WO2007073022A1 - Procede de fabrication de verres plastiques photochromes - Google Patents

Procede de fabrication de verres plastiques photochromes Download PDF

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Publication number
WO2007073022A1
WO2007073022A1 PCT/KR2006/001907 KR2006001907W WO2007073022A1 WO 2007073022 A1 WO2007073022 A1 WO 2007073022A1 KR 2006001907 W KR2006001907 W KR 2006001907W WO 2007073022 A1 WO2007073022 A1 WO 2007073022A1
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WO
WIPO (PCT)
Prior art keywords
lens
over
coating
hard
reaction temperature
Prior art date
Application number
PCT/KR2006/001907
Other languages
English (en)
Inventor
Sang Min Lee
Original Assignee
Covis Optic Co., Ltd.
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
Application filed by Covis Optic Co., Ltd. filed Critical Covis Optic Co., Ltd.
Publication of WO2007073022A1 publication Critical patent/WO2007073022A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a method for manufacturing photochromic plastic lens. More specifically, the present invention relates to a method for manufacturing photochromic plastic lens that enhances a surface hardness of the lens without deterioration in photochromic properties and reduction in production efficiency, thereby ensuring stability in hard-coating and multi-coating and enabling production of a non- frame glass.
  • Photochromism is defined as a light- induced reversible change of color, e.g., change of colorless-transparence into a specific color upon exposure to ultraviolet (UV) radiation.
  • the materials inducing this phenomenon are known as "photochromies".
  • the photochromies are used to produce a photochromic lens.
  • the photochromic lens is transparent or light in color indoors where there is no sun light (UV radiation), but becomes as dark as sunglasses upon exposure to UV radiation. Thereafter, indoors where there is no UV radiation, the photochromic lens exhibits an original color, i.e., transparent or light color.
  • Such photochromic lens is valuable for people wearing glasses even indoors for visual correction. Accordingly, the photochromic lens enables visual correction and function of a sunglass.
  • Photochromic plastic lenses are generally produced by adding slightly a photochromic compound to a monomer and polymerizing the mixture.
  • the photochromic compound may be selected from spiropyran, spiroxazine, fulguide, chromene, diazo compound and diarylethene.
  • the polymer must secure a predetermined space therein to enable the photochromic compound to easily exhibit its functionality.
  • photochromic plastic lenses disadvantageously have weak physical properties (e.g., hardness), as compared to general lenses for visual correction. Meanwhile, general plastic lenses are subjected to hard-coating to enhance surface hardness, thereby ensuring prevention of the occurrence of scratches or scars.
  • Korean Patent Laid-open No. 2004-0094928 discloses a polymeric composition comprising a polycycloalkane-based difunctional monomer and a photochromic compound, and an optical product using the polymeric composition.
  • Korean Patent Laid-open No. 2002-0090995 discloses a photochromic composition comprising an aromatic radical monomer, a photochromic compound (e.g., spirobenzopyran) having an absorption wave equal to or greater than 250 nm, and a photopolymerization initiator.
  • Korean Patent Laid-open No. 2005-0026650 discloses a photochromic lens.
  • the photochromic lens comprises a radical monomer, spirobenzopyran as a photochromic compound, various colorants and a photopolymerization initiator. Accordingly, the photochromic lens undergoes color change from light color (e.g., yellow, red and blue) to deep color (e.g., black, gray and deep blue) upon exposure to light radiation.
  • light color e.g., yellow, red and blue
  • deep color e.g., black, gray and deep blue
  • a method for manufacturing photochromic plastic lens comprising the steps of: [12] mixing 10 to 30% by weight of dimethylol tricyclodecane diacrylate or methacrylate; and 70 to 90% by weight of a monomer selected from diacrylate, dimethacrylate, and a copolymer of acrylate and dimethacrylate, with 0.001 to 10% by weight of a photochromic compound selected from spiropyran, spiroxazine, fulguide, fulgimide, chromene and diazo compound;
  • the present invention relates to a method for manufacturing a photochromic plastic lens that improves a surface hardness of the lens without deterioration in photochromic properties and reduction in production efficiency, thereby ensuring stable hard-coating and multi-coating, and enabling production of a non-frame glass.
  • the method according to the present invention will be described in detail at each step.
  • the main monomer constituting an optical resin of the present invention may be a monomer selected from diacrylate, dimethacrylate and a copolymer of acrylate and dimethacrylate, which are well-known in the art. It has been reported that the diacrylate monomer enables the photochromic compound to easily exhibit its functionality.
  • Dimethylol tricyclodecane diacrylate or methacrylate is copolymerized with the main monomer to form a copolymer.
  • PCT Publication No. WO 96/0038486 discloses dimethylol tricyclodecane diacrylate and methacrylate.
  • Polycycloalkane within the molecule has a bulky stereo- structure and thus secures a sufficient space within the copolymer, thereby enabling the photochromic compound to easily exhibit its functionality.
  • polycycloalkane hinders oxygen from accessing the photochromic compound, owing to its steric hindrance effect, thereby obtaining an increase in life time of the photochromic compound.
  • (methacrylate) are preferably about 70 to 90% by weight and about 10 to 30% by weight, respectively. If the content of dimethylol tricyclodecane diacrylate (methacrylate) is lower than 10%, the photochromic property of the compound may decrease. Meanwhile, if the content of dimethylol tricyclodecane diacrylate (methacrylate) is higher than 30%, the hardness of a polymerized resin may decrease, thereby causing considerable deterioration in moldability and workability.
  • the monomer may be selected from any well-known monomers in the art.
  • the addition of 0.001 to 10 wt% of the photochromic compound to the monomer enables the polymerized resin to have photochromicity.
  • the photochromic compound may be selected from spiropyran, spiroxazine, fulguide, fulgimide, chromene and diazo compound.
  • redial polymerization initiators represented by Formulas 1 and 2 above are added to the mixture, respectively, based on the total weight of the mixture.
