KR20020000934A - Frame-retardant polypropylene resin composotion - Google Patents

Abstract

PURPOSE: Provided is a flame retardant polypropylene resin composition which has excellent impact resistance, high thermal resistance and flame retardance of 5V grade at thickness of a thin film. CONSTITUTION: The polypropylene resin composition comprises (a) 31 to 61 wt% of a polypropylene resin, (b) 13 to 35 wt% of an organic halide flame retardant, (c) 3 to 21 wt% of antimony trioxide, (d) 3 to 30 wt% of magnesium hydroxide, and (e) 2 to 15 wt% of polyethylene chloride. The polypropylene resin is a monopolymer of polypropylene or a crystalline copolymer of polypropylene with one or more selected from a group consisting of ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptene, 1-octene and 1-decene. The polypropylene resin has a met flow index of 0.1 to 60g/10min.

Description

Flame retardant polypropylene resin composition {FRAME-RETARDANT POLYPROPYLENE RESIN COMPOSOTION}

The present invention relates to a flame retardant polypropylene resin composition having excellent mechanical properties such as impact resistance and exhibiting high flame retardancy, and more particularly, comprising a specific ratio of an organic flame retardant, an inorganic flame retardant, and an antimony compound based on a polypropylene resin. It relates to a flame retardant polypropylene resin composition.

Polypropylene resins are widely used in the fields of automobiles, building materials, electrical parts, etc. in the form of injection molded products, films, blow molded products due to their excellent processing characteristics, chemical resistance, weather resistance, and high sliding properties. Various organic or inorganic flame retardants are added to give. Generally, the flame retardation of a polypropylene resin is performed by the combined addition of an organic or inorganic flame retardant and antimony trioxide.

As a flame-retardant polypropylene resin composition containing such a flame retardant, a composition obtained by adding decabromodiphenyl ether, bis (pentabromophenyl) ethane or the like as a bromine-based flame retardant (Japanese Patent Application Laid-Open No. Hei 8-120126, No. 7) -76640), a composition obtained by adding a tetrabromo bisphenol A-based or tetrabromo bisphenol S-based flame retardant (JP-A-8-302102), a hydrous inorganic compound such as magnesium hydroxide, aluminum hydroxide or hydrotalcite Obtained by adding to a polypropylene resin (Japanese Patent Laid-Open Nos. 53-92855, 54-29350, 54-77658, 56-26954, 57-87462 and 60-110738) ), Polyethylene with a melt index of 0.01 to 2.0, halogen compounds (e.g., decabromodiphenyl ether or dodecachloro-dodecahydromethanodibenzocyclooctene), powder talc, kaolin, A composition obtained by adding at least one inorganic filler selected from the group consisting of cyanite, silica and diatomite to polypropylene resin (Japanese Patent Publication No. 55-30739) and ammonium phosphate (or amine phosphate), ring structure = C = A composition obtained by adding a reaction product of a nitrogen compound having an O (or = C = S or = NH) and an aldehyde or an oligomer (or polymer) of 1,3,5-triazine derivative to a polypropylene resin (Japan Published Patent Publication Nos. 52-146452 and 59-147050).

However, a composition prepared by adding an inorganic compound such as magnesium hydroxide to a polypropylene resin to prepare a highly flame retardant composition has a deterioration in moldability and when a composition obtained by adding a decabromo phenyl-based compound to polypropylene is used. Formability is not so bad, but there is a problem that the impact strength of the composition is sharply lowered. In addition, the compositions are based on a vertical burn test of UL Subject 94 ("Combustibility Test for Plastic Materials for Mechanical Components" by Underwrites Laboratories Incorporation) at a thin thickness. One test (hereinafter abbreviated as "UL94 vertical combustion test") results can achieve V-0 grade flame retardancy at 1/32 inch thickness, but it is difficult to achieve high flame retardancy of 5V grade. Therefore, these compositions are not suitable for use in components requiring high flame resistance, impact resistance, and heat resistance at the same time as 1/32 inch thickness.

