CN1118360A - Modified polyolefin composition and laminated structure using the same - Google Patents

Modified polyolefin composition and laminated structure using the same Download PDF

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Publication number
CN1118360A
CN1118360A CN95105629A CN95105629A CN1118360A CN 1118360 A CN1118360 A CN 1118360A CN 95105629 A CN95105629 A CN 95105629A CN 95105629 A CN95105629 A CN 95105629A CN 1118360 A CN1118360 A CN 1118360A
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composition
ethylene
weight
mfr
flow rate
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CN1113080C (en
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河内秀史
村重国昭
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Mitsui Petrochemical Industries Ltd
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Mitsui Petrochemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Abstract

The invention relates to a modified polyolefine composite and a laminar structure which uses the composite. The laminar structure comprises a composite layer which consists of the polyolefine composite and a resin layer which is positioned at least at one surface of the composite layer. An outer layer of the tubular laminar structure consists of the modified polyolefine composite and can be made into a product without watermark by a method of co-extrusion and cooling.

Description

The laminar structure of modified polyolefin compositions and use said composition
The laminar structure that the present invention relates to modified polyolefin compositions and use said composition.More specifically say, the present invention relates to when adopting coextrusion and cooling to form the tubular layer laminated structure, to prevent the concavo-convex modified polyolefin compositions of periphery direction generation rib-loop shape at pipe, and by using said composition to avoid taking place the laminar structure of watermark (water marks).
Become or the ethylene/vinyl alcohol copolymer layer is the middle layer with aramid layer, and be known as outer field laminar structure with the new LDPE (film grade) of high pressure processing and amorphism or low-crystalline ethylene/alpha-olefin copolymer.But the shortcoming of this laminating material is an appearance poor, and this is because in being coextruded into above-mentioned composition and resin into the water-cooled work program behind the laminating material of tubular form, and it is outer can to produce watermark.Another shortcoming is that the molten state composition is poor at the sliding of axle, to such an extent as to will damage circulation ratio.
An object of the present invention is to provide modified polyolefin compositions.
Another object of the present invention provides and is suitable for use as the laminating material skin, especially with polymeric amide or the ethylene/vinyl alcohol copolymer layer outer field modified polyolefin compositions as the laminating material in middle layer.
Another object of the present invention provides has the splendid adhesive capacity to polymeric amide or ethylene/vinyl alcohol copolymer, and does not have the modified polyolefin compositions of watermark as laminating material outer the time.
Another object of the present invention provides such modified polyolefin compositions, and the molten state when producing laminating material of this combination has splendid sliding in axle, that is: described modified polyolefin compositions has splendid circulation ratio when producing laminating material.
Another object of the present invention provides the laminar structure of the polyolefin compositions that uses above-mentioned modification.
Other purpose of the present invention and advantage will be become clearer by following explanation.
Purpose above the present invention and advantage will be finished by the modification polyene composition that comprises following ingredients: (A) new LDPE (film grade) of high pressure processing, its melt flow rate (MFR): 0.1-10g/ minute, density: 0.915-0.935g/cm 3, (B) Alathon and/or ethylene/alpha-olefin copolymer, basic melt flow rate (MFR): 0.1-30g/10 minute, density: 0.910-0.965/cm 3, be line style basically, and by using transition-metal catalyst preparation and (C) amorphous or low-crystalline ethylene/alpha-olefin copolymer, melt flow rate (MFR): 0.1-10g/10 minute, density was less than 0.900g/cm 3Wherein each composition (A), (B) and amount (C) are respectively 50-70% (weight), 20-45% (weight) and 5-30% (weight) based on these compositions (A), (B) and gross weight meter (C), and these compositions (A), (B) and a part (C) have been used the modification of unsaturated carboxylic acid or derivatives thereof at least.
Modified polyolefin compositions of the present invention comprises above-mentioned composition (A), (B) and (C), and these parts that become to send out are carried out graft modification with the unsaturated carboxylic acid or derivatives thereof at least.
