Polyethylene resin composition

Abstract: The object of the present invention is to provide a poly­ ethylene resin composition which is improved in anti-block­ ing and slipping properties, and further in antistatic proper­ ties without deteriorating the excellent properties of poly­ ethylene, such as transparency and heat sealability. The inventive polyethylene resin composition com­ prises (A) polyethylene, (B) a zeolite or an anhydrous amorphous aluminosili­ cate having the basic particle characteristics of zeolite as prepared by acid-treating zeolite, (C) fatty acid amide having a melting point of not more than 130 °C, and (D) an antistatic agent.

Description: BACKGROUND OF THE INVENTION The present invention relates to a polyethylene resin composition which can be effectively used as wrapping material, agricultural film material and so forth; in particularly it relates to a polyethylene resin composition comprising polyethylene, an anhydrous amorphous aluminosilicate, a fatty acid amide having a melting point of not more than 130°C and an antistatic agent. Polyethylenes, such as straight-chain low density polyethylene (LLDPE) are used as wrapping materials, agricultural film materials and so forth because of their excellent mechanical properties, heat sealability and transparency. These polyethylenes, however, have a disadvantage of being tacky, that is, since the polyethylenes have poor sliding properties and also are liable to cause blocking, they tend to cause problems such as a reduction in the efficiency of operation during the process of production or fabrication of films, and problems at the time of wrapping. From JP-B-16 134/1977 it is already known that powdered zeolite can be added to polypropylene to improve its antiblocking properties. From JP-A-59-129 240 ("Chem. Abstr.", Vol. 102, No. 4, page 43, ref. 25 649 f) polyethylene resin compositions are known which contain 100 parts of LLDPE (linear low-density polyethylene) and 0,5 to 2,0 parts of zeolithe and which exhibit high environmental stress cracking resistance. However, these known polyethylene compositions do not meet the requirements of modern wrapping materials in regard to anti-blocking and slipping properties and in regard to antistatic properties without deteriorating the excellent properties of polyethylene, such as transparency and heat sealability. Therefore, the object of the present invention is to provide a polyethylene resin composition which is improved in anti-blocking and slipping properties and further in antistatic properties without deteriorating the excellent properties of polyethylene, such as transparency and heat sealability. As a result it has been found that the above object can be attained according to the present invention by adding to polyethylene an anhydrous amorphous aluminosilicate having the basic particle characteristics of zeolite as prepared by acid-treating zeolite, and if necessary, specific fatty acid amide and antistatic agent in specified amounts based on the weight of polyethylene. SUMMARY OF THE INVENTION Subject-matter of the present invention is a polyethylene resin composition comprising: (A) 100 parts by weight of polyethylene, (B) 0,01 to 2,0 parts by weight of an anhydrous amorphous aluminosilicate having the basic particle characteristics of zeolite as prepared by acid-treating zeolite, (C) 0 to 1,5 parts by weight of fatty acid amide having a melting point of not more than 130°C, and (D) 0 to 3,0 parts by weight of an antistatic agent. The polyethylene resin composition of the present invention is improved in anti-blocking and slipping properties and further in antistatic properties over the prior art without deteriorating the excellent properties of polyethylene, such as transparency and heat sealability. Since according to the present invention an anhydrous amorphous aluminosilicate having the basic particle characteristics of zeolite as prepared by acid-treating zeolite is employed as component (B), it does not adsorb water unlike zeolite subjected to the usual heat dehydration treatment. Consequently, it is able to avoid the adverse influences of water at the molding step, and thus according to the present invention a polyethylene film having excellent antiblocking and slipping properties can be obtained. Such an effect of the present invention is obvious from the comparison between the examples and the comparative examples following below. According to preferred embodiments of the present invention the used polyethylene is a low density polyethylene, in particular a straight-chain low density polyethylene consisting of 80 to 99,8, preferably 