CN116745350A - Curable composition and optical material comprising the same - Google Patents
Curable composition and optical material comprising the same Download PDFInfo
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- CN116745350A CN116745350A CN202280008605.8A CN202280008605A CN116745350A CN 116745350 A CN116745350 A CN 116745350A CN 202280008605 A CN202280008605 A CN 202280008605A CN 116745350 A CN116745350 A CN 116745350A
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- 230000003287 optical effect Effects 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- -1 episulfide compound Chemical class 0.000 claims abstract description 88
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 68
- 239000011593 sulfur Substances 0.000 claims abstract description 67
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims description 41
- 125000004977 cycloheptylene group Chemical group 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 35
- 125000004956 cyclohexylene group Chemical group 0.000 claims description 30
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 14
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 claims description 12
- 125000000732 arylene group Chemical group 0.000 claims description 9
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 125000004978 cyclooctylene group Chemical group 0.000 description 19
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 19
- 239000011521 glass Substances 0.000 description 18
- 238000001723 curing Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
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- 238000006243 chemical reaction Methods 0.000 description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- JNMWHTHYDQTDQZ-UHFFFAOYSA-N selenium sulfide Chemical compound S=[Se]=S JNMWHTHYDQTDQZ-UHFFFAOYSA-N 0.000 description 7
- 229960005265 selenium sulfide Drugs 0.000 description 7
- 125000004979 cyclopentylene group Chemical group 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- 239000005341 toughened glass Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000002896 organic halogen compounds Chemical class 0.000 description 3
- 229910000338 selenium disulfide Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 150000003553 thiiranes Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 150000003568 thioethers Chemical group 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- WMWQTUBQTYZJRI-UHFFFAOYSA-N 1-(4-methoxyphenyl)-n,n-dimethylmethanamine Chemical compound COC1=CC=C(CN(C)C)C=C1 WMWQTUBQTYZJRI-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical group CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- UDGNCGOMVIKQOW-UHFFFAOYSA-N 4-[(dimethylamino)methyl]-n,n-dimethylaniline Chemical compound CN(C)CC1=CC=C(N(C)C)C=C1 UDGNCGOMVIKQOW-UHFFFAOYSA-N 0.000 description 1
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical compound N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003974 aralkylamines Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 210000005252 bulbus oculi Anatomy 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- QVQGTNFYPJQJNM-UHFFFAOYSA-N dicyclohexylmethanamine Chemical compound C1CCCCC1C(N)C1CCCCC1 QVQGTNFYPJQJNM-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
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- 150000002118 epoxides Chemical class 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
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- 125000005241 heteroarylamino group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
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- 230000002045 lasting effect Effects 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- JAOPKYRWYXCGOQ-UHFFFAOYSA-N n,n-dimethyl-1-(4-methylphenyl)methanamine Chemical compound CN(C)CC1=CC=C(C)C=C1 JAOPKYRWYXCGOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012011 nucleophilic catalyst Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
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Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present application relates to a curable composition for forming a high refractive index optical material and an optical material comprising the same, and more particularly, to a curable composition for forming a high refractive index optical material comprising an episulfide compound and a sulfur-containing polymer compound and an optical material comprising the same.
Description
Technical Field
Cross Reference to Related Applications
The present application claims the benefits and priorities of korean patent application No. 10-2021-0031499 filed on 3 months 10 of 2021 and korean patent application No. 10-2022-0026941 filed on 3 months 2 of 2022, the contents of which are incorporated herein by reference in their entireties.
The present disclosure relates to curable compositions for forming high refractive index optical members and optical materials comprising the same.
Background
High refractive index polymers (high refractive index polymer, hrep) are generally defined as polymer materials having a refractive index of 1.50 or more and are used as coating/sealing materials for improving light extraction efficiency of Light Emitting Diodes (LEDs), or microlens materials for image sensors.
In general, a glass lens may cause serious damage to an eyeball of a user when broken, and is high in density and thus heavy in weight, thus causing discomfort during lasting wear, while a lens using a high refractive index polymer is lighter than a glass lens, thus being comfortable to wear, less fragile, and relatively safer than a glass lens even if damaged, and capable of realizing various colors.
However, since the refractive index and chromatic aberration (abbe number) generally have a trade-off relationship in a high refractive index polymer, there is a problem in that lenses or the like using such a high refractive index polymer have a relatively low abbe number. When the glass transition temperature is low and thus the lens is used for a device or the like, there is a problem in that deformation or the like occurs due to heat generation.
Disclosure of Invention
Technical problem
An object of the present application is to provide a curable composition for forming a high refractive index optical material which is lighter than glass or tempered glass or the like used in existing lenses, has excellent strength and hardness, can realize various colors, can realize a high refractive index, has a low yellowness index value, thus has excellent optical characteristics, and has a high glass transition temperature, thus being less deformed, and an optical material comprising the same.
Technical proposal
Provided herein are curable compositions for forming high refractive index optical materials comprising an episulfide compound and a sulfur-containing polymer compound.
Also provided herein are optical materials comprising an episulfide compound and a sulfur-containing polymer compound.
Hereinafter, the curable composition according to specific embodiments of the present application and the optical material including the same will be described in detail.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. Unless specifically indicated or apparent from the context, singular references include plural references thereto.
As used herein, the terms "comprises/comprising" or "having" and the like are intended to specify the presence of stated features, regions, integers, steps, actions, elements, and/or components, but do not preclude the presence or addition of different ones.
As used herein, "episulfide compound" means a compound comprising one or more episulfides, wherein episulfide means a compound in which the oxygen (O) atom of an epoxide is replaced with a sulfur (S) atom.
As used herein, "sulfur-containing polymer compound" means a polymer that substantially contains sulfur atoms.
As used herein, "cured" means both thermally cured and photo-cured, and "curable composition" means thermally and/or photo-curable composition.
As used herein, high refractive index means a refractive index of about 1.600 or more at a wavelength region of 350nm to 800nm or at a wavelength of 632.8 nm.
As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; and a heterocyclic group comprising at least one of N, O and S atoms, or a substituent which is unsubstituted or linked via two or more of the substituents exemplified above. For example, a "substituent in which two or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl, or it may also be interpreted as a substituent to which two phenyl groups are linked.
According to one embodiment of the present application, there is provided a curable composition for forming a high refractive index optical material, the curable composition comprising an episulfide compound and a sulfur-containing polymer compound, wherein the sulfur-containing polymer compound comprises a compound selected from the group consisting of a compound containing S n+1 (n is an integer of 1 to 20) and at least one of selenium and sulfur-containing repeating units.
The present inventors found that a composition comprising an episulfide compound and a sulfur-containing polymer compound, and an optical material comprising the same are lighter than glass or tempered glass or the like used in existing lenses, have excellent physical properties such as strength and hardness, have high transmittance and low yellowness index (y.i.) and thus have excellent optical properties, have a high glass transition temperature and thus have less thermal deformation, and thus can provide an optical material capable of replacing glass or plastic materials previously used, and completed the present application.
Accordingly, the curable composition and an optical material including the same can replace existing glass or optical glass, and are usefully used as a display substrate, a display protective film, a touch panel, a lens of an image sensor such as a wearable device, a coating/sealing material for improving light extraction efficiency such as a Light Emitting Diode (LED), or the like.
The sulfur-containing polymer compound included in the curable composition may include a compound selected from the group consisting of a sulfur-containing compound n+1 (n is an integer of 1 to 20) and at least one of selenium and sulfur-containing repeating units.
The sulfur-containing polymer compound may be used as a curing agent for curing a curable composition containing an episulfide compound, whereby the glass transition temperature may be raised to 65 ℃ or more and a high refractive index of 1.710 or more may be exhibited while improving optical characteristics in terms of transmittance, haze and yellowness of an optical material as a cured product of the curable composition.
For example, the sulfur-containing polymer compound may include a repeating unit represented by chemical formula 1 or 2.
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
R 1 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; substituted or unsubstituted cycloalkylene having 3 to 40 carbon atoms; a substituted or unsubstituted arylene group having 5 to 30 carbon atoms; a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, comprising at least one of an oxygen (O), nitrogen (N), and sulfur (S) atom; -R a OR b -；-R c COOR d -；-R e SO 2 R f -or-R g SOR h -，R a To R h Each independently is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 5 to 30 carbon atoms,
n is an integer of 1 to 20,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
R 2 is a substituted or unsubstituted sub-group having 1 to 20 carbon atomsAn alkyl group; substituted or unsubstituted cycloalkylene having 3 to 40 carbon atoms; a substituted or unsubstituted arylene group having 5 to 30 carbon atoms; a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, comprising at least one of an oxygen (O), nitrogen (N), and sulfur (S) atom; -R a OR b -；-R c COOR d -；-R e SO 2 R f -or-R g SOR h -，R a To R h Each independently is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 5 to 30 carbon atoms,
a and b are each independently an integer of 0 or more and 10 or less, and
a+b is an integer of 1 or more and 20 or less.
For example, a and b may each independently be 0 or greater and 7 or less, 0 or greater and 5 or less, or 1 or greater and 3 or less, and a+b may be 1 or greater and 10 or less, 2 or greater and 7 or less, or 3 or greater and 5 or less.
In chemical formula 1, n may be 1 to 20, 1 to 18, 5 to 15, or 8 to 13. For example, chemical formula 1 may be a repeating unit represented by the following chemical formula 1-1 or 1-2.
[ chemical formula 1-1]
[ chemical formulas 1-2]
In chemical formulas 1-1 and 1-2, R 1 As defined above.
Further, chemical formula 2 may be one selected from the repeating units represented by the following chemical formulas 2-1 to 2-4.
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
In the chemical formulas 2-1 to 2-4, R 2 As defined above.
At R 1 And R is 2 In the definition of (c), the substituted or unsubstituted alkylene group having 1 to 20 carbon atoms may be methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butyl, pentylene, isopentylene, neopentylene, tert-pentylene, hexylene, 2-methylpentylene, heptylene, 1-ethylpentylene, octylene, 2-ethylhexyl, isooctylene, nonylene, isononyl, decylene, isodecylene, undecylene or dodecylene.
Further, the alkylene group having 1 to 20 carbon atoms may be substituted with a halogen group, and for example, the halogen group may be a fluoro group, a bromo group, or a chloro group.
In addition, at R 1 And R is 2 In the definition of (a), the substituted or unsubstituted cycloalkylene group having 3 to 40 carbon atoms may be 1, 3-cyclopentylene group, 1,3- (2-methyl) cyclopentylene group, 1,4- (2-methyl) cyclopentylene group, 1,5- (2-methyl) cyclopentylene group, 1,3- (2-ethyl) cyclopentylene group, 1,4- (2-ethyl) cyclopentylene group and 1,5- (2-ethyl) cyclopentylene groupAmyl, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, 1,3- (2-methyl) cyclohexylene, 1,4- (2-methyl) cyclohexylene, 1,5- (2-methyl) cyclohexylene and 1,6- (2-methyl) cyclohexylene, 1,3- (2-ethyl) cyclohexylene, 1,4- (2-ethyl) cyclohexylene, 1,5- (2-ethyl) cyclohexylene, 1,6- (2-ethyl) cyclohexylene, 1,3- (2-propyl) cyclohexylene, 1,4- (2-propyl) cyclohexylene, 1,5- (2-propyl) cyclohexylene 1,6- (2-propyl) cyclohexylene, 1,3- (2-isopropyl) cyclohexylene, 1,4- (2-isopropyl) cyclohexylene, 1,5- (2-isopropyl) cyclohexylene, 1,6- (2-isopropyl) cyclohexylene, 1,3- (2-butyl) cyclohexylene, 1,4- (2-butyl) cyclohexylene, 1,5- (2-butyl) cyclohexylene and 1,6- (2-butyl) cyclohexylene, 1,3- (2-sec-butyl) cyclohexylene, 1,4- (2-sec-butyl) cyclohexylene, 1,5- (2-sec-butyl) cyclohexylene, 1,6- (2-sec-butyl) cyclohexylene, 1,3- (2-tert-butyl) cyclohexylene, 1,4- (2-tert-butyl) cyclohexylene, 1,5- (2-tert-butyl) cyclohexylene, 1,6- (2-tert-butyl) cyclohexylene, 1, 2-cycloheptylene, 1, 3-cycloheptylene, 1, 4-cycloheptylene, 1,3- (2-methyl) cycloheptylene, 1,4- (2-methyl) cycloheptylene, 1,5- (2-methyl) cycloheptylene, 1,6- (2-methyl) cycloheptylene and 1,7- (2-methyl) cycloheptylene, 1,3- (2-ethyl) cycloheptylene, 1,4- (2-ethyl) cycloheptylene, 1,5- (2-ethyl) cycloheptylene, 1,6- (2-ethyl) cycloheptylene and 1,7- (2-ethyl) cycloheptylene, 1,3- (2-propyl) cycloheptylene, 1,4- (2-propyl) cycloheptylene, 1,5- (2-methyl) cycloheptylene, 1,7- (2-ethyl) cycloheptylene, 1,3- (2-ethyl) cycloheptylene, 1,6- (2-methyl) cycloheptylene, 1,7- (2-ethyl) cycloheptylene, 1,3- (2-ethyl) cycloheptylene, 1, 7-isopropyl) cycloheptylene, 1,6- (2-ethyl) cycloheptylene and 1, 3-isopropyl) cycloheptylene, 1,3- (2-butyl) cycloheptylene, 1,4- (2-butyl) cycloheptylene, 1,5- (2-butyl) cycloheptylene, 1,6- (2-butyl) cycloheptylene and 1,7- (2-butyl) cycloheptylene, 1,3- (2-sec-butyl) cycloheptylene, 1,4- (2-sec-butyl) cycloheptylene, 1,5- (2-sec-butyl) cycloheptylene, 1,6- (2-sec-butyl) cycloheptylene, 1,7- (2-sec-butyl) cycloheptylene, 1,3- (2-tert-butyl) cycloheptylene, 1,4- (2-tert-butyl) cycloheptylene, 1,5- (2-tert-butyl) cycloheptylene, 1,6- (2-tert-butyl) cycloheptylene, 1,7- (2-tert-butyl) cycloheptylene, 1, 2-cyclooctyl,1, 3-cyclooctylene, 1, 4-cyclooctylene and 1, 5-cyclooctylene, 1,3- (2-methyl) cyclooctylene, 1,4- (2-methyl) cyclooctylene, 1,5- (2-methyl) cyclooctylene, 1,6- (2-methyl) cyclooctylene, 1,7- (2-methyl) cyclooctylene, 1,8- (2-methyl) cyclooctylene, 1,3- (2-ethyl) cyclooctylene, 1,4- (2-ethyl) cyclooctylene, 1,5- (2-ethyl) cyclooctylene, 1,6- (2-ethyl) cyclooctylene, 1,7- (2-ethyl) cyclooctylene, 1,8- (2-ethyl) cyclooctylene, 1,3- (2-propyl) cyclooctylene, 1,4- (2-propyl) cyclooctylene, 1,5- (2-propyl) cyclooctylene, 1,6- (2-propyl) cyclooctylene, 1,7- (2-propyl) cyclooctylene, 1,8- (2-propyl) cyclooctylene, 1,3- (2-ethyl) cyclooctylene, 3- (2-propyl) bicyclooctyleneAlkyl), 2,5- (1, 4-di +_)>Alkyl) and 2,6- (1, 4-di +_>Alkyl), 2, 4-morpholinylene, 3, 4-morpholinylene, 2, 5-tetrahydrofuranylene, 3, 4-tetrahydrofuranylene, 1, 2-pyrrolidinylene, 1, 3-pyrrolidinylene, 2, 5-pyrrolidinylene and 3, 4-pyrrolidinylene, and also 1, 2-piperidinylene, 1, 3-piperidinylene, 1, 4-piperidinylene, 2, 3-piperidinylene or 2, 6-piperidinylene.
In addition, at R 1 And R is 2 In the definition of (C) a substituted or unsubstituted arylene group having 5 to 30 carbon atoms may be 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 1, 2-naphthylene, 2, 3-naphthylene, 1, 4-naphthylene, 1, 5-naphthylene, 2, 6-naphthylene, 1, 8-naphthylene, 2, 5-pyrene and 3, 4-pyrene, 2, 3-pyridylene, 2, 4-pyridylene, 2, 5-pyridylene, 2, 6-pyridylene, 3, 5-pyridylene, 2, 4-pyrimidylene, 2, 5-pyrimidylene, 2, 3-pyrazinylene, 2, 5-pyrazinylene and 2, 6-pyrazinylene, 3, 5-pyrazolylene, 1, 2-imidazolylene, 1, 4-imidazolylene, 1, 5-imidazolylene, 2, 4-imidazolylene, 2, 5-imidazolylene, 2, 4-imidazolylene, 4-thiazolylene, 3, 4-thiazolylene and 3-thiazolylene1,2, 4-triazinylene), 2,4- (1, 3, 5-triazinylene), 3, 5-quinaldine, 3, 6-quinaldine, 3, 8-quinaldine, 5, 8-quinaldine, 3, 5-quinolinylene, 3, 6-quinolinylene, 3, 8-quinolinylene, 5, 8-quinolinylene, 2, 4-benzimidazolylene, 2, 5-benzimidazolylene and 1, 3-isoquinolylene, 1, 4-isoquinolylene, 1, 5-isoquinolylene, 1, 6-isoquinolylene, 2-methyl-1, 3-phenylene, 2-methyl-1, 4-phenylene, 2-methyl-1, 5-phenylene, 2-methyl-1, 6-phenylene 2, 3-dimethyl-1, 4-phenylene, 2, 3-dimethyl-1, 5-phenylene, 2, 3-dimethyl-1, 6-phenylene, 2, 4-dimethyl-1, 3-phenylene, 2, 4-dimethyl-1, 5-phenylene, 2, 4-dimethyl-1, 6-phenylene, 2, 5-dimethyl-1, 3-phenylene, 2, 5-dimethyl-1, 4-phenylene, 2, 5-dimethyl-1, 6-phenylene, 2,4, 5-trimethyl-1, 3-phenylene, 2,4, 5-trimethyl-1, 6-phenylene, 2,4, 6-trimethyl-1, 3-phenylene, 2-ethyl-1, 4-phenylene, 2-ethyl-1, 5-phenylene, 2-ethyl-1, 6-phenylene, 2, 3-diethyl-1, 4-phenylene, 2, 3-diethyl-1, 5-phenylene, 2, 3-diethyl-1, 6-phenylene, 2, 4-diethyl-1, 3-phenylene, 2, 4-diethyl-1, 5-phenylene, 2, 4-diethyl-1, 6-phenylene, 2, 5-diethyl-1, 3-phenylene, 2, 5-diethyl-1, 4-phenylene, 2-methoxy-1, 3-phenylene, 2-methoxy-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2-methoxy-1, 6-phenylene, 2, 3-dimethoxy-1, 4-phenylene, 2, 3-dimethoxy-1, 5-phenylene, 2, 3-dimethoxy-1, 6-phenylene, 2, 4-dimethoxy-1, 3-phenylene, 2, 4-dimethoxy-1, 5-phenylene, 2, 4-dimethoxy-1, 6-phenylene, 2-dimethoxy-1, 5-phenylene, 2, 4-ethoxy-1, 5-phenylene, 2, 3-dimethoxy-1, 5-ethoxy-phenylene, 2, 3-ethoxy-1, 5-phenylene, 2, 3-dimethoxy-1, 4-ethoxy-1, 5-phenylene, 2, 3-dimethoxy-ethoxy-1, 5-phenylene, 2, 3-diethoxy-1, 4-phenylene, 2, 3-diethoxy-1, 5-phenylene, 2, 3-diethoxy-1, 6-phenylene, 2, 4-diethoxy-1, 3-phenylene, 2, 4-diethoxy-1, 5-phenylene, 2, 4-diethoxy-1, 6-phenylene, 2-chloro-1, 3-phenylene, 2-chloro-1, 4-phenylene, 2-chloro-1, 5-phenylene, 2-chloro-1, 6-phenylene, 2, 3-dichloro-1, 4-phenylene, 2, 3-dichloro-1, 5-phenylene, 2, 3-dichloro-1, 6-phenylene, 2, 4-dichloro-1, 3-phenylene, 2, 4-dichloro-1, 5-phenylene, 2-hydroxy-1, 3-phenylene, 2-hydroxy-1, 4-phenylene, 2-hydroxy-1, 5-phenylene, 2-hydroxy-1, 6-phenylene, 2, 3-dihydroxy-1, 4-phenylene, 2-cyano-1, 3-phenylene, 2-cyano-1, 4-phenylene, 2-cyano-1, 5-phenylene, 2-cyano-1, 6-phenylene, 2, 3-dicyano-1, 4-phenylene or 2, 3-dicyano-1, 5-phenylene.
For example, R 1 And R is 2 And may each independently be methylene, ethylene, propylene, isopropylene, cyclohexylene, cycloheptylene, phenylene, methylphenyl, ethylphenylene, methoxyphenylene, or ethoxyphenylene.
The sulfur-containing polymer compound may comprise any one of the following repeating units.
Since the sulfur-containing polymer compound contains the above-mentioned repeating unit, there is no problem such as a decrease in refractive index even when stored for a long period of time at room temperature. In the case of the sulfur-containing polymer compound containing no repeating unit as described above, there may be a problem of lowering of the refractive index when stored at room temperature for a long period of time (for example, 200 hours or more, 240 hours or more, or 300 hours or more).
The sulfur-containing polymer compound may contain 1 to 1000, 2 to 800, 5 to 500, or 10 to 200 repeating units of chemical formula 1 or chemical formula 2.
In addition, the sulfur-containing polymer compound may have a weight average molecular weight of 250 to 50,000, 500 to 40,000, or 1,000 to 30,000. When the weight average molecular weight of the sulfur-containing polymer compound is too large, there are problems in that the solubility in the episulfide compound is low, and it is difficult to obtain uniform physical properties such as uniform refractive index deviation and transparency deviation in the production of optical materials. When the weight average molecular weight is too small, the refractive index of the optical material formed after curing may be low.
As used herein, weight average molecular weight (Mw) refers to polystyrene-equivalent weight average molecular weight as measured by Gel Permeation Chromatography (GPC). In measuring the polystyrene-equivalent weight average molecular weight measured by GPC, a detector and an analytical column, for example, a commonly known analytical device and a differential refractive index detector can be used, and commonly applied temperature conditions, solvents, and flow rates can be used. Specific examples of measurement conditions include a temperature of 30 ℃, chloroform solvent, and a flow rate of 1 mL/min. Specific examples of measurement conditions are as follows: a Waters PL-GPC220 instrument was used and a Polymer Laboratories PLgel MIX-B300 mm length column was used. The temperature was evaluated at 160℃and 1,2, 4-trichlorobenzene was used for the solvent at a flow rate of 1 mL/min. Samples were prepared at a concentration of 10mg/10mL and then supplied in an amount of 200 μl, and the value of Mw can be determined using a calibration curve formed with polystyrene standards. 9 polystyrene standards having a molecular weight of 2,000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000 were used.
Meanwhile, the content of the sulfur-containing polymer compound may be 1 to 30 wt%, 2 to 25 wt%, or 5 to 20 wt%, based on 100 wt% of the total curable composition. When the content of the sulfur-containing polymer compound is too large, there is a problem that haze of an optical material formed after curing increases and yellowness also increases, and when the content of the sulfur-containing polymer compound is too small, there is a problem that refractive index of an optical material formed after curing decreases.
The sulfur-containing polymer compound may be prepared by the following reaction scheme 1 or reaction scheme 2, but is not limited thereto.
Reaction scheme 1
Reaction scheme 2
The sulfur-containing polymer compound can be prepared by reacting sulfur (nS) or selenium disulfide (SeS) 2 ) Dissolving in Na 2 S in aqueous solution, and then polymerizing it with a difunctional organohalogen compound. At this time, in schemes 1 and 2, R 1 、R 2 And n is defined as above, na 2 The aqueous S solution can be Li 2 S aqueous solution or K 2 The S aqueous solution, and the bifunctional organohalogen compound may be a polyfunctional organohalogen compound having three or more functional groups, a bifunctional or polyfunctional organotoluene sulfonate compound, a bifunctional or polyfunctional organomethane sulfonate compound, or the like.
Formed in reaction scheme 2Is can be +.>But is not limited to, one example of (wherein a+b is 3).
Conventionally, a thiol compound containing a thiol group (-SH) is contained in a curable composition for forming a high refractive index optical material, but in the case of using a composition of a thiol compound, a curing reaction is performed immediately after mixing, and the viscosity increases sharply, and furthermore, rapid curing causes a streak phenomenon, which causes a problem that an optical material formed from such a composition is inferior in optical characteristics and physical characteristics.
However, since the curable composition for forming a high refractive index optical material according to one embodiment contains a sulfur-containing polymer compound, a rapid curing reaction does not occur immediately after mixing, whereby long-term storage is possible, and a streaking phenomenon due to rapid curing is also unlikely to occur.
The episulfide compound contained in the curable composition can be represented by the following chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, the chemical formula is shown in the drawing,
R 3 and R is 4 Each independently is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R 5 and R is 6 Each independently is a single bond or an alkylene group having 1 to 10 carbon atoms,
a is an integer from 0 to 4, and
b is an integer from 0 to 6.
The episulfide compound can contain a high content of sulfur (S) atoms having a large atomic refractive index in the molecule due to the above-described specific chemical structure, and by such a high sulfur atom content, the refractive index of the cured product can be increased.
In addition, the episulfide compound can be cured by ring-opening polymerization, and the alkylene sulfide group formed by ring-opening polymerization of the episulfide group can further improve the high refractive index of the cured product.
Meanwhile, in chemical formula 3, R 3 And R is 4 May each be independently hydrogen or methyl, but is not limited thereto.
In addition, R 5 And R is 6 Each independently may be a single bond, methylene, ethylene, propylene, isopropylene, butylene or isobutylene, but is not limited thereto.
Further, a and b may each independently be 0 or 1.
A of chemical formula 3 refers to the carbon number of the alkylene group contained in the thioether repeating unit, and if a is too large, the length of the carbon chain in the molecule may be lengthened, and thus, the glass transition temperature of the cured product may be lowered, the heat resistance of the cured product may be deteriorated, and the relative sulfur content may be lowered, and thus, the refractive index of the cured product may be lowered.
B of chemical formula 3 refers to the number of repetitions of a thioether repeating unit in which an alkylene group is linked through a sulfur (S) atom, and if b is too large, the length of a carbon chain in a molecule may be lengthened, and thus, the glass transition temperature of a cured product may be lowered and the heat resistance of the cured product may be deteriorated.
Further, the compounds represented by chemical formula 3 may be used alone or in combination of two or more.
The episulfide compound may include, for example, at least one selected from the group consisting of: bis (β -cyclopropyl) sulfide, bis (β -cyclopropyl) disulfide, bis (β -cyclopropyl thio) methane, 1, 2-bis (β -cyclopropyl thio) ethane, 1, 3-bis (β -cyclopropyl thio) propane, and 1, 4-bis (β -cyclopropyl thio) butane, but are not limited thereto.
The episulfide compound may be included in a content of 50 to 99 wt%, 60 to 95 wt%, or 65 to 85 wt%, based on 100 wt% of the total curable composition. If the content of the episulfide compound is too large, the refractive index may be lowered or physical properties and optical properties of the finally produced optical material may be deteriorated. If the content of the episulfide compound is too small, the yellowness of the finally produced optical material may increase.
Furthermore, the weight ratio of sulfur-containing polymer compound to episulfide compound may be 1:2 to 1:30, 1:3 to 1:25, 1:4 to 1:20, 1:4 to 1:15, or 1:4 to 1:13. If the content of the episulfide compound is too small as compared with the sulfur-containing polymer compound, there may be a problem in that the yellowness may be increased and the polymer compound may not be completely dissolved. If the content of the episulfide compound is too high as compared with the sulfur-containing polymer compound, the refractive index of the formed optical material may be low, or physical properties or optical properties may be deteriorated.
The curable composition for forming the high refractive index optical material may contain sulfur (S 8 ) Granules, selenium sulphide (SeS) 2 ) Particles or mixtures thereof. The curable composition comprises sulfur particles and/or selenium sulphide particles so that the refractive index can be further increased and the haze and yellowness index can be reduced.
Sulfur (S) 8 ) The particles may have a particle size of 1 μm to 200 μm, 2 μm to 180 μm, or 3 μm to 170 μm. If the particle size of the sulfur particles is too small, it is possible thatThe shape of the particles cannot be maintained, and if the particle size is too large, the transmittance of the high refractive index plastic substrate may decrease and the haze may increase.
In addition, selenium sulphide (SeS) 2 ) The particles may have a particle size of 1 μm to 200 μm, 5 μm to 180 μm, or 10 μm to 170 μm. If the particle size of the selenium sulfide particles is too small, the shape of the particles may not be maintained, while if the particle size is too large, the transmittance of the high refractive index plastic substrate may decrease and the haze may increase.
Particle size can be determined by, for example, dynamic light scattering, laser diffraction, centrifugal sedimentation, FFF (Field Flow Fractionation ), pore resistance, scanning Electron Microscopy (SEM) analysis, transmission Electron Microscopy (TEM) analysis, and the like.
When the curable composition further comprises sulfur particles and/or selenium sulphide particles, the content of sulfur particles may be 0.1 to 30 wt%, 1 to 20 wt%, 2 to 15 wt%, or 3 to 10 wt% relative to 100 wt% of the curable composition. Further, the selenium disulfide particles may be present in an amount of 0.1 to 30 wt%, 0.5 to 20 wt%, or 0.8 to 15 wt% relative to 100 wt% of the curable composition.
The curable composition may comprise a catalyst. The catalyst is not particularly limited as long as it is a catalyst generally used in curable compositions for forming high refractive index optical materials, but the catalyst may be, for example, a nucleophilic catalyst including amine or phosphine.
For example, the catalyst may include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and the like; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, N-dicyclohexylmethylamine, N-ethyl-N-isopropyl-2-amine, N-dimethylcyclohexylamine, etc.; hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, and the like; phosphorus compounds such as triphenylphosphine and the like; and pyridine compounds such as 2-bromopyridine and the like. Furthermore, as commercially available catalysts, there may be mentioned, for example, 2MZ-a, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (product name of imidazole-based compound) manufactured by Shikoku Kasei Kogyo co., ltd; U-CAT3503N, UCAT3502T (product name of blocked isocyanate of dimethylamine) manufactured by San-Apro Ltd; DBU, DBN, U-CATSA102, U-CAT5002 (dicycloamidine compound and salts thereof); etc.
The catalyst may be present in an amount of 0.001 to 10 wt%, 0.01 to 5 wt%, or 0.1 to 1 wt% based on 100 wt% of the total curable composition. If the content of the catalyst is too much, there is a problem in that the curing speed may be increased and thus the storage stability of the composition may be deteriorated, whereas if the content of the catalyst is too little, there is a problem in that the curing speed may be lowered and thus the heat curing process may be lengthened.
In addition, the curable composition may further contain other additives for imparting a specific function to the display substrate in the technical field to which the present application pertains, such as UV absorbers, bluing agents, pigments, and the like.
According to another embodiment of the present application, there is provided an optical material comprising: episulfide compounds and sulfur-containing polymer compounds.
The description above regarding the curable composition applies to the episulfide compound, the sulfur-containing polymer compound, and the sulfur particles, selenium disulfide, the catalyst, and other additives that may be further contained in the optical material.
Such optical materials may be prepared by curing the curable compositions described above. Specifically, the above curable composition or a homogeneous composition containing the curable composition and various additives is prepared, and the composition may be injected into a mold made of glass, metal, or polymer resin, etc. combined with a resin gasket, and heated and cured. Wherein, in order to facilitate removal of the finally prepared resin after molding, the mold may be treated with a release agent in advance, or a release agent may also be added to the above composition before use.
The curing temperature may vary depending on the kind and content of the compound used, etc., but may be generally carried out at about 50 ℃ to about 120 ℃, or about 60 ℃ to about 100 ℃, and the curing time may be about 0.1 hour to about 72 hours, or about 0.5 hour to about 24 hours.
The curing reaction may be carried out by combining the following processes: a process of maintaining the predetermined polymerization temperature for a certain time, a temperature increasing process, a temperature decreasing process, etc., as described above, and after the end of the reaction, a post-treatment may be performed at about 50 ℃ to about 150 ℃, or about 80 ℃ to about 120 ℃ for about 10 minutes to about 3 hours to prevent deformation.
The optical material released after polymerization may be configured with various functions by a subsequent process of dyeing, coating, or the like.
The refractive index of the optical material according to another embodiment may be 1.710 or more, 1.715 to 1.850, or 1.720 to 1.800 as measured at a wavelength of 500nm or more and 750nm or less, 550nm or more and 700nm or less, 600nm or more and 650nm or less, or 632.8 nm.
Further, the optical material may have a very high transmittance, specifically, a transmittance value of 75% or more, 77% or more, 80% to 99%, or 85% to 99% when the thickness is 1mm as measured according to JIS K7361.
Further, the optical material may have a very low haze value, specifically, a haze value of 35% or less, 33% or less, 31% or less, 25% or less, 20% or less, 10% to 1% as measured according to JIS K7136 when the thickness is 1mm.
Further, the glass transition temperature of the optical material may be 65 ℃ or more, 67 ℃ or more, 68 ℃ or more, 70 ℃ to 99 ℃, or 72 ℃ to 99 ℃.
Further, the Yellowness Index (YI) of the optical material may be 0.1 to 50, 1 to 40, 1 to 35, 1 to 20, 1 to 15, or 1 to 10.
The optical material according to another embodiment may be contained in a wearable device, and in particular, it may be used in place of glass or tempered glass for a lens of a wearable device.
That is, the optical material has a high refractive index equivalent to that of glass, is lighter than glass or tempered glass, has excellent optical and mechanical characteristics such as hardness and strength, and has a high glass transition temperature, and thus, can be used as a lens of a wearable device such as an augmented reality device or a virtual reality device that can be heated.
Advantageous effects
According to the present disclosure, there are provided a curable composition for forming a high refractive index optical material which is lighter than glass or tempered glass or the like used in existing lenses, has excellent strength and hardness, can realize various colors, can realize a high refractive index, has low haze and yellowness index values, and thus has excellent optical characteristics, and has a high glass transition temperature, and thus is less deformed, and an optical material including the same.
Detailed Description
Hereinafter, the actions and effects of the present application will be described more specifically with reference to specific embodiments of the present disclosure. However, these examples are presented merely as illustrations of the application and the scope of the claims of the application is not determined thereby.
Example 1
60mg of the following 50A (n is 10, weight average molecular weight: 2,500), 948mg of an episulfide compound (70A below), 48mg of selenium sulfide particles (SeS) 2 Particle size: 50 μm), 144mg sulfur particles (S) 8 Particle size: 50 μm), 4mg or less of the catalyst (hereinafter, C1), and the mixed solution was filtered using a glass filter having a pore size of 0.45 μm. Then, a glass slide having a thickness of 1mm was placed on each side of an LCD glass having a width of 10cm and a height of 10cm, and about 1g of the above mixed solution was applied on the center of the LCD glass, which was then covered with another LCD glass, thereby preparing a mold. Placing it in an oven and curing at about 60 DEG CAbout 12 hours. After removal from the oven, the LCD glass was removed to obtain a plastic specimen as a flat optical material. The thickness of the plastic specimen was about 1mm when measured using a thickness gauge (model: ID-C112 XBS) manufactured by Mitutoyo corporation.
Examples 2 to 7
A curable composition and an optical material as a cured product thereof were prepared in the same manner as in example 1 except that the compounds and contents shown in the following table 1 were used for the sulfur-containing compound, episulfide compound, selenium sulfide particle, sulfur particle and catalyst.
Comparative example 1
1,000mg of sulfur particles were added to a 5ml vial and stirred at 130 ℃ until completely dissolved. After all the sulfur was dissolved 538mg of Divinylbenzene (DVB) was added and the mixture was stirred at 130 ℃ for 150 minutes. Then, the mixed solution was dropped into a simple mold, solidified at a temperature of 130℃for 12 hours, and cooled at room temperature for 1 hour to prepare a plastic specimen having a thickness of about 1mm.
Comparative examples 2 to 4
A curable composition and an optical member as a cured product thereof were prepared in the same manner as in example 1 except that the compounds and contents shown in the following table 1 were used for the episulfide compound, selenium sulfide particles, sulfur particles and catalyst. Meanwhile, 70B used in comparative examples 2 to 4 is as follows.
TABLE l
Physical property assessment
1. Evaluation of transmittance, haze and yellowness index
For each of the optical materials of examples and comparative examples, NDH-5000 manufactured by Nippon Denshoku Industries Co.LTD was used, transmittance (JIS K7361) and haze (JIS K7136) were measured in the thickness direction of the cured product based on a standard thickness of 1mm, and the results are shown in Table 2 below.
Further, for each sample, the yellowness index was measured using a colorimeter, and the results are shown in table 2 below.
2. Measurement of glass transition temperature (Tg)
For each of the optical materials of examples and comparative examples, the glass transition temperature was measured using a Differential Scanning Calorimeter (DSC) manufactured by TA Instrument inc, and the results are shown in table 2 below.
3. Refractive index measurement
For each of the optical materials of examples and comparative examples, refractive index values were measured at a wavelength of 632.8nm using a SPA-4000 prism coupler manufactured by Sairon Technology, and the results are shown in table 2 below.
TABLE 2
Referring to table 2, it was determined that the samples including the compositions according to the embodiments of the present disclosure exhibited not only excellent optical characteristics, including a high glass transition temperature (Tg) and a refractive index of 1.7261 or more, but also a high transmittance of 79.2% or more, a low haze of 30.7% or less, and a low yellowness index of 14.5 or less.
On the other hand, comparative example 1 in which the sulfur-containing polymer compound of the present disclosure was not used was determined to have significantly lower transmittance and significantly higher yellowness index and haze compared with examples, and thus optical characteristics were poor.
Further, comparative examples 2 to 4 in which the thiol group-containing compound (70B) was used instead of the sulfur-containing polymer of the present disclosure were determined to have lower refractive indices and significantly lower glass transition temperatures than the examples.
4. Assessment of refractive index Change amount
For the optical materials of examples 4 and 8 and comparative example 1, accurate refractive indices were measured using prism couplers.
Specifically, the refractive index of the optical material was measured over time at room temperature, and the results are shown in table 3 below. In addition, the difference between the maximum refractive index and the minimum refractive index is represented by ΔRI, and the average refractive index value is represented by RI Average of And (3) representing.
TABLE 3
From table 3, it was determined that in examples 4 and 8, even when having a high average refractive index of 1.7309 or more, the refractive index hardly changed with time. Meanwhile, it was determined that in comparative example 1, the refractive index significantly changed with time.
Claims (13)
1. A curable composition for forming a high refractive index optical material comprising an episulfide compound and a sulfur-containing polymer compound,
wherein the sulfur-containing polymer compound comprises a compound selected from the group consisting of sulfur-containing compounds n+1 (n is an integer of 1 to 20) and at least one of selenium and sulfur-containing repeating units.
2. The curable composition of claim 1, wherein:
the sulfur-containing polymer compound comprises a repeating unit represented by the following chemical formula 1 or 2:
[ chemical formula 1]
In the chemical formula 1 described above, a compound having the formula,
R 1 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; substituted or unsubstituted cycloalkylene having 3 to 40 carbon atoms; a substituted or unsubstituted arylene group having 5 to 30 carbon atoms; a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, comprising at least one of an oxygen (O), nitrogen (N), and sulfur (S) atom; -R a OR b -；-R c COOR d -；-R e SO 2 R f -or-R g SOR h -，R a To R h Each independently is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 5 to 30 carbon atoms,
n is an integer of 1 to 20,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
R 2 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; substituted or unsubstituted cycloalkylene having 3 to 40 carbon atoms; a substituted or unsubstituted arylene group having 5 to 30 carbon atoms; a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, comprising at least one of an oxygen (O), nitrogen (N), and sulfur (S) atom; -R a OR b -；-R c COOR d -；-R e SO 2 R f -or-R g SOR h -，R a To R h Each independently is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 5 to 30 carbon atoms,
a and b are each independently an integer of 0 or more and 10 or less, and
a+b is an integer of 1 or more and 20 or less.
3. The curable composition of claim 2, wherein:
R 1 and R is 2 Each independently is methylene, ethylene, propylene, isopropylene, cyclohexylene, cycloheptylene, phenylene, methylphenylene, ethylphenylene, methoxyphenylene, or ethoxyphenylene.
4. The curable composition of claim 1, wherein:
the sulfur-containing polymer compound comprises any one of the following repeating units selected from:
5. the curable composition of claim 1, wherein:
the weight ratio of the sulfur-containing polymer compound to the episulfide compound is 1:2 to 1:30.
6. The curable composition of claim 1, wherein:
the curable composition for forming a high refractive index optical material further comprises sulfur (S 8 ) Granules, selenium sulphide (SeS) 2 ) Particles or mixtures thereof.
7. The curable composition of claim 6 wherein:
said sulfur (S) 8 ) The particles have a particle diameter of 1 μm to 200 μm, and
the selenium sulphide (SeS) 2 ) The particle size of the particles is 1 μm to 200. Mu.m.
8. The curable composition of claim 1, wherein:
the episulfide compound is represented by the following chemical formula 3:
[ chemical formula 3]
In the chemical formula 3, the chemical formula is shown in the drawing,
R 3 and R is 4 Each independently is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R 5 and R is 6 Each independently is a single bond or an alkylene group having 1 to 10 carbon atoms,
a is an integer from 0 to 4, and
b is an integer from 0 to 6.
9. The curable composition of claim 8 wherein:
the episulfide compound includes at least one selected from the group consisting of: bis (β -cyclopropyl) sulfide, bis (β -cyclopropyl) disulfide, bis (β -cyclopropyl thio) methane, 1, 2-bis (β -cyclopropyl thio) ethane, 1, 3-bis (β -cyclopropyl thio) propane, and 1, 4-bis (β -cyclopropyl thio) butane.
10. An optical material comprising an episulfide compound and a sulfur-containing polymer compound,
wherein the sulfur-containing polymer compound comprises a compound selected from the group consisting of sulfur-containing compounds n+1 (n is an integer of 1 to 20) and at least one of selenium and sulfur-containing repeating units.
11. The optical material of claim 10, wherein:
the optical material has a glass transition temperature of 65 ℃ or higher.
12. The optical material of claim 10, wherein:
the optical material has a refractive index of 1.710 or more measured at a wavelength of 500nm or more and 750nm or less.
13. The optical material of claim 10, wherein:
the optical material has a Yellowness Index (YI) of 0.1 to 50.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0031499 | 2021-03-10 | ||
| KR10-2022-0026941 | 2022-03-02 | ||
| KR1020220026941A KR20220127151A (en) | 2021-03-10 | 2022-03-02 | Curable composition and optical material |
| PCT/KR2022/003257 WO2022191574A1 (en) | 2021-03-10 | 2022-03-08 | Curable composition and optical member comprising same |
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| CN116745350A true CN116745350A (en) | 2023-09-12 |
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| CN202280008605.8A Pending CN116745350A (en) | 2021-03-10 | 2022-03-08 | Curable composition and optical material comprising the same |
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