CN1283710C - Polyethylene series resin for hollow formed body and hollow formed body made therefrom - Google Patents

Polyethylene series resin for hollow formed body and hollow formed body made therefrom Download PDF

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Publication number
CN1283710C
CN1283710C CNB031018378A CN03101837A CN1283710C CN 1283710 C CN1283710 C CN 1283710C CN B031018378 A CNB031018378 A CN B031018378A CN 03101837 A CN03101837 A CN 03101837A CN 1283710 C CN1283710 C CN 1283710C
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mfr
polyethylene
load
under
jis
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CN1438263A (en
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岩政健司
根本美喜雄
和贺义隆
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Prime Polymer Co Ltd
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Mitsui Chemical Industry Co Ltd
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    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • E06B9/26—Lamellar or like blinds, e.g. venetian blinds
    • E06B9/264—Combinations of lamellar blinds with roller shutters, screen windows, windows, or double panes; Lamellar blinds with special devices
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • E06B9/26—Lamellar or like blinds, e.g. venetian blinds
    • E06B9/264—Combinations of lamellar blinds with roller shutters, screen windows, windows, or double panes; Lamellar blinds with special devices
    • E06B2009/2643—Screens between double windows
    • E06B2009/2646—Magnetic screen operator

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  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

To provide a polyethylene resin for blow molded products having high density and excellent in buckling strength and bottle ESCR (environmental stress crack resistance) and scarcely causing environmental stress cracking and to provide the blow molded product composed of the resin. In the polyethylene resin, a melt flow rate (MFR) (JIS K 7210 measured at 190deg C, under 2.16 kg load; unit: g/10 min) is 0.1-2.0 and a density (JIS K 6922-2, using a measuring sample annealed for 30 min with boiling water; unit: kg/m3) is 957-967 and Mz (Z is an average molecular weight) satisfies the formula Mz>=-4*105log MFR+1.2*106. A polyethylene in which a value [(MFR21.6)/(MFR2.16)] obtained by dividing a value of a melt flow rate (MFR21.6) measured under 21.6 kg load with a value of a melt flow rate (MFR2.16) measured under 2.16 kg load is <=200 is preferably sued as the polyethylene resin.

Description

Slush molding body and function polyethylene-based resin and the hollow molded body of making by this resin
Technical field
The hollow molded body that the present invention relates to slush molding body and function polyethylene-based resin and make by this resin, reach the hollow molded body of making by this resin in particular to the slush molding body and function polyethylene-based resin that can be modulated into bending strength, anti-carrying capacity of environment (bottle ESCR) and anti-drop impact excellence and hollow molded body that have good appearance.
Background technology
Now, from resources conseravtion and reduction waste amount aspect, need to cut down the resin usage quantity in the hollow molded body.
But, for example, for the hollow molded body of making by polyethylene used in the containers such as washing composition, particularly high density polyethylene(HDPE), when filling content liquid and when conveying etc. required bending strength, exist the tendency that increases container wall thickness, increases the resin usage quantity.Even reduce container wall thickness, reduce the resin usage quantity, but in order to ensure bending strength, it is effective using high-density, high rigid polyethylene resin.But, be the 957kg/m that is better than the bending strength of bottle using density 3During above polythene material, if storage as washing composition, softening agent, the SYNTHETIC OPTICAL WHITNER of content liquid, will be difficult to practicability because of the be full of cracks of bottle ESCR deficiency generation container.
Therefore, though people expect to occur a kind of can modulate have high-density, thin-walled is thick and the bending strength excellence and polyethylene hollow molded body environmental stress resistance cracking excellence be the slush molding body and function polyethylene-based resin made of resin and the hollow molded body of making by this resin by high density polyethylene(HDPE).
Summary of the invention
In order to solve the problem of following prior art and producing as described above, the object of the present invention is to provide a kind of density height, bending strength excellence and bottle ESCR excellence and the difficult slush molding body and function polyethylene-based resin of environmental stress crack and the hollow molded body of making by this resin of producing.
