CN1666856A - Multi-layered membrane capable of sterilizing by heating - Google Patents
Multi-layered membrane capable of sterilizing by heating Download PDFInfo
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- CN1666856A CN1666856A CN 200410028395 CN200410028395A CN1666856A CN 1666856 A CN1666856 A CN 1666856A CN 200410028395 CN200410028395 CN 200410028395 CN 200410028395 A CN200410028395 A CN 200410028395A CN 1666856 A CN1666856 A CN 1666856A
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Abstract
The invention relates to the multi-layer film of heat killing bacteria, which is composed of the external, the middle and the internal layers. The film does not contain the industrial additive or chemical modifier and produces minimum influence on the medical solution in the capsule, and it can implement safe melting and jointing. It has strong blocking performance to the steam and the small influence on the pH value of the substances. In addition, it does not contain PVC and plastic reinforcing agent.
Description
Technical field
Plural layers can be processed into soft capsule bag, and are suitable for encapsulating and hold soup with the shape of this seed capsules bag.At present commonly used is with soup, as is used for the disposable sack that the outer input liquid that absorbs of intestines is packed into and made by polyvinyl chloride-(PVC) or non-PVC material.
This seed capsules bag can guarantee that except having sack flows empty compressed capability fully, also must satisfy other performance standards, as transparency, pasteurization ability under 121 ℃ of temperature at first has enough mechanical strengths under line load in the commissure, well the steam blocking capability, be used for common wiper seal circle, bearing capacity during as pressure injection, and from the viewpoint of pharmaceutics, as far as possible little by the influence that encapsulates contained thing in the capsule bag of back.For being adapted to above-mentioned character, it is favourable selecting a kind of layer structure based on polyolefinic plural layers for use.But the defective of this polyolefin film is, when welding will with the contacted skin of welding workpiece of heat, with and bag staggered relatively side on internal layer of the same race or valve gear member (Portelement) only exist very trickle temperature contrast between the internal layer of welding mutually.This very trickle temperature contrast will cause membrane structure more or less even softening fully, and therefore can produce loss road (WegflieBen) phenomenon of uncontrollable each layer when applying fusion pressure in the melting zone.Generally this makes the welding result have defective.In addition, generally the polyacrylic copolymer of using as matrix material is to lack impact flexibility, thereby makes when taking place such as the capsule bag situation that accident falls from Infusion support, and the dynamic load ability just seems not enough and the capsule bag can be torn near weld bond.
Brief summary of the invention
The present invention relates to a kind of coextrusion, and do not contain industrial auxiliary agent and/or chemical modifier, and can utilize the burning-on method that continues heating to come welding, but and in general heat sterilization process, be used as welding medicinal fluid bag sterilization, based on polyolefinic multilayer film.This multilayer film has following character, promptly particularly, can carry out safe welding and do not have tiny leakage or even when in bag, valve gear member being arranged, also can not come off, and from the pharmaceutics angle, consequently as far as possible little to the influence of leaving the soup in the bag in.In addition, feature of the present invention also is to have very high steam blocking capability, and the situation that liquid loss that therefore can make between preservation term to be occurred and the active material that causes thus concentrate is reduced to minimum.Another advantage is to make the pH value of content in the capsule bag only be subjected to influencing this and can present seldom when pasteurization is handled by multilayer film and/or valve gear member.Multilayer film is not contain PVC also not contain the plasticizer that is generally used among the PVC, but contains the polyacrylic terpolymer as key component.
Prior art
Multilayer film has used for many years, for example, and in food industry, and at medical science, pharmaceutical field, many Tunic is used for solution bag or is used for dry dense as second encapsulating material (comprehensively encapsulation) and first encapsulating material The purposes of the medicine of contracting thing or tablet form also is long-standing. In the last few years, except tradition use soft Outside the PVC film, recently also with the solution of non-PVC multi-layer film for the production of above-mentioned medical science, pharmaceutical use Bag.
The film that is used for above-mentioned solution bag in the market all has the shortcoming of steam blocking capability difference, and/or the welding of above-mentioned valve gear member is not enough, and often owing to this valve gear member makes the mobile degree of pH value when the heat kill bacterium too high, so just can not or be difficult to be applicable to, particularly the capsule bag of small size.
