US20020138921A1 - Method for coloring a transparent article made of polycarbonate and resulting article - Google Patents

Method for coloring a transparent article made of polycarbonate and resulting article Download PDF

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Publication number
US20020138921A1
US20020138921A1 US09/974,399 US97439901A US2002138921A1 US 20020138921 A1 US20020138921 A1 US 20020138921A1 US 97439901 A US97439901 A US 97439901A US 2002138921 A1 US2002138921 A1 US 2002138921A1
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Prior art keywords
article
layer
thickness
colouring agent
polycarbonate
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Abandoned
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US09/974,399
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English (en)
Inventor
Gilles Baillet
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EssilorLuxottica SA
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Essilor International Compagnie Generale dOptique SA
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Assigned to ESSILOR INTERNATIONAL COMPAGNIE GENERALE D'OPTIQUE reassignment ESSILOR INTERNATIONAL COMPAGNIE GENERALE D'OPTIQUE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAILLET, GILLES
Publication of US20020138921A1 publication Critical patent/US20020138921A1/en
Priority to US10/844,045 priority Critical patent/US6911055B2/en
Priority to US11/054,980 priority patent/US7179848B2/en
Abandoned legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2005—Treatments with alpha, beta, gamma or other rays, e.g. stimulated rays
    • 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
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/0007—Manufacturing coloured articles not otherwise provided for, e.g. by colour change
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/004—Dyeing with phototropic dyes; Obtaining camouflage effects
    • 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
    • B29C2035/0827—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 UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/002—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • B29L2011/0016—Lenses
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/93—Pretreatment before dyeing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/933—Thermosol dyeing, thermofixation or dry heat fixation or development
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention concerns in general terms a method for colouring a transparent polycarbonate article, for example an optical or ophthalmic article, and in particular a lens.
  • PC polycarbonate
  • Ophthalmic lenses made from conventional organic material are generally coloured by dipping in aqueous baths of dispersed dyes, the baths being maintained at a temperature of the order of 95° C.
  • polyester links in the copolymer skeleton is essential since it is the polyester bond which is broken by the irradiation and which allows the subsequent penetration of the dye.
  • the depths of penetration of the pigments are small, about 10 to 15 nm.
  • the document teaches that the copolymer must then contain a higher proportion of polyester.
  • the majority of the polycarbonate materials used for ophthalmic optics are homopolycarbonate materials.
  • this method particularly intended for colouring PC ophthalmic lenses, and in particular spectacle lenses, must not only be simple but also give the coloration desired by the customer.
  • the method must allow variable intensity of coloration : shade A (light), shade B (medium), shade C (dark).
  • the method must not significantly alter the essential properties of the lens such as transparency, resistance to shock and to scratches.
  • a PC article thus treated may be coloured with ease, in particular by means of dispersions and aqueous solutions of dyes and pigments.
  • the method for colouring a transparent article made of polycarbonate not containing polyester groups comprises:
  • the method of the invention may obviously also comprise the irradiation of the article to provoke the photodegradation of the polycarbonate material on two opposite faces of the article (each of the faces being subjected to the photodegradation), thus forming two photodegraded surface layers of the polycarbonate material of the article, each having a thickness of at least 1 to 2 ⁇ m.
  • the two faces of the article are then placed in contact with the colouring agent so as to diffuse the colouring agent within a thickness of at least 1 to 2 ⁇ m for each of the two photodegraded surface layers.
