CN100427541C - Plastic container - Google Patents
Plastic container Download PDFInfo
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- CN100427541C CN100427541C CNB2004100563506A CN200410056350A CN100427541C CN 100427541 C CN100427541 C CN 100427541C CN B2004100563506 A CNB2004100563506 A CN B2004100563506A CN 200410056350 A CN200410056350 A CN 200410056350A CN 100427541 C CN100427541 C CN 100427541C
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- multipolymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/003—Suspension means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
Abstract
Disclosed is a plastic container having a wall comprising a layer made of a composition comprising a major amount of crystalline propylene-ethylene-butene-1 copolymer which has specific structural unit proportions and a specific melt flow rate and a minor amount of ethylene-alpha-olefin copolymer which has specific structural unit proportions, a specific melt flow rate and a specific density, the container being superior in flexibility, impact strength at low temperatures anddurability.
Description
Technical field
The present invention relates to plastic containers.
Background technology
By the container that acrylic resin is made, be good such as many aspect of performances such as thermotolerance, rigidity, chemical resistant properties and water vapour barrier propertys, so they are applied widely.But this class container exists the problem of transparency difference, has proposed many schemes that are used for improving their transparencys now.
For instance, known a kind of container by utilizing a kind of resin combination to obtain, described resin combination comprises: the propylene-ethylene random copolymer resin of 98-70 weight % and 2-30 weight % use ethene-hexene-1 copolymer resin of metallocene catalyst polymerisation and based on the described composition of 100 weight parts, the advanced higher fatty acid derivative of 0.02-1.0 weight part (referring to JP-A-2001-181455).This container has the transparency of improvement.But when it was heat-treated, the described advanced higher fatty acid derivative that is present in the container will be moved to the surface of container, thereby had reduced its transparency, perhaps made surfaces of tacky.Therefore, still exist improved space.
On the other hand, the container that known a kind of resin is made, described resin comprises crystalline propylene copolymer and crystalline ethylene multipolymer, described crystalline propylene copolymer in 230 ℃ of melt flow rate (MFR)s that record be 0.3-8g/10min, propylene content be 82-96.5 weight %, ethylene content be 3-8 weight % and contain 4 or the alpha-olefin content of above carbon atom be 0.5-10 weight %, and described crystalline ethylene multipolymer is that 0.3-50g/10min and density are 900-935kg/m in 190 ℃ of melt flow rate (MFR)s that record
3, wherein, described crystalline ethylene multipolymer is to carry out blended (referring to JP-A-8-47980) based on the quantity of described crystalline propylene copolymer 4-0.05 weight %.But its transparency is still not enough.
Summary of the invention
Summary of the invention
The purpose of this invention is to provide a kind of plastic containers, it is flexible and has good shock strength that when low temperature even it is heat-treated, its transparency also only has very little reduction, can not become very sticking.
The invention provides a kind of plastic containers, its wall comprises the thin layer of being made by a kind of composition, described composition contains feature [1] and the crystalline polypropylene-ethene-1-Butylene copolymer of [2] and the ethene-alpha-olefin copolymer that the 1-30 weight part has feature [3], [4] and [5] that the 70-99 weight part has following regulation, wherein, two kinds of multipolymers is 100 weight parts in conjunction with quantity:
[1] the structural unit content that to have the structural unit content that is derived from propylene be 70-97 weight %, be derived from ethene is that 1-10 weight % and the structural unit content that is derived from butene-1 are 2-20 weight %,
[2] having the melt flow rate (MFR) that records under the load of 230 ℃ temperature and 2.16kgf is 1-10g/10min,
[3] for a kind of ethene with contain the multipolymer of 4-12 carbonatom, described multipolymer have the structural unit that is derived from ethene be 50 weight % or more than,
[4] have the melt flow rate (MFR) that under the load of 190 ℃ temperature and 2.16kgf, records be 0.1-50g/10min and
[5] density that has is 865-898kg/m
3
First embodiment of the present invention is about a kind of plastic containers, its wall is made of single thin layer, described thin layer is to have as above the composition that the crystalline polypropylene-ethene-1-Butylene copolymer of the feature [1] of regulation and [2] and 1-30 weight part have an ethene-alpha-olefin copolymer of the feature [3] as above stipulated, [4] and [5] by the described 70-99 of containing weight part to make, wherein, two kinds of multipolymers is 100 weight parts in conjunction with quantity.
Second embodiment of the present invention is about a kind of plastic containers, its wall is made of two or more thin layers, described thin layer contains at least one thin layer to has as above the composition that the crystalline polypropylene-ethene-1-Butylene copolymer of the feature [1] of regulation and [2] and 1-30 weight part have an ethene-alpha-olefin copolymer of the feature [3] as above stipulated, [4] and [5] by the described 70-99 of containing weight part and makes, wherein, two kinds of multipolymers is 100 weight parts in conjunction with quantity.
