CN1215886C - Formula and preparing process for artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out - Google Patents
Formula and preparing process for artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out Download PDFInfo
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- CN1215886C CN1215886C CN 02124135 CN02124135A CN1215886C CN 1215886 C CN1215886 C CN 1215886C CN 02124135 CN02124135 CN 02124135 CN 02124135 A CN02124135 A CN 02124135A CN 1215886 C CN1215886 C CN 1215886C
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 229920003023 plastic Polymers 0.000 claims abstract description 11
- 239000004033 plastic Substances 0.000 claims abstract description 11
- 229920000249 biocompatible polymer Polymers 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 210000001508 eye Anatomy 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- RDWSYOVJDBEKDB-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)but-3-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C=C)OC(=O)C(C)=C RDWSYOVJDBEKDB-UHFFFAOYSA-N 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 4
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- -1 ormolu Substances 0.000 description 7
- 210000004279 orbit Anatomy 0.000 description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 206010061218 Inflammation Diseases 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 206010061842 Entropion Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007159 enucleation Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- 239000012188 paraffin wax Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
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- Prostheses (AREA)
Abstract
The present invention relates to a formula for artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out and a preparation method thereof, which belongs to the field of biomedicine. The artificial eyeball holder of the present invention is prepared from an initiating agent, a cross-linking agent, a biocompatible polymer monomer and a pore-forming agent. The present invention has the preparation method that 1) the initiating agent, the cross-linking agent and the biocompatible polymer monomer are mixed and prepared into solution; 2) a spherical hollow cavity in a mould is filled with the screened pore-forming agent (with the particle diameter of 300 to 600 micrometers); the mould is placed in a plastic bunsen beaker with the same size to the radius of the bottom of the mould; the solution in step 1 is poured into the plastic bunsen beaker until the mould is soaked, sealed and polymerized under the protection of nitrogen gas; 3) the mould is destroyed, a shaped spherical body is taken out, and excessive parts are removed; 4) a product in step 3 is immersed in deionized water which is replaced each 8 hours and is taken out after 72 hours to obtain the required artificial eyeball holder. The artificial eyeball holder adopts a one-step forming process and has the advantages of precise shape and good cavity communication structure. The porosity of the artificial eyeball holder can be up to more than 75%. The artificial eyeball holder has low material density and can not generate excess pressure on an eyeground.
Description
Technical field:
The invention belongs to biomedical sector, relate to a kind of preparation method that is used to fill the artificial eye holder of eye socket.
Background technology:
Artificial eye holder is to carry out after eyeball excise or ophthalmic hold enucleation, and the eye socket volume reduces, and for preventing the eye socket implant that postoperative eye socket deformity, entropion adopt, has the effect of treatment and beauty treatment simultaneously.Once used some materials in early days as glass, ormolu, plastics, cartilage, fat deposit, silicone etc., but all because complication and undesirable in various degree, as: plastics easily skid off, fat deposit easily is absorbed, silicone has rejection etc., the shortcoming of these material maximums is fixing eye muscle, gives ocular prosthesis vigor and vitality.Use at present synthetic material mainly concentrate on porous material such as polyethylene (MEDPORE, porouspolyethylene), aluminium sesquioxide (Al
2O
3), pottery and hydroxyapatite (HA) etc., but these materials are because its surface is hard, so be easy to generate inflammatory reaction.
Summary of the invention:
The purpose of this invention is to provide a kind of better biocompatibility that has, be difficult for the prescription and the preparation method of the artificial eye holder of initiation inflammatory reaction.
Artificial eye holder of the present invention is made by initiator, cross-linking agent, biocompatible polymer monomer and pore former.Said initiator is a radical initiator, as azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), dibenzoyl peroxide (BPO), dilauroyl peroxide, potassium peroxydisulfate, Ammonium persulfate. etc.Said cross-linking agent is N,N methylene bis acrylamide, DIETHYLENE GLYCOL (DVG), vinyl ethylene glycol dimethacrylate (EDMA) etc.Said polymer monomer is methyl acrylic ester and acrylic compounds such as 2-hydroxyethyl methacry-late (HEMA), methyl methacrylate (MMA), methacrylic acid-2-ethoxy ethyl ester (EEMA), methacrylic acid (MA) etc.Said pore former is NaCl, KCl, Na
2CO
3, NH
4HCO
3, NaHCO
3, water soluble particle such as white sugar.
Its manufacturing process at first is to make a band handle ball, ball is by low melting point high polymer such as Polyethylene Glycol, paraffin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyacrylamides etc. are made, and diameter is 10～30 millimeters, and the clavate of inserting a diameter again and be 3～8 millimeters on ball becomes a band handle ball.