Composition (A) is the new LDPE (film grade) of high pressure processing, and its melt flow rate (MFR) (measuring down at 190 ℃ under 2.16kg load according to ASTM D1238) is 0.1-10g/10 minute, density 0.915-0.935g/cm 3Its preferred melt flow rate (MFR) is 0.2-5g/10 minute, and preferred density is 0.910-0.935g/cm 3
Composition (B) is an ethene polymers, it comprises Alathon and ethylene/alpha-olefin copolymer, its melt flow rate (MFR) is (according to ASTM D1238, under 2.16kg load 190 ℃ temperature measuring) be 0.1-30g/10 minute, width is 0.910-0.965g/cm, and it is to use for example ziegler produced of transition-metal catalyst.As the preferred ethylene/alpha-olefin copolymer of composition (B) be ethene with the alpha-olefin with 3-20 carbon atom be the random copolymers of line style basically.Preferred alpha-olefin is the alpha-olefin with 4-10 carbon atom.The example of alpha-olefin preferably includes propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.Particularly preferred alpha-olefin is 1-butylene and 4-methyl-1-pentene.Preferred embodiment with the ethylene/alpha-olefin copolymer of transition-metal catalyst production comprises ethylene/propylene olefinic random copolymer, ethene/1-butylene random copolymers and ethene/4-methyl-1-pentene random copolymers.
The repeating unit of the derived from ethylene that the ethene polymers of composition (B) comprises, preferred 100-80% (weight), more preferably 100-90% (weight).
Composition (B) can be the combination of equal thing of ethene and ethylene/alpha-olefin copolymer.For example: composition (B) can be the combination of multipolymer of the ethylene/alpha-olefin of the Alathon of 0.5-40 weight part and 60-99.5 weight part, and above weight part is all based on the total of two kinds of polymkeric substance.
The preferred 0.2-5g/10 of polyvinyl melt flow rate (MFR) of composition (B) minute.Its density is preferably 0.920-0.950g/cm 3, more preferably 0.930-0.950g/cm 3
Composition (C) is amorphous or the ethylene/alpha-olefin alkyl polymers of low-crystalline, and its melt flow rate (MFR) (according to ASTM D1238, at load 2.16kg, temperature is measured down for 190 ℃) is 0.1-10g/10 minute, and density is less than 0.900g/cm 3
Ethylene/alpha-olefin copolymer (C) is ethene and the random copolymers with alpha-olefin of 3-20 carbon atom preferably.Can should be mentioned that for alpha-olefin and to regard to those that composition (B) ethylene/alpha-olefin copolymer mentions, the wherein alpha-olefin of preferred 3-4 carbon atom.The preferred embodiment of ethylene/alpha-olefin copolymer (C) comprises the ethylene/propylene olefinic random copolymer, ethene/1-butylene random copolymers.
Ethylene/alpha-olefin copolymer (C) comprises preferred 50-90% (mole), more preferably the repeating unit of the derived from ethylene of 60-80% (weight).
The melt flow rate (MFR) of ethylene/alpha-olefin copolymer (C) is preferably 0.1-10g/10 minute, the preferred 0.85-0.89g/cm of its density 3
Ethylene/alpha-olefin copolymer (C) with such physical properties is recorded by the X ray method and is generally the amorphism multipolymer or degree of crystallinity is less than 4% low-crystalline multipolymer.
Modified polyolefin compositions of the present invention comprises the composition (A) of 50-70% (weight), the composition (B) of 20-45% (weight) and the composition (C) of 5-30% (weight), preferred compositions comprises the composition (A) of 52-60 (weight), the composition (B) of 25-40% (weight) and the composition (C) of 10-20% (weight), and above percentage number average is based on composition (A), (B) and total weight (C).
In composition of the present invention, composition (A), (B) and a part (C) are with the graft modification of unsaturated carboxylic acid or derivatives thereof at least.Part or all of composition (A), (B) and a certain composition (C) can be graft modification, or part or all of several mixture of ingredients can be graft modification.In other words, can carry out graft modification for a composition or mixture of ingredients.Preferably graft modification of composition (B).
The example of unsaturated carboxylic acid and derivative thereof comprises: for example vinylformic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, Ba Dousuan, iso-crotonic acid and Nadic acid of unsaturated carboxylic acid (suitable-two rings [2 of bridge, 2,11] heptan-5-alkene-2, the 3-dicarboxylic acid) and derivative for example carboxylic acid halides, acid amides, imide, acid anhydrides and ester.