  • the kind and content of redial polymerization initiators have a great effect on the hardness of polymerized resin.
  • replacement by other redial polymerization initiators or addition of the initiators in the content out of the range defined above leads to greater deterioration in the hardness and coating stability of final products (lenses). This is the reason that non- polymerization causes unstability in molding of lens and unreactants inhibits coating of lens.
  • redial polymerization initiators represented by Formulas 1 and 2 are added in a content of 0.7% and 0.04% by weight, based on the total weight of the mixture, respectively.
  • a mold acting as a die is assembled for lens production.
  • a mold and B mold having a predetermined diopter (D.P.) are assembled with a tape or gasket while an emptied space within each mold is maintained.
  • the mixture is injected into the resulting mold, followed by first polymerizing under the following conditions, thereby molding a lens.
  • the polymerization is also called as "thermal curing reaction”.
  • the molded lens is separated from the mold. At this time, the separation is preferably carried out while the temperature of 60+5 0 C was maintained.
  • the lens is subjected to general washing. During the washing, residues and foreign materials remaining on the surface of the lens are removed.
  • the washing is required for stabilization of the lens surface and coating film upon a subsequent coating by removal of the foreign materials inhibiting an adherence of the coating film.
  • the washing is preferably conducted using a plurality of washing baths. That is, washing with a cleaner is carried out in some baths, and washing with hot water or distilled water is carried out in the remaining baths. It is most preferable to use a washer including twelve to fourteen washing baths. 40 to 60% by weight of a cleaner is used in 1-2 washing baths, 20 to 40% by weight of a cleaner is used in 3-4 washing baths.
  • the cleaner may be selected from any cleaners containing an anionic surfactant commonly used in the art.
  • the cleaner containing both anionic and nonionic surfactants is preferably used.
  • the cleaner used herein was Neozol-LC 600 (available from Neopharm. Co., Ltd. Korea).
  • the lens is subjected to second-polymerization (thermal curing reaction) under the following conditions to manufacture a photochromic plastic lens.
  • the manufactured photochromic plastic lens is subjected to hard-coating.
  • the hard- coating is carried out by dipping the lens in a hard solution. That is, the lens is dipped in the hard solution, i.e., a coating liquid containing a silicon resin, thereby forming a silicon resin film with a high hardness on the surface thereof.
  • a hard solution i.e., a coating liquid containing a silicon resin, thereby forming a silicon resin film with a high hardness on the surface thereof.
  • Common hard-coating processes associated with a glass lens may be applied to the hard-coating of the present invention.
  • the hard solution used herein was 8H (available fromLG Chem. Ltd.).
  • the hard-coated lens is subjected to multi-coating, i.e., formation of multi thin films by alternative deposition of a low-refractive dielectric and a high-refractive dielectric, thereby reducing surface reflection.
  • SiO may be used as the low-refractive dielectric.
  • ZrO , TiO , ITO, Y O , ZnS and La O may be used as the high-refractive dielectric.
  • the deposition is conducted under a reduced pressure of about 1 x 10 to about 5 x 10-
  • LC 600 (available from Neopharm. Co., Ltd. Korea) as a cleaner was introduced into 1-2 baths and 3-4 baths in a content of 54% and 34% by weight, respectively. Hot water was filled with 5-8 baths. Distilled water was filled with 9-12 baths. The resulting lens was sufficiently washed through twelve washing baths.
  • the lens is subjected to second-polymerization (thermal curing reaction) under the following conditions, thereby manufacturing a photochromic plastic lens.
  • the manufactured photochromic plastic lens is dipped in a hard solution (8HTM, available from LG Chem. Ltd., Korea) to form a silicon hard-film having a thickness of 2 D.
  • a hard solution (8HTM, available from LG Chem. Ltd., Korea) to form a silicon hard-film having a thickness of 2 D.
  • SiO and ZrO were alternatively deposited under vacuum on the hard-coated lens obtained in Example 1.
  • the deposition is conducted under a reduced pressure of about 2 x 10 Torr using a vapor-deposition chamber for deposition of a glass lens.
  • Five coating thin films were deposited oneach oftheconcave and convex sides of lens, in the order SiO ->ZrO ->SiO ->ZrO ->SiO
  • SEM scanning electron microscope
  • V-60TM (WAKO) as a radical polymerization initiator was used exclusively.
  • a lens was washed in the same manner as in Example 1, except that hot water and distilled water only were used without using any cleaner.
  • V-70 (WAKO) as a radical polymerization initiator was used exclusively.
  • a lens was washed in the same manner as in Example 1, except that hot water and distilled water only were used without using any cleaner.
  • Second polymerization was conducted in the same manner as in Example 1. It could be confirmed that the overall polymerization was incomplete and 20% product defect was occurred.
  • V-65TM WAKO
  • V-70TM WAKO
  • Example 1 and Comparative Examples 1 to 4 was tested for surface hardness. The test was carried out by drop ball test (DBT). After dropping a ball of 27 g at a height of 1.2 M ten times, damage to the lens was evaluated. The lens manufactured in Example 1 was not damaged at all and maintained its original state. On the other hand, each of the lenses manufactured in Comparative Examples 1 to 3 got damaged (about 30 to 50%). The lens manufactured in Comparative Example 4 was slightly cracked.
  • DBT drop ball test
  • the method of the present invention enables considerable improvement in a surface hardness of the lens without deterioration in photochromic properties (e.g., life time and rate) and reduction in production efficiency.
  • photochromic plastic lens manufactured by the method has a surface hardness, comparable to general lenses, thereby enabling functional coating such as hard-coating and multi-coating, and being suitable for production of a non- frame glass, which could not be realized in the art.
  • the photochromic plastic lens contributes to practical use of photochromic lens, which has had practical limitation due to its low hardness in spite of its many advantages.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)
  • Optical Filters (AREA)