In DE19515254C2, put down in writing a kind of PVC that do not contain, but pasteurization is handled and is handled the immovable basically multilayer film of back performance at pasteurization under at least 121 ℃.It has a skin, and supporting course and at least one are positioned at intermediate layer between the two, and wherein, outer and supporting course is understood fusion when being higher than 121 ℃, and shows that the vicat softening temperature of polymer is higher than about 121 ℃.Wherein at least one intermediate layer is by polyacrylic homopolymers or copolymer, LDPE, and the SEBS-block copolymer, SIS, the mutual mixture of PIB and/or above-mentioned polymer, perhaps and have 〉=0.9g/cm
3Density and its vicat softening temperature be lower than about 70 ℃ polypropylene and form jointly together.Skin and supporting course are between 1: 4.5 to 1: 9 for the thickness ratio in intermediate layer.
A kind of plural layers in DE19615254C2, have also been put down in writing, it constitutes: the thin polymeric outer layer of being made up of polyacrylic homopolymers or copolymer analog, at least one is by a) polyacrylic homopolymers and/or copolymer and b) tack coat that constitutes of the polypropylene composite formed of at least a thermoplastic elastomer (TPE) and/or mixture, and a kind of heat sealable and by c) a kind of polyacrylic homopolymers and/or copolymer and d) the polypropylene composite internal layer that constitute and that tack coat is close to formed of at least a thermoplastic elastomer (TPE).This wherein, the gradient that the fusing point of thin layer exists a kind of temperature of layer from outside to inside to descend, thus make that when standing temperature action the fusion of internal layer will be early than outer and take place.
Defective among the DE19615254C2 is by using polyacrylic homopolymers or copolymer, to seem too small in the temperature difference described in the fusion process, and particularly can not realize safe welding when utilizing hard part (Hartteil).In addition, use polyacrylic homopolymers or copolymer if use the skin of virgin pp in the intermediate layer, when then having only component when thermoplastic elastomer (TPE) very high, or as be shown in the examples, in addition obviously used plasticizer after, maybe can obtain enough impact flexibility.But this has also caused the deficiency of steam and air blocking capability.
A kind of plural layers in EP0229475B1, have been put down in writing with two mutual bonding layers, wherein ground floor is by a kind of polypropylene, poly copolymer and a kind of modifier are formed, and the second layer is made up of polypropylene and a kind of modifier of modifier that is different from the ground floor.These plural layers also optionally have bonding and the 3rd layer of being made up of polypropylene and a kind of modifier with the second layer.Described structure is owing to used the polyethylene composition in outer and intermediate layer, therefore in relevant weldable, but the transparency and bactericidal properties aspect have obvious defects.In addition, first, second and the interlayer bonding quality between possible the 3rd layer also are shortcomings.
The plural layers of putting down in writing among the EP0199871B1, it contains as outer field polyacrylic copolymer or flexible polyester, as the polymeric material in intermediate layer and as the polyacrylic copolymer of internal layer, a kind of polyacrylic copolymer or flexible polyester of modification.If use flexible polyester, then these plural layers are involved is not based on pure polyolefin-based film.In addition, in order in the intermediate layer, to obtain the interlayer bonding effect between necessary and the pure polyolefin polymer, just need an adhesive layer in addition again.And if use internal layer and/or the skin of the copolymer of polyacrylic copolymer or modified polypropene as membrane structure, then unfavorable to weldability.
But put down in writing a kind of multilayer film of high frequency welding among the WO9513918, it has the ground floor be made up of polyacrylic copolymer and SEBS-block copolymer and by the bonding ground floor and the second layer be made up of polypropylene, non-polypropylene polyolefin, a kind of polymer that is vulnerable to excite in the RF district and a kind of polymer compatibility agent.Because above-mentioned membrane structure, and particularly owing to used polypropylene copolymer and SEBS-block copolymer in one of in two-layer, so need enough can hot bactericidal properties and the situation of transparency under, can not utilize the burning-on method that continues heating to process processing reliably to described film.Contain chemical modifier and a kind of polymer that is vulnerable to excite in the RF district one of in two-layer, and their can be discharged into impurity in the solution of splendid attire in the capsule bag.