The object of the present invention is to solve the drawbacks of the polypropylene flame retardant resin composition as described above to add an organic halogen flame retardant and magnesium hydroxide as an inorganic flame retardant as an organic halogen flame retardant and a flame retardant enhancer, and as an impact modifier and flame retardant By using chlorinated polyethylene, it is to provide a highly excellent flame retardant polypropylene resin composition having 5 V class flame retardancy at impact resistance, high heat resistance and thin film thickness.

The flame retardant polypropylene resin composition of the present invention comprises (A) 31 to 61% by weight of polypropylene resin, (B) 13 to 35% by weight of organic halogen flame retardant, (C) 3 to 21% by weight of antimony trioxide, (D) magnesium hydroxide 3 It is characterized by including-30 weight% and (E) 2-15 weight% of chlorinated polyethylene.

As used herein, the term "polypropylene" refers to propylene olefin block copolymers and propylene homopolymers containing 50% by weight or more of propylene polymerized units.

In the flame retardant polypropylene resin composition of the present invention, (A) the polypropylene resin is a crystalline polypropylene homopolymer or ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptene, 1 A crystalline copolymer of polypropylene and a compound selected from the group consisting of octene and 1-decene or two or more compounds selected from the group may be used, and the polypropylene resin has a melt flow index of 0.1 to 60 g / 10 minutes. Preferably, what is 0.3-40 g / 10min can be used. If the melt flow index of the polypropylene resin is less than 0.1 g / 10 minutes, the molding pressure becomes excessive during injection molding, a flow mark occurs on the surface of the molded body, and there are appearance defects. The product has the drawback that the impact resistance of the product is drastically lowered and the flammable melt easily degrades.

There is no restriction | limiting in particular regarding the stereoregularity of the polypropylene resin in this invention, As long as it is crystalline polypropylene, any polypropylene may be sufficient for achieving the objective of this invention. Specifically, crystalline polypropylene having an isotactic pentad fraction of 0.80 to 0.99, preferably 0.85 to 0.99 and particularly preferably 0.90 to 0.99 as measured by ¹³ C-NMR (nuclear magnetic resonance spectrum) is suitable.

In the resin composition of this invention, the compounding quantity of the said (A) polypropylene resin is 31 to 61 weight%, Preferably it is 35 to 58 weight%. When the blending amount is less than 31% by weight, the obtained resin composition is excellent in heat resistance but inferior in molding processability and impact resistance, and in excess of 61% by weight, in terms of molding processability and impact resistance, but inferior in heat resistance and flame resistance, It is not preferable because the flame retardancy and impact resistance cannot be used for a material that requires simultaneously.

In the present invention, the (B) bromine-based flame retardant has a bromine content of 30% by weight or more, and is represented by the following general formula (I).

(I)

(Wherein R represents oxygen or an alkylene group having 1 to 6 carbon atoms, and i and j are integers of 0 to 5).

In the above formula, the alkylene group is preferably a methylene group. When the amount of the brominated flame retardant is less than 13% by weight, the flame retardant effect is not sufficient, and it is difficult to obtain ULV 5V flame retardancy, which is not preferable. When the amount of the brominated flame retardant (B) exceeds 35% by weight, It is not preferable because it impairs mechanical properties, and in particular, impact resistance and tensile stiffness are lowered and electrical properties are also lowered.

(C) Antimony trioxide used as a flame retardant adjuvant in this invention can use a general commercial item. Although antimony trioxide is powder form, the average particle diameter is 0.2-5.0 micrometers. The blending amount is 3 to 21% by weight based on the total composition. If the amount of antimony trioxide is less than 3% by weight, the synergistic effect with bromine-based flame retardant is insignificant, and UL94 5V-class flame retardancy cannot be obtained. If it exceeds 21% by weight, the content necessary for synergy with bromine-based flame retardant is no longer exceeded. It does not exert a flame retardant increase effect, the impact resistance is sharply falling. Antimony trioxide (C) and bromine flame retardant (B) show synergistic effect in flame retardancy, and the amount of antimony trioxide compounded is 1/6 to 2/1 of bromine flame retardant to maximize the flame retardant effect.

