CN103923384A - Polypropylene combined cover outer cover material for infusion containers - Google Patents
Polypropylene combined cover outer cover material for infusion containers Download PDFInfo
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- CN103923384A CN103923384A CN201410135769.4A CN201410135769A CN103923384A CN 103923384 A CN103923384 A CN 103923384A CN 201410135769 A CN201410135769 A CN 201410135769A CN 103923384 A CN103923384 A CN 103923384A
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- polypropylene
- cover
- pipe compound
- enclosing cover
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polypropylene combined cover outer cover material for infusion containers, which consists of the following components in parts by weight: 40.0-60.0 parts of polypropylene, 15.0-30.0 parts of polyethylene, 15.0-35.0 parts of elastomer, 3.0-6.0 parts of liquid paraffin, 0.1-0.3 part of antioxidant, 0.1-0.3 part of slipping agent and 0.1-0.3 part of anti-reflection agent. The invention also provides a production method of the polypropylene combined cover outer cover material for infusion containers. The tensile force value of the polypropylene combined cover outer cover for infusion containers is 50+/-5N and the pull tab is easy to open, so that the usability is improved. The injection molding temperature and pressure of the polypropylene combined cover outer cover material for infusion containers are lower and the forming manufacturability is good.
Description
Technical field
The present invention relates to a kind of polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound and production method thereof, belong to technical field of medicine packaging.
Background technology
At present, polypropylene, because of advantages such as mechanical strength is high, nontoxic, heat-resisting, chemical-resistant resistance, easy-formation processing, has been widely used in medical packaging industry, become in synthetic resins increase the fastest, new product development is the fastest, one of most active kind.In transfusion package industry, produce infusion vessel polypropylene combination cover enclosing cover modifying material tradition and adopt polypropylene and the olefin type elastomer of the medical grade trade mark to carry out blend, control proportioning, by extruding pelletization, thereby improve polypropylene low temperature fragility.
Infusion vessel polypropylene combination cover modification proprietary material is applied more late at home, domestic relatively less to the research of polypropylene combination cover modifying material, patent is less, and also there is certain deficiency in partial monopoly goods, as, the earliest in domestic patent CN1718626A, the tensile strength of material higher (10-22MPa), elongation at break is on the low side (398-786%), and sterilising temp (115 DEG C) is lower than national standard temperature (121 DEG C); Patent CN101974176A compares CN1718626A, and the tensile strength of its material is slightly improved (being reduced to about 10MPa), and elongation at break obviously improves (being increased to approximately 900%).But this type of patent is mainly improved polyacrylic correlation intensity by adding elastomerics, has increased melt viscosity, is difficult for machine-shaping; The defects such as meanwhile, this class polypropylene combination cover enclosing cover ubiquity draw ring opening force is bigger than normal, draw ring is easily broken.
Along with developing rapidly of domestic medical and health industry, the requirement of polypropylene Combined medical bottle cap and Medical combined cover manufacturer quantity increase severely thereupon.Nearly family more than 100 of domestic current infusion vessel polypropylene combination cover factory, as Sichuan Chongzhou Junjian Plastic Co., Ltd., Chengdu Push Medical Plastics Packaging Co., Ltd., the Changjiang river, Jiangsu Gai Ye company limited, Taizhou plain Huangyan Jia Yan plastic cement company limited etc.Combined medical bottle cap has exceeded ten thousand tons/year by polypropylene modification material demand.And along with the increasingly stringent of national Bureau of Drugs Supervision to medical packaging material hygienic requirements, the technological gap of Combined medical bottle cap is increasingly outstanding, combination cover is badly in need of improving by polypropylene material quality.
Summary of the invention
For the deficiency of present polypropylene combination cover enclosing cover (comprise above-mentioned patent described in combination cover enclosing cover) correlated performance, the invention provides a kind of modified polypropene, as the PP Pipe Compound of infusion vessel polypropylene combination cover enclosing cover.This modified polypropene material has good temperature applicability and resistance to deterioration; Lower separating out, can effectively ensure quality of liquid medicine; Melt fluidity is good, easier injection moulding; Gained combination cover enclosing cover goods are sparkling and crystal-clear, have good gloss and the transparency; Enclosing cover draw ring opening force is moderate, and it is easier that draw ring is opened.
The present invention also provides above-mentioned modification polypropylene dedicated production method.