The slush molding body and function polyethylene-based resin that utilizes melting mixing or multistage polymerization to obtain of the present invention is characterized by: by adopting multistage polymerization or use multistage polymerization and melting mixing to obtain simultaneously, melting index (MFR; JIS K7210,190 ℃, 2.16kg load, unit is gram/10 minutes) be 0.1～2.0, (JIS K6922-2, working sample use the wire rod that will the extrude 30 minutes resulting samples of annealing, units/m to density in boiling water from the MFR tester 3) be in 957～967 the scope, and Mz (Z molecular-weight average) satisfies formula Mz 〉=-4 * 10 5Log MFR+1.2 * 10 6, with the melting index (MFR of 21.6kg load measurement 21.6) be worth divided by the melting index (MFR with the 2.16kg load measurement 2.16) the ratio [(MFR of value 21.6)/(MFR 2.16)] be below 200.
With regard to above-mentioned polyethylene-based resin, be preferably melting index (MFR with the 21.6kg load measurement 21.6) be worth divided by the melting index (MFR with the 2.16kg load measurement 2.16) the ratio [(MFR of value 21.6)/(MFR 2.16)] be 30～190 polyethylene.
And polyethylene hollow molded body of the present invention contains the layer that one deck is made by above-mentioned slush molding body and function polyethylene-based resin at least, is applicable to storage washing composition, SYNTHETIC OPTICAL WHITNER or softening agent etc.
Embodiment
Below, specifically describe slush molding body and function polyethylene-based resin of the present invention and use the hollow molded body of this resin.
Slush molding body and function polyethylene-based resin
Slush molding body and function polyethylene-based resin of the present invention, melting index (MFR; JIS K7210,190 ℃, the 2.16kg load, unit is for restraining/10 minutes) and be/10 minutes scope of 0.1～2.0 gram, be preferably/10 minutes scope of 0.1～1.0 gram, more preferably/10 minutes scope of 0.1～0.7 gram.If melting index is in this scope, from the formability aspect, for preferably.
And (JIS K6922-2, working sample MFR count wire rod to its density, boiling water slow cooling in 30 minutes, units/m 3) be 957～967kg/m 3, be preferably 957～963kg/m 3Scope.If density is in this scope, from the bending strength aspect, for preferably.
And slush molding body and function polyethylene-based resin of the present invention is characterized by: the Mz (Z molecular-weight average) that measures with GPC (gel permeation chromatography) satisfies formula Mz 〉=-4 * 10 5Log (MFR)+1.2 * 10 6The meaning of " Mz satisfies this scope " is meant in the ratio of molecular-weight average and exists high molecular weight components, if Mz in this scope, is preferred aspect bottle ESCR.
Mz (Z molecular-weight average) is to use Waters corporate system GPC-150C to measure as following.
Separator column is that 2 of Tosoh (strain) system TSK GMH 6HT and 2 of TSK GMH 6HTL add up to 4, column temperature is 140 ℃, mobile phase is used orthodichlorobenzene (with the pure pharmaceutical worker's industry of light (strain) system), use the BHT (3 of 0.025 weight %, the 5-di-tert-butyl hydroxy toluene) (military field pharmaceutical industries (strain) system) as oxidation inhibitor, moves with 1.0ml/ minute speed, and sample solution concentration is 0.1 weight %, the sample injection rate is 500 microlitres, uses the differential refractometer as detector.Use the polystyrene standard of Tosoh (strain) system to proofread and correct separator column, be scaled polyethylene by standard law.
And, with regard to above-mentioned polyethylene-based resin, with the melting index (MFR of 21.6kg load measurement 21.6kg) with melting index (MFR with the 2.16kg load measurement 2.16kg) ratio [(MFR 21.6)/(MFR 2.16)] be generally below 200, be preferably 190～30, more preferably 180～40, can access sufficient shock strength like this, particularly enough dropping strengths.
The polyethylene-based resin that the present invention is used, it not only can be high density polyethylene(HDPE) with MFR as described above and density and Mz relational expression, and ethylene single-polymer, also can use ethene and a small amount of alpha-olefin, for example alpha-olefin copolymers such as the following propylene of 10 moles of %, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 3-Methyl-1-pentene, 4-methyl-1-pentene close resulting ethylene.These alpha-olefins both can use separately, also can two or morely use in combination.