The specific examples of such derivative comprises: maleic anhydride (malenyl anhydride), monomethyl maleate, dimethyl maleate and toxilic acid glycidyl ester.
Wherein, preferred unsaturated dicarboxylic acid or its acid anhydrides more preferably use toxilic acid, Nadic acid and basic acid anhydrides.They can use separately or two or more are used in combination.The preferred 0.01-5% of graft ratio (weight), more preferably 0.01-3% (weight).
For carrying out graft reaction, can use multiple known ordinary method.For example: the method that can mention has: by carrying out the method for graft reaction and form solution and carry out the method for graft reaction to wherein adding grafted monomer by polymkeric substance being dissolved in the solvent with polymer melt and to wherein adding grafted monomer (unsaturated carboxylic acid or derivatives thereof).Under above-mentioned any situation, all preferably in the presence of radical initiator, carry out graft reaction, to carry out graft reaction effectively.
Graft reaction carries out under the temperature between 60-350 ℃ usually.The common consumption of radical initiator is 0.01-1 weight part (based on 100 parts by weight polymer meters).
Comprise benzoyl peroxide as the spendable organo-peroxide of radical initiator and organic polyester, dichlorobenzoyl peroxide, dicumyl peroxide, tert-butyl peroxide, 2,5-dimethyl-2,5-two (peroxide benzoate base) hexin-3,1,4-two (t-butylperoxy sec.-propyl) hexin-3,2,5-dimethyl-2,5-(tert-butyl peroxide) benzene, the peroxidation lauryl, t-butyl peroxy-acetate, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, t-butylperoxyl benzoate, cross the toluylic acid tert-butyl ester, t-butylperoxy isobutylate, cross the Zhong Xin tert-butyl acrylate, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, cross the withered ester of PIVALIC ACID CRUDE (25) and cross the diethylacetic acid tert-butyl ester, and other azo-compound comprises: Diisopropyl azodicarboxylate and azo-bis-iso-dimethyl.
Wherein preferably include dialkyl for example dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3,2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane and 1,4-two (t-butylperoxy sec.-propyl) benzene.
For obtaining modified polyolefin compositions of the present invention, can carry out graft reaction for composition (A), (B) and mixture (C).Perhaps, part or all carries out graft modification with one or both one-tenth (A), (B) with (C), and the composition of the modification that obtains is then kneaded with unmodified composition fusion, obtains composition of the present invention.For obtaining described composition, preferable methods comprises: (B) carries out graft modification to composition, then with the modified product that obtains with composition (A) and composition (C) melting mixing.
For industrial production, preferably or (C) and the method kneaded with the forcing machine fusion of unmodified composition with altered contents (A), (B).
Here, graft ratio be defined as grafted unsaturated carboxylic acid or derivatives thereof based on grafting before the weight percent (%) of composition (A), (B) and gross weight meter (C).
The melt flow rate (MFR) of the modified polyolefin compositions of the present invention that obtains like this is 0.1-5g/ minute.
Modified polyolefin compositions of the present invention can be compatibly as the skin of laminar structure, especially with polymeric amide or ethylene/vinyl alcohol copolymer skin as the laminar structure in middle layer.
Thereby, the invention provides the laminar structure that comprises following ingredients: the resin layer that has composition layer according to modified polyolefin compositions of the present invention (after, will comprise to be called for short and make " composition layer ") and at least one side according to the composition of modified polyolefin compositions of the present invention.
Resin as the resin layer that constitutes laminar structure can use various thermoplastic resins for example polyolefine, polyester, polymeric amide and ethylene/vinyl alcohol copolymer.Wherein, more preferably use polymeric amide and ethylene/vinyl alcohol copolymer.
As polymeric amide, for example can use nylon 6, nylon 66 and MMD nylon (two a methylene phenyl diamine copolymer polymeric amide).
The ethylene/vinyl alcohol copolymer preferably contains 20-50% (mole), the units derived from ethylene of preferred 25-48% (mole).
They can make the saponification of corresponding ethylene/acetic acid ethylene acid copolymer by conventional methods.
