TW593500B - Polyethylene resin composition for rotational molding and rotational molded product using the composition - Google Patents

Abstract

The polyethylene resin composition for rotational molding according to the invention is a composition comprising an ethylene-alpha-olefin copolymer (A) having a density of 0.880 to 0.930 g/cm<3> and MFR of 0.01 to 5 g/10 min and an ethylene homopolymer or an ethylene-alpha-olefin copolymer (B) having a density of 0.931 to 0.974 g/cm<3> and MFR of 0.5 to 20 g/10 min, wherein the weight ratio ((A)/(B)) of the component (A) to the component (B) is in the range of 10/90 to 50/50, and a blend consisting of these components (A) and (B) has a density of 0.920 to 0.960 g/cm<3> and MFR of 1 to 10 g/10 min. The component (A) is preferably a copolymer prepared by the use of a metallocene type olefin polymerization catalyst, and the component (B) is preferably a (co)polymer prepared by the use of a metallocene type or Ziegler type olefin polymerization catalyst. The rotational molded product of the invention comprises the polyethylene resin composition. According to the invention, a polyethylene resin composition for rotational molding which has excellent rotational moldability and is capable of producing rotational molded products superior to the conventional polyethylene rotational molded products in impact resistance and environmental stress crack resistance, and a rotational molded product using the composition can be provided.

Description

593500

V. Description of the invention (Printed by the Ministry of Intellectual Property, Co-operative Society, The present invention relates to a polyethylene glycol composition and a plastic product made from the composition. More specifically, the present invention relates to the use in preparing Hollow moldings ^ complex mold cake water renewal_Polyethene compound, which is a polyethylenimide compound used for second moulding, so that the composition can be made with excellent impact resistance and environmental stress cracking resistance ESCR (environmental stress crack coffee) _ The present invention also relates to rotomolded products made from this composition. (26) Various products such as jars, containers, daily necessities, The garden uses external products. The materials used to make these products require special mechanical properties such as impact resistance and environmental stress crack resistance (ESCR). These properties are excellent. As rotomolding materials that meet these needs, Poly has been mainly used. Articles made with Nissei Nikkei rotomolding are excellent in impact resistance, rigidity, and environmental resistance, and are capable of cracking money-sincerity_ is excellent, but it is excellent in all aspects of performance:, is very Less. Therefore, we can balance here The surface is much better, and plastic products are expected.-The Japanese Patent Publication No. 194537/1997, which is inserted, describes h-lipids, which contain ethylene-α-dilute hydrocarbon random copolymers with a density of ( Please read the notes on the back before: this page}

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-! I I -1 · • —-1 I i · This paper size applies to China CNS) A4 size (• n n. 593500