The magnesium hydroxide (D) used as the inorganic flame retardant in the present invention plays a very important role in the composition. In other words, when the resin composition burns, synergy between bromine-based flame retardant and indium trioxide, magnesium hydroxide, an inorganic flame retardant, absorbs the heat of reaction generated during combustion of the resin by endothermic reaction and decomposes into a vapor form, so the flame retardancy is highly improved. In addition, it prevents the flammable melt from falling during combustion, so that it does not generate drip material specified in 5V class flame retardancy in UL94 flammability test. The amount of magnesium hydroxide is preferably 3 to 30% by weight based on the total resin composition. If the blending amount is less than 3% by weight, it is difficult to sufficiently absorb the generated heat generated during the combustion of the resin, so that the flame retardant increase effect is insignificant, and the effect of preventing drip when the melt falls is not preferable. In addition, when the blending amount is added more than 30% by weight, the fluidity of the resin is lowered, mechanical properties such as impact resistance and tensile strength are inferior, and moldability is not preferable.

Inorganic flame retardant used in the present invention is preferably used a surface-treated with a silane coupling agent or a metal stearic acid, the mechanical properties such as impact resistance of the composition is inferior when the surface treatment is not used Not.

The chlorinated polyethylene (E) used in the present invention is a polyethylene in which a part of hydrogen is substituted with chlorine, and thus the polyethylene substituted with chlorine functions as a rubber rather than an inherent property of polyethylene, and thus impact modifiers and flame retardants in resin compositions containing the same. As it brings effect at the same time. The chlorinated ethylene may improve the flame resistance of the resin composition by imparting a halogen content in the resin composition while improving the impact resistance of the resin composition. In the composition of the present invention, the chlorinated polyethylene used as the impact modifier and the flame retardant aid is suitably about 20 to 50% of chlorine, and the amount of the compound is required to be 2 to 15% by weight based on the total resin composition. If the content of chlorine in the chlorinated polyethylene is less than 20%, the degree of contribution to improving the impact resistance is insignificant. If the content of the chlorinated polyethylene exceeds 50%, the thermal stability of the chlorinated polyethylene itself is low. In addition, when the amount of chlorinated polyethylene is less than 2% by weight, a sufficient impact reinforcing effect cannot be obtained. On the contrary, when it exceeds 15% by weight, the thermal stability is severely lowered.

In the flame-retardant resin composition of the present invention, various additives can be used to further improve mechanical properties such as rigidity and heat resistance. For example, fillers such as talcum talc, silica, clay, kaolin, glass fiber, calcium carbonate, fillers such as mica, and the like, may be used alone or in combination of two or more.

By mixing and kneading the above components, a flame-retardant polypropylene resin molding material is produced and molded by any molding method such as injection molding or extrusion molding to obtain a polypropylene resin molded article.

The polypropylene resin molded article obtained as described above has magnesium hydroxide as an inorganic flame retardant in the state where brominated flame retardant and antimony trioxide are mixed as a flame retardant, and act as a flame retardant as a flame retardant. It is found that molded articles made of such highly functional resin compositions are highly desirable for use as electrical and electronic parts, automobiles, and building materials by combining polyethylene with excellent impact resistance and heat resistance while obtaining high flame resistance of UL94 5V.

The flame retardant polypropylene resin composition of the present invention can be prepared by the following method. Namely, a specified amount of (A) polypropylene resin, (B) bromine flame retardant having the structure of general formula (I), (C) antimony trioxide, (D) inorganic flame retardant, magnesium hydroxide, (E) chlorinated polyethylene and The various additives described above are charged into a stirring / mixing apparatus (e.g., a Henschel mixer (trade name), a super mixer or a tumbler mixer), and the compound is stirred and mixed for 1 to 10 minutes. The pellets are melted and kneaded at a temperature using a rolling mill or an extruder.

The invention may be understood in more detail by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended specific claims.

How to measure

1) Izod impact strength

The injection molded molded article had a thickness of 3.2 mm and was based on the ASTM D256 test specification.

2) Heat deflection temperature

Test specimens 127.0 mm long, 12.7 mm wide, and 6.4 mm thick were molded using an injection molding machine and carried out by a method under a load of 4.6 kgf in ASTM D648 test specification.

3) flame retardant

The "burning test of plastic materials for mechanical parts" of UL Subject 94 (Underlights Laboratories Inc.) was based on the vertical combustion test performed on the vertical (5V) and horizontal plate tests. The thickness of the specimen used was 1/32 inch.