High density polyethylene(HDPE) with above-mentioned such character, can be made ethene or ethene and carbonatoms by the middle-pressure process of the low-pressure process of Z-type catalyst, aromatic ring alkene metal derivative catalyzer etc., Karen Phillips method etc. is that 3～20 alpha-olefin carries out the polyreaction modulation and forms.
In the present invention, the copolymerization of ethene and alpha-olefin is carried out in the liquid phase of gas phase or paste-like or solution.In slurry polymerization, both can also can use alkene itself as solvent with unreactive hydrocarbons as solvent.
When implementing slurry polymerization process or solution polymerization, in-50 ℃～250 ℃ scope, when implementing gaseous polymerization, polymerization temperature is preferably the scope at 20～100 ℃ usually at 0～120 ℃ to polymerization temperature usually.Polymerization pressure is generally under normal pressure and even the 100 atmospheric pressurized conditions, and polymerization can use in intermittent type, semi continuous, the continous way any mode to carry out.And, also can adopt the above polymerization of the different two-stage of reaction conditions, can quicken to comprise the single-stage of prepolymerization, multistage polyreaction.
And, because Mz is the mean molecule quantity algorithm that increases the high molecular weight components influence, although exist high molecular weight components to increase, so can reach the target zone of MFR and Mz because of flowability.Specifically, because molecular weight distribution broadens and has high molecular weight components, so can make MFR and Mz become the relation of claim scope.And, wide and have a polyethylene of high molecular weight components in order to make molecular weight distribution, can be by adopting multistage polymerization (use secondary polymerization, three grades of reactors such as polymerization continuously, make the different poly method of molecular weight density continuously) or melting mixing or using the method for multistage polymerization and melting mixing simultaneously, two or more low molecular weight polyethylenes and High molecular weight polyethylene are mixed, make Mz and MFR reach target zone.
And, in polyethylene-based resin of the present invention, sneak into the polyethylene made from high-pressure process, also can reach above-mentioned rerum natura.Under these circumstances, using density is 910～935kg/m 3About high-pressure polyethylene.Can be generally 100～65/0～35 in weight ratio, be preferably and use polyethylene-based resin of the present invention and high-pressure polyethylene in 100～80/0～20 the scope.If mixed high-voltage polyethylene in such scope is from the formability aspect, for preferably.
And, in above-mentioned polyethylene-based resin or polyethylene-based resin composition, in the scope of not destroying the hollow molded body rerum natura, also can cooperate various additives.As such additive, specifically, can enumerate weighting agent, weathering resistance stablizer, heat-resisting stabilizing agent, antistatic agent, slipproofing agent, antifogging agent, lubricant, pigment, dyestuff, nucleator, softening agent, fire retardant, hydrochloric acid absorbent etc.
Hollow molded body
Hollow molded body of the present invention is made by polyethylene-based resin as described above or polyethylene-based resin composition.Hollow molded body of the present invention both can form with individual layer as monolayered vessel, also can be formed by two-layer above multilayer as laminated vessel.
For example under by the two-layer situation that forms laminated vessel, wherein the polyethylene-based resin that preferably used by the invention described above of one deck forms, another layer can be by the resin formation different with the polyethylene-based resin that forms above-mentioned one deck, perhaps, the polyethylene-based resin that also can preferably be used by the invention described above but have with the polyethylene-based resin of the used different rerum naturas of polyethylene-based resin of above-mentioned one deck forms.
With regard to above-mentioned different resin, for example can enumerate polymeric amide (nylon 6, nylon 66, nylon 12, copolymerization nylon etc.), ethylene-vinyl alcohol co-polymer, polyester (polyethylene terephthalate etc.), modified polyolefin etc.
Polyethylene hollow molded body of the present invention is to form with the modulation of existing well-known slush molding (blow molding) method.The whole bag of tricks is arranged in the blow molding method, be divided into extrusion and blow molding method, secondary blow molding method, injection moulding substantially.In the present invention, especially preferably adopt the extrusion and blow molding method.