Description of drawings
Figure 1 shows that the synoptic diagram of the container that makes among the embodiment 1 that uses third-angle projection.
The explanation of preferred implementation
The main composition that is used for plastic containers of the present invention contains following composition: the crystalline polypropylene-ethene-1-Butylene copolymer of a kind of feature [1] with following regulation and [2] and a kind ofly have the feature [3] of following regulation, an ethene-alpha-olefin copolymer of [4] and [5].
Being used for propylene-ethylene-butene of the present invention-1 multipolymer is a kind of crystalline copolymer of being made up of propylene, ethene and butene-1, and described multipolymer contains the structural unit that is derived from propylene of 70-97 weight %, the structural unit that is derived from ethene of 1-10 weight % and the structural unit that is derived from butene-1 of 2-20 weight %.In the present invention, crystalline polymer is to represent a kind of like this polymkeric substance, and the melting heat that is recorded by differential scanning calorimeter is 20J/g or bigger.The melting heat that is used for ethylene-propylene-1-Butylene copolymer of the present invention is preferably 20-100J/g, and more preferably 25-90J/g is preferably 30-80J/g especially.In the present invention, the melting heat of multipolymer is that following method is measured.At first, according to following method, use by PerkinElmer, differential scanning calorimeter DSC-VII or suitable with it surveying instrument that Inc. makes produce the crystal melting curve.Melting heat (J/g) is to calculate around area partly according to resulting crystal melting curve and its baseline.
(1) by moulding, makes the thin slice of a diameter 65mm and thickness 100 μ m 230 ℃ of temperatures.
(2) adopt tapping and plugging machine, the diameter by described thin slice punching 5mm that step (1) is made prepares sample.
By the scales/electronic balance weighing sample.
(3) sample that makes in the step (2) is put in the sample disc.
(4) under nitrogen atmosphere, the sample in the described sample disc is applied thermal hysteresis as follows (thermal hysteresis):
(i) with the speed of 300 ℃/min, described sample is heated to 220 ℃ from 24 ℃,
(ii) in heating (i) afterwards, described sample kept 5 minutes at 220 ℃,
(iii) step (ii) after, with the speed of 300 ℃/min, described sample is cooled to 150 ℃,
(iv) after cooling (iii), described sample kept 1 minute at 150 ℃,
(V) step (iv) after, with the speed of 5 ℃/min, described sample is cooled to 50 ℃,
(vi) cooling (v), described sample 50 ℃ kept 1 minute and
(Vii) (vi),, described sample is heated to 180 ℃ in step with the speed of 5 ℃/min.
In the present invention, can use single, two or more propylene-ethylene-butene-1 multipolymer.For instance, two or more different multipolymers of molecular weight can adopt.A kind of replacement scheme is that two or more different multipolymers of described three kinds of structural unit content can adopt.
For the crystalline polypropylene-ethene-1-Butylene copolymer with feature [1] and [2], having the structural unit content that is derived from ethene is that 1.3-8 weight % and the structural unit content that is derived from butene-1 are 2.5-15 weight %, suits.Preferably is that it is that 1.5-5 weight % and the structural unit content that is derived from butene-1 are 3-12 weight % that described multipolymer has the structural unit content that is derived from ethene.Suitable especially is that it is that 2-3 weight % and the structural unit content that is derived from butene-1 are 4-10 weight % that described multipolymer has the structural unit content that is derived from ethene.If the described content that is derived from the structural unit of ethene is lower than 1 weight %, the perhaps described content that is derived from the structural unit of butene-1 is lower than 2 weight %, and then the flexible of container will variation.If the described content that is derived from the structural unit of ethene is higher than 10 weight %, the perhaps described content that is derived from the structural unit of butene-1 is lower than 20 weight %, and then the thermotolerance of container will variation.
Structural unit that is derived from ethene described in described propylene-ethylene-butene-1 multipolymer and the described structural unit that is derived from butene-1 in conjunction with content, be 3-30 weight %, be preferably 3.8-23 weight %, more preferably 4.5-17 weight %.If describedly be lower than 3 weight % in conjunction with content, then described container tends to flexible variation, and if describedly be higher than 30 weight % in conjunction with content, then container tends to the thermotolerance variation.
