KR100878948B1 - Propylene composition with flame retardant - Google Patents

Abstract

A flame retardant propylene composition is provided to suppress the efflorescence without the degradation of moldability or mechanical property, thereby being suitable for a cladding material of an industrial wire. A flame retardant propylene composition having abrasion resistance comprises a base resin 100 parts by weight, inorganic retardant 20-200 parts by weight and additive 0.1-10 parts by weight. The base resin comprises a polypropylene copolymer resin 29-89 weight%, mixed resin 10-70 weight%, and mixture 1-20 weight% of modified rubber resin and ethylene copolymer having polarity, wherein the mixed resin is obtained by blending a ethylenic copolymer resin including a polyolefin - alpha - copolymer resin and acetate- or acrylate-based resin. The polypropylene copolymer resin is at least one mixture selected from homopolymer polypropylene, random copolymer polypropylene, and block polymer polypropylene.

Description

Flame retardant polypropylene resin composition

The present invention relates to a flame retardant polypropylene resin composition having improved flexibility and whitening, and more specifically, an ethylene-based resin comprising a polypropylene copolymer resin, a polyolefin-α-copolymer resin, and an acetate or acrylate resin. Regarding the base resin comprising a hybrid of a blended copolymer resin, a modified rubber resin, and an ethylene copolymer having a polarity, the copolymer resin includes an additive such as an inorganic flame retardant, an antioxidant, or a processing aid. It relates to a polypropylene resin composition. The present invention relates to an invention that can effectively utilize the effects of the invention when used as a coating material for industrial wires because of excellent physical properties such as suppressing whitening and improved flexibility.

Conventionally, a large amount of magnesium hydroxide or an inorganic filler was added to a polypropylene resin in order to prepare a resin composition having high flame retardancy, but the composite resin thus prepared significantly reduced moldability and mechanical properties, requiring a certain tensile strength or elongation rate. There was a limit to the application to the wire. More specifically, in the case of Korean Patent Registration No. 10-0612405, there is a limitation in using it as an electric wire due to lack of flame retardancy and flexibility.

In order to solve such a conventional problem, a method of adding an elastomer portion to the matrix resin composition has been proposed in the Republic of Korea Application No. 10-1988-17334, etc., the purpose of wrapping the elastomer portion of the inorganic flame retardant to solve the whitening phenomenon In addition, a method of introducing a polar group to the polypropylene portion has also been proposed. However, the polarization of the polypropylene part causes problems in mechanical properties due to the decomposition of the polypropylene, and the relative amount of polypropylene increases so that the whitening phenomenon is not sufficiently improved, and it does not contribute to securing wear resistance. It was.

The development of a polypropylene resin composition for producing a product having flame retardancy, strong wear resistance, and strong physical properties such that whitening is hardly generated is a problem that has not yet been solved in the related industry. Efforts have been made to this day, and the present invention has been made under such a technical background.

The technical problem to be achieved by the present invention on the basis of the above-mentioned conventional problems, to provide a flexibility to the flame-retardant polypropylene resin composition and to develop a polypropylene composite resin composition that can minimize the whitening phenomenon, such a technical problem It is an object of the present invention to provide a flame retardant polypropylene resin composition with improved flexibility and whitening that can be achieved.

The flame-retardant polypropylene resin composition having a flexibility provided in the present invention for achieving the technical problem to be achieved by the present invention is 29 to 89% by weight of polypropylene copolymer resin, polyolefin-α-copolymer and acetate-based or acrylate 100 parts by weight of a base resin comprising 10 to 70% by weight of a blended ethylene copolymer resin containing an acrylic resin and 1 to 20% by weight of a mixture of an ethylene copolymer having a polarity with a modified rubber. It characterized in that it comprises 20 to 200 parts by weight of the inorganic flame retardant and 0.1 to 10 parts by weight of the additive.

Although the flame retardant polypropylene resin composition having the wear resistance of the present invention includes an inorganic flame retardant to express flame retardancy, the whitening phenomenon can be removed or reduced without changing moldability or mechanical properties by changing the composition to enhance flexibility. Because of this, it can be used as a sheath of an industrial wire that requires strong durability and flexibility, and has an advantage of reducing cost and weight and volume by reducing insulation thickness compared to existing wire.

