CN1457972A - Blow molded poly olefin hollow container for medical use and preparing process - Google Patents
Blow molded poly olefin hollow container for medical use and preparing process Download PDFInfo
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- CN1457972A CN1457972A CN 02147402 CN02147402A CN1457972A CN 1457972 A CN1457972 A CN 1457972A CN 02147402 CN02147402 CN 02147402 CN 02147402 A CN02147402 A CN 02147402A CN 1457972 A CN1457972 A CN 1457972A
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Abstract
The present invention provides a kind of hollow container made of the composite comprising three components including ethylene/alpha-olefin copolymer, low-density polyethylene and polypropylene and with specific performance. The hollow container is used as medical packing bottle for solution, blood, medicine tablet, capsule, bolus and cosmetics. The container has good transparency and high heat stability and is sanitary.
Description
Technical field
The present invention relates to a kind of medical blow molding polyolefin hollow container and preparation technology thereof, belong to plastic products and medical macromolecular materials field.This hollow container can be used for medical infusion bottle, contains blood container, also can be used for the packing of tablet, capsule, pill and the packing of cosmetics etc., and this hollow container has high transparent, good heat-resistant stability and wholesomeness.
Background technology
Low density polyethylene (LDPE) (LDPE) has than long-chain branch on strand, thereby its fusion tension force is high and good in the high shear current downflow, is suitable for blow molding and becomes the hollow container that wall thickness is even, the surface is good, has a wide range of applications with resin as blow molding.But the LDPE fusing point is lower, is doing must be through containers for medical use such as infusion bottle that high-temperature sterilization is handled the time, and its hear resistance is bad.The mechanical strength of LDPE is lower in addition, and also difficulty reaches medical blow molding product requirements.Take into account processability simultaneously for improving hear resistance, adopt ethylene/alpha-olefin copolymer (HDPE or LLDPE) and the medical hollow container of LDPE blended composition blow molding.Along with the development of instructions for use, require at present to improve this based article the transparency so that in the distinguish containers medicine whether sneak into foreign matter.And only adopt HDPE or LLDPE can not satisfy relevant transparent requirement with the composition that mixes of LDPE.The medical plastic bottle further research and development have been carried out abroad for this reason, mainly contain two kinds of methods at present and improve the transparency and hear resistance of this based article: the one, adopt to have the different polyethylene of property or carry out blend with nucleator, the method of carrying out extrusion-blown modling with composition, the 2nd, adopt multi-layer co-extruded method.First method such as Japan Patent JP10007848, this invention is in narrow molecular weight distribution, has in the ethylene/alpha-olefin copolymer of specific melt flow rate (MFR), add the LDPE with specific melt flow rate (MFR) and mix, the composition that obtains has improved the transparency and mobile with the container that common blend method is made; Japan Patent JP10081795 adopts density (d) 0.880～0.935g/cm
3, melt flow rate (MFR) (MFR) 0.05～60g/10min polyethylene composition, said composition is formed and to be: component (A): ethene, alpha olefin copolymer, (MFR:0.3～80g/10min d=0.86～0.925g/cm
3) weight content 99～60%; Component (B): Alathon or the (MFR:0.01～5.0g/10min d=0.93～0.965g/cm of the alpha olefin copolymer except that component (A)
3) 1～40%; 0.002～2 part of component (C) nucleator, nucleator is anti-reflection nucleators such as sorbose alcohols, owing to added this nucleator, impels polyethylene grainiess granular and has improved the transparency of container.Second method such as Japan Patent JP07124244, its containers for medical use composition comprise that component (A) low density polyethylene (LDPE) makes internal layer, component (B) LLDPE (density 〉=0.920g/cm
3) as outer, the intermediate layer is component (E), (E) is the composition of component (C) and component (D), is the crystalline copolymer of Main Ingredients and Appearance for crystalline polypropylene or with the crystalline polypropylene (C), (D) is amorphous polypropylene or polybutene.
In the prior art, adopt low density polyethylene (LDPE) and ethylene blend composition to prepare its transparency of hollow container in the first method and be still waiting further raising; Though and can further improve the transparency with nucleator, the compatibility of nucleator and polyethylene matrix is bad, wholesomeness is difficult to guarantee, and the cost of goods is higher.Second method adopts multi-layer co-extruded to improve the performance of medical hollow container, and this method needs special-purpose extruder, and raw material is multiple, the cost height.
