WO1984000370A1 - Resin for lens with high refractive index and lens composed of it - Google Patents

Resin for lens with high refractive index and lens composed of it Download PDF

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Publication number
WO1984000370A1
WO1984000370A1 PCT/JP1983/000217 JP8300217W WO8400370A1 WO 1984000370 A1 WO1984000370 A1 WO 1984000370A1 JP 8300217 W JP8300217 W JP 8300217W WO 8400370 A1 WO8400370 A1 WO 8400370A1
Authority
WO
WIPO (PCT)
Prior art keywords
refractive index
lens
resin
acid
parts
Prior art date
Application number
PCT/JP1983/000217
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Katsuyoshi Sasagawa
Teruo Hyugaji
Masao Imai
Kimio Kanno
Original Assignee
Mitsui Toatsu Chemicals
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
Priority claimed from JP57117821A external-priority patent/JPS598709A/ja
Priority claimed from JP57205451A external-priority patent/JPS5996113A/ja
Application filed by Mitsui Toatsu Chemicals filed Critical Mitsui Toatsu Chemicals
Priority to GB08404583A priority Critical patent/GB2133023B/en
Priority to NLAANVRAGE8320201,A priority patent/NL185215C/xx
Priority to DE19833390081 priority patent/DE3390081T1/de
Publication of WO1984000370A1 publication Critical patent/WO1984000370A1/ja

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/20—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/22—Esters containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/14—Esters of polycarboxylic acids
    • C08F218/16—Esters of polycarboxylic acids with alcohols containing three or more carbon atoms

