TW539721B - Plastic lens material, production process of the material, composition for plastic lens, plastic lens obtained by curing the composition, and production method of the plastic lens - Google Patents

Abstract

To provide a plastic lens material free of changing into a white and turbid material during the storage for a long period of time, a production process of the material, a plastic lens composition containing the material, a plastic lens obtained by curing the composition, and a production method of the plastic lens. To provide a plastic lens material comprising a compound in which a part or all of 1,4-cyclohexane dicarboxylate structural units are a cis structure; a production process of the material; a plastic lens composition containing the material; a plastic lens obtained by curing the composition; and a production method of the plastic lens.

Description

539721 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (1) Technical Field This invention relates to plastic lens materials, a method for manufacturing the material, a plastic lens composition containing the material, A plastic lens obtained by curing the composition and a method for manufacturing the same. More specifically, it relates to a plastic lens material capable of producing a plastic lens capable of suppressing the generation of stained spots, and a composition for a plastic lens capable of suppressing mold damage during casting polymerization, and a method for manufacturing the material, including the material. A composition for a plastic lens, a plastic lens obtained by curing the composition, and a method for manufacturing the plastic lens. Current technology In recent years, plexiglass has been widely used in optical materials, such as cameras, televisions, radios, telescopes, spectacles, and lenses. In particular, ophthalmic lenses have progressed from inorganic glass to organic glass, especially plastic lenses. Therefore, plastic lenses are required to be lighter, easier to mold, have better dyeability, and less likely to produce stains. Resins for plastic lens materials currently used include, for example, polystyrene resins, polycarbonate resins, polymethacrylate resins, poly [diethylene glycol bis (allyl carbonate)] resins, and the like. In addition, the physical properties and manufacturing method of the resin are as described above, and they are described in detail in, for example, the Plastic Age (ν〇1 35, 198 to 202 (1989), etc.) Among them, the characteristics of the plastic lens from each resin are as follows. Although polystyrene resin plastic lenses have a high refractive index, they have disadvantages such as birefringence or light scattering. In addition, plastic lenses from polycarbonate resin are suitable for Chinese papers (CNS) A4 (210X297) %) -4-(Please read the notes on the back before filling in this page}

539721 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) Although it has high impact resistance, it has disadvantages such as poor solvent resistance and scratch resistance. A plastic lens derived from a polymethylmethacrylate resin has a low refractive index 'and insufficient impact resistance. In contrast, plastic lenses derived from poly [diethylene glycol bis (allyl carbonate)] resin (for example, European Patent Publication No. 0473 1 63 Kogyo) have a low refractive index of 1.498, Excellent impact resistance, high Abbe number, etc. are particularly suitable for the excellent characteristics of plastic lenses for spectacles, so they are most often used. In addition, the polymerization reaction of poly [diethylene glycol bis (allyl carbonate)] resin is slower than that of propylene resin, so it is easy to control the polymerization reaction and become a uniform polymerization reaction. Allyl carbonate)] plastic lens with resin has the characteristics of less optical strain. In addition, regarding the dyeability of plastic lenses derived from poly [diethylene glycol bis (allyl carbonate)], it is known that when plastic lenses obtained by casting molding are dyed by a general method of immersion in a dyeing solution at a high temperature, The dyeing density is better than plastic lenses from other resins. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, plastic lenses from poly [diethylene glycol bis (allyl carbonate)] resin are placed in lens molds. There are disadvantages of mold damage. The general plastic lens manufacturing method is to polymerize monomers between 25 glass molds, that is, cast polymerization, and the molds need to be washed after casting. The cleaning method is generally to use a strong alkaline solution or a strong acid. Because glass is different from metal, it is not easy to deteriorate due to cleaning, so it is suitable. In addition, since glass is easily honed, surface roughness can be reduced. ^ Zhang scale is applicable to China National Standard (CNS) A4 specifications (210X297 mm 1 ^ 1 539721 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) The general polymerization step is accompanied by a hardening shrinkage reaction. However, the glass surface curve of the lens must be completely determined by the mold. Therefore, the monomer is required to have good adhesion to the glass during polymerization. In addition, the lens needs to be removed from the glass mold after the polymerization of the monomer, so the following steps are actually required. Use a wedge to pry open the mold. Because this step will release a lot of energy, it will often have an impact. When using this force to peel it off, the glass mold will be damaged. That is, some glass molds will be pulled out, making the glass mold unusable. Therefore, the lens manufacturing process will be disordered. Generally, it will affect the production of plastic lenses by several%. A small amount of release agent is added to reduce mold damage, but this method will affect other characteristics of the lens, such as the scratch-resistant coating given in the subsequent steps. Adhesiveness, etc. Therefore, using a release agent cannot be a solution to this problem. Reducing the above problems Techniques are disclosed in, for example, Japanese Patent Publication No. 10-5 1 3 5 7 4, International Publication No. W09 9/1 7 1 37, or WO 9 9/3 8 8 9. Table No. 10—5 1 3 5 7 4 discloses that the use of diallyl phthalate oligomers can somewhat improve mold damage during peeling. However, this technique cannot meet the standard. Moreover, the addition of diallyl Phthalate can increase the refractive index of hardened lenses, so it cannot be applied to molds for plastic lenses derived from poly [diethylene glycol bis (allyl carbonate)] resins. In addition, there is a problem of weatherability. 〇9 9/1 7 1 3 7 or W9 9/3 8 8 9 9 discloses the use of cyclohexane dicarboxylic acid (please read the precautions on the back before filling this page) V "

This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -6-539721 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

5. Description of the invention (4) The diallyl ester oligomer having an ester structure can improve mold damage at the time of peeling and ‘uniform dyeing, which is one of the characteristics required for the dyeability of plastic lenses’, that is, it has an effect of reducing staining spots. However, this publication contains a fine propyl vinegar oligomer compound, which is one of the di-residual acid ester structures of cyclohexane, and is relatively crystalline. Therefore, there is a problem of turbidity during long-term storage at a temperature below normal temperature. Therefore, although the temperature of the compound can be re-dissolved by any method and used as a raw material for plastic lenses, excessive heating will deteriorate the structure of the compound or reduce the improvement of the purpose of adding the compound. In addition, a heating step is required during use, which is not conducive to the economic problem of energy. Problems to be Solved by the Invention The present invention focuses on the problem of the turbidity of a diallyl ester oligomer containing a cyclohexane dicarboxylic acid ester structure under normal temperature storage, and aims to improve the crystallinity of the compound. That is, the object of the present invention is to provide a method for improving the peeling effect of a plastic lens from a mold more easily, as disclosed in International Publication Patent No. 09 9/1 7 1 37 or WO 09 9/3889 9. And plastic lens material with dyeing effect, manufacturing method of the material, plastic lens composition containing the material, plastic lens obtained by curing the composition, and manufacturing method of the plastic lens. Solution to the problem In order to solve the above problem, the present inventors applied the Chinese National Standard (CNS) A4 to the physical properties of the diallyl ester oligomer containing a cyclohexane dicarboxylic acid ester structure, and to consider the effect of preventing cloudiness. Specifications (210x29 < 7mm) Tyt C— (Please read the precautions on the back before filling this page), 11