90 to 99 mol% of an ethylene unit and 0,2 to 20, preferably 1 to 10 mol% of an α-olefin unit having 3 to 12, preferably 6 to 12 carbon atoms. According to a further preferred embodiment of the present invention the low density polyethylene is a blend of straight-chain low density polyethylnene and high pressure process low density polyethylene. The fatty acid amide used according to the present invention is preferably selected from the class consisting of erucic acid amide, stearic acid amide, oleic acid amide, behenic acid amide, N-stearylbutyrlc acid amide, N-stearylcaprylic acid amide, N-stearyllauric acid amide, N-stearylstearic acid amide, N-stearylbehenic acid amide, N-oleyloleic acid amide, N-oleylbehenic acid amide, N-butylerucic acid amide, N-octylerucic acid amide and N-laurylerucic acid amide. The antistatic agent used according to the present invention is preferably selected from the class consisting of cationic compounds, anionic compounds, nonionic compounds and amphoteric compounds, in particular it is polyoxyethylene alkylamine, polyoxyethylene alkylamide, their fatty acid esters or their glycerine fatty acid esters. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION There are no special limitations to polyethylene which is used in the present invention as the component (A). However, as the component (A), low density polyethylene can be used preferably. Particularly preferred in the present invention is the use of straight-chain low density polyethylene (LLDPE). Also a blend of the above LLDPE and a high pressure process low density polyethylene can be used as the component (A). This LLDPE is prepared by copolymerizing ethylene and 0,2 to 20 mol% or, preferably 0,5 to 15 mol% or, more preferably 1 to 10 mol% of one or more of α-olefins having 3 to 12 carbon atoms, such as propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, octene-1, and decene-1 in the liquid phase or the gas phase. Such LLDPEs have a density of 0,910 to 0,960 g/cm³, preferably 0,915 to 0,940 g/cm³, and a melt index (MI) of 0,5 to 10 g/10 min, preferably 0,8 to 6,0 g/10 min. This LLDPE is also prepared by copolymerizing in the liquid phase or the gas phase 90 to 99 mol% of an ethylene unit, 0,4 to 9,5 mol%, preferably 0,5 to 5 mol% of an α-olefin unit (having 3 to 4 carbon atoms; e.g., propylene and butene-1), and 0,4 to 9,5 mol%, preferably 0,5 to 5 mol% of an α-olefin unit (having 6 to 12 carbon atoms; e.g., hexene-1, 3-methyl-pentene-1, 4-methyl-pentene-1, octene-1 and decene-1. Suitable examples of such LLDPEs are an ethylene-propylene-octene-1 copolymer and an ethylene-butene-octene-1 copolymer. Particularly suitable is the ethylene-butene-octene-1 copolymer. For these LLDPE, the melt flow rate (MFR=flow rate/melt index; the flow rate is measured according to ASTM D-1238 under Condition E, ten times the weight used in the melt index test as described below) is 18 to 52 and preferably 23 to 48, the density (measured according to JIS K7110: the density gradient tube method) is 0,910 to 0,940 g/cm³ and preferably 0,910 to 0,936 g/cm³, and the melt index (MI: measured according to ASTM D-1238 under Condition E: 190°C) is 0,1 to 10 g/10 min and preferably 0,5 to 5 g/10 min. If MFR is less than 17, the moldability of the resin composition is decreased. On the other hand, if MFR is in excess of 52, transparency is deteriorated. When MFR is within the range of 23 to 48, there can be obtained a resin composition having good impact resistance. The above LLDPE can be produced by known methods. For example, α-olefins are fed to the polymerization system in such a manner that each α-olefin unit content is within the above specified range and then random copolymerised in the liquid phase or the gas phase to produce the desired LLDPE. In this case, the ratio of the α-olefins supplied is controlled by suitably choosing the type of the α-olefin, the polymerization temperature and the ethylene partial pressure. In the present invention, as the component (B), an anhydrous amorphous aluminosilicate having the basic particle characteristics of zeolite as prepared by acid-treating zeolite is used. The anhydrous amorphous aluminosilicate which is used as the component (B) of the present invention has the basic particle characteristics of zeolite, such as a particle form and a particle size distribution, but is anhydrous and amorphous and does not have the crystal structure that zeolite has. The term "amorphous zeolite" as used herein includes both a zeolite in the X-ray diffraction pattern of which no diffraction peak is observed, and a zeolite in the X-ray diffraction pattern of which the