Summary of the invention
One of purpose of the present invention is at above-mentioned deficiency of the prior art, and the medical hollow container with ethylene (HDPE or LLDPE), low density polyethylene (LDPE) (LDPE), the preparation of polypropylene (PP) three component polyolefin compositions is provided.Two of purpose of the present invention provides the method that adopts this hollow container of preparation.
The quality of weighing a kind of material transparency has many performance indications, comprising light transmittance and mist degree.Light transmittance is the luminous flux and the percent value that incides the luminous flux on the material surface of permeable material, and light transmittance is an important performance indexes that characterizes the resin transparent degree, and the light transmittance of resin is high more, and its transparency is just good more.Mist degree is the percent value of permeable material scatter light flux and permeable material luminous flux, and mist degree can be weighed the unintelligible or muddy degree of transparent or semitransparent material, and the generation of mist degree causes owing to material internal or outer surface light scattering.Mist degree is low more, and the transparency of material is good more.Crystallization macromolecular material such as PP, PE are because its strand has higher regularity, thereby have higher crystallizing power, and forming big crystal, incident light enters in the macromolecular material and will be reflected like this, thereby the light transmittance of material is descended, and the transparency of material descends.Simultaneously, because these materials are that the hemihedral crystal material wherein contains crystalline region and amorphous area, the different uniformities of material structure that make with the index of refraction of amorphous area in crystalline region descend, thereby the scatter light flux of material is improved, and mist degree improves, and the transparency of material also descends.We make it improve the transparency of material less than visible wavelength by the size that reduces spherocrystal.The size of spherocrystal is by the decision of the process conditions of the structure of polymer and crystallization.By the analysis to the material The Nomenclature Composition and Structure of Complexes, the preferred three component polyolefin compositions of the present invention come blowing to prepare medical hollow container.
Composition of the present invention comprises (in parts by weight):
Component A:50～90, B component: 50～10, component C:0.01～30.
Component A is density 0.915～0.926g/cm
3, the linear low density polyethylene (LLDPE) (LLDPE) of melt flow rate (MFR) (190 ℃, the 2.16Kg counterweight) 1.0～5g/10min, 122～124 ℃ of fusing points; B component is density 0.910～0.926g/cm
3, the low density polyethylene (LDPE) (LDPE) of melt flow rate (MFR) (190 ℃, the 2.16Kg counterweight) 0.5～10g/10min, 108～110 ℃ of fusing points; Component C is density 0.900～0.910g/cm
3, melt flow rate (MFR) (230 ℃, the 2.16Kg counterweight) 3.0～20g/10min polypropylene (PP), 163～167 ℃ of fusing points.
Component A consumption is lower than 50 parts, and when the B component consumption was higher than 50 parts simultaneously, the hear resistance of composition descended, and does not reach the high-temperature sterilization requirement, and component A consumption is higher than 90 parts, and the B component consumption is lower than 10 parts, and then processing characteristics is bad, and the transparency descends.Not remarkable when the consumption of component C is lower than 0.01 part to transparency raising, when consumption is higher than 30 parts,, do not reach instructions for use because the compatibility of component C and component A and B component causes the composition mechanical property to reduce than missionary society yet.Better form and be: component A:70～80, B component: 30～20, component C:0.05～20.
Component A and B component can be respectively single polyethylene in the composition of the present invention, also can be the blends that multiple polyethylene is formed.
Composition of the present invention also can add the usual auxiliaries systems such as antioxidant of component D:0.01～2.0 part, as phenolic antioxidant and/or phosphite ester kind antioxidant.
The process conditions of control preparation hollow container are to separate the process that twines between the strand in the preparation process in order to utilize, and shorten its crystallization time, thereby make it form incomplete crystal in crystallization process, improve the transparency of material.Therefore the process conditions that prepare hollow container are very important.Medical package container of the present invention adopts and squeezes the stretch blow moulding preparation, and preparation process condition is 110 ℃～230 ℃ of temperature, 20～80 rev/mins of extruder rotating speeds.Can adopt draw ratio 〉=20: 1, the single screw extrusion machine of screw diameter 〉=30 is produced, and can be made into 50 milliliters～10 liters hollow container, and the best is 200 milliliters～5 liters a hollow container, the light transmittance of hollow container 〉=65%.
