CN104059319A - Application of 6'-azacyclo substituted-9'-acyloxy esterified spirooxazine photochromic compound to contact lens - Google Patents

Application of 6'-azacyclo substituted-9'-acyloxy esterified spirooxazine photochromic compound to contact lens Download PDF

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CN104059319A
CN104059319A CN201410280449.8A CN201410280449A CN104059319A CN 104059319 A CN104059319 A CN 104059319A CN 201410280449 A CN201410280449 A CN 201410280449A CN 104059319 A CN104059319 A CN 104059319A
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substituted
azacyclo
acyloxy
esterification
photochromic compound
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杨晓莉
张雅雯
周刘煜
袁晟磊
蔡健
吕乐
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Jinling Institute of Technology
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Abstract

The invention provides application of 6'- azacyclo substituted-9'-acyloxy esterified spirooxazine photochromic compound to contact lens. The 6'- azacyclo substituted-9'-acyloxy esterified spirooxazine photochromic compound is prepared into photochromic contact lenses by an osmosis or blending or polymerization method. The compound prepared by the method provided by the invention can be applied to photochromic contact lenses, has quick photochromic response, high fade speed, complete fade and fatigue resistance in a polymer medium, and solves the problems of practicality and or potential use limit in the prior art.

Description

The application of 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound in contact lens
Technical field
The present invention relates to chemical field, be specifically related to the preparation method of a kind of 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound.
Background technology
In the production of domestic existing photochromic contact lenses, the photochromic raw material of high-quality mostly relies on import, exploitation have independent intellectual property right, optical Response is good, fatigue resistance is good, photochromic compound, and it is significant to apply it to contact lens production field.
Summary of the invention
The invention provides a kind of 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound and apply in contact lens, solved that the existing photochromic low-response of photochromic compound in contact lens field application, fading rate are slow, the defect such as fade not exclusively causes the limited problem of its practical or potential applicability.
For achieving the above object, the technical solution adopted in the present invention is:
A preparation method for 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound, is characterized in that, specifically comprises following three steps:
The first step: intermediate 1-nitroso-group-2,7 dihydroxy naphthalene phenol (II) synthetic:
2,7 dihydroxy naphthalene phenol first at-5 ℃～0 ℃ with NaNO 2reaction, then with R 1h reacts and obtains intermediate 1-nitroso-group-2,7 dihydroxy naphthalene phenol (II) under heating condition; Or 2,7 dihydroxy naphthalene phenol directly reacts with NaNO2 and obtains intermediate 1-nitroso-group-2,7 dihydroxy naphthalene phenol (II) at-5 ℃～0 ℃;
Second step: the preparation of intermediate Luo oxazine (III),
1-nitroso-group-2,7 dihydroxy naphthalene phenol (II) reacts with 1,3,3-trimethylammonium-dimethylene indoline Hybrid Heating in solvent, preparation Luo oxazine (III); Described solvent is methyl alcohol, ethanol or trieline;
The 3rd step: finished product 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound (I) synthetic:
Spiral shell oxazine (III) be take diox and triethylamine as catalyzer reacts with corresponding acyl chlorides, makes 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound (I);
Wherein, R 1for substituted or non-substituted morpholinyl, pyrrolidyl, piperidyl, decahydroquinolyl, piperidyl, Decahydroisoquinolinpreparation base or indoline base, described substituting group is halogen or C 1～6alkyl;
R 2for methacryloyl, benzoyl, halogeno-benzene formyl radical, methoxybenzoyl base, C 1～6alkylbenzene formyl radical, phenyl benzoyl, phenoxy group benzoyl, pyridine formyl radical, 9H-Fluorenone-2-formyl radical or 9-ethyl-9H-carbazole-2-formyl radical, described substituting group is halogen, C 1～6alkyl, C 1～6alkoxyl group, phenyl or phenoxy group.
Preferably, R 2for methacryloyl, benzoyl, p-chlorobenzene formacyl or p-anisoyl.
Preferably, described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is applied in contact lens by osmose process, and described osmose process is about to described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound and is penetrated into colourless contact lens surface.