539721 A 7 B7 V. Description of the invention (5) The resin composition containing additives and its composition are studied intensively. As a result, it was found that when the bis-propyl ester compound containing the cyclohexane dicarboxylic acid structural unit is controlled, the crystalline structure and the trans structural ratio of the cyclohexane dicarboxylic acid structural unit can be crystallized at room temperature. The plastic lens material will not produce white turbidity during chemical conversion. It also features a plastic lens composition containing the material and a polyallyl carbonate having a specific structure, and a plastic lens obtained by hardening the composition can simultaneously solve the shortcomings of the hardened stained spots, and completed the present invention. That is, the present invention (I) is a compound of a plastic lens material characterized by a compound represented by the following general formula (1) as a terminal group and the base not represented by the following general formula (2) as a repeating unit Part of or all 1,4-cyclohexanedicarboxylic acid esters are formed by cis-structured compounds-(Please read the notes on the back before filling this page) system

As far as possible, · The wave scale is applicable to the Chinese National Standard (CNs) A4 specification (210X297 mm). 8-

539721 A7 ____ B7 V. Description of the invention (6) (where R1 is independently allyl or methallyl, and X is each independently a polyvalent alcohol having 2 to 6 carbons having 2 to 6 hydroxyl groups Derived organic residue. However, X may have an ester bond to have a branch structure with the above general formula (1) as a terminal group and the above general formula (2) as a repeating unit. The "cis" and "trans" records refer to the geometrical isomerization of compounds. More specifically, they are the "Iwahikari Dictionary of Chemistry", 3rd Edition Supplement (February 5, 1987). "Geometric heterogeneity". The present invention (I I) is a method for manufacturing a plastic lens material of the present invention (I), which is characterized by comprising the following first and second steps. Step 1: In the presence of a catalyst, react 1,4-cyclohexanedicarboxylic acid and cispropanol and / or methallyl alcohol containing a cis structure to obtain 1,4-cyclohexanedi Carboxylate step. Second step: A step of obtaining a compound for plastic lens material by transesterifying a 1,4-cyclohexane di-residue & valent alcohol obtained in the first step in the presence of a catalyst. The present invention (III) is a general plastic lens composition, which is characterized by: there are at least one of the plastic lens materials of the invention (I) and the paper size is applicable to China National Standards (CNS) A4 Specifications (21Gx 297 ^) · 9 _ (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 539721 A7

At least one or more essential ingredients in the compound represented by the general formula (3) 5. Description of the invention (7 following (please read the precautions on the back before filling this page) General formula (3)

H0 \, 〇, C, 〇, R2 II 8 II L 〇J (wherein Y is one or more organic residues derived from polyvalent saturated fluorene having 2 to 20 carbon groups having 2 to 6 hydroxyl groups, R 2 is allyl or methallyl. However, each of R 2 may be independent. When the number of hydroxyl groups of γ is n, s is an integer from 0 to n-1, and t is an integer from 1 to η. And s + t = n.) In addition, the "total hardening component" described in this specification refers to the plastic lens material represented by the present invention (I), the compound represented by the general formula (3), and the present invention (I ) The total amount of units of copolymerized plastic lens material or compound represented by general formula (3). The present invention (IV) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a composition for plastic lenses, characterized in that 'the mass of the composition for plastic lenses of the present invention (III) is at least one mass unit free Radical polymerization initiator 0.1 to 10 mass units. The invention (V) is a plastic lens obtained by hardening the composition for a plastic lens of the invention (II) or (IV). The present invention (VI) is a paper sheet made of the plastic lens of the present invention (V). The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 539721 A7 B7. 5. Description of the invention. Modes The present invention will be described in more detail below. First, the compound for a plastic lens material of the present invention (I) will be explained. The present invention (I) is a general plastic lens material, which is characterized in that the compound represented by the following general formula (I) is a terminal group, and the compound represented by the following general formula (2) is a repeating unit, Some or all of the 1,4-cyclohexanedicarboxylate structural units are formed from compounds with a cis-structure. General formula (1) (Please read the notes on the back before filling this page) R :、 ο one 〆

\ CNO ο Consumption cooperation for employees in the Intellectual Property Bureau of the Ministry of Economic Affairs (2)

(Wherein R 1 is independently allyl or methallyl, and X is independently i is a polyvalent alcohol having 2 to 6 hydroxyl groups and having 2 to 20 carbon atoms. National Standard (CNS) A4 Specification (210X297mm) -11- 539721 A7 B7 V. Description of the Invention (9) Organic residues. However, X can be ester-bonded to have the above general formula (1) as the terminal group and A branched structure using the above-mentioned general formula (2) as a repeating unit. Generally, a stereoisomer having a cis structure and a trans structure in a 1,4-cyclohexanedicarboxylate structure unit. The present invention (I) The plastic lens material shown is characterized in that the 1,4-cyclohexanedicarboxylate structural unit contains a cis-structure. Only the compound formed from the self-trans structure will be affected by the structure unit to some extent, and the general wealth will be lost. The crystallinity and fluidity at room temperature tend to be cloudy. In order to maintain the fluidity at room temperature, 30% or more of the total 1 '4-cyclohexanedicarboxylic acid structural unit is preferred to be a cis structure. And more preferably 50% or more. In the general formula (1), R1 is independently allyl or methallyl In addition, in the general formula (2), each of X is independently an organic residue derived from a polyvalent alcohol having 2 to 20 carbon atoms having 2 to 6 hydroxyl groups. The "R 1 each independently" refers to the general formula (1) Both of the end groups shown are Greek, or both are methallyl, or one is flammyl and the other is methallyl. The "X is independent of each other" It means that in the following structural formula (1), which is an example of the repeating unit shown in the general formula (2), the m X contained in the repeating structure is independent of each other. _ 装-(Please read the precautions on the back before filling (This page) Order i #. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -12-539721 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (10) (where X is independently Organic residues derived from a polyvalent alcohol having 2 to 2 carbon atoms of 6 hydroxyl groups, m is 0 or an integer of 1 or more) For example, m X in the structural formula (1) may be Organic residues derived from a polyvalent alcohol (ie, one organic residue derived from each of the m polyvalent alcohols), or organic residues derived from the same polyvalent alcohol (ie, 'there are m Organic residues derived from one polyvalent alcohol), or several of m X are organic residues derived from the same polyvalent alcohol, and other organic residues derived from other polyvalent alcohols are a mixed structure. The hybrid structure may be completely random or partially overlapped. When part or all of X is an organic residue derived from a polyvalent alcohol having three or more hydroxyl groups, the part or all of X may have an ester bond using an ester bond to have a general formula (1) as a terminal group and general formula (2) as Repeat the branch structure of the unit. That is, when, for example, X has an organic residue derived from trimethylolpropane which is an example of a trivalent saturated alcohol, the plastic lens material shown in the present invention (I) may have a partial structure shown in the following structural formula (2) . Structural formula (2) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 public envy) -13- I installed — (Please read the precautions on the back before filling this page), 11

539721 V. Description of the invention (11)

Printed by the Employees' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs. Some or all of X may be an organic residue derived from a polyvalent alcohol having three or more hydroxyl groups. In the general formula (2), 'X's are each independently one or more organic residues derived from a polyvalent saturated alcohol having 2 to 20 carbon atoms having 2 to 6 hydroxyl groups. The "polyvalent saturated alcohol having 2 to 20 carbon atoms having 2 to 6 hydroxyl groups" means the following. First, specific examples of the divalent saturated alcohol include 'ethylene glycol, propylene glycol, 1,3-propanediol, 1' 4-butanediol, 1,3-butanediol, neopentyl glycol, hexamethylene glycol, and 1,4 The first ring has its own dimethyl alcohol. Specific examples of the trivalent or higher polyvalent saturated alcohol include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, and the like. In addition, it is not limited to this example, and it includes 2 彳 包 包 主 寺 and 寺 寺 寺, which are contained in the main bond such as diethylene glycol, dipropylene glycol, triethylene glycol, and polyethylene glycol. In terms of the fluidity of the compound represented by the plastic lens material of the present invention (I), the polyvalent saturated alcohol is preferably propylene glycol or neopentyl glycol. More preferred is propylene glycol. This paper size applies to China National Standard (CNS) A4 specification (210x297mm Γ " (Please read the precautions on the back before filling this page) _pack-、-=% »539721 A7 B7 Employees’ Intellectual Property Bureau, Ministry of Economic Affairs, Consumption Printed by the cooperative V. Description of the invention (12) There is no particular limitation on the number of repeats based on the general unit (2) of the repeat unit of the plastic lens material of the present invention (I). Moreover, different repeat numbers can be mixed and used. Materials, or materials with a repeating number of 0 and compounds with a repeating number of 1 or more. However, in order to accomplish the purpose of the present invention, it is not appropriate to use a compound with a repeating number of only 0. The present invention (I) The repeating unit of the plastic lens material is shown in the general formula (2). The number of repeating bases is generally an integer from 1 to 50. Plastic lens materials made of only compounds with a repeating number of 50 or more are used for plastics. When the composition for a lens is lowered due to a reduction in the allyl concentration, a hardening delay occurs during hardening, and when the uncured compound remains, the mechanical properties such as the mechanical properties of the hardened material are reduced, which is not preferable. Preferably, plastic lenses Totalization The repeating number of the compound is an integer of 1 to 50, and an integer of 1 to 30 is more preferable, and an integer of 1 to 10 is more preferable. The plastic lens material of the present invention (I) will remain due to manufacturing conditions. 1,4-Cyclohexanedicarboxylate raw material, but it can be used directly as a plastic lens material. However, the total amount of 1'4-Cyclohexanedicarboxylate raw material added to the plastic lens material of the invention (I) is If the compound of general formula (3) is added at a mass of 70 or more, as described later in the composition for plastic lenses, it will not be conducive to staining spots or mold damage when the cured product is peeled from the glass mold. "Dicarboxylic acid esters" include 2 carboxyl allyl 1 '4 -cyclohexanedicarboxylic acid diallyl esters, or homomethyl fluorenyl 1' 4 monocyclohexanedicarboxylic acid diacetate. Methallyl ester, or 1 allyl and 1 methallyl 1,4-cyclohexanedicarboxylic acid allyl

(Please read the precautions on the back before filling this page) 1 ··· 11

539721 A7 · ---------- 5. Description of the invention (13) ^ ~ Methyl allyl esters and the like. The present invention (π) will be explained below. The present invention (II) is a method for manufacturing a plastic lens material according to the present invention (), which is characterized by including the following first step and second step. First step: In the presence of a catalyst, 'react 1,4-cyclohexane containing cis structure = carboxylic acid and allyl alcohol and / or methallyl alcohol to obtain 1,4-cyclohexanedicarboxylic acid Steps of acid esters. Second step: A step of obtaining a plastic lens material by transesterifying the 1,4-cyclohexane di-residual acid ester and the polyvalent alcohol obtained in the first step in the presence of a catalyst. Further, a method for producing a plastic lens material according to the present invention (I) in which the 1,4-cyclohexanedicarboxylic acid ester structural unit contains a cis isomer is as follows. That is, the first step of esterifying the 1,4-cyclohexanedicarboxylic acid ester and allyl alcohol and / or methallyl alcohol containing the cis structure under the catalyst, to obtain 1,4-cyclohexyl Alkane dicarboxylic acid esters. The "1,4-cyclohexanedicarboxylic acid ester" is the same as described above, and includes 1,4-cyclohexanedicarboxylic acid diallyl ester, 1,4-cyclohexanedicarboxylic acid diallyl ester, 1,4 monocyclohexyl dicarboxylic acid diallyl ester allyl methallyl ester and the like. Then in the presence of the catalyst, the 1,4-cyclohexanedicarboxylic acid ester and ^ clothing — f Please read the notes on the back ^ before filling this page]-Order

Printed on the paper by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm). 16-Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economy. 539721 A7 B7_ ) The second step of transesterification of the polyvalent alcohol is to obtain the objective plastic lens material. But it is not limited to this example, and steps such as refining may be added if necessary. The catalyst used in the first step is generally a catalyst capable of synthesizing an ester from a carboxylic acid and an alcohol, and is not particularly limited. The most preferable one is an acid catalyst, and specific examples thereof include, but are not limited to, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and hydrochloric acid. Among them, P-toluenesulfonic acid and methanesulfonic acid are preferred. The reaction temperature in the first step is not particularly limited, but will be affected by the boiling point of the solvent used as the entrainer, preferably 60 ° C to 140 ° C, and more preferably 80 ° C to 120 ° C. Also, depending on the solvent used. When necessary, a solvent can be used in the first step ', and the solvent used without hindering the esterification reaction is not particularly limited. Specific examples include, but are not limited to, benzene, toluene, xylene, and cyclohexane. Among them, benzene and toluene are preferred. The catalyst used in the second step is generally a catalyst that can be used for transesterification, and is not particularly limited. Particularly preferred is an organometallic compound. Specific examples include titanium tetraisopropoxide, titanium tetrabutoxide, Butyltin oxide, dioctyltin oxide, acetoacetone, acetoacetone pin, etc. are not limited to this example. Among them, dibutyltin oxide and dioctyltin oxide are preferred. The reaction temperature in the second step is not particularly limited. It is preferably 100 ° C to 230 ° C, more preferably 120 t to 200 ° C, but it is limited to its boiling point when using a solvent. The second step generally does not use a solvent, but a solvent may be used if necessary. The solvent used is not particularly limited so long as it does not hinder the transesterification reaction. Specific examples include, but are not limited to, benzene, toluene, xylene, and cyclohexane. Among them, benzene and toluene are preferred. It can also be used without solvent as mentioned above (please read the precautions on the back before filling this page)

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -17-539721 A7 B7 V. Description of the invention (15). The composition for a plastic lens of the present invention (III) or (IV) will be described below. The present invention (III) is a general plastic lens composition, characterized in that it contains at least one or more of the plastic lens materials of the present invention (I) and at least one or more of the compounds represented by the following general formula (3) Essential ingredients General formula (3) ΙΡΐ; clothing — (Please read the precautions on the back before filling this page) ΗΟ \ mmrn —, 〇, C / 〇, ¥ II s II 0 imm — ^ Order (where γ is One or more organic residues derived from a polyvalent saturated alcohol having 2 to 20 carbon atoms having 2 to 6 hydroxyl groups, and R 2 is allyl or methallyl. However, each of R 2 is independently independent When Y is the number of hydroxyl groups, s is an integer from 0 to η-1, t is an integer from 1 to η, and s + t = n.) The present invention (IV) is a composition for a plastic lens, It is characterized in that the composition for a plastic lens of the present invention (in) contains at least one mass unit of at least one radical polymerization initiator at a mass of 100. A method for synthesizing the compound represented by the general formula (3) contained in the composition for a plastic lens of the present invention (III) or (IV) may be a known method. For example, in the presence of a catalyst, a method of transesterifying a diallyl carbonate and a polyvalent alcohol (Special Publication No. 3-6 6 3 2 7) makes the paper size of the paper applicable to the Chinese national standard (CNS ) Α4 size (210X297 mm)

Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-18- 539721 A7 B7 _V. Description of the invention (16) Method for the reaction of propanol, phosgene and polyvalent alcohol under dehydrochloric acid (US Patent No. 237 0 565, US Patent No. 2592058), etc., but not limited to this example. General formula (3)

HO \ 一一 S ο, cuo 2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where Y is a base with 2 and alcohol. However, each R 2 I 0 to η-1 An integer,) 2 to 6 hydroxyl groups in the general formula (3), 2 to 6 hydroxyl groups, carbon number of 2 saturated alcohols, propylene glycol, 1,4-butane hexamethylene glycol, 1, 4 to 3 or more valences Polyvalent saturated alkane, trimethylolethane, alcohol, etc. In addition, a polyvalent saturated organic residue containing 2 to 20 carbon atoms of 6 to 6 hydroxyl groups in the polyvalent saturated alcohol containing an ether group on the main chain including diethanol and the like, and R 2 is allyl or methallyl I Independent. When the number of hydroxyl groups of fluorene is η, s is an integer from 1 to η, and s + t = n. , Y is one or more derivatized organic residues having 2 to 6 carbon atoms and having 2 to 6 carbon atoms. The "polyvalent saturated alcohol having 2 to 20" is shown below. Specific examples include glycols, ethylene glycol, etc. and alcohols such as pentaerythritol, monoglycidyl, dipropylene glycol, divalent saturated alcohols, etc., propylene glycol, 1,3-butanediol, neopentyl glycol, glycerol , Trimethylolpropene pentaerythritol, sorbitan triethylene glycol, polyethylene but not limited to this example. Also use ethylene glycol, propylene glycol, two (please read the precautions on the back before filling this page)

This paper size applies the Zhongguanjia Standard (CNS) A4 specification (210x297 mm) -19 539721 A 7 B7 V. Description of the invention (17) Propylene glycol is preferred, and diethylene glycol is more preferred. When the polyvalent saturated alcohol used is diethylene glycol, the obtained polyallyl carbonate is diethylene glycol bis (allyl carbonate), specifically, for example, the product name of p PG, c R — 3 9 or Akzo Nobel's trade name is Nouryset 200. In the general formula (3), R2 is an allyl group or a methallyl group. However, each of R 'is independent. For example, when η = 3, the general formula (3) is a mixture of compounds represented by the following structural formula (3) to structural formula (5). Structural formula (3) (Please read the precautions on the back before filling this page) ο

CHO / 0 Construction (4

HO ο CHO / ο \

2 R structure

HO

/ ο \

CMO / ο Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy At this time, for example, the three R 2 of the structural formula (3) may be, all three are storage propyl groups, or all three are methallyl groups, or two One is allyl; one is allyl; or one is allyl and two are methallyl. Also, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -20-539721 A7 B7 V. Description of the invention (18) Two R2 of formula (4) and R of structural formula (5) are also Ask each other. (Please read the notes on the back before filling this page) In the general formula (3), “Y” is one or more organic residues derived from a polyvalent saturated alcohol having 2 to 6 carbon atoms and 2 to 2 carbon atoms. When a compound having an organic residue derived from a polyvalent saturated alcohol having a hydroxyl number of Y exceeding an integer of 6 is used in a composition for a plastic lens, the impact resistance of the plastic lens obtained by curing is poor and unfavorable. Also, when a compound having an organic residue derived from a polyvalent saturated alcohol having an integer number of hydroxyl groups lower than 2 (that is, 1) is used in a composition for a plastic lens, the heat resistance of the cured plastic lens may be extremely reduced or Solvent resistance. When the number of hydroxyl groups of Y is η, s is an integer from 0 to η-1 't is an integer from 1 to η, and s + t is η. In general formula (3), t may be an integer of at least 1 or more, but in terms of the final plastic lens physical properties, it is better to use as much hydroxyl group as possible by the carbonate group. The compound represented by the general formula (3) varies depending on the ratio of each compound whose t is lower than η, but it is more preferable that the compound with t = η is 80% by mass or more, and more preferably 90% by mass or more. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed all the hardened physical properties contained in the plastic lens composition of the present invention (III) or (IV). The addition amount of the plastic lens material shown in the present invention (I) is preferably 0. · 05 to 30% by mass, and more preferably 0.5 to 15% by mass. When the amount of the material added is less than 2% by mass, the effect of reducing stains cannot be found. When the added amount exceeds 30% by mass, there is no problem in performance, but it is not economical. Also, for the addition of all hardening components contained in the plastic lens composition of the present invention (III) or (IV), the addition of the compound represented by the general formula (3) is applicable to the Chinese National Standard (CNS) A4 specification (210X297) (Centi) -21-539721 A7 B7 5. Description of the invention (19) The amount is preferably 50 to 99.95 mass%, and more preferably 70 to 98 mass%. When the added amount is less than 50% by mass, the mechanical properties and optical properties of the plastic lens obtained by curing the composition will be reduced. If it is more than 99.95% by mass, poor dyeing is caused. In addition, in the plastic lens composition of the present invention (III) or (IV), one or more of the main purposes can be added so long as the total hardening component contained in the resin composition for the plastic lens of the present invention does not exceed 20% by mass. In order to adjust the viscosity of the composition, the monomer can be copolymerized with the plastic lens material represented by the present invention (I) or the polyallyl carbonate represented by the general formula (3). The monomer is, for example, a monomer having an acrylic group, a vinyl group, or an allyl group. Monomers having propylene groups such as meth (meth) acrylate, isobornyl (poly (meth) acrylates, etc.), monomers having vinyl groups such as ethylene acetate, ethylene benzoate, etc., having allyl Monomers such as 1,3-cyclohexanedicarboxylic acid diallyl, etc., but is not limited to this example, and without impairing the physical properties of the plastic lens obtained by hardening, diallyl phthalate can be used , Diallyl terephthalate, diallyl isophthalate, allyl benzoate, etc. Considering the workability of the movable mold, the plastic of the present invention (III) or (IV) The viscosity of the lens composition is generally 10 to 10,000 mPa · S at 25 ° C, more preferably 10 to 10,000 mPa · S, and more preferably 10 to 2000. mPa-S. The "viscosity" refers to the measurement of a rotational viscometer. The detailed rotational viscometer is described in the Iwami Ricoh Chemical Dictionary, 3rd edition, 1 June 1997. 3rd edition, 8th brush. This paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -22- (Please read the precautions on the back before filling this page),-Member of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Industrial and Consumer Cooperatives 539721 A7 B7 V. Description of the invention (20) The amount of the monomer added to all the hardening components contained in the plastic lens composition of the present invention is 20% by mass or less, and 10% by mass The following is better, more preferably 5% by mass or less. When the amount exceeds 20% by mass, the physical properties such as the optical characteristics required for the plastic lens obtained by curing the resin will be reduced. In addition, it can be used for plastic lenses. The types of polyallyl carbonate and allyl oligomer contained in the composition, the addition ratio, and the physical properties such as the optical characteristics required for the plastic lens obtained by curing, and monomers are appropriately selected. Plastics of the invention (IV) The composition for a lens is preferably added with a radical polymerization initiator as a hardener. The radical polymerization initiator that can be added to the plastic lens composition of the present invention (IV) is not particularly limited. Properties such as properties can be known without adverse effects. However, the radical polymerization initiator used in the present invention is preferably soluble in other components present in the hardened composition, Those who can generate free radicals at 30 to 120 ° C. Specific examples of free radical polymerization initiators that can be added include diisopropyl peroxydicarbonate, cyclohexane peroxydicarbonate, and di-η-propyl Peroxydicarbonate, disec-butylperoxydicarbonate, t-butylperbenzoate, etc., but it is not limited to this example, and in terms of hardenability, diisopropylperoxydicarbonate Esters are preferred. The addition amount of the radical polymerization initiator to all the hardening components 100 mass units contained in the plastic lens composition of the present invention (III) is 0.1 to 10 mass units, and 1 to 5 masses. The unit is better. When it is less than 0.1 mass unit, the hardening of the composition will be insufficient, and when it exceeds 10 mass unit, it will not be economical. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) · 23-(Please read the precautions on the back before filling this page)

1T i # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 539721 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) The plastic lens composition of the present invention (III) or (IV) may be Add general dyes, pigments and other colorants or UV absorbers, mold release agents, and antioxidants to improve the performance of plastic lenses. Colorants such as anthracene-based, azo-based, carbon-key-based, D-quinoline-based, quinoneimine-based, indigo-based, and cyanine-based organic pigments, or organic dyes such as ice dyes and sulfur dyes, or Titan Yellow, yellow iron oxide, zinc yellow, chrome orange, molybdenum red, Ming purple, Ming blue, Ming green, chromium oxide, titanium oxide, zinc sulfide, carbon black and other inorganic pigments. Release agents such as stearic acid, butyl stearate, zinc stearate, ammonium stearate, fluorine-based compounds, silicon compounds, and the like. UV absorbers such as triazoles such as 2- (2-hydroxy-tert-butylphenyl) benzotriazole, benzophenones such as 2,4-dihydroxybenzophenone, 4-tert-butyl Hindered amines such as salicylates such as phenylphenylsalicylate, and bis- (2,2,6'6, -tetramethyl-4piperidyl) sebacate. Antioxidants such as 2,6-bis-tert-4, 4-methylphenylhydrazone, tetra- [methylated 3- (3 ', 5 / -di-tert-butyl-4 4-hydroxyphenyl) propionic acid Esters] Phenols such as methane, sulfurs such as dilauryl-3,3-thiodipropionate, and phosphorus-based antioxidants such as trinonylphenyl phosphate. The total added amount of colorants such as dyes and pigments, and ultraviolet absorbers, mold release agents, and antioxidants to all the hardening components contained in the plastic lens composition of the present invention is preferably 1 mass unit or less. The present invention (v) will be explained below. (Please read the notes on the back before filling this page), v't »

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -24 539721 A7 B7 V. Description of the invention (22) The invention (V) is a plastic lens' which is the invention (IΠ) or (IV) The composition for plastic lens is hardened. (Please read the precautions on the back before filling out this page} The refractive index of the plastic lens of the present invention at 25 ° C needs to be 1.497 to 1.505. Manufactured from the compound represented by general formula (3) The mold used for plastic lenses (refractive index 1 · 4 9 8 (2 5 ° C)) is only suitable for making plastics with the same refractive index. That is, when using the same mold, changing the refractive index will change the lens ability. To obtain a plastic lens with the same ability, different molds are required to form the composition of the high-refractive-index lens. Therefore, without changing the mold, the plastic lens material shown in the present invention (I) and the general formula (3) are used. When the compound and the monomer lens material that can be copolymerized with the plastic lens material of the present invention (I) or the compound of the general formula (3) are used to improve the lens characteristics, the refractive index of the obtained lens cannot be limited. Therefore, the plastic lens of the present invention has The refractive index at 25 ° C is preferably 1.498 to 1.550, and more preferably 1.498 to 1.503. The present invention (VI) will be explained at the end. Employee Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs The invention (VI) is printed as, A method for manufacturing a plastic lens of the present invention (V) is to harden the composition for a plastic lens of the present invention (III) or (IV) to form a plastic lens. The molding applicable to the composition for a plastic lens of the present invention The processing method is casting. Specifically, for example, after adding a radical polymerization initiator to the composition, it is injected into a mold fixed with a rubber gasket or a distance adjuster through a pipeline, and then molded in a method such as hardening by heating in an oven. The material of the mold used is metal or glass. The paper size of general plastic lenses is applicable to China National Standard (CNS) A4 specification (210X297 mm) -25-539721 A7 __B7_ V. Description of the invention (23) ( Please read the precautions on the back before filling in this page) The molds need to be cleaned after casting, and the cleaning is generally performed with strong alkali or strong acid. Because glass is different from metal, it is not easy to deteriorate and easy to grind after washing. The surface roughness is very small and it is better. The composition for plastic lenses of the present invention (III) or (IV) is widely used in plastic lenses having a cyclohexane ring structure. (Allyl carbonate)] is the raw material, so the refractive index of plastic lenses is easy to approach 1 · 498. Therefore, it has the advantage of directly using the current one without changing the mold for molding. The curing temperature during molding is about 30 t: To 120 ° C, and preferably 40 ° C to 100 ° C. In addition, considering the shrinkage or strain during hardening, the method of hardening the temperature is to increase the temperature and slowly harden, It is generally from 0.5 to 100 hours, and preferably from 3 to 50 hours, more preferably from 10 to 30 hours. The dyeing method of the plastic lens of the present invention is not particularly limited, and may be a known plastic lens Staining method. Among them, a general dip dyeing method is preferred. The "immersion dyeing method" refers to a method of 'dispersing a disperse dye and a surfactant in water at the same time to prepare a dyeing solution, and immersing a plastic lens in the dyeing solution under heating to dye. The method of dyeing plastic lenses printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is not limited to the dip dyeing method, and other known methods can also be used, such as the method of sublimating organic pigments to dye plastic lenses (Special Publication 3 5 — 1 3 No. 8 4), a method of sublimating a sublimable dye to stain plastic lenses (Japanese Patent Publication No. 56-1 59376, Japanese Patent Publication No. 1 2 7 7 8 14). However, for ease of operation, a dip dyeing method is preferred. This paper size applies the Chinese national standard CNS) A4 specification (210X297 public director) — 539721 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (24) Examples The invention will be described in detail in the following examples. But not limited to this example. The measurement methods of various physical properties are as follows. 1 · Refractive index (n D) and Abbe number A test piece of 9 mm X 1 6 mm X 4 mm was made, and the refractive index (n D ) And Abbe number. The contact liquid used was α-bromonaphthalene. 2 · Viscosity Measured at 25 ° C using a Type B viscometer (B U 8 type) manufactured by Tokyo Keiki Co., Ltd. 3 · Barcol hardness Measured in accordance with J I s K — 6 9 1 1 using 9 3 4 — 1 type. 4 · Evaluate the staining method and stains. 0 · 8g of Smica basket—E—FBL (made by Sumitomo Chemical Industry Co., Ltd.) and 0 · 5 < water are added to a 1 < beaker and dissolved by stirring. . After heating in a water bath to 80 ° C, hold the hardened plastic lens samples in the disperse dye solution in a non-overlapping manner, immerse them at 80 ° C for 10 minutes, take them out, wash them thoroughly, and place them in 30 Dry in a hot air oven at ° C. Chang's scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) -27------- (Please read the precautions on the back before filling this page)

1T 539721 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (25) Observe the obtained dyed plastic lens samples visually, and take the appearance of uneven dyeing and stained spots as defective products. The number of defects among 30 hardened samples was calculated. 5. Method for determining the cis / trans ratio of an allyl ester resin Judging by the integral ratio of the peak derived from the cis-structure and the peak derived from the trans-structure in the 4 〇 Μ Η z 1 Η — N M R spectrum. J 1,4 Preparation of diallyl monocyclohexanedicarboxylate Example 1) 1 '4 monocyclohexanedicarboxylic acid (cis / trans di 6 · 5 / 3.5) (Eastman (Made by the company) 1000 g, allyl alcohol 1012 g, benzene 800 g, and P-toluenesulfonic acid 20 g were placed in a 3 < three-port circle with a reflux cooler with a Dean Stark device In the bottom flask, the temperature of the oil bath was adjusted to 100 ° C, and the reaction was started. During the reaction, purified water was removed from a .3 < three-neck round bottom flask using a Dean Stark device. After the completion of the reaction for 15 hours, the solution in the three-necked round bottom flask was transferred to a 5 < separation funnel, and the funnel was shaken until the liquid became two-phase separated and left to stand. The aqueous phase was removed thereafter. 50,000 g of a 1 wt% aqueous sodium hydroxide solution was added to a 5 < separation funnel, and the same operation was performed. Next, the step of adding 500 g of a 1 wt% sodium chloride aqueous solution into 5 < separation funnel 2 times was performed twice, and then benzene and excess allyl alcohol were distilled off from the organic phase by an evaporator, and then carried out by a distillation device. Vacuum distillation. After distillation at 147 ° C to 150 ° C / 0 · 4kPa, 1300 g of a colorless transparent liquid (hereinafter referred to as "sample a") was obtained. The liquid was analyzed by gas chromatography. As a result, 1,4-dicyclohexanedicarboxylic acid diallyl was used in accordance with the Chinese national standard (~ CNS) A4 specification (1T〇 ^ 297 ^ Fj-Γ28 ^-:-) ---- Fei Yi_ 丨 (Please read the precautions on the back before filling this page), 1Τ

539721 A7 V. Explanation of the invention (26) The analysis conditions for the cis-structure and trans-structure ratio of 6 · 5 / spectral method are as follows. Equipment: GC-1 4 B (manufactured by Shimadzu Corporation). Tester ·· Hydrogen flame ionization tester. Column: G-column. Temperature conditions: The starting temperature was raised to 7 ° C at 2 ° C / min. 2 0 ° C 'and hold at 220 ° C for 10 minutes. . Also 'gas phase color --------- (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in addition to the 1,4-cyclohexanedicarboxylic acid (anti- Formula (100%) (manufactured by Arugi) i OOg instead of i, 4 monocyclohexanedicarboxylic acid (cis / trans = 7/3) (manufactured by Eastman) 1000 Except for 0 g, the other steps are the same as those in Production Example 1 of 1,4-dicyclohexanedicarboxylate. ° to 15 °. After steaming in a 0.4 kPa manner, 1 300 g of a colorless transparent liquid (hereinafter referred to as "sample B") was obtained. The liquid was analyzed by thermal phase chromatography, and as a result, the trans structure of 4-dicyclohexyldicarboxylate was 100%. In addition, the mixed sample A and sample B were prepared so that the ratio of the cis-structure to the trans-structure was 1,2,4-dicyclocyclodicarboxylic acid diallyl ester (hereinafter referred to as ". 口 p C") and cis The ratio of the formula structure to the trans structure is 4/5 of a diallyl dicyclohexanedicarboxylate (hereinafter referred to as "Sample D") and the ratio of the cis structure to the trans structure is 3/7, 4 Cyclohexanedicarboxylic acid (hereinafter referred to as "Sample E").

1T

539721 Μ B7 V. Description of the invention (27) (Production of allyl ester compounds-1) Add sample A500 · 0g, propylene glycol 100 · 5g, dibutyltin oxide 0 · 50 g to 1 with a distillation device < three ports The flask was heated to 180 ° C under a stream of nitrogen, and the allyl alcohol formed was distilled off. After distilling 11.5 g of allyl alcohol, the pressure in the reaction system was reduced to 1.3 kPa to accelerate the distillation speed of allyl alcohol. The theoretical amount of allyl alcohol was distilled off, and then heated for 1 hour, and then maintained at 180 ° C-0 · 13 k P a for 1 hour. After the reactor was cooled, the allyl ester compound (hereinafter referred to as ^ sample F ") Gas chromatograph ('GC-1 4 B' manufactured by Shimadzu Scientific Corporation) Hydrogen flame ionization tester, using column 0V — 1 70 0 · 5 m temperature conditions fixed at 160 ° C) As a result of the analysis, the sample contained 1 ′ 4 mono-hexanedicarboxylic acid diallyl alcohol at 13% by weight. The ratio of cis-structure to trans-structure in the 1,4-monocyclohexanedicarboxylate structural unit of sample F obtained from 4 0 MHz iH — NMR (diluted solvent: CDC13) was 6 · 5/3 · 5. Figure 1 is a 400MHz iH-NMR spectrum of sample F. The assignment and integration of the chart are shown in Table 1. (Production of allyl ester compounds-_2__) Except replacing sample A 50 g with sample C 5 0 0 · 0 g, the production of other allyl ester compounds-1, obtained allyl ester compounds (hereinafter referred to as "Sample G" 4 4 8 g. Gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-1 4 B 'am n ^ i ϋϋ nm · min am In (Please read the precautions on the back before filling in this page)

1T The printed standards for employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs apply the Chinese National Standard (CNS) A4 specifications (2i0X 297 mm) -30-~ ^ 539721 A7 B7 Explanation (28) A hydrogen flame ionization tester using a column 0V-170 0 · 5 m temperature conditions fixed at 16 0 t :) analysis, the result sample G contains 1, 4 dicyclohexane dicarboxylic acid diallyl Ester 1 3% by weight. 4 0 0 MHz 1 Η — N M R (diluted solvent: C D C 1 3) In the 1,4-cyclohexanedicarboxylate structural unit of the sample G, the ratio of the cis-structure to the trans-structure is 2/8. Fig. 2 is a 400 MHz iH-NMR spectrum of sample G. The assignment and integration of the graph are shown in Table 1. 1 Preparation of Allyl Ester Compounds-3) Except replacing Sample A 50 0. 0 g with Sample D 5 0 0. 0 g, the production of other allyl ester compounds-1, allyl ester compounds (below It is called "sample Η" 4 4 8 g. Using a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC — 1 4 B, hydrogen flame ionization tester, column 0V-17 0 · 5 m) (Fixed at 160 ° C). As a result, the sample Η contained 1.4% by weight of diallyl 1,4-cyclohexanedicarboxylate. 40 MHz iH — NMR (diluted solvent: CDC 13) In the 1,4-cyclohexanedicarboxylate structural unit of rhenium, the ratio of the cis structure to the trans structure is 5/5. Figure 3 is a 400MHz iH-NMR spectrum of the sample rhenium. Shown in 2. (Production of Allyl Ester Compounds 4) _ ---------- Pack-(Please read the precautions on the back before filling this page) Order

This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -31-539721 A7 B7 V. Description of invention (29)

Except replacing sample A 50000g with sample E 50000g, the production of other allyl ester compounds-1, allyl ester compound C was hereinafter referred to as "sample I" 4 48 g. A gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-1 4 B, hydrogen flame ionization tester, using column 0V-1 70 · 5 m temperature conditions fixed at 160 ° C) analysis results Sample I contained 1.4% by weight of diallyl monocyclohexanedicarboxylate. The ratio of cis-structure to trans-structure in the 1,4-cyclohexanedicarboxylic acid ester structural unit of Sample I of Sample I obtained at 4 0 MHz iH — NMR (diluted solvent: CDC 13) was 3/7. Figure 4 is a 400 MHz iH-NMR spectrum of Sample I. The assignment and integration of the figure are shown in Table 2. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297 mm) · 32-539721 A7 B7

V. Description of the invention (3Q gJ3 = / ^ w > — \ 一 Γ 丨 丨 I5,., 5 e Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Consumer Electronics Co., Ltd.