Abstract

L'invention porte sur un procédé de fabrication de verres plastiques photochromes, et plus spécifiquement sur un tel procédé améliorant la dureté superficielle des verres sans nuire à leur propriétés photochromes ni au rendement de production, tout en assurant la stabilité de la couche dure et des couches multiples et permettant de produire des lunettes sans cercles. Ledit procédé se base sur la sélection optimale du type et du rapport de mélange de l'initiateur de polymérisation, et sur le réglage précis de la polymérisation thermique. Lesdits verres ont une dureté comparable à celles des verres usuels ce qui permet la formation de couche dure et des couches multiples stables et la production de lunettes sans cercles, ce que ne permettait pas l'art antérieur.
PCT/KR2006/001907 2005-12-21 2006-05-22 Procede de fabrication de verres plastiques photochromes WO2007073022A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020050126680A KR100568409B1 (ko) 2005-12-21 2005-12-21 광변색성 플라스틱 렌즈의 제조방법
KR10-2005-0126680 2005-12-21

Publications (1)

Publication Number Publication Date
WO2007073022A1 true WO2007073022A1 (fr) 2007-06-28

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Application Number Title Priority Date Filing Date
PCT/KR2006/001907 WO2007073022A1 (fr) 2005-12-21 2006-05-22 Procede de fabrication de verres plastiques photochromes

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KR (1) KR100568409B1 (fr)
WO (1) WO2007073022A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6487607A (en) * 1987-09-29 1989-03-31 Mitsubishi Rayon Co Production of photochromic molded article
JPH04208919A (ja) * 1990-11-30 1992-07-30 Seed:Kk フォトクロミックハードコンタクトレンズ
WO2000019246A2 (fr) * 1998-09-29 2000-04-06 Corning S.A. Preparation de pieces organiques de qualite optique, en particulier des lentilles organiques
US20010020061A1 (en) * 1994-12-12 2001-09-06 Florent Frederic Henri Temperature stable and sunlight protected photochromic articles
JP2003098302A (ja) * 2001-09-25 2003-04-03 Nof Corp プラスチック光学材料用単量体組成物、その硬化物及びレンズ
US6602603B2 (en) * 1999-07-02 2003-08-05 Ppg Industries Ohio, Inc. Poly(meth)acrylic photochromic coating
JP2004078054A (ja) * 2002-08-22 2004-03-11 Nof Corp プラスチック光学材料用単量体組成物、フォトクロミック光学材料及びレンズ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6487607A (en) * 1987-09-29 1989-03-31 Mitsubishi Rayon Co Production of photochromic molded article
JPH04208919A (ja) * 1990-11-30 1992-07-30 Seed:Kk フォトクロミックハードコンタクトレンズ
US20010020061A1 (en) * 1994-12-12 2001-09-06 Florent Frederic Henri Temperature stable and sunlight protected photochromic articles
WO2000019246A2 (fr) * 1998-09-29 2000-04-06 Corning S.A. Preparation de pieces organiques de qualite optique, en particulier des lentilles organiques
US6602603B2 (en) * 1999-07-02 2003-08-05 Ppg Industries Ohio, Inc. Poly(meth)acrylic photochromic coating
JP2003098302A (ja) * 2001-09-25 2003-04-03 Nof Corp プラスチック光学材料用単量体組成物、その硬化物及びレンズ
JP2004078054A (ja) * 2002-08-22 2004-03-11 Nof Corp プラスチック光学材料用単量体組成物、フォトクロミック光学材料及びレンズ

Also Published As

Publication number Publication date
KR100568409B1 (ko) 2006-04-05

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