The present invention adopts following technical scheme:
Polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound of the present invention, described polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound is made up of polypropylene, polyethylene, elastomerics, oxidation inhibitor, slipping agent, transparent agent, and the weight proportion of each component is as follows:
Described elastomerics is thermoplastic elastomer, is one or more the mixing in olefin hydrocarbons thermoplasticity elastic body or styrene series thermoplastic elastomer.Wherein, described olefin hydrocarbons thermoplasticity elastic body is ethylene-vinyl acetate copolymer (EVA), polyethylene octene elastomer (POE) or terpolymer EP rubber (EPDM); Described styrene series thermoplastic elastomer is SBS (SBS) or hydrogenation level SBS elastomerics (SEBS).Further, more preferably polyethylene octene elastomer (POE) of described elastomerics.
Described whiteruss is medical grade mineral oil, is commonly called as medical grade white oil.
Described oxidation inhibitor is antioxidant 1010 and irgasfos 168 preferably 1～2:1 of 1～3:1(in mass ratio) mixing, the Chinese of antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin, the Chinese of irgasfos 168 three [2,4-di-tert-butyl-phenyl] phosphorous acid ester entirely by name.
Described slipping agent is amide substance, is preferably one or both the mixing in erucicamide or amine hydroxybenzene, more preferably erucicamide.Wherein, the chemistry of erucicamide is by name: cis-13-docosene acid amides.The chemistry of amine hydroxybenzene is by name: (Z)-9-octadecenic acid acid amides.
Described transparent agent is transparent nucleater, be preferably organic transparent nucleater or polymer-type transparent nucleater, described organic transparent nucleater is aryl phosphoric acids salt transparent nucleater, glucitols transparent nucleater, carboxylic acid metal's salt transparent nucleater or branching amides transparent nucleater.Wherein, preferably two (2, the 4-di-tert-butyl-phenyl) sodium phosphates, 2 of aryl phosphoric acids salt transparent nucleater, 2-methylene radical-bis-(4,6-di-n-butyl phenol) sodium phosphate or methylene-bis (2,4-di-tert-butyl-phenyl) aluminum phosphate; The preferred Millad3905[1 of glucitols transparent nucleater, 3:2,4-dibenzylidene sorbitol], Millad3940[1,3:2,4-bis-(4-methyl-benzal) sorbyl alcohol] or Millad3988[1,3:2,4-bis-(3,4-dimethyl benzylidene)-D-glucitol]; Carboxylic acid metal's salt transparent nucleater preferred sodium benzoate, n-butylbenzene al formate or p-tert-butyl benzoic acid oxyaluminum; Branching amides transparent nucleater preferably 1,3,5-tri-t-butyl carboxamide base benzene; Polymer-type transparent nucleater preferably polyethylene basic ring butane, polyvinyl eyclohexane, polyvinyl pentamethylene, polyvinyl-2-methylcyclohexane or poly 3 methyl butene 1.Further, described transparent agent is preferably Millad3988.
The present invention also provides the production method of described polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound, and described method comprises the steps:
(a) elastomerics and whiteruss are pressed to formula metering batching, after high-speed mixing, place 2-4 hour, make elastomerics fully swelling, oil-filled, obtain swelling elastomerics;
(b) polypropylene, polyethylene, slipping agent, oxidation inhibitor, transparent agent are pressed to formula metering batching, and the swelling elastomerics that adds step (a) to obtain, after high-speed mixing is even, be heated to 170 DEG C-190 DEG C and melt extrude granulation, make polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound.
Further, the weight proportion of the each component of described polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound is preferably:
In above-mentioned step,
Described step (a) is mixed elastomerics and whiteruss, and the speed of high-speed mixing is preferably 2000-3000r/min, and mixing time is 4-6min.Step (a), by making elastomerics fully swelling, reduces the loss of course of processing lubricant whiteruss, improves the mobility of melt simultaneously, improves the toughness of goods and the opening force of reduction draw ring.
The speed of described step (b) high-speed mixing is preferably 2000-3000r/min, and mixing time is 4-6min.
The melt temperature of described step (b) is preferably 170 DEG C-190 DEG C.
Its advantage of polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound of the present invention is as follows:
1, by the swelling elastomerics of whiteruss, the swelling elastomerics of gained not only can improve the toughness of goods better, and the interpolation of whiteruss, increases elastomeric melt flow rate (MFR), and resulting product is compared with the easier injection moulding of CN101974176A modifying material.Meanwhile, swelling elastomerics can, the in the situation that of identical proportioning, on the basis that corresponding over-all properties is provided, also can reduce the cost of pure thermoplastic elastomer.