Described propylene-ethylene-butene-1 multipolymer is preferably a kind of multipolymer that satisfies following formula (1).If satisfy formula (1), then container tends to have good especially thermotolerance.More preferably a kind of multipolymer that satisfies following formula (2) of described propylene-ethylene-butene-1 multipolymer.More preferably a kind of again multipolymer that satisfies following formula (3) of described propylene-ethylene-butene-1 multipolymer:
x+1＜y (1)
x+2＜y (2)
x+3＜y (3)
Wherein, x represents to be derived from the content (weight %) of the structural unit of ethene, and y represents to be derived from the content (weight %) of the structural unit of butene-1.
Under the load of 230 ℃ temperature and 2.16kgf, record and (hereinafter be expressed as (230 ℃ of MFR, 2.16kgf) the melt flow rate (MFR) of described propylene-ethylene-butene-1 multipolymer be 1-10g/10min, be preferably 1.5-8g/10min, more preferably 2-6g/10min.If MFR (230 ℃, 2.16kgf) be lower than 1g/10min, then vessel surface becomes coarse in its moulding process, thereby causes its transparency to reduce.If MFR (230 ℃, 2.16kgf) be higher than 10g/10min, then the low temperature impact strength of container will variation, and its flexible meeting is affected.
The content of propylene-ethylene-butene in described composition-1 multipolymer is the 70-99 weight part, be preferably the 75-97 weight part, 80-96 weight part more preferably, be preferably the 82-95 weight part especially, wherein, described propylene-ethylene-butene-1 multipolymer is 100 weight parts with the quantity that combines of ethene-alpha-olefin copolymer hereinafter described.If described propylene-ethylene-butene-1 multipolymer is lower than 70 weight parts, then the thermotolerance of container will variation.If described propylene-ethylene-butene-1 multipolymer is higher than 99 weight parts, then the low-temperature impact of container will be not enough.
Be used to prepare the method for described propylene-ethylene-butene-1 multipolymer, can be a kind of like this method, in this method, propylene, ethene and butene-1 are to carry out polymeric in the presence of a kind of polymerisation catalysts that contains transistion metal compound, and described method is disclosed among the JP-A-11-228629.These monomeric polyreactions for instance, can be solution polymerization, mass polymerization and vapour phase polymerization.These monomers can carry out polymerization by a kind of single polymerization process, perhaps alternatively, carry out polymerization by a kind of multi-stage polymeric process of being made up of the combination of these polymerization processs.Consider production cost, it is preferred using gas phase polymerization process.
Described ethene-alpha-olefin copolymer is represented ethene and contains the multipolymer of the alpha-olefin of 4-12 carbon atom that this multipolymer contains the structural unit that at least 50 weight % are derived from ethene.The content of structural unit that is derived from ethene is preferably up to 55 weight %, more preferably up to 60 weight %, more more preferably up to 65 weight %.The example of described alpha-olefin comprises butene-1,4-methylpentene-1, hexene-1, octene-1 and decylene-1.Preferred alpha-olefin is butene-1 and hexene-1.Described ethene-alpha-olefin copolymer (B) can be a kind of mixture by molecular weight or alpha-olefin kind two kind or the above kind ethene-alpha-olefin copolymers different with content.
The amount that contains the alpha-olefin of 4-12 carbon atom be generally 5 weight % or more than, be preferably 8 weight % or more than, more preferably 10 weight % or more than.
Under the load of 190 ℃ temperature and 2.16kgf, record and (hereinafter be expressed as (190 ℃ of MFR, 2.16kgf) the melt flow rate (MFR) of ethene-alpha-olefin copolymer be 0.1-50g/10min, be preferably 0.5-40g/10min, 1-30g/10min more preferably, 2-20g/10min more preferably again.
If MFR (190 ℃, 2.16kgf) be lower than 0.1g/10min, then the discrete particles of ethene-alpha-olefin copolymer will become coarse in the container, thereby causes the transparency of container poor.If MFR (190 ℃, 2.16kgf) be higher than 50g/10min, then the low temperature impact strength of container will become not enough.
The density of ethene-alpha-olefin copolymer is 865-898kg/m
3, be preferably 868-897kg/m
3, 870-896kg/m more preferably
3
If described density is lower than 865kg/m
3, then the density difference between ethene-alpha-olefin copolymer and propylene-ethylene-butene-1 multipolymer will become very big, and the transparency of container will variation.And, if described density is higher than 898kg/m
3, then the density difference between ethene-alpha-olefin copolymer and propylene-ethylene-butene-1 multipolymer also can become very big, and the transparency of container also can variation.
The preparation method of ethene-alpha-olefin copolymer can be a kind of like this method, in this method, ethene and alpha-olefin are to carry out polymeric in the presence of a kind of catalyzer (metallocene catalyst) that contains transistion metal compound, described transistion metal compound contains and comprises a kind of group that contains the Cyclopeutadiene type anion frame, and described method is disclosed among the JP-A-3-234717.These monomeric polyreactions can be known polymerization process, for instance, can be solution polymerization, slurry polymerization, vapour phase polymerization and high-pressure ion polymerization.