Definitions

  • the present invention relates to a lens resin having a high refractive index and a lens made of the resin.
  • plastic lenses are lighter, less fragile, and can be dyed, so in recent years, eyeglass lenses, camera lenses, and other lenses have been developed. It has begun to spread in Japan.
  • C-39 As a resin widely used for this purpose, the following is called “C-39” (hereinafter referred to as “CR-39”).
  • CR-39 There is a polymerized resin.
  • the refractive index [nd] of this resin is 1.50, which is smaller than that of an inorganic glass lens (: nd about 1.52).
  • nd In order to obtain the same optical characteristics as the lens, it is necessary to increase the center thickness, the edge thickness, and the curvature of the lens, and it is inevitable that the overall thickness becomes large. For this reason, a lens resin having a higher refractive index is desired.
  • Polycarbonate bottles (nd 1.58 to 1.59) and polystyrene (nd 1.58-1.60) are already known as high refractive index resins.
  • these resins are all two-dimensional polymers in structure and are thermoplastic, so that they are very similar to eyeglass lenses.
  • the present inventors have intensively studied to improve the above-mentioned drawbacks, and as a result, the refractive index as a specific bifunctional monomer and a homopolymer was 1.
  • a monofunctional monomer having an aromatic ring that is capable of undergoing radical polymerization and having a refractive index of 55 or more it has a high refractive index, and has excellent workability such as balling and impact resistance.
  • a resin for a high-refractive index lens having excellent compatibility between a monofunctional monomer and a bifunctional monomer during copolymerization and hardly causing polymerization distortion can be obtained.
  • the present invention has been achieved.
  • the present invention has the general formula (1)
  • X represents a chlorine or bromine atom
  • 11 represents 2 or 4
  • m represents 0 or 1
  • R represents a hydrogen atom or a methyl group.
  • Esters of the novel nucleated ⁇ -gen-substituted benzene dicarboxylic acids represented by the general formula U) as the first monomer according to the present invention are nuclei.
  • Nuclear halogen-substituted benzene dicanolevonic acid and trioctyl acetic acid methyl ester can be used as a triethylamine. It can be obtained by performing an esterification reaction using an enzyme.
  • 2,4-dichloroterephthalanolic acid bisester 2,2,4-dichloroterephthalanolic acid bis (: ⁇ -meth (Chiral) ester, 2,4 dichloroterephthalic acid bis (polycarbonate poryl methyl ethyl) ester, 2,4 dik Loterephthalanic acid bis (jS-methyl aryloxycanoleboninolemethyl) ester, .2, 4 -jib mouth moterephthalic acid bis ⁇ ⁇ ⁇ ⁇ ⁇ 2 2 2 2?????
  • x represents a chlorine or bromine atom
  • a represents a hydrogen atom or a methyl group
  • the resulting resin has a refractive index and a monofunctional monomer for copolymerization.
  • the preferred esters include tetrachlorophthalic acid bisester, tetrachlorophthalic acid bis ( ⁇ -methacrylate). (T-phenylene) estenolate tetrabromomophthalate bis-aryl ester and tetrabromophthalate bis- [ ⁇ -methylary Le) Estel power ⁇
  • the second monomer a radical having a refractive index of 1.55 or more as a homopolymer is used. Both are copolymerized using a polymerizable monofunctional monomer having an aromatic ring.
  • the second monomer may be any as long as it satisfies the above requirements. However, the second monomer has good compatibility with the bifunctional monomer represented by the general formula (I), and is suitable for injection in casting polymerization. Those that maintain uniform liquid properties at this time are preferred.
  • Preferred as such a monofunctional monomer are those represented by the general formula (110)
  • R represents a hydrogen atom or a methyl group
  • ⁇ represents
  • X I a chlorine or bromine atom
  • z is an oxygen or sulfur atom
  • q is an integer from 0 to 5
  • r is 0 or 1.
  • Typical examples include the aryl ester of a nuclear chalcogen-substituted benzoic acid.
  • ⁇ -methylaryl ester such as 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, Peric acid, 25-Dichlorobenzoic acid, 26-Dichlorobenzoic acid, 34-Dichloroorthobenzoic acid, 35-Dichlorobenzoic acid, 23,6-Tri Black mouth benzoic acid, pentachlorobenzoic acid 2 -Bromobenzoic acid, 3-'Bumobenzoic acid aryl ester or / 9-methyl alcohol ester You.
  • a nuclear halogen-substituted aryl carbonate or an iS-methyl aryl carbonate for example, 2-cyclohexyl phenol, 3 -Chloro phenol, 41, Chloro phenol, 2, 3-Dichloro phenol, 2, 4-Dichloro phenol, 2 , 5-Cyclo mouth, 2,6-Cyclo nose, 3,4-Cyclo nose, 3,5-Cyclo nose Enol, 24,5-Tri-mouthed mouth, 2,4,6-Tri- ⁇ alpha mouth, 2, 3, 4, 6, 6, Tetra Chromophenol, Pentacrophenol, 2-Bromophenol ⁇
  • a acrylate or a methacrylate having an aromatic ring for example, phenyl acrylate, phenyl methacrylate, chlorinated phthalate Enrichment, Nuclear chlorine-substituted phenylmethacrylate, Nuclear bromine-substituted phenylmethacrylate, Nuclear bromine-substituted phenolic metal RELEASE, PENGANO REACTOR RELEASE, BENZEL META RELEASE, Nucleus Chlorine Replacement Benzilla Clearate, Nucleus Chlorine Replacement Benzilla There are tactrate, nuclear bromine-substituted benzyl acrylate, and nuclear bromine-substituted benzyl metal acrylate.
  • Still other specific kilns include styrene or a nuclear halogen-substituted styrene, for example, a nucleus salt, isan styrene, or a nuclear bromine-substituted styrene. is there .
  • R is a hydrogen atom or a methyl group
  • X is a chlorine or bromine atom
  • Z is an oxygen or sulfur atom
  • r is 0 or 1
  • s is 1 to Represented by an integer of 5), i.e., an aryl ester of a nuclear halogen-substituted benzoic acid or a / 3-methylaryl ester, a nuclear halogen atom
