CN1058453C - Multilayer film and container - Google Patents

Multilayer film and container Download PDF

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Publication number
CN1058453C
CN1058453C CN93120900A CN93120900A CN1058453C CN 1058453 C CN1058453 C CN 1058453C CN 93120900 A CN93120900 A CN 93120900A CN 93120900 A CN93120900 A CN 93120900A CN 1058453 C CN1058453 C CN 1058453C
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layer
density
weight
ethylene
resin
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CN1089549A (en
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渡边克司
冈本英志
谷口裕久
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Otsuka Pharmaceutical Factory Inc
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Otsuka Pharmaceutical Factory Inc
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Priority claimed from PCT/JP1994/000245 external-priority patent/WO1995022456A1/en
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Abstract

A multilayer film according to the present invention is a 5-layer film consisting of ethylene alpha -olefin copolymer, and the densities of resin constituting the layers are as follows starting with the outermost: first layer: 0.935-0.950 g/cm<3>, second layer: not more than 0.920 g/cm<3>, third layer: 0.925-0.950 g/cm<3>, fourth layer: not more than 0.920 g/cm<3>, fifth layer: 0.925-0.940 g/cm<3>. A container according to the present invention is molded by using this multilayer film and has high thermal resistance, blocking resistance, tensile strength, flexibility and transparency. Therefore, the multilayer film and container according to the present invention are suitably used for medical purposes.