Hollow container of the present invention, can be used on medical infusion bottle, contain blood container, also can be used for the packing of tablet, capsule, pill and the packing of cosmetics, have the good transparency, hear resistance, mechanical property and biology, chemical property and mouldability, can test by high-temperature sterilization.The high-temperature sterilization test is that container is placed the high-temperature sterilization pressure cooker, at 109 ℃ of following boiling 45min, takes out then, and container should not deform, and keeps higher light transmittance and lower mist degree.
With the specific embodiment effect of the present invention is described below.
The specific embodiment
Embodiment 1
Adopting screw diameter is 90, and draw ratio is 30: 1, and blow-up ratio is that 2.5: 1 single screw extrusion machine prepares 5 liters medical cleaning liquid packaging bag.Process conditions:
Four sections temperature die temperatures of three sections temperature of two sections temperature of one section temperature rotating speed
120 ℃ 170 ℃ 200 ℃ 210 ℃ 200 ℃ 30 rev/mins
Made packing container light transmittance is 70%, and good heat resistance can be tested by high-temperature sterilization, and can pass through the low temperature drop test.Experimental technique froze 4 hours-25 ℃ of refrigerator and cooled for container is filled water, and the water in the container all build-ups ice.Container is taken out from refrigerator, rapidly container is fallen from 1 meter eminence, packing is not broken.Biological property: acute toxicity test, intracutaneous test, hemolytic test, transplant experiment are qualified.
Chemical property: particulate content 2 μ m 11 in the leaching liquor, 2 of 5 μ m.The leaching liquor preparation method presses GB 16175 " medical organosilicon material biological assessment test method ".
Content of beary metal≤2 μ g/ milliliters.
Embodiment 2
Adopting screw diameter is 65, and draw ratio is 28: 1, and blow-up ratio is that 3: 1 single screw extrusion machine prepares disposable infusion bottle, and the volume of bottle is 250 milliliters.
Process conditions:
Four sections temperature die temperatures of three sections temperature of two sections temperature of one section temperature rotating speed
110 ℃ 160 ℃ 180 ℃ 180 ℃ 180 ℃ 40 rev/mins
The performance light transmittance 66.7% of made container, good heat resistance can be tested by high-temperature sterilization.Biological property: acute toxicity test, intracutaneous test, hemolytic test, transplant experiment are qualified.Chemical property: particulate content 2 μ m 13 in the leaching liquor, 3 of 5 μ m.The leaching liquor preparation method presses GB 16175 " medical organosilicon material biological assessment test method ".
Content of beary metal≤2 μ g/ milliliters.
Each component of embodiment composition therefor forms and composition properties sees Table 1.
The composition of each component of table 1. embodiment and composition properties
| Embodiment 1 | Embodiment 2 | |
| Component A | ????A1 | ????A2 |
| Umber | ????70 | ????70 |
| B component | ????B | ????B |
| Umber | ????30 | ????30 |
| Component C | ????C2 | ????C1 |
| Umber | ????0.05 | ????1 |
| Component D | ????D1 | |
| Umber | ????0.05 | |
| Light transmittance | ????73.0 | ????71.7 |
| Mist degree | ????38 | ????35 |
| After the sterilization | ||
| Light transmittance | ????72.1 | ????69.6 |
| Mist degree | ????45 | ????43 |
The performance of component among the embodiment:
A1: density 0.919g/cm
3, melt flow rate (MFR) 1.8g/10min;
A2: density 0.922g/cm
3, melt flow rate (MFR) 2.2g/10min;
B: density 0.921g/cm
3, melt flow rate (MFR) 2.5g/10min;
C1: density 0.905g/cm
3, melt flow rate (MFR) 6.5g/10min;
C2: density 0.905g/cm
3, melt flow rate (MFR) 8.3g/10min;
D1: four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2,4-di-tert-butyl-phenyl ester) are in the mixture of 1: 1 ratio.