Example 1

4.4 kg of crystalline ethylene-propylene block copolymer having a melt index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) of polypropylene resin, 3 g / 10 min, bis (pentabromo as bromine-based flame retardant Phenyl) ethane [brand name: S-8010, Albermale, USA] 2.1 kg, antimony trioxide [trade name: SW, Ilsung antimony company] 700 g, magnesium hydroxide as an inorganic flame retardant [trade name: Kisuma5A, Japan Kyowa Chemical (Kyowa) chemical)] 2.0 kg, chlorinated polyethylene (trade name: Tyrin 3611P, Dow Chemical Co., Ltd.) and 10 g of calcium stearate as an additive were charged in a Henschel mixer (trade name), followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 180 to 260 ° C. using an extruder having a diameter of 30 mm to prepare pellets.

Examples 2-4 and Comparative Examples 1-4

The same components as in Example 1 were charged in a Henschel mixer (trade name) except that the compounding amount of the polypropylene resin, the brominated flame retardant, and the magnesium hydroxide was replaced with the content ratios shown in Table 1, followed by stirring and mixing. The prepared mixture was melted and extruded under the same conditions as in Example 1 to prepare pellets.

The pellets obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were dried at 100 ° C. for 3 hours, and molded using an injection molding machine in which the maximum temperature of the cylinder was fixed at 230 ° C. to test the flame resistance and mechanical properties. After preparing a predetermined test piece for, the results of measuring the flame retardancy, mechanical properties are shown in Table 1.

As can be seen in Table 1, Examples 1 to 4 manufactured in accordance with the present invention have high Izod impact strength and heat deformation temperature, and have a high flame retardant property of UL94 flame retardancy of 5V. However, in Comparative Examples 1 to 4, impact resistance, heat resistance, and 5V class flame retardancy could not be achieved at the same time.

Example 5

4.1 kg of crystalline ethylene-propylene block copolymer having a melt index (melt flow rate of molten resin for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin, and bis (pentabromo as bromine-based flame retardant Phenyl) ethane [brand name: S-8010, Alberta US] 2.1 kg, antimony trioxide [brand name: SW, Ilsung antimony company] 1.0 kg, magnesium hydroxide [trade name: Kisuma5A, Japan Kwawa Chemical Co., Ltd.] 2.0 kg as an inorganic flame retardant , 800 g of chlorinated polyethylene (Tyrin 3611P, Dow Chemical Co., Ltd.) and 10 g of calcium stearate as an additive were charged to a Henschel mixer (trade name), followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 180 to 260 ° C. using an extruder having a diameter of 30 mm to prepare pellets.

Examples 6-8 and Comparative Examples 5-7

The same components as in Example 5 were charged to a Henschel mixer (trade name) except that the compounding amounts of the polypropylene resin, the brominated flame retardant and the antimony trioxide, magnesium hydroxide, and chlorinated polyethylene were respectively replaced by the content ratios shown in Table 1. After stirring and mixing, the resulting mixture was melted and extruded under the same conditions as in Example 5 to prepare pellets.

The pellets obtained in Examples 6 to 8 and Comparative Examples 5 to 7 were dried at 100 ° C. for 3 hours and molded using an injection molding machine having a maximum temperature of 230 ° C. to test flame resistance and mechanical properties. After preparing a predetermined test piece for, the results of measuring the flame retardancy, mechanical properties are shown in Table 1.

As can be seen in Table 1, Examples 6 to 8 manufactured in accordance with the present invention have high Izod impact strength and heat deformation temperature, and have a high flame retardant property of UL94 flame retardant 5V class. However, in the case of Comparative Example 5 in which the compounding amount of chlorinated polyethylene is less than 2% by weight, the effect that contributed to the flame retardancy was not sufficient, so that flame retardancy of 5V grade could not be obtained. Achievement, but there was a problem that the heat resistance is sharply lowered.

