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WO1998029766A1 - Lentille optique en plastique a haut indice de refraction - Google Patents

Lentille optique en plastique a haut indice de refraction Download PDF

Info

Publication number
WO1998029766A1
WO1998029766A1 PCT/JP1997/004869 JP9704869W WO9829766A1 WO 1998029766 A1 WO1998029766 A1 WO 1998029766A1 JP 9704869 W JP9704869 W JP 9704869W WO 9829766 A1 WO9829766 A1 WO 9829766A1
Authority
WO
WIPO (PCT)
Prior art keywords
lens
refractive index
plastic lens
compound
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1997/004869
Other languages
English (en)
Japanese (ja)
Inventor
Tadashi Kobayashi
Yuyoshi Saito
Chieko Hirakawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Lite Optical Co Ltd
Original Assignee
Asahi Lite Optical 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 Asahi Lite Optical Co Ltd filed Critical Asahi Lite Optical Co Ltd
Publication of WO1998029766A1 publication Critical patent/WO1998029766A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
    • 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
    • G02B1/041—Lenses

Definitions

  • the present invention relates to a high-refractive-index plastic lens excellent in impact resistance, heat resistance and dyeing properties used for various optical lenses such as spectacle lenses.
  • Plastic lenses are lighter, harder to break, and easier to dye than glass lenses. After passing through acrylic resin, polycarbonate resin, and ADC resin, plastic lenses today have a high refractive index. Are used, and those with a refractive index of more than 1.6 are on the market. However, while plastic lenses have the advantages described above, they are inferior to glass lenses in abrasion resistance or heat resistance. Various improvements and efforts have been made to improve this defect.
  • a method of improving the abrasion is mainly studied by modifying the lens surface, and a method of applying an organic gay compound or a hard coat liquid containing an organic gay compound and an inorganic compound, an organic compound or an inorganic compound, Has been put to practical use.
  • the refractive index is 1.6 or more
  • the edge thickness around the lens can be reduced, and a good-looking lens is obtained.
  • the thickness of the central portion is reduced as much as possible in order to reduce the weight of the lens, and the aspherical design makes it possible to improve aberrations and further reduce the thickness of the peripheral portion.
  • a lens having a higher refractive index than the ADC resin represented by CR-39 of PPG for example, in Japanese Patent Application Laid-Open No. 63-46213, a polymer of a xylylenediocyanate compound and a polythiol compound is disclosed. A polyurethane lens consisting of is disclosed. Japanese Unexamined Patent Publication No.
  • 2-279589 discloses a polyurethane lens having a higher refractive index.
  • these polyurethane lenses are inferior in heat resistance to ADC resins, and are generally used for dyeing or surface coating of lenses that require post-processing with a heat history of about 60 to 95 ° C.
  • the post-processing involves significant deformation of the central portion.
  • Dyeing at low temperature not only requires a long processing time, but also has a drawback that a desired dyeing concentration cannot be obtained in some cases, and is extremely disadvantageous.
  • Japanese Patent Application Laid-Open No. 2-279591 discloses the use of a special aliphatic thiol having three or more hydroxyl groups or mercapto groups.
  • Japanese Patent Application Laid-Open No. 3-56525 discloses that at least 50% of the reactive functional groups are -SH groups, and that the functional groups have at least three functional groups that are reactive with the isocyanate. It is disclosed to use acyclic saturated monomers.
  • Japanese Patent Application Laid-Open No. 6-122478 proposes a specific aliphatic thiol compound.
  • Japanese Patent Application Laid-Open No. 5-148340 mainly discloses a rigid 1,4-dithiane ring.
  • a polyurethane having a chain, or a polyurethane having a dithiolane ring is proposed in JP-A-5-105677.
  • the present invention comprises a sulfur-containing polyurethane obtained by polymerizing at least one kind of polyisocyanate compound and two or more kinds of polythiols and / or sulfur-containing polyol compounds, and is an essential component of the polythiol.
  • the present invention relates to a high-refractive-index plastic lens for optics having a heat deformation temperature of not less than 59 and a heat deformation temperature of not less than 95 ° C. and a method for producing the same.
  • the polyisocyanate is selected from aliphatic, aromatic or alicyclic diisocyanate, and is preferably selected from aromatic or alicyclic diisocyanate. Specific examples include m-xylylene diisocyanate, tolylene diisocyanate, 4,4 'diphenylmethane diisocyanate, tetramethyl-m-xylylene diisocyanate, and Sophoronediisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethanediisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, 2,2'-dimethyldihexylhexylmethane Isocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2,2,1] heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2,2,1] h
  • polythiol examples include dithiol or polythiol such as pentaerythritol toltrathixoglycolate, pentaerythritol toltrathrax (3-mercaptopropione), 1,2-bis [:( 2-mercaptoethyl) thio] 13-mercaptopropane Are preferably used.