0 920-0 · 9] 5g / cm3, the refining flow index (melt theory) is Bu Zhou Ke / 10 minutes' molecular distribution (Mw / Mn) is 2-3, the particle size is not greater than 30 mesh. The rotomolded products made from this tree are particularly excellent in balancing impact resistance, rigidity, and environmental stress crack resistance (ESCR), and there is no problem in terms of use. However, the rotomolded products it can provide are superior to polyethylene resins made of rotomolded products made of the above resins in terms of impact resistance and environmental stress cracking resistance (ESCR), and are still desired. Under these circumstances, 'the inventors of the present invention have conducted earnest research + research to meet these needs, and as a result, they have found that polyethylene rotomolded articles made by rotomolding the following resin compositions are It is excellent in impact resistance and resistance to environmental stress cracking. This resin composition contains: (A) ethylene-α-olefin copolymer, which contains ethylene and an α-olefin having 3 to 20 carbon atoms, and the density (ASTM D1505 ) Is 0.880-0 · 930g / cm3, and the melt flow rate (ASTM D1238 '190 C' load 2.16Kg) is 〇. 5 g / 10 minutes, including printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Unloaded ethylene homogenates' or co-products of ethylene and alpha-dilute hydrocarbons with 3-20 carbon atoms. Its bifurcation degree is 0.93 to 0.9974 g / cm3, and the solution flow rate is 0.5 to 20 g / 10 minutes, in which the (A) / (B) weight ratio is in a specific range, and the ethylene-olefin copolymerization is included. The density of the blend of the polymer (A) and the ethylene homopolymer or the ethylene-olefin copolymer (B) is 0.992 to 960 g / cm3, and the melt flow rate is 1 to 10 g / 10 minutes. The present invention has been completed based on this finding. OBJECTS OF THE INVENTION 6. DESCRIPTION OF THE INVENTION (Objectives, η months ^ objectives)-to provide a kind of rotational impact resistance and environmental stress crack resistance made of a combination of polyethylene resins for rotational molding Provide a stigma composition: Inventive phase n A rotomolded product according to the present invention. A polyethylene resin composition is a resin composition comprising: (A) 3 α-olefins having ethylene and γ 3-20 carbon atoms. Ethylene-α-olefin copolymer, its density (ASTM D15Q5) is G. __Q. It is g / cm3, and the body flow rate (MFR) (ASTM D1238, 190 ° C, load: 2.16Kg) is 0.01-1. 5 g / 10 minutes, and (B) ethylene homopolymer containing ethylene or ethylene olefin containing 1 ^ -olefin printed by the consumer cooperative of employees of the Intellectual Property Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs with 3 to 20 carbon atoms Copolymer whose density (ASTM D1505) is 0.931- (H74g / cin3, melt flow rate (MFR) (ASTMD1238, 190 ° C, load: 2.16Kg) is 0.5-20 g / 10 minutes, where: · Weight of ethylene ~ α-olefin copolymer (A) and ethylene homopolymer or ethylene-α-olefin copolymer (B) The ratio [(A) / (Β)] is 10 / 90-50 / 50, and the paper is composed of ethylene ~ α-olefin copolymer (A) and ethylene homopolymer or ethylene-α- € milk) 8 specifications (210, 乂 297 mm) ^ 3500 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Density of the blend consisting of olefin copolymer (B) (ASTM D1505 ) Is ^ • 92〇 ~ .960g / cm3, and the melt flow rate (MFR) (ASTM D1238, 19 ° C, load: 2.16Kg) is H0 g / 10 minutes. According to the application of the present invention, Ming The following four specific schemes can be adopted for the rotomolded polyethylene resin composition. These specific schemes are based on the production of ethylene-α-olefin co-products (A), ethylene homopolymers (B), and ethylene olefin copolymers (B). (1) A resin composition in which an ethylene-α-olefin copolymer (A), an ethylene homopolymer (B), and an ethylene-α-olefin copolymer (B) are used. Each of them is (co) polymerized using a metallocene type olefin polymerization catalyst (2) A resin composition in which an ethylene-olefin copolymer is a copolymer made using a diocene metallocene-type olefin polymerization catalyst, and an ethylene homopolymer (B) and an ethylene-α ~ dilute hydrocarbon copolymer ( β) is prepared using a ziegler type olefin polymerization catalyst; (3) a resin composition in which an ethylene-α-olefin copolymer (A), an ethylene homopolymer (B), and an ethyl alcohol The homing-α-dilute hydrocarbon copolymer (B) is prepared using a Ziegler-type olefin polymerization catalyst;

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This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm (4) —a resin composition, which is prepared using a hydrocarbon copolymerization catalyst for the polymerization of zilerene㈣ hydrocarbons.) ΫMetal type Among the olefin polymerization catalysts and compounds ⑷-⑷, it is preferable to prepare resin compositions 剂 each of which contains a metallocene-type polymerization polymerization catalyst =: Γ; Γα-olefin copolymer ⑷, and a combination of The Greer-type olefin was polymerized 4 ^, 2 fine homopolymers and ethylene-α, smoke copolymer ⑻. 223 Preparation of Ethylene Diene with a Metallocene-type Olefin Polymerization Catalyst-'/ ά 物 (Α)' Ziegler-type olefin polymerization catalyst for preparing thin homopolymer or ethylene-α_dilute hydrocarbon copolymer The rhenium composition is superior. The rotomolded article according to the present invention contains the above-mentioned polyethylene resin composition for rotomolding. The polyethylene resin composition for rotomolding according to the present invention and the rotomolded article made from the composition are described in detail below. The polyethylene resin composition for rotomolding according to the present invention contains an ethylene-α-olefin copolymer (A) and an ethylene homopolymer or an ethylene-α-olefin copolymer (β) having a density different from that of the copolymer (A). ), When this resin composition consists of ethylene-α-