Next is a mfg. moulding die, and mold materials is silicone rubber, firming agent, and its proportioning is a silicone rubber: firming agent=100: 3～10 (weight ratio).Will by prescription claim silicone rubber and firming agent mixing and stirring, will be with the handle ball to be pressed into wherein then, not to handle residue 1/3 outside.After the normal temperature cure 12 hours, mould is put into 70 degrees centigrade of baking ovens heating 12 hours, extract rod, inclining high polymer after the fusing.Mould is put into water boiled 10 minutes, clean for several times, promptly obtain required mould.Can regulate the diameter of spherical cavity by changing the sphere diameter, the diameter that changes rod can be regulated the diameter of reinforced passage.
After mould makes, again the monomer of initiator, cross-linking agent, biocompatible polymer is mixed mutually, be mixed with solution.
The formula proportion of three kinds of components is a polymer monomer: cross-linking agent: initiator is 10ml: 0.1g: 40mg,
Get the pore former of particle diameter in 300～600 micrometer ranges with the standard screen sieve then.To sieve again pore former fill up spherical cavity in the mould by reinforced road, then mould is placed the plastic beaker identical with the mold bottom radius size, the solution of preparing is poured in the beaker; flood mould, nitrogen protection, sealing; under 20 ℃-90 ℃, polyase 13--36 hours.Or after feeding nitrogen protection, sealing was with the Co60 irradiation of ultraviolet or 5～45GY/min 0.5--8 hour.
Ruin mould again, in type spheroid is taken out, with near the redundance reinforced road of file removal.The spheroid that makes is soaked into deionized water, under 20 ℃～90 ℃, changed deionized water in per 8 hours, take out after 72 hours, the pore former dissolving is removed, promptly get artificial eye holder of the present invention.
Therefore the manufacturing process of artificial eye holder of the present invention can be stated as:
1. the monomer with initiator, cross-linking agent, biocompatible polymer mixes mutually, is mixed with solution.
2. get the pore former of particle diameter in 300～600 micrometer ranges with the standard screen sieve.
3. will sieve pore former fill up spherical cavity in the mould by reinforced road, then mould is placed the plastic beaker identical with the mold bottom radius size, the solution in the first step is poured in the beaker; flood mould, nitrogen protection, sealing; at 20 ℃--under 90 ℃, polyase 13--36 hours.Or after feeding nitrogen protection, sealing was with the Co60 irradiation of ultraviolet or 5～45GY/min 0.5-8 hour.
4. ruin mould, in type spheroid is taken out, with near the redundance reinforced road of file removal.
5. goods in 4 are soaked into deionized water, under 20 ℃～90 ℃, changed deionized water in per 8 hours, take out after 72 hours, promptly get required artificial eye holder.
Use method of the present invention, the preparation artificial eye holder has following characteristics and advantage:
1. adopt the once-forming method, can obtain accurate profile and good connection opening structure.
2. the porosity of artificial eye holder can reach more than 75%, and the aperture is adjustable.
3. density of material is little, and soft durometer can be regulated by proportioning, can not produce excessive pressure to the optical fundus.
Description of drawings:
Fig. 1 is that band handle ball sketch map Fig. 2 is a die profile
Fig. 3 is the profile photo of artificial eye holder.
The specific embodiment:
Embodiment 1
1. get 10 milliliters of methacrylic acids-2-ethoxy ethyl ester (EEMA), 0.1 gram DIETHYLENE GLYCOL, 40 milligrams of AIBN obtain solution in beaker.
2. get the NH of particle diameter in 300 microns～400 micrometer ranges by the standard screen sieve
4HCO
3
3. in the spherical cavity of mould, fill it up with sieve in the step 2 NH
4HCO
3
4. mould is placed plastic beaker, add the solution that has prepared,, feed nitrogen protection to flooding mould, sealing, under 60 ℃, polymerisation in bulk 36 hours.
5. take out complete spheroid, remove the irregularity part, be put into then in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Embodiment 2
1. get 7 milliliters of 2-hydroxyethyl methacry-lates (HEMA), 3 milliliters of methyl methacrylates (MMA), 0.1 gram DIETHYLENE GLYCOL, 40 milligrams of AIBN obtain solution in beaker.
2. get the white sugar of particle diameter in 450～520 micrometer ranges by the standard screen sieve
3. in the spherical cavity of mould, fill it up with sieve in the step 2 white sugar.
4. mould is placed plastic beaker, add the solution that has prepared, to flooding mould, feed nitrogen protection, ultraviolet radiation 5 hours are used in sealing.
5. take out complete spheroid, remove the irregularity part, be put into then in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Embodiment 3
1. get 10 milliliters of 2-hydroxyethyl methacry-lates (HEMA), 0.1 gram N,N methylene bis acrylamide, 40 milligrams of ABVN obtain solution in beaker.
2. get the NaCl of particle diameter in 450～520 micrometer ranges by the standard screen sieve.
3. in the spherical cavity of mould, fill it up with sieve in the step 2 NaCl.
4. mould is placed plastic beaker, add the solution that has prepared,, feed nitrogen protection to flooding mould, sealing, under 70 ℃, polymerisation in bulk 24 hours.
5. take out complete spheroid, remove the irregularity part, be put into then in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Embodiment 4
1. get 7 milliliters of 2-hydroxyethyl methacry-lates (HEMA), 3 milliliters of methacrylic acids (MA), 0.1 gram N,N methylene bis acrylamide, 50 milligrams of potassium peroxydisulfates obtain solution in beaker.
2. get the KCl of particle diameter in 300～400 micrometer ranges by the standard screen sieve.
3. in the spherical cavity of mould, fill it up with sieve in the step 2 KCl.
4. mould is placed plastic beaker, add the solution that has prepared, to flooding mould, feed nitrogen protection, sealing was with Co60 radiation (45GY/min) 5 hours.
5. take out complete spheroid, remove the irregularity part, be put into then in the deionized water, under 25 ℃, changed deionized water in per 8 hours, take out after 72 hours.
Claims (2)
1. artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out, the said artificial eye holder of its feature is by initiator, cross-linking agent, biocompatible polymer monomer and pore former are made, said initiator is a radical initiator, for: azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, potassium peroxydisulfate or Ammonium persulfate., said cross-linking agent is N, the N-methylene-bisacrylamide, DIETHYLENE GLYCOL or vinyl ethylene glycol dimethacrylate, said polymer monomer is: 2-hydroxyethyl methacry-late, methyl methacrylate, methacrylic acid-2-ethoxy ethyl ester or methacrylic acid, said pore former is a water soluble particle, for: NaCl, KCl, Na
2CO
3, NH
4HCO
3, NaHCO
3Or white sugar, by initiator, cross-linking agent and biocompatible polymer monomer wiring solution-forming, the formula proportion of three kinds of components is a polymer monomer in the solution: cross-linking agent: initiator is 10ml: 0.1g: 40mg,
The pore former consumption is as the criterion to fill up mould, and the mixed solution consumption is as the criterion to flood mould.
2. the preparation method of artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out, its feature is made up of the following step:
1) with initiator, cross-linking agent, the monomer of biocompatible polymer mixes mutually, be mixed with solution, said initiator is a radical initiator, for: azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, potassium peroxydisulfate or Ammonium persulfate., said cross-linking agent is N, the N-methylene-bisacrylamide, DIETHYLENE GLYCOL or vinyl ethylene glycol dimethacrylate, said polymer monomer is: 2-hydroxyethyl methacry-late, methyl methacrylate, methacrylic acid-2-ethoxy ethyl ester or methacrylic acid
By initiator, cross-linking agent and biocompatible polymer monomer wiring solution-forming, the formula proportion of three kinds of components is a polymer monomer in the solution: cross-linking agent: initiator is 10ml: 0.1g: 40mg,
2) get the pore former of particle diameter in 300～600 micrometer ranges with the standard screen sieve, said pore former is a water soluble particle, for: NaCl, KCl, Na
2CO
3, NH
4HCO
3, NaHCO
3Or white sugar,
3) will sieve pore former fill up spherical cavity in the mould by reinforced road; then mould is placed the plastic beaker identical, the 1st with the mold bottom radius size) step in solution pour in the beaker, flood mould; nitrogen protection; sealing, at 20 ℃--under 90 ℃, polyase 13--36 hours; or after feeding nitrogen protection; sealing was with the Co60 irradiation of ultraviolet or 5～45GY/min 0.5-8 hour
4) ruin mould, in type spheroid is taken out, with near the redundance reinforced road of file removal,
5) with 4) in goods be soaked into deionized water, under 20 ℃～90 ℃, changed deionized water in per 8 hours, take out after 72 hours, promptly get required artificial eye holder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02124135 CN1215886C (en) | 2002-07-12 | 2002-07-12 | Formula and preparing process for artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02124135 CN1215886C (en) | 2002-07-12 | 2002-07-12 | Formula and preparing process for artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1397352A CN1397352A (en) | 2003-02-19 |
| CN1215886C true CN1215886C (en) | 2005-08-24 |
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ID=4745345
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|---|---|---|---|
| CN 02124135 Expired - Fee Related CN1215886C (en) | 2002-07-12 | 2002-07-12 | Formula and preparing process for artificial eyeball holder one-step shaped by bulk-polymerzed particles filtering out |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101904775B (en) * | 2010-06-25 | 2013-07-24 | 西安交通大学 | Tissue-like manufacture die based on spheroid elementary unit and preparation process |
| CN102049063A (en) * | 2010-12-14 | 2011-05-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Material for preparing expandable artificial eye table and application thereof |
-
2002
- 2002-07-12 CN CN 02124135 patent/CN1215886C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1397352A (en) | 2003-02-19 |
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