height of the diffraction peak is decreased to not more than a half of the original height and which is substantially amorphous. The anhydrous amorphous aluminosilicate to be used as the component (B) of the present invention may be an amorphous aluminosilicate which is made anhydrous by subjecting it to heat dehydration treatment in advance, or an amorphous aluminosilicate which is made anhydrous through heat treatment at the time of kneading with the other components. The average particle diameter of the anhydrous amorphous aluminosilicate to be used as the component (B) of the present invention is preferably 0,5 to 5 µm and more preferably 1,5 to 3,5 µm. Furthermore it is preferred for the anhydrous amorphous aluminosilicate to have such a particle size distribution that particles having a particle diameter falling within the range of 1/2 to 3/2 of the average particle diameter constitute not less than 50 % of all particles. It is preferred that the particle form of the component (B) be spherical or cubic provided that the edges are round, and that the particle surface be smooth. The above anhydrous amorphous aluminosilicate can be prepared by various methods. One of the methods is illustrated below. Zeolite to be used as the starting material may be natural or synthetic. It is preferred to use zeolite in which the molar ratio of SiO₂ to Al₂O₃ (SiO₂/Al₂O₃) is not more than 5/1, especially not more than 4/1. The reason for this is that the characteristic crystal structure of zeolite having a SiO₂/Al₂O₃ molar ratio falling within the above specified range is readily decomposed by the acid treatment as described hereinafter. Representative examples of such zeolites are A-type zeolite, P-type zeolite, X-type zeolite and Y-type zeolite. They can be used alone or in combination with each other. Particularly preferred in the present invention is to use A-type zeolite and X-type zeolite which are nearly spherical in the shape. This zeolite is then subjected to acid treatment. This acid treatment provides zeolite which is substantially amorphous while holding the basic particle characteristics thereof. This acid treatment is carried out by adding an acid such as sulfuric acid and phosphoric acid, or an acid substance to an aqueous slurry of zeolite. In this acid treatment, pH of the aqueous slurry of zeolite is adjusted to 4.5-9 and preferably 5-7; that is, made weakly acidic. If the pH of the aqueous slurry is less than 4.5, the basic particle characteristics of zeolite, such as a particle form and a particle size distribution, undesirably undergo serious changes, or the whole particles are undesirably dissolved or disappear. On the other hand, if the pH of the aqueous slurry is in excess of 9, the zeolite is undesirably difficult to make amorphous. The above-prepared amorphous aluminosilicate having the basic particle characteristics of zeolite is subjected to heat dehydration treatment to provide anhydrous amorphous aluminosilicate. This heat dehydration treatment is carried out by heating the above amorphous aluminosilicate at a temperature of not less than 240°C, preferably 250 to 500°C. In the manner as described above, the component (B) of the present invention is obtained. Since the component (B) has been subjected to the above defined acid treatment, it does not adsorb water unlike zeolite subjected to the usual heat dehydration treatment. Thus, the adverse influences of water exerted at the molding step can be substantially prevented. Furthermore the component (B) does not substantially deteriorate the transparency inherent to polyethylene. The component (B) is usually of the Na type, and the cation exchange capability characteristics of zeolite substantially disappears. However, by utilizing the slightly remaining cation exchange capability, Na⁺ can be replaced with other cations such as Ca⁺⁺, Mg⁺⁺, Ba⁺⁺, Zn⁺⁺ and Pb⁺⁺. Furthermore it may be coated with metal hydroxides such as the hydroxides of aluminum, titanium, zirconium and antimony, or amorphous silica, for example. In the present invention, the component (B) is added in an amount of 0.01 to 2.0 parts by weight, preferably 0.05 to 1.5 parts by weight per 100 parts by weight of the above component (A). If the amount of the component (B) added is less than 0.01 part by weight, anti-blocking cannot be increased. On the other hand, if the amount of the component (B) added is in excess of 2.0 parts by weight, transparency is undesirably decreased. In the present invention, as the component (C), fatty acid amide having a melting point of not more than 130°C, preferably 60 to 120°C is used. Examples of such fatty