Preferably, described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is applied in contact lens by blending method, described blending method is before production, 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound without-C=C-unsaturated double-bond is joined in the starting monomer of contact lens, then prepare eyeglass.
Preferably, described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is applied in contact lens by polymerization, and described polymerization is about to 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound with-C=C-unsaturated double-bond and reacts with contact lens starting monomer and prepare eyeglass.
Further, described starting monomer mainly comprises polymethylmethacrylate, polymethyl acrylic acid-beta-hydroxy ethyl ester and poly N-vinyl pyrrolidone.
Further, the amount of filling of described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is the 0.5%-5% of starting monomer molecular weight.
Further, in described polymerization, also need to dose initiator, the consumption of described initiator is the 0.1-1.6% of starting monomer molecular weight.
Further, described initiator is thermal initiator, and described thermal initiator is the mixture of Diisopropyl azodicarboxylate or azo two (2,4-methyl pentane nitrile) or Diisopropyl azodicarboxylate and azo two (2,4-methyl pentane nitrile).
Further, described initiator is light trigger, and described light trigger is one or more in benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether.
The invention has the advantages that:
The photochromic compound making through method of the present invention, be applied in photochromic contact lenses, in polymeric media, show fabulous photochromic behavior, photochromic responsiveness, fading rate and fatigue resistance, solved the problem of its practical or potential applicability restriction in prior art.
Accompanying drawing explanation
Fig. 1 is the fatigue resistance test pattern of the photochromic material that makes of one embodiment of the invention 2 in PMMA film.
Embodiment
Embodiment 1
A preparation method for 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound, is characterized in that, specifically comprises following three steps:
The first step: intermediate 1-nitroso-group-2,7 dihydroxy naphthalene phenol (II) synthetic:
2,7 dihydroxy naphthalene phenol first at-5 ℃～0 ℃ with NaNO 2reaction, then with R 1h reacts and obtains intermediate 1-nitroso-group-2,7 dihydroxy naphthalene phenol (II) under heating condition; Or 2,7 dihydroxy naphthalene phenol directly at-5 ℃～0 ℃ with NaNO 2reaction obtains intermediate 1-nitroso-group-2,7 dihydroxy naphthalene phenol (II);
Second step: the preparation of intermediate Luo oxazine (III),
1-nitroso-group-2,7 dihydroxy naphthalene phenol (II) reacts with 1,3,3-trimethylammonium-dimethylene indoline Hybrid Heating in solvent, preparation Luo oxazine (III); Described solvent is methyl alcohol, ethanol or trieline;
The 3rd step: finished product 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound (I) synthetic:
Spiral shell oxazine (III) be take diox and triethylamine as catalyzer reacts with corresponding acyl chlorides, makes 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound (I);
Wherein, R 1for substituted or non-substituted morpholinyl, pyrrolidyl, piperidyl, decahydroquinolyl, piperidyl, Decahydroisoquinolinpreparation base or indoline base, described substituting group is halogen or C 1～6alkyl;
R 2for methacryloyl, benzoyl, halogeno-benzene formyl radical, methoxybenzoyl base, C 1～6alkylbenzene formyl radical, phenyl benzoyl, phenoxy group benzoyl, pyridine formyl radical, 9H-Fluorenone-2-formyl radical or 9-ethyl-9H-carbazole-2-formyl radical, described substituting group is halogen, C 1～6alkyl, C 1～6alkoxyl group, phenyl or phenoxy group.
Preferably, R1 is further selected from
Preferably, R 2be selected from
Preferably, R 2further be selected from methacryloyl, benzoyl, p-chlorobenzene formacyl or p-anisoyl.Embodiment 2
Synthesizing of 1-nitroso-group 2,7 dihydroxy naphthalene:
The 2,7 dihydroxy naphthalene of 10g is dissolved in the 100mlNaOH aqueous solution to (concentration is: 0.625mol/L), be placed in cryosel and bathe, keep temperature-2～-3 ℃, slowly add the NaNO of 4.31g 2, stir lower aqueous sulfuric acid (the 8ml vitriol oil: 15ml water) that drips.After dropwising, continue to stir one hour under-2～-3 ℃ of conditions, stop stirring, filter, washing filtrate, to neutral, obtains product 1-nitroso-group 2,7 dihydroxy naphthalene with being spin-dried for organic phase after extracted with diethyl ether.Infrared: ν (cm -1): 3188 (ν O-H), 1530 (ν N-O), 1654,1610 (aromatic ring frames), 1308,1226 (ν C-O), 839 (ν C-N).Ultimate analysis, C 10h 7o 3n: measured value (theoretical value)/%:C63.49 (63.52); H3.71 (3.70); N7.43 (7.41).
1,3,3-trimethylammonium-6 '-morpholinyl-9 '-hydroxyl-spiral shell [synthesizing of 2,3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine]:
1.89g (0.01mol) 1-nitroso-group-2, the morpholine of 7-dihydroxy naphthlene and 1.74g (0.02mol) passes into nitrogen reflux 5h in 50ml trieline, drips 1.73g, (0.01mol) 1, the mixed solution of 3,3-trimethylammonium-dimethylene indoline and 10ml trieline.Continue heating reflux reaction, stopped reaction after 36h, filtered while hot, is spin-dried for to obtain product with silica gel column chromatography column purification (PE:EA=2:1) after filtrate is concentrated.Productive rate 1.63%; Fusing point: 246～248 ℃; Nuclear-magnetism: 1H NMR (500MHz, DMSO): δ 6.41-9.81 (10H, m, ArH, H-2 '), 3.80 (4H, t, J=6.8Hz, 2CH 2), 2.95 (t, J=5.8Hz, 2CH 2), 2.67 (3H, s, CH3), 1.26 (6H, s, CH3).MS(ESI):calcd.for[M+H] +430.51；found430.1。
1,3,3-trimethylammonium-6 '-morpholinyl-9 '-methacryloxypropyl-spiral shell [synthesizing of 2,3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine]:
1,3 of 0.429g (1mmol), 3-trimethylammonium-6-morpholinyl-9 '-hydroxyl-spiral shell [2, benzene, 10ml diox and the (0.3g of 3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine], 70ml, triethylamine mixing solutions 3mmol), fully stirring and dissolving.Control 5 ℃ of temperature of reaction, drip benzole soln (methacrylic chloride: 0.31g, the benzene: 5ml), dropwise rear recovery temperature of reaction and cause room temperature r.t.=23 ℃, stirring reaction 10 hours of methacrylic chloride.React complete, suction filtration, revolves steaming by filtrate and obtains pale solid 1,3,3-trimethylammonium-6-morpholinyl-9 '-methacryloxypropyl-spiral shell [2,3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine] 0.39g (productive rate 78.43%).Fusing point: 193～195 ℃; 1hNMR (500MHz, CDCl 3): δ 5.77-8.27 (10H, m, ArH, H-2 '), 3.93 (4H, t, J=4.50Hz, 2CH 2), 3.06 (4H, d, J=3.85Hz, 2CH 2), 2.7 (3H, s, CH 3), 2.11 (3H, s, CH 3), 1.28 (6H, s, CH 3).MS(ESI):calcd.for[M+H] +498.58；found498.2。
Detect
This photochromic material (1,3,3-trimethylammonium-6 '-morpholinyl-9 '-methacryloxypropyl-spiral shell [2,3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine]) adopt osmose process to join (mass ratio: 0.5%) in PMMA contact lens, then use the UV-irradiation of 365nm, can be observed PMMA from the colourless blueness that becomes,, with ultraviolet spectrophotometer (U.S. Varian UV1101), can observe after illumination at 600nm meanwhile -1there is maximum absorption band in place.
The photoresponse effect of the PMMA film that embodiment 2 makes under daylight is as following table:
The compound time Embodiment 2
The initial photoresponse time 6s
The maximum photoresponse time 90s
Initial fading time 10s
The fading end point time 79s
The fatigue resistance of the photochromic material that embodiment 2 makes in PMMA film, is shown in shown in accompanying drawing 1.
Embodiment 3
Adopt the method for copolymerization to join (mass ratio: 1%) in PMMA the photochromic material of embodiment 2 gained, selecting benzoin dimethylether is initiator, consumption is 0.1%, then use the UV-irradiation of 365nm, can be observed its color from the colourless blueness that becomes, meanwhile, at 595nm-1 place, there is maximum absorption band after can observe illumination with ultraviolet spectrophotometer (U.S. Varian UV1101).
Embodiment 4
Adopt the method for copolymerization to join (mass ratio: 1%) in PHEMA the photochromic material of embodiment 2 gained, selecting Diisopropyl azodicarboxylate is initiator, consumption is 0.3%, then use the UV-irradiation of 365nm, can be observed its color from the colourless blueness that becomes, meanwhile, at 595nm-1 place, there is maximum absorption band after can observe illumination with ultraviolet spectrophotometer (U.S. Varian UV1101).
Embodiment 5
1,3,3-trimethylammonium-6 '-indyl-9 '-hydroxyl-spiral shell [synthesizing of 2,3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine]
1.89g (0.01mol) 1-nitroso-group-2,7-dihydroxy naphthlene and 1.74g (0.02mol) indyl passes into nitrogen reflux 5h in 50ml methyl alcohol, drip 1.73g (0.01mol) 1,3, the mixed solution of 3-trimethylammonium-dimethylene indoline and 10ml methyl alcohol.Back flow reaction 36h stopped reaction, filtered while hot, is spin-dried for to obtain product with purification by silica gel column chromatography (PE:EA=2:1) after filtrate is concentrated.Productive rate: 1.48%; Fusing point: 124-126 ℃; Nuclear-magnetism: 1H NMR (500MHz, DMSO): δ 6.07-9.89 (13H, m, ArH, H-2 '), 3.86 (2H, t, J=8.50, CH2), 3.08 (2H, s, CH2), 2.67 (3H, s, CH3), 1.26 (6H, d, J=4.9,2CH3).MS(ESI):calcd.for[M+H]+462.21；found462.3。
1,3,3-trimethylammonium-6 '-indyl-9 '-methacryloxypropyl-spiral shell [synthesizing of 2,3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine]
1,3 of 0.462g (1mmol), 3-trimethylammonium-6 '-indyl-9 '-hydroxyl-spiral shell [2, benzene, 10ml diox and the (0.3g of 3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine], 70ml, triethylamine mixing solutions 3mmol), fully stirring and dissolving.Control 5 ℃ of temperature of reaction, drip benzole soln (methacrylic chloride: 0.31g, the benzene: 5ml), dropwise rear recovery temperature of reaction and cause room temperature r.t.=23 ℃, stirring reaction 10 hours of methacrylic chloride.React complete, suction filtration, revolves steaming by filtrate and obtains yellow-green colour solid 1,3,3-trimethylammonium-6 '-morpholinyl-9 '-methacryloxypropyl-spiral shell [2,3 '-[3H]-naphtho-[2,1-b] [Isosorbide-5-Nitrae] oxazine].Productive rate: 51.3%; Fusing point: 248-250 ℃; Nuclear-magnetism: 1H NMR (500MHz, DMSO): δ 6.32-8.32 (13H, m, ArH, H-2 '), 6.30 (1H, s, CH), 5.78 (1H, s, CH), 3.89 (2H, t, J=12.30Hz, CH2), 3.17 (2H, s, CH2), 2.76 (3H, s, CH3), 2.11 (3H, s, CH3) 1.34 (6H, s, CH3).MS(ESI):calcd.for[M+H]+530.63；found530.3。
Detect
This photochromic material adopts osmose process to join (mass ratio: 1.5%) in PMMA, then use the UV-irradiation of 365nm, can be observed PMMA from the colourless blueness that becomes, meanwhile, at 595nm-1 place, there is maximum absorption band after can observe illumination with ultraviolet spectrophotometer (U.S. Varian UV1101).
Embodiment 6
Adopt the method for copolymerization to join (mass ratio: 0.5%) in PNVP the photochromic material of embodiment 5 gained, selecting Benzoin ethyl ether is initiator, consumption is 0.1%, then use the UV-irradiation of 365nm, can be observed its color from the colourless blueness that becomes, meanwhile, with ultraviolet spectrophotometer (U.S. Varian UV1101), can observe after illumination at 590nm -1there is maximum absorption band in place.
Embodiment 7
Adopt the method for copolymerization to join (mass ratio: 0.5%) in PHEMA the photochromic material of embodiment 2 gained, select azo two (2,4-methyl pentane nitrile) be initiator, consumption is 0.1%, then use the UV-irradiation of 365nm, can be observed its color from the colourless blueness that becomes, meanwhile, at 590nm-1 place, occur maximum absorption band after can observe illumination with ultraviolet spectrophotometer (U.S. Varian UV1101).
To sum up draw, 6 '-azacyclo substituted-9 ' that the present invention makes-acyloxy esterification spirooxazine photochromic compound has the performances such as photochromic response is fast, fading rate fast, fade completely, fatigue resistance is strong in polymeric media.
Embodiment 8
The making processes of photochromic contact lenses can adopt following three kinds of modes to carry out:
Osmose process: i.e. 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is penetrated into colourless contact lens surface;
Blending method: before production, just join in the starting monomer of contact lens, then prepare eyeglass without-C=C-unsaturated double-bond 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound;
Polymerization: be about to 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound with-C=C-unsaturated double-bond and react with contact lens starting monomer and prepare eyeglass.
The starting monomer of photochromic contact lenses comprises and specifically mainly comprises polymethylmethacrylate (PMMA), polymethyl acrylic acid-beta-hydroxy ethyl ester (P-HEME), poly N-vinyl pyrrolidone (P-NVP).
The amount of filling of 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is the 0.5%-5% of starting monomer molecular weight.
For polymerization, also need to dose initiator, its consumption is the 0.1-1.6% of polymer monomer molecular weight, it can be thermal initiator, as Diisopropyl azodicarboxylate, azo two (2,4-methyl pentane nitrile) can be also their mixture, can be also light trigger as benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, or their mixture.
Above-described embodiment is just to allow one of ordinary skilled in the art can understand content of the present invention and implement according to this for technical conceive of the present invention and feature being described, its objective is, can not limit the scope of the invention with this.Every equivalent variation or modification that according to the present invention, the essence of content has been done, all should be encompassed in protection scope of the present invention.

Claims (8)

  1. The application of 1.6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound in contact lenses, it is characterized in that: described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is applied in contact lens by osmose process, described osmose process is about to described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound and is penetrated into colourless contact lens surface.
  2. 2. the application of 6 '-azacyclo substituted-9 ' according to claim 1-acyloxy esterification spirooxazine photochromic compound in contact lenses, it is characterized in that: described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is applied in contact lens by blending method, described blending method is before production, 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound without-C=C-unsaturated double-bond is joined in the starting monomer of contact lens, then prepare eyeglass.
  3. 3. the application of 6 '-azacyclo substituted-9 ' according to claim 1-acyloxy esterification spirooxazine photochromic compound in contact lenses, it is characterized in that: described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is applied in contact lens by polymerization, described polymerization is about to 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound with-C=C-unsaturated double-bond and reacts with contact lens starting monomer and prepare eyeglass.
  4. 4. the application in contact lenses according to 6 '-azacyclo substituted-9 ' described in claim 2 or 3-acyloxy esterification spirooxazine photochromic compound, is characterized in that: described starting monomer mainly comprises polymethylmethacrylate, polymethyl acrylic acid-beta-hydroxy ethyl ester and poly N-vinyl pyrrolidone.
  5. 5. the application in contact lenses according to 6 '-azacyclo substituted-9 ' described in claim 2 or 3-acyloxy esterification spirooxazine photochromic compound, is characterized in that: the amount of filling of described 6 '-azacyclo substituted-9 '-acyloxy esterification spirooxazine photochromic compound is the 0.5%-5% of starting monomer molecular weight.
  6. 6. the application of 6 '-azacyclo substituted-9 ' according to claim 3-acyloxy esterification spirooxazine photochromic compound in contact lenses, it is characterized in that: in described polymerization, also need to dose initiator, the consumption of described initiator is the 0.1-1.6% of starting monomer molecular weight.
  7. 7. the application of 6 '-azacyclo substituted-9 ' according to claim 6-acyloxy esterification spirooxazine photochromic compound in contact lenses, it is characterized in that: described initiator is thermal initiator, described thermal initiator is the two or Diisopropyl azodicarboxylate of Diisopropyl azodicarboxylate or azo and the mixture of azo pair.
  8. 8. the application of 6 '-azacyclo substituted-9 ' according to claim 6-acyloxy esterification spirooxazine photochromic compound in contact lens, it is characterized in that: described initiator is light trigger, described light trigger is one or more in benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether.
CN201410280449.8A 2014-06-20 2014-06-20 Application of 6'-azacyclo substituted-9'-acyloxy esterified spirooxazine photochromic compound to contact lens Pending CN104059319A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104402903A (en) * 2014-11-20 2015-03-11 南京邮电大学 Photochromic compound and preparation method and application thereof
EP3992695A4 (en) * 2019-06-27 2023-05-10 Menicon Co., Ltd. Ophthalmic medical instrument including photochromic polymer and production method for ophthalmic medical instrument

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104402903A (en) * 2014-11-20 2015-03-11 南京邮电大学 Photochromic compound and preparation method and application thereof
CN104402903B (en) * 2014-11-20 2016-08-24 南京邮电大学 Photochromic compound and its preparation method and application
EP3992695A4 (en) * 2019-06-27 2023-05-10 Menicon Co., Ltd. Ophthalmic medical instrument including photochromic polymer and production method for ophthalmic medical instrument

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Application publication date: 20140924

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