WO2006091608A2 - Photochromic product made from a reaction mixture - Google Patents

Photochromic product made from a reaction mixture Download PDF

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Publication number
WO2006091608A2
WO2006091608A2 PCT/US2006/006141 US2006006141W WO2006091608A2 WO 2006091608 A2 WO2006091608 A2 WO 2006091608A2 US 2006006141 W US2006006141 W US 2006006141W WO 2006091608 A2 WO2006091608 A2 WO 2006091608A2
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WO
WIPO (PCT)
Prior art keywords
pre
photochromic
polymer
product
primary
Prior art date
Application number
PCT/US2006/006141
Other languages
French (fr)
Other versions
WO2006091608A3 (en
Inventor
Ronald Wiand
Original Assignee
Softlight, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to US65615605P priority Critical
Priority to US60/656,156 priority
Application filed by Softlight, Inc. filed Critical Softlight, Inc.
Publication of WO2006091608A2 publication Critical patent/WO2006091608A2/en
Publication of WO2006091608A3 publication Critical patent/WO2006091608A3/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00Producing optical elements, e.g. lenses or prisms
    • B29D11/00865Applying coatings; tinting; colouring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made
    • G02B1/04Optical elements characterised by the material of which they are made made of organic materials, e.g. plastics
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • G02B5/23Photochromic filters

Abstract

A substrate is made by polymerizing a reaction mixture of a major amount of a primary pre-polymer which is cross-linkable and a minor amount of a secondary pre- polymer which is not cross-linkable to form a reaction product, such as an optical lens, which is then contacted with a photochromic moiety to imbibe or diffuse the moiety into at least a surface layer of the reaction product.

Description

PHOTOCHROMIC PRODUCT MADE FROM A REACTION MIXTURE

Background of the Invention

The present invention relates to transparent and semi-transparent polymeric articles having a photochromic nature and to their method of making. In a preferred embodiment, the present invention relates to photochromic optical lenses.

Although the present invention is broadly applicable to transparent and semitransparent polymeric articles having a photochromic characteristic, it is particularly useful in conjunction with photochromic optical lenses. Photochromic molecules and uses for photochromic molecules have been known for many years, but there remains a challenge with respect to imbibing or otherwise incorporating such molecules into suitable substrates such as optical lenses. In order to impart the photochromic characteristic to the lens material, the photochromic molecules must be able to readily change between activated and inactivated states. It is theorized that such changes of state are facilitated by suitably large interstitial spaces. However, provision of suitable interstitial spaces without detrimental impact on the physical characteristics of the lens is problematic. Furthermore, the photochromic moieties used in plastic lenses are relatively large and difficult to imbibe into the lens material.

In the "imbibing" technique, a plastic lens is first polymerized from an optical quality monomer in a mold until polymerization is substantially complete. Then a surface of the lens is contacted with a photochromic moiety which is imbibed or diffused into the lens surface. This technique provides a surface layer of the lens with photochromic moiety. Imbibing techniques tend to be difficult to control and are relatively slow and expensive processes. In short, there remains a need for further improvements in techniques or methods for providing articles such as lenses with photochromic characteristics. There is a need for a process that provides large enough spaces within a substrate to accept relatively large photochromic molecules and allow the molecules to freely change state to thereby exhibit the full range of their photochromic performance. Furthermore, there remains a need for lower cost methods which are suitable for use in articles such as planar lenses and inexpensive reading lenses as well as in relatively expensive ophthalmic lenses. There remains a need for further improvements in the longevity of the photochromic characteristic of the lenses. There also remains a need for photochromic lenses or other photochromic articles which can quickly change from an activated to an inactivated state.

The present invention provides an improved substrate and an improved method for imparting photochromic qualities to substrates. The present invention is useful to make all sorts of photochromic articles or products, and such articles and products are within the broad scope of the invention disclosed herein. However, the present invention is particularly well suited for use in making lenses for eyeglasses. Further understanding of this invention will be had from the following disclosure.

Brief Summary of the Invention

In accordance with the present invention, an article has a substrate comprised of a cross-linked organic polymer matrix. The polymeric matrix is polymerized from reaction mixture containing a primary prepolymer or monomer reactant with cross-linkable moieties, such as an allyl diglycol carbonate monomer, and a secondary prepolymer or monomer reactant which is without cross-linkable moieties, but which is soluble or dispersible in the reaction mixture. A suitable secondary reactant is an ethoxylated nonylphenol acrylate monomer. The secondary reactant polymerizes during the simultaneous polymerization of the primary reacatant but without crosslinking and is believed to cause a more open structure in the resulting polymeric matrix. Thus, the polymeric matrix is porous and readily accepts diffusion of a photochromic moiety therein. In a preferred embodiment, the article is an optical lens.

In accordance with the method of the present invention, a substrate is made by the steps of: providing a reaction mixture comprising a primary cross-linkable pre- polymer and a secondary non-crosslinkable pre-polymer to form a polymeric matrix;

simultaneously polymerizing said primary and secondary pre-polymers; and

infusing an effective amount of a photochromic moiety into said polymeric matrix.

In one preferred embodiment of the present invention, the method is used to make a transparent article. In another preferred embodiment of the present invention the method is used to make a lens.

Detailed Description of the Invention

The present invention is a polymeric substrate obtained by a method wherein a primary pre-polymer and a secondary prepolymer are simultaneously polymerized to form a porous polymeric matrix which is then contacted with a photochromic moiety which is imbibed or diffused into at least a surface layer of the matrix. It is believed that the secondary prepolymer interferes with the cross-linking of the primary polymer and provides relatively large intersticial spaces in the polymeric matrix. This provides a porous matrix suitable for imbibing or diffusion of a photochromic moiety therein and allows the photochromic moiety plenty of room to freely change from activated to inactivated states. It will be appreciated by those skilled in the art that the present invention is broadly applicable to make substrates which may be used in conjunction with many different photochromic products or articles of manufacture. Examples of products which can comprise or include substrates of this invention include but are not limited to window panes, such as window panes in homes or other energy efficient buildings or solar structures, sun roofs, windshields or lights for automobiles, signs, compact discs, digital audio discs, and plastic optical articles generally. While it is contemplated that most advantage will be taken from use of this invention in transparent or semi-transparent products, this invention can be used to make products that are not transparent, where, for example it may be desired to reduce reflection, or to darken or change the color or appearance of the product. Many different products or articles may be produced with a desirable photochromic effect. AU of these products are considered to be within the broad scope of the present invention.

A preferred embodiment of this invention is a photochromic plastic optical lens. Another preferred embodiment is a photochromic eyeglass frame. A further preferred embodiment is a photochromic eyeglass frame with photochromic lenses. Where the embodiment is a lens, the lens may be an ophthalmic lens or a planar lens. Planar lenses are generally of consistent thickness. Ophthalmic lenses may be spherical or aspheric, monofocal, bifocal, trifocal, multifocal, invisible multi-focal or progressive, semi-finished or finished piano blank for sunglasses and do not have a consistent thickness from center to edge. Ophthalmic lenses are relatively difficult to coat or infuse with a photochromic moiety to obtain a consistent photochromic effect. In accordance with the present invention, however, a consistent photochromic layer of consistent thickness can be provided in an ophthalmic lens. Of course, it should be noted that in some cases it may be desirable to have a gradient effect in a lens, i.e., greater darkening in a top of the lens than the bottom of the lens. This effect can also be achieved within the scope of this invention.

The products of the present invention can be made by the method of the present invention which comprises the steps of: providing a reaction mixture comprising a primary cross-linkable pre- polymer and a secondary non-crosslinkable pre-polymer to form a polymeric matrix;

simultaneously polymerizing said primary and secondary pre-polymers to form a polymeric matrix; and

infusing an effective amount of a photochromic moiety into at least a surface layer of said polymeric matrix.

In one preferred embodiment of the present invention, the method is used to make a transparent article. In another preferred embodiment of the present invention the method is used to make a lens.

As used herein, the term primary pre-polymer includes monomeric moieties as well as oligomers, dimers, etc. so long as the moiety is polymerizable and cross-links during polymerization. The primary pre-polymer is polymerized and cross-linked simultaneously with a secondary pre-polymer to form a polymeric substrate. Suitable primary pre-polymers are well known and may be ultraviolate cross-linkable pre-polymers, radiation cross-linkable pre-polymers or thermally cross-linkable pre-polymers. Initiation of polymerization and/or cross-linking may be by ultraviolet or electron beam radiation or heat or a combination thereof.

For an optical quality lens, the present method requires an optical quality polymerizable pre-polymer having an index of refraction between 1.440 and 1.90. Suitable primary pre-polymers for use in making lenses are liquid and must be placed in a desired lens mold before initiation of polymerization. Examples of suitable primary pre-polymers include monomers, homopolymers and copolymers of polyol(allyl carbonate) monomers, homopolymers and copolymers of polyfunctional acrylate monomers, polyacrylates, poly(alkylacrylates) such as polymethylmethacrylate), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), polyvinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), polyurethanes, polycarbonates, poly(ethylene-terephthalate), polystyrene, copoly(styrene-methylmethacralate), copoly(styrene-acrylonitrile), poly(vinylbutyral), and homopolymers and copolymers of diallylidene pentaerythritol, such as copolymers with polyol(allyl carbonate) monomers, e.g. diethylene glycol bis(allyl carbonate), and acrylate monomers. Transparent copolymers and blends of the transparent polymers are suitable as matrix materials. A preferred primary pre- polymer is diethlene glycol bis allyl carbonate, (CR-39) monomer.

As used herein, the term "secondary" pre-polymer includes monomelic moieties as well as oligomers, dimers, etc. so long as the moiety is polymerizable and does not crosslink during polymerization. The secondary pre-polymer is polymerized simultaneously with the primary pre-polymer to form the desired polymeric substrate. Suitable secondary pre- polymers are well known and may be ultraviolate initiated pre-polymers, radiation initiated pre-polymers or thermally initiated pre-polymers. Thus, initiation of polymerization may be by ultraviolet or electron beam radiation or heat or a combination thereof. Preferred secondary pre-polymers include monofunctional pre-polymers such as ethoxylated iionylphenol acrylates, e.g., SR-504 (molecular weight 450) from Sartomer, Exton PA. Alternatively, the secondary pre-polymer can be a high molecular weight difunctional monomer which physically interferes with the primary pre-polymer to increase interstitial spaces in the polymer, such as ethoxylated bisphenol A diacrylate (molecular weight 512) and propoxylated neopentyl glycol diacrylate (molecular weight 328). Generally speaking it has been found that suitable secondary pre-polymers have a molecular weight of from about 220 to about 1660. It has also been found that the secondary pre-polymer should have a refractive index of from about 1.440 to about 1.55 and a specific gravity of from about 1.10 to about 1.40 grams per cubic centimeter. For an optical quality lens, the present method requires that the secondary pre-polymer have an index of refraction between 1.45 and 1.90 and, of course, the secondary pre-polymer must be soluble or dispersible in the primary pre- polymer. It is contemplated that the reaction mixture of the present invention will comprise a major amount of primary pre-polymer and a minor amount of secondary pre-polymer. It is also contemplated that the reaction mixture may comprise other components as is conventional in the art. For example, a suitable reaction mixture may include a polymerization initiator, a cross-linking agent, a UV absorber, or other additives conventionally used in the manufacture of lenses. Suitable initiators, cross-linking agents, additives and other lens materials for use in the present invention are disclosed in United States Patent No. 5,882,556, March 16, 1999 to Perrott et al. which is specifically incorporated by reference herein.

Any suitable photochromic moiety may be imbibed or diffused into the polymeric matrix resulting from polymerization of the reaction mixture. Suitable photochromic moieties are well-known in the art and include photochromic moieties selected from the group consisting of anthraquinones, naphtopyrans, phhalocyanines, spiro-oxazines, chromenes, pyrans including spiro-pyrans and fulgides photochromic moieties. Suitable photochromic moieties include but are not limited to those_disclosed in United States Patents Nos. 5,882,556 March 16, 1999 to Perrott et al. which patent is specifically incorporated by reference herein. In addition to photochromic molecules, it is contemplated that other moieties such as a non-photochromic dye or UV stabilizers and antioxidants may be imbibed or diffused into the polymeric substrate.

A preferred embodiment of the present invention is a method for making a photochromic lens. In accordance with this method, a mold is prepared by filling it with a liquid reaction mixture of the present invention. Curing of the primary and secondary prepolymers reaction mixture is begun by heating or otherwise initiating curing as is conventional in the art and disclosed, for example, in the aforementioned United States Patent No. 5,882,556. The pre-polymer reaction mixture is allowed to react to a substantially cured state, i.e., the mixture is substantially solid lens. The substrate is then ready to receive the desired photochromic moiety. Photochromic molecules can be infused or permeated into the entire lens or into a surface layer portion of the lens by contacting the surface with a solution of photochromic molecules. Of course, the photochromic moiety can be brought into contact with a surface or surfaces of the substrate to accomplish its permeation therein by various methods including, but not limited to, coating a solution containing the photochromic moiety onto the surface of the substrate, applying a layer of polymeric film having the photochromic moiety dissolved or suspended therein to the surface of the substrate and then heating the film near to but below the melting point of the photochromic moiety for a time sufficient to incorporate the photochromic moiety into the surface layer, or any of the methods for incorporating photochromic compounds into a surface of a host material disclosed in United States Patent No. 5,066,818 November 19, 1991 to Gemert et al. for "Photochromic Naphtopyran Compounds" which patent is specifically incorporated by reference herein.

Further understanding of the present invention will be had from the following examples.

Example 1

A primary pre-polymer is prepared from diethylene glycol bis(allyl carbonate) (CR.39) monomer from PPG by stirring and prepolymerizing the monomer for 1 minute at 500C with an aliphatic peroxy initiator diisoproypyl peroxydicarbonate. Stirring is continued for a further 12 hours while lowering the temperature to 50C. A small amount (5%) of secondary pre-polymer, ethoxylated nonylphenol acrylate (SR-504 from Sartomer) is dispersed throughout the primary prepolymer to form a reaction mixture which is introduced into a glass mold sized to produce a 70mm round by 2mm thick piano lens blank. The mold is then placed in a curing oven at a temperature of 78° C. After 12 hours the reaction mixture reaches a solid state and is removed from the mold. The reaction mixture is a lens which has good physical properties suitable for use as an optical lens and to have a porous structure with interstitial spaces well suited to absorb a photochromic moiety. At least one planar surface of the lens is contacted with a photochromic solution which imbibes, absorbs or infuses photochromic moieties into the porous surface layer. The photochromic solution is Reversacal Corn yellow from Keystone Aniline Corporation. The resultant lens exhibits superior Photochromic qualities. It is then treated with UV inhibitors and scratch resistant coated to enhance the life of the Photochromic effect and the scratch resistance of the treated lens.

Example 2

The procedures of Example 1 are followed except that a 10 mole ethoxylated bisphenol A diacrylate, SR-602 from Sartomer, is substituted for the ethoxylated nonylphenol acrylate used as the secondary pre-polymer in Example 1. Similar good results are obtained.

Claims

What is claimed is:
A method of making a photochromic substrate, said method comprising the steps of:
providing a reaction mixture comprising a primary cross-linkable pre- polymer and a secondary non-crosslinkable pre-polymer to form a polymeric matrix;
simultaneously polymerizing said primary and secondary pre-polymers to form a polymeric matrix; and
infusing an effective amount of a photochromic moiety into at least a surface layer of said polymeric matrix.
1. The method of claim 1 wherein said primary pre-polymer is selected from the group consisting of methyl methacrylate allyl diglycol carbonate monomer and pre-polymers made therefrom.
2. The method of claim 1 wherein said primary pre-polymer is a multifunctional polycarbonate.
4. A product made by the method of claim 1.
5. The product of claim 4 wherein said product is an optical lens.
6. The product of claim 4 wherein said product is in operative association with an automotive vehicle.
7. The product of claim 4 wherein said product is in operative association with an architectural structure.
PCT/US2006/006141 2005-02-24 2006-02-21 Photochromic product made from a reaction mixture WO2006091608A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US65615605P true 2005-02-24 2005-02-24
US60/656,156 2005-02-24

Publications (2)

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WO2006091608A2 true WO2006091608A2 (en) 2006-08-31
WO2006091608A3 WO2006091608A3 (en) 2009-04-16

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994637A (en) * 1974-08-16 1976-11-30 Dornier System Gmbh Rotary piston engine of trochoidal design
US4994208A (en) * 1989-04-18 1991-02-19 Ppg Industries, Inc. Photochromic polymeric article
US5730911A (en) * 1995-03-03 1998-03-24 Essilor International-Compagnie General D'optique Process for the manufacture of a substrate made of transparent organic glass and substrate thus obtained

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994637A (en) * 1974-08-16 1976-11-30 Dornier System Gmbh Rotary piston engine of trochoidal design
US4994208A (en) * 1989-04-18 1991-02-19 Ppg Industries, Inc. Photochromic polymeric article
US5730911A (en) * 1995-03-03 1998-03-24 Essilor International-Compagnie General D'optique Process for the manufacture of a substrate made of transparent organic glass and substrate thus obtained

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WO2006091608A3 (en) 2009-04-16

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