acid amides are erucic acid amide, stearic acid amide, oleic acid amide, behenic acid amide, N-stearylbutyric acid amide, N-stearylcaprylic acid amide, N-stearyllauric acid amide, N-stearylstearic acid amide, N-stearylbehenic acid amide, N-oleyloleic acid amide, N-oleylbehenic acid amide, N-butylerucic acid amide, N-octylerucic acid amide, and N-laurylerucic acid amide. Of these compounds, erucic acid amide is particularly preferred. If, however, fatty acid amide having a melting point in excess of 130°C is used as the component (C), anti-blocking properties are undesirably decreased. The component (C) mainly contributes to an increase in slipping and sliding properties. In the present invention, the amount of the component (C) added is 0 to 1.5 parts by weight, preferably 0.03 to 1.0 part by weight per 100 parts by weight of the component (A). If the amount of the component (C) added is in excess of 1.5 parts by weight, heat sealability is undesirably decreased. In the present invention, it is preferred to use erucic acid amide as the component (C). In this case, the suitable amount of the erucic acid amide used is 0.05 to 0.4 part by weight for the general films (having a thickness of 20 to 30 µm), 0.05 to 0.2 part by weight for agricultural films (having a thickness of 50 to 60 µm), and not more than 0.1 part by weight for heavy duty films (having a thickness of 150 to 200 µm). In the present invention, as the component (D), an antistatic agent is used. Any of cationic, anionic, nonionic and amphoteric antistatic agents can be used. Representative examples of such antistatic agents are cationic compounds such as primary amine salts, tertiary amines, quaternary ammonium compounds and pyridine derivatives, anionic compounds such as sulfated oil, soap, sulfated ester oil, sulfated amide oil, sulfuric acid ester salts of olefins, fatty alcohol sulfuric acid ester salts, alkylsulfuric acid ester salts, fatty acid ethylsulfonic acid salts, alkylnahpthalenesulfonic acid salts, alkylbenzenesulfonic acid salts, succinic acid ester sulfonic acid salts, and phosphoric acid ester salts, nonionic compounds such as partial fatty acid esters of polyhydric alcohols, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acid, ethylene oxide adducts of fatty acid amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of alkylnaphthols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and polyethylene glycol, and amphoteric compounds such as carboxylic acid derivatives and imidazoline derivatives. Of the above compounds, nonionic compounds are preferred. Particularly preferred are polyoxyethylene-alkylamine and polyoxyethylene alkylamide, and their fatty acid esters and glycerine fatty acid esters. In the present invention, the amount of the component (D) added is 0 to 3.0 parts by weight, preferably 0.1 to 1.5 parts by weight per 100 parts by weight of the component (A). If the amount of the component (D) added is in excess of 3.0 parts by weight, tackiness and whitening undesirably readily occur as a result of bleeding. The polyethylene resin composition of the present invention comprised the above components (A), (B), (C) and (D). If desired, additives such as a lubricant, an antioxidant, a weathering agent, an anti-fogging agent, and a colorant can be added to the polyethylene resin composition of the present invention. Representative examples of the lubricant are metal soaps such as calcium stearate, zinc stearate, and barium stearate. As the antioxidant, phenol-, phosphorous-, amine- and sulfurbased antioxidants can be used. The polyethylene resin composition of the present invention is prepared by mixing the above components by the usual method. More specifically, (1) the polyethylene resin composition of the present invention can be prepared by melt mixing the above components at 160 to 230°C by the use of a Banbury's mixer, a cokneader, or a knead-extruder, for example, or (2) the polyethylene resin composition of the present invention can be prepared by first preparing a master batch containing high concentrations of the components (B), (C) and (D), and mixing the master batch with polyethylene as the component (A) at the time of film formation. The polyethylene resin composition of the present invention as prepared above is molded into a film, for example, by the use of various film molding apparatuses, and is used as a wrapping material, or an agricultural film, for example. According to the polyethylene resin composition of the present invention, a polyethylene film having excellent antiblocking and slipping properties can be used. Thus, troubles such as formation of