CN101880402B - Surface modification method for medical grade silicon rubber - Google Patents
Surface modification method for medical grade silicon rubber Download PDFInfo
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- CN101880402B CN101880402B CN2010102145488A CN201010214548A CN101880402B CN 101880402 B CN101880402 B CN 101880402B CN 2010102145488 A CN2010102145488 A CN 2010102145488A CN 201010214548 A CN201010214548 A CN 201010214548A CN 101880402 B CN101880402 B CN 101880402B
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- silicon rubber
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- 229920002529 medical grade silicone Polymers 0.000 title claims abstract description 67
- 229920001971 elastomer Polymers 0.000 title claims abstract description 66
- 239000005060 rubber Substances 0.000 title claims abstract description 66
- 238000002715 modification method Methods 0.000 title abstract 5
- 238000005468 ion implantation Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000260 silastic Polymers 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 13
- 239000007943 implant Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 238000009832 plasma treatment Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 8
- 229920002379 silicone rubber Polymers 0.000 abstract 2
- 239000011664 nicotinic acid Substances 0.000 abstract 1
- 239000004945 silicone rubber Substances 0.000 abstract 1
- 230000010148 water-pollination Effects 0.000 abstract 1
- 238000009736 wetting Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 206010052428 Wound Diseases 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035479 physiological effects, processes and functions Effects 0.000 description 2
- 210000004872 soft tissue Anatomy 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- 206010062575 Muscle contracture Diseases 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 102000003970 Vinculin Human genes 0.000 description 1
- 108090000384 Vinculin Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 208000006111 contracture Diseases 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a surface modification method for a medical grade silicon rubber. The surface modification method is an ion implantation method, the implanted ions are C ions, the ion source is a graphite with the purity more than 99% and the material to be treated is the medical grade silicon rubber. In the process of ion implantation, the ion energy is 10kev, the using amount of ions is 1.0*10<15> ions/cm<2>, the beam density is 0.6 mA/cm<2>, and the residual gas pressure is no more than 1*10<-4>Pa; and in the surface modification method, the C ions serving as the major elements of the human body are selected as the implanted ions, so that the hydrophily of the surface of the silicon rubber, namely the affinity with an organism, is enhanced, and the silicon rubber after being implanted into the human body can be comparable with histocytes, and the deformation and displacement of a medical silicone rubber implant are avoided. Meanwhile, the surface modification method of the invention overcomes the defects of poor peeling, poor stability and complicated processing steps, and the like existing in conventional plasma treatment, graft copolymerization and bionic coating, and the like.
Description
Technical field
The present invention relates to a kind of method of modifying of medical subsidiary material, particularly a kind of surface modifying method of medical grade silicon rubber.
Background technology
The deformity and the operating method of damaged main dependence of body surface organization's organ that reasons such as congenital or wound cause are rebuild, are repaired.Adopting soft tissue filling material to implant in deformity and defect, is its main therapeutic modality, also meets modern medicine substitutes " with the trauma repair wound " with " not having wound reparation " development trend.Yet; The key issue that the restriction clinical therapeutic efficacy further improves is: the nonabsorbable organic polymer material surface that is widely used in the soft tissue filling at present is the intensive hydrophobicity; Cause histiocytic consistency relatively poor; Fibrillar connective tissue forms parcel around material, packing thickens in time, contracture, is prone to cause embedded material distortion displacement.At present, material of new generation such as expanded PTFE, high density polyethylene(HDPE) etc. have got into clinical application, but the particle that wearing and tearing cause causes the anti-property of inflammatory easily, and vesicular structure is prone to conceal bacterium and causes infection, has all limited effect.Compare with above material, although the surface property of Zylox is poor, it has good physical and chemical stability, physiology inertia, erosion resistance and processing characteristics, is still clinical packing material the most commonly used at present.But the surface property of Zylox is poor, and cell tissue is difficult in its surface adhesion, even implant for a long time, does not still observe with the adhesion of tissue and combines, and causes the distortion displacement of Zylox implant easily.Therefore, be necessary Zylox is carried out surface-treated, increase the wetting ability of material surface; Then can strongthener the cell compatibility on surface; Cell is strengthened in its surperficial adhesion and transfer ability, and this modification possibility breakthrough bottleneck further improves result of treatment.In the prior art, organic polymer materials such as Zylox are carried out surface-treated, can take methods such as plasma treatment, graft copolymerization, bionical coating.After the plasma treatment, the polar group that material surface forms overturns easily and gets into the body phase, and modified effect can fail in time gradually; The film that plasma polymerization forms often curls and breaks because of internal stress produces, or because of with matrix be that non-covalent bonds produces and peels off.Grafting copolymerization process makes the polymer surfaces activation through chemical reaction, introduces special groups again, and the surface group instability and the step of formation are cumbersome; Bionical coating covers the material of one deck biologically active above that through methods such as spraying, sputters on the basis that does not change material surface character, also existence condition wayward with problems such as step is cumbersome.