593500 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () When the olefin copolymer (A) is composed of ethylene homopolymer or ethylene 1_ thin smoke q q, the density and melt of this resin composition _ The speed is in a specific range. Ethylene ... Di-copolymer (n The ethylene-α-_ copolymer used in the present invention is a copolymer of ethylene and an alpha-olefin of 3 to 20 carbon atoms. ) Is 80 0.930 g / cm, and the optimal value is 0.885-0.925 g / cm3, more preferably 890,920 g / cm 'its solution flow rate (position) (AsT, please 238,190 c' load 2.16Kg) 0 · G1-5 g / 1 ◦min, preferably 0.05-4.5 g / 10min, more preferably 0-1.4.0 g / 10 min. Α- of 3-20 carbon atoms Examples of olefins include propylene, butene, pentene, 2-methyl-1-butene, 3-monomethyl + butene, and hexene. 3-monomethyl-pentene, 4-methyl-1- Pentylene, 3,3-Difluorenyl-1-butene, 1-heptene, methylhexene, —methyl-1-pentene, trimethyl-1-butene, ethyl-1-pentene Ene, buxene, fluorenyl-1-pentene, dimethyl- 丨 -hexene, trimethyl- 丨 -pentene, ethyl- 丨 hexene, fluorenylethyl-1-pentene, di Ethyl--butene, propyl--pentene, decene, fluorenyl-bronone, difluorenyl-1-octene, trimethylen-1-heptene. Ethyl -1-octene, methylethyl-1-heptene, diethyl-1-hexene, dodecene, hexadecene. These α-olefins can be used alone, or two kinds Or multiple combinations. 10 This paper size is applicable to China National Standard (CNS) Α4 specification (210 × 297 mm) —---- Please read the back first, the notes and notes

The description of the line description (+ = You = ::, poly_ is a diethyl ether—named as ewuwuwu,-, a diethyl compound with the above-mentioned properties— :: == r, combined anti-refinement: =: two: Copolymerization and ΓΓ, the ethylene homopolymer or homopolymer or ethylene homopolymer = ethylene homopolymer or ethylene-α, hydrocarbon copolymer =) '疋 polymer containing only ethylene 938-, or a copolymer of Otome with 3_2Q carbon atoms, its density (ASTM _5) is Q. 931M). 974_3, preferably G. 935-G. 970 g / em3, more preferably ο. 938- G. 968 g / cm3, solution flow rate (MFR) (ASTM D1238, 190 ° C, load: 2 16Kg) 2 0.5-20 g / lOmin, preferably 丨 .19 g / l0 Minutes, more preferably A— = grams / 10 minutes. Examples of the α_lean hydrocarbons of 3 to 20 carbon atoms include the same ones as the α_olefins of 3 to 20 carbon atoms used to constitute the aforementioned ethylene-α-thin copolymer (a). Alpha olefins of 3-20 carbon atoms can be used alone, or two or more of 593500 A7 V. Description of the invention (B7 Excellent:: Ethylene selected for use in the present invention-"butene copolymer, ethylene + scale Copolymer 3 = ^ ethyl ~ + ― 4-methyl + pentylene copolymer or ethene copolymer, ethylene (B) resin red-naturalizing agent storage-olefin copolymerization