  • the thickness of the photodegraded surface layer or the photodegraded surface layers is preferably from 2 to 20 ⁇ m, and better 2 to 10 ⁇ m.
  • the colouring agent may be diffused throughout the entire thickness of the photodegraded surface layer or layers.
  • the UV radiation of the step of photodegradation by irradiation preferably has a wavelength such that, during the irradiation, at least 50%, preferably at least 60%, and even more preferably at least 65% of the energy of the irradiation originates from the part of the radiation with wavelength. 320 nm.
  • the energy of the irradiation of the article due to the part of the UV radiation with wavelength 320 nm is from 2.4 to 48 J/cm 2 , preferably 10 to 30 J/cm 2
  • the energy of the irradiation of the article due to the part of the UV radiation with wavelength>320 nm is from 0.9 J/cm 2 to 15 J/cm 2 , and better from 2 J/cm 2 to 8 J/cm 2 .
  • UV radiation has a wavelength range from 200 to 400 nm).
  • the time during which each point of one of the faces is subjected to the irradiation is less than 10 minutes, preferably less than 2 minutes and even more preferably less than 30 seconds.
  • the optimal duration of the photodegradation step during which the energies listed above are received by the lens vary from 0.1 to 10 seconds, generally and preferably from 0.4 to 4 seconds.
  • the UV radiation suitable for the method of the invention may be obtained, for example, by using a UV “H” lamp from the FUSION UV SYSTEM Company at 50% of its nominal power or a UV “D” lamp from the same Company at 40% of its nominal power.
  • the UV irradiation of the polycarbonate article must be such that the photo-ageing essentially proceeds according to an “intrinsic” photochemistry, i.e. surface attack.
  • an “intrinsic” photochemistry i.e. surface attack.
  • Any polycarbonate not containing polyester groups is suitable for the present invention.
  • polycarbonate should be understood to include the homopolycarbonates and the copolycarbonates and sequenced copolycarbonates, with the proviso that copolycarbonates containing polyester groups are excluded.
  • polycarbonates are commercially available, for example from the Companies GENERAL ELECTRIC COMPANY under the trade name LEXAN®, TEIJIN under the trade name PANLITE®, BAYER under the trade name BAYBLEND®, MOBAY CHEMICAL Corp. under the trade name MAKROLON® and DOW CHEMICAL Co. under the trade name CALIBRE®.
  • the preferred polycarbonates are the homopolycarbonates, in particular the homopolycarbonates of bisphenol-A and of tetramethyl-3,5-bisphenol-A (TMBPA).
  • the polycarbonate material preferably contains an effective quantity of a UV absorber.
  • UV absorbers are adjuvants which are well known in the polymer field and are commercially available.
  • UV absorbers include the benzotriazoles, the benzophenones, the dihydroxybenzophenones, the benzimidazoles and the phenyl benzoates.
  • the benzotriazoles include the benzotriazoles of formula:
  • R 1 represents H or an alkyl radical, preferably C 1 -C 6
  • R 2 represents H or an alkyl radical, preferably C 1 -C 8 .
  • X represents H or Cl.
  • the benzophenones include compounds of formula:
  • R 3 is an alkyl radical, preferably C 1 -C 13 .
  • the dihydroxybenzophenones include compounds of formula:
  • R 4 is an alkyl radical, preferably C 1 -C 8 .
  • the phenyl benzoates include compounds of formula:
  • R 5 represents H or an alkyl radical, preferably C 1 -C 4 .
  • R 6 and R 7 represent H or OH.
  • the proportion of UV absorber in the polycarbonate material generally varies from 0 to 10% by weight with respect to the total weight of the material, preferably from 0 to 5%, and more preferably about 2.5% by weight.
  • the polycarbonate material may contain any other conventionally used adjuvant which does not impair the optical properties of the material, such as antioxidants, internal or external lubricants, flame retardants and antistatic agents in their usual proportions.
  • any dye or pigment conventionally used for colouring transparent polymer articles may be used, including photochromic dyes and pigments.
  • a UV absorber may also be diffused at this stage.
  • the conventionally used dyes include the azo dyes and the anthraquinone dyes.
  • the azo dyes may include monoazo dyes, for example of formula:
  • R 8 and R 9 are aryl or heterocyclic radicals, preferably heterocyclic, or diazo dyes, for example of formula:
  • R 10 , R 11 and R 12 are aryl or heterocyclic radicals, preferably heterocyclic.
