WO2001073482A1 - Lentille plastique a base d'episulfure a indice de refraction eleve et a aptitude a la teinture satisfaisante, et procede de production correspondant - Google Patents

Lentille plastique a base d'episulfure a indice de refraction eleve et a aptitude a la teinture satisfaisante, et procede de production correspondant Download PDF

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Publication number
WO2001073482A1
WO2001073482A1 PCT/JP2001/002600 JP0102600W WO0173482A1 WO 2001073482 A1 WO2001073482 A1 WO 2001073482A1 JP 0102600 W JP0102600 W JP 0102600W WO 0173482 A1 WO0173482 A1 WO 0173482A1
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WO
WIPO (PCT)
Prior art keywords
compound
lens
refractive index
plastic lens
weight
Prior art date
Application number
PCT/JP2001/002600
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English (en)
Japanese (ja)
Inventor
Yuyoshi Saito
Tadashi Kobayashi
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 WO2001073482A1 publication Critical patent/WO2001073482A1/fr

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    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
    • 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 an easily dyeable high refractive index plastic lens and a method for producing the same. More particularly, the present invention relates to a high-refractive-index plastic lens having improved dyeing properties of a resin obtained by polymerizing and curing a compound having an episulfide group, and a method for producing the same.
  • plastic lenses have characteristics such as light weight, resistance to breakage, and ease of dyeing compared to inorganic glass lenses, so they have become widely used for eyeglass lenses that emphasize fashion. It has become As the resin for the ophthalmic lens, diethylene glycol bisaryl carbonate resin 39) has been used.
  • this CR-39 resin has a refractive index of 1.50, and when used in an ophthalmic lens, the thickness of the negative lens increases, and the thickness of the center increases with the positive resist, and the appearance of the eyeglass wearer increases. On top of that, it was not always satisfactory. In order to remedy this drawback, plastic lens materials with higher refractive index have been developed. As methods for increasing the refractive index, methods such as introduction of a halogen (excluding fluorine) atom, introduction of an aromatic ring, and introduction of a sulfur atom have been proposed.
  • Japanese Patent Application Laid-Open No. 7150/80 Japanese Patent Application No. 9-1100979, Japanese Patent Application Laid-Open No. 11-14070, Japanese Patent Application No. 11-1601 Japanese Unexamined Patent Application Publication No. Hei 11-1-83702, Japanese Unexamined Patent Publication No. Hei 1-189592, Japanese Unexamined Patent Publication No.
  • the optical material obtained by curing the ebisulfide group-containing compound disclosed therein also has significantly poor dyeability as compared with CR-39 or a fluorinated plastic lens, and the glass lens of the plastic lens is difficult to obtain. The superiority of the lens cannot be fully demonstrated, and improvement is desired.
  • JP-A-11-166370 discloses that a compound containing at least one active hydrogen other than an S ⁇ group is contained in a compound containing an ebisulfide group. Also disclosed are compositions containing hydroxy (meta) acrylates and titanium glycolates. However, in order to achieve high dyeability even with this technique, a large amount of active hydrogen compounds other than the episulphide group-containing compound must be added, resulting in a decrease in the refractive index and a decrease in heat resistance. I will invite you. Also, Japanese Patent Application Laid-Open No.
  • H10-2928787 discloses a compound having an episulfide group-containing compound and one or more SH groups per molecule for the purpose of improving the oxidation resistance of the obtained resin.
  • a composition comprising a compound has been proposed, the refractive index has been lowered because the improvement in dyeing properties is due to the addition of glycidol and the like.
  • Japanese Patent Application Laid-Open No. 11-248901 discloses that a plastic lens obtained by cast polymerization of a compound having two or more epulsulfide groups in one molecule is referred to as a disperse dye.
  • a method of immersing in a dyeing bath containing a carrier comprising a halogenated aromatic hydrocarbon is disclosed.
  • Japanese Patent Application Laid-Open No. 11-279957 discloses that a plastic lens includes a plastic lens.
  • a method of dyeing after immersion in sulfuric acid, aromatic sulfonic acid, catechol, etc. is disclosed.However, when a deep color is required, the dyeability is not sufficiently improved and the degree of dyeing is not sufficient.
  • the carrier component in the above has a bad influence on the working environment.
  • a high-density dye having a refractive index of 1.7 or more which is obtained by curing a composition containing a compound having an ebisulfide group, has a high refractive index.
  • An object of the present invention is to provide a refractive index lens and a method for manufacturing the same. Disclosure of the invention
  • the present inventors have conducted intensive studies on the composition of a resin obtained by curing a composition containing a compound having an episulfide group as a main component, and as a result, by appropriately blending a thiol compound, The inventors have found that a bra and a stick lens having high heat deformation resistance and high dyeing property can be obtained without lowering the rate, and the present invention has been completed.
  • the easily dyeable high refractive index plastic lens of the present invention It is obtained by curing a resin raw material composition containing a compound having a sulfide group, a polythiol compound having three or more functional groups and a dithiol compound as a main component, and the content of the dithiol compound in the composition is three or more. 5 to 40% by weight based on the total amount of the polythiol compound and dithiol compound.
  • a compound having two or more ebisulphide groups in one molecule is preferably used.
  • Japanese Unexamined Patent Publication No. Hei. Gazette Japanese Patent Application Laid-Open No. 9-1100979, Japanese Patent Application Laid-Open No. 9-2555701, Japanese Patent Application No. 1 1-14 0 0 70, Japanese Patent Application No. 11-1 No. 8 950, Japanese Patent No. 1 1 — 1 8 3 7 0 No. 2, No. 1 1 — 3 0 2 3 5 No. 9, Japanese Unexamined Patent Application Publication No. Ebisulfide compounds exemplified in gazettes and the like can be used.
  • Representative compounds include compounds having a linear aliphatic skeleton, compounds having a branched aliphatic skeleton, compounds having an aliphatic cyclic skeleton, compounds having an aromatic skeleton, and compounds having a heterocycle in the skeleton. Can be mentioned. Specific examples of compound names include bis (2,3—epitipropyl) ether, bis (2,3—epitipropyl) sulfide, and 1,2—bis (2,3—epitipropyl).
  • the polythiol compound used in the present invention is a compound having three or more functional groups, that is, thiol groups in a molecule.
  • compound names are: 1, 2, 3—trimercaptopropane, 2—mercaptomethyl-1,3, -dimercaptoprononone, 2—mercaptomethyl-1,4, -dimercaptobutane, 2— ( 2—Mercaptoethylthio) 1,3, —Dimercaptopropane, 1,1,1—Tris (mercaptomethyl) propane, Trimethicone-l-promon tris (2—Mercaptoacetate), Tri Methyl liposome “Lebronontris (3—Mecaptopropionate), 1,2—Bis (2—Mercaptoethylthio) —3—Mercaptoprononone, 4—Mercaptomethyl-1,3,6—Dithia-1 Trifunctional compounds such as 1,8-octanedithiol, pentaerythritol tolitol thixoglycolate, pentane erythritol tolte trakis ( Examples include 4-functional
  • the dithiol compounds used in the present invention include benzodithiol, 1,3-dimercaptopropane, 1,4-butandithiol, di (2-mercaptoethyl) ether, 1,4— Bis (mercaptomethyl.) Benzene, bis (4-mercaptophenyl) sulfide, 1,2-dimercaptobenzene, 1,4 dimercaptobenzene, di (2-mercaptoethyl) sulfide, ethylene glycol dithiopro Bionnet , 1, 3 — dimercaptocyclohexane, ⁇ , 4 — dimercaptocyclohexane, dimercaptomethyl-1-thiane, dimercaptoethyl — 1,4 dithiane, dimercaptomethyl-1,4 — dithiane, dimer (Mercaptomethyl) spirobi (m-dithiane) and di (mercaptoethyl) spirobi (m-dit
  • the amount of the thiol compound used depends on the performance of the resin required in the post-processing step or as an eyeglass lens, the amount of the ebisulfide compound or the thiol compound.
  • the amount is appropriately selected depending on the kind, but is usually 2 to 40 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the ebisulfide compound.
  • the amount is less than 2% by weight, the resulting resin will become more colored at the end of polymerization, the resin will become brittle, and if it is more than 40% by weight, the refractive index will decrease, If the softening point is too low, it may be deformed due to the heat history in the post-processing process such as dyeing or hard coating.
  • the use amount of the dithiol compound is preferably 5 to 40% by weight based on the total amount of the thiol compound of the polythiol compound and the dithiol compound. If the amount is less than 5% by weight, the effect of improving the dyeability will be insufficient. If the amount is more than 40% by weight, the refractive index will decrease and the heat deformation temperature will decrease significantly. It is not suitable as a refractive index lens.
  • a typical polymerization method for producing a plastic lens for eyeglasses using the curable resin material composition of the present invention is a casting polymerization method. Specifically, after degassing and mixing a compound having an episulfide group, a polythiol compound, a dithiol compound, a curing catalyst, and, if necessary, a resin modifier, a gasket or a tape is used to manufacture an eyeglass lens. After pouring into two glass-type or metal-type shells arranged via a, they are polymerized and cured. Heat is usually used for polymerization and curing. Polymerization conditions The polymerization is determined by the composition of the monomer composition of the resin raw material and the type and amount of the curing catalyst.
  • the polymerization is carried out at a temperature of 20 to 150 ° C. for 1 to 40 hours.
  • the temperature may be kept at a constant temperature for a certain time, but in some cases, it is preferable to gradually raise the temperature over 1 to 40 hours.
  • amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, mineral acids, Lewis acids, organic acids, tetraphenyl salts Borated acids can be used as the curing catalyst.
  • amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, and the like are particularly preferred.
  • UV absorbers In addition to the curing catalyst, UV absorbers, antioxidants, light stabilizers, pulling agents, etc. may be added as necessary to improve the properties of the resin. it can.
  • the plastic lens of the present invention is immersed in a dye bath in which the dye is dissolved or dispersed, preferably at a temperature of 85 ° C. or higher.
  • the dyeing bath is not particularly limited as long as it is a dye system that can withstand the color temperature. However, from the viewpoint of the stability of the dye, a water-based disperse dye system is preferred.
  • the purpose is to provide antistatic properties, abrasion resistance, antireflection, improved chemical resistance, antifogging properties, and water resistance? 3) Apply antistatic coating, hard coating, anti-reflection coating, water-repelling coating, etc. to obtain practical lenses.
  • Stainability A lens with a sphere of minus 4 dips, a center thickness of 1.05 mm was prepared, immersed for 1 hour in a 5 ° C dye bath in which BPI gray dye was dispersed, and then washed with water. It was dyed by drying the temple. Using this stained lens, the staining concentration was calculated by the following equation from the measurement value obtained using a color lens checker CD-1A manufactured by Asahi Spectroscopy Co., Ltd.
  • the weight part was put in a flask and mixed while defoaming under reduced pressure of about 5 mmHg for 2 hours. This was poured into a glass mold prepared in advance and polymerized and cured by holding at 80 ° C for 15 hours. After being removed from the polymerization furnace, it was washed for 3 minutes by a washing machine that sprayed a liquid jet nozzle. 'After drying at room temperature, the mold was released from the glass mold and annealed at 100 ° C for 1 hour to obtain a plastic lens.
  • the refractive index of this lens was 1.70, and the staining density was 15%. No deformation was seen.
  • the refractive index of this lens was 1.71, and the staining density was 14%. No deformation was seen.
  • the refractive index of this lens was 1.70, and the staining density was 15%. No deformation was seen.
  • the refractive index of this lens was 1.70, and the staining density was 2%.
  • the plastic lens of the present invention has excellent optical properties such as a high refractive index, and also exhibits excellent performance in heat resistance and dyeability, and is therefore extremely useful as an eyeglass lens.

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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)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Afin de conférer une résistance à la chaleur et une aptitude à la teinture élevées à une lentille plastique à indice de réfraction élevé que l'on obtient par durcissement d'un composé comportant un groupe épisulfure, on fabrique une lentille par polymérisation et durcissement d'une composition constituée essentiellement d'un composé comportant un groupe épisulfure, d'un composé polythiol ayant une fonctionnalité supérieure ou égale à 3, et d'un composé dithiol, ledit composé dithiol étant présent à raison de 5 à 40 % en poids, en fonction de la somme que représentent le composé polythiol et le composé dithiol. La lentille ainsi produite présente un indice de réfraction élevé, une grande résistance thermique et une aptitude à la teinture satisfaisante.
PCT/JP2001/002600 2000-03-29 2001-03-28 Lentille plastique a base d'episulfure a indice de refraction eleve et a aptitude a la teinture satisfaisante, et procede de production correspondant WO2001073482A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000092284 2000-03-29
JP2000-92284 2000-03-29

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WO2001073482A1 true WO2001073482A1 (fr) 2001-10-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023156222A (ja) * 2022-04-12 2023-10-24 益豊新材料股▲ふん▼有限公司 ポリチオール組成物、光学材料用重合性組成物およびその製造方法
US12065544B2 (en) 2018-11-13 2024-08-20 Lg Chem, Ltd. Curable composition and optical element comprising cured product thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11100428A (ja) * 1997-09-26 1999-04-13 Sumitomo Seika Chem Co Ltd 光学材料用組成物並びにプラスチックレンズおよびその製造方法
JPH11100435A (ja) * 1997-09-26 1999-04-13 Kureha Chem Ind Co Ltd 光学材料用組成物およびプラスチックレンズ
JPH11258402A (ja) * 1998-03-13 1999-09-24 Mitsui Chem Inc 高屈折率樹脂用組成物及び該組成物を硬化させてなるプラスチックレンズ及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11100428A (ja) * 1997-09-26 1999-04-13 Sumitomo Seika Chem Co Ltd 光学材料用組成物並びにプラスチックレンズおよびその製造方法
JPH11100435A (ja) * 1997-09-26 1999-04-13 Kureha Chem Ind Co Ltd 光学材料用組成物およびプラスチックレンズ
JPH11258402A (ja) * 1998-03-13 1999-09-24 Mitsui Chem Inc 高屈折率樹脂用組成物及び該組成物を硬化させてなるプラスチックレンズ及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12065544B2 (en) 2018-11-13 2024-08-20 Lg Chem, Ltd. Curable composition and optical element comprising cured product thereof
JP2023156222A (ja) * 2022-04-12 2023-10-24 益豊新材料股▲ふん▼有限公司 ポリチオール組成物、光学材料用重合性組成物およびその製造方法
JP7454023B2 (ja) 2022-04-12 2024-03-21 益豊新材料股▲ふん▼有限公司 ポリチオール組成物、光学材料用重合性組成物およびその製造方法

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