When using a metallocene-type dilute hydrocarbon polymerization catalyst and an olefin copolymer as the ethylene-α-dilute hydrocarbon copolymer (A) prepared in the present invention, it is possible to use dimetallocene lysene polymerization Reaction catalytic polymer or ethylene-a—, shovel Qiu ~ Q bang, take two Λ as ethylene homopolymer or ethylene ... and use the Ziegler-type polymerization catalyst to prepare dilute agoethylene-a-olefin The copolymer can be used as an ethylene homopolymer or an ethylene-olefin copolymer (B). When using ethylene-α ,, ~, * produced by using a Ziegler-type olefin polymerization catalyst as the ethylene 1-olefin copolymer of the present invention, it is prepared by using a Ziegler-type olefin polymerization catalyst. The ethylene homopolymer 'ethylene olefin copolymer was taken as the ethylene homopolymer or the ethylene-α-olefin copolymer (B). Ethylene produced by tinctures are all 12 paper sizes applicable to Chinese National Standards (CNS) M specifications (Xianguo Gongdong 593500 A7 B7 V. Description of the invention (-In the above case, the use of metallocene polymerization polymerization The catalyst is a mixture of ethylenic α-olefin copolymer (a) and an ethylene homopolymer (component IX) prepared by using a Ziegler-type olefin polymerization catalyst. Please read the Ministry of Economy first. Intellectual Property Bureau Employees' Consumer Cooperatives Printed Polyethylene Compounds The polyethylene resin composition for rotomolding according to the present invention contains ethylene-α-olefin copolymer (A) and ethylene homopolymer or ethylene-olefin Copolymer ⑻. In this resin composition, the weight ratio [(a) / (B)] of the ethylene-olefin copolymer (A) and the ethylene homopolymer or the ethylene-α to olefin copolymer (β) is 1%. / 90-50 / 50, preferably 15 / 85-45 / 55, and more preferably 20 / 80-40 / 60. As for the polyethylene resin composition for rotomolding according to the present invention, ethylene-a-olefin Copolymer (Α) and ethylene homopolymer or ethylene-α-olefin copolymer (B) The resulting blend has a density (ASTMD 1505) of 0.992-0.960 g / cm3, preferably 0.922-0. 958 g / cm3, and more preferably 0.925-0. 955 g / cm3. , Particularly preferably 0.930-0.955g / cm3, and the melt flow rate (MFR) (ASTM D1238, 190 ° C, load: 2.16Kg) is 1-10 g / 10 minutes, preferably 1.5-5 g / 10 minutes' is more preferably 2.0-8 g / 10 minutes. When this resin combination is noted, item ·

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13 'The paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 5. Description of the invention () The excess and degree of the material are in the above range, and a rotomolded product with excellent rigidity can be produced. When the dazzling body flow rate of the composition is at the upper strength, the resin composition exhibits excellent roll plasticity = a polyethlenol roll system 2 which is seen from the outside. This garment has a good resin composition, and it may be 66, 俾 As described above, the polyethylene-containing 1-inspection material for rotomolding according to the present invention is mixed with ethylene or ethylene. = Copolymer (B). α To this polyethylene resin composition, additives such as organic fillers, antioxidants' heat stabilizers, ultraviolet light absorbers, flame retardants, throwing agents, lubricants, foaming agents, colorants, The amount of mold agent and weather stabilizer should not affect the purpose of the present invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the polyethylene resin composition for rotomolding according to the present invention may be powder or granular, and when rotomolding is to be performed, the composition only requires powder. When the polyethylene resin composition for rotomolding according to the present invention is in the form of granules, the granules are pulverized into a powder before being subjected to rotomoulding. It is desirable that the particle size of the polyethylene resin composition powder for rotomolding according to the present invention is not more than 30 mesh, and preferably 40 to 100 mesh. When the particle size of the powder used is