Description

Plural layers and container
The present invention relates to plural layers and use it and the container that is shaped.In more detail, relate to, particularly as the container of storing medicinal liquid and blood etc. at medical field.
As medical multi-layered container always, can enumerate the container that constitutes by following polythylene resin.
* the spy opens clear 62-64363 *
Be made of straight-chain low density polyethylene, the density of ectonexine is 0.920g/cm 3More than, the not enough 0.920g/cm of the density in intermediate layer 3Trilaminar bag.
* the spy opens clear 63-248633 *
By 3 layers of container that straight-chain low density polyethylene constitutes, the density of ectonexine is 0.910-0.940g/cm 3, the density in intermediate layer is 0.880-0.905g/cm 3, both density contrasts are 0.01g/cm 3More than.
* the spy opens flat 3-277365 *
Outer is 0.920g/cm by density 3Above straight-chain low density polyethylene, the intermediate layer is 0.915g/cm by density 3Following straight-chain low density polyethylene, internal layer is 0.918g/cm by density 33 layers of bag that above side chain low density polyethylene (LDPE) constitutes.
* the spy opens flat 4-266759 *
Is 0.930g/cm by ectonexine in density 3The density of mixing 5-40% in the following long-chain side chain low density polyethylene (LDPE) is 0.945g/cm 3The resin of above high density polyethylene (HDPE), the intermediate layer is 0.920g/cm in density 3Mix the bag more than three layers that the poly resin of above-specified high density more than 15% constitutes in the following straight-chain low density polyethylene.
But, at least a following shortcoming is arranged on the above-mentioned article.
* because ectonexine constitutes with ldpe resin,, in the sterilization process under high temperature conditions such as autoclaving and hot water sterilization, sealing intensity and landing intensity have been reduced so thermostability is insufficient.
* after the sterilization of above-mentioned hot conditions, be easy to adhere.
* in order to keep all intensity of thin film, must increase thickness.
* because hot strength is not enough, can not improve bag speed.
* in heated sealant, because heating-up temperature can not be too high, so can not finish sealing at short notice.
* after sterilization or the like, the transparency and flexibility descend.
Therefore, the object of the present invention is to provide overcome above-mentioned shortcoming fully be suitable for medical thin film and container.
To achieve the above object, are 5 layer films that constitute by ethylene according to the feature of plural layers of the present invention, constitute the density of the resin of each layer, begin by skin be in turn:
The 1st layer: 0.935-0.950g/cm 3
The 2nd layer: 0.920g/cm 3Below
The 3rd layer: 0.925-0.950g/cm 3
The 4th layer: 0.920g/cm 3Below
The 5th layer: 0.925-0.940g/cm 3
In addition, in the plural layers of the invention described above, the density that also can mix below 10% weight in the 5th layer of resin is 0.945g/cm 3Above ethylene.
Further, in the plural layers of the invention described above, the resin that constitutes the 2nd layer and the 4th layer preferably
(1) density by 40-60% weight is 0.900-0.920g/cm 3Ethylene, the density of 40-60% weight is less than 0.900g/cm 3Ethylene ' alpha '-olefin class elastomer and be 0.955g/cm less than the density of 5% weight 3The hybrid resin that above high density polyethylene (HDPE) constitutes,
(2) density by 20-60% weight is 0.900-0.920g/cm 3Ethylene, the density of 40-60% weight is less than 0.900g/cm 3Ethylene ' alpha '-olefin class elastomer, and the following density of 30% weight is 0.935-0.945g/cm 3The hybrid resin that constitutes of ethylene, perhaps,
(3) density by 20-50% weight is 0.935-0.045g/cm 3Ethylene and the not enough 0.900g/cm of the density of 50-80% weight 3The hybrid resin that constitutes of ethylene ' alpha '-olefin class elastomer.
Also have, the thickness of each of thin film of the present invention layer with respect to all thickness of thin film, is preferably the 1st layer of 5-15%, the 2nd layer of 35-45%, the 3rd layer of 3-10%, the 4th layer of 35-45%, the 5th layer of 5-15%.
The resin that constitutes thin film of the present invention is ethylene arbitrarily, can enumerate for example propylene as alpha-olefin, 1-butylene, 1-amylene, the 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, the 1-nonene, 1-decene, the 1-endecatylene, carbon numbers such as 1-dodecylene are the alkene of 3-12.
Further, as containers for medical use of the present invention, be characterised in that and use above-mentioned plural layers to be shaped.
Plural layers of the invention described above and container, with original comparing, thermostability improves, simultaneously, and anti-cohesiveness, hot strength, flexibility, the transparency are also better.
Fig. 1 is the front elevation of a kind of better container of the present invention.
Then, to the resin of each layer of film of the present invention and container, and the method for making of film of the present invention and container is done more detailed description.
* about the 1st layer
Because must have mechanical strength (particularly hot strength), heat resistance is so use density to be 0.935-0.950g/cm3The resin of scope, preferential 0.935-0.945g/ cm3, specifically use density at 0.940g/cm3About resin. Wherein, preferably divides (190 ℃) for melt flow rate (MFR) for 1.5-2.5g/10, and fusing point is 130 ℃ of 120-. Thickness is preferably the 5-15% of gross thickness.
* about the 2nd layer
