CN102863720A - Medical polyvinyl chloride (PVC) material sterilized by gamma ray radiation - Google Patents

Medical polyvinyl chloride (PVC) material sterilized by gamma ray radiation Download PDF

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CN102863720A
CN102863720A CN2012104183816A CN201210418381A CN102863720A CN 102863720 A CN102863720 A CN 102863720A CN 2012104183816 A CN2012104183816 A CN 2012104183816A CN 201210418381 A CN201210418381 A CN 201210418381A CN 102863720 A CN102863720 A CN 102863720A
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gamma rays
adopt
pvc material
parts
medical pvc
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CN2012104183816A
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张晓�
董合军
李静
李显明
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Chengdu Xinjin Shifeng Medical Instrument Co Ltd
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Chengdu Xinjin Shifeng Medical Instrument Co Ltd
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Abstract

The invention discloses a medical polyvinyl chloride (PVC) material sterilized by gamma ray radiation, which is characterized in that the modified material comprises the following components by weight: 100 parts of PVC resin powder; 0.02-0.5 part of a hindered amine light stabilizer; 30-50 parts of a plasticizer; 0.8-1.5 parts of a stabilizer; 0.3-1.2 parts of an antioxidant; an auxiliary stabilizer; 1-6 parts of epoxidized soybean oil; and 0.2-0.8 part of a lubricant. The medical PVC material can be extruded into vessels through extrusion process which is used for general soft PVC material, and no yellowing and no obvious decrease of mechanical properties happen after the material is sterilized under the radiation of 25kGy.

