WO2001077717A1 - Procede permettant de produire un verre en resine episulfure sulfuree et verre ainsi obtenu - Google Patents

Procede permettant de produire un verre en resine episulfure sulfuree et verre ainsi obtenu Download PDF

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Publication number
WO2001077717A1
WO2001077717A1 PCT/JP2001/002909 JP0102909W WO0177717A1 WO 2001077717 A1 WO2001077717 A1 WO 2001077717A1 JP 0102909 W JP0102909 W JP 0102909W WO 0177717 A1 WO0177717 A1 WO 0177717A1
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WIPO (PCT)
Prior art keywords
lens
resin
polymerization
refractive index
raw material
Prior art date
Application number
PCT/JP2001/002909
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English (en)
Japanese (ja)
Inventor
Kazunori Kagei
Yuyoshi Saito
Yoshihiro Yamamoto
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 WO2001077717A1 publication Critical patent/WO2001077717A1/fr

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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
    • 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 a high refractive resin lens using a sulfur-containing ebisulfide resin and a method for producing the same.
  • plastic lenses Compared with inorganic glass, plastic lenses have characteristics such as light weight, resistance to breakage, and easy coloring, and have been widely used for eyeglass lenses that emphasize fashionability.
  • Diethylene glycol bisaryl carbonate resin (CR-39) has been used as the resin for spectacle lenses.
  • this CR_39 has a refractive index of 1.50, and when used for spectacle lenses, the negative lens has a thicker core and the plus lens has a medium thickness. The wearing feeling or appearance was not always satisfactory for the spectacle wearer. To remedy this drawback, plastic lenses with higher refractive index have been developed.
  • Resin is used as a typical resin, and a high-refractive-index resin lens having a refractive index of 1.6 to 1.7 has been put to practical use.
  • the refractive index of inorganic glass lenses is still higher, and further development of optical resins is being pursued in order to follow this trend, and resin products obtained by polymerizing and curing a compound having an episulphide group have been proposed.
  • excellent properties with a refractive index of 1.70 or more are obtained, and a high refractive index resin with a refractive index of 1.74 is also on the market.
  • this sulfur-containing ebisulphide resin having a refractive index of 1.74 is not easy to handle because it has a strong off-flavor in the lens molding process and is anaerobic, so that uncured portions adhere to the surroundings.
  • plastic lenses for eyeglasses have fatal drawbacks such as reddish color when exposed outdoors, and yellow in normal long-time heat polymerization. Change.
  • a high-refractive index resin of 1.74 is difficult to obtain, a study for eliminating these disadvantages is being actively conducted. + '
  • the problem to be solved by the present invention is to provide a high-refractive-index plastic lens for spectacles in which the red coloring and yellowing of a resin lens using a sulfur-containing ebisulfide resin are eliminated. Disclosure of the invention
  • the resin lens of the present invention has a maximum polymerization temperature in the range of 80 to 14 ° C. and a light transmittance after molding in the molding of an extremely high refractive index lens made of sulfur-containing ebisulfide resin. It is characterized in that an ultraviolet absorber is added in such an amount as to significantly drop from the vicinity of the optical region of 420 nm to the region on the shorter wavelength side.
  • the maximum polymerization temperatures are the polymerization temperatures of cast polymerization for molding lens raw materials and heat polymerization for annealing to remove the distortion of the molded product after mold release and stabilize the form. It refers to the maximum temperature for performing polymerization.
  • Sulfur-containing episulfide resin has a refractive index of 1.74, which is the highest refractive index for a lens resin, but it becomes reddish in weathering tests such as outdoor exposure. Cannot be put to practical use.
  • Inventors of the present invention have found from numerous experimental examples that ultraviolet absorbers are extremely effective in eliminating specific polymerization conditions and reddish color, and have led to the present invention. It is a thing.
  • the value of around 420 nm was found to be the center value of the most favorable condition because the addition of a small amount of the ultraviolet absorber causes some variation in the product, so As a result, the average transmittance of visible light can be kept high.However, when the color tone of the lens is adjusted by using a blueing prescription described later, light transmission in the range of 420-43 O nm is achieved. Conditions that significantly reduce the rate can also be put to practical use. In addition, it is preferable that the light transmittance at a wavelength of 400 nm is less than 10% because the reddish coloring can be prevented by removing rays having a wavelength shorter than 420 nm as much as possible.
  • sulfur-containing Ebisulfide resin is used as an eyeglass lens, use a specified mold and gasket to determine the properties of the lens in the environment in which it will be used.