In order to keep the high flexibility of container, the ethyleneα-olefincopolymer of this layer use, preferably density is 0.920g/cm3Below, preferred density is 0.890-0.905g/ cm3 In addition, using straight copolymer is good keeping aspect transparent, wishes that also MFR is that 0.5-4.0g/10 divides (190 ℃), and fusing point is in 105-120 ℃ scope. Also have, at the resin compound that can use on this one deck more than 2 kinds, the density of 40-60% weight that suitable especially is is 0.900-0.920g/cm3Resin and the density of 40-60% weight less than 0.900g/cm3The elastomeric mixture of ethylene ' alpha '-olefin class. Have, in the above-mentioned hybrid resin, density that can undermixing 5% weight is 0.955g/ cm again3Above high density polyethylene (HDPE) perhaps mixes below 30% weight, below preferred 20% weight, density is 0.935-0.945g/cm3Ethyleneα-olefincopolymer, can in the situation that does not reduce flexibility, improve heat resistance thus. This high density polyethylene (HDPE) can be alpha olefin copolymer or homopolymers. As other resin compound of this layer use, the density that can enumerate by 20-50% weight is 0.935-0.945g/cm3Ethyleneα-olefincopolymer and the not enough 0.900g/cm of the density of 50-80% weight3Ethylene ' alpha '-olefin class elastomer. In addition, when using hybrid resin, all density of resin is set in the above-mentioned scope. It is 35-45% that the thickness of this layer is preferably gross thickness.
* about the 3rd layer
In order to guarantee all intensity of film (stiffness), in the layer of this center, use density at 0.925-0.950g/cm3Resin in the scope is preferably at 0.925-0.940g/ cm3Scope in. No matter resin straight chain shape or a chain are all good, but for good with the compatibility of other layer, and in order to keep the transparency, preferably use the polymer of straight chain shape. In addition, preferably its MFR is that 1.5-2.5g/ divides (190 ℃), and fusing point is 120-130 ℃ scope.
In addition, the resin of this layer use also can use the hybrid resin of 2 kinds of ethyleneα-olefincopolymers, at this moment, uses at least the density of 40-60% weight to be 0.935-0. 945g/cm3Resin, further, select the ethyleneα-olefincopolymer of suitable other, make mixed density in above-mentioned scope.
Thickness is approximately the 3-10% of gross thickness.
* about the 4th layer
Preparation and above-mentioned the 2nd layer of used identical resin are with the flexibility of assurance container. The thickness of this layer etc. is also selected in above-mentioned the 2nd layer scope.
* about the 5th layer
Prepare anti-adherence, heat-resistant resin, it is not adhered in high-temperature sterilization, and easily hot melt applies. Specifically use density to be 0.925-0.940g/cm3Resin. This resin can adopt the same resin with above-mentioned the 3rd layer of employing, but in order to increase heat resistance, the density that also can mix maximum 10% weight is 0.945g/cm3Above resin. At this moment, all density of resin is also in the scope of the company of being set in. Thickness can be the 5-15% of gross thickness.
As the manufacture method of film of the present invention, can enumerate water-cooled or decide cold type and jointly push aeration, jointly push T mold method, dry type layered manner, extruding layered manner etc. From performance, particularly transparent, the angle of economy and wholesomeness is set out, and preferably water-cooled is pushed aeration and common extruding T mold method jointly. In either method, each layer resin must be made film under melt temperature, if temperature has surpassed, then a part of resin generation thermal decomposition is because catabolite may cause the decline of performance. Therefore, the temperature conditions during thin film fabrication of the present invention is generally 150-250 ℃, preferred 170-200 ℃. In addition, consist of the resin of each layer, in order to keep the transparency, the difference of MFR should be as best one can little.
Such as the thickness of the above-mentioned film of the present invention that makes, be generally 100-300 μ, can suitably increase and decrease by application target etc., even the thickness about 200 μ can keep sufficient intensity.
As the manufacture method of container of the present invention, will use the usual way severing such as the above-mentioned tubulose that makes or tabular film, heat seal, the methods such as reusable heat sealing are installed in container finish etc., make the container of regulation shape and size. As thermosealed condition, can be in the scope of about 120 °-160 ℃ of temperature. As being the film about 200 μ concerning thickness, in the said temperature scope, can seal complete in the short time of second at 0.5-3. In addition, if the oral area material is to be made by straight-chain low density polyethylene, because can be well deposited with the internal layer of film of the present invention, so comparatively suitable.
<embodiment 〉
To the evaluation experimental of the container that uses plural layers of the present invention to be shaped to make, following describing.
At first, the laminated plates with synthetic resin shown in the table 1 and layer formation is shaped with water-cooled co-extruded aeration respectively.Then, be the containers for medical use of 500ml with its capacity that is shaped as shown in Figure 1.The heat seal of thin film carried out for 2 seconds at 140 ℃ when in addition, container was shaped.
And then, to resulting containers for medical use 1, estimate various characteristics with following method.That is,
For thermostability, behind its filling solution,, carry out after autoclaving handles visualization distortion, broken bag, the state of sealing leak in 40 minutes at 110 ℃.
For dip test, after about 4 ℃ of cold preservations, container from 3 directions, is respectively fallen visualization broken bag, the state of sealing leak 5 times by the height of 1.2m.
For flexibility, the discharge property naturally of visualization internal solution.
For the transparency, fill distilled water, carry out carrying out visualization after autoclaving handles, and then the water absorbance of carrying out 450nm is measured.
Also have the whole outward appearance of visualization, investigation gauffer, adhesion, distortion, the situation of broken bag.
On the other hand, as a comparative example with above-mentioned same, the laminated plates shaping with synthetic resin shown in the table 2 and layer formation forms containers for medical use with it with main points same as described above, estimates its various characteristics.
Also have, the contracted notation in table 1 and the table 2, as follows respectively.
PE-1=straight chain medium density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.940g/cm 3,
MFR=2.1g/10 branch (190 ℃))
PE-2=straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.900g/cm 3, MFR=0.9g/10 branch (190 ℃))
PE-3=straight chain medium density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.930g/cm 3, MFR=2.1g/10 branch (190 ℃))
The high density polyethylene (HDPE) (ethylene butene-1 copolymer) that mixes 5% weight among the above-mentioned PE-3 of PE-4=
(Mitsui petrochemistry system; Density=0.956g/cm 3, MFR=0.9g/10 branch (190 ℃)) the density=0.931g/cm of mixture<hybrid resin 3
PE-5=is by straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/cm 3, MFR=2.1g/10 branch (190 ℃)) and 45.5% weight,
Ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) and 50% weight
And high density polyethylene (HDPE) (homopolymer)
(Mitsui petrochemistry system; Density=0.965g/cm 3, MFR=15g/10 branch (190 ℃)) and 4.5% weight
Density=the 0.905g/cm of the hybrid resin<hybrid resin that constitutes 3
PE-6=is by straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/c 3, MFR=2.1g/10 branch (190 ℃)) and 47.5% weight,
Ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) and 50% weight
And height polyethylene (homopolymer)
(Mitsui petrochemistry system; Density=0.965g/cm 3, MFR=15g/10 branch (190 ℃)) and 2.5% weight
Density=the 0.904g/cm of the hybrid resin<hybrid resin that constitutes 3
PE-7=is by straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.905g/cm 3, MFR=2.9g/10 branch (190 ℃)) and 45.5% weight,
Ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) and 50% weight
And high density polyethylene (HDPE) (homopolymer)
(Mitsui petrochemistry system; Density=0.965g/cm 3, MFR=15g/10 branch (190 ℃)) and 4.5% weight
Density=the 0.898g/cm of the hybrid resin<hybrid resin that constitutes 3
PE-8=is by straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/cm 3, MFR=2.9g/10 branch (190 ℃)) and 40% weight,
Ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) and 50% weight
And the density=0.905g/cm of the hybrid resin<hybrid resin of PE-110% weight formation 3
PE-9=is by straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/cm 3, MFR=2.9g/10 branch (190 ℃)) and 45% weight,
Ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) 50% weight and
The hybrid resin that PE-15% weight constitutes
Density=the 0.904g/cm of<hybrid resin 3
PE-10=straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/cm 3, MFR=2.9g/10 branch (190 ℃)) and 1: 1 the hybrid resin of PE-1
Density=the 0.930g/cm of<hybrid resin 3
PE-11=straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0 925g/cm 3, MFR=2.3g/10 branch (190 ℃))
PE-12=is by straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/cm 3, MFR=2.9g/10 branch (190 ℃)) and 30% weight,
Ethylene 1-butylene elastomer (Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) and 50% weight
And the hybrid resin of PE-120% weight formation
Density=the 0.907g/cm of<hybrid resin 3
PE-13=straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/cm 3, MFE=2.9g/10 branch (190 ℃)) and 20% weight,
Ethylene 1-butylene elastomer (Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃))
The hybrid resin that 50% weight and PE-130% weight constitute
Density=the 0.909g/cm of<hybrid resin 3
PE-14=is by ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) 70% weight and
The hybrid resin that PE-130% weight constitutes
Density=the 0.902g/cm of<hybrid resin 3
PE-15=is by ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃)) 60% weight and
The hybrid resin that PE-140% weight constitutes
Density=the 0.907g/cm of<hybrid resin 3
PE-16=is by straight-chain low density polyethylene (ethylene butene-1 copolymer)
(Mitsui petrochemistry system; Density=0.920g/cm 3, MFR=2.9g/10 branch (190 ℃))
Table 1 (continuing)
No. Outer ←---→ internal layer Gross thickness (μ) Thermostability Dip test Flexibility The transparency Outward appearance Overall merit
The kind of resin (thickness (μ)) Visual Absorbance (%)
12 PE-1 (15) PE-12 (80) PE-3 (10) PE-12 (80) PE-3 (15) 200 84.6
13 PE-1 (15) PE-13 (80) PE-3 (10) PE-13 (80) PE-3 (15) 200 83.9
14 PE-1 (15) PE-14 (80) PE-3 (10) PE-14 (80) PE-3 (15) 200 83.2
15 PE-1 (15) PE-15 (80) PE-3 (10) PE-15 (80) PE-3 (15) 200 81.3
Table 2
PE-17=high density polyethylene (HDPE) (homopolymer)
(Mitsui petrochemistry system; Density=0.965g/cm 3, MFR=15g/10 branch (190 ℃))
PE-18=ethylene 1-butylene elastomer
(Mitsui petrochemistry system; Density=0.885g/cm 3, MFR=0.5g/10 branch (190 ℃))
In addition, ◎ represents very good, and zero expression is good, and △ represents bad a little, and X represents bad.
Table 1
By table 1 and table 2 as can be known, thin film of the present invention and container have good flexibility, thermostability, intensity, the transparency.
Plural layers of the present invention and container have
* the high temperature such as high pressure resistant steam sterilization and hot water sterilization sterilization.
* can reduce all thickness of film.
* because hot strength is good, can be used for bag.
* be difficult for adhering.
* heat seal at short notice at high temperature, sealing is also good.
* can keep excellent flexibility and the transparency after the sterilization.
Etc. advantage. Can perform well in the containers for medical use aspects such as infusion bag, bags of blood.