Description

A kind of medical PVC material that can adopt the gamma Rays sterilization
Technical field
The present invention relates to the material modified field of PVC, be specifically related to a kind of medical PVC material that can adopt the gamma Rays sterilization.
Background technology
At medical instruments field, sterilization method is mainly ethylene oxide sterilizing at present, the gamma ray sterilization, three kinds of steam sterilizings, domestic main employing ethylene oxide sterilizing is because there is contaminate environment in oxyethane, residual harmful, sterilization time and parsing time is the shortcoming such as very long all.Europe gradually adopts the gamma ray sterilization, because ray or high-power electron beam are free to penetrate any common wrapping material, so adopt the packing of the medicine equipment of irradiation sterilization, need not consider ventilation property, efficient is high, and non-environmental-pollution is residual without obnoxious flavour.Yet, if the medical PVC material that uses in the existing disposable medical consumptive material is adopted γ ray sterilization, its PVC molecular chain can rupture under high-octane impact, the material jaundice, mechanical property reduces a lot, so common medical PVC material is not suitable for irradiation sterilization.
Summary of the invention
Can not adopt the situation of gamma ray sterilization for medical PVC material on the market, the object of the invention is to develop and a kind ofly can adopt the gamma Rays sterilization, and the medical PVC material of xanthochromia can not occur.
In order to achieve the above object, the present invention has adopted following technical scheme: the consumption of each material composition of the present invention is also groped to sum up to draw through the contriver in a large number, each composition consumption all has preferably effect in the following weight parts ratio range: a kind of medical PVC material that can adopt gamma Rays sterilization, by weight ratio meter this material modifiedly made by following composition:
Polyvinyl chloride resin powder: 100 parts
Hindered amine light stabilizer: 0.02~0.5 part
Softening agent: 30 ~ 50 parts
Stablizer: 0.8 ~ 1.5 part
Antioxidant: 0.3 ~ 1.2 part
Auxiliary stabilizer: 1 ~ 6 part of epoxy soybean oil
Lubricant: 0.2 ~ 0.8 part.
Optimum, described a kind of medical PVC material that can adopt the gamma Rays sterilization is counted by weight ratio this and is material modifiedly made by following composition:
Polyvinyl chloride resin powder: 100 parts
Hindered amine light stabilizer: 0.5 part
Softening agent: 45 parts
Stablizer: 1.5 parts
Antioxidant: 0.6 part
Auxiliary stabilizer: 6 parts of epoxy soybean oils
Lubricant: 0.7 part.
In the mentioned component, in order to reach optimal effectiveness, the polyvinyl chloride resin powder polymerization degree that this patent adopts is 600 ~ 1500; Described stablizer is calcium zinc stabilizer or organotin stabilizer; Described softening agent is DOP, hexanaphthene-1,2-dioctyl phthalate diisononyl esters (DINCH) or trioctyl trimellitate (TOTM); Described hindered amine light stabilizer is 944,770,622,540,3346 photostabilizers of the vapour Bagong HALS of department class or the photostabilizer of other company's same molecular formulas; Described antioxidant is the oxidation inhibitor of phosphorous acid esters, such as diisooctyl phenyl phosphite, trisnonyl phenyl phosphite or tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; Described lubricant is selected from polyethylene wax, oxidized polyethlene wax, stearic acid, silicone oil or adipic acid pentaerythritol ester.
Preparation can adopt the method for the medical PVC material of gamma Rays sterilization to include following steps:
(1) batch mixing: high-speed mixer adds polyvinyl chloride resin powder, stablizer and hindered amine light stabilizer when low speed mixing, this low speed mixing speed is 441rpm; Add antioxidant and softening agent after temperature to 65 ℃, epoxy soybean oil changes over to behind the 1.5min at a high speed, and this speed that runs up is 877rpm; After temperature reaches 110 ℃, add lubricant, continue to be stirred to 135 ℃ of blowings to cold pot, until material temperature is down to 30 ℃, it is for subsequent use to get material;
(2) granulation: the material that step (1) is obtained uses SJSZ-65 model twin screw extruder extruding pelletization, adopts air-cooled die-surface pelletizing mode, finally obtains adopting the medical PVC material of gamma Rays sterilization.
The hindered amine as light stabilizer (HALS) that the present invention adopts is the organic amine compound that a class has space steric effect, because it has hydroperoxide decomposition, quencher excited oxygen, catches free radical, the effective function such as group recyclable regenerative, it is a class photostabilizer of domestic and international consumption maximum.The action principle of hindered amine type light stabilizer is that it can produce nitroxyl free radical (〉 N-O under heating or ultraviolet light irradiation), this free radical can be caught the free radical that the superpolymer oxidation produces, and suppresses the generation of superpolymer photo-oxidative degradation reaction.And the applicant draws by a large amount of experimental demonstrations, adopt and a certain amount of hindered amine as light stabilizer of adding in the polyvinyl chloride resin powder, help again with specific softening agent, stablizer, antioxidant, auxiliary stabilizer and lubricant, the medical PVC material that it makes is PVC molecular chain easy fracture not under high-octane impact when gamma Rays is sterilized, material is without jaundice, and mechanical property is without obvious decline.