  • the above resin was cast and heat-polymerized while gradually increasing the temperature within the range of 30 ° C to less than 80 ° C to form a plurality of lenses.
  • a lens having the following was obtained. These lenses were divided into two sets, and one set was subjected to scratch-resistant coating processing (hereafter referred to as hard coating) at 110 ° C, and the other sets were exposed to red when exposed outdoors. I have.
  • an ultraviolet absorber added to prevent deterioration in the resin molded product was added, and after the lens molded under the above polymerization conditions was exposed outdoors, the reddish color was slightly reduced. Focusing on this, the amount and variety of UV absorbers were set variously, and the light transmittance was measured and compared. As a result, as a condition common to very little coloring, the wavelength positions at which the light transmittance exhibits a remarkable drop are almost the same. I found something.
  • the UV absorber include benzophenone-based, salicylic acid-based, cyanoacrylate-based, and benzotriazole-based agents, but the compatibility with the resin and the amount of the additive may be slightly different. Therefore, there are various options.
  • Benzotriazole-based resins are preferred as the episulfide resin, but those with a small amount of addition and high UV absorption efficiency are selected.
  • the amount of the UV absorber added is preferably in the range of 0.01 to 4.0% by weight relative to the resin, and if too much, the transparent molded product is colored yellow, which impairs the value of the product. If it is too small, discoloration cannot be removed.
  • 1 to 3% by weight of benzotriazole-based tinuvin 320 from Ciba-Geigy Inc. is used as an ultraviolet absorber, and the amount of 1/1000 of the target is used. Since there are varieties that can be achieved, it is not meaningful to limit the amount of addition.
  • the ultraviolet absorber referred to in the present invention means all substances having the action, and is not limited to the above-mentioned ultraviolet absorber.
  • a hard-coated lens is usually heated at an appropriate temperature in the range of 80 ° C to 120 ° C in order to polymerize the formed hard-coating film. If the polymerization temperature is too low, there is a case in which deformation occurs due to the pressure of the jig holding the lens due to heating in the hard coating process in the subsequent process. From this, it was determined that the lower limit of the casting polymerization temperature at the time of molding the lens raw material was 80 ° C. In the present invention, the range of the maximum polymerization temperature is set to 80 to 140 ° C. in all the polymerization steps for obtaining a lens, and the range of the heating temperature is within this range.
  • the resin lens according to the present invention has a refractive index of 1.74, which is currently the highest It has a high refractive index, has optical properties approaching the refractive index of inorganic glass of 1.8, has a thin lens barrel, surpasses inorganic glass in terms of dyeability and weight, and has a hard coat.
  • sulfur-containing ebisulfide resin requires at least the conditions of casting and heat polymerization and reduction of light transmittance in the short wavelength side region of visible light in order to enhance weather resistance.
  • it since it does not have complete colorless transparency, it is possible to enhance the value of the product by adjusting the color tone to give a transparent feeling.
  • a colorant is added to the resin of the lens raw material and / or the hard coat material to be subsequently processed, and the reflected light in the antireflection layer is adjusted. It is also possible to adjust the color tone.
  • Fig. 1 (a) is a graph showing the entire light transmittance of raw material No. 1, and (b) is a graph enlarging a part of it.
  • Figure 2 (a) is a graph showing the entire light transmittance of raw material No. 7, and (b) is a graph in which a part of it is enlarged.
  • Fig. 3 (a) is a graph showing the entire light transmittance of raw material No. 2, and (b) is a graph enlarging a part of it.
  • Fig. 4 (a) is a graph showing the entire light transmittance of raw material No. 4, and (b) is a graph enlarging a part thereof.
  • Fig. 5 (a) is a graph showing the entire light transmittance of raw material No. 8, and (b) is a graph enlarging a part of it.
  • BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described with reference to tables and drawings.
  • Table 1 shows the results of examining the relationship between the heat polymerization conditions of the sulfur-containing ebisulfide resin used in the present invention and the ultraviolet absorber. The resin molded body before being completed as a lens was referred to as a raw material.
  • Table 1 Redness test
  • Table 1 shows the results of the exposure test.
  • the casting polymerization temperature of the lens raw material shows only the highest temperature and the heating time among the long polymerization times. Shows whether or not annealing is performed after demolding to remove mechanical distortion, the heating temperature, and the result of adding 1% of tinuvin 320 as an ultraviolet absorber to prevent red color change. .
  • This result indicates that the degree of discoloration is closely related to casting and heat polymerization conditions when an ultraviolet absorber is added.
  • numbers 1, 3, 5, and 7 indicate the raw material numbers of the lenses. It matches.
  • discoloration red indicates that the resin has a strong reddish tint. If the discoloration is simply described, the resin itself slightly yellows due to casting and heat polymerization conditions, and the degree of yellowing and redness are mixed. It shows what they are meeting.
  • Table 2 shows an example in which the addition amount of the UV absorber was changed to 3% by weight to obtain a lens with extremely little coloration in appearance.
  • the relationship between the polymerization conditions and the addition amount of the UV absorber was closely related. For example, improvement in discoloration is seen as shown in Table 2 for raw material numbers 4 and 6 for raw material numbers 3 and 5 in Table 1. It can be understood that the range of particularly preferable polymerization conditions is limited. In this example, as an example, the result of using 3% by weight of benzotriazole-based tinuvin 320 as an ultraviolet absorber is shown.
  • Table 2 also shows the basis for determining the polymerization conditions of the present invention. That is, raw material No.
  • Raw material No. 8 was substantially heat-polymerized at 140 ° C, and raw material 8 that had been annealed for an additional hour had discolored, but had not been annealed. Although the raw wood slightly discolored, a less colored one was obtained by adjusting the color tone such as pulling.
  • the heating temperature of 140 ° C is a favorable condition for morphological stability.
  • Table 1 the raw material without addition of the UV absorber was suitable for the polymerization conditions, but it turned red in the exposure test.
  • an ultraviolet absorber is added to prevent resin deterioration due to light rays.
  • an object of the present invention is to reduce light rays in a shorter wavelength region than near 420 nm. In this way, the color balance of the resin lens is changed to eliminate the redness.
  • the figure is an enlarged view for a light transmittance of 70% or more.
  • the casting polymerization temperature was in the range of 30 to 80 ° C
  • the annealing was performed at 110 ° C for 3 hours
  • the UV absorber was added. Not something.
  • Raw material number 1 before exposure shown in FIG. 1 (a) shows the essential light transmittance when the sulfur-containing ebisulfide resin used in the present invention is molded as a lens. It is almost constant between 420 and 700 nm and has a transmittance of 83% or more. As a result of the annealing, the color slightly yellowed and the transmittance decreased between 400 and 420 nm, but the transmittance still exceeded 76%. It is almost transparent visually. However, it was strongly red-yellow-colored in a four-day outdoor exposure test, making it impractical. Figure 1 shows this phenomenon enlarged
  • Figure 2 (a) shows that the casting polymerization at molding was performed at a high temperature of 140 ° C, and the resin molding was performed at a high temperature. Indicates an excess rate. These polymerization conditions were aimed at complete curing of the resin, but since it had already turned yellow when removed from the heating furnace,
  • Figs. 3, 4, and 5 show examples of the addition of 3% of an ultraviolet absorber as a preferable condition.
  • the numbers 2, 4, and 8 indicate the raw material numbers.
  • Figures 3 and 4 show the light transmittance of the raw material with almost no discoloration after outdoor exposure
  • Figure 5 shows the light transmittance of raw material No. 8, which was heated too long at the upper limit temperature and was red. This is an example in which yellow coloring is visually recognized.
  • the raw material will take on a slight yellow tint, but the raw material will be slightly green due to the use of a blueing agent.
  • a practically usable raw material can be provided. In this case, although the light transmittance slightly decreases, the hue balance can be reduced to zero by supplementing the light in the insufficient wavelength range.
  • composition of the chemicals for lens molding and the polymerization conditions are shown below.
  • Example 2 The liquid prepared in Example 1 was poured into a glass mold, the temperature was gradually raised to 30 to 120 ° C., and the polymerization was completed in 15 hours.
  • the resin lens obtained by releasing the mold after cooling was subjected to an outdoor exposure test for 4 days. As a result, as shown in Table 2, the lens hardly discolored.
  • the resin lens obtained in Example 1 was annealed at 110 ° C. for 3 hours and subjected to a 4-day outdoor exposure test.
  • This lens corresponds to raw material No. 4 in Table 2, and as shown in Table 2, hardly discolored.
  • a plastic lens obtained in the same manner as in Example 1 was subjected to a 4-day outdoor exposure test on the plastic lens obtained in the same manner as in Example 1 except for the ultraviolet absorbent only from the liquid prepared in Example 1. As a result, as shown in Table 1, the lens turned strongly reddish brown. .
  • the plastic lens obtained in Comparative Example 1 was annealed at 110 ° C. for 3 hours, and the same outdoor exposure test was performed. This lens corresponds to the raw material number 3 in Table 1, and as shown in Table 1, the lens turned strongly reddish brown. [Example 4]
  • the lens obtained by the present invention is suitably used as a spectacle lens.

Abstract

L'invention concerne un verre de lunettes organique présentant un indice de réfraction élevé fabriqué à partir d'une résine épisulfure sulfurée; ce verre de lunettes ne pas en compte la couleur rouge et présente une propriété anti-jaunissement. Le procédé permettant de mouler un verre fabriqué à partir d'une résine épisulfure sulfurée et présentant un indice de réfraction extrêmement élevé se caractérise en ce que les températures de polymérisation maximums sont comprises dans une plage allant de 80 à 140 °C et qu'un absorbeur UV est incorporé dans une proportion telle que la transmittance après moulage diminue considérablement au fur et à mesure que la longueur d'ondes diminue de 420 nm, dans la zone de lumière visible, jusqu'au côté de la longueur d'ondes la plus courte. Ces températures de polymérisation maximums sont les températures utilisées pour la polymérisation par coulage, procédé consistant à mouler un matériau de verre brut, et les températures utilisées pour la polymérisation thermique, procédé au cours duquel l'objet moulé est extrait du moule puis recuit afin d'éliminer sa distorsion et de stabiliser sa forme. A savoir, ces températures sont les températures maximums permettant de réaliser des polymérisations importantes.
PCT/JP2001/002909 2000-04-05 2001-04-04 Procede permettant de produire un verre en resine episulfure sulfuree et verre ainsi obtenu WO2001077717A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2000103970 2000-04-05
JP2000-103970 2000-04-05
JP2001-102863 2001-04-02
JP2001102863 2001-04-02

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WO2001077717A1 true WO2001077717A1 (fr) 2001-10-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9995950B2 (en) 2016-01-29 2018-06-12 Carl Zeiss Vision International Gmbh Spectacle lens for car drivers
JP2019066827A (ja) * 2017-09-28 2019-04-25 三井化学株式会社 フォトクロミックレンズ

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761665A2 (fr) * 1995-08-16 1997-03-12 Mitsubishi Gas Chemical Company, Inc. Composés de sulfide alcoyle contenant des groupes épisulfide
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
JP2000147201A (ja) * 1998-11-06 2000-05-26 Ito Kogaku Kogyo Kk 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
EP0761665A2 (fr) * 1995-08-16 1997-03-12 Mitsubishi Gas Chemical Company, Inc. Composés de sulfide alcoyle contenant des groupes épisulfide
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
JP2000147201A (ja) * 1998-11-06 2000-05-26 Ito Kogaku Kogyo Kk プラスチックレンズ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9995950B2 (en) 2016-01-29 2018-06-12 Carl Zeiss Vision International Gmbh Spectacle lens for car drivers
JP2019066827A (ja) * 2017-09-28 2019-04-25 三井化学株式会社 フォトクロミックレンズ

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