Modulate the hollow molded body that forms as described above, be applicable to SYNTHETIC OPTICAL WHITNER container, detergent container, SYNTHETIC OPTICAL WHITNER with in the purposes such as container, for example can be suitable for sending out the tensio-active agent that home services such as agent, treatment agent use and use with container with container or SYNTHETIC OPTICAL WHITNER as makeup, washing composition, soft machining agent, shampoo, profit.
(invention effect)
The first slush molding body and function polyethylene-based resin of the present invention is characterized by: melting index (MFR; JIS K7210,190 ℃, 2.16kg load, unit are for restraining/10 minutes) be 0.1～2.0, (JIS K6922-2, working sample MFR count wire rod to density, boiling water slow cooling in 30 minutes, units/m 3) be 957～967kg/m 3Scope, and satisfy formula Mz 〉=-4 * 10 with the Mz (Z molecular-weight average) that GPC (gel permeation chromatography) measures 5LogMFR+1.2 * 10 6Even the container of thin-walled property also has enough bending strengths and environmental stress resistance cracking.
And if slush molding body and function polyethylene-based resin of the present invention is according to JIS K 7210 and at 190 ℃ of mensuration, that use the 21.6kg load measurement down melting index (MFR 21.6) value and the melting index (MFR that uses the 2.16kg load measurement 2.16) the ratio [(MFR of value 21.6)/(MFR 2.16)] be below 200, then dropping strength is also excellent.
Slush molding body and function polyethylene-based resin of the present invention and hollow molded body can be applicable to that washing composition, shampoo, profit send out in the purposes such as the container of agent, SYNTHETIC OPTICAL WHITNER, soft machining agent, makeup, wax, edible oil, mayonnaise, refining horseradish etc., tanks, ointment jar, oil drum, hopper.
(embodiment)
Below, by embodiment the present invention is described, but the present invention is not limited by these embodiment.
And melting index (MFR), density and Mz (Z molecular-weight average), tensile yield strength and environmental stress crack resistance F50 value are measured according to following method.
MFR:JIS K7210,190 ℃, the 2.16kg load.
Density: JIS K6922-2, measure sample MFR meter wire rod, boiling water slow cooling in 30 minutes.
Mz: use Waters corporate system GPC-150C, measure as followsly, separator column is that 2 of Tosoh (strain) system TSK GMH 6HT and 2 of TSK GMH6HTL add up to 4, column temperature is 140 ℃, mobile phase is used orthodichlorobenzene (with the pure pharmaceutical worker's industry of light (strain) system), use the BHT (3 of 0.025 weight %, the 5-di-tert-butyl hydroxy toluene) (military field pharmaceutical industries (strain) system) is as oxidation inhibitor, speed with 1.0ml/ minute moves, sample solution concentration is 0.1 weight %, the sample injection rate is 500 microlitres, uses the differential refractometer as detector.Use the polystyrene standard of Tosoh (strain) system to proofread and correct separator column, be scaled polyethylene by standard law.
Tensile yield strength:, use the test piece of JIS K71604 type to measure according to JIS K7160.
Environmental stress resistance cracking F50 value:, use 10% aqueous solution of ア Application ロ Star Network ス Co630 to measure as tensio-active agent according to ASTM D1693B method.
(embodiment 1)
Under the situation of ethene and 1-butylene coexistence, use catalyzer, make by multistage polymerization, 2.16kg load MFR down is that MFR under 0.8 gram/10 minutes, the 21.6kg load 80 restrains/10 minutes and density is 959kg/m 3Polyethylene, with similarly make through multistage polymerization, 2.16kg load MFR down is that MFR under 0.04 gram/10 minutes, the 21.6kg load 7.4 restrains/10 minutes and density is 959kg/m 3Polyethylene carry out melting mixing with 80: 20 ratio.MFR under the poly 2.16kg load that this melting mixing makes is that MFR 50 grams/10 minutes and the density under 0.41 gram/10 minutes, the 21.6kg load is 959kg/m 3, the Mz that is measured by GPC is 16.7 * 10 5
And tensile yield strength is 130kJ/m 2, environmental stress resistance cracking F50 value is 300 hours.Its result is as shown in table 1.