Claims (6)
1. the hollow container of polyolefin composition preparation, composition comprises in parts by weight: component A:50～90, B component: 50～10, component C:0.01～30; Component A is density 0.915～0.926g/cm
3, melt flow rate (MFR) 1.0～5g/10min rises LDPE; B component is density 0.910～0.926g/cm
3, the LDPE of melt flow rate (MFR) 0.5～10g/10min; Component C is density 0.900～0.910g/cm
3, the PP of melt flow rate (MFR) 3.0～20g/10min;
The volume of hollow container is 50 milliliters～10 liters.
2. hollow container as claimed in claim 1 is characterized in that 122～124 ℃ of the fusing points of its composition component A, 108～110 ℃ of the fusing points of B component, and 163～167 ℃ of the fusing points of component C, component A:70～80, B component: 30～20, component C:0.05～20.
3. hollow container as claimed in claim 1 is characterized in that light transmittance 〉=65% of hollow container, and the volume of hollow container is 200 milliliters～5 liters.
4. the preparation technology of hollow container according to claim 1 adopts and squeezes the stretch blow moulding preparation, and condition is: 110～230 ℃ of extruder temperatures, 20～80 rev/mins of rotating speeds, draw ratio 〉=20: 1, the single screw extrusion machine of screw diameter 〉=30.
5. as the preparation technology of hollow container as described in the claim 4, it is characterized in that with screw diameter be 90, draw ratio is 30: 1, and blow-up ratio is 2.5: 1 a single screw extrusion machine, process conditions:
Four sections temperature die temperatures of three sections temperature of two sections temperature of one section temperature rotating speed
120 ℃ 170 ℃ 200 ℃ 210 ℃ 200 ℃ 30 rev/mins.
6. as the preparation technology of hollow container as described in the claim 4, it is characterized in that with screw diameter be 65, draw ratio is 28: 1, and blow-up ratio is 3: 1 a single screw extrusion machine, process conditions:
Four sections temperature die temperatures of three sections temperature of two sections temperature of one section temperature rotating speed
110 ℃ 160 ℃ 180 ℃ 180 ℃ 180 ℃ 40 rev/mins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021474028A CN100415495C (en) | 2002-05-15 | 2002-10-21 | Blow molded poly olefin hollow container for medical use and preparing process |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02110372.0 | 2002-05-15 | ||
| CN2002110372.0 | 2002-05-15 | ||
| CN02110372 | 2002-05-15 | ||
| CNB021474028A CN100415495C (en) | 2002-05-15 | 2002-10-21 | Blow molded poly olefin hollow container for medical use and preparing process |
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| Publication Number | Publication Date |
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| CN1457972A true CN1457972A (en) | 2003-11-26 |
| CN100415495C CN100415495C (en) | 2008-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021474028A Expired - Fee Related CN100415495C (en) | 2002-05-15 | 2002-10-21 | Blow molded poly olefin hollow container for medical use and preparing process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101001789B (en) * | 2004-07-06 | 2010-12-08 | 塞巴尔两合公司 | Lightweight flexible plastic tubes and method for making same |
| CN103448930A (en) * | 2013-09-09 | 2013-12-18 | 山东新华医疗器械股份有限公司 | Preparation method of cartridge hydrogen peroxide capsule |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01163240A (en) * | 1987-12-18 | 1989-06-27 | Showa Denko Kk | Olefin resin composition for injection blow molding |
| ES2339215T3 (en) * | 1999-01-27 | 2010-05-18 | TETRA LAVAL HOLDINGS & FINANCE SA | STRATIFIED PACKAGING MATERIAL FOR PAPER CONTAINER. |
-
2002
- 2002-10-21 CN CNB021474028A patent/CN100415495C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101001789B (en) * | 2004-07-06 | 2010-12-08 | 塞巴尔两合公司 | Lightweight flexible plastic tubes and method for making same |
| CN103448930A (en) * | 2013-09-09 | 2013-12-18 | 山东新华医疗器械股份有限公司 | Preparation method of cartridge hydrogen peroxide capsule |
| CN103448930B (en) * | 2013-09-09 | 2015-09-23 | 山东新华医疗器械股份有限公司 | The preparation method of cartridge hydrogen peroxide capsule |
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| Publication number | Publication date |
|---|---|
| CN100415495C (en) | 2008-09-03 |
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