  • the dithiol compound represented by H s- m (1) (where n is an integer of 1 to 4 and m is an integer of 1 to 3) is an important constituent element of the present invention. It is selected from ethanedithiol, di (2-mercaptoethyl) sulfide, 1,4-butandithiol, 4,8-dithiaundecane-11,11-dithiol.
  • the amount used is determined so as to obtain the desired heat distortion temperature and refractive index according to the type or amount of the polyisocyanate and polythiol used at the same time, but generally 3 to 4 in polythiol. When the amount is less than this range, good dyeing performance cannot be obtained. When the amount is more than this range, thermal deformation is strong and good lens performance cannot be obtained.
  • Polythiols other than those represented by the general formula (1) are dithiol litho Or tetrathiol, and is preferably contained in the isocyanate-reactive compound in an amount of 60 to 97 mol%.
  • the urethane-based plastic lens resin of the present invention is produced by heating and curing a diisocyanate compound and a polythiol compound. At this time, in order to adjust the polymerization rate to a desired reaction rate, a known reaction catalyst used in the production of polyurethane may be appropriately added. Further, a crosslinking agent, a light stabilizer, an ultraviolet absorber, a blueing agent, an antioxidant, and the like can be added according to the purpose such as improvement of weather resistance.
  • the lens of the present invention is usually obtained by casting polymerization.
  • a diisocyanate compound and a polythiol compound are mixed, defoamed if necessary, then injected into a pre-assembled metal or glass mold, and gradually heated from a low temperature to a high temperature. And polymerize. When the polymerization is completed, separate from the mold and release to obtain a plastic lens.
  • the mixing ratio of the disocyanate compound to the polythiol compound is such that the molar ratio of the functional group of NCOZSH is preferably in the range of 0.5 to 1.5, and is substantially equimolar.
  • other monomers besides the above components can be appropriately mixed and used as long as the desired physical properties are not impaired.
  • the anti-static treatment, hard coat treatment, anti-reflection treatment, dyeing treatment, and other practical treatments It can be a tall lens.
  • a lens having a spherical power of minus 6 diopters was prepared, immersed in a dye bath at 95 ° C in which a gray dye of BPI was dispersed for 15 minutes, washed with water, and dried. After drying, the degree of deformation of the center portion and the outer edge of the lens was visually determined.
  • the obtained lens had a power minus 6.02 diopter, a refractive index and an Abbe number of 1.61 and 41, respectively, and a heat deformation temperature of 122 ° C. As a result of staining under the above conditions, the staining concentration was 43%. Comparative Example 1
  • a plastic lens was obtained in the same manner as in Example 1 using dibutyltin dichloride.
  • the frequency was minus 6.00 dip
  • the refractive index and Abbe number were 1.60 and 40, respectively
  • the heat distortion temperature was 142 ° C
  • the staining concentration was 15%.
  • a plastic lens was obtained in the same manner as in Example 1 by using dibutyltin dichloride.
  • the frequency was minus 6.03 diopters
  • the refractive index and Abbe number were 1.62 and 41, respectively
  • the heat distortion temperature was 118 ° C
  • the staining concentration was 18%.
  • a plastic lens was obtained in the same manner as in Example 1 using di (2-mercaptoethyl) sulfide g (0.10 mol) and dibutyltin dichloride.
  • the frequency was minus 6.03 diopters
  • the refractive index and the Abbe number were 1.62 and 42
  • the heat distortion temperature was 108 ° C
  • the staining concentration was 35%. Comparative Example 3
  • a plastic lens was obtained in the same manner as in Example 1 using dibutyltin dichloride.
  • the frequency is minus 6.02 diopters, the refractive index and Abbe number are 1.62 and 42, respectively, and the heat distortion temperature is 120.
  • the staining concentration was 16%.
  • the lens made of the urethane resin of the present invention exhibits excellent heat resistance and excellent dyeing performance while having excellent optical properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Lentille optique en plastique à haut indice de réfraction comprenant - pour avoir une thermorésistance élevée et une excellente aptitude à la teinture - une résine d'uréthane sulfuré obtenue par polymérisation d'au moins un composé de polyisocyanate avec au moins deux polythiols et/ou des composés de polyol sulfuré, sachant que les polythiols renferment comme ingrédient essentiel un composé de dithiol de formule générale HS-[-(-CH2-)-nS-]-mH. Dans ladite formule, n est un entier compris entre 1 et 4 et m est un entier allant de 1 à 3. La lentille, établie à partir de monomères où les polythiols ont un pourcentage molaire en di(2-mercaptoéthyl) sulfure compris entre 3 et 40 %, à titre d'exemple de composé au dithiol obtenu par polymérisation donnée sous échauffement, a les propriétés suivantes : indice de réfraction égal ou supérieur à 1,59, température de déformation à chaud de 95 °C ou plus et excellente aptitude à la teinture.
PCT/JP1997/004869 1996-12-27 1997-12-26 Lentille optique en plastique a haut indice de refraction Ceased WO1998029766A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8/349789 1996-12-27
JP34978996A JPH10186101A (ja) 1996-12-27 1996-12-27 光学用高屈折率プラスチックレンズ

Publications (1)

Publication Number Publication Date
WO1998029766A1 true WO1998029766A1 (fr) 1998-07-09

Family

ID=18406133

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1997/004869 Ceased WO1998029766A1 (fr) 1996-12-27 1997-12-26 Lentille optique en plastique a haut indice de refraction

Country Status (3)

Country Link
JP (1) JPH10186101A (fr)
TW (1) TW364063B (fr)
WO (1) WO1998029766A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2801586A1 (fr) * 2013-05-07 2014-11-12 Bruno Bock Chemische Fabrik GmbH & Co. KG Résine de coulée à base de polythiouréthane dotée d'une résistance supérieure à la rupture et d'un faible poids spécifique
CN110330784A (zh) * 2019-07-24 2019-10-15 上海康耐特光学有限公司 一种聚氨酯混合物及其制备方法和应用、包含其的改性镜片

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018070865A (ja) * 2016-10-25 2018-05-10 三井化学株式会社 光学材料用重合性組成物、該組成物から得られた光学材料及びその製造方法
JP6562521B2 (ja) 2017-09-29 2019-08-21 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ 光学部材用樹脂の製造方法、光学部材用樹脂、眼鏡レンズ及び眼鏡
KR20250067860A (ko) * 2022-10-14 2025-05-15 미쯔이가가꾸가부시끼가이샤 폴리티올 조성물, 중합성 조성물, 수지, 성형체, 광학 재료 및 렌즈

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60199016A (ja) * 1984-03-23 1985-10-08 Mitsui Toatsu Chem Inc チオカルバミン酸ｓ―アルキルエステル系レンズ用樹脂の製造方法
JPH01302202A (ja) * 1988-02-17 1989-12-06 Mitsui Toatsu Chem Inc 高屈折率プラスチックレンズ及びその製造方法
JPH02802A (ja) * 1988-02-22 1990-01-05 Mitsui Toatsu Chem Inc 高屈折率プラスチックレンズ及びその製造方法
JPH02153302A (ja) * 1988-02-17 1990-06-13 Mitsui Toatsu Chem Inc 高屈折率光学素子及びプラスチックレンズの製造方法及び該方法により得られる光学素子並びにプラスチックレンズ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60199016A (ja) * 1984-03-23 1985-10-08 Mitsui Toatsu Chem Inc チオカルバミン酸ｓ―アルキルエステル系レンズ用樹脂の製造方法
JPH01302202A (ja) * 1988-02-17 1989-12-06 Mitsui Toatsu Chem Inc 高屈折率プラスチックレンズ及びその製造方法
JPH02153302A (ja) * 1988-02-17 1990-06-13 Mitsui Toatsu Chem Inc 高屈折率光学素子及びプラスチックレンズの製造方法及び該方法により得られる光学素子並びにプラスチックレンズ
JPH02802A (ja) * 1988-02-22 1990-01-05 Mitsui Toatsu Chem Inc 高屈折率プラスチックレンズ及びその製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2801586A1 (fr) * 2013-05-07 2014-11-12 Bruno Bock Chemische Fabrik GmbH & Co. KG Résine de coulée à base de polythiouréthane dotée d'une résistance supérieure à la rupture et d'un faible poids spécifique
WO2014180666A1 (fr) * 2013-05-07 2014-11-13 Bruno Bock Chemische Fabrik Gmbh & Co. Kg Résine moulée à base de polythio-uréthane présentant une résistance élevée à la rupture et un faible poids spécifique
US9994667B2 (en) 2013-05-07 2018-06-12 Bruno Bock Chemische Fabrik GmbH and Co. KG Polythiourethane-based casting resin having high fracture resistance and low specific weight
CN110330784A (zh) * 2019-07-24 2019-10-15 上海康耐特光学有限公司 一种聚氨酯混合物及其制备方法和应用、包含其的改性镜片

Also Published As

Publication number Publication date
TW364063B (en) 1999-07-11
JPH10186101A (ja) 1998-07-14

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