(condition of molding of individual layer hollow molded body)
Then, use extrusion blow molding machine (Japan's system steel (strain) system, model: JEB-15), poly mold temperature be 200 ℃, resin extruded amount be 50kg/ hour, die temperature be under 20 ℃ the condition of molding with this blow moulded polyethyene moulding, the cylinder bottles (individual layer hollow molded body) and the inner capacities that obtain inner capacities and be 780ml, weight 25 grams and 35 grams are that 2.5L, weight are the bottles with handles (individual layer hollow molded body) of 130 grams.
(individual layer hollow molded body shatter test method repeatedly)
Bottle with obtaining as described above carries out shatter test repeatedly according to following method.Its result is as shown in table 1.
With inner capacities is that 780ml, weight are that 25 monolayer bottles that restrain are filled with water, make this bottle vertical, under 0 ℃ atmosphere surrounding, should fall repeatedly from certain altitude by bottle, maximum 10 times, be determined in the drop test and make water from bottle, drain to the required drop number repeatedly in outside because of breaking.Carrying out this experiment quantity n is 10, measures bottle to breaking required average drop number.The ground that is used for the bottle shatter test, what use is that level places the thickness on the cement flooring to be the iron plate more than the 2mm.
(individual layer hollow molded body anti-reflecting bending strength test method)
With inner capacities is that 780ml, weight are the monolayer bottles of 35 grams, is to compress under 30 ℃ of conditions with the Intron universal testing machine 15mm/ minute, test temperature, with the maximum strength that obtains as bending strength.Its result is as shown in table 1.
(individual layer hollow molded body bottle ESCR test method(s))
In inner capacities is that 780ml, weight are the following content liquid of filling 78cc in the 35 cylinder bottles that restrain, in inner capacities is that 2.5L, weight are the following content liquid of filling 250cc in 130 bottles with handles that restrain, and seal, preservation under 65 ℃ of conditions is observed bottle until breaking the required time.The quantity n that measures with bottle is respectively 10, after on-test, writes down the 1st bottle until breaking the required time, and it the results are shown in the table 1.
Chlorine is SYNTHETIC OPTICAL WHITNER: flower king (strain) system キ Star チ Application Ha イ one
Oxygen is SYNTHETIC OPTICAL WHITNER: Lion (strain) system て ま な Block ラ イ ト
Softening agent: flower king (strain) system Ha ミ Application グ
Shampoo: the super gentle shampoo of FT Shiseido (strain) system
(3 kinds 5 layers of hollow molded body method of forming and bottle ESCR test method(s))
Use extrusion blow molding machine (Japan's system steel (strain) system, model: JB-105PC), mold temperature be 200 ℃, resin extruded amount be 10kg/ hour, die temperature be under 20 ℃ the condition of molding with this blow moulded polyethyene moulding, obtaining inner capacities is that 500ml, weight are the cylinder bottles of 25 grams.
The thickness constituent ratio of each layer is: polyethylene: adhering resin: ethylene-vinyl alcohol copolymer: adhering resin: polyethylene=41: 3: 2: 3: 41.In addition, adhering resin uses Mitsui Chemicals (strain) system ア De マ one NB508, and ethylene-vinyl alcohol copolymer is used Kuraray (strain) system Eberl F101B.
In the bottle of gained, filling chlorine is SYNTHETIC OPTICAL WHITNER (flower king (strain) system キ Star チ Application Ha イ one) 50cc, and airtight, and preservation under 65 ℃ of conditions is observed bottle until breaking the required time.The quantity n that measures with bottle is respectively 10, after on-test, writes down the 1st bottle until breaking the required time, and it the results are shown in the table 1.
(2 kinds 2 layers of hollow molded body method of forming and bottle ESCR test method(s))
Use extrusion blow molding machine (Placo (strain) system, model: Placo-3B-50-40), mold temperature be 200 ℃, resin extruded amount be 8kg/ hour, die temperature be under 20 ℃ the condition of molding with this blow moulded polyethyene moulding, obtaining inner capacities is that 1000ml, weight are the cylinder bottles of 40 grams.Skin is a polyethylene, and internal layer is individual layer slush molding product crushed material, and the thickness constituent ratio of each layer is: skin: internal layer=80: 20.