The present invention relates to a flame retardant polypropylene resin composition, to be described in more detail,

Polyethylene copolymer resin 29 to 89% by weight, polyolefin-α-copolymer resin and 10 to 70% by weight of a blended ethylene copolymer resin including an acetate or acrylate resin and ethylene having a polarity with the modified rubber resin To 100 parts by weight of the base resin consisting of 1 to 20% by weight of the mixture of the copolymer,

20 to 200 parts by weight of inorganic flame retardant and 0.1 to 10 parts by weight of an additive.

The polypropylene copolymer resin constituting the base resin uses at least one polypropylene resin selected from homo polymer polypropylene, random copolymer polypropylene, and block polymer polypropylene. Preferably, random copolymer polypropylene is most preferably used if the purpose for reducing or eliminating whitening is strong.

Here, in relation to the numerical value range of the polypropylene copolymer resin, if it is less than 29% by weight, the heat resistance is lowered, which is not preferable, and if it exceeds 89% by weight, the flame retardancy and flexibility are lowered, and the whitening phenomenon is severe, which is not preferable. .

In addition, the polypropylene copolymer resin preferably has a melt flow index (MI) of 0.1 to 10.

The polyolefin-α-copolymer resin, which is a component of the hybrid resin constituting the base resin, is used to improve the mechanical properties such as the tensile strength and elongation of the present invention and the whitening phenomenon, and the polyolefin-α-copolymer resin is polypropylene It is preferable to use an -α-olefin copolymer resin, and the polypropylene-α-olefin copolymer resin refers to a copolymer containing propylene including propylene-octane, propylene-butene or ethylene propylene and the like. It is more preferable to use one or more copolymer resins in consideration of compatibility with the polypropylene resin which is a component of the base resin.

Here, with respect to the numerical range of the content of the polyolefin-α-copolymer, if it is less than 10% by weight, the elongation and filler loading resistance, cold resistance decreases, and the whitening phenomenon increases, which is undesirable. Exceeding the weight percent decreases heat resistance, tensile strength, harness resistance, abrasion resistance, and the like, which is undesirable.

In addition, it is preferable to use a polyolefin-α-copolymer having a melt flow index (MI) of 5 to 20.

Ethylene-based copolymer resin, which is a component of the hybrid resin constituting the base resin, includes all acetate-based resins including at least one selected from ethylene-vinyl acetate copolymer resin, ethylene-methacrylate copolymer resin and ethylene-ethyl acrylate copolymer resin. Or an ethylene copolymer resin including an acrylate type can be used.

In addition, it is preferable to use the ethylene copolymer resin having a melt flow index (MI) of 5 to 20.

The hybrid resin constituting the base resin is characterized by containing 20 to 70% by weight of polyolefin-α-copolymer resin and 30 to 80% by weight of ethylene-based copolymer resin, based on the total weight of the hybrid resin. Here, when the polyolefin-α-copolymer resin is less than 20% by weight, the polarity of the resin portion is too high, the filler loading property of the flame retardant is lowered, the mechanical properties such as wear resistance is lowered, if exceeding 70% by weight The compatibility with the ethylene-based copolymer resin is lowered, causing a problem of lowering tensile strength, elongation, and the like.

The modified rubber resin, which is a constituent of the hybrid constituting the base resin, is anhydrous to all kinds of thermoplastic elastomers including rubber resins (polyolefin elastomers) such as ethylene-butene, ethylene-octene, ethylene-propylene, propylene-butene, and propylene octane. Use of rubber resin grafted with one or more polar group-containing compounds selected from those having imparted polarity properties using all kinds of polar molecules such as maleic acid, silane and stearic acid, oleic acid or fatty acids such as acids containing amino groups It is preferable.