The main composition that is used for plastic containers of the present invention can contain: a kind of contain at least 90 weight % be derived from propylene structural unit crystalline polypropylene-ethylene copolymer and a kind ofly contain crystalline polypropylene-1-Butylene copolymer that at least 65 weight % are derived from the structural unit of propylene, unless effect of the present invention is affected.
Add low propylene-ethylene copolymers or propene-1-butene-1 multipolymer of MFR, can improve the low temperature impact strength of container.Add high propylene-ethylene copolymers or propene-1-butene-1 multipolymer of MFR, can improve the transparency of container.
Propylene-ethylene-butene-1 multipolymer and ethene-alpha-olefin copolymer total amount based on 100 weight parts, propylene-ethylene copolymers and propene-1-butene-1 multipolymer in conjunction with content, can be up to 30 weight parts, preferably can be up to 25 weight parts, more preferably can be up to 20 weight parts.
In propylene-ethylene copolymers, be derived from the content of the structural unit of ethene, be preferably 3-10 weight %, 3.5-8 weight % more preferably, and 4-7 weight % more preferably again.Be lower than 3 weight % if be derived from the content of the structural unit of ethene, then container tends to flexible variation.If content is higher than 10 weight %, then container tends to the thermotolerance variation.
In propene-1-butene-1 multipolymer, be derived from the content of the structural unit of butene-1, be preferably 3-35 weight %, 4-30 weight % more preferably, and 5-25 weight % more preferably again.Be lower than 3 weight % if be derived from the content of the structural unit of butene-1, then container tends to flexible variation.If content is higher than 35 weight %, then container tends to the thermotolerance variation.
The MFR that propylene-ethylene copolymers and propene-1-butene-1 multipolymer has (230 ℃, 2.16kgf) be 0.1-100g/10min, be preferably 0.3-50g/10min, more preferably 0.5-30g/10min.If MFR (230 ℃, 2.16kgf) be lower than 0.1g/10min, then vessel surface becomes coarse in its moulding process, thereby causes its transparency to reduce.The MFR (230 ℃ 2.16kgf) cause the container molding property handled poor, and container will have poor low temperature impact strength that are higher than 100g/10min.
The preparation method of propylene-ethylene copolymers and propene-1-butene-1, for instance, can be a kind of like this method, in this method, monomer is to carry out polymeric in a kind of containing in the presence of the transistion metal compound polymerisation catalysts, and described method is disclosed among the JP-A-11-228629.These monomeric polyreactions for instance, can be solution polymerization, mass polymerization and vapour phase polymerization.These monomers can carry out polymerization by a kind of single polymerization process, perhaps alternatively, carry out polymerization by a kind of multi-stage polymeric process of being made up of the combination of these polymerization processs.Consider production cost, it is preferred using gas phase polymerization process.
The composition that contains described propylene-ethylene-butene-1 multipolymer and ethene-alpha-olefin copolymer, except propylene-ethylene-butene-1 multipolymer and ethene-alpha-olefin copolymer, also can contain following additive, as talcum, lime carbonate, mica, glass fibre, carbon fiber, neutralizing agent, antioxidant, thermo-stabilizer, weathering agent (weathering agent), lubricant, the UV absorption agent, static inhibitor, release agent (antiblocking agent), antifogging agent, defoamer, dispersion agent, mould inhibitor (antifungus agent), white dyes, dyestuff and pigment are unless effect of the present invention is affected.
Based on propylene-ethylene-butene-1 multipolymer of 100 weight parts and ethene-alpha-olefin copolymer total amount in conjunction with quantity, additive be the 0.001-5 weight part in conjunction with quantity.
In one embodiment of the invention, plastic containers have the wall of being made up of single thin layer, described thin layer is to have as above the composition that the crystalline polypropylene-ethene-1-Butylene copolymer of the feature [1] of regulation and [2] and 1-30 weight part have an ethene-alpha-olefin copolymer of the feature [3] as above stipulated, [4] and [5] and make by containing the 70-99 weight part, wherein, two kinds of multipolymers is 100 weight parts in conjunction with quantity.In this case, the thickness of described composition thin layer roughly can determine according to the application of described container, does not do special restriction.
Another embodiment of the invention is about a kind of multilayer plastic container, and its wall is made of two or more thin layers, comprises the thin layer that at least one is made by described composition.Except that described composition thin layer, constitute the example of the material of one or more thin layers, comprise ethylene-vinyl alcohol copolymer, polyamide resin and pet resin.And, also can adopt the composition that makes by the circulation flash distillation thing (flashes) that in plastic containers moulding process of the present invention, produces.In multilayer plastic container, the thickness of wall roughly can determine according to the application of container, does not do special restriction.The thickness of the thin layer of making by main composition, be preferably described wall total thickness 30% or more than, more preferably 40% or more than, be preferably especially 50% or more than.