V. Description of the invention (in the above-mentioned Fanyuan, it has excellent rotational plasticity, and can obtain a rotomolded α mouth σ with a good appearance. Obtained: the ethylene 1 card tobacco copolymer; ^ cloth resin composition can be prepared as follows: a dilute hydrocarbon copolymer (B) and the above additives, ethylene homopolymers, or additives such as extruders and Banbury mixers, are melt-kneaded with a common kneading device ^ or a Hanschel mixer, and 4 secrets are crushed. I The money pulverization method made the kneaded powder into powder. The polyethylene composition for rotomolding continuously selected into A can be copolymerized with ethylene atom Γ olefin in the presence of a goldlocene olefin polymerization catalyst to prepare ethylene 1, 2K, and Preparation of Ziegler-type polymerization catalysts 2 _-step homopolymerization or silk _n 3_2G preparations Ethyl redene 1 card domain Resin composition is made into powder. In operation = You can use 彳 "clothes to mix the tree test compound with the added ship. 乂 Yita ethylene 1-ene smoke copolymer ⑴ and ethylene homopolymer or ethyl return-ene: ^ co * * (B ) It is made of catalyst for homopolymerization of hydrocarbons from grelerene. The tumbling polyethylene resin composition according to the present invention can be pulverized through continuous copolymerization steps and a touch or silk step. Type olefin polymerization reaction catalyst age will be a heteroatom A7 B7 V. Inventor 57 polymerization or this order t copolymerization to produce ethylene-α-olefin copolymer (A), homopolymerization catalyst exists Next, kappa (β) or ethylene and a hydrocarbon of 3 carbon atoms (B); knead the fat composition to make a powder. Before pulverization, it can be set to melt-knead the Shuzhi composition and additives. OK The polyethylene resin composition for rotomolding can be obtained by continuous advancement: a total of homopolymerization or copolymerization steps, _ pulverization to make 3-20 objects, polymerization, dehybridization age, and then the ethylene and muons are found, To prepare ethylene 1-do prostitutes ^ Homopolymerization or copolymerization is based on the existence of a catalyst for the polymerization of dimetallocene-type hydrocarbons. Homopolymerization to prepare ethylene homopolymers or copolymerization of ethylene with 3-20 carbons to prepare ethylene-α-olefin copolymers; post-crushing or mechanical crushing The obtained dendritic compound is made into powder. In humans, the kneading device can melt the resin composition and additives to knead the rotomolded product. ^ According to the rotomolded product of the present invention, the above-mentioned polyethylene for rotomolding is prepared by The tree is said to be made by rotomolding. The rotomolded polyethylene resin composition is powder as described above. &Quot; 16 210X297 mm) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Making L, description of the invention (Rotomolding Roots of the present invention, A man, a rocking mold + a rotary tool, or an inner surface and melting. Then, later The cymbals are distributed in the mold of the hibiscus. The two handles and the crotch, and the handles formed on the inner surface of the mold are taken out. In this way, the rotomolded product of the present invention is obtained. The surface may be embossed or unnecessary. The ene resin composition contains two special private-copolymers, or a special ethylene-α-olefin copolymer, and a 5-ene homopolymer. A blend of these two (co) polymers is provided. Density and specific rate of wealth. Therefore, this polyethylene resin group 5 has excellent roll plasticity and can produce better impact resistance and environmental stress opening clothing (ESOR) than ordinary Rotomolded articles of polyethylene molded products. ^ The rotomolded articles according to the present invention are made of the polyethylene resin composition of the present invention. Therefore, the rotomolded articles of the present invention have impact resistance and "environmental stress cracking resistance (ESCR)". In terms of advantages, it is superior to the usual polyethylene products. Therefore, the polyethylene resin composition for rotomolding according to the present invention is suitable for manufacturing hollow products and products with complicated shapes. More specifically, the polyethylene of the present invention

Please read 'Notes'