Claims (7)

1. plural layers is characterized in that it being 5 layer films that are made of ethylene, constitute the density of the resin of each layer, are begun by skin to be in turn
The 1st layer: 0.935-0.950g/cm 3
The 2nd layer: 0.920g/cm 3Below
The 3rd layer: 0.925-0.950g/cm 3
The 4th layer: 0.920g/cm 3Below
The 5th layer: 0.925-0.940g/cm 3
2. the plural layers of claim 1 record, wherein in the resin of the internal layer shown in aforesaid right requires 1 the 5th layer, mixing the following density of 10% weight is 0.945g/cm 3Above ethylene.
3. the plural layers of claim 1 record, wherein the 2nd layer and the 4th layer of used resin are 0.900-0.920g/cm for the density by 40-60% weight 3Ethylene, the not enough 0.900g/cm of the density of 40-60% weight 3Ethylene ' alpha '-olefin class elastomer and the density of less than 5% weight be 0.955g/cm 3The hybrid resin that above high density polyethylene (HDPE) constitutes.
4. the plural layers of claim 1 record, wherein the 2nd layer and the 4th layer of used resin are 0.900-0.920g/cm for the density by 20-60% weight 3Ethylene, the not enough 0.900g/cm of the density of 40-60% weight 3Ethylene ' alpha '-olefin class elastomer and the following density of 30% weight be 0.935-0.945g/cm 3The hybrid resin that constitutes of ethylene.
5. the plural layers of claim 1 record, wherein the 2nd layer and the 4th layer of used resin are 0.935-0.945g/cm for the density by 20-50% weight 3Ethylene and the not enough 0.900g/cm of the density of 50-80% weight 3The hybrid resin that constitutes of ethylene ' alpha '-olefin class elastomer.
6. plural layers of each record among the claim 1-5, wherein the ratio of the thickness of each layer is in following scope:
The 1st layer: 5-15%
The 2nd layer: 35-45%
The 3rd layer: 3-10%
The 4th layer: 35-45%
The 5th layer: 5-15%
7. a container is characterized in that this container is film formed with multi-layer thin, and said plural layers are 5 layer films that are made of ethylene, constitute the density of each layer resin, are begun to be followed successively by by skin:
The 1st layer: 0.935~0.950g/cm 3,
The 2nd layer: 0.920g/cm 3Below,
The 3rd layer: 0.925~0.950g/cm 3,
The 4th layer: 0.920g/cm 3Below,
The 5th layer: 0.925~0.940g/cm 3
CN93120900A 1992-12-04 1993-12-03 Multilayer film and container Expired - Lifetime CN1058453C (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP32583292 1992-12-04
JP325832/1992 1992-12-04
JP325832/92 1992-12-04
JP184221/1993 1993-07-26
JP18422193 1993-07-26
JP184221/93 1993-07-26
PCT/JP1994/000245 WO1995022456A1 (en) 1992-12-04 1994-02-17 Multilayer film and container

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Publication Number Publication Date
CN1089549A CN1089549A (en) 1994-07-20
CN1058453C true CN1058453C (en) 2000-11-15

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY134275A (en) * 2002-05-17 2007-11-30 Otsuka Pharma Co Ltd Multi-layer film and medicine container using the same
KR101211552B1 (en) * 2004-08-16 2012-12-12 니프로 가부시키가이샤 Medical multi-layered container and plural chamber container

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58216061A (en) * 1982-06-07 1983-12-15 テルモ株式会社 Medical container
EP0216509A2 (en) * 1985-08-23 1987-04-01 Showa Denko Kabushiki Kaisha Medical bag
JPS63248633A (en) * 1987-03-30 1988-10-14 キヨ−ラク株式会社 Plastic vessel
JPH0440956A (en) * 1990-06-06 1992-02-12 Showa Denko Kk Bag for medical treatment
JPH04266759A (en) * 1991-02-21 1992-09-22 Showa Denko Kk Medical bag

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58216061A (en) * 1982-06-07 1983-12-15 テルモ株式会社 Medical container
EP0216509A2 (en) * 1985-08-23 1987-04-01 Showa Denko Kabushiki Kaisha Medical bag
JPS63248633A (en) * 1987-03-30 1988-10-14 キヨ−ラク株式会社 Plastic vessel
JPH0440956A (en) * 1990-06-06 1992-02-12 Showa Denko Kk Bag for medical treatment
JPH04266759A (en) * 1991-02-21 1992-09-22 Showa Denko Kk Medical bag

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