In the gained bottle, filling chlorine is SYNTHETIC OPTICAL WHITNER (flower king (strain) system キ Star チ Application Ha イ one) 100cc, also airtight, and preservation under 65 ℃ of conditions is observed bottle until breaking the required time.The quantity n that measures with bottle is respectively 10, after on-test, writes down the 1st bottle until breaking the required time, and it the results are shown in the table 1.
(embodiment 2)
Except in embodiment 1, using MFR 2.16kgBe 0.29 gram/10 minutes, MFR 21.6kgBe that 39 grams/10 minutes, density are 959kg/m 3, Mz is 16.0 * 10 5, tensile yield strength is 170kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(embodiment 3)
Except in embodiment 1, using but adjust the MFR that obtains by multistage polymerization continuous production low molecular weight compositions and high molecular weight components without melting mixing 2.16kgBe 0.38 gram/10 minutes, MFR 21.6kgBe that 57 grams/10 minutes, density are 959kg/m 3, Mz is 18.7 * 10 5, tensile yield strength is 110kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(embodiment 4)
Except in embodiment 1, using MFR 2.16kgBe 0.16 gram/10 minutes, MFR 21.6kgBe that 25 grams/10 minutes, density are 959kg/m 3, Mz is 20.0 * 10 5, tensile yield strength is 220kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(embodiment 5)
Except in embodiment 1, using MFR 2.16kgBe 0.49 gram/10 minutes, MFR 21.6kgBe that 56 grams/10 minutes, density are 960kg/m 3, Mz is 15.4 * 10 5, tensile yield strength is 120kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(embodiment 6)
Except in embodiment 1, using MFR 2.16kgBe 0.29 gram/10 minutes, MFR 21.6kgBe that 30 grams/10 minutes, density are 961kg/m 3, Mz is 16.0 * 10 5, tensile yield strength is 180kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(comparative example 1)
Except in embodiment 1, using MFR 2.16kgBe 0.36 gram/10 minutes, MFR 21.6kgBe that 35 grams/10 minutes, density are 955kg/m 3, Mz is 12.1 * 10 5, tensile yield strength is 210kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(comparative example 2)
Except in embodiment 1, using MFR 2.16kgBe 0.36 gram/10 minutes, MFR 21.6kgBe that 35 grams/10 minutes, density are 959kg/m 3, Mz is 12.5 * 10 5, tensile yield strength is 200kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(comparative example 3)
Except in embodiment 1, using MFR 2.16kgBe 0.40 gram/10 minutes, MFR 21.6kgBe that 84 grams/10 minutes, density are 959kg/m 3, Mz is 20.1 * 10 5, tensile yield strength is 80kJ/m 2Polyethylene replace carrying out research similarly to Example 1 beyond the polyethylene among the embodiment 1.It the results are shown in the table 1.