2, by selecting proportioning, the content of suitable oxidation inhibitor and adjustment oxidation inhibitor, polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound ageing resistance is improved, and the defect that goods are placed aging yellowing for a long time improves.
3, by adding component PE, reduced elastomeric content, in reducing costs, not obvious to reducing the Toughness of goods, improve the low temperature adaptability of goods.Meanwhile, by adding component PE and transparent agent, increase the transparency of goods, made goods more glossy.Wherein, the interpolation of PE reduces the degree of crystallinity of PP; The effect of nucleator is played in the interpolation of transparent agent, makes the crystal size of PP less, makes that goods are more transparent, gloss.
4, by adding component PE and whiteruss, reduce the fusing point of modified polypropene, made enclosing cover and infusion bottle sealing more firm, can effectively protect quality of liquid medicine.
5, the value of thrust of enclosing cover is 50 ± 5N, draws bad unlatching compared with CN101974176A modifying material injection moulding bottle cap to open easily, and use properties is improved.Polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound injection temperature provided by the invention and pressure are lower, and moulded manufacturability is good.
Brief description of the drawings
Accompanying drawing 1 is the production technological process of polypropylene combined cover for transfusion container PP Pipe Compound of the present invention.
Embodiment
Below in conjunction with drawings and Examples, further illustrate the technical scheme of this explanation, but protection scope of the present invention is not limited to this.
In an embodiment, polyacrylic model is GM1600E, is produced by China Petro-chemical Co..Poly model is 2426H, and by yanshan petrochemical, company limited produces; Elastomerics is polyethylene octene elastomer (POE), and model is 8150, is produced by du pont company; Whiteruss (medical grade white oil) is produced by Hangzhou chemical reagent company limited; Slipping agent is erucicamide, and by Nanjing, Tian Xin Chemical Co., Ltd. provides; Transparent agent is that the trade mark is Millad3988, and by Beijing, plasticizing trade Co., Ltd provides; The model of oxidation inhibitor is 1010 and 168, and by Yixing City angel synthetic chemistry, company produces.
Embodiment 1
Get POE and the 5Kg medical grade white oil of 25Kg, with the speed high-speed mixing of 2000r/min 5 minutes, then place 2 hours, obtain swelling elastomerics.
Get the polypropylene of 48kg, the polyethylene of 22Kg, the erucicamide of 0.1Kg, the oxidation inhibitor (mixing of antioxidant 1010 and irgasfos 168 mass ratio 2:1) of 0.1Kg transparent agent Millad3988 and 0.3Kg and above-mentioned swelling elastomerics 30Kg are at 170 DEG C-190 DEG C, with the speed high-speed mixing of 2000r/min 5 minutes, then extruding pelletization, makes infusion vessel polypropylene combination cover enclosing cover PP Pipe Compound.
Embodiment 2
Get elastomerics and the 5.6Kg medical grade white oil of 28Kg, with the speed high-speed mixing of 2000r/min 5 minutes, then place 2 hours, obtain swelling elastomerics.
Get the polypropylene of 46.4kg, the polyethylene of 20Kg, the erucicamide of 0.15Kg, the oxidation inhibitor (mixing of antioxidant 1010 and irgasfos 168 mass ratio 2:1) of 0.15Kg transparent agent Millad3988 and 0.3Kg and above-mentioned swelling elastomerics 33.6Kg are at 170 DEG C-190 DEG C, with the speed high-speed mixing of 2000r/min 5 minutes, then extruding pelletization, makes infusion vessel polypropylene combination cover enclosing cover PP Pipe Compound.
Embodiment 3
Get elastomerics and the 6Kg medical grade white oil of 30Kg, with the speed high-speed mixing of 2000r/min 5 minutes, then place 2 hours, obtain swelling elastomerics.
Get the polypropylene of 46kg, the polyethylene of 18Kg, the erucicamide of 0.2Kg, the transparent agent Millad3988 of 0.3Kg and the oxidation inhibitor of 0.3Kg (mixing of antioxidant 1010 and irgasfos 168 mass ratio 1:1) and above-mentioned swelling elastomerics 36Kg are at 170 DEG C-190 DEG C, with the speed high-speed mixing of 2000r/min 5 minutes, then extruding pelletization, makes infusion vessel polypropylene combination cover enclosing cover PP Pipe Compound.
Embodiment 4
Get elastomerics and the 5.4Kg medical grade white oil of 27Kg, with the speed high-speed mixing of 2000r/min 5 minutes, then place 2 hours, obtain swelling elastomerics.
Get the polypropylene of 42.6kg, the polyethylene of 27Kg, the erucicamide of 0.15Kg, the transparent agent Millad3988 of 0.2Kg and the oxidation inhibitor of 0.3Kg (mixing of antioxidant 1010 and irgasfos 168 mass ratio 1:1) and above-mentioned swelling elastomerics 32.4Kg are at 170 DEG C-190 DEG C, with the speed high-speed mixing of 2000r/min 5 minutes, then extruding pelletization, makes infusion vessel polypropylene combination cover enclosing cover PP Pipe Compound.
The made infusion vessel polypropylene combination cover enclosing cover PP Pipe Compound of embodiment 1-4 is through detecting, and is white in color in appearance, translucent, and color and luster is even, machinery-free impurity, and size of particles is upper is in any direction 3-5mm.Readily oxidizable substance is 0.7 ± 0.2ml, heavy metal content is all no more than 1,000,000/.
Concrete data are as shown in table 1.
The special the performance test results of table 1 polypropylene combination cover enclosing cover
Polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound is tried out in infusion vessel polypropylene combination cover enclosing cover is produced.Result shows, the aspect such as the polypropylene combination cover enclosing cover composite behaviour manufactured by modified polypropene, outward appearance, draw ring opening force, sealing effect, ageing-resistant performance is all up to state standards, and production technique is simple, can be applicable.
Comparative example 1
According to the scheme of CN101974176A, after 40kg Low Density Polyethylene, 20kg ethylene block copolymerization polypropylene, 30kg polyolefine expanding material (linear low density polyethylene), 0.5kg nucleator (DBS) are mixed, use twin screw extruder extruding pelletization, make polypropylene outer cover material.Carry out Performance Detection according to table 1, result demonstration is with its gained enclosing cover in appearance compared with poor, the low in glossiness of this patent goods transparency, and opening force is bigger than normal, and precipitate (stripping experiment gained non-volatile matter) is bigger than normal, other relevant test data is more approaching, refers to table 1 the performance test results.
Claims (10)
1. a polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound, it is characterized in that described polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound is made up of polypropylene, polyethylene, elastomerics, oxidation inhibitor, slipping agent, transparent agent, the weight proportion of each component is as follows:
Described elastomerics is one or more the mixing in olefin hydrocarbons thermoplasticity elastic body or styrene series thermoplastic elastomer;
Described slipping agent is amide substance;
Described transparent agent is transparent nucleater.
2. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, is characterized in that described olefin hydrocarbons thermoplasticity elastic body is ethylene-vinyl acetate copolymer, polyethylene octene elastomer or terpolymer EP rubber; Described styrene series thermoplastic elastomer is SBS or hydrogenation level SBS elastomerics.
3. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, is characterized in that described whiteruss is medical grade mineral oil.
4. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, is characterized in that described oxidation inhibitor is antioxidant 1010 and the irgasfos 168 mixing of 1～3:1 in mass ratio.
5. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, is characterized in that described slipping agent is one or both the mixing in erucicamide or amine hydroxybenzene.
6. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, it is characterized in that described transparent agent is organic transparent nucleater or polymer-type transparent nucleater, described organic transparent nucleater is aryl phosphoric acids salt transparent nucleater, glucitols transparent nucleater, carboxylic acid metal's salt transparent nucleater or branching amides transparent nucleater.
7. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 6, it is characterized in that, described aryl phosphoric acids salt transparent nucleater is two (2,4-di-tert-butyl-phenyl) sodium phosphate, 2,2-methylene radical-bis-(4,6-di-n-butyl phenol) sodium phosphate or methylene-bis (2,4-di-tert-butyl-phenyl) aluminum phosphate; Described glucitols transparent nucleater is 1,3:2,4-dibenzylidene sorbitol, 1,3:2,4-bis-(4-methyl-benzal) sorbyl alcohol or 1,3:2,4-bis-(3,4-dimethyl benzylidene)-D-glucitol; Described carboxylic acid metal's salt transparent nucleater is Sodium Benzoate, n-butylbenzene al formate or p-tert-butyl benzoic acid oxyaluminum; Described branching amides transparent nucleater is 1,3,5-, tri-t-butyl carboxamide base benzene; Described polymer-type transparent nucleater is polyvinyl tetramethylene, polyvinyl eyclohexane, polyvinyl pentamethylene, polyvinyl-2-methylcyclohexane or poly 3 methyl butene 1.
8. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, is characterized in that described transparent agent is 1,3:2,4-bis-(3,4-dimethyl benzylidene)-D-glucitol; Described slipping agent is erucicamide; Described elastomerics is polyethylene octene elastomer.
9. polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, is characterized in that the weight proportion of the each component of described polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound is:
10. the production method of polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound as claimed in claim 1, is characterized in that described method comprises the steps:
(a) elastomerics and whiteruss are pressed to formula metering batching, after high-speed mixing, place 2-4 hour, obtain swelling elastomerics;
(b) polypropylene, polyethylene, slipping agent, oxidation inhibitor, transparent agent are pressed to formula metering batching, and the swelling elastomerics that adds step (a) to obtain, after high-speed mixing is even, be heated to 170 DEG C-190 DEG C and melt extrude granulation, make polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound.
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| CN201410135769.4A CN103923384B (en) | 2014-04-04 | 2014-04-04 | Polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410135769.4A CN103923384B (en) | 2014-04-04 | 2014-04-04 | Polypropylene combined cover for transfusion container enclosing cover PP Pipe Compound |
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| CN103923384A true CN103923384A (en) | 2014-07-16 |
| CN103923384B CN103923384B (en) | 2017-01-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832586A (en) * | 2017-02-14 | 2017-06-13 | 苏州创扬医药科技股份有限公司 | The material and preparation method of a kind of modified polypropene combination cover |
| CN107177113A (en) * | 2017-05-10 | 2017-09-19 | 蚌埠精工制药机械有限公司 | A kind of easy-to-draw ageing-resistant infusion bottle cap material |
| CN109082005A (en) * | 2018-06-29 | 2018-12-25 | 威海联桥新材料科技股份有限公司 | A kind of Medical connector material and preparation method thereof |
| CN109306125A (en) * | 2018-09-30 | 2019-02-05 | 威海联桥新材料科技股份有限公司 | A kind of oxygen humidification bottle bottle body material and preparation method thereof |
| CN113480799A (en) * | 2021-08-25 | 2021-10-08 | 合诚技术股份有限公司 | Medical EVA catheter material with surface frosted effect and preparation method and application thereof |
Citations (1)
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|---|---|---|---|---|
| CN101974176A (en) * | 2010-10-21 | 2011-02-16 | 湖北大学 | Special material for infusion bottle (bag) ring pull covers and preparation method thereof |
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2014
- 2014-04-04 CN CN201410135769.4A patent/CN103923384B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974176A (en) * | 2010-10-21 | 2011-02-16 | 湖北大学 | Special material for infusion bottle (bag) ring pull covers and preparation method thereof |
Non-Patent Citations (1)
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|---|
| 李俊卿: ""聚丙烯成核剂"", 《山西化工》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832586A (en) * | 2017-02-14 | 2017-06-13 | 苏州创扬医药科技股份有限公司 | The material and preparation method of a kind of modified polypropene combination cover |
| CN107177113A (en) * | 2017-05-10 | 2017-09-19 | 蚌埠精工制药机械有限公司 | A kind of easy-to-draw ageing-resistant infusion bottle cap material |
| CN109082005A (en) * | 2018-06-29 | 2018-12-25 | 威海联桥新材料科技股份有限公司 | A kind of Medical connector material and preparation method thereof |
| CN109306125A (en) * | 2018-09-30 | 2019-02-05 | 威海联桥新材料科技股份有限公司 | A kind of oxygen humidification bottle bottle body material and preparation method thereof |
| CN113480799A (en) * | 2021-08-25 | 2021-10-08 | 合诚技术股份有限公司 | Medical EVA catheter material with surface frosted effect and preparation method and application thereof |
| CN113480799B (en) * | 2021-08-25 | 2023-09-29 | 合诚技术股份有限公司 | Medical EVA catheter material with surface frosting effect, and preparation method and application thereof |
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| CN103923384B (en) | 2017-01-04 |
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