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Description of the invention (31) Credit ratio printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs inch cn inch cn 6 8.4 3.6 8.4 3.6 4.2 1.8 4 4 2 4 2 _ ^ Jii ii ^ a _ ii Country ίϋ ίϋ SS iliiiSS SS sweep < ιηΆ ^^ ΙίΚέΚ @ S SSKi'til · NWN ^ ^ Delete surface delete IM turn φπ γ ^ γτγ > r ^ rm r ^ rm igpxr 5pH Delete surface delete delete turn ^ 3Π φπ ^ ΧΠ φπ Sp22 Eglin \ ^ mm \ ^ \ ^ m 'w ^ JZ: CDCDCD (DT3O ^ 〇C > i) cdX) Β D. pi oo oo oo ° oo oo ^ OO OO OO ° oo oo inch 1Ό O u〇 »〇X l inch ... O un i〇ll cn uo co 〇wn CN inch ΌΟ, Ocouno CNOO ——One inch inch ΚΓ) iT) cn O csi ^^ DCTNOcnuno cooo rH rH rH 1 ~~ ICNJCS1CN1 inch inch unwnun EK— < ng ng ng 1 Please Read the 5% on the back first, and then the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 34-539721 A7 B7 V. Description of the invention (32) Example 1 Add diethylene glycol as shown in Table 3. Alkyl allylic carbonate (manufactured by pp G, trade name CR ~ 3 9) 9 5 · 0 weight unit, sample F 5 0 and a basis weight of diisopropyl peroxy dicarbonate pp) a completely homogeneous solution of the composition by weight of the unit 3 'kneading, the viscosity was measured at this time. Next, the container containing the solution was placed in a desiccator capable of decompression, and decompressed in a vacuum drum for about 15 minutes to degas the solution. The solution composition was poured into a mold made of a combination of a glass mold for plastic lenses and a resin gasket in a cautious manner without using a gas by using a syringe, and was placed in an oven at 40 t for 7 hours, 40 to 6 〇t for 10 hours, 60 to 80 ° C for 3 hours, 80 ° C for 1 hour, and 8 5 t for 2 hours to heat and harden. Table 3 shows the measurement results of the refractive index, Abbe number, and Barcol hardness of the obtained lenses, and the evaluation results of the staining spots. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210X 297 mm) -35-539721 A7 B7 V. Invention Explanation u Today) Comparative Example 2 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇 Transparent liquid transparent liquid 1 Comparative example 1 95.0 5.0 Transparent liquid white turbid liquid Example 5 95.0 5.0 Transparent liquid Transparent liquid Example 4 95.0 5.0 Transparent liquid Transparent liquid mmmm 〇 • 〇un · 〇 \ ΓΟ 鳏 鳏 m ΐ $ ΣΣZ SS 嫠 嫠 集 〇U < 6 〇. 〇 \ 〇〇 鳏 | g 嫠 嫠 嫠 嫠 集 〇K * 〇m. 〇 \ IT) 05 ^ Liu cxi dr; Η- 壏 〇0 Jun 吒 Sao LO Liu ^ S ^ i 〇K This is like C < l 襞 $$ 忒 忒 CD ^ tL, Ο K ^ 鹚 S5 鹚 feed g 5 ng ng ng ng _ Μ _ r chain ^ UIAi 'UJAi ^ Teng Lu _ _ 酹 Zhao Teng (Please read the precautions on the back before filling this page) Clothing. Order f This paper size applies Chinese national standards ( CNS) A4 specification (210X 297 mm) 539721 A7 _ B7 V. Description of the invention (34) Actual Ai columns 2 to 5 and comparative examples 1 to 2 (Please read the notes on the back before filling this page) According to Table 3 The results shown in Table 3 are shown in Table 3 after adding the "composition composition to measure the viscosity in the same manner as in Example 1, and then measuring the refractive index, Abbe number, Pap hardness, and evaluation of staining spots of the lens after curing." Appearance change I (Storage stability test) Sample F, Sample G, Sample Η, and Sample I were stored at 25 ° C for 2 weeks, and the appearance of the sample after production and after 2 weeks were compared visually. The results are shown in Table 4. . In addition, Sample F, Sample G, Sample Η, and Sample I 'after the manufacture and after 2 weeks were mixed to obtain a resin composition for a plastic lens, and the appearances were compared in the same manner. Table 5 shows the results. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 4] Sample F Sample G Sample Η Sample I Appearance after manufacture Transparent liquid Transparent liquid Transparent liquid Transparent liquid Appearance after storage at 15 ° C for 2 weeks Transparent liquid white Liquid-like liquid Transparent liquid White-like liquid-37- 夂 National Standard for Paper (0 Milk) 8 4 Specifications (210 mm 297 mm) 539721 A7 7 Β 5. Description of the invention Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 100 1.501 5 8 33 10 1- ί 1 Comparative Example 1 95.0 5.0 oo CN CO 1.503 55 3 1 1 un 〇 • 〇〇 OO m 1.503 55 3 1 1 Inch base 〇 • 〇in · CTn un CO rsj cn 1.503 55 31! 1 Example 3 ο • ο · ON m 1.502 56 32 2 CN 90.0 8.0 m cn cn 1.503 54 28 1 Example 1 〇 • 〇 On oo oo 1.503 55 3 1 j 1 Nouryset200 Sample F Sample G Sample H Sample I Viscosity (25 ° c) (mPa · s) Initiator IPP (weight unit) Refractive index (nD) Abbe number (^ D) Poor hardness of Pap hardness (number) Teng Yi _1 _ Sweep ( (Please read the notes on the back before filling out this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 539721 A7-V. Description of the invention (36) According to the above-mentioned Tables 3, 4 and 5, the invention can be manufactured with good security # Stained lenses. (Please read the precautions on the back before filling in this page.) Effect of the Invention From the above, it is known that the compounds for plastic lens materials of the present invention can solve the causes of diallyl ether oligomers that currently contain cyclohexanedicarboxylate structures It has relatively high crystallinity, and it has a problem of white turbidity during long-term storage at a temperature lower than normal temperature. It is a compound with excellent handleability. In addition to the compound for the plastic lens material, the plastic lens composition containing the compound also has good storage stability, so it can be directly used in the current plastic molding method without special treatment after long-term storage. In addition, the plastic lens obtained by curing the composition has fewer stain spots than the old product, so the plastic lens can be produced more efficiently. Brief description of the drawing The picture shows the compound used in the plastic lens material described in the example 400 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