Medical PVC material of the present invention can be according to the expressing technique shaping catheter of general flexible PVC material, and product is behind the 25kGy irradiation sterilization, and without xanthochromia, mechanical property is without obvious decline.
Embodiment
Embodiment 1
Weighing:
Polyvinyl chloride resin powder: 100kg
Hindered amine light stabilizer: the photostabilizer 944 of the vapour Bagong HALS of department class is 0.5kg
Softening agent: DOP 45kg
Stablizer: calcium zinc stabilizer 1.5kg
Oxidation inhibitor: trisnonyl phenyl phosphite 0.6kg
Auxiliary stabilizer: epoxy soybean oil 6kg
Lubricant: silicone oil 0.7kg.
The preparation method is as follows:
Batch mixing: (1) batch mixing: high-speed mixer adds polyvinyl chloride resin powder and calcium zinc stabilizer and hindered amine light stabilizer under low-speed running: the photostabilizer 944 of the vapour Bagong HALS of department class, and this low-speed running speed is 441rpm; Add oxidation inhibitor trisnonyl phenyl phosphite, plasticizer DOP and auxiliary stabilizer epoxy soybean oil after temperature to 65 ℃, change over to behind the 1.5min at a high speed, this speed that runs up is 877rpm; After temperature reaches 110 ℃, add lubricant silicone oil, continue to be stirred to 135 ℃ of blowings to cold pot, until material temperature to 30 ℃, it is for subsequent use to get material.
Granulation: the material that step (1) is obtained uses SJSZ-65 model twin screw extruder extruding pelletization, adopts air-cooled die-surface pelletizing mode, finally obtains adopting the medical PVC material of gamma Rays sterilization.
Each section of forcing machine temperature sees Table 1.
Each section of table 1 forcing machine temperature
Figure 2012104183816100002DEST_PATH_IMAGE001
45 rev/mins of driving screw rotating speeds, main frame vacuum tightness is: 0.09 MPa.
Embodiment 2
Can adopt the medical PVC material preparation method of gamma Rays sterilization as described in Example 1.Difference is that each raw material and concrete amount are:
The polymerization degree is 600 ~ 1500 polyvinyl chloride resin powder: 100kg
Hindered amine light stabilizer: the photostabilizer 944 of the vapour Bagong HALS of department class is 0.5kg
Softening agent: DOP 45kg
Stablizer: calcium zinc stabilizer 1.5kg
Oxidation inhibitor: trisnonyl phenyl phosphite 0.6kg
Auxiliary stabilizer: epoxy soybean oil 6kg
Lubricant: silicone oil 0.7kg.
Embodiment 3
Can adopt the medical PVC material preparation method of gamma Rays sterilization as described in Example 1.Difference is that each raw material and concrete amount are:
The polymerization degree is 600 ~ 1500 polyvinyl chloride resin powder: 100kg
Hindered amine light stabilizer: the photostabilizer 944 of the vapour Bagong HALS of department class is 0.02kg
Softening agent: DOP 30kg
Stablizer: calcium zinc stabilizer 0.8kg
Oxidation inhibitor: trisnonyl phenyl phosphite 0.3kg
Auxiliary stabilizer: epoxy soybean oil 1kg
Lubricant: silicone oil 0.2kg.
Embodiment 4
Can adopt the medical PVC material preparation method of gamma Rays sterilization as described in Example 1.Difference is that each raw material and concrete amount are:
The polymerization degree is 600 ~ 1500 polyvinyl chloride resin powder: 100kg
Hindered amine light stabilizer: the photostabilizer 944 of the vapour Bagong HALS of department class is 0.2kg
Softening agent: DOP 45kg
Stablizer: calcium zinc stabilizer 1.5kg
Oxidation inhibitor: trisnonyl phenyl phosphite 0.6kg
Auxiliary stabilizer: epoxy soybean oil 6kg
Lubricant: silicone oil 0.7kg.
Embodiment 5
Can adopt the medical PVC material preparation method of gamma Rays sterilization as described in Example 1.Difference is that each raw material and concrete amount are:
The polymerization degree is 600 ~ 1500 polyvinyl chloride resin powder: 100kg
Hindered amine light stabilizer: the photostabilizer 944 of the vapour Bagong HALS of department class is 0.5kg
Softening agent: DOP 50kg
Stablizer: calcium zinc stabilizer 1.5kg
Oxidation inhibitor: trisnonyl phenyl phosphite 1.2kg
Auxiliary stabilizer: epoxy soybean oil 6kg
Lubricant: silicone oil 0.8kg.
Embodiment 1 products obtained therefrom is carried out following performance test, seen table 2-table 3 for details
Table 2 present embodiment 1 product and existing flexible PVC product physicals contrast table
Figure 116680DEST_PATH_IMAGE002
Table 3 present embodiment 1 product is made biological property detection table when medical
Figure 2012104183816100002DEST_PATH_IMAGE003
Same, embodiment 2-embodiment 5 has also been done corresponding benchmark test, the benchmark test result of test-results and embodiment 1 is without significant difference, so do not do deposited stating at this.

