CA2230646A1 - Method and composition for the manufacture of ophthalmic lenses - Google Patents
Method and composition for the manufacture of ophthalmic lenses Download PDFInfo
- Publication number
- CA2230646A1 CA2230646A1 CA002230646A CA2230646A CA2230646A1 CA 2230646 A1 CA2230646 A1 CA 2230646A1 CA 002230646 A CA002230646 A CA 002230646A CA 2230646 A CA2230646 A CA 2230646A CA 2230646 A1 CA2230646 A1 CA 2230646A1
- Authority
- CA
- Canada
- Prior art keywords
- radiation
- photoinitiator
- activated
- initiator
- wavelength range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00432—Auxiliary operations, e.g. machines for filling the moulds
- B29D11/00442—Curing the lens material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0833—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using actinic light
Landscapes
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Eyeglasses (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
A curing method for ophthalmic lenses or semi-finished lens blanks wherein a curable resin is first exposed to radiation in the wavelength range of 400-800 nm and subsequently subjected to heat or radiation of different wavelength or intensity than that used in the first step. The polymerizable resin preferably comprises: (1) a first photoinitiator that is activated by radiation in the wavelength range of 400-800 nm and (2) a thermal initiator which is activated by heat, or a second photoinitiator which is activated by radiation of different wavelength or intensity than that used to activate the first photoinitiator.
Description
W O 97/09170 PCTrUS96/14098 k~-l~ A~D COMPOSITION FOR ~E MU~n~FACllnRE
OF ~H~ MTC T-FIELD OF l~HE lNV~NLlON:
This invention relates to improved methods by which plastic resins can be cured to form ophth~lmic lenses, semifinished blanks and optical preforms. Ophthalmic lenses o~ten have complex geometries, with certain prescriptions having variations in thicknesses across the optic area of greater than an order of magnitude.
Since the curing process is accompanied by shrinkage, a key objective of curing process development efforts is to be able to accommodate shrinkage without unduly increasing the cure time. I have developed a curing method for ophth~1 mi c lenses that uses visible light to initiate cure, while nevertheless crea~ing a colorless product.
~A~r-RO~ND:
Curing of organic polymerizable resins to form ophthalmic lenses and semifinished blanks has traditionally involved the use of thermal polymerization initiators as described, for example, in US Paten~
W O 97/09170 PCTrUS96/14098 3,038,210, issued to Hungerford, et al., and US Patent 3,222,432, issued to Gr~n~p~ret~ More recently, photocuring processes have been disclosed involving the use of ultraviolet initiators, for example, US Patent 4,166,088, issued to Neefe, and US Patent Nos. 5,364,256 and 4,879,318 to Lipscomb. Photocuring processes have allowed the development of cure cycles that are considerably shorter than standard thermal curing cycles.
In all cases, it is necessary to ensure that the cure profile, which determines the rate of shrinkage, allows the cure of the bulk resin to take place in a controlled fashion while the surface still retains substantial adhesion to the mold. In this way, the lens does not undergo a prerelease, does not develop optical aberratlons caused by the formation of local heterogeneities in the resin mass due to uneven flow, and does not develop surface defects or cracks due to resin shrinkage.
In U.S. Patent No. 4,919,850, issued to me, I
disclose a two stage cure process involving the use of ultraviolet polymerization initiators that allow the resin to gel under a low level of ultraviolet illumination. In this way, the initial cure rate is 25 maintained at a low level, until the resin mass becomes a gel and mass flow ceases within the curing lens. This is important, because the risk of developing optical aberrations is highest at the initial stages of the curing process when local exotherms can induce optical 30 aberrations through resin flow. After the material has undergone gelation, the cure rate is accelerated by increasing ultraviolet light intensity. Increasing Y
light intensity also serves to maintain the pace o~
curing as the initiator becomes depleted.
35 Alternatively, the cure rate is also accelerated in the second stage by using W light of a shorter wavelength.
CA 02230646 l998-02-27 W O 97/09170 PCTrUS96/14098 A commercial version of this process has now been introduced by the Rapidcast Corporation.