For the other, the other is 1 \ 2 \ 3 \ 4 ZZ Schematic diagram Schematic diagram Η 顺 M / (V 'w · \ / (V spectrum light R Μ Ν I Η 品 6 sample Η Η ζ Η Μ ο ο 4 of Η spectrum light R Μ Ν / 5 4) 8 G \ 口 ρρ2-like-I 'formula ζ Η Μ Η spectrum light R Μ Ν ζ Η Μ ο ο 4 of Η 品 品 Μ Μ ο 〇ο) 4 5 / I 5 style, Η Η Spectral light R Μ Ν Spectral light R Μ Ν -39- This paper size applies to China National Standard (CNS) A4 specifications (210x297 mm) 539721 A7 B7 5 、 Explanation of invention (37) (cis / trans = 3/7 (Please read the notes on the back before filling out this page) Printed on the paper standard of the China National Standards (CNS) A4 size (210X297mm) _ 40-

Claims (1)

539721 Amendment 91 Zheng P2 and T ~? Ij Modular Formula No. 90107535 Chinese patent application scope of the Republic of China1. A plastic lens material characterized by 1) The base shown is a terminal group and the following general formula (2) Among the compounds in which the unit is repeated, a part or all of the 1,4-cyclohexanedicarboxylate structural unit is formed by a compound having a cis structure. (1) —, -------— (Please (Read the notes on the back before filling out this page) Order · General formula (2 X, ο one \ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, CNO ο (where R 1 is independently allyl or methallyl, and X is independently 2 to 6 Organic residues derived from polyhydric alcohols having 2 to 20 carbons of each hydroxyl group, and X may have an end group with general formula (1) as the terminal group and repeated units with general formula (2) by using an ester bond. The structure of the branch chain.) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 539721 A8 B8 C8 ------- D8___ VI. Scope of patent application 2 Plastic lens material, in which the cis-structure ratio to all 1,4-cyclohexanedicarboxylic acid ester structural units is more than 30%. 3 · If the plastic lens material of the scope of patent application item 1 or 2 is multivalent The alcohol is propylene glycol. 4 · A method for manufacturing a plastic lens material such as the scope of claims 1 or 2 of the patent application, which comprises the following first step and second step; The first step: in the presence of a catalyst, Structure of 1,4-cyclohexanedicarboxylic acid and allyl alcohol and / Step of reacting methallyl alcohol to obtain 1,4-cyclohexanedicarboxylic acid ester. Second step: In the presence of a catalyst, the 1,4-cyclohexanedicarboxylic acid ester obtained in the first step and A step of transesterifying a polyvalent alcohol to obtain a compound for a plastic lens material. 5 · The manufacturing method of item 4 in the scope of the patent application, wherein the catalyst used in the first step is P-toluenesulfonic acid, methanesulfonic acid At least one selected from the group of acid, sulfuric acid, and hydrochloric acid. 6 · The manufacturing method according to item 4 of the scope of patent application, wherein the catalyst used in the second step is titanium tetraisopropoxide, titanium tetrabutoxide, At least one selected from the group consisting of butyltin oxide, dioctyltin oxide, acetoacetone, and acetoacetone. 7. A composition for plastic lenses, characterized by containing 0.05% to 30% by mass. As for the plastic lens material in the scope of patent application No. 1 or 2, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-2-(Please read the precautions on the back before filling this page), install · Order the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs Company printed 539721 Α8 B8 C8 D8 6. At least one or more kinds of patent applications and 50% to 99.95% by mass of the compound represented by the following general formula (3): At least one general formula (3) Γηο: 1 1 · s 11 -〇 ″ (where Y is one or more organic residues derived from a polyvalent saturated alcohol having 2 to 20 carbon atoms having 2 to 6 hydroxyl groups, and R 2 is allyl or methyl Benzopropyl, however, each R2 may be independent, and when the number of hydroxyl groups of Y is η, s is an integer from 0 to η-1, t is an integer from 1 to η, and s + t = n). 8. The composition for a plastic lens according to item 7 of the patent application scope, which contains at least one or more of the plastic lens materials according to item 1 or 2 of the patent application scope: 0.05 to 30% by mass and, general formula (3) At least one or more of the compounds shown: 50 to 99.5% by mass, and monomers that can be copolymerized with the plastic lens material or the compound represented by the general formula (3) as in the patent application scope item 1 or 2 At least one of these: 0 to 2 ◦ Mass%. 9. The composition for a plastic lens according to item 7 of the patent application scope, wherein the compound represented by the general formula (3) is diethylene glycol diallyl carbonate. 10. The composition for a plastic lens according to item 8 of the scope of patent application, wherein the compound represented by the general formula (3) is diethylene glycol diallyl carbonate. 1 1. If you apply for the plastic lens composition in item 7 of the β patent scope, (please read the precautions on the back before filling this page), ^ 1 printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) Α4 Specification (210X297 mm) _ 3-539721 A8 B8 C8 D8 々, in the scope of patent application for plastic lens composition 1 0 〇 mass unit contains at least one or more free radical polymerization initiators 0 · 1 to 10 mass units. (Please read the precautions on the back before filling in this page) 1 2 · If the composition for plastic lens for item 8 of the patent application scope, the plastic lens composition contains at least one kind of free radical polymerization Agent 0.1 to 10 mass units. 1 3. The plastic lens composition according to item 11 of the scope of patent application, wherein at least one or more radical polymerization initiators contain diisopropyl peroxide dicarbonate. 1 4. The plastic lens assembly and product according to item 12 of the patent application scope, wherein at least one or more of the radical polymerization initiators contain diisopropyl peroxide dicarbonate. 1 5 · —A plastic lens obtained by hardening a composition for a plastic lens as described in item 7 of the patent application. 1 6 · —A plastic lens obtained by hardening a composition for a plastic lens as described in item 8 of the patent application. 1 7 · —A plastic lens obtained by hardening a composition for a plastic lens as described in item 9 of the patent application scope. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 18 · — a kind of plastic lens, which is obtained by hardening the composition for plastic lens such as the scope of patent application No. 10. 19 · The plastic lens of item 15 in the scope of patent application, characterized in that the refractive index at 25 ° C is 1.497 to 1.550. 2 0. The plastic lens according to item 16 of the patent application scope is characterized in that the refractive index at 25 ° C is 1.497 to 1.55. 2 1 · If the plastic lens of item 17 in the scope of patent application is characterized by the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 4-539721 A8 B8 C8 D8 6. The scope of patent application is 25 ° The refractive index of C is 1.497 to 1.505. (Please read the precautions on the back before filling out this page) 2 2. If the plastic lens of item 18 of the patent application scope is characterized by a refractive index at 25 ° C of 1.497 to 1.505. 2 3 · — A method for manufacturing a plastic lens, characterized in that the method for manufacturing a plastic lens according to item 15 of the patent application scope is that the polymerization temperature is 30 to 120 ° C, and the polymerization time is 0.5 to 1 〇 〇Hours of casting polymerization 〇 2 4-A method for manufacturing plastic lenses, characterized in that the method for manufacturing plastic lenses as described in item 16 of the patent application scope is: polymerization temperature: V0 to 120 ° C, polymerization time 0 5 to 100 hours of casting polymerization. 2 5 · A method for manufacturing a plastic lens, which is characterized in that the method for manufacturing a plastic lens according to item 17 of the scope of patent application is that the polymerization temperature is 30 to 120 ° C, and the polymerization time is 0.5 to 100. Hours of casting polymerization 0- 2 6 · —A method for manufacturing plastic lenses, characterized in that the method for manufacturing plastic lenses as described in item 18 of the patent application scope is that the polymerization temperature is 30 to 1 2 0 C 'polymerization time 0 · 5 to 1000 hours of prayer and congregation Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- This paper size applies to China National Standard (CNS) A4 (210X297 mm)