Example 9

4.4 kg of crystalline ethylene-propylene block copolymer having a melt index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin, 3 kg / 10 min, decabromo phenyl ether as a brominated flame retardant [Product name: S-102E, US Albert Mail] 2.1 kg, antimony trioxide [trade name: SW, Ilsung antimony company] 700 kg, magnesium hydroxide as an inorganic flame retardant [trade name: Kisuma5A, Japan Kawawa Chemical Co., Ltd.] 2.0 kg, chlorinated polyethylene [ Trade name: Tyrin 3611P, Dow Chemical Co., Ltd. 800 g and 10 g of calcium stearate as an additive were charged to a Henschel mixer (trade name), followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 180 to 260 ° C. using an extruder having a diameter of 30 mm to prepare pellets.

Comparative Examples 8-9

The same components as in Example 9 were charged to a Henschel mixer (trade name) except that the polypropylene content and the bromine-based flame retardant were replaced with the flame retardant shown in Table 1, followed by stirring and mixing. Pellets were prepared by melting and extruding under the same conditions as those in 9.

The pellets obtained in Comparative Examples 8 to 9 were dried at 100 ° C. for 3 hours, and molded using an injection molding machine having a maximum temperature of 230 ° C. to prepare a constant test piece for testing flame resistance and mechanical properties. After that, the results of measuring flame retardancy and mechanical properties are shown in Table 1.

As can be seen in Table 1, Example 9 manufactured according to the present invention has a high Izod impact strength and heat deformation temperature, and has a high flame retardant property of UL94 flame retardant 5V class. However, when the brominated flame retardant uses a flame retardant other than the above general formula (I) such as tetrabromo bisphenol A or tetrabromo bisphenol S, it is not possible to obtain a 5 V class flame retardant.

Table 1 (Unit: 100g)

(week)

Component (A): Polypropylene resin [BJ300 (brand name): Samsung General Chemical Co., Ltd. product]

Component (B) -1: Bromine type flame retardant, bis (pentabromophenyl) ethane [brand name: S-8010, United States Alberte

Solar radiation]

Component (B) -2: Brominated flame retardant, decabromo phenyl ether [brand name: S-102E, United States

Albert Mail Company]

Component (B) -3: Brominated flame retardant, tetrabromo bisphenol A-bis (2, 3- dibromopropyl ether)

Le) [brand name: PE68, American Great lakes company]

Component (B) -4: Brominated flame retardant, tetrabromo bisphenol S system [brand name: Nonnen52, Japan floor

Vichy (Marubishi Chemical Company)

Ingredient (C): Antimony trioxide [brand name: SW, Ilsung antimony company]

Component (D) -1: magnesium hydroxide [brand name: Kisuma5A, Japan Kyowa Chemicals Corporation]

Ingredient (D) -2: Talc [brand name: KCN5200, Koshi Corporation]

Component (E): Chlorinated polyethylene [brand name: Tyrin 3611P, Dow Chemical Company]

As can be seen from the above examples and comparative examples, the polypropylene resin composition prepared according to the present invention has excellent impact resistance and heat resistance, and exhibits high flame retardancy of UL94 flame retardancy of 5V class even at a thin thickness of 1/32 inch. It is suitable for use in manufacturing electric appliances, automobile parts, building materials, interior decoration materials, etc. where such performance is required.

Claims (5)

(A) 31 to 61% by weight of polypropylene resin, (B) 13 to 35% by weight of organic halogen flame retardant, (C) 3 to 21% by weight of antimony trioxide, (D) 3 to 30% by weight of magnesium hydroxide, (E) chlorination A flame retardant polypropylene resin composition comprising 2 to 15% by weight of polyethylene. The method of claim 1, wherein the polypropylene resin is a crystalline polypropylene homopolymer or a crowd consisting of ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptene, 1-octene and 1-decene Flame retardant polypropylene resin composition, characterized in that the crystalline copolymer of at least one compound selected from polypropylene. The flame-retardant polypropylene resin composition according to claim 1 or 2, wherein the melt flow index of the polypropylene resin is 0.1 to 60 g / 10 minutes. The flame retardant polypropylene resin composition according to claim 1, wherein the organohalogen-based flame retardant has a structure of the following general formula (I); (I) (Wherein R represents oxygen or an alkylene group having 1 to 6 carbon atoms, and i and j are integers of 0 to 5). The flame retardant polypropylene resin composition according to claim 1, wherein the average particle diameter of the antimony trioxide is 0.2 to 5.0 mu m.