  • the anthraquinone dyes may be represented by the formula:
  • R 13 and R 14 represent H, OH, an amino group, an alkoxy group, a fluorocarbon group or an acylamino group.
  • Other dyes may be infrared absorbers or laser dyes.
  • the infrared absorbers include the following compounds:
  • R represents H or an alkyl, preferably C 1 -C 4 .
  • the laser dyes include dyes containing one or more chromophores selected from one or more porphyrin complexes modified by metals to form metal porphyrin complexes.
  • chromophores examples include vanadyl t-butylated phthalocyanine and tin chloride phthalocyanine which absorb at a wavelength of 694 nm and are thus suitable for protection against a ruby laser.
  • the photochromic dyes and pigments include the spirooxazines and the chromenes.
  • Photochromic dyes and pigments of the chromene type are described, amongst others, in the patents and patent applications WO 90/07507, WO 92/09593, WO 93/17071, FR 2 688 782, EP-401958, EP-562915, U.S. Pat. No. 3,567,605 and U.S. Pat. No. 5,066,818.
  • the preferred dyes and pigments are the azo and anthraquinone dyes and pigments.
  • the step of colouring the article consists of placing the face corresponding to the photodegraded surface layer of the polycarbonate article in contact with a colouring agent, for example in the form of a solution or dispersion of one or more dyes or pigments, using entirely conventional methods such as dipping in a colouring bath or by centrifugal deposit of a colouring solution on the photodegraded face of the article.
  • a colouring agent for example in the form of a solution or dispersion of one or more dyes or pigments
  • the contact of the photodegraded face of the article with the colouring agent is preferably carried out by dipping in a colouring bath.
  • the colouring baths and solutions are conventionally aqueous solutions and dispersions of a dye or a pigment or mixtures of dyes and pigments.
  • These baths and solutions preferably also contain an effective quantity of a surface-active agent, in particular an alkyl benzene sulfonate.
  • a surface-active agent in particular an alkyl benzene sulfonate.
  • the proportion of surface-active agent in the baths or solutions generally varies from 0 to 3%, preferably 0.2% by weight.
  • the temperature of the colouring baths and solutions, during the colouring step is generally between 85 and 100° C., in general about 94 to 95° C.
  • the articles are preferably subjected to a thermal treatment to stabilize the coloration, at a temperature preferably higher than 100° C. and possibly reaching 140° C., preferably about 130° C., for a sufficient time to fix the coloration, generally 1 hour or more, preferably about 2 hours.
  • the primer coats serve essentially as tack coats to improve the adhesion of the hard anti-abrasion coatings on the article.
  • Any primer composition conventionally used for transparent polymer articles, such as ophthalmic lenses, may be used in the method of the invention, in particular conventional shockproof primer layers.
  • Preferred primer compositions include compositions based on thermoplastic polyurethanes, such as those disclosed in the Japanese patents 63-141001 and 63-87223, poly(meth)acrylic primer compositions, such as those disclosed in the patent U.S. Pat. No. 5,015,523, compositions based on thermosetting polyurethanes, such as those disclosed in the patent EP-04041 11 and compositions based on poly(meth)acrylic latexes and polyurethane latexes, such as those disclosed in the patents U.S. Pat. No. 5,316,791 and EP-0680492, WO 98/02376.
  • thermoplastic polyurethanes such as those disclosed in the Japanese patents 63-141001 and 63-87223
  • poly(meth)acrylic primer compositions such as those disclosed in the patent U.S. Pat. No. 5,015,523
  • compositions based on thermosetting polyurethanes such as those disclosed in the patent EP-04041 11
  • the preferred primer compositions are the compositions based on polyurethanes and compositions based on latexes, particularly the polyurethane latexes.
  • the poly(meth)acrylic latexes are latexes of copolymers mainly consisting of a (meth)acrylate, such as for example ethyl, butyl, methoxy or ethoxyethyl (meth)acrylate, with a generally smaller proportion of at least one other comonomer, such as for example styrene.
  • a (meth)acrylate such as for example ethyl, butyl, methoxy or ethoxyethyl (meth)acrylate
  • at least one other comonomer such as for example styrene.
  • the preferred poly(meth)acrylic latexes are acrylate-styrene copolymer latexes.