(table 1)
Unit Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 1 Comparative example 2 Comparative example 3
The MFR2.16kg load Restrain/10 minutes 0.41 0.29 0.38 0.16 0.49 0.29 0.36 0.36 0.4
Density kg/m 3 959 959 959 959 960 961 955 959 959
Mz 16.7×10 5 16.0×10 5 18.7×10 5 20×10 5 15.4×10 5 16.0×10 5 12.1×10 5 12.5×10 5 20.1×10 5
-4×10 5log(MFR)+1.2×10 6 13.5×10 5 14.2×10 5 13.7×10 5 15.2×10 5 13.2×10 5 14.2×10 5 13.8×10 5 13.8×10 5 13.6×10 5
The MFR21.6kg load Restrain/10 minutes 50 39 57 25 56 30 35 35 84
MFR21.6kg load/MFR2.16kg load 122 134 150 156 114 103 97 97 210
Bending strength N 310 310 310 310 320 340 270 310 310
Tensile yield strength KJ/m 3 130 170 110 220 120 180 210 200 80
Dropping strength Hour 6.8 7.1 5.2 8.1 5.9 7.9 7 6.2 2.8
Environmental stress resistance be full of cracks (F50) Hour 300 400 350 500 250 230 300 50 500
Individual layer hollow molded body bottle ESCR (the cylinder bottle: the content liquid chlorine is a SYNTHETIC OPTICAL WHITNER) Hour More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 110 More than 500
Individual layer hollow molded body bottle ESCR (the cylinder bottle: the content liquid oxygen is a SYNTHETIC OPTICAL WHITNER) Hour More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 210 More than 500
Individual layer hollow molded body bottle ESCR (cylinder bottle: the content liquid softening agent) Hour More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 320 More than 500
Individual layer hollow molded body bottle ESCR (cylinder bottle: the content liquid shampoo) Hour More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 400 More than 500
Individual layer hollow molded body bottle ESCR (bottle with handles: the content liquid chlorine is a SYNTHETIC OPTICAL WHITNER) Hour More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 30 More than 500
3 kinds 5 layers hollow molded body bottle ESCR (the content liquid chlorine is a SYNTHETIC OPTICAL WHITNER) Hour More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 50 More than 500
2 kinds 2 layers hollow molded body bottle ESCR (the content liquid chlorine is a SYNTHETIC OPTICAL WHITNER) Hour More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 More than 500 80 More than 500

Claims (4)

1. slush molding body and function polyethylene-based resin that utilizes melting mixing or multistage polymerization to obtain is characterized in that:
By adopting multistage polymerization or use multistage polymerization and melting mixing to obtain simultaneously,
According to JIS K7210 and the melting index MFR that measures under 190 ℃, 2.16kg load is 0.1～2.0 gram/10 minutes, and the density that is to use the wire rod that will extrude from the MFR tester to anneal in boiling water to measure under the situation of 30 minutes resulting samples according to JIS K6922-2 and at working sample is at 957～967kg/m 3Scope in, and satisfy formula Mz 〉=-4 * 10 with the Z molecular-weight average Mz of gel permeation chromatography 5lOg MFR+1.2 * 10 6,
According to JIS K7210 and at 190 ℃, the melting index MFR that under 21.6kg load, measures 21.6Value and the melting index MFR that under the 2.16kg load, measures 2.16The ratio MFR of value 21.6/ MFR 2.16Be below 200.
2. slush molding body and function polyethylene-based resin as claimed in claim 1 is characterized in that: according to JIS K7210 and at 190 ℃, the melting index MFR that measures under 21.6kg load 21.6Value and the melting index MFR that under the 2.16kg load, measures 2.16The ratio MFR of value 21.6/ MFR 2.16Be 30～190.
One kind contain at least one deck by claim 1 or 2 described slush molding body and function polyethylene-based resins constitute the layer hollow molded body.
4. hollow molded body as claimed in claim 3 is characterized in that: packing into is selected from least a in washing composition, SYNTHETIC OPTICAL WHITNER and the softening agent.
CNB031018378A 2002-02-01 2003-01-22 Polyethylene series resin for hollow formed body and hollow formed body made therefrom Expired - Lifetime CN1283710C (en)

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CN1171939C (en) * 2000-04-21 2004-10-20 三井化学株式会社 Polyethene resin for blow moulding and moulded article thereof
KR100702492B1 (en) * 2005-08-11 2007-04-02 삼성토탈 주식회사 High density polyethylene resin for blow molding with excellent gloss and stiffness and resin composition comprising the same
CN101384627A (en) * 2006-02-15 2009-03-11 三井化学株式会社 Ethylene resin and blow-molded article comprising the same
TWI529102B (en) * 2010-12-27 2016-04-11 Kao Corp Packaging body
CN116063763A (en) * 2021-11-01 2023-05-05 中国石油化工股份有限公司 Polyethylene composition and peroxide crosslinked polyethylene pipe
KR20230158162A (en) 2022-05-10 2023-11-20 대흥 아이 비 엔 주식회사 Manufacturing method of eco-friendly container with excellent chemical resistance

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