A disadvantage of the two stage process, as disclosed in U.S. Patent No. 4,919,850 is that it typically uses two curing chambers for efficient implementation.
SU~$~RY OF I~E lNV~-~-lON:
An advantage of the present invention is that a process is provided which can be efficiently implemented using a single chamber.
Another advantage of the invention is that the scope of the two stage curing process is expanded, rendering it applicable to resin formulations covering a wide range o~ chemical reactivities, f~nctionalities, shrinkage properties, and thermal expa~sion characteristics.
According to an embodiment of the present invention, a curing method for ophthalmic lenses or semi-finished lens blanks is described wherein a curable resin is ~irst exposed to radiation in the wavelength range o~ 400-800 NM. Then, the curable resin is subjected to heat or radiation of di~erent wavelength or intensity than that used in the ~irst step. The polymerizable resin preferably comprises: (1) a first photoinitiator that is activated by radiation in the wavelength range 400-800 NM and (2) a thermal initiator which is activated by heat, or a second photoinitiator which is activated by radiation of different wavelength or intensity than that used to activate the first photoinitiator.
According to another embodiment of the invention, an ophthalmic lens, semi~inished blank or optical pre~orm is provided according to any of the methods described or claimed herein.
The above and other objects, advantages and embodiments will become readily apparent to those of skill in the art upon reading the description and claims set forth below.
Unless indicated to the contrary, each reference cited herein is incorporated by reference in its entirity.
DETATT-~n DESCRIPTION OF TRE lNV~N-LlON:
I have developed a cure process that utilizes room light in a first stage to initiate cure and reach the gel state. A second stage of the cure process can subsequently be completed, by application of thermal energy, by application of W light, or both. The initial curing stage may take place either directly under room light, or in chambers employing visible light bulbs.
Since polymerization initiators which are activated by visible light are generally highly colored, it may appear at first sight that their use would be incompatible with the proposed application (i.e., to make an ophthalmic lens which is preferably colorless, or water white). Recently, a new class of photopolymerization initiators has been commercialized which begin as a colored species and are activated by visible light, but upon activation form colorless photodissociation products. I discovered that such photoinitiators can be used to develop cure processes for ophthalmic lenses and semi-finished blanks.
A preferred photoinitiator is BAPO, available from Ciba Geigy Corp. This photopolymerization initiator is actually a mixture of two photoinitiators, Bisdimethoxybenzoyl Trimethylpentyl Phosphine Oxide (25~, by weight) and 2-Hydroxy 2-Methyl 1-Phenyl Propanone (75~ by weight). The phosphine oxide derivative absorbs visible light in the wavelength range 400-450 NM range, and initiates polymerization of resins incorporating acrylic, methacrylic, vinylic or allylic derivatives.
=
Under normal room illumination, the cure rate is slow. Therefore, the mold assemblies do nct require cooling or other temperature control to undergo gelation. Nevertheless, precise temperature control does produce a more uniform product and improves product consistency and yield. If temperature control mechanisms are provided, they should be employed to control the temperature at or near room temperature, i.e., at about 15~C to 35~C.
While not wishing to be bound by any particular theory, it is believed that this photoinitiator works in the following fashion. The phosphine oxide derivative is activated and undergoes photodissociation under room light, leaving the acetophenone derivative unaffected.
15 The phosphine oxide derivative undergoes bleaching on photodissociation, so that the polymerizing resin mass becomes less colored as polymerization progresses. Once the resin has undergone gelation, the mold assembly is placed in a chamber equipped with ultraviolet light 20 bulbs emitting radiation in the wavelength range of 300-380 NM. The near ultraviolet radiation activates the acetophenone derivative, causing the curing process to become accelerated. At the same time, the dissociation of the phosphine oxide derivative is completed, 25 completing the bleaching process. A residual faint yellow hue can be corrected by an addition of a small amount of a bluing additive, such as TINOPAL (available from Ciba Geigy Corp.) to the resin formulation.
When W photoinitiators (such as the acetophenone 30 derivative) are used during the second stage of cure, the mold assembly may be heated along a preestablished r temperature profile, ultimately reaching a final temperature in the range of about 90~-150~C, to complete 1 the cure process and to obtain a final lens product with 35 a glass transition temperature in the range of about 100~-175~C. If no heat is applied and the temperature maintained at or near room temperature, the final W 097/09170 PCT~US96114098 product has a lower glass transition temperature (e.g., in the range of about 30~-50~C). In all cases, the cure t process should be completed. The extent of the cure process can be monitored, for example, by a differential 5 sc~nn-ng calorimetric analysis of the material after cure. Whether heating is necessary to complete the cure generally depends on the monomers used in the resin formulation. Thus, if monomers used in the formulation can form homopolymers which have glass transition 10 temperatures considerably above the room temperature (15~-30~C), then an elevated temperature is desirable to complete the cure process.
Alternatively, a phosphine oxide derivative may be used which initiates cure under visible light as before.
15 However, a thermal polymerization initiator, such as a peroxide, a peracetate, a percarbonate or an azo derivative may be used to complete the second stage (post-gel cure) by placing the mold assembly in a thermal curing oven, typically a convection oven.
The two stage polymerization process described above may be carried out in glass molds, in metal molds or in a combination thereof. Metal molds with reflective inner surfaces may be especially useful in reflecting radiation back into the resin mass and conducting excess heat away from the resin mass. Metal molds may also be made thinner, and thus can have a lower thermal mass than glass molds. Alternatively, glass molds with metallized sur~aces may be employed for resin formulations which require a metal mold for adhesion and thus prevent prerelease during cure.
The two stage polymerization method can be employed to produce lenses from resin formulations covering a wide range of chemical reactivities, functionalities, shrinkage properties, and thermal expansion characteristics. Both monomers and oligomers may be employed, and polymeric or small molecular weight additives can be included to alter physical properties of the resin formulation, such as viscosity and sur~ace energy, as well as chemical proper~ies of the formulation, such as oxidative and photothermal or hydrolytic stability.
OF ~H~ MTC T-FIELD OF l~HE lNV~NLlON:
This invention relates to improved methods by which plastic resins can be cured to form ophth~lmic lenses, semifinished blanks and optical preforms. Ophthalmic lenses o~ten have complex geometries, with certain prescriptions having variations in thicknesses across the optic area of greater than an order of magnitude.
Since the curing process is accompanied by shrinkage, a key objective of curing process development efforts is to be able to accommodate shrinkage without unduly increasing the cure time. I have developed a curing method for ophth~1 mi c lenses that uses visible light to initiate cure, while nevertheless crea~ing a colorless product.
~A~r-RO~ND:
Curing of organic polymerizable resins to form ophthalmic lenses and semifinished blanks has traditionally involved the use of thermal polymerization initiators as described, for example, in US Paten~
W O 97/09170 PCTrUS96/14098 3,038,210, issued to Hungerford, et al., and US Patent 3,222,432, issued to Gr~n~p~ret~ More recently, photocuring processes have been disclosed involving the use of ultraviolet initiators, for example, US Patent 4,166,088, issued to Neefe, and US Patent Nos. 5,364,256 and 4,879,318 to Lipscomb. Photocuring processes have allowed the development of cure cycles that are considerably shorter than standard thermal curing cycles.
In all cases, it is necessary to ensure that the cure profile, which determines the rate of shrinkage, allows the cure of the bulk resin to take place in a controlled fashion while the surface still retains substantial adhesion to the mold. In this way, the lens does not undergo a prerelease, does not develop optical aberratlons caused by the formation of local heterogeneities in the resin mass due to uneven flow, and does not develop surface defects or cracks due to resin shrinkage.
In U.S. Patent No. 4,919,850, issued to me, I
disclose a two stage cure process involving the use of ultraviolet polymerization initiators that allow the resin to gel under a low level of ultraviolet illumination. In this way, the initial cure rate is 25 maintained at a low level, until the resin mass becomes a gel and mass flow ceases within the curing lens. This is important, because the risk of developing optical aberrations is highest at the initial stages of the curing process when local exotherms can induce optical 30 aberrations through resin flow. After the material has undergone gelation, the cure rate is accelerated by increasing ultraviolet light intensity. Increasing Y
light intensity also serves to maintain the pace o~
curing as the initiator becomes depleted.
35 Alternatively, the cure rate is also accelerated in the second stage by using W light of a shorter wavelength.
CA 02230646 l998-02-27 W O 97/09170 PCTrUS96/14098 A commercial version of this process has now been introduced by the Rapidcast Corporation.
A disadvantage of the two stage process, as disclosed in U.S. Patent No. 4,919,850 is that it typically uses two curing chambers for efficient implementation.
SU~$~RY OF I~E lNV~-~-lON:
An advantage of the present invention is that a process is provided which can be efficiently implemented using a single chamber.
Another advantage of the invention is that the scope of the two stage curing process is expanded, rendering it applicable to resin formulations covering a wide range o~ chemical reactivities, f~nctionalities, shrinkage properties, and thermal expa~sion characteristics.
According to an embodiment of the present invention, a curing method for ophthalmic lenses or semi-finished lens blanks is described wherein a curable resin is ~irst exposed to radiation in the wavelength range o~ 400-800 NM. Then, the curable resin is subjected to heat or radiation of di~erent wavelength or intensity than that used in the ~irst step. The polymerizable resin preferably comprises: (1) a first photoinitiator that is activated by radiation in the wavelength range 400-800 NM and (2) a thermal initiator which is activated by heat, or a second photoinitiator which is activated by radiation of different wavelength or intensity than that used to activate the first photoinitiator.
According to another embodiment of the invention, an ophthalmic lens, semi~inished blank or optical pre~orm is provided according to any of the methods described or claimed herein.
The above and other objects, advantages and embodiments will become readily apparent to those of skill in the art upon reading the description and claims set forth below.
Unless indicated to the contrary, each reference cited herein is incorporated by reference in its entirity.
DETATT-~n DESCRIPTION OF TRE lNV~N-LlON:
I have developed a cure process that utilizes room light in a first stage to initiate cure and reach the gel state. A second stage of the cure process can subsequently be completed, by application of thermal energy, by application of W light, or both. The initial curing stage may take place either directly under room light, or in chambers employing visible light bulbs.
Since polymerization initiators which are activated by visible light are generally highly colored, it may appear at first sight that their use would be incompatible with the proposed application (i.e., to make an ophthalmic lens which is preferably colorless, or water white). Recently, a new class of photopolymerization initiators has been commercialized which begin as a colored species and are activated by visible light, but upon activation form colorless photodissociation products. I discovered that such photoinitiators can be used to develop cure processes for ophthalmic lenses and semi-finished blanks.
A preferred photoinitiator is BAPO, available from Ciba Geigy Corp. This photopolymerization initiator is actually a mixture of two photoinitiators, Bisdimethoxybenzoyl Trimethylpentyl Phosphine Oxide (25~, by weight) and 2-Hydroxy 2-Methyl 1-Phenyl Propanone (75~ by weight). The phosphine oxide derivative absorbs visible light in the wavelength range 400-450 NM range, and initiates polymerization of resins incorporating acrylic, methacrylic, vinylic or allylic derivatives.
=
Under normal room illumination, the cure rate is slow. Therefore, the mold assemblies do nct require cooling or other temperature control to undergo gelation. Nevertheless, precise temperature control does produce a more uniform product and improves product consistency and yield. If temperature control mechanisms are provided, they should be employed to control the temperature at or near room temperature, i.e., at about 15~C to 35~C.
While not wishing to be bound by any particular theory, it is believed that this photoinitiator works in the following fashion. The phosphine oxide derivative is activated and undergoes photodissociation under room light, leaving the acetophenone derivative unaffected.
15 The phosphine oxide derivative undergoes bleaching on photodissociation, so that the polymerizing resin mass becomes less colored as polymerization progresses. Once the resin has undergone gelation, the mold assembly is placed in a chamber equipped with ultraviolet light 20 bulbs emitting radiation in the wavelength range of 300-380 NM. The near ultraviolet radiation activates the acetophenone derivative, causing the curing process to become accelerated. At the same time, the dissociation of the phosphine oxide derivative is completed, 25 completing the bleaching process. A residual faint yellow hue can be corrected by an addition of a small amount of a bluing additive, such as TINOPAL (available from Ciba Geigy Corp.) to the resin formulation.
When W photoinitiators (such as the acetophenone 30 derivative) are used during the second stage of cure, the mold assembly may be heated along a preestablished r temperature profile, ultimately reaching a final temperature in the range of about 90~-150~C, to complete 1 the cure process and to obtain a final lens product with 35 a glass transition temperature in the range of about 100~-175~C. If no heat is applied and the temperature maintained at or near room temperature, the final W 097/09170 PCT~US96114098 product has a lower glass transition temperature (e.g., in the range of about 30~-50~C). In all cases, the cure t process should be completed. The extent of the cure process can be monitored, for example, by a differential 5 sc~nn-ng calorimetric analysis of the material after cure. Whether heating is necessary to complete the cure generally depends on the monomers used in the resin formulation. Thus, if monomers used in the formulation can form homopolymers which have glass transition 10 temperatures considerably above the room temperature (15~-30~C), then an elevated temperature is desirable to complete the cure process.
Alternatively, a phosphine oxide derivative may be used which initiates cure under visible light as before.
15 However, a thermal polymerization initiator, such as a peroxide, a peracetate, a percarbonate or an azo derivative may be used to complete the second stage (post-gel cure) by placing the mold assembly in a thermal curing oven, typically a convection oven.
The two stage polymerization process described above may be carried out in glass molds, in metal molds or in a combination thereof. Metal molds with reflective inner surfaces may be especially useful in reflecting radiation back into the resin mass and conducting excess heat away from the resin mass. Metal molds may also be made thinner, and thus can have a lower thermal mass than glass molds. Alternatively, glass molds with metallized sur~aces may be employed for resin formulations which require a metal mold for adhesion and thus prevent prerelease during cure.
The two stage polymerization method can be employed to produce lenses from resin formulations covering a wide range of chemical reactivities, functionalities, shrinkage properties, and thermal expansion characteristics. Both monomers and oligomers may be employed, and polymeric or small molecular weight additives can be included to alter physical properties of the resin formulation, such as viscosity and sur~ace energy, as well as chemical proper~ies of the formulation, such as oxidative and photothermal or hydrolytic stability.
Claims (10)
1. A curing method for ophthalmic lenses or semi-finished lens blanks comprising:
(A) providing a mold and a polymerizable resin, said polymerizable resin comprising (1) a first photoinitiator that is activated by radiation in the wavelength range 400-800 NM
and (2) an initiator selected from the group consisting of (a) a thermal initiator which is activated by heat and (b) a second photoinitiator which is activated by radiation of different wavelength or intensity than that used to activate the first photoinitiator;
(B) exposing the curable resin to radiation in the wavelength range of 400-800 NM; and (C) subsequently subjecting the curable resin to a curing environment selected from (1) heat and (2) radiation of different wavelength or intensity than that used in step (B).
(A) providing a mold and a polymerizable resin, said polymerizable resin comprising (1) a first photoinitiator that is activated by radiation in the wavelength range 400-800 NM
and (2) an initiator selected from the group consisting of (a) a thermal initiator which is activated by heat and (b) a second photoinitiator which is activated by radiation of different wavelength or intensity than that used to activate the first photoinitiator;
(B) exposing the curable resin to radiation in the wavelength range of 400-800 NM; and (C) subsequently subjecting the curable resin to a curing environment selected from (1) heat and (2) radiation of different wavelength or intensity than that used in step (B).
2. The method of claim 1, further comprising heat treating subsequent to step (C).
3. The method of claim 1, in which light delivered by incandescent light bulbs is used to provide said radiation in the wavelength range of 400-800 NM.
4. The method of claim 1, in which light delivered by fluorescent light bulbs is used to provide said radiation in the wavelength range of 400-800 NM.
5. The method of claim 1, in which step (B) further comprises control of temperature in the range 15°C-45°C.
6. The method of claim 1, in which said first photoinitiator is Bisdimethoxybenzoyl Trimethylpentyl Phosphine Oxide.
7. The method of claim 1, in which said second photoinitiator is selected as the initiator.
8. The method of claim 7, in which said second photoinitiator is .2-Hydroxy 2-Methyl 1-Phenyl Propane.
9 The method of claim 1, in which said thermal initiator is selected as the initiator.
10. The method of claim 11, in which said thermal initiator is selected from the group consisting of a peroxide, a peracetate, a percarbonate and an azo derivative.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52281595A | 1995-09-01 | 1995-09-01 | |
| US08/522,815 | 1995-09-01 | ||
| PCT/US1996/014098 WO1997009170A1 (en) | 1995-09-01 | 1996-09-03 | Method and composition for the manufactue of ophthalmic lenses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2230646A1 true CA2230646A1 (en) | 1997-03-13 |
Family
ID=24082484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002230646A Abandoned CA2230646A1 (en) | 1995-09-01 | 1996-09-03 | Method and composition for the manufacture of ophthalmic lenses |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0847330A1 (en) |
| JP (1) | JP2001510404A (en) |
| KR (1) | KR19990044298A (en) |
| CN (1) | CN1200696A (en) |
| AU (1) | AU6963596A (en) |
| BR (1) | BR9610409A (en) |
| CA (1) | CA2230646A1 (en) |
| IL (1) | IL123478A0 (en) |
| MX (1) | MX9801691A (en) |
| WO (1) | WO1997009170A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK1080381T3 (en) * | 1998-04-15 | 2005-09-12 | Alcon Mfg Ltd | High refractive index materials for ophthalmic devices made using a crosslinking process after polymerization |
| US6313187B2 (en) | 1998-04-15 | 2001-11-06 | Alcon Manufacturing, Ltd. | High refractive index ophthalmic device materials prepared using a post-polymerization cross-linking method |
| US6419873B1 (en) * | 1999-03-19 | 2002-07-16 | Q2100, Inc. | Plastic lens systems, compositions, and methods |
| US6630083B1 (en) | 1999-12-21 | 2003-10-07 | Johnson & Johnson Vision Care, Inc. | Methods and compositions for the manufacture of ophthalmic lenses |
| JP4878796B2 (en) * | 2004-09-06 | 2012-02-15 | 富士フイルム株式会社 | Manufacturing method of optical film |
| US7838570B2 (en) * | 2005-01-14 | 2010-11-23 | Xerox Corporation | Radiation curable inks |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4919850A (en) * | 1988-05-06 | 1990-04-24 | Blum Ronald D | Method for curing plastic lenses |
-
1996
- 1996-09-03 JP JP51132697A patent/JP2001510404A/en active Pending
- 1996-09-03 KR KR1019980701535A patent/KR19990044298A/en not_active Application Discontinuation
- 1996-09-03 AU AU69635/96A patent/AU6963596A/en not_active Abandoned
- 1996-09-03 IL IL12347896A patent/IL123478A0/en unknown
- 1996-09-03 CA CA002230646A patent/CA2230646A1/en not_active Abandoned
- 1996-09-03 WO PCT/US1996/014098 patent/WO1997009170A1/en not_active Application Discontinuation
- 1996-09-03 BR BR9610409-0A patent/BR9610409A/en not_active Application Discontinuation
- 1996-09-03 CN CN96197964A patent/CN1200696A/en active Pending
- 1996-09-03 EP EP96930670A patent/EP0847330A1/en not_active Withdrawn
-
1998
- 1998-03-02 MX MX9801691A patent/MX9801691A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BR9610409A (en) | 1999-12-21 |
| JP2001510404A (en) | 2001-07-31 |
| MX9801691A (en) | 1998-11-29 |
| CN1200696A (en) | 1998-12-02 |
| KR19990044298A (en) | 1999-06-25 |
| AU6963596A (en) | 1997-03-27 |
| WO1997009170A1 (en) | 1997-03-13 |
| IL123478A0 (en) | 1998-09-24 |
| EP0847330A1 (en) | 1998-06-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |