WO2013073194A1 - Polymerizable composition, optical article obtained therefrom and method for the production of said optical article - Google Patents
Polymerizable composition, optical article obtained therefrom and method for the production of said optical article Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- 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
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- 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
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2125/00—Compositions for processes using internal mould release agents
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Abstract
Description
[PTL 2] Japanese Laid-Open Patent Publication No. 63-046213
[PTL 3] Japanese Laid-Open Patent Publication No. 07-324118
[PTL 4] Japanese Laid-Open Patent Publication No. 08-003267
[PTL 5] Japanese Laid-Open Patent Publication No. 09-110955
wherein the polyisocyanate(s) (A) is at least one bifunctional or higher functional alicyclic polyisocyanate compound,
the polythiol(s) (B) is at least one compound selected from polythiols represented by the following general formula (B1):
wherein l and m, the same or different from each other, represent an integer from 1 to 4; n represents an integer from 1 to 3; r represents an integer from 1 to 4; and R represents hydrogen or a methyl group and, when n is different from 1, the R groups are the same as or different from each other,
the thiol(s) (C) is at least one compound selected from thiols represented by the following general formula (3):
wherein R1, R2, R3, the same or different from each other, are selected from -(CH2)n-SH, -S-(CH2)n-SH and -R-S-(CH2)n-SH, wherein R is an alkylene group having from 1 to 10 carbon atoms, n is an integer ranging from 1 to 3, said compound represented by the general formula (3) containing at least two SH groups and at least a -S- bridge and
the catalyst(s) (D) is at least one polymerization catalyst selected from metal compounds, quaternary ammonium salts, organic sulfonic acids, tertiary amines and their inorganic or organic salts.
wherein R represents alkylene groups, the same or different from each other, having from 1 to 6 carbon atoms; R1 represents alkyl groups, the same or different from each other, having from 1 to 10 carbon atoms; n is an integer ranging from 1 to 6; m is an integer ranging from 1 to 6; p is an integer ranging from 1 to 4; q is equal to 0 or 1 and p+q is equal to 4.
wherein R1, R2, R3, the same or different, are selected from a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or an alicyclic group containing from 3 to 20 carbon atoms, said groups possibly containing heteroatoms such as N, O, P, S or halogen.
wherein R2 and R4, the same or different, represent a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or a cyclo-aliphatic group containing from 3 to 20 carbon atoms; R3 and R5, the same or different, represent an alkylene group containing from 1 to 3 carbon atoms and m and p, independently from each other, are 0, 1 or 2.
- injecting a polymerizable composition according to any of (1) to (11) into a mould and let it polymerize, forming an optical article;
- depositing sequentially a hard coating layer and an anti-reflection layer in sequence on said optical article.
The above optical material, in addition, is characterized in that it has a favourable compromise between a high refractive index and transparency.
The polyisocyanate(s) (A) is at least one bifunctional or higher functional alicyclic polyisocyanate compound.
The polythiol(s) (B) is at least one compound selected from polythiols represented by the following general formula (B1):
In the general formula (B1), l and m, the same or different from each other, represent an integer from 1 to 4; n represents an integer from 1 to 3; r represents an integer from 1 to 4; and R represents hydrogen or a methyl group and, when n is different from 1, the R groups are the same as or different from each other.
The thiol(s) (C) is at least one compound selected from thiols represented by the following general formula (3):
In the general formula (3), R1, R2, R3, the same or different from each other, are selected from -(CH2)n-SH, -S-(CH2)n-SH and -R-S-(CH2)n-SH, wherein R is an alkylene group having from 1 to 10 carbon atoms, n is an integer ranging from 1 to 3, said compound represented by the general formula (3) containing at least two SH groups and at least a -S- bridge.
The catalyst(s) (D) is at least one polymerization catalyst selected from metal compounds, quaternary ammonium salts, organic sulfonic acids, tertiary amines and their inorganic or organic salts.
The polyisocyanate(s) (A) is a compound with a cyclic skeleton, not containing any aromatic ring and with two or more isocyanate groups.
The polyisocyanate(s) (A) is preferably selected from 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl) cyclohexane, bis(4-isocyanatecyclohexyl)methane and bis (isocyanatemethyl)-bicyclo[2.2.1]heptane or mixtures thereof.
1,2-bis(isocyanatemethyl)cyclohexane, cyclohexane diiso-cyanate, methylcyclohexane diisocyanate, 2,2-bis(4-isocyanatecyclohexyl)propane, 3,8-bis(isocyanatemethyl) tricyclodecane, 3,9-bis(isocyanatemethyl)tricyclodecane, 4,8-bis(isocyanatemethyl)tricyclodecane and 4,9-bis (iso-cyanatemethyl)tricyclodecane, or mixtures thereof.
The weight percentage of free isocyanate groups in said polyisocyanate(s) (A) ranges from 20% to 50% by weight with respect to the total weight of polyisocyanate(s) (A) and, preferably, ranges from 25% to 45% by weight with respect to the total weight of polyisocyanate(s) (A).
The polyisocyanate (E) can be an aliphatic or aromatic compound, containing at least two isocyanate groups in the molecule. In addition the polyisocyanate (E) can also contain at least one sulfur atom and the like. The polyisocyanate (E) can be a dimer, trimer or a pre-polymer.
Examples of aliphatic polyisocyanates containing sulfur comprise: bis(isocyanatemethyl)sulfide, bis(iso-cyanethyl)sulfide, bis(isocyanaepropyl)sulfide, bis(iso-cyanatemethyl)sulfone, bis(isocyanatemethyl)disulfide, bis-(isocyanate propyl) disulfide, bis(isocyanatemethyl-thio)methane, bis (isocyanatemethylthio)ethane, bis(iso-cyanate-ethylthio) methane, bis(isocyanate-ethylthio)ethane, 1,5-diisocyanate-2-isocyanatomethyl-3-thiapentane,
bis(3-isocyanatemethylphenyl)sulfide,
bis(4-isocyanatemethylphenyl)sulfide,
bis(3-isocyanatemethylbenzyl)sulfide,
bis(4-isocyanatemethylbenzyl)sulfide,
bis(3-isocyanatemethylphenyl)disulfide and
bis(4-isocyanatemethylphenyl)disulfide.
The polymerizable composition according to the present invention also comprises polythiol(s) (B) which is at least one compound selected from polythiols represented by the following general formula (B1).
In the formula (B1), l represents an integer from 1 to 4, preferably 1 or 2; m represents an integer from 1 to 4, preferably 1 or 2; n represents an integer from 1 to 3, preferably 1 or 2, more preferably 1; r represents an integer from 1 to 4, preferably 1 or 2, more preferably 1; R represents hydrogen or a methyl group, and when n is different from 1, the R groups are the same or different from each other.
When the polymerizable composition of the present invention includes the compound represented by the general formula (B1), a resin or optical material having an excellent balance between impact strength and hardness, and an excellent tintability, can be obtained.
Specific examples of polythiols (B1) include:
ethylene glycol bis(mercaptoacetate), ethylene glycol bis(mercaptopropionate),
ethylene glycol bis(mercaptobutyrate),
diethylene glycol bis(mercaptoacetate),
diethylene glycol bis(mercaptopropionate),
diethylene glycol bis(mercaptobutyrate),
triethylene glycol bis(mercaptoacetate),
triethylene glycol bis(mercaptopropionate),
triethylene glycol bis(mercaptobutyrate). These compounds can be present in the polymerizable composition alone or in a combination of two or more thereof.
ethylene glycol bis(mercaptoacetate), ethylene glycol bis(mercaptopropionate), diethylene glycol bis (mercaptoacetate), or diethylene glycol bis (mercaptopropionate).
In the formula (B2), R represents alkylene groups, the same or different, having from 1 to 6 carbon atoms; R1 represents alkyl groups, the same or different, having from 1 to 10 carbon atoms; n is an integer ranging from 1 to 6; m is an integer ranging from 1 to 6; p is an integer ranging from 1 to 4; q is equal to 0 or 1 and p+q is equal to 4.
The thiols (B2) can be aliphatic or aromatic.
Examples of aliphatic thiols include:
methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2-cyclohexanedithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl ether, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane.
2,3-dimercapto-1-propanol(3-mercaptopropionate), 3-mercapto-1,2-propanediol bis(2-mercaptoacetate), 3-mercapto-1,2-propanediol di(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), glycerin tris(2-mercaptoacetate), glycerin tris(3-mercaptopropionate), 1,4-cyclohexanediol bis(2-mercaptoacetate), 1,4-cyclohexanediol bis(3-mercaptopropionate), hydroxymethylsulfide bis(2-mercaptoacetate), hydroxymethylsulfide bis(3-mercaptopropionate), hydroxyethylsulfide(2-mercaptoacetate), hydroxyethylsulfide(3-mercaptopropionate), hydroxymethyldisulfide(2-mercaptoacetate), hydroxymethyldisulfide(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl), thiodipropionic acid bis(2-mercaptoethyl).
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,
1,2,3-tris(mercaptomethyl)benzene,
1,2,4-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyl)benzene,
1,2,3-tris(mercaptoethyl)benzene,
1,3,5-tris(mercaptoethyl)benzene,
1,2,4-tris(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene,
1,2,3,5-tetrakis(mercaptomethyl)benzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene,
1,2,3,4-tetrakis(mercaptoethyl)benzene,
1,2,3,5-tetrakis(mercaptoethyl)benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene,
2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl,
Among the above compounds, preferred thiols (B2) are the following: pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane(3-mercaptopropionate).
The polymerizable composition according to the present invention also comprises thiol(s) (C) which is at least one selected from compounds represented by general formula (3)
In the formula (3), R1, R2, R3, the same or different, are selected from -(CH2)n-SH, -S-(CH2)n-SH and -R-S-(CH2)n-SH, wherein R is an alkylene group having from 1 to 10 carbon atoms, n is an integer ranging from 1 to 3, said compound represented by the general formula (3) containing at least two SH groups and at least one bridge -S-.
The molar ratio of the mercapto group belonging to the polythiols (B1), the thiol(s) (C) and possibly the thiols (B2) with respect to the isocyanate group in the polyisocyanate(s) (A) is preferably within the range of 0.8 to 1.2, preferably within the range of 0.85 to 1.15, and even more preferably within the range of 0.9 to 1.1. In these ranges, a thiourethane resin is obtained, which is suitable for use as optical material, in particular, a material for producing lenses for eye-glasses.
Furthermore, from the view of the effects of the present invention, the weight ratio of the polythiols (B1) to the thiol(s) (C) is preferably from 5:95 to 90:10.
- aliphatic compounds (a) having one or more sulfide bonds, and at least two SH groups, said aliphatic compounds at the same time having a total number of SH groups and OH groups equal to 2 or more;
- alicyclic compounds (b) having at least two sulfide bonds, and at least two SH groups, said compounds at the same time having a total number of SH groups and OH groups equal to 2 or more.
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri-thiaundecane, tetrakis(mercaptomethyl)methane, bis-(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis-mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis-(mercaptomethylthio)methane,
bis(2-mercaptoethylthio)methane,
1,2-bis(mercaptomethylthio)ethane,
1,2-bis(2-mercaptoethylthio)ethane,
1,3-bis(mercaptomethylthio)propane,
1,3-bis(2-mercaptoethylthio)propane,
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
1,1,3,3-tetrakis(mercaptomethylthio)propane, tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane and
bis(2,3-dimercaptopropyl)sulfide or mixtures thereof.
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane.
The polymerizable composition of the present invention preferably comprises thiol(s) (C) which is at least one compound selected from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 2,5-bis(mercaptomethyl)-1,4-dithiane.
The polymerizable composition of the present invention also comprises catalyst(s) (D) which is at least one polymerization catalyst selected from metal compounds, preferably organometallic, quaternary ammonium salts, organic sulfonic acids, tertiary amines and relative inorganic or organic salts.
In the general formula (4), R1, R2, R3, the same or different, are selected from a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or an alicyclic group containing from 3 to 20 carbon atoms. These groups can contain heteroatoms such as N, O, P, S or halogen.
In particular, examples of liquid tertiary amines are:
methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) sebacate.
In the above-mentioned embodiment, the compound (iii) above which is not used includes "triethylamine, tri-n-propylamine, triisopropylamine, methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate", or "triethylamine, methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate".
In the "embodiment in which a compound other than the compound (i) or (iii) above is used as a polymerization catalyst", a metal compound, a quaternary ammonium salt, or an organic sulfonic acid can be used as the polymerization catalyst.
Examples of organic acids to be combined with a tertiary amine to form a salt comprise formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid, p-toluenesulfonic acid, methanesulfonic acid, diacid monoester phosphates, diacid diester phosphates.
The above catalysts can be used in the polymerizable composition according to the present invention, either individually or combined with two or more compounds.
In the general formula (5), R2 and R4, the same or different, represent a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or a cyclo-aliphatic group containing from 3 to 20 carbon atoms; R3 and R5, the same or different, represent an alkylene group containing from 1 to 3 carbon atoms and m and p, independently, are 0, 1 or 2.
The release agents can be added to the polymerizable composition alone or in a combination of two or more.
The polymerizable compositions can also contain additives typically used in the field of the production of polymeric articles, such as, for example, photo-stabilizing compounds, UV-absorbers, antioxidants and bluing agents, dyes soluble in the polymerizable composition or adhesion promoting agents.
The mixing of the ingredients of the polymerizable composition is usually carried out at a temperature of 25 degrees C or lower, when, in addition to the monomer to be used, a catalyst, an internal detaching agent, and other additives, are present.
When the solubility of the catalyst, the internal release agent, and additives in the monomer is not sufficiently high, they can be heated before being dissolved in the monomer and in the resin modifier.
The polymerization is generally effected at a temperature ranging from -50 to 150 degrees C, for a time ranging from 1 hour to 50 hours. The curing of the resin is preferably effected at a temperature within the range of 10 to 150 degrees C for a time of 1 to 25 hours. The polymerization can be effected by maintaining the mould at the desired temperature or slowly bringing the mould to the desired temperature.
The optical article of the present invention can be obtained in various forms, by simply changing the type of mould.
The above-mentioned thiourethane resin can also be used for producing prisms, optical fibres, data-collecting substrates, filters and other manufactured products.
An object of the present invention also relates to a method for producing an optical article comprising the following phases:
- injecting a polymerizable composition according to the present invention into a mould and polymerizing it, forming an optical article;
- depositing in sequence on said optical article, at least one hard coating layer and an anti-reflection coating.
When coating layers are present on both sides of the resin body of the lens, there can be the same sequence of superimposed layers on each side, or different sequences.
When the optical lens comprises a primer layer, the surface of the body of the lens can be subjected to treatment, such as treatment with alkalis, plasma, or ultraviolet rays, in order to improve the adhesion of the primer layer.
The tinting process comprises a first preparation phase of a dyebath including an aqueous solution in which the dye is dispersed and to which the possible surfactant is added, if necessary. The bath can also be obtained by dispersing or dissolving the dye and possible surfactant in a mixture of water and an organic solvent.
EXAMPLES
- refractive index (ne) and Abbe number (Abbe value e line): measured at 20 degrees C using a Pulfrich refractometer.
- density measured according to Archimedes' principle.
- Rockwell hardness determined according to ASTM D-785.
50.8 g of 2,5(6)-bis(isocyanatemethyl)bicyclo-[2.2.1]heptane were poured into a 300 ml conical beaker; 0.035 g of dimethyl tin dichloride were then added as catalyst, 0.10 g of Zelec UN (ester of a phosphate acid, produced by Stepan Co., Ltd.,) as releasing agent, and 1.50 g of Viosorb 583 as UV-ray absorber were then added and subjected to mixing at room temperature for 10 minutes or slightly longer, obtaining a homogenous solution. 25.7 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.5 g of ethylene glycol bis(3-mercaptopropionate) were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-micrometer Teflon filter and then injected into a glass mould - consisting of two half-moulds kept closed by means of a washer - heated to a temperature ranging from 20 to 120 degrees C. The polymerization reaction was left to proceed for 20 hours. After cooling, a colourless, transparent resin platelet was obtained, which was easily released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5972, Abbe value e line=39.2, specific density = 1.30. The Izod impact strength was extremely high, equal to 112 KJ/m2, and the Rockwell hardness was sufficient, as it proved to be 105 M, i.e. a value equal to or higher than 100 M. As a result of the tinting test, the %T measurement at 452 nm showed a good tintability, as the %T was equal to 24.0%. The results are shown in Table 1.
46.2 g of 2,5(6)-bis(isocyanatemethyl)-bicyclo-2.2.1]heptane and 4.2 g of hexamethylene diisocyanate were poured into a 300 ml conical beaker; 0.035 g of dimethyl tin dichloride, 0.10 g of Zelec UN, and 1.50 g of Viosorb 583 were then added and subjected to mixing at room temperature for 10 minutes or slightly longer, obtaining a homogenous solution. 25.9 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.7 g of ethylene glycol bis(3-mercaptopropionate) were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-micrometer Teflon filter and then injected into a mould as in Example 1. The polymerization reaction was carried out under the same conditions as Example 1. After cooling, a colourless transparent resin platelet was obtained, which was easily released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5965, Abbe value e line = 39.6, specific density = 1.30. The Izod impact strength was equal to 112 KJ/m2 and the Rockwell hardness was 111 M. As a result of the tinting test, the %T measurement at 452 nm showed good tintability, as the %T was equal to 11.0%. The results are shown in Table 1.
58.7 g of bis(4-isocyanatecyclohexyl)methane were poured into a 300 ml conical beaker; 0.088 g of dimethyl tin dichloride, 0.10 g of Zelec UN, and 1.50 g of Viosorb 583 were then added and subjected to mixing at room temperature, for 10 minutes or slightly longer, obtaining a homogenous solution. 37.2 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 4.1 g of ethylene glycol bis(3-mercaptopropionate) were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-micrometer Teflon filter and then injected into a mould as in Example 1. The polymerization reaction was carried out under the same conditions as Example 1. After cooling, a colourless transparent resin platelet was obtained, which was easily released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5969, Abbe value e line = 39.2, specific density = 1.23. The Izod impact strength was equal to 114 KJ/m2, and the Rockwell hardness was 114 M. As a result of the tinting test, the %T measurement at 452 nm showed good tintability, as the %T was equal to 29.6%. The results are shown in Table 1.
47.3 g of bis(4-isocyanatecyclohexyl)methane and 9.7 g of hexamethylene diisocyanate were poured into a 300 ml conical beaker; 0.088 g of dimethyl tin dichloride, 0.10 g of Zelec UN, and 1.50 g of Viosorb 583 were then added and subjected to mixing at room temperature, for 10 minutes or slightly longer, obtaining a homogenous solution. 36.6 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 6.4 g of ethylene glycol bis(3-mercaptopropionate) were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-micrometer Teflon filter and then injected into a mould as in Example 1. The polymerization reaction was carried out under the same conditions as Example 1. After cooling, a colourless transparent resin platelet was obtained, which was easily released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5966, Abbe value e line = 39.2, specific density = 1.24. The Izod impact strength was equal to 107 KJ/m2, and the Rockwell hardness was 102 M. As a result of the tinting test, the %T measurement at 452 nm showed good tintability, as the %T was equal to 27.7%. The results are shown in Table 1.
46.1 g of bis(4-isocyanatecyclohexyl)methane and 11.5 g of 2,5(6)-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane were poured into a 300 ml conical beaker; 0.088 g of dimethyl tin dichloride, 0.10 g of Zelec UN, and 1.50 g of Viosorb 583 were then added and subjected to mixing at room temperature, for 10 minutes or slightly longer, obtaining a homogenous solution. 36.0 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 6.4 g of ethylene glycol bis(3-mercaptopropionate) were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-micrometer Teflon filter and then injected into a mould as in Example 1. The polymerization reaction was carried out under the same conditions as Example 1. After cooling, a colourless transparent resin platelet was obtained, which was easily released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5979, Abbe value e line = 39.2, specific density = 1.24. The Izod impact strength was equal to 128 KJ/m2 and the Rockwell hardness was 110 M. As a result of the tinting test, the %T measurement at 452 nm showed good tintability, as the %T was equal to 33.5%. The results are shown in Table 1.
45.7 g of bis(4-isocyanatocyclohexyl)methane and 11.4 g of 2,5(6)-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane were poured into a 300 ml conical beaker, 0.088 g of dimethyl tin dichloride, 0.10 g of Zelec UN and 1.50 g of Viosorb 583 were then added and subjected to mixing at room temperature for 10 minutes or longer, obtaining a homogenous solution. Then, 35.8 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 7.1 g of bis(3-mercaptopropionate)1,4-butanediol were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-?m Teflon filter and then injected into a mould consisting of a glass mould and a tape, and heated to a temperature ranging from 20 to 120 degrees C. The polymerization reaction was left to proceed for 20 hours. After cooling, a colorless, transparent resin platelet was obtained, which was released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5971, Abbe value e line = 39.2 and specific density = 1.24.
Example using trioctylmethylammonium chloride (TOMAC)
49.5 g of bis(4-isocyanatocyclohexyl)methane and 8.7 g of 2,5(6)-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane were poured into a 300 ml conical beaker, 2.5 g of trioctylmethylammonium chloride, 0.10 g of Zelec UN and 1.50 g of Viosorb 583 were then added and subjected to mixing at 40 degrees C for 10 minutes or longer, obtaining a homogenous solution. After cooling to room temperature, 37.6 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 4.2 g of ethylene glycol bis(3-mercaptopropionate) were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-?m Teflon filter and then injected into a mould consisting of a glass mould and a tape, and heated to a temperature ranging from 20 to 120 degrees C. The polymerization reaction was left to proceed for 20 hours. After cooling, a colorless, transparent resin platelet was obtained, which was released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.598, Abbe value e line = 39.3 and specific density = 1.23.
50.6 g of 2,5(6)-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane were poured into a 300 ml conical beaker; 0.035 g of dimethyl tin dichloride, 0.10 g of Zelec UN, and 1.50 g of Viosorb 583 were then added and subjected to mixing at room temperature, for 10 minutes or slightly longer, obtaining a homogenous solution. 25.5 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 g of pentaerythritol tetrakis(3-mercaptopropionate) were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-micrometer Teflon filter and then injected into a mould as in Example 1. The polymerization reaction was carried out under the same conditions as Example 1. After cooling, a colourless transparent resin platelet was obtained, which was released from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5980, Abbe value e line = 39.2, and specific density = 1.30. The Izod impact strength was equal to 92 KJ/m2, and the Rockwell hardness was 114 M. As a result of the tinting test, the %T measurement at 452 nm did not show a particularly good tintability, as the %T was equal to 44.2%. The results are shown in Table 1.
60.1 g of bis(4-isocyanatecyclohexyl)methane were poured into a 300 ml conical beaker; 0.10 g of dimethyl tin dichloride, 0.10 g of Zelec UN, and 1.50 g of Viosorb 583 were then added and subjected to mixing at room temperature, for 10 minutes or slightly longer, obtaining a homogenous solution. 30.9 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were subsequently added, followed by mixing, obtaining a homogenous solution. The mixture was stirred at 20 degrees C or lower, and degassed under a vacuum of 400 Pa or less for 30 minutes or more. The mixture was filtered through a 1-micrometer Teflon filter and then injected into a mould consisting of a mould as in Example 1. The polymerization reaction was carried out under the same conditions as Example 1. After cooling, a colourless transparent resin platelet was obtained, which was detached from the mould.
The optical properties of the resin obtained were as follows: ne = 1.5996, Abbe value e line = 39.1, and specific density = 1.23. The Izod impact strength was equal to 88 KJ/m2, and the Rockwell hardness was 114 M. As a result of the tinting test, the %T measurement at 452 nm did not show a particularly good tintability, as the %T was equal to 50.8%. The results are shown in Table 1.
wherein the polyisocyanate(s) (A) is at least one bifunctional or higher functional alicyclic polyisocyanate compound,
the polythiol(s) (B) is at least a compound selected from polythiols represented by the following general formula:
wherein l and m, the same or different from each other, represent an integer from 1 to 4; n represents an integer from 1 to 3; and R represents hydrogen or a methyl group and, when n is different from 1, the R groups are the same as or different from each other,
the thiol(s) (C) is at least one compound selected from thiols having general formula (3)
wherein R1, R2, R3, the same or different from each other, are selected from -(CH2)n-SH, -S-(CH2)n-SH and -R-S-(CH2)n-SH, wherein R is an alkylene group having from 1 to 10 carbon atoms, n is an integer ranging from 1 to 3, said compound having general formula (3) containing at least two SH groups and at least a -S- bridge and
the catalyst(s) (D) is at least a polymerization catalyst selected from metal compounds, quaternary ammonium salts, organic sulfonic acids, tertiary amines and their inorganic or organic salts, provided that if the catalyst is a tertiary amine, the polymerizable composition does not comprise monoacid diester phosphates in a molar ratio tertiary amine/diester monoacid phosphates within the range of 1/1.3 to 1/20.
b. The polymerizable composition according to a, further comprising at least one compound selected from the thiols having general formula (B2)
wherein R represents alkylene groups, the same or different from each other, having from 1 to 6 carbon atoms; R1 represents alkyl groups, the same or different from each other, having from 1 to 10 carbon atoms; n is an integer ranging from 1 to 6; m is an integer ranging from 1 to 6; p is an integer ranging from 1 to 4; q is equal to 0 or 1 and p+q is equal to 4.
c. The polymerizable composition according to a or b, wherein the polyisocyanate(s) (A) is selected from 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(iso-cyanatemethyl)cyclohexane, bis(4-isocyanatecyclo-hexyl)methane, and bis(isocyanatemethyl)-bicyclo-[2.2.1]heptane.
d. The polymerizable composition according to any of a to c, wherein the polyisocyanate(s) (A) is a combination of at least two compounds selected from bis(4-isocyanatecyclohexyl)methane, bis(isocyanate-methyl)-bicyclo[2.2.1]heptane, 1,3-bis(isocyanatemethyl)-cyclohexane, and 1,4-bis(isocyanatemethyl)cyclohexane.
e. The polymerizable composition according to any of a to d, wherein in polythiols (B1), l and m, the same or different, represent an integer ranging from 1 to 2 and n is 1.
f. The polymerizable composition according to any of a to e, also comprising a polyisocyanate (E) selected from a non-cyclic aliphatic polyisocyanate, an aromatic polyisocyanate, an aliphatic polyisocyanate containing sulfur atoms, an aromatic polyisocyanate containing sulfur atoms, preferably a non-cyclic aliphatic polyisocyanate.
g. The polymerizable composition according to a to f, wherein the polyisocyanate (E) is selected from m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate or mixtures thereof, more preferably from pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, or octamethylene diisocyanate.
h. The polymerizable composition according to any of a to g, wherein the thiol(s) (C) is selected from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri-thiaundecane, and 2,5-bis(mercaptomethyl)-1,4-dithiane.
i. The polymerizable composition according to any of a to h, wherein the molar ratio between the mercapto groups belonging to the polythiols (B1), the thiol(s) (C) and possibly the thiols (B2) with respect to the isocyanate groups of the polyisocyanate(s) (A) varies within the range of 0.8-1.2, preferably within the range of 0.85-1.15, even more preferably within the range of 0.9-1.1.
j. The polymerizable composition according to any of a to i, wherein the catalyst comprises a tertiary amine having general formula (4)
wherein R1, R2, R3, the same or different, are selected from a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or an alicyclic group containing from 3 to 20 carbon atoms, said groups possibly containing heteroatoms such as N, O, P, S or halogen.
k. The polymerizable composition according to any of a to j, also comprising an internal releasing agent consisting of a diester monoacid phosphate represented by the following general formula (5):
wherein R2 and R4, the same or different, represent a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or a cyclo-aliphatic group containing from 3 to 20 carbon atoms; R3 and R5, the same or different, represent an alkylene group containing from 1 to 3 carbon atoms and m and p, independently from each other, are 0, 1 or 2.
l. An optical article obtainable through the polymerization of the polymerizable composition according to any of a to k.
m. An optical lens, in particular for eye-glasses, comprising an optical article according to l, and further comprising a hard coat layer and an anti-reflective coating layer.
n. A method for manufacturing an optical article comprising the following phases:
- injecting a polymerizable composition according to any of a to k into a mould and let it polymerize, forming an optical article;
- depositing sequentially a hard coating layer and an anti-reflection layer in sequence on said optical article.
Claims (14)
- A polymerizable composition comprising polyisocyanate(s) (A), polythiol(s) (B), thiol(s) (C) and catalyst(s) (D),
wherein the polyisocyanate(s) (A) is at least one bifunctional or higher functional alicyclic polyisocyanate compound,
the polythiol(s) (B) is at least one compound selected from polythiols represented by the following general formula (B1):
wherein l and m, the same or different from each other, represent an integer from 1 to 4; n represents an integer from 1 to 3; r represents an integer from 1 to 4; and R represents hydrogen or a methyl group and, when n is different from 1, the R groups are the same as or different from each other,
the thiol(s) (C) is at least one compound selected from thiols represented by the following general formula (3):
wherein R1, R2, R3, the same or different from each other, are selected from -(CH2)n-SH, -S-(CH2)n-SH and -R-S-(CH2)n-SH, wherein R is an alkylene group having from 1 to 10 carbon atoms, n is an integer ranging from 1 to 3, said compound represented by the general formula (3) containing at least two SH groups and at least a -S- bridge and
the catalyst(s) (D) is at least one polymerization catalyst selected from metal compounds, quaternary ammonium salts, organic sulfonic acids, tertiary amines and their inorganic or organic salts. - The polymerizable composition according to claim 1, further comprising at least one compound selected from the thiols having general formula (B2)
wherein R represents alkylene groups, the same or different from each other, having from 1 to 6 carbon atoms; R1 represents alkyl groups, the same or different from each other, having from 1 to 10 carbon atoms; n is an integer ranging from 1 to 6; m is an integer ranging from 1 to 6; p is an integer ranging from 1 to 4; q is equal to 0 or 1 and p+q is equal to 4. - The polymerizable composition according to claim 1 or 2, wherein the polyisocyanate(s) (A) is selected from 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(iso-cyanatemethyl)cyclohexane, bis(4-isocyanatecyclo-hexyl)methane, and bis(isocyanatemethyl)-bicyclo-[2.2.1]heptane.
- The polymerizable composition according to any of claims 1 to 3, wherein the polyisocyanate(s) (A) is a combination of at least two compounds selected from bis(4-isocyanatecyclohexyl)methane, bis(isocyanate-methyl)-bicyclo[2.2.1]heptane, 1,3-bis(isocyanatemethyl)-cyclohexane, and 1,4-bis(isocyanatemethyl)cyclohexane.
- The polymerizable composition according to any of claims 1 to 4, wherein in polythiols (B1), l and m, the same or different, represent an integer ranging from 1 to 2 and n is 1.
- The polymerizable composition according to any of claims 1 to 5, further comprising a polyisocyanate (E) selected from a non-cyclic aliphatic polyisocyanate, an aromatic polyisocyanate, an aliphatic polyisocyanate containing sulfur atoms, an aromatic polyisocyanate containing sulfur atoms, preferably a non-cyclic aliphatic polyisocyanate.
- The polymerizable composition according to claim 6, wherein the polyisocyanate (E) is selected from m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate or mixtures thereof, more preferably from pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, or octamethylene diisocyanate.
- The polymerizable composition according to any of claims 1 to 7, wherein the thiol(s) (C) is selected from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri-thiaundecane, and 2,5-bis(mercaptomethyl)-1,4-dithiane.
- The polymerizable composition according to any of claims 2 to 8, wherein the molar ratio between the mercapto groups belonging to the polythiols (B1), the thiol(s) (C) and possibly the thiols (B2) with respect to the isocyanate groups of the polyisocyanate(s) (A) varies within the range of 0.8-1.2, preferably within the range of 0.85-1.15, even more preferably within the range of 0.9-1.1.
- The polymerizable composition according to any of claims 1 to 9, wherein the catalyst comprises a tertiary amine having general formula (4)
wherein R1, R2, R3, the same or different, are selected from a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or an alicyclic group containing from 3 to 20 carbon atoms, said groups possibly containing heteroatoms such as N, O, P, S or halogen. - The polymerizable composition according to any of the claims 1 to 10, further comprising an internal releasing agent consisting of a diester monoacid phosphate represented by the following general formula (5):
wherein R2 and R4, the same or different, represent a linear or branched aliphatic group containing from 1 to 20 carbon atoms, or a cyclo-aliphatic group containing from 3 to 20 carbon atoms; R3 and R5, the same or different, represent an alkylene group containing from 1 to 3 carbon atoms and m and p, independently from each other, are 0, 1 or 2. - An optical article obtained through the polymerization of the polymerizable composition according to any of claims 1 to 11.
- An optical lens, in particular for eye-glasses, comprising the optical article according to claim 12, a hard coat layer and an anti-reflective coating layer.
- A method for manufacturing an optical article comprising the following phases:
- injecting a polymerizable composition according to any of claims 1 to 11 into a mould and let it polymerize, forming an optical article;
- depositing sequentially a hard coating layer and an anti-reflection layer in sequence on said optical article.
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KR1020147012387A KR101665831B1 (en) | 2011-11-18 | 2012-11-16 | Polymerizable composition, optical article obtained therefrom and method for the production of said optical article |
BR112014010976A BR112014010976A2 (en) | 2011-11-18 | 2012-11-16 | polymerizable composition, optical article obtained therefrom and method for producing said optical article |
JP2014523863A JP5961262B2 (en) | 2011-11-18 | 2012-11-16 | Polymerizable composition, optical member obtained using the same, and method for producing the optical member |
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Also Published As
Publication number | Publication date |
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KR101665831B1 (en) | 2016-10-12 |
JP2015504099A (en) | 2015-02-05 |
EP2780387A4 (en) | 2015-07-01 |
KR20140074386A (en) | 2014-06-17 |
JP5961262B2 (en) | 2016-08-02 |
US9527948B2 (en) | 2016-12-27 |
EP2780387B1 (en) | 2018-11-07 |
CN104011103B (en) | 2016-08-24 |
ITMI20112102A1 (en) | 2013-05-19 |
EP2780387A1 (en) | 2014-09-24 |
BR112014010976A2 (en) | 2017-06-06 |
CN104011103A (en) | 2014-08-27 |
TW201335208A (en) | 2013-09-01 |
US20140327869A1 (en) | 2014-11-06 |
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