Page Binding V. Description of the invention (, resin composition _ Yu size A or small spheres, gardening supplies, cabinets, mechanical parts, and pirates, products, products, materials. "Hollow mold with hollow parts Considering the following implementations, the present invention is further described, but it should be recognized that the present invention is by no means limited to these examples. The ethylene-α-thin smoke copolymers used in the Examples and Comparative Examples and Ethylene homopolymer was prepared as follows. Di- and ethylene in α-olefin copolymers-"η (1) Ethylene-1-hexene copolymer (M-PE (1)) Catalyst: Polymerization of di-metallocene-type olefins containing errors Reaction catalyst density (ASTM D1505): 0.905g / cm3 MFR (ASTM D1238, 190 ° C, load: 2.16Kg) printed by the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs: 1 g / 10 minutes (2) Ethylene-1- Hexene copolymer (M-PE (2)) catalyst: thorium-containing metallocene catalyst for olefin polymerization (ASTM D1505) ···· 905g / cm3 MFR (ASTM D1238, 19 (TC, load: 2) · 16Kg): 4 grams 18 This paper size applies to Chinese National Standard (CNS) A4 (21〇297297) 0 (5 3 9 5 Printed by A7 B7 of the Consumer Cooperatives of the Ministry of Intellectual Property Bureau of the People's Republic of China 5. Description of the invention () / 10 minutes (3) Ethylene-1-butene copolymer (Z-PE (1)) Catalyst: Ziegler-type olefin polymerization catalyst Density (ASTM D1505): 0.957g / cm3 MFR (ASTM D1238, 190 ° C, load: 2.16Kg): 8.3g / 10min (4) Ethylene-propylene copolymer (Z-PE (2)) Catalyst: Ziegler-type olefin polymerization catalyst density (ASTM D1505): 0.966g / cm3 MFR (ASTMD1238, 190 ° C, load: 2.16Kg): 12 · 5 g / 10 minutes (5) ethylene-propylene copolymer (Z -PE (3)) Catalyst: Ziegler-type olefin polymerization catalyst Density (ASTM D1505): 0.970g / cm3 MFR (ASTM D1238, 190 ° C, load: 2.16Kg): 16 g / 10 minutes (6) Ethylene-propylene copolymer (Z-PE (4)) catalyst: Ziegler-type olefin polymerization catalyst density (ASTM D1505): 0.965g / cm3 MFR (ASTM D1238, 190 ° C, load ·· 2 · 16Kg) ·· 11 g / 10 min (7) Ethylene homopolymer (Z-PE (5)) Catalyst: Ziegler-type olefin polymerization catalyst This paper is applicable to Chinese National Standard (CNS) A4 210 X 297 mm) (Please read the back of the precautions to fill out this page)

593500 A7 __ B7 V. Description of the invention () Density (ASTM D1505): 0.968g / cm3 MFR (ASTM D1238, 190 ° C, load: 2.16Kg): 5. 2 g / 10 minutes (8) Ethylene-4- 曱1-pentene copolymer (z-PE (6)) catalyst: Ziegler-type olefin polymerization catalyst density (ASTM D1505): 0 · 944g / cm3 MFR (ASTM D1238, 190 ° C, load ·· 2.16 Kg) 7.1 g / 10 minutes Example 1 A single screw extruder with a diameter of 40 mra was used at 20 (rc) to 30 parts by weight of ethylene-1-hexene copolymer (M-PE) and 7 〇Parts by weight of ethylene + butene copolymer (Z-PE⑴) are melt-kneaded to prepare a polyethylene resin composition. Then, the fibrous compound is subjected to cold-wire crushing and preparation _ not larger than the purpose, in a cylindrical container And set the rotational molding time conditions at the mold temperature 2 as follows: heating time: minutes' and cooling time: 5 minutes. (2 cylindrical containers). A 3 mm molded product (round). Samples were taken from the molded product and tested in accordance with the following methods: the Nelson's rigidity test, the cantilever cylindrical tensile test, the Austrian scale tester, and the environmental stress crack resistance test.

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Page of Ministry of Economic Affairs and Intellectual Property Bureau of China

W500 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China, the invention description is printed. The results are shown in Table 1. Formula test method (1) Tensile test according to ASTM D-638 at a tensile speed of 50 millimeters / The stress, tensile strength at break, and elongation at break when mosquitoes are generated in minutes (2) Olson stiffness test The Olson stiffness test is performed according to ASTM D-747. (3) Izod impact test according to JIS K-7110 Izod impact test at notch condition at -20 ° C (4) Environmental stress cracking test Environmental stress cracking according to ASTM D-1698 at 5 (TC using Antarox (CO-630) solution Test. A sample with a thickness of gmm was used. The values in Table 1 indicate 50% break time (hours). Example 2 A polyethylene resin composition was produced in the same manner as in Example 1, except that ethylene-1 -The amount of hexene copolymer (M-PE (1)) is 40 parts by weight, and 60 parts by weight of ethylene-propylene copolymer (Z-PE (2)) is used instead of 70 parts by weight of ethylene-1-butene copolymer (Z-PE (1)). 21 This paper is suitable for financial standards (CNS) M specifications (21 () &gt; &lt; 297) ) C7