  • Such acrylate-styrene copolymer latexes are commercially available from the Company ZENECA RESINS under the trade name NEOCRYL®.
  • Polyurethane latexes are also known and commercially available.
  • polyurethane latexes include those containing polyester groups.
  • Such latexes which are commercially available include NEOREZ® from the Company ZENECA RESINS and WITCOBOND® from the Company BAXENDEN CHEMICAL.
  • Mixtures of these latexes in particular of polyurethane latex and poly(meth)acrylic latex, may also be used as primers.
  • primer compositions may be deposited on the faces of the article by dipping or centrifugation, then dried at a temperature of at least 70° C. and up to 100° C., preferably of the order of 90° C., for a time ranging from 2 minutes to 2 hours, generally of the order of 15 minutes, to form primer layers with thicknesses, after baking, of 0.2 to 2.5 ⁇ m, preferably 0.5 to 1.5 ⁇ m.
  • the method of the invention also includes the formation of a layer of a hard anti-abrasion coating on the faces of the article, in particular the photodegraded face of the article, preferably coated with a primer coat.
  • any composition conventionally used for this purpose, in particular in the ophthalmic optics field, may be used.
  • compositions for hard anti-abrasion coating include compositions based on poly(meth)acrylate and compositions based on alkoxysilane hydrolysate, in particular epoxysilane hydrolysate, such as those disclosed in the French patent 93 02649 and the patent U.S. Pat. No. 4,211,823.
  • a preferred composition for hard anti-abrasion coating comprises a hydrolysate of epoxysilane and of dialkyldialkoxysilane, a colloidal filler, such as colloidal silica, TiO 2 or Sb 2 O 5 and a catalyst, preferably an aluminium chelate, such as aluminium acetylacetonate, the remainder consisting essentially of solvents conventionally used for the formulation of such compositions.
  • the hydrolysate used is preferably a hydrolysate of -glycidyloxypropyl trimethoxysilane (GLYMO) and dimethyl diethoxysilane (DMDES).
  • GLYMO -glycidyloxypropyl trimethoxysilane
  • DMDES dimethyl diethoxysilane
  • composition is obtained by hydrolysis of a mixture of 224 parts by weight of GLYMO and 120 parts of DMDES, to which is added 718 parts by weight of colloidal silica 30% in methanol, 15 parts of aluminium acetylacetonate and 44 parts of ethylcellosolve.
  • the primer coat is not necessary to adhere the anti-abrasion coating.
  • the thickness of the anti-abrasion coating is generally between 1 and 10 ⁇ m and more particularly between 2 and 6 ⁇ m.
  • the method of the invention may also include the formation of an anti-reflection layer on the hard anti-abrasion coating layer.
  • the anti-reflection coating may be composed of a mono-or multilayer film, of dielectric materials such as SiO, SiO 2 , Si 3 N 4 , TiO 2 , ZrO 2 , Al 2 O 3 , MgF 2 or Ta 2 O 5 , or their mixtures. It is thus possible to prevent the appearance of a reflection at the lens-air interface.
  • This anti-reflection coating is generally applied by vacuum deposit according to one of the following techniques:
  • the film In the case where the film consists of a single layer, its optical thickness must be equal to ⁇ /4 where ⁇ is a wavelength between 450 and 650 nm.
  • a combination may be used corresponding to the respective optical thicknesses ⁇ /4- ⁇ /2- ⁇ /4 or ⁇ /4- ⁇ /4- ⁇ /4.
  • the invention also concerns transparent polycarbonate articles, such as optical glasses or lenses, with two opposite principal faces and comprising at least one photodegraded surface layer on one of the principal faces with a thickness of at least 1 ⁇ m, generally from 2 to 20 ⁇ m, and preferably 2 to 10 ⁇ m, in the entire thickness of which is dispersed a colouring agent.
  • the article preferably comprises two photodegraded surface layers on the two opposite principal faces of the article, each having a thickness of at least 1 ⁇ m, generally from 2 to 20 ⁇ m, and preferably 2 to 10 ⁇ m, in which is dispersed the colouring agent.
  • the article may be coated on one or two faces with a primer coat, a hard anti-abrasion coating and optionally an anti-reflection coating, as described above with respect to the method of the invention.
  • FIG. 1 a schematic frontal view of a device for performing the step of irradiation of a transparent article, such as a lens, made from polycarbonate, according to the method of the invention.
  • FIG. 2 a graph of the radiation spectrum of the UV light source of the device of FIG. 1.