wrinkle and attachment of dust do not occur at a slitter in production of films, or at the fabrication steps of printing, bag-making or the like, and the productivity can be greatly increased. In the polyethylene resin composition of the present invention, excellent properties characteristic of polyethylene, such as transparency, heat sealability and appearance are not deteriorated at all, and thus the polyethylene resin composition of the present invention is of practical value and further is improved in antistatic properties, for example. In the case that LLDPE produced by copolymerizing the specified monomers is used as component (A), a polyethylene film which is excellent in properties such as impact resistance and transparency and further in antiblocking, slipping and antistatic properties can be obtained. Since the anhydrous amorphous aluminosilicate having the basic particle characteristics of zeolite as prepared by acid-treating zeolite is used as component (B), it is able to avoid the adverse influences of water at the molding step, and thus a polyethylene film having excellent antiblocking and slipping properties can be obtained. Accordingly the polyethylene resin composition of the present invention is useful in production of various wrapping materials, agricultural film materials and so forth. The present invention is described in greater detail with reference to the following examples. EXAMPLES 1 TO 8, AND COMPARATIVE EXAMPLES 1 TO 5 Predetermined amounts of the compounds (A), (B) and (C) as shown in Table 1 were compounded, kneaded in a twin screw kneader at 200°C, and extruded in a tubular form at an extrusion temperature of 190°C by the use of an extruder having a diameter of 50 mm. The film thus produced having a thickness of 20 µm was measured by the following methods, and the results are shown in Table 1. Physical Property Measuring Methods (1) Blocking Properties Two 5 cm x 25 cm test pieces were superposed, and 9 kg of a load was placed thereon. The assembly was allowed to stand at 60°C for 3 hours. Then the two pieces were separated in an up-and-down direction at a pulling speed of 200 mm/min, and the maximum value (g/100 cm²) was determined. (2) Static Coefficient of Friction Measured according to ASTM D 1894. (3) Visible Transparency Narrow transmitted light amount measured by the use of a visible transparency testor (manufactured by Toyo Seiki Seisakujo) (4) Heat Sealability A 4x 20 cm test piece was heat sealed with a heat seal width of 1 x 2.5 cm and under a pressure of 0,2 MPa (2 kg/cm²) for 1 second and then allowed to stand for 30 minutes. Then the sealed part was separated at a pulling speed of 200 mm/min, and the strength (g) was measured. (5) Antistatic Properties The antistatic properties were evaluated by the Ash Test method and rated as follows. o ... Even if the film is approached to ash to a height of 1 to 3 cm, no attachment of ash occurs. ▵ ... Even if the film is approached to ash to a height of 3 to 7 cm, no attachment of ash occurs. x ... If the film is approached to a height of not more than 7 cm, attachment of ash occurs. EXAMPLES 9 AND 10 A 90 µm thick film was produced in the same manner as in Examples 1 to 9, and was measured for physical properties. The results are shown in Table 1. EXAMPLE 11 A film was produced in the same manner as in Example 1 except that a blend of 80 wt% of the same straight chain low density polyethylene as used in Example 1 and 20 wt% of high pressure process low density polyethylene (density, 0.921 g/cm³; MI, 3.0 g/10 min) was used as the component (A) and the amount of the component (B) added was changed to 0.5 part by weight, and then was measured for physical properties. The results are shown in Table 1. EXAMPLE 12 A film was produced in the same manner as in Example 1 except that a blend of 80 wt% of the same straight chain low density polyethylene as used in Example 1 and 20 wt% of high pressure process low density polyethylene (density, 0.921 g/cm³; MI, 3.0 g/10 min) was used as the component (A), the amount of the component (B) added was changed to 0.3 part by weight and the amount of the component (C) added was changed to 0.15 past by weight, and then was measured for physical properties. The results are shown in Table 1. EXAMPLES 13 TO 21, AND COMPARATIVE EXAMPLES 6 TO 11 Films were produced in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 5 except that the predetermined amounts of the components (A), (B), (C) and (D) as shown in Table 1 were used, and then were measured for physical properties. The results are shown in Table 1. EXAMPLES 22 AND 23 90 µm thick films were produced