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V. Creation instructions (θ The polyethylene resin composition was manufactured by the same method as in Example 1. The amount of the different ethylene: buhexylene copolymer (M-PE (2)) was 30 parts by weight, and 7 was used. 〇Parts by weight of vinylene filaments (Z-PEE) instead of 7 (] parts by weight of ethylene-1-butene copolymer (Z-PE (1)). Please read the back first and then the “Use and Reality_Phase_” method, Use this polyethylene resin composition to granulate powder that is not larger than 3G mesh ', and perform rotomolding on this powder to obtain a molded product.. Note the next page ... Take the sample from the molded product and perform the tensile test in the above method. Olson rigidity test, cantilever impact test, and environmental stress cracking test. The results are shown in Table 1. Example 5 θ A polyethylene resin composition was manufactured in the same manner as in Example 1, except that 'ethene The amount of the dioxin copolymer (M-PEE) was 25 parts by weight, and 75 parts by weight of the ethylene homopolymer (ζ_ρΕ⑸) was used instead of 70 parts by weight of the butene copolymer (Z-ρε (1)). In the same manner as in Example 1, using this polyethylene resin composition Prepared particle size; f greater than 30 mesh powder 'and minus county surplus _ plastic products. 俣 23 This paper size is applicable to Zhongguan ★ 榡 rate (CNS) (2 offer 297 directors). Printed-^ 93500, description of the invention (samples are taken from plastic products with k handle, the above == inspection, Peng Kehong inspection and Wei stress ΜΜΙ In a polymerization reactor, in the presence of the wrong dichemical agent, the Ethylene reacts with dihexyl _5) is a 4th exposure STM_ negative, ^ = top 1 g / 1G min ethylene + hexahexylene copolymer (㈣ (^) load. 2 Ma) (M-PE (3) In another polymerization reactor having a reaction of string%, in this reactor, in the presence of a metallocene-containing olefin polymerization catalyst, ethylene is copolymerized to prepare a density (ASTM D1505) is 0.957 g / cm3, _ (A ^ D1238 '190 ° C, load: 2.16Kg) is 8.8 g / 10 minutes, and the ethylene-copolymer printed by the consumer property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a hexene copolymer. (M-PE⑷) 'from which the density (ASTM D1505) was 0.940 g / cm3, and the MFR (ASTMD 1238, 19 (TC, load: 2.16 Kg)) was &amp; 9 g / 10 min polyethylene resin composition. In this resin composition, an ethylene-hexene copolymer (M-PE (3)) and an ethylene-1-hexene copolymer (M_pE (4)) The weight ratio is 30/70. Then 'in the same manner as in Example 1, use this polyethylene resin composition _____24 &quot; ^ Paper size is applicable to China National Standard (CMS) A4 specification (210 × 297 cm) — 593500 C7

V. Creation instructions (preparation of granules with a particle size of not more than 30 meshes and 48 mils, to obtain molded products. Uncle, Ya, this powder was subjected to rotomolding to obtain the rigidity test from the molded products. , Cantilever beam punching II: The tensile test is ordered in the above method, and is shown in Table 丨 and the environmental stress cracking test. The results are listed in Comparative Example 1. The particle size is not significantly different from the method used in Example 1_. Ethylene methyl + pentylene copolymerization was used in the polyethylene resin% 1. Face ☆ Yatsushiro yoke, this product was rotomolded to obtain a molded product 0, from the molded product Take out the sample and perform the tensile test, Olson rigid test, material test and Wei stress county test in the above method. The results are shown in Table 1. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 (210X297mm) 593500 A7

7 B Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Comparative implementation 1 I 1 I 1 1 0.944 r—Η · Example oo 6.0.904 Γ '&lt; 0.957 〇〇〇6 30/70 0. 940 CO Example 5 1 0.905 τ—Η 1 ij 0.968 CNI LO 25/75 0. 951 inch CO οα CXI Example 4 0.950 inch 0.965 τ—Η 30/70 0.945 oo CD Example 3 0.905 1 Ή 1 1 0.970 CO 45/55 0.940 οα CO CD 1 Example 2 〇〇 \ 〇τ—-Η 0.966 12.5 40/60 0.940 ο α CO CJD 1 Example 1 1 0.905 τ—Η 0.957 CO 〇6 30 / 70 0.940 CO CO BU1 · i Ethylene-α-olefin copolymer (A) Density (g / cm3) MFR (g / 10 min) Ethylene homopolymer or ethylene / α-olefin copolymer (B) Density ( g / cm3) MFR (g / 10 min) Weight ratio of resin components (A) to (B) Resin component or resin property density (g / cm3) MFR (g / 10 min) Rotomolded product properties Tensile failure stress (MPa) # (Please read the precautions on the back before filling in this page) 26 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Order 593500 A7 B7 V. Invention () 9209 BU

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SM (s) (m / f) (Jq) SS3. Miscellaneous K-l «s ^^^^ d, p, l &lt; co. Kill the black dove to win customers.荽 Entertainment is completed 邋) Ling Bang ^ (5 令 戚 ^^ 学 # 荽 ^ 奥 鹊 | # 銮 9-1: # 婚 驷 .1 (Zanxiong) (Please read the notes on the back before filling out this page)

、 1T This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)

Claims (1)

593500 Bismuth · C8 --- _ D8 VI. Application for Patent A type of polyethylene resin composition for rotomolding, which is characterized in that it contains: (A) α-containing ethylene and 3-20 carbon atoms — Ethylene-j-dilute hydrocarbon copolymer of olefins, its density (ASTM D1505) is 0.888-0.993 g / cm3, melt flow rate (MFR) (ASTM D1238, 19 (TC, load: 2. 16Kg) is 0.01-5 g / 10 minutes, and (B) an ethylene homopolymer containing ethylene or an ethylene-α-olefin copolymer containing ethylene and an α-olefin with 3_2 carbon atoms, and its density ( (ASTM D1505) is 0.931-0.974g / cm3, and the melt flow rate (MFR) (ASTMD1238, 190 C, load: 2.16Kg) is 0.5-20 g / 10 minutes, in which ethylene-α- The weight ratio [(A) / (B)] of the olefin copolymer (A) to the ethylene homopolymer or the ethylene-α-olefin copolymer (B) is 10 / 90-50 / 50, and the ethylene-α- The density (ASTM D1505) of the blend consisting of the olefin copolymer (A) and ethylene homopolymer or ethylene-α-olefin copolymer (B) is 920 · 920-0 · 960g / cm3, and the melt flow rate (MFR) (ASTM D1238, 1 90 ° C, load: 2.16Kg) is 1-10 g / 10 minutes. 2. The polyethylene resin composition for rotomoulding according to item 1 of the patent application scope, wherein the ethylene-α-olefin copolymer (A), ethylene homopolymer (B) and ethylene-α-olefin copolymer (β) are all prepared by using a metallocene-type olefin polymerization catalyst. 3. As described in item 1 of the scope of patent application Polyethylene resin combination for rotomolding ___ —_28 _____ _ This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order-Ministry of Economic Affairs Printed by the Consumer Cooperative of the Property Bureau. 6. Scope of patent application = should be 1: 1 :: ene smoke copolymer ⑴ is a diene metallocene-type dilute hydrocarbon polymerized ugly H, polymer ', and ethylene homopolymer ⑻ and Echan 1- Dilute smoke and carbon (B) are difficult to prepare with Ziegler-type polymerization polymerization. ^ • Rolled polyethylene resin composition as described in item 1 of the scope of patent application * * ethylene ~ α-dilute hydrocarbon Copolymers ⑷, ethylene homopolymers ⑻, and ethylene α ~ ene co-heterocycles are prepared using Ziegler ㈣ hydrocarbon polymerization catalysts 5. The polyethylene resin composition for rotomoulding according to item 1 of the scope of the patent application, wherein the ethylene-α-olefin copolymer (A) is prepared using a Ziegler-type olefin polymerization catalyst, and ethylene The homopolymer (B) and the ethylene-olefin copolymer (B) are prepared using a metallocene-type olefin polymerization catalyst. 6. The polyethylene resin composition according to any one of claims 1 to 5, wherein the powder particle diameter of the polyethylene resin composition is not greater than 30 mesh. 7 · A rotomolded product comprising the polyethylene resin composition for rotomolding according to any one of claims 1 to 5 of the scope of patent application. 8 · — A rotomolded product comprising the polyethylene resin composition for rotomolding according to item 6 of the scope of patent application. 29 This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) &gt; 1-I! 1 — · (Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperatives system