Search

EP-4347683-B1 - CURABLE PHOTOCHROMIC COMPOSITION

EP4347683B1EP 4347683 B1EP4347683 B1EP 4347683B1EP-4347683-B1

Inventors

  • REDDY, Ramaiahgari
  • KUMAR, ANIL

Dates

Publication Date
20260506
Application Date
20210526

Claims (13)

  1. A curable photochromic composition comprising: (a) at least one photochromic material; (b) an active hydrogen group-containing component comprising: (i) an active hydrogen group-containing fluorinated polymer having an active hydrogen group equivalent weight ranging from 200 to 5000 g/mole and a number average molecular weight ranging from 5,000 to 50,000 g/mole, and (ii) a polymer having at least two active hydrogen groups per molecule, a number average molecular weight of at least 1000 g/mole, and an equivalent weight of at least 500 g/mole; and (c) a curing agent comprising functional groups which are reactive with active hydrogen groups, wherein the curing agent comprises polyisocyanate.
  2. The curable photochromic composition of claim 1, wherein the active hydrogen group-containing component (b) further comprises: (iii) a compound having at least 3 active hydrogen groups per molecule and an equivalent weight of less than or equal to 480 g/mole.
  3. The curable photochromic composition of claim 1 or claim 2, wherein the active hydrogen group-containing fluorinated polymer (i) comprises a fluoroethylene vinyl ether copolymer.
  4. The curable photochromic composition of any one of claims 1 to 3, wherein each active hydrogen group of the active hydrogen group-containing component (b) is independently selected from the group consisting of hydroxyl groups, thiol groups, primary amino groups, and secondary amino groups.
  5. The curable photochromic composition of any one of claims 1 to 4, wherein each active hydrogen group of the active hydrogen group-containing resinous component (b) is a hydroxyl group.
  6. The curable photochromic composition of any one of claims 1 to 5, wherein the active hydrogen group-containing polymer (ii) is selected from the group consisting of polycarbonate polyols, polyester polyols, polyether polyols, polyurethane polyols, co-polymers thereof, and mixtures thereof.
  7. The curable photochromic composition of any one of claims 1-6, wherein the active hydrogen group-containing fluorinated polymer (i) is present in an amount of 0.1 to 30% by weight based on total weight of solids of the curable photochromic composition.
  8. The curable photochromic composition of any one of claims 1 to 7, wherein the photochromic material (a) comprises a compound selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, and mixtures thereof.
  9. The curable photochromic composition of any one of claims 1 to 8, further comprising an additive selected from the group consisting of photoinitiators, thermal initiators, polymerization inhibitors, solvents, ultraviolet light absorbers, hindered amine light stabilizers, antioxidants, heat stabilizers, mold release agents, rheology control agents, leveling agents, free radical scavengers, adhesion promoters, plasticizers, and mixtures thereof.
  10. A polymeric photochromic film formed from the curable photochromic composition of any one of claims 1 to 9.
  11. An article comprising: (A) a substrate; and (B a photochromic layer over at least a portion of the substrate, wherein the photochromic layer is formed from the curable composition of any one of claims 1 to 9.
  12. The article of claim 11, wherein the substrate (A) comprises a polymeric material selected from the group consisting of polycarbonate, polycyclic alkene, polyurethane, poly(urea)urethane, polythiourethane, polythio(urea)urethane, polyurea, poly(allyl carbonate) polymers, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and mixtures thereof.
  13. The article of claim 11 or claim 12, wherein the article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles; or wherein the article is an ophthalmic article, and the ophthalmic article is selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors; or wherein the article is a display article, and the display article is selected from the group consisting of screens, monitors, and security elements.

Description

FIELD The present invention relates to curable photochromic compositions, which include a photochromic compound, an active hydrogen group-containing polymer, such as a fluorinated polymer, and a curing agent. Photochromic articles prepared from such compositions are also provided. BACKGROUND In response to certain wavelengths of electromagnetic radiation (or "actinic radiation"), photochromic compounds, such as indeno-fused naphthopyrans, typically undergo a transformation from one form or state to another form, with each form having a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds are transformed from a closed-form, which corresponds to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound, to an open-form, which corresponds to an activated (or colored) state of the photochromic compound. In the absence of exposure to actinic radiation, such photochromic compounds are reversibly transformed from the activated (or colored) state, back to the unactivated (or bleached) state. Compositions and articles, such as optical lenses, that contain photochromic compounds or have photochromic compounds applied thereto (e.g., in the form of a photochromic coating composition) typically display colorless (e.g., clear) and colored states that correspond to the colorless and colored states of the photochromic compounds contained therein or applied thereto. Photochromic compounds can be used in curable compositions to form, for example, cured layers, such as cured films or sheets that are photochromic. With cured photochromic films, such as cured photochromic coatings, it is typically desirable that they provide a combination of hardness and photochromic performance. Generally, the kinetics associated with the reversible transformation of a photochromic compound between a closed-form (unactivated / colorless) and an open-form (activated / colored) is faster in a soft matrix, but slower in a hard matrix (of the cured film in which the photochromic compound resides). Cured photochromic films having a soft matrix typically have reduced hardness, while those having a hard matrix typically have increased hardness. CN 104 628 928 A relates to a photochromic fluorocarbon resin and related preparation method and application thereof. US 2012/0145973 A1 relates to photochromic materials that include one or more indeno-fused naphthopyrans having certain groups at the 7, 11 and 13 positions thereof, and at the position alpha to the pyran ring oxygen thereof, as well as to photochromic articles and compositions that include such indeno-fused naphthopyrans. It would be desirable to develop curable photochromic compositions that provide cured photochromic layers having acceptable hardness, improved kinetics, and improved dye fatigue. SUMMARY The present invention is directed to a curable photochromic composition comprising: (a) at least one photochromic material;(b) an active hydrogen group-containing component comprising: (i) an active hydrogen group-containing fluorinated polymer having an active hydrogen group equivalent weight ranging from 200 to 5000 g/mole and a number average molecular weight ranging from 5,000 to 50,000 g/mole; and(ii) a polymer having at least two active hydrogen groups per molecule, a number average molecular weight of at least 1000 g/mole, and an equivalent weight of at least 500 g/mole; and(c) a curing agent comprising functional groups which are reactive with active hydrogen groups, wherein the curing agent comprises polyisocyanate. The present invention also provides an article comprising: (A) a substrate; and(B) a photochromic layer over at least a portion of the substrate, wherein the photochromic layer is formed from the curable composition described above. DETAILED DESCRIPTION As used herein, the articles "a", "an", and "the" include plural referents unless otherwise expressly and unequivocally limited to one referent. Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges or sub-ratios subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all sub-ranges or sub-ratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but not limited to 1 to 6.1, 3.5 to 7.8, and 5.5 to 10. Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term "about". As used herein, "at least one of" is synonymous with "one or more of", whether the elements are listed conjunctively or disjunctively. For example, the phrases "at least on