The plural layers of being put down in writing in EP0738589B1 have 2 to 5 layers.Ground floor comprises a kind of by mixture that polyacrylic homopolymers or copolymer and elastomer constituted.Adhere to that the second layer on the ground floor then includes a kind of homogeneous and its density is less than or equal to 0.89g/cm
3Ethylene/alpha-olefin-copolymer.This second layer is obviously as tack coat and make on the second layer and to adhere to the 3rd layer.And the every other layer of describing as preferred forms comprises polyethylene, ethylene/vinyl acetate copolymer, ethylene/methacrylic acid ester copolymer, ethylene/alpha-olefin copolymer, anhydride modified binding agent, polyamide, copolyamide or polyester.Described two-layer film configuration is defective, because the ethylene/alpha-olefin copolymer of homogeneous has just reached its fusing point when temperature＜100 ℃, therefore and consider in quality to be impossible with this membrane structure as the solution bag of welding, particularly when carrying out the vapours sterilization processing under 121 ℃.
Put down in writing a kind of among the EP0380145 by ground floor and the multilayer tablet that the second layer constituted that adheres on the ground floor.Wherein ground floor is by polyacrylic homopolymers or copolymer, and a kind of polymer by part ethene and propylene and butylene combined polymerization prescription, it makes layer have elastic performance, and a kind of layer that also can provide is formed with the modifier of elastic performance.The second layer then is by a kind of polymer, paper or metal forming constituted.The polymer that constitutes the second layer is by polyamide, orientation polyamide, and oriented polypropylene (OPP) or oriented polyester are formed.The polymer of the second layer can be only with suitable bonding or tack coat and mutually bonding with the ground floor of the multilayer tablet of this invention.Consider that from pharmaceutics these binding agents or tack coat can become problem owing to its component is transferred in the interior soup of solution bag.In addition, compare smaller interlaminar bonding effect with the coextrusion structure, can under the use occasion of different medicinal fluid bags, bring problem.In addition, the vinyl component of sealant also can cause temperature tolerance too small, and this will cause in possible sterilization process, produces with the contacted internal layer of packing down at 121 ℃ and hinders sealing.
In EP0301773A2, put down in writing a kind of multilayer film with layer 2-4.All each layers are by random copolymer of propylene, ethene-butene-1 copolymer and may be able to provide the three one-tenth branch of elastic property to form.Because all each layers all have this similar constituent, therefore this film has only very trickle temperature difference between skin and sealant.This point has reliable fusion process constant and high-quality welding effect with regard to being unfavorable for reaching especially.
Put down in writing a kind of packaging film among EP0803352 and the EP0588223A2, it comprises a sealant and a carrier layer that is made of thermoplastic polymer that a kind of mixture of being made up of polypropylene terpolymer and vinyl polymerization product constitutes.The composition of described sealant has the fusing point that is near or below corresponding sterilization temperature (121 ℃), and therefore membrane structure particularly has the trend that produces the insoluble obstruct phenomenon of uncontrollable internal layer in the marginal zone of sack when sterilization processing.In addition, the vinyl polymerization product exists with fusion phase state under 121 ℃ sterilization temperature, and sealant also contacts with regard to content in direct and the capsule bag simultaneously.This is very problematic from pharmaceutics.
The multilayer film of being put down in writing among the WO98/36905, its structure by one outer and with bag in the contacted internal layer of content, and a lot of intermediate layer that is arranged between the ectonexine constitutes.Its ectomesoderm is made up of polypropylene, and internal layer is made up of polyethylene or polyethylene and ethylene copolymers.The a lot of intermediate layers that are arranged between the ectonexine have nothing in common with each other, and its difference is that the softening point of ethylene contents and used polymer is different.Because a lot of intermediate layers is arranged, so membrane structure is very complicated, and its performance also influences each other because of the adhesion strength of each layer.On the bed boundary of each layer, might produce layering effect, and this can produce negative influence to the physical property of film.For the temperature stability that is suitable for the common heating sterilization process to the selection of polyethylene in the internal layer or poly copolymer requirement as strictness.
Put down in writing a kind of multi-layer flexible pipe among the EP0380270A2, it is by an intermediate layer of being made up of the polyethylene and ethylene copolymers that can give the flexible pipe flexibility or polyvinyl chloride or polyvinylidene chloride, and a stable on heating internal layer and a skin of being made up of polypropylene or modified polypropene copolymer constitute.This structure with stable on heating internal layer is the safe welding that is not suitable for the capsule bag.Do not have under the situation of PVC requiring to some extent, employed intermediate layer material is not suitable for common pasteurization.
Put down in writing a kind of thermally-sterilized medical hollow bag among the EP0765654B1.It has one by intimal surface that matrix-phase-polymeric system constituted, and this wherein matrix polymer be a kind of Natene or polyacrylic homopolymers or polyacrylic copolymer, and the gathering compound is a kind of styrene block copolymer and/or a kind of ethene-alpha-olefin copolymer.This membrane structure is the most uncertain.When carrying out heat-sterilization process, the non-mutually bonding character on this internal layer surface can cause very poor and have only when the material combination that just can make sealing under high-temperature very on the physical property, this will be when solution bag carries out welding, particularly when using hard-valve gear member, formation do not have firm welding and thereby dangerous weld seam, and membrane structure can not receive damage owing to very high melting welding temperature.
Purpose of the present invention
In view of above-mentioned cited prior art and the defective that links to each other with these prior aries, but therefore task of the present invention be to provide a kind of utilize continue heat welded method and valve gear member also can safe welding and the pasteurization sterilization, based on the polyolefinic multilayer film of no plasticizer.This film is seen the as far as possible little soup that has influence on from the pharmaceutics angle, and has very high steam blocking capability.
Detailed content
The solution of task noted earlier is the kind that is that a kind of beginning is addressed, and the multilayer film with the described feature of claim 1 characteristic.It preferred embodiment then is the content of the dependent claims under the claim 1.Task of the present invention also is the purposes of claim 7 and 8 described films.
According to the present invention, multilayer film has three at least without the bonding mutually layer of binding agent, promptly satisfies skin, intermediate layer and the internal layer of certain specific function.In a special embodiment, the material component of intermediate layer and internal layer is identical.
Multilayer film is further being processed in the process of encystation bag, outer can contacting on surface direct and the welding workpiece, and therefore need very high melt temperature.According to the present invention, skin is made up of polyacrylic homopolymers, and particularly utilizes styrene-ethylene/butylene-block copolymer of 0-30% or styrene-ethylene/propylene-based block copolymer to carry out modification and improve impact flexibility at low temperatures.Preferred skin contains styrene-ethylene/butylene-block copolymer of 5-10%.Outer physical property aspect relevant impact flexibility is obviously will be inferior to internal layer especially at low temperatures.For this reason, outer field layer thickness will preferably be at most 9% of total film thickness.
Biggest quality part is occupied in the intermediate layer in multilayer film, and is used to improve integrally-built impact flexibility.This layer contains polyacrylic terpolymer and/or the random heterophasic copolymer of polypropylene of 20-80%, the poly copolymer of 0-40%, styrene-ethylene/butylene of 0-60%-block copolymer or styrene-ethylene/propylene-block copolymer.
The internal layer of multilayer film must be itself and embed valve gear member reliably, and can be carrying out as far as possible little temperature and weld interval welding, but and will be sterilizing under greater than 121 ℃ temperature.In order to make membrane structure bear structural stress as few as possible, can have lower melting welding temperature be exactly particular importance.According to the present invention, internal layer is made of polyacrylic terpolymer and/or propylene copolymer, and to utilize styrene-ethylene/butene block copolymer of 5-50% or styrene-ethylene/propylene-based block copolymer to carry out modification especially at low temperatures, to improve impact flexibility.Internal layer preferably is made up of the polyacrylic terpolymer of 70-80% and styrene-ethylene/butene block copolymer of 20-30%.
Have the intermediate layer of same composition and internal layer and as the flexible program of particular embodiment, because its homogeneous texture in the bed boundary particularly, and having advantage aspect layering and the impact flexibility.
Multilayer film is produced by coetrusion, and preferred water cools off rapidly.
What particularly the polymeric material of all each layers all is suitable for is that they are not contain industrial additive and/or chemical modifier and plasticizer, as mineral oil.Like this, by this encapsulating material, multilayer film just only can produce minimum possible influence to soup in sterilization processing and storage.
Multilayer film is exactly the barrier effect of multilayer film for the liquid loss as a major criterion of first encapsulating material of soup.Because this liquid loss, the solution active material will produce concentration phenomena, thereby has just surpassed unallowed certain level value.This liquid loss has just determined the service life of product.The selection of multilayer film form will make can obtain extraordinary steam blocking capability again when better impact flexibility is arranged.
Illustrate:
So-called " multilayer film " refers to the thermoplastic with the layer of a plurality of coextrusion, and these layers are mutually with continuous weld seam bonding.
So-called " polyacrylic terpolymer " is characterized in that a kind of other two kinds of polypropylene molecular chain that monomer carries out modification of utilizing in polymerization process.
So-called " polyacrylic copolymer " is characterized in that a kind of polypropylene molecular chain of utilizing another kind of copolymer to carry out modification in polymerization process.
So-called " polyacrylic homopolymers " is characterized in that generally only containing the polymer of propylene as element.
So-called " poly copolymer " is meant ethylene/alpha-olefin copolymer, and this polymer normally obtains by one or more alpha-olefin modifications in ethylene polymerization.Ethylene/alpha-olefin copolymer generally has 0.86 to 0.94g/cm
3Density range.
So-called " styrene-ethylene/butene block copolymer and styrene-ethylene/propylene-based block copolymer " is meant that those use common methods that polypropylene is carried out impact-modified synthetic thermoplastic elastomer.
So-called " polyolefin " is meant with olefin homo, the olefin polymer that the terpolymer form of the copolymer of alkene and alkene exists and above-mentioned polymer-modified.
So-called " impact flexibility " is meant the character of material opposing dynamic load(loading).
The rete that so-called " layering " is meant each bonding is because of getting loose of being subjected to that external influence factor produces.
So-called " impact modifying agent " is meant those by being blended into molten condition, and improves the polymeric material of polypropylene impact flexibility, as styrene-ethylene/butene block copolymer.
So-called " the random heterophasic copolymer of polypropylene " is meant a kind of multiphase polymer structure by polypropylene matrix and rubber phase.
Description of drawings
Fig. 1 is the cross-sectional view of multilayer film of the present invention.
Outer 1 has the highest temperature tolerance in the whole membrane structure, and is made of the polyacrylic homopolymers with one or more impact modifying agent modifications.It is that direct and hot welding workpiece is contacted in its surface in fusion process.
PP terpolymer and one or more impact modifying agents are contained in intermediate layer 2.This layer determined the impact flexibility of multilayer film.
Internal layer 3 is made of PP terpolymer and/or PP copolymer and one or more impact modifying agents.This layer is used under alap temperature, carries out fast sealing with the air flue member of capsule bag side staggered relatively or embedding.
Below will further elaborate the present invention according to embodiment.
Embodiment 1:
Outer :-97%PP 41E4 cs278, Huntsman company, the polyacrylic homopolymers of USA/-3%Tuftec H1062, Asahi, the described composition of Japan/styrene-ethylene/butene block copolymer mixes with molten condition with the composite steps of separating, and for further using granulation.
Intermediate layer :-75%TD 120 BF, Borealis, Austria/ter-polymers-20%Tuftec H 1062, Asahi, Japan/styrene-ethylene/butene block copolymer-5%Engage 8003, DOW, USA/ vinyon
Described composition mixes with molten condition with the composite steps of separating, and for further using granulation.
Internal layer :-85%TD 120 BF, Borealis, Austria/terpolymer-15%Tuftec H1062, Asahi, the described composition of Japan/styrene-ethylene/butene block copolymer mixes with molten condition with the composite steps of separating, and for further using granulation.
Normally used operating parameter is having the coextrusion system film on the film device that is blow molded into of water-cooled processing in the production of use polypropylene.
Film is made the gross thickness of 200 μ m, and the thickness of its ectomesoderm and internal layer is 15 μ m, and intermediate layer thickness is 170 μ m.
But prepared film is the vapours sterilization, and can utilize the welding workpiece that has been heated to 125 ℃ to carry out firm welding.
Embodiment 2:
Outer :-97%PP 41E4 cs278, Huntsman company, the polyacrylic homopolymers of USA/-3%Tuftec H1062, Asahi, the described composition of Japan/styrene-ethylene/butene block copolymer mixes with molten condition with the composite steps of separating, and for further using granulation.
Intermediate layer :-75%TD 120 BF, Borealis, Austria/ter-polymers-20%Tuftec H 1062, Asahi, Japan/styrene-ethylene/butene block copolymer-5%Engage 8003, DOW, USA/ vinyon
Described composition mixes with molten condition with the composite steps of separating, and for further using granulation.
Internal layer :-75%TD 120 BF, Borealis, Austria/terpolymer-20%Tuftec H1062, Asahi, Japan/styrene-ethylene/butene block copolymer-5%Engage 8003, DOW, USA/ vinyon
Described composition mixes with molten condition with the composite steps of separating, and for further using granulation.
Embodiment 3:
Outer :-97%PP41E4 cs 278, Huntsman company, the polyacrylic homopolymers of USA/-3%Tuflec H1062, Asahi, Japan/styrene-ethylene/butene block copolymer
Described composition mixes with molten condition with the composite steps of separating, and for further using granulation.