  • a transparent polycarbonate article such as a lens 1 is transported by means of a conveyor belt 2 under a UV radiation source.
  • the UV radiation source for example a UV “D” lamp from the Company FUSION UV SYSTEM operating at 40% of its nominal power, comprises a bulb 3 and a reflector 4 focussing the light beam through a ground quartz screen 5 onto the lens 1 transported by the belt 2.
  • the width of the light beam falling on the lens is about 1 cm.
  • the photodegradation energy received over 4 seconds by the lens is thus 16 J/cm 2 for the part of the UV radiation with wavelength. 320 nm and 5.73 J/cm 2 for the part of the UV radiation>320 nm.
  • the polycarbonate material of the lens 1 is photodegraded, on the upper face of the article, over a depth of at least 1 ⁇ m.
  • the belt speed and thus the energy received by the lens may obviously be varied as a function of the lamp used and the desired depth of the photodegraded layer, the conditions being always maintained so that the depth of the photodegraded surface layer of the polycarbonate article is at least 1 ⁇ m and preferably at least 2 ⁇ m.
  • the belt speed is generally from 5 cm/minute to 60 cm/minute, preferably from 10 cm/minute to 30 cm/minute, to obtain the desired irradiation energies.
  • the irradiation must be such that the temperature reached by the irradiated article remains less than the glass transition temperature (Tg) of the polycarbonate article.
  • the lens is subjected to the irradiation treatment on the two principal faces to form two photodegraded surface layers of at least 1 ⁇ m thickness on each of the faces of the article 1.
  • the article 1 is coloured, for example by dipping in a colouring bath.
  • the colouring bath is generally at a temperature of 85-100° C., and the time spent in the bath may vary from 10 minutes to 1 hour or more, and is in general from 30 minutes to 1 hour.
  • the table below shows the compositions of the colouring baths, and the colour obtained.
  • Bath 1 Bath 2 Bath 3 Colour green Colour grey Colour brown Water 1 l 1 l 1 l AKBS 2 ml 2 ml 2 ml Blue TERATOP ® GLF 1.25 g 3.95 g 0.95 g Yellow TERATOP ® GNL 9.5 g 8 g 12 g Red TERATOP ® 3G 0.1 g 0.75 g 0.33 g
  • the article After removal of the article from the colouring bath, the article is generally subjected to a treatment to wash off the excess of the colouring agent by immersion in an aqueous solution of polyethylene glycol at 55° C., then rinsed with deionised water at 55° C.
  • the article is preferably subjected to a thermal treatment to stabilize the colour, in which the article is heated to 130° C. for 2 hours.
  • the coloured article was pre-treated with a soda solution at 50° C. for 4 minutes, then immersed for 4 minutes in a primer composition, for example a polyurethane latex (Polyester/polyol from the BAXENDEN Company) at 5° C. After removal, the primer coat was dried at 80° C. for 20 minutes and let cool for 15 minutes.
  • a primer composition for example a polyurethane latex (Polyester/polyol from the BAXENDEN Company) at 5° C. After removal, the primer coat was dried at 80° C. for 20 minutes and let cool for 15 minutes.
  • the lens was then immersed for 4 minutes in a hard anti-abrasion coating composition at 5° C.
  • the hard anti-abrasion coating composition deposited was then baked for 3 hours at 100° C.
  • a coloured PC article was thus obtained with a primer coat and a layer of hard anti-abrasion coating on both faces.
  • the anti-abrasion coating composition was prepared as follows:
  • the theoretical dry extract of the composition contained 13% of solid matter originating from the hydrolysed DMDES.
  • the lenses were blown with compressed air to remove burrs and dust.
  • the transmission index ⁇ ⁇ (in accordance with standards ISO/CIE 10526: 1991 and ISO/CIE 10527: 1991 and the draft standard ISO/DIS 8980-3 of 1997) was determined.
  • the transmission index ⁇ was 17-30%, corresponding to classification 2 as determined in the draft standard ISO/DIS 8980-3.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Eyeglasses (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Physical Vapour Deposition (AREA)
US09/974,399 1999-04-08 2001-10-09 Method for coloring a transparent article made of polycarbonate and resulting article Abandoned US20020138921A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/844,045 US6911055B2 (en) 1999-04-08 2004-05-12 Method for coloring a transparent article made of polycarbonate and resulting article
US11/054,980 US7179848B2 (en) 1999-04-08 2005-02-10 Method for coloring a transparent article made of polycarbonate and resulting article