To the preparation method of container of the present invention be made an explanation below.Should be noted that, though will be mainly the preparation method of container with wall that the single thin layer made by described main composition forms be described, but laminated vessel also can make by using the multi-layer forming machine to use following instruction for the multi-layer forming technology.
Container of the present invention can be by mixing propylene-ethylene-butene-1 multipolymer, ethene-alpha-olefin copolymer and other composition if desired to obtain a kind of mixture, to mediate mixture and make to obtain the described composition of a kind of composition and moulding.
Be used to mix the method for propylene-ethylene-butene-1 multipolymer, ethene-alpha-olefin copolymer and other composition if desired, do not do special restriction.For instance, can adopt a kind of method of mixing described composition by means of conventional mixing device that comprises.
The example of described mixing device comprises Henschel mixing tank (trade(brand)name), Super mixing tank (trade(brand)name), ribbon blender and rotating cylinder (tumbler).
Be used to mediate from the method for mixing the mixture that propylene-ethylene-butene-1 multipolymer, ethene-alpha-olefin copolymer and other composition if desired obtain, do not do special restriction.For instance, can adopt mediate the method that device is mediated described composition a kind of comprising by means of routine.The example of described kneading device comprises single screw extrusion machine, multiple screw extruder, Banbury honey refining machine, kneader and roller mill.Mixing device can be connected with the device of container molding with the kneading device.
The condition of mediating is not done special restriction, unless in kneading process and shear-stress, the outside of resin molten resin in the long-time delay of mediating device apply heat and shear heat and obviously degenerate, perhaps form a kind of insufficient and inhomogeneous dispersion state.
The example of the method for moulding container of the present invention comprises jet moulding, compression molding, jet compression moulding method, pressure moulding method, vacuum moulding, extrusion-blown modling method, sprays blow moulding and spray the stretch-blow method.
In these technology, extrusion-blown modling method, injection blow moulding and injection stretch-blow method are preferred, and the extrusion-blown modling method is especially preferred.The container that is made by the extrusion blow-moulding method is suitable especially, and this is because they have good flexible, transparent, low temperature impact strength and thermotolerance.
As for the production of plastic containers of the present invention, can adopt conventional blow machine.For instance, a kind of blow machine has such zone, form blank at this place by following method: pass through a mould continuously or discontinuously, during the composition extrusion die of plasticating that will mediate in forcing machine was concrete, described mould had the shape of product inner chamber and blows the device of pressurized gas in the described mould cavity.Available have: the reciprocating type blow moulding machine of extruding, wherein mould to-and-fro movement between forcing machine and blow moulding machine; With rotary extrusion blow molding machine, wherein two or more moulds are installed on the horizontal or vertical circuit orbit and described mould is rotation continuously.
The summary of the method for use extrusion blow molding machine production plastic containers of the present invention is as described below.
To pack into raw material fusing in the forcing machine, and in the cylindrical shell of forcing machine, mediate, then by extruding the formation tubular blank in mould and the slit between the axle core that is installed on described extrusion machine one end.The blank of extruding is trapped between two half modules (they combine and limit cavity).Then, in blank, be blown into pressurized gas.Because the effect of described pressurized gas, described blank is formed as the shape of described mould cavity, and then cooling.Afterwards, open two half modules, eject the container that obtains.
A kind of preferred extrusion and blow molding method is as described below.
Mediate described raw material as for fusing, can adopt single screw rod, combined threaded rod, toothed gear pump etc.The blank continuously or intermittently can be extruded.Be used to form mould and the shape of axle core and the slit between material and described mould and described axle core of blank, do not do special restriction.Blank shrinks or the thickness distribution of amplification (blow up) ratio that makes described blank have to be suitable for being scheduled in order to prevent to extrude, and the thickness of blank can be controlled by means of the blank controller.In the extrusion of blank, can in blank, be blown into pressurized gas.People can clamp the bottom of extruding blank and be blown into pressurized air then in described blank.
Do not do special restriction for resin temperature, mold temperature, pressurized gas kind, blowing pressure and blowing time, unless effect of the present invention is affected.
