 14 100 12 6 0.2 0.1 V0 21,800 ○ △ Comparative Example 15 100 12 6 0.2 0.1 V0 22,000 ○ △ Example 11 100 12 6 0.2 0.1 V0 19,500 ○ ○ Example 12 100 12 6 0.2 0.1 V0 18,900 ○ ○ Example 13 100 6 6 6 0.2 0.1 V0 19,100 ○ ○

(A) 1: HJ500 (propylene homopolymer, MFR = 12, Samsung General Chemical)

(A) 2: BJ700 (propylene block copolymer, MFR = 20, Samsung General Chemical)

(B) 1: Nonnen-52 (brand name, bis (3,5-dibromo, 4-dibromo puroxy phenyl) sulfone, marubishi)

(B) 2: PE-68 (brand name, tetrabromo bisphenol A-bis (2,3-dibromo propylether), great lake)

(B) 3: S-102E (trade name, decabromo diphenyl ether, albermar)                     

(C): antimony trioxide Sb-W (brand name, Cheil nonflammation)

(D) 1: NA-11 (brand name, sodium 2,2'- methylenebis- (4,6-di-t- butylphenyl) phosphate, asahidenka)

(D) 2: Al-PTBBA (brand name, aluminum hydroxy di-t butyl benzoate, cell)

(D) 3: NC-4 (Brand name, Bis (p-Ethylbenziridine) Sorbitol, Mitsui Dohatsu Chemical)

(E) 1: FS402 (trade name, Shiba Gai)

(E) 2: IRGANOX-1010 (brand name, pentaarithyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxy phenyl) -propionate], Ciba-Geigi)

(E) 3: IRGANOX-1076 (brand name, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, Ciba-Geigy)

According to the present invention, it is possible to provide a flame retardant polypropylene resin composition which is excellent in flame retardancy and which does not lower rigidity, glossiness and discoloration resistance.

Claims (3)

(A) 100 parts by weight of polypropylene, (B) bis (3,5-dibromo, 4-dibromo furoxy phenyl) sulfone or tetrabromo bisphenol A-bis (2,3-dibromo as flame retardant Propyl ether) 1 to 30 parts by weight, (C) 1 to 15 parts by weight of antimony trioxide as flame retardant aid, (D) 0.01 to 1 parts by weight of cyclic sodium phosphate as nucleating agent, and (D) 0.01 to 1 hydroxyl amine as antioxidant Flame retardant polypropylene resin composition comprising a weight part. The flame retardant polypropylene resin composition according to claim 1, wherein the cyclic sodium phosphate is represented by the following Chemical Formula 1. [Formula 1]

In said formula, R is a C1-C4 alkyl group. The flame retardant polypropylene resin composition according to claim 1, wherein the hydroxyl amine is represented by the following Chemical Formula 2. [Formula 2]