The ethylene-based copolymer having polarity as a constituent of the hybrid constituting the base resin is characterized in that it contains a modified linear low density polyethylene resin or a modified ethylene-vinyl acetate copolymer. Here, the modified linear low density polyethylene resin or modified ethylene-vinyl acetate copolymer is a linear low-density polyethylene resin or ethylene-vinyl acetate copolymer is to give a polar property by using polar molecules such as maleic anhydride, silane and fatty acid At least one polar group, preferably grafted, preferably having a melt flow index of (MI) 5-20.

Herein, when the hybrid material constituting the base resin is less than 1% by weight, elongation, filler loading, cold resistance decreases, and bleaching increases, and when it exceeds 20% by weight, mechanical properties, wear resistance, etc. This decreasing problem occurs.

 In addition, the hybrid is characterized by containing 20 to 90% by weight of the modified rubber resin and 10 to 80% by weight of the ethylene copolymer based on the total weight of the mixture. Here, when the modified rubber resin is less than 20% by weight, compatibility between the ethylene-based copolymer resin and polypropylene, which is a base resin, is lowered, resulting in a problem that mechanical strength such as tensile strength and elongation wear resistance is lowered. If the weight% is exceeded, the affinity with the flame retardant is reduced, so that the filler loading property is lowered, resulting in a problem of lowering mechanical properties.

The inorganic flame retardant consists of pure magnesium hydroxide or aluminum hydroxide without surface treatment, or vinylsilane, aminosilane, stearic acid And magnesium hydroxide or aluminum hydroxide surface-treated with any material selected from oleic acid or a polymer which is a special polymer for coating.

Here, when the content range of the content of the inorganic flame retardant is less than 20 parts by weight with respect to 100 parts by weight of the base resin, a problem of reducing the flame retardancy occurs, and when it exceeds 200 parts by weight, a problem of reducing the mechanical properties.

The additive is characterized in that it comprises one or more selected from antioxidants, processing aids, copper antioxidants and halogen scavenger. Here, if the additive is less than 0.1 parts by weight, a problem in which the effect of the additive is inadequate occurs, and if it exceeds 10 parts by weight, the additive acts as an impurity, which lowers workability during extrusion, and also causes a problem of deterioration of physical properties of the product. do.

Here, the antioxidant may include at least one selected from a primary antioxidant and a secondary antioxidant. In addition, the processing aid may include one or more selected from gum, internal and external lubricants and wax components.

The flame-retardant polypropylene resin composition having the above composition has excellent electrical properties including mechanical properties and electrical insulation including flexibility, and improved flexibility and whitening phenomenon, so that it can exert excellent workability during wire extrusion and harness work, and thus covering the wire Very suitable for use as such.

Hereinafter, specific examples will be described to help understand the present invention. However, the scope of the present invention is not limited by the following examples.

Example  1 to 4 and Comparative example  1 to 6

A flame retardant polypropylene resin composition was prepared containing the components and component ratios shown in Table 1 below.

Take 60g of polypropylene, mix 12.5g of polyolefin-α-copolymer and 12.5g of ethylene-vinyl acetate copolymer resin to prepare hybrid resin, and dry blending by mixing 5g of modified rubber and modified linear low density polyethylene resin. To prepare a base resin. 100 mg of the base resin was taken, melted in a kneader of a batch type, and 150 g of an inorganic flame retardant and 3 g of an antioxidant were mixed therein, and then, a polypropylene resin composition was prepared by an extrusion molding process.