  • a substituted phenolic or thiophenolic aryl carbonate or a ⁇ -methyl aryl carbonate is particularly preferred to use a substituted phenolic or thiophenolic aryl carbonate or a ⁇ -methyl aryl carbonate.
  • the resin of the present invention obtained by copolymerizing with a monofunctional monomer represented by CD has structural units represented by the following general formulas (V) and [ ⁇ ].
  • X represents a chlorine or bromine atom
  • II represents 2 or 4
  • m represents 0 or 1
  • R represents a hydrogen atom or a methyl group.
  • R is a hydrogen atom or a methyl group
  • Y is
  • X represents a chlorine or -bromine atom
  • z represents an oxygen or sulfur atom
  • q represents an integer from 0 to 5
  • r represents 0 or 1.
  • the ester represented by the above-mentioned one-branch type (I) cannot be unequivocally limited because its preferred use ratio is different depending on its type.
  • the amount is less than 10% by weight, the surface hardness of the resin obtained by copolymerization is remarkably reduced. If it exceeds 80% by weight, the impact resistance is lowered, so that it is not preferable.
  • the total ratio of one or more of the above-mentioned second monomers copolymerized with the ester represented by the general formula (I) is 290 times
  • the radical initiator used in the copolymerization to obtain the lens resin of the present invention is not particularly limited, and may be any of known peroxides, P-cloths, and the like.
  • Benzo Reno. Oxyside, Jissopropirha 0 Oxikabonet, Ji-2-ech
  • Peroxides such as peroxide and azo compounds such as azobisisobutyronitrile are used at a ratio of 0.01 to 5% by weight.
  • the lens resin of the present invention is prepared by a mixture of at least one of the esters represented by the general formula U), at least one of the second monomers described above, and a radical initiator.
  • a well-known casting polymerization method that is, a mold mold combining a gasket or spacer with a glass or metallic mold.
  • additives such as an ultraviolet absorber, an antioxidant, a coloring inhibitor, and a gay dye may be appropriately added to the mixture before polymerization as needed.
  • a small amount of a bifunctional monomer other than the ester represented by a single-sided U) such as CR-39 may be added.
  • the lens resin of the present invention thus obtained is a resin having a high refractive index, excellent workability such as balling, and excellent impact properties.
  • OMPI And can be used for spectacle lenses, camera lenses and other lenses o
  • test kiyoshi are parts by weight, and the percentages are percentages by weight.
  • test methods were used for the lens resin obtained in the examples for the refractive index, lapping workability, impact resistance, and yellowing test by exposure to ultraviolet light.
  • Refractive index Measured at 20'C with an Abbe refractometer.
  • Tetrab mouth Motereftanoleic acid 1 Stirring force to a mixture of 9.3 parts and 40 parts of isopropropyl alcohol S 50 parts of 50% aqueous solution 13 parts In addition, stirring was continued for 30 minutes, and then 12.6 parts of arylbromide and 1.0 part of triethylamine were added, and the mixture was heated until isopropanol was refluxed and maintained for 8 hours. After allowing to cool, the reaction mixture was reduced and concentrated, and then 50 parts of black mouth solution was added and the solution dissolved was poured into the separation port, washed with heavy water and water, and then washed with organic solution. The white solid obtained by concentrating the layer is recrystallized from vinegar to give a colorless amorphous form.
  • compound C 26 parts were obtained. A portion of this liquid was recrystallized from ligroin to obtain columnar crystals.C melting point 71-72 ° C) o
  • reaction solution was poured into a liquid separating port, washed with dilute hydrochloric acid and then with water, and the pale yellow organic layer obtained was dried with calcium chloride and then activated charcoal. Processing and kuro ho
  • the copolymerization was carried out while keeping the temperature at 100 X: for 2 hours.
  • the resin was removed from the mold and subjected to measurement of refractive index, workability test, impact resistance test, and ultraviolet resistance test.
  • the resulting colorless and transparent lens has a refractive index of 1.597, and has good rubbing and impact resistance, as well as excellent UV resistance test results.
  • bifunctional monomer used in the present invention In order to compare the compatibility between the bifunctional monomer used in the present invention and various monofunctional monomers, tetrachloroterephthalic acid was used as the bifunctional monomer. Select the diester and mix it with various monofunctional monomers at a weight ratio of 2: 1 and heat to complete solution, then 60X It was kept for 2 hours in a thermostat kept at, and the presence or absence of crystal precipitation was observed.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/JP1983/000217 1982-07-08 1983-07-07 Resin for lens with high refractive index and lens composed of it WO1984000370A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB08404583A GB2133023B (en) 1982-07-08 1983-07-07 Resin for lens with high refractive index and lens composed of it
NLAANVRAGE8320201,A NL185215C (nl) 1982-07-08 1983-07-07 Hars voor lenzen met hoge brekingsindex en van deze hars vervaardigde lenzen.
DE19833390081 DE3390081T1 (de) 1982-07-08 1983-07-07 Harz für Linsen mit hohem Brechungsvermögen und aus derartigem Harz hergestellte Linsen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP57117821A JPS598709A (ja) 1982-07-08 1982-07-08 高屈折率レンズ用樹脂
JP57205451A JPS5996113A (ja) 1982-11-25 1982-11-25 高屈折率レンズ用樹脂