In laminar structure of the present invention, the above-mentioned resin layer that is present at least one side of composition layer preferably comprises the resin that is selected from polymeric amide and ethylene/vinyl alcohol copolymer.
In addition, the layer of order below laminar structure of the present invention preferably has: composition layer, above-mentioned resin layer, composition layer.
Can not cause the product of watermark can be at the cooling stages of productive zone laminated structure by obtaining with the outermost layer of composition layer as laminar structure.
Can pass through according to laminar structure of the present invention, and it is made with the molten state lamination modified polyolefin compositions and resin fusion.
Laminar structure can be shaped to desired form by methods such as extrusion molding, casting, blowings.Laminar structure of the present invention can advantageously be shaped to tubulose by coextrusion.This piped laminar structure that is shaped to is processed, for example become the tube container of food packaging film, makeup etc.
The present invention illustrates in greater detail with reference to embodiment, but the present invention is not limit by these embodiment.Embodiment 1
To have the layer of following composition under following condition, to be coextruded into be 3 layers of pipe.Skin and internal layer
Composition (A), (B) and (C) be:
New LDPE (film grade) (HPLDE-1) melt flow rate (MFR) of the high pressure processing of 52% (weight) is 4, and density is 0.918g/cm 3, composition (A),
52% (weight) ethylene/propene copolymer (LLDPE-1) makes with transition-metal catalyst, and melt flow rate (MFR) is 1, and density is 0.953g/cm 3, composition (B-1),
The polyethylene (MAH-PE) of 8% (weight) graft modification; Can will obtain with 2% (weight) maleic anhydride graft by the linear ethylene homopolymer that uses transition-metal catalyst to make, melt flow rate (MFR) 4, density are 0.965g/cm 3, composition (B-2) and
15% (weight) ethene/butene-1 copolymer (EBR-1), melt flow rate (MFR) 3.5, density 0.885g/cm 3, degree of crystallinity is less than 5%, composition (C),
With composition (A), (B) and (C) knead 200 ℃ of fusions and obtain modified polyolefin compositions with the single shaft forcing machine.The melt flow rate (MFR) of composition is 1.7, and its density is 0.921g/cm 3With the polyolefinic composition of the modification that obtains like this with having the 40mm diameter, the forcing machine coextrusion of the screw rod of 100mm useful length.The middle layer
Hand over Kuraray Co., the Eval EP-F (trade(brand)name, melt flow rate (MFR) 1.3) that Ltd. produces is as ethylene/vinyl alcohol copolymer (being called EVOH later on), with its at 225 ℃ with having the 30mm diameter, the forcing machine coextrusion of useful length 750mm.
The temperature of mouthful mould is 220 ℃, with 5m/ minute speed with resin extruded, water-cooled in the tank of the 50cm of membrana oralis back, and be shaped to tubing.Can be decided to be skin/middle layer/internal layer=150/50/250 μ m as for every layer thickness.The skin of tubing and the situation that exists of the adhesion strength between the middle layer, kinetic friction coefficient and watermark are shown in table 1.
Peel off method by 180 ℃ and measure adhesion strength.
Kinetic friction coefficient is by will managing incision, and impose 200g load thereon, and stretching with 50mm/ minute speed on stainless steel plate records.