division Example Comparative example One 2 3 4 One 2 3 4 5 6 Polypropylene Copolymer Resin (Unit: wt%) 30 47.5 65 70 50 50 50 50 30 50 Hybrid resin (unit: wt%) Polyolefin-α-Copolymer 34.5 23.75 12.5 5 45 - - 22.5 34.5 34.5 Ethylene-Vinyl Acetate Copolymer 34.5 23.75 12.5 5 - 45 - - 34.5 34.5 Hybrid (Unit: wt%) Modified rubber resin 0.5 2.5 5 10 5 - 5 5 0.5 0.5 Modified Linear Low Density Polyethylene Resin 0.5 2.5 5 10 - 5 - - 0.5 0.2 Polyolefin Elastomer Resin (Unit: wt%) - - - - - - 45 22.5 - - Base resin weight% (weight part) 100% by weight (100 parts by weight) Inorganic flame retardant (unit: parts by weight) Hydroxide-magnesium, Mg (OH) ₂ 150 150 150 150 150 150 150 150 270 150 Additive (unit: parts by weight) Antioxidant 3 3 3 3 3 3 3 3 3 3 1. Polypropylene copolymer resin: As a polypropylene random copolymer resin, the brand name R724J of LG-Caltex (Korea) is used. 2. Polyolefin- (alpha) -copolymer: Polyolefin- (alpha) -propylene, Mitsui Chemicals (Japan). 3. Using ethylene. 3. Ethylene-vinyl acetate copolymer resin: Use of Hanwha Chemical Co., Ltd., 1152 EVA. 4. Modified rubber resin: Mitsui Corporation (Japan) trade name MA-8510 is used. 5. Modified linear low density polyethylene resin: As an ethylene butene system, Fusabond 226D from DuPont is used. 6. Polyolefin elastomer resin: Using the Engage 8150 brand name of DuPont Dow Elastomers (USA) 7. Magnesium hydroxide; As magnesium hydroxide, the brand name Magnifin H5 of Albemarlesa (Germany) is used. 8. Antioxidant: Use Songnox 1010 under the name Songwon.

Experimental Example

After the test specimens were prepared using the compositions having the compositions of Examples 1 to 4 and Comparative Examples 1 to 6, tensile properties, whitening at bending deformation, abrasion resistance, flexibility, and flame retardancy were measured. The results are shown in Experimental Examples 1 to 4 and Comparative Experimental Examples 1 to 6 in the order of Examples and Comparative Examples.

Tensile Properties Experiment

According to ASTM D 638, test specimens were prepared, and tensile strength and elongation were measured using a universal testing machine .

Bending deformation  Whitening phenomenon experiment

In the case of the actual wire insulation material, it was judged visually whether whitening phenomenon occurred when bending deformation was performed under the conditions of a resin thickness of 1 mm and a radius of curvature of 5 mm, using the compositions of Examples and Comparative Examples to evaluate under the same conditions. After extrusion molding a specimen having a mm thickness, a cylindrical specimen having a diameter of 2 mm was prepared under a condition of a bending radius of 5 mm, and the appearance of whitening phenomenon was observed visually at the same radius of curvature.

Wear Resistance Test

As a needle scraper experiment, a weight of 710 g was placed on a needle of 0.45sq, and a worn thickness was measured after 300 round trips of a sample having a width of 2 mm × thickness 1 mm × length of 100 mm. If it is 50 micrometers or less in abrasion resistance, it is evaluated as appropriate.

Flexibility experiment

It was measured using 3-point bending mode using Dynamic Mechanical Analysis (DMA) and the flexural strength was less than 1000kgf / cm ³ .

Flame Retardant Experiment

 A horizontal flame retardant test was conducted using a flame retardant tester. After installing the wire sample horizontally, using a Bunsen burner, apply flame for 15 seconds using a flame of 10 cm in length and 5 cm in flame, and then the time until the flame applied to the wire disappears naturally. Was measured. If the time is less than 30 seconds, it is evaluated as appropriate.

division Experimental Example Comparative Experiment One 2 3 4 One 2 3 4 5 6 Tensile properties Tensile Strength (Mpa) 12 18 24 28 8 32 38 8 7 9 Elongation (%) 950 680 340 150 1300 90 70 400 60 30 Whitening phenomenon none none none none none plenty Very many plenty Very black Very many Abrasion Resistance (μm) 41 12 4 One 35 87 13 31 185 167 flexibility 300 500 800 900 900 1200 1100 1050 2500 1400 Flame retardant 29 22 15 24 27 29 28 30 5 43