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9904409A FR2792010B1 (fr) 1999-04-08 1999-04-08 Procede de coloration d'un article transparent en polycarbonate et article obtenu
FR99/04409 1999-04-08
PCT/FR2000/000792 WO2000061857A1 (fr) 1999-04-08 2000-03-30 Procede de coloration d'un aritcle transparent en polycarbonate et article obtenu

Related Parent Applications (1)

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PCT/FR2000/000792 Continuation WO2000061857A1 (fr) 1999-04-08 2000-03-30 Procede de coloration d'un aritcle transparent en polycarbonate et article obtenu

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/844,045 Continuation US6911055B2 (en) 1999-04-08 2004-05-12 Method for coloring a transparent article made of polycarbonate and resulting article

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US20020138921A1 true US20020138921A1 (en) 2002-10-03

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US09/974,399 Abandoned US20020138921A1 (en) 1999-04-08 2001-10-09 Method for coloring a transparent article made of polycarbonate and resulting article
US10/844,045 Expired - Fee Related US6911055B2 (en) 1999-04-08 2004-05-12 Method for coloring a transparent article made of polycarbonate and resulting article
US11/054,980 Expired - Fee Related US7179848B2 (en) 1999-04-08 2005-02-10 Method for coloring a transparent article made of polycarbonate and resulting article

Family Applications After (2)

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US10/844,045 Expired - Fee Related US6911055B2 (en) 1999-04-08 2004-05-12 Method for coloring a transparent article made of polycarbonate and resulting article
US11/054,980 Expired - Fee Related US7179848B2 (en) 1999-04-08 2005-02-10 Method for coloring a transparent article made of polycarbonate and resulting article

Country Status (10)

Country Link
US (3) US20020138921A1 (de)
EP (1) EP1171664B1 (de)
JP (1) JP2003500552A (de)
AT (1) ATE275658T1 (de)
AU (1) AU761600B2 (de)
CA (1) CA2369737C (de)
DE (1) DE60013582T2 (de)
ES (1) ES2226806T3 (de)
FR (1) FR2792010B1 (de)
WO (1) WO2000061857A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050250870A1 (en) * 2004-05-04 2005-11-10 Essilor International Compagnie Generale D'optique Curable adhesive composition and its use in the optical field
FR2881230A1 (fr) * 2005-01-25 2006-07-28 Essilor Int Methode de coloration d'une lentille optique comprenant un primaire d'impression, et lentille optique teintee comprenant un tel primaire d'impression
WO2016016681A1 (en) * 2014-07-30 2016-02-04 Essilor International (Compagnie Générale d'Optique) Method for dyeing a transparent article made of a polymeric substrate with gradient tint