Plastic containers of the present invention comprise the aforesaid composition that contains specific propylene-ethylene-butene-1 multipolymer and special ethylene-alpha-olefin copolymer.Therefore, described container has good shock strength, flexible and transparent, and discharges smell still less.And when they were heat-treated, they showed lower transparency reduction, and their surface can not become very sticking.So they are suitable for various application widely, for example, liquid package container, food container, containers for medical use, automatic utensil, household electrical appliance, mechanicals and groceries.In particular, they can be used as containers for medical use suitably, for example are used to hold and carry the container of soup such as blood ingredient solution, normal saline solution, electrolytic solution, dextran preparation, mannitol formulations, carbohydrate preparation, amino acid preparation and lipid microballoon.
Embodiment
Embodiment
The present invention will be by being described further referring to following embodiment.But the present invention is not restricted to these embodiment.
Be used for the evaluation method of described embodiment and comparative example, as described below.
1. melt flow rate (MFR) (MFR)
The MFR of propylene-ethylene-butene-1 multipolymer and propylene-ethylene copolymers (g/10min) is according to JIS K 7210, and Condition 14 records at 230 ℃.The MFR of resin combination (g/10min) also records under condition same as described above.The MFR of ethene-alpha-olefin copolymer (g/10min) records at 190 ℃ according to JIS K 6760
2. density (d)
Density (the kg/m of polymkeric substance
3) record according to JIS K 6760-1981.
3. modulus in flexure (FM)
The modulus in flexure of compressed moulding thin slice (MPa) records according to JIS K 7106.
4.IZOD shock strength (Izod)
The sample that has the V otch according to JIS K 7110 preparations.When through in thermostatted, depositing 24 hours or after the longer time, measure the IZOD shock strength (kJ/m of described sample in 0 ℃
2).
5. turbidity and transmittance
The turbidity (%) of the pressing mold thin slice that the 1mm that makes according to JIS K 6758 is thick and transmittance (%) record according to JIS K 7105.
6. the crash resistance of container
The 500g water of packing in container is fixed to the upper the polypropylene cap.When through in thermostatted, depositing 24 hours or after the longer time, described container was highly freely dropped on the concrete floor from 1.2m in 5 ℃, adopt described whereabouts container body weight multiple 10 times.Falling behind the situation of observing described container down through 10 times.10 test bottles with same structure are carried out identical test.The ratio (%) of damaged bottle number and whole test bottle numbers is used for representing to have the crash resistance of this class formation bottle.
7. the turbidity of container and transmittance
By cutting the centre portions of container, prepare a sample.Measure the turbidity (%) and the transmittance (%) of described sample according to JIS K 7105.
8. the thermotolerance of container
The suspension hook that use forms on described container bottom hangs container, and makes it to deposit 20 minutes in 121 ℃ in thermostatic chamber.Afterwards, with its cool to room temperature, and cut the centre portions of described container side wall.Like this, just make a sample.Record the turbidity (%) and the transmittance (%) of described sample according to JIS K 7105.
9. container viscosity
Use is formed on the suspension hook on the described container bottom, container is hung, and make it to deposit 20 minutes in 121 ℃ in a thermostatic chamber.Afterwards, with it room temperature cooling 24 hours, then, the centre portions by cutting described container body for the vertical 225mm of each size and laterally the rectangle of 50mm make two samples.These two samples are forced together by their outer surface layers, and have thereon under the situation of a bottom size size for the 9.5kg weight of 225mm * 50mm, make it in thermostatted, to deposit 3 hours in 60 ℃.Lower sample is fixed, and used anchor clamps at the fixing upper sample of one end.When tensile loading improves with 20gf/min speed, upper sample is pulled up.When described sample is peelled off, record tensile loading (gf/100cm
2).It is big more that institute's rheme is stretched load, and then its viscosity is big more.
10. melting heat
Use is by PerkinElmer, and the differential scanning calorimeter DSC-VII that Inc. makes makes the watery fusion curve of polymkeric substance according to preceding method, then calculates melting heat (J/g).
The polymkeric substance that is used for embodiment and comparative example is as described below.
1. propylene-ethylene-butene-1 multipolymer
Propylene-ethylene-butene-1 multipolymer (1):
MFR (230 ℃ 2.16kgf) are 3.8g/10min.The content that is derived from the structural unit of ethene is respectively 2.4 weight % and 6.8 weight % with the content that is derived from the structural unit of butene-1.The melting heat that is recorded by differential scanning calorimeter is 70.9J/g.
2. propylene-ethylene copolymers
Propylene-ethylene copolymers (1):
MFR (230 ℃ 2.16kgf) are 1.5g/10min.The content that is derived from the structural unit of ethene is 5.6 weight %.
3. ethene-alpha-olefin copolymer
Ethene-alpha-olefin copolymer (1):
A kind of by Sumitomo Chemical Co., ethene-hexene-1 multipolymer of the Excellen FX CX2001 by name that Ltd makes.This is a kind of multipolymer that makes in the presence of metallocene catalyst.(190 ℃ is that 2.0g/10min and density are 896kg/m 2.16kgf) to its MFR
3
Ethene-alpha-olefin copolymer (2):
A kind of by Sumitomo Chemical Co., ethene-hexene-1 multipolymer of the Excellen FX CX4002 by name that Ltd makes.This is a kind of multipolymer that makes in the presence of metallocene catalyst.Its MFR (190 ℃, 2.16kgf) be 8.0g/10min, its density is 883kg/m
3
Ethene-alpha-olefin copolymer (3):
A kind of by Sumitomo Chemical Co., Ltd makes ethene-hexene-1 multipolymer of Excellen FX CX5007 by name.This is a kind of multipolymer that makes in the presence of metallocene catalyst.Its MFR (190 ℃, 2.16kgf) be 17.7g/10min, its density is 875kg/m
3
Ethene-alpha-olefin copolymer (4):
A kind of by Sumitomo Chemical Co., ethene-1-Butylene copolymer of the Excellen VL VL100 by name that Ltd makes.This is a kind of multipolymer that makes in the presence of the Ti-Mg catalyzer.Its MFR (190 ℃, 2.16kgf) be 0.8g/10min, its density is 900kg/m
3
Ethene-alpha-olefin copolymer (5):
The Sumikathene-L by name a kind of by Sumitomo Chemical Co., that Ltd makes
Ethene-1-Butylene copolymer of FS250A.This is a kind of multipolymer that makes in the presence of the Ti-Mg catalyzer.Its MFR (190 ℃, 2.16kgf) be 1.8g/10min, its density is 922kg/m
3
Embodiment 1
The propylene-ethylene-butene of 94 weight parts-1 multipolymer (1) and 6 parts by weight of ethylene-alpha-olefin copolymer (1) mix, then add 0.01 weight parts water talcum DHT-4C (by Kyowa ChemicalIndustry Co., Ltd makes) and 0.1 weight part Irganox B220 (by Ciba SpecialtyChemicals manufacturing), and mix at Henschel mixer.The gained mixture is melted kneading in 230 ℃ temperature and the screw speed of 100rpm in having the single screw extrusion machine of perfect thread type screw rod that diameter is 40mm.Like this, just obtain a kind of resin combination.The MFR of resin combination is 3.9g/10min.The blending ratio of multipolymer and the MFR of composition are as shown in table 1.And the modulus in flexure that the pressing mold thin slice of being made by described resin combination has is 760MPa, and the Izod shock strength is 3.5kJ/m
2, transmittance is 89.1%, turbidity is 33.6%.Described thin slice has good flexible, the low temperature impact strength and the transparency.The physical properties of described compression molding thin slice is summarised among the table 3.
Use is by the Japan Steel Works, the blow molding machine NB3B that Ltd makes, and it has the perfect thread type screw rod that diameter is 50mm, and described resin combination is extruded and forms hot blank in mould and 210 ℃ of rates of extrusion with 5kg/h of axle core temperature.Hot blank is trapped between the mould that is controlled at 14 ℃, is that the pressurized air of 0.3MPa is blown in the described blank with pressure, continues 20 seconds.Like this, just can make one and have the container of linking up with in its bottom, described container weight is 28g, and its sidewall thickness is about 0.4mm, and its volume is 600ml, and its shape as shown in Figure 1.In Fig. 1, mark a, b and the c of height, length and the width of expression container are respectively 208mm, 94mm and 55mm.The transmittance of described container is 91.8%, and turbidity is 3.5%, and transmittance after heat treatment and turbidity are respectively 90.4% and 8.4%, and it peels off load and is 25.6g/100cm
2Described container has good flexible, transparent, thermotolerance and wholesomeness.The physical properties of hollow container is as shown in table 4.
Embodiment 2-6
According to embodiment 1 same procedure, mediate by fusing and to be selected from propylene-ethylene-butene-1 multipolymer of blending ratio as described in Table 1 and the multipolymer of ethene-alpha-olefin copolymer, prepare resin combination.And, also according to making container with embodiment 1 same procedure.The physical properties of the physical properties of described resin combination and the container made by described composition is summarised among table 3 and the table 4 respectively.These containers have good flexible, the transparency and thermotolerance, and show littler viscosity.
Comparative example 1-7
According to embodiment 1 same procedure, mediate by fusing and to be selected from propylene-ethylene-butene-1 multipolymer of blending ratio as described in Table 2 and the multipolymer of ethene-alpha-olefin copolymer, prepare resin combination.And, also according to making a kind of container with embodiment 1 same procedure.The physical properties of the physical properties of described resin combination and the container made by described composition is summarised among table 3 and the table 4 respectively.These containers have good flexible, and still, its shock strength, the transparency and viscosity degree are all relatively poor.