As confirmed through Table 2, in the experimental example of the present invention, the whitening phenomenon was slightly generated or did not occur, but the whitening phenomenon occurred in other comparative experiments except the comparative example 1, in particular, the comparative example 3 In this case, it was confirmed that the degree of whitening phenomenon was very large. In addition, in the case of the experimental example, although the overall physical properties are somewhat lower than Comparative Experimental Example 1, it can be seen that the flexibility is much better. In Comparative Example 5, it can be seen that the mechanical properties decrease due to the addition of an excessive amount of inorganic flame retardant, in Comparative Example 6, when too small a small amount of the hybrid constituting the base resin of the present invention is elongation rate It can be seen that the fall, the whitening phenomenon increases. In Comparative Example 2, which is an experiment of Comparative Example 2 which does not use polyolefin-α-copolymer resin and modified rubber resin, and Comparative Experiment 3, which is an experiment of Comparative Example 3 using polyolefin elastomer resin, elongation is not very good. In addition, it can be seen that the bleaching phenomenon occurs severely.

Experimental examples show that the polypropylene resin prepared at the composition and composition ratio of the present invention has excellent anti-whitening effect, flame retardancy and flexibility, and particularly, when the characteristics of the present invention are used for coating industrial cables, etc. It can be seen that the effect can be exerted better.

Claims (10)

29 to 89% by weight of polypropylene copolymer resin, 10 to 70% by weight of mixed resin of ethylene-based copolymer including polyolefin-α-copolymer resin and acetate-based or acrylate-based resin and modified rubber To 100 parts by weight of the base resin consisting of 1 to 20% by weight of the mixture of the resin and the ethylene-based copolymer having a polarity, Flame retardant polypropylene resin composition having abrasion resistance, characterized in that it comprises 20 to 200 parts by weight of inorganic flame retardant and 0.1 to 10 parts by weight of additives. The method of claim 1, wherein the polypropylene copolymer resin constituting the base resin is at least one member selected from homopolymer (polypropylene), random copolymer (random copolymer) polypropylene and block polymer (block polymer) polypropylene Flame retardant polypropylene resin composition. The polyolefin-α-copolymer resin according to claim 1, wherein the polyolefin-α-copolymer resin is used, and the propylene-α-olefin copolymer resin is used in polypropylene-octene, polypropylene-butene, and polypropylene-ethene. Flame retardant polypropylene resin composition characterized in that the selected one or more copolymer resins are mixed. The flame retardant according to claim 1, wherein the ethylene copolymer resin is mixed with at least one copolymer resin selected from ethylene-vinyl acetate copolymer resin, ethylene-methacrylate copolymer resin, and ethylene-ethyl acrylate copolymer resin. Polypropylene resin composition. The flame retardant polypropylene resin composition according to claim 1, wherein the hybrid resin contains 20 to 70% by weight of polyolefin-α-copolymer resin and 30 to 80% by weight of ethylene-based copolymer resin. 2. The modified rubber resin according to claim 1, wherein the modified rubber resin is one selected from maleic anhydride, silane and stearic acid or oleic acid phosphoric acid in a rubber resin containing at least one selected from ethylene-butene, ethylene-octene, ethylene-propylene and propylene-butene. A flame retardant polypropylene resin composition characterized by grafting a compound having at least one polar group. The method of claim 1, wherein the ethylene copolymer having a polarity comprises a modified linear low density polyethylene resin or modified ethylene-vinyl acetate copolymer, wherein the linear low density polyethylene resin or ethylene-vinyl acetate copolymer is maleic anhydride, silane And at least one polar group-containing compound selected from fatty acids which are amino silanes, stearic acid or oleic acid. The flame retardant polypropylene resin composition according to claim 1, wherein the hybrid contains 20 to 90 wt% of a modified rubber resin and 10 to 80 wt% of an ethylene copolymer. The method of claim 1, wherein the inorganic flame retardant is magnesium hydroxide or aluminum hydroxide, the surface treatment is omitted; or Magnesium hydroxide or aluminum hydroxide surface-treated with any material selected from vinylsilane, aminosilane, stearic acid and oleic acid or a polymer which is a special polymer for coating; Flame retardant polypropylene resin composition comprising a The flame retardant polypropylene resin composition according to claim 1, wherein the additive contains at least one selected from an antioxidant, a processing aid, a copper antioxidant, and a halogen remover.