Intermediate layer 80%Excellen EPX EP.3721, Sumitomo, Japan/random heterophasic copolymer-20%Engage 8003, DOW, USA/ vinyon
Internal layer-75%TD 120 BF, Borealis, Austria/terpolymer-20%Tuftec H1062, Asahi, Japan/styrene-ethylene/butene block copolymer-5%Engage 8003, DOW, USA/ vinyon
Described composition mixes with molten condition with the composite steps of separating, and for further using granulation.
Use the common operating parameter of using in the polypropylene production having the coextrusion system film on the film device that is blow molded into of water-cooled processing.
Film is made the gross thickness of 200 μ m, and wherein outer field thickness is 15 μ m, and centre/interior layer thickness is 185 μ m.
But prepared film is the vapours sterilization, and can utilize the welding workpiece that has been heated to 125 ℃ to carry out firm welding.
Claims (8)
1. but multilayer film pasteurization and that form by skin, intermediate layer and an internal layer, it is characterized in that skin is made of the polyacrylic homopolymers with one or more impact modifying agent modifications, the intermediate layer contains the polyacrylic terpolymer and/or the random heterophasic copolymer of polypropylene of useful one or more impact modifying agent modifications, and internal layer is by polyacrylic terpolymer and/or polyacrylic copolymer with one or more impact modifying agent modifications.
2. multi-layered membrane capable of sterilizing by heating as claimed in claim 1 is characterized in that, internal layer and intermediate layer have identical materials and form.
3. multi-layered membrane capable of sterilizing by heating as claimed in claim 1 is characterized in that impact modifying agent is selected from styrene-ethylene/butene block copolymer or styrene-ethylene/propylene-based block copolymer, polyethylene and ethylene copolymers, polyethylene plastomers.
4. multi-layered membrane capable of sterilizing by heating as claimed in claim 1 is characterized in that, the gross thickness of multilayer film at 50 μ m between the 350 μ m.
5. multi-layered membrane capable of sterilizing by heating as claimed in claim 1 is characterized in that, multilayer film is flat film or hose membrane.
6 multi-layered membrane capable of sterilizing by heatings as claimed in claim 1 is characterized in that, multilayer film is by coetrusion production.
As one of claim 1-6 can thermally-sterilized multilayer film, it is characterized in that this film is used to produce medical bag.
8. as the multi-layered membrane capable of sterilizing by heating of one of claim 1-6, it is characterized in that this film is used to produce the capsule bag of medical multi-cavity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410028395 CN1666856A (en) | 2004-03-11 | 2004-03-11 | Multi-layered membrane capable of sterilizing by heating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410028395 CN1666856A (en) | 2004-03-11 | 2004-03-11 | Multi-layered membrane capable of sterilizing by heating |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010164747 Division CN101913277B (en) | 2004-03-11 | 2004-03-11 | Multilayer film capable of heat sterilization |
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| CN1666856A true CN1666856A (en) | 2005-09-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018058354A1 (en) * | 2016-09-28 | 2018-04-05 | Dow Global Technologies Llc | Multilayer film and pouch with same |
| CN109535544A (en) * | 2018-10-08 | 2019-03-29 | 福建鸿利印刷材料工贸有限公司 | A kind of multi-functional high-intensity packing film and preparation method thereof |
| CN112584815A (en) * | 2018-08-21 | 2021-03-30 | 费森尤斯卡比德国有限公司 | Transfusion bag |
-
2004
- 2004-03-11 CN CN 200410028395 patent/CN1666856A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018058354A1 (en) * | 2016-09-28 | 2018-04-05 | Dow Global Technologies Llc | Multilayer film and pouch with same |
| CN110072698A (en) * | 2016-09-28 | 2019-07-30 | 陶氏环球技术有限责任公司 | Multilayer film and its sack |
| US11059257B2 (en) | 2016-09-28 | 2021-07-13 | Dow Global Technologies Llc | Multilayer film and pouch with same |
| CN110072698B (en) * | 2016-09-28 | 2022-04-15 | 陶氏环球技术有限责任公司 | Multilayer film and bag thereof |
| CN112584815A (en) * | 2018-08-21 | 2021-03-30 | 费森尤斯卡比德国有限公司 | Transfusion bag |
| CN109535544A (en) * | 2018-10-08 | 2019-03-29 | 福建鸿利印刷材料工贸有限公司 | A kind of multi-functional high-intensity packing film and preparation method thereof |
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Application publication date: 20050914 |