Table 1
Table 2
Table 3
Table 4
According to the present invention, can make a kind of plastic containers, it is flexible and has good low temperature impact strength that even it is heat-treated, its transparency also only has very little reduction, and it is very sticking can not become.
Claims (6)
1. plastic containers, its wall comprises the thin layer of being made by a kind of composition, described composition contains feature [1] and the crystalline polypropylene-ethene-1-Butylene copolymer of [2] and the ethene-alpha-olefin copolymer that the 1-30 weight part has feature [3], [4] and [5] that the 70-99 weight part has following regulation, wherein, two kinds of multipolymers is 100 weight parts in conjunction with quantity:
[1] the structural unit content that to have the structural unit content that is derived from propylene be 70-97 weight %, be derived from ethene is that 1-10 weight % and the structural unit content that is derived from butene-1 are 2-20 weight %,
[2] having the melt flow rate (MFR) that records under the load of 230 ℃ temperature and 2.16kgf is 1-10g/10min,
[3] for a kind of ethene with contain the multipolymer of 4-12 carbonatom, described multipolymer have the structural unit that is derived from ethene be 50 weight % or more than,
[4] have the melt flow rate (MFR) that under the load of 190 ℃ temperature and 2.16kgf, records be 0.1-50g/10min and
[5] density that has is 865-898kg/m
3
2. the described container of claim 1, wherein, described propylene-ethylene-butene-1 multipolymer satisfies following formula (1):
x+1＜y (1)
Wherein, x represents to be derived from the content of the structural unit of ethene, and y represents to be derived from the content of the structural unit of butene-1, by weight percentage.
3. claim 1 or 2 described containers, wherein said wall is made up of a single thin layer of being made by described composition.
4. claim 1 or 2 described containers, wherein said wall comprises that by two or more at least one is made by described composition that the thin layer of thin layer forms.
5. claim 1 or 2 described containers, wherein said container makes by extrusion and blow molding.
6. claim 1 or 2 described containers, wherein said container is a kind of containers for medical use.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003-206727 | 2003-08-08 | ||
| JP2003206727 | 2003-08-08 | ||
| JP2003206727 | 2003-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1590450A CN1590450A (en) | 2005-03-09 |
| CN100427541C true CN100427541C (en) | 2008-10-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100563506A Expired - Fee Related CN100427541C (en) | 2003-08-08 | 2004-08-06 | Plastic container |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20050042401A1 (en) |
| CN (1) | CN100427541C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090136758A1 (en) * | 2005-09-01 | 2009-05-28 | Sumitomo Chemical Company, Limited | Non-mutually-adhesive pellet, process for producing non-mutually-adhesive pellet, and process for producing rubber molding |
| CA2956454A1 (en) * | 2014-08-01 | 2016-02-04 | The Coca-Cola Company | Small carbonated beverage packaging with enhanced shelf life properties |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001219518A (en) * | 2000-02-08 | 2001-08-14 | Showa Denko Plastic Products Co Ltd | Laminated film |
| JP2003103727A (en) * | 2001-09-28 | 2003-04-09 | Showa Denko Plastic Products Co Ltd | Laminate, sealant film and container |
| CN1410261A (en) * | 2001-09-28 | 2003-04-16 | 昭和电工塑料产品株式会社 | Laminate, Sealing film and container |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382631A (en) * | 1988-09-30 | 1995-01-17 | Exxon Chemical Patents Inc. | Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions |
| JP3258830B2 (en) * | 1994-09-29 | 2002-02-18 | 株式会社興人 | Polyolefin-based heat-shrinkable laminated film |
| SG87876A1 (en) * | 1998-12-25 | 2002-04-16 | Sumitomo Chemical Co | Propylene based resin composition |
| BE1012775A3 (en) * | 1999-07-06 | 2001-03-06 | Solvay | Flexible polymer compositions propylene. |
-
2004
- 2004-07-30 US US10/902,050 patent/US20050042401A1/en not_active Abandoned
- 2004-08-06 CN CNB2004100563506A patent/CN100427541C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001219518A (en) * | 2000-02-08 | 2001-08-14 | Showa Denko Plastic Products Co Ltd | Laminated film |
| JP2003103727A (en) * | 2001-09-28 | 2003-04-09 | Showa Denko Plastic Products Co Ltd | Laminate, sealant film and container |
| CN1410261A (en) * | 2001-09-28 | 2003-04-16 | 昭和电工塑料产品株式会社 | Laminate, Sealing film and container |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1590450A (en) | 2005-03-09 |
| US20050042401A1 (en) | 2005-02-24 |
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