Publications (1)

Publication Number Publication Date
WO1984000370A1 true WO1984000370A1 (en) 1984-02-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1983/000217 WO1984000370A1 (en) 1982-07-08 1983-07-07 Resin for lens with high refractive index and lens composed of it

Country Status (7)

Country Link
EP (1) EP0112927B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU562310B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CH (1) CH660369A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE3390081T1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB2133023B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL185215C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1984000370A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3332872A1 (de) 1983-09-12 1985-04-04 Optische Werke G. Rodenstock, 8000 München Reflexionsvermindernder belag fuer ein optisches element aus organischem material
JPS60104041A (ja) * 1983-11-11 1985-06-08 Tokuyama Soda Co Ltd アリルカ−ボネ−トの製造方法
AU578446B2 (en) * 1984-01-27 1988-10-27 Mitsubishi Rayon Company Limited Dimethallyl phtholate plastic lens
JPS617314A (ja) * 1984-06-20 1986-01-14 Kureha Chem Ind Co Ltd 高屈折率レンズ
EP0176874A3 (en) * 1984-09-19 1988-02-10 Toray Industries, Inc. A highly-refractive plastic lens
US4622376A (en) * 1985-06-27 1986-11-11 Ppg Industries, Inc. Composition of aromatic poly(allylcarbonate), styrene materials, and crosslinker containing three or more ethylenically unsaturated groups for producing polymer of high refractive index and low yellowness
US4959429A (en) * 1985-11-22 1990-09-25 Ppg Industries, Inc. Cyclohexenic additives for producing polycarbonate polymers of high refractive index and low yellowness
US7520735B2 (en) 2003-01-23 2009-04-21 Baker Hughes Incorporated Nested bellows expansion member for a submersible pump

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56145910A (en) * 1980-04-14 1981-11-13 Seiko Epson Corp Resin for high-refractive index plastic lens
JPS5799601A (en) * 1980-12-15 1982-06-21 Hoya Corp Low dispersion lens with high refractive index

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56145910A (en) * 1980-04-14 1981-11-13 Seiko Epson Corp Resin for high-refractive index plastic lens
JPS5799601A (en) * 1980-12-15 1982-06-21 Hoya Corp Low dispersion lens with high refractive index

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0112927A4 *

Also Published As

Publication number Publication date
CH660369A5 (de) 1987-04-15
EP0112927A1 (en) 1984-07-11
DE3390081C2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1988-07-21
EP0112927B1 (en) 1987-02-11
GB2133023A (en) 1984-07-18
NL185215B (nl) 1989-09-18
NL8320201A (nl) 1984-06-01
EP0112927A4 (en) 1984-11-16
DE3390081T1 (de) 1984-07-12
GB8404583D0 (en) 1984-03-28
NL185215C (nl) 1990-02-16
AU562310B2 (en) 1987-06-04
GB2133023B (en) 1985-07-24
AU1709783A (en) 1984-02-08

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