The assessment that there is situation in watermark by water-cooled after the outward appearance of observation tube assess the situation that rib-loop shape concavo-convex (watermark) takes place in the outer peripheral edges direction of pipe.In table 1, O represents no watermark, and watermark takes place in the X representative.Embodiment 2-4
Repeat the program identical with embodiment 1, the composition that just constitutes the modified polyolefin compositions of skin and internal layer becomes the composition shown in the table 1, and obtains the result shown in the table 1.Comparative example 1-2
Undertaken by the method identical with embodiment 1, the composition that just constitutes the modified polyolefin compositions of outer and internal layer becomes composition shown in the table 1, obtains the result shown in the table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1 Comparative example 2
Interior layer composition and outer layer composition (weight part) melt flow rate (MFR) (g/10min) density (g/cm 3) HPLDPE-2??52 LLDPE-1???25 MAH-PE????8 EBR-1?????15 1.7 0.921 HPLDPE-2??52 LLDPE-2???25 MAH-PE????8 EPR-1?????15 1.9 0.923 HPLDPE-3?52 LLDPE-2??25 MAH-PE???5 EBR-1????15 1.1 0.919 ?HPLDPE-4???52 ?LLDPE-2????25 ?MAH-PE?????8 ?EPR-1??????15 ?2.3 ?0.923 ?HPLDPE-2?77 ?MAH-PE???8 ?EPR-1????15 ?2.6 ?0.923 ?HPLDPE-3??80 ?MAH-PE????5 ?EBR-1?????15 ?1.3 ?0.918
The middle layer EVOH EVOH EVOH ?EVOH ?EVOH ?EVOH
Kinetic friction system number 0.52 0.65 0.60 ?0.65 ?0.80 ?1.00
Adhesion strength between skin and the internal layer (g/15mm) 990 1000 400 ?860 ?660 ?450
Watermark O O 0 ?O ?X ?X
The following meaning of abbreviation representative in the table 1:
HPLDPE-1: the new LDPE (film grade) of high pressure processing (melt flow rate (MFR): 4, density: 0.918g/cm 3)
HPLDPE-2: the new LDPE (film grade) of high pressure processing (melt flow rate (MFR): 2,5, density: 0.932g/cm 3)
HPLDPE-3: the new LDPE (film grade) of high pressure processing (melt flow rate (MFR): 3, density: 0.927g/cm 3)
HPLDPE-4: the new LDPE (film grade) of high pressure processing (melt flow rate (MFR): 1, density: 0.918g/cm 3)
LLDPE-1: be basically line style ethylene/butylene-1 multipolymer (melt flow rate (MFR): 1, density: 0.953g/cm 3)
LLDPE-2: be basically line style ethylene/butylene-1 multipolymer (melt flow rate (MFR): 1, density: 0.935g/cm 3)
MAH-PE: be grafted with the Alathon of the modification of 2% (weight) maleic anhydride, be basically line style (melt flow rate (MFR): 4, density: 0.965g/cm 3)
BER-1: ethylene/butylene-1 multipolymer (melt flow rate (MFR): 3.5, density: 0.885g/cm 3)
EPR-2: ethylene/propene copolymer (melt flow rate (MFR) 3, density: 0.870g/cm 3) embodiment 5
Use Toray Co., Aimiran (trade(brand)name) CM1021XF that Ltd produces is that 30mm, useful length be the forcing machine of the screw rod of 750mm at 250 ℃ with having diameter as polymeric amide, by with embodiment 1 in identical method extrude.
The temperature of mouthful mould is 250 ℃, with 5m/ minute speed with resin extruded, water-cooled in the tank of the 50cm of membrana oralis back, and be shaped to tubing.Can be decided to be skin/middle layer/internal layer=150/50/250 μ m as for every layer thickness.The skin of tubing and the situation that exists of the adhesion strength between the middle layer, kinetic friction coefficient and watermark are shown in table 2.Embodiment 6 and comparative example 3-4
Repeat the program identical with embodiment 5, it is the composition shown in the table 2 that the composition that just constitutes the modified polyolefin compositions of outer and internal layer is handed over, and evaluates obtaining the result shown in the table 2.