Research surface, the degree of roughness of material surface is also closely related with wetting ability, and material surface is coarse more, its surface-area is increased and increases with the affinity ability of water; In addition, the increase of material surface functional group, and the increase of surface free energy all can make its wetting ability strengthen.
To above-mentioned deficiency, a kind of organic polymer material need be provided, especially the surface modifying method of medical grade silicon rubber makes it can keep strengthening its wetting ability on its former basis that has superiority, and improves its medical performance.
Summary of the invention
In view of this; The surface modifying method that the purpose of this invention is to provide a kind of medical grade silicon rubber; The wetting ability of the medical grade silicon rubber after it is handled through this method strengthens now; After the medical grade silicon rubber after the modification is by implant into body, can produce stronger adhesive power with histocyte, improve the consistency of the two simultaneously; In addition, modified effect is lasting, and the silastic surface modified film can not produce with matrix and peel off, and the modification on surface do not influence the character of material body, and making step is simple, and is with low cost.
The objective of the invention is to realize: a kind of surface modifying method of medical grade silicon rubber through following technical scheme; Said surface modifying method is an ion implantation, and injecting ion is the C ion, and ion source is a purity greater than 99% graphite; Pending material is a medical grade silicon rubber; In the ion implantation process, ion energy is 5-30kev, and ion dose is 1 * 10
14Ions/cm
2-1 * 10
16Ions/cm
2, beam current density is not more than 0.6mA/cm
2, residual gas pressure is not more than 1 * 10
-3Pa.
Further, in the ion implantation process, ion energy is 10kev, and ion dose is 1 * 10
15Ions/cm
2, beam current density is 0.6mA/cm
2, residual gas pressure is 1 * 10
-4Pa;
Further, pending silastic surface need use acetone as medium, in the ultrasonic cleaning appearance, cleans.
The invention has the beneficial effects as follows: first; Owing to adopt ion implantation method to carry out surface modification treatment to medical grade silicon rubber; This surface modifying method is a kind of purified non-harmful process for treating surface, need not under hot environment, to carry out, thereby can not influence the character of pending medical grade silicon rubber; A series of physics and chemical interaction take place by ionic fluid and matrix surface and a new upper layer forming in ion implanted layer, can not peel off between it and the matrix; Second; Surface modifying treatment of the present invention can form the micrographics structure at material surface; Increase the surfaceness and the surface free energy of medical grade silicon rubber material, thereby strengthened the wetting ability of medical grade silicon rubber greatly, improved the consistency of medical grade silicon rubber and human body cell; Make between the Zylox of human tissue cell and implantation and produce adhesive power, thereby avoided the distortion displacement of medical grade silicon rubber implant.The 3rd, adopt ion implantation that existing medical grade silicon rubber is carried out surface-treated, overcome deficiencies such as the peeling off of existence such as the processing of existing process for modifying surface ionic medium body, graft copolymerization, bionical coating, poor stability, process step be loaded down with trivial details.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified;
Accompanying drawing 1 is the scanning electron microscopic observation image of embodiment 1 gained medical grade silicon rubber;
Accompanying drawing 2 is the scanning electron microscopic observation image of embodiment 2 gained medical grade silicon rubbers;
Accompanying drawing 3 is the scanning electron microscopic observation image of embodiment 3 gained medical grade silicon rubbers;
Accompanying drawing 4 is the scanning electron microscopic observation image of untreated medical grade silicon rubber;
Accompanying drawing 5 is the atomic force microscope observation image of embodiment 1 gained medical grade silicon rubber;
Accompanying drawing 6 is the atomic force microscope observation image of embodiment 2 gained medical grade silicon rubbers;
Accompanying drawing 7 is the atomic force microscope observation image of embodiment 3 gained medical grade silicon rubbers;
Accompanying drawing 8 is the atomic force microscope observation image of untreated medical grade silicon rubber;
Accompanying drawing 9 is the x-ray photoelectron ability spectrogram of embodiment 1 gained medical grade silicon rubber;
Accompanying drawing 10 is the x-ray photoelectron ability spectrogram of embodiment 2 gained medical grade silicon rubbers;
Accompanying drawing 11 is the x-ray photoelectron ability spectrogram of embodiment 3 gained medical grade silicon rubbers;
Accompanying drawing 12 is the x-ray photoelectron ability spectrogram of untreated medical grade silicon rubber;
Accompanying drawing 13 is that the laser confocal microscope of the medical grade silicon rubber of embodiment 1 gained is observed image;
Accompanying drawing 14 is that the laser confocal microscope of the medical grade silicon rubber of embodiment 2 gained is observed image;
Accompanying drawing 15 is that the laser confocal microscope of the medical grade silicon rubber of embodiment 3 gained is observed image;
Accompanying drawing 16 is that the laser confocal microscope of untreated medical grade silicon rubber is observed image.