Claims (9)

1. medical PVC material that can adopt gamma Rays sterilization is characterized in that: by weight ratio meter this material modifiedly made by following composition: polyvinyl chloride resin powder: 100 parts
Hindered amine light stabilizer: 0.02~0.5 part
Softening agent: 30 ~ 50 parts
Stablizer: 0.8 ~ 1.5 part
Antioxidant: 0.3 ~ 1.2 part
Auxiliary stabilizer: 1 ~ 6 part of epoxy soybean oil
Lubricant: 0.2 ~ 0.8 part.
2. a kind of medical PVC material that can adopt gamma Rays sterilization according to claim 1 is characterized in that: by weight ratio meter this material modifiedly made by following composition:
Polyvinyl chloride resin powder: 100 parts
Hindered amine light stabilizer: 0.5 part
Softening agent: 45 parts
Stablizer: 1.5 parts
Antioxidant: 0.6 part
Auxiliary stabilizer: 6 parts of epoxy soybean oils
Lubricant: 0.7 part.
3. a kind of medical PVC material that can adopt the gamma Rays sterilization according to claim 1 is characterized in that the described polyvinyl chloride resin powder polymerization degree is 600 ~ 1500.
4. a kind of medical PVC material that can adopt the gamma Rays sterilization according to claim 1 and 2 is characterized in that described stablizer is that described stablizer is calcium zinc stabilizer or organotin stabilizer.
5. a kind of medical PVC material that can adopt gamma Rays sterilization according to claim 1 and 2 is characterized by softening agent and is selected from DOP, hexanaphthene-1, a kind of in 2-dioctyl phthalate diisononyl esters, the trioctyl trimellitate.
6. a kind of medical PVC material that can adopt the gamma Rays sterilization according to claim 1 and 2 is characterized in that described hindered amine light stabilizer is 944,770,622,540,3346 photostabilizers of the vapour Bagong HALS of department class.
7. a kind of medical PVC material that can adopt gamma Rays sterilization according to claim 1 and 2, it is characterized in that described antioxidant is selected from a kind of in diisooctyl phenyl phosphite, trisnonyl phenyl phosphite, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
8. a kind of medical PVC material that can adopt the gamma Rays sterilization according to claim 1 is characterized in that described lubricant is polyethylene wax, oxidized polyethlene wax, stearic acid, silicone oil or adipic acid pentaerythritol ester.
9. prepare the method that can adopt the medical PVC material of gamma Rays sterilization as claimed in claim 1 or 2, it is characterized in that the method may further comprise the steps:
(1) batch mixing: high-speed mixer adds polyvinyl chloride resin powder, stablizer and hindered amine light stabilizer when low speed mixing, this low speed mixing speed is 441rpm; Add antioxidant and softening agent after temperature to 65 ℃, epoxy soybean oil changes over to behind the 1.5min at a high speed, and this speed that runs up is 877rpm; After temperature reaches 110 ℃, add lubricant, continue to be stirred to 135 ℃ of blowings to cold pot, until material temperature is down to 30 ℃, it is for subsequent use to get material;
(2) granulation: the material that step (1) is obtained uses SJSZ-65 model twin screw extruder extruding pelletization, adopts air-cooled die-surface pelletizing mode, finally obtains adopting the medical PVC material of gamma Rays sterilization.
CN2012104183816A 2012-10-29 2012-10-29 Medical polyvinyl chloride (PVC) material sterilized by gamma ray radiation Pending CN102863720A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103113694A (en) * 2013-02-25 2013-05-22 高邮市汉升高分子材料有限公司 Preparation method of anti-gamma ray medical flexible polyvinyl chloride mask material
CN104072915A (en) * 2014-07-10 2014-10-01 上海新上化高分子材料有限公司 Radiation-resistant sterile medical polyvinyl chloride material and preparation method thereof
JP2016044297A (en) * 2014-08-27 2016-04-04 リケンテクノス株式会社 Vinyl chloride resin composition
CN110698786A (en) * 2019-10-22 2020-01-17 常州康宝高分子科技有限公司 Anti-irradiation medical particle and preparation method thereof
CN110922695A (en) * 2019-12-06 2020-03-27 苏州奥凯高分子材料股份有限公司 Cobalt 60 irradiation-resistant sterilized PVC medical packaging sheet and preparation method thereof
CN111499988A (en) * 2020-05-12 2020-08-07 中国科学院长春应用化学研究所 Modified polyvinyl chloride, preparation method thereof, irradiation-resistant sterilization venous indwelling needle connecting hose and indwelling needle
CN116082759A (en) * 2022-11-17 2023-05-09 浙江天原医用材料有限公司 Gamma ray resistant modified PVC granule and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1359972A (en) * 2001-12-29 2002-07-24 中国科学院长春应用化学研究所 Process for preparing weatherability polyvinyl chloride film containing hindered amine as light stabilizer
CN1894323A (en) * 2003-11-12 2007-01-10 科聚亚公司 Liquid microemulsion stabilizer composition for halogen-containing polymers
CN102321316A (en) * 2011-08-25 2012-01-18 上海恒方大高分子材料科技有限公司 Medical polyvinyl chloride (PVC) material for gamma-ray irradiation disinfection and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1359972A (en) * 2001-12-29 2002-07-24 中国科学院长春应用化学研究所 Process for preparing weatherability polyvinyl chloride film containing hindered amine as light stabilizer
CN1894323A (en) * 2003-11-12 2007-01-10 科聚亚公司 Liquid microemulsion stabilizer composition for halogen-containing polymers
CN102321316A (en) * 2011-08-25 2012-01-18 上海恒方大高分子材料科技有限公司 Medical polyvinyl chloride (PVC) material for gamma-ray irradiation disinfection and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103113694A (en) * 2013-02-25 2013-05-22 高邮市汉升高分子材料有限公司 Preparation method of anti-gamma ray medical flexible polyvinyl chloride mask material
CN104072915A (en) * 2014-07-10 2014-10-01 上海新上化高分子材料有限公司 Radiation-resistant sterile medical polyvinyl chloride material and preparation method thereof
JP2016044297A (en) * 2014-08-27 2016-04-04 リケンテクノス株式会社 Vinyl chloride resin composition
CN110698786A (en) * 2019-10-22 2020-01-17 常州康宝高分子科技有限公司 Anti-irradiation medical particle and preparation method thereof
CN110922695A (en) * 2019-12-06 2020-03-27 苏州奥凯高分子材料股份有限公司 Cobalt 60 irradiation-resistant sterilized PVC medical packaging sheet and preparation method thereof
CN111499988A (en) * 2020-05-12 2020-08-07 中国科学院长春应用化学研究所 Modified polyvinyl chloride, preparation method thereof, irradiation-resistant sterilization venous indwelling needle connecting hose and indwelling needle
CN111499988B (en) * 2020-05-12 2021-01-08 中国科学院长春应用化学研究所 Modified polyvinyl chloride, preparation method thereof, irradiation-resistant sterilization venous indwelling needle connecting hose and indwelling needle
CN116082759A (en) * 2022-11-17 2023-05-09 浙江天原医用材料有限公司 Gamma ray resistant modified PVC granule and application thereof

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Application publication date: 20130109