Table 2
Embodiment 5 Embodiment 6 Comparative example 3 Comparative example 4
Interior layer composition and outer layer composition (weight part) melt flow rate (MFR) (g/10m+n) density (g/cm 3) HPLDPE-1??52 LLDPE-1???25 MAH-PE????8 EBR-1?????15 1.7 0.921 HPLDPE-2???52 LLDPE-2????25 MAH-PE?????8 EPR-1??????15 1.9 0.923 HPLDPE-2???77 MAH-PE?????8 EPR-1??????15 2.6 0.922 HPLDPE-3??80 MAH-PE????5 EBR-1?????15 1.3 0.918
The middle layer Polymeric amide Polymeric amide Polymeric amide Polymeric amide
Kinetic friction system number 0.58 0.62 0.85 1.05
Adhesion strength between skin and the internal layer (g/15mm) Can not peel off Can not peel off Can not peel off Can not peel off
Watermark O O X X
The following meaning of abbreviation representative in the table 2:
HPLDPE-1: the new LDPE (film grade) of high pressure processing (melt flow rate (MFR): 4, density: 0.918g/cm 3)
HPLDPE-2: the new LDPE (film grade) of high pressure processing (melt flow rate (MFR): 2.5, density: 0.932g/cm 3)
HPLDPE-3: the new LDPE (film grade) of high pressure processing (melt flow rate (MFR): 3, density: 0.927g/cm 3)
LLDPE-1: be basically line style ethylene/butylene-1 multipolymer (melt flow rate (MFR): 1, density: 0.953g/cm 3)
LLDPE-2: be basically line style ethylene/butylene-1 multipolymer (melt flow rate (MFR): 1, density: 0.935g/cm 3)
MAH-PE: be grafted with the Alathon of the modification of 2% (weight) maleic anhydride, be basically line style (melt flow rate (MFR): 4, density: 0.965g/cm 3)
BER-1: ethylene/butylene-1 multipolymer (melt flow rate (MFR): 3.5, density: 0.885g/cm 3)
EPR-2: ethylene/propene copolymer (melt flow rate (MFR): 3, density: 0.870g/cm 3)

Claims (8)

1. the modification polyene composition that comprises following ingredients: (A) new LDPE (film grade) of high pressure processing, its melt flow rate (MFR): 0.1-10g/ minute, density: 0.915-0.935g/cm 3, (B) Alathon and/or ethylene/alpha-olefin copolymer, its melt flow rate (MFR): 0.1-30g/10 minute, density: 0.910-0.965g/cm 3, be line style basically, and by using the transition-metal catalyst preparation and (c) ethylene/alpha-olefin copolymer of amorphous or low-crystalline, melt flow rate (MFR): 0.1-10g/10 minute, density was less than 0.900g/cm 3Wherein each composition (A), (B) and amount (C) are respectively 50-70% (weight), 20-45% (weight) and 5-30% (weight) based on these compositions (A), (B) and gross weight meter (C), and at least these compositions (A), (B) and a part (C) through the modification of unsaturated carboxylic acid or derivatives thereof.
2. according to the modified polyolefin compositions of claim 1, wherein composition (B) is the combination of Alathon and ethylene/alpha-olefin copolymer.
3. according to the modified polyolefin compositions of claim 2, wherein said Alathon is graft modification.
4. according to the modified polyolefin compositions of claim 1, wherein the graft ratio of unsaturated carboxylic acid or derivatives thereof is composition (A), (B) and (C) 0.001-5% of gross weight (weight).
5. the laminar structure that comprises composition layer, it contains the modified polyolefin compositions of claim 1 and is present in the resin layer of described composition layer one side at least.
6. according to the laminar structure of claim 5, the described resin layer that wherein is present in described composition layer one side at least is the resin that is selected from polymeric amide and ethylene/vinyl alcohol copolymer.
7. according to the laminar structure of claim 5, wherein with described composition, resin layer and composition layer lamination successively.
8. according to the laminar structure of claim 5, be tubular form.
CN95105629A 1994-06-06 1995-06-06 Modified polyolefin composition and laminated structure using the same Expired - Lifetime CN1113080C (en)

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JP2643348B2 (en) * 1988-09-01 1997-08-20 三井石油化学工業株式会社 Polyethylene resin composition and film
MY107391A (en) * 1989-07-19 1995-11-30 Mitsui Chemicals Inc Polyolefin resin composition, and crosslinked molded article and process for the production thereof.
CA2103401C (en) * 1992-11-19 2002-12-17 Mamoru Takahashi Ethylene copolymer composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100398597C (en) * 1998-03-10 2008-07-02 三井化学株式会社 Ethylene copolymer composition and uses thereof
US11312092B2 (en) 2014-11-20 2022-04-26 Avery Dennison Corporation Tiled retroreflector with multi-stage dicing
CN104558760A (en) * 2014-12-03 2015-04-29 南宁市金装塑料彩印有限公司 High-strength food packaging film

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MY130585A (en) 2007-06-29
TW326461B (en) 1998-02-11

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