in the same manner as in Examples 13 to 21 and then were measured for physical properties. The results are shown in Table 1. COMPARATIVE EXAMPLE 12 to 20 and 23 to 27 Films were produced in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 4 except that the predetermined amounts of the components (A), (B), (C) and (D) as shown in Table 2 were used, and then were measured for physical properties. The results are shown in Table 2. COMPARATIVE EXAMPLES 21 AND 22 90 µm thick films were produced in the same manner as In Comparative Examples 12 TO 20, and then were measured for physical properties. The results are shown in Table 2. COMPARATIVE EXAMPLES 28 TO 36 and 39 to 43 Films were produced in the same miner as in Examples 1 to 8 and Comparative Examples 1 to 5 except that the predetermined amounts of the components (A), (B), (C) and (D) as shown in Table 3 were used, and then were measured for physical properties. The results are shown in Table 3. COMPARATIVE EXAMPLES 37 AND 38 90 µm thick films were produced in the same manner as in Examples 37 TO 45, and then were measured for physical properties. The results are shown in Table 3. EXAMPLES 24 TO 31, AND COMPARATIVE EXAMPLES 44 TO 48 Films were produced in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 5 except that the predetermined amounts of the components (A), (B), (C) and (D) as shown in Table 4 were used, and then were measured for physical properties. The results are shown in Table 4. EXAMPLES 32 AND 33 90 µm thick films were produced in the same manner as in Examples 24 TO 31, and then were measured for physical properties. The results are shown in Table 4. EXAMPLES 34 TO 43 COMPARATIVE EXAMPLES 49 TO 54 Films were produced in the same manner as in Examples 24 TO 31 and Comparative Examples 45 TO 48 except that the predetermined amounts of the components (A), (B), (C) and (D) as shown in Table 4 were used, and then were measured for physical properties. The results are shown in Table 4. EXAMPLES 44 AND 45 90 µm thick films were produced in the same manner as in Examples 34 TO 43, and then were measured for physical properties. The results are shown in Table 4.

Claims: A polyethylene resin composition comprising: (A) 100 parts by weight of polyethylene, (B) 0.01 to 2.0 parts by weight of an anhydrous amorphous aluminosilicate having the basic particle characteristics of zeolite as prepared by acid-treating zeolite, (C) 0 to 1.5 parts by weight of fatty acid amide having a melting point of not more than 130°C, and (D) 0 to 3.0 parts by weight of an antistatic agent. The polyethylene resin composition as claimed in Claim 1, wherein the polyethylene is low density polyethylene. The polyethylene resin composition as claimed in Claim 2, wherein the low density polyethylene is straight-chain low density polyethylene consisting of 80 to 99.8 mol% of an ethylene unit and 0.2 to 20 mol% of an α-olefin unit having 3 to 12 carbon atoms. The polyethylene resin composition as claimed in Claim 2 or 3, wherein the low density polyethylene is straight-chain low density polyethylene consisting of 90 to 99 mol% of an ethylene unit, 0.4 to 9.5 mol% of an α-olefin unit having 3 to 4 carbon atoms and 0.4 to 9.5 mol% of an α-olefin unit having 6 to 12 carbon atoms. The polyethylene resin composition as claimed in any of Claims 2 to 4, wherein the low density polyethylene is a blend of straight-chain low density polyethylene and high pressure process low density polyethylene. The polyethylene resin composition as claimed in any of Claims 1 to 5, wherein the fatty acid amide is selected from the class consisting of erucic acid amide, stearic acid amide, oleic acid amide, behenic acid amide, N-stearylbutyric acid amide, N-stearylcaprylic acid amide, N-stearyllauric acid amide, N-stearylstearic acid amide, N-stearylbehenic acid amide, N-oleyloleic acid amide, N-oleylbehenic acid amide, N-butylerucic acid amide, N-octylerucic acid amide, and N-laurylerucic acid amide. The polyethylene resin composition as claimed in any of Claims 1 to 6, wherein the antistatic agent is selected from the class consisting of cationic compound, anionic compound, nonionic compound and amphoteric compound. The polyethylene resin composition as claimed in any of Claims 1 to 7, wherein the antistatic agent is polyoxyethylene-alkylamine, polyoxyethylene alkylamide, their fatty acid esters or their glycerine fatty acid esters.

Inventors: AZUMA YUTAKA, TANAKA YOSHIKATSU, AZUMA, YUTAKA, TANAKA, YOSHIKATSU
Applicants: IDEMITSU PETROCHEMICAL CO, IDEMITSU PETROCHEMICAL CO. LTD.
Application year: 1986
Main classification: C08L23
IPC codes: C08K5, C08K3, C08L23