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2904431B1 (fr) * 2006-07-31 2008-09-19 Essilor Int Article d'optique a proprietes antistatiques et anti-abrasion, et procede de fabrication
US20090089942A1 (en) * 2007-10-09 2009-04-09 Bayer Materialscience Llc Method of tinting a plastic article
JP5467670B2 (ja) * 2008-03-31 2014-04-09 株式会社ニデック 染色方法及び染色装置
WO2010087327A1 (ja) * 2009-01-27 2010-08-05 静岡県 レーザマーキング方法
JP5619472B2 (ja) * 2010-05-13 2014-11-05 山本化成株式会社 眼鏡レンズ
JP6010349B2 (ja) * 2011-06-09 2016-10-19 株式会社ニデック 染色方法及び染色装置
US8658967B2 (en) 2011-06-29 2014-02-25 Kla-Tencor Corporation Optically pumping to sustain plasma

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567605A (en) 1966-03-30 1971-03-02 Ralph S Becker Photochemical process
JPS53111336A (en) 1977-03-11 1978-09-28 Toray Ind Inc Coating composition
JPS57133286A (en) * 1981-02-10 1982-08-17 Kogyo Gijutsuin Surface dyeing of polyolefine type plastic
JPH0642002B2 (ja) 1983-07-29 1994-06-01 セイコーエプソン株式会社 プラスチックレンズ
JPS6250336A (ja) * 1985-08-30 1987-03-05 Showa Denko Kk プラスチツクレンズの表面処理方法
GB8610709D0 (en) 1986-05-01 1986-06-04 Plinkington Bros Plc Photochromic lenses
JPH0762722B2 (ja) 1986-09-30 1995-07-05 ホ−ヤ株式会社 プラスチックレンズ
JPH0679084B2 (ja) 1986-12-04 1994-10-05 ホーヤ株式会社 プラスチックレンズ
JPH01118682A (ja) * 1987-10-28 1989-05-11 Agency Of Ind Science & Technol ポリカーボネートフィルムの表面染色
US4931221A (en) 1988-12-30 1990-06-05 Ppg Industries, Inc. Photochromic spiropyran compounds
EP0388660A3 (de) 1989-02-23 1990-10-10 Showa Denko Kabushiki Kaisha Photochrome Verbindung
FR2647790A1 (fr) 1989-06-05 1990-12-07 Essilor Int Composes photochromiques de type indolino-spiro-oxazine, leur procede de preparation, compositions et articles photochromiques contenant de tels composes
FR2647789B1 (fr) 1989-06-05 1994-07-22 Essilor Int Composes photochromiques de type indolino-spiro-oxazine, leur procede de preparation, compositions et articles photochromiques contenant de tels composes
DE69015886T2 (de) 1989-06-05 1995-08-03 Tokuyama Corp Fotochromische Verbindung, deren Zusammensetzung und Verwendung.
JP3196780B2 (ja) 1989-06-20 2001-08-06 日本板硝子株式会社 プラスチックレンズの製造法
US5066818A (en) 1990-03-07 1991-11-19 Ppg Industries, Inc. Photochromic naphthopyran compounds
US5244602A (en) 1990-12-03 1993-09-14 Ppg Industries, Inc. Photochromic naphthopyrans
JPH04353529A (ja) * 1991-05-30 1992-12-08 Teijin Ltd ポリエステルの表面改質法
US5238981A (en) 1992-02-24 1993-08-24 Transitions Optical, Inc. Photochromic naphthopyrans
FR2688782A1 (fr) 1992-03-19 1993-09-24 Essilor Int Nouveaux chromenes heterocycliques et leur utilisation dans le domaine de l'optique ophtalmique.
US5316791A (en) 1993-01-21 1994-05-31 Sdc Coatings Inc. Process for improving impact resistance of coated plastic substrates
FR2702486B1 (fr) 1993-03-08 1995-04-21 Essilor Int Compositions de revêtement antiabrasion à base d'hydrolysats de silanes et de composés de l'aluminium, et articles revêtus correspondants résistants à l'abrasion et aux chocs.
JPH06265830A (ja) * 1993-03-11 1994-09-22 Nikon Corp 着色されたプラスチックレンズ
US5443597A (en) * 1994-03-23 1995-08-22 Gentex Optics, Inc. Method of tinting polycarbonate-polyester copolymers
FR2723218A1 (fr) 1994-07-29 1996-02-02 Essilor Internal Cie Gle Optique Composes photochromiques de structure spiro (indoline-(2,3')-benzoxazine) a groupement cyano en 6', et leur utilisation dans le domaine de l'optique ophtalmique
US5697406A (en) 1996-07-12 1997-12-16 Miller Brewing Company System for detecting missing vent tubes on a bottle filling apparatus

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050250870A1 (en) * 2004-05-04 2005-11-10 Essilor International Compagnie Generale D'optique Curable adhesive composition and its use in the optical field
US7439278B2 (en) 2004-05-04 2008-10-21 Essilor International Compagnie Generale D'optique Curable adhesive composition and its use in the optical field
FR2881230A1 (fr) * 2005-01-25 2006-07-28 Essilor Int Methode de coloration d'une lentille optique comprenant un primaire d'impression, et lentille optique teintee comprenant un tel primaire d'impression
WO2006079715A1 (fr) * 2005-01-25 2006-08-03 Essilor International (Compagnie Generale D'optique) Methode de coloration d'une lentille optique comprenant un primaire d'impression, et lentille optique teintee comprenant un tel primaire d'impression
US20080127432A1 (en) * 2005-01-25 2008-06-05 Essilor International (Compagnie Generale D'optiqu Method For Coloring an Optical Lens Comprising a Printing Primer, and Optical Colored Lens Comprising Such a Printing Primer
US8740996B2 (en) 2005-01-25 2014-06-03 Essilor International (Compagnie Generale D'optique) Method for coloring an optical lens comprising a printing primer, and optical colored lens comprising such a printing primer
WO2016016681A1 (en) * 2014-07-30 2016-02-04 Essilor International (Compagnie Générale d'Optique) Method for dyeing a transparent article made of a polymeric substrate with gradient tint
CN106536172A (zh) * 2014-07-30 2017-03-22 埃西勒国际通用光学公司 用于以梯度色调对由聚合物基材制成的透明物品进行染色的方法
US10201944B2 (en) * 2014-07-30 2019-02-12 Essilor International Method for dyeing a transparent article made of a polymeric substrate with gradient tint

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US20050170186A1 (en) 2005-08-04
JP2003500552A (ja) 2003-01-07
DE60013582D1 (de) 2004-10-14
AU3823300A (en) 2000-11-14
FR2792010B1 (fr) 2001-07-27
US6911055B2 (en) 2005-06-28
EP1171664B1 (de) 2004-09-08
AU761600B2 (en) 2003-06-05
EP1171664A1 (de) 2002-01-16
WO2000061857A1 (fr) 2000-10-19
ES2226806T3 (es) 2005-04-01
DE60013582T2 (de) 2005-03-31
CA2369737C (fr) 2010-08-10
WO2000061857A8 (fr) 2002-08-08
ATE275658T1 (de) 2004-09-15
US7179848B2 (en) 2007-02-20
CA2369737A1 (fr) 2000-10-19
FR2792010A1 (fr) 2000-10-13
US20040265572A1 (en) 2004-12-30

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