Embodiment
The present invention is applied to the surface modifying method of medical grade silicon rubber with the ion implantation technique that tradition is used for metal, semiconductor material surface modification; Because ion implantation is a kind of purified non-harmful process for treating surface; Need not under hot environment, to carry out, thereby can not influence the character of pending medical grade silicon rubber; Simultaneously, a series of physics and chemical interaction take place by ionic fluid and matrix surface and a new upper layer forming in ion implanted layer, can not peel off between it and the matrix, in conjunction with very firmly; The present invention adopts ion implanter that medical grade silicon rubber is carried out surface-treated, and in the ion implantation process, injecting ion is the C ion; Use purity greater than 99% graphite as ion source; Pending material is a medical grade silicon rubber, and ion energy is 10keV, and ion dose is 1 * 10
14Ions/cm
2-1 * 10
16Ions/cm
2, beam current density is not more than 0.6mA/cm
2, residual gas pressure is not more than 1 * 10
-3Pa.
As to further improvement of the present invention, pending silastic surface need use acetone as medium, in the ultrasonic cleaning appearance, cleans, to guarantee the degree of cleaning on pending medical grade silicon rubber surface.
Embodiment 1, and in the ion implantation process, ion source is that purity is 99.5% graphite, and pending material is a medical grade silicon rubber, and ion energy is 5kev, and ion dose is 1 * 10
14Ions/cm
2, beam current density is 0.5mA/cm
2, residual gas pressure is 1 * 10
-4Pa carries out surface treatment through ion implantation under the above-mentioned parameter condition, can obtain the medical grade silicon rubber that wetting ability is strong, consistency good, stability is strong.
Embodiment 2, and in the ion implantation process, ion source is that purity is 99.5% graphite, and pending material is a medical grade silicon rubber, and ion energy is 10kev, and ion dose is 1 * 10
15Ions/cm
2, beam current density is 0.6mA/cm
2, residual gas pressure is 1 * 10
-4Pa carries out surface treatment through ion implantation under the above-mentioned parameter condition, can obtain the medical grade silicon rubber that wetting ability is strong, consistency good, stability is strong.
Embodiment 3, and in the ion implantation process, ion source is that purity is 99.5% graphite, and pending material is a medical grade silicon rubber, and ion energy is 30kev, and ion dose is 1 * 10
16Ions/cm
2, beam current density is 0.6mA/cm
2, residual gas pressure is 1 * 10
-3Pa carries out surface treatment through ion implantation under the above-mentioned parameter condition, can obtain the medical grade silicon rubber that wetting ability is strong, consistency good, stability is strong.
The modification medical grade silicon rubber of above-mentioned 3 embodiment gained is carried out various performance tests, and the result is following:
Extremely shown in Figure 4 like Fig. 1; The medical grade silicon rubber of above-mentioned three embodiment gained is analyzed with ESEM; Under 20000 times of magnifications, observe; And compare with the medical grade silicon rubber that does not carry out ion implantation processing; Not observing the ion implantation back of C has notable difference with the medical grade silicon rubber that does not carry out ion implantation processing, explain that C is ion implantation after, be on the micro-scale to the change of material surface structure; Therefore explanation adopts ion implantation that the medical grade silicon rubber material is carried out the character that surface-treated can't change pending medical grade silicon rubber, has still kept advantages such as the good physical and chemical stability of conventional medical Zylox, physiology inertia, erosion resistance and workability.
, the medical grade silicon rubber of above-mentioned three embodiment gained is observed with AFM, and compared to shown in Figure 8 like Fig. 5 with the medical grade silicon rubber that does not carry out ion implantation processing; Find through after the ion implantation processing; The configuration of surface obvious difference of material, the medical grade silicon rubber surface of the ion implantation processing of process all presents rugged " projection ", from AFM (AFM), can find out; After the C atom injects; Material surface becomes coarse by smooth, has increased surface-area, so strengthen through the wetting ability of ion implantation surface-treated medical grade silicon rubber material.
Extremely shown in Figure 12 like Fig. 9; The medical grade silicon rubber of above-mentioned three embodiment gained and the medical grade silicon rubber that do not carry out ion implantation processing are carried out XPS (x-ray photoelectron power spectrum) analyze, find to adopt the C atom to carry out ion implantation processing after, variation has all taken place in three peaks of expression Si, C, O; It is as shown in the table for the ratio of each component; The condition of surface that has changed pending medical grade silicon rubber material after C injects is described, and the per-cent of C increases with IR, also increase gradually.Above result has replaced part Si after proving that the C atom injects, and has interrupted original Si-O, makes the free energy on surface improve, thereby has increased the wetting ability of medical grade silicon rubber.
Shown in Figure 13 to 16; Do not carry out cell cultures (L929 cell) with carrying out ion implantation medical grade silicon rubber with the medical grade silicon rubber that adopts the C atom to carry out after the ion implantation processing; Grey color part representes to adhere to the cell of material surface among the figure; With can see obviously that from figure cell obviously improves at the growth conditions on the medical grade silicon rubber surface of carrying out ion implantation processing, cell is sprawled and is superior to unmodified material; The cell edges white point is represented the button albumen vinculin of cell adhesiveness; It is thus clear that the proteic expression of ion implantation back button is obviously increased, explain that the adhesion situation between cell and the process medical grade silicon rubber material of ion implantation processing also significantly improves, adhesive power obviously strengthens.
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the aim and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the power claimed range of the present invention.
Claims (2)
1. the surface modifying method of a medical grade silicon rubber; It is characterized in that: said surface modifying method is an ion implantation, and injecting ion is the C ion, and ion source is a purity greater than 99% graphite; Pending material is a medical grade silicon rubber; In the ion implantation process, ion energy is 10kev, and ion dose is 1 * 10
15Ions/cm
2, beam current density is 0.6mA/cm
2, residual gas pressure is 1 * 10
-4Pa.
2. the surface modifying method of medical grade silicon rubber according to claim 1, it is characterized in that: pending silastic surface need use acetone as medium, in the ultrasonic cleaning appearance, cleans.
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CN2010102145488A CN101880402B (en) | 2010-06-30 | 2010-06-30 | Surface modification method for medical grade silicon rubber |
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CN101880402A CN101880402A (en) | 2010-11-10 |
CN101880402B true CN101880402B (en) | 2012-06-27 |
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CN103044699B (en) * | 2011-10-11 | 2014-10-22 | 中国科学院理化技术研究所 | Method for preparing medical high polymer material by adopting ion implantation technology |
CN104530503B (en) * | 2015-01-28 | 2016-04-20 | 河南职业技术学院 | The preparation method of the tire that a kind of earth-catching property is good |
CN104721875B (en) * | 2015-03-18 | 2017-03-01 | 华南理工大学 | A kind of hydrophilic silicone rubber medical dressing and preparation method thereof |
CN110092938B (en) * | 2019-04-24 | 2022-02-11 | 中国人民解放军陆军军医大学第二附属医院 | Method for modifying silicon rubber material by using double ions and product thereof |
CN112376033B (en) * | 2020-11-27 | 2021-07-23 | 中国科学院兰州化学物理研究所 | C. Method for preparing low-friction fluorosilicone rubber surface by Al double-element injection |
CN112376031B (en) * | 2020-11-27 | 2021-07-13 | 中国科学院兰州化学物理研究所 | Method for preparing low-friction high-wear-resistance silicone rubber surface by injecting low-temperature electron beam excited plasma into carbon nanoclusters |
CN116373367B (en) * | 2023-05-29 | 2023-09-19 | 昂凯生命科技(苏州)有限公司 | Preparation method and application of cervical biological sample self-sampling device |
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CN101351890A (en) * | 2006-09-07 | 2009-01-21 | 胜高股份有限公司 | Semiconductor substrate for solid state imaging device, solid state imaging device, and method for manufacturing them |
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CN101351890A (en) * | 2006-09-07 | 2009-01-21 | 胜高股份有限公司 | Semiconductor substrate for solid state imaging device, solid state imaging device, and method for manufacturing them |
Non-Patent Citations (2)
Title |
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Hiroshi Tsuji et.al.Immobilization of extracellular matrix on polymeric materials by carbon-negative-ion implantation.《Nuclear Instruments and Methods in Physics Research B》.2005,第237卷459–464. * |
Junzo Ishikawa.Applications of heavy-negative-ion sources for materials science (invited).《Review of Scientific Instruments》.2000,第71卷1036-1041. * |
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