JPWO2009119576A1 - Photosensitive composition for forgery prevention hologram and forgery prevention hologram medium - Google Patents
Photosensitive composition for forgery prevention hologram and forgery prevention hologram medium Download PDFInfo
- Publication number
- JPWO2009119576A1 JPWO2009119576A1 JP2010505671A JP2010505671A JPWO2009119576A1 JP WO2009119576 A1 JPWO2009119576 A1 JP WO2009119576A1 JP 2010505671 A JP2010505671 A JP 2010505671A JP 2010505671 A JP2010505671 A JP 2010505671A JP WO2009119576 A1 JPWO2009119576 A1 JP WO2009119576A1
- Authority
- JP
- Japan
- Prior art keywords
- hologram
- compound
- fine particles
- photosensitive composition
- polymerizable compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 230000002265 prevention Effects 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 131
- 239000010419 fine particle Substances 0.000 claims abstract description 84
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 6
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000004075 alteration Effects 0.000 abstract description 2
- -1 ester compound Chemical class 0.000 description 92
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 59
- 239000000377 silicon dioxide Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000004593 Epoxy Chemical group 0.000 description 7
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- ALVGSDOIXRPZFH-UHFFFAOYSA-N [(1-diazonioimino-3,4-dioxonaphthalen-2-ylidene)hydrazinylidene]azanide Chemical compound C1=CC=C2C(=N[N+]#N)C(=NN=[N-])C(=O)C(=O)C2=C1 ALVGSDOIXRPZFH-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000003566 oxetanyl group Chemical group 0.000 description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000004438 BET method Methods 0.000 description 5
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- 125000006839 xylylene group Chemical group 0.000 description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 3
- 150000002440 hydroxy compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SANIRTQDABNCHF-UHFFFAOYSA-N 7-(diethylamino)-3-[7-(diethylamino)-2-oxochromene-3-carbonyl]chromen-2-one Chemical compound C1=C(N(CC)CC)C=C2OC(=O)C(C(=O)C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=CC2=C1 SANIRTQDABNCHF-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000004038 photonic crystal Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- POTYORUTRLSAGZ-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) prop-2-enoate Chemical compound ClCC(O)COC(=O)C=C POTYORUTRLSAGZ-UHFFFAOYSA-N 0.000 description 1
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- NPENBPVOAXERED-UHFFFAOYSA-N (4-benzoylphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 NPENBPVOAXERED-UHFFFAOYSA-N 0.000 description 1
- JMMVHMOAIMOMOF-UHFFFAOYSA-N (4-prop-2-enoyloxyphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=C(OC(=O)C=C)C=C1 JMMVHMOAIMOMOF-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-UHFFFAOYSA-N 0.000 description 1
- FSAONUPVUVBQHL-UHFFFAOYSA-N 1,3-bis(4-azidophenyl)prop-2-en-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=CC(=O)C1=CC=C(N=[N+]=[N-])C=C1 FSAONUPVUVBQHL-UHFFFAOYSA-N 0.000 description 1
- OQZQDGSYKKFLTE-UHFFFAOYSA-N 1-(4-azidophenyl)-3-phenylprop-2-en-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C(=O)C=CC1=CC=CC=C1 OQZQDGSYKKFLTE-UHFFFAOYSA-N 0.000 description 1
- HYRIDYFBEXCCIA-UHFFFAOYSA-N 1-(4-azidophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N=[N+]=[N-])C=C1 HYRIDYFBEXCCIA-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- HWEONUWVYWIJPF-OWOJBTEDSA-N 1-azido-4-[(e)-2-(4-azidophenyl)ethenyl]benzene Chemical compound C1=CC(N=[N+]=[N-])=CC=C1\C=C\C1=CC=C(N=[N+]=[N-])C=C1 HWEONUWVYWIJPF-OWOJBTEDSA-N 0.000 description 1
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- VYMSWGOFSKMMCE-UHFFFAOYSA-N 10-butyl-2-chloroacridin-9-one Chemical compound ClC1=CC=C2N(CCCC)C3=CC=CC=C3C(=O)C2=C1 VYMSWGOFSKMMCE-UHFFFAOYSA-N 0.000 description 1
- 229940117900 2,2-bis(4-glycidyloxyphenyl)propane Drugs 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- MLIWQXBKMZNZNF-UHFFFAOYSA-N 2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1C(=CC=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-UHFFFAOYSA-N 0.000 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical class C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- MWSPXTHIGURRBI-UHFFFAOYSA-N 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-bis(3,4,5-trimethoxyphenyl)imidazol-2-yl]-4,5-bis(3,4,5-trimethoxyphenyl)imidazole Chemical compound COC1=C(OC)C(OC)=CC(C=2C(=NC(N=2)(C=2C(=CC=CC=2)Cl)N2C(=C(N=C2C=2C(=CC=CC=2)Cl)C=2C=C(OC)C(OC)=C(OC)C=2)C=2C=C(OC)C(OC)=C(OC)C=2)C=2C=C(OC)C(OC)=C(OC)C=2)=C1 MWSPXTHIGURRBI-UHFFFAOYSA-N 0.000 description 1
- MHDULSOPQSUKBQ-UHFFFAOYSA-N 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MHDULSOPQSUKBQ-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- FDZMLNCJBYFJBH-UHFFFAOYSA-N 2-[(2,3-dibromophenoxy)methyl]oxirane Chemical compound BrC1=CC=CC(OCC2OC2)=C1Br FDZMLNCJBYFJBH-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- LYLVMFZJHCGZOR-UHFFFAOYSA-N 2-[2-[2-[2-[1-(2-hydroxyethyl)-4,5-dihydroimidazol-2-yl]propan-2-yldiazenyl]propan-2-yl]-4,5-dihydroimidazol-1-yl]ethanol;hydrochloride Chemical compound Cl.N=1CCN(CCO)C=1C(C)(C)N=NC(C)(C)C1=NCCN1CCO LYLVMFZJHCGZOR-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- VFYHHERJNPKXIX-UHFFFAOYSA-N 3,3-diethyloxetane Chemical compound CCC1(CC)COC1 VFYHHERJNPKXIX-UHFFFAOYSA-N 0.000 description 1
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 1
- HPINXYMPRYQBGF-UHFFFAOYSA-N 3-ethyl-3-[[3-[(3-ethyloxetan-3-yl)methoxy]-2,2-bis[(3-ethyloxetan-3-yl)methoxymethyl]propoxy]methyl]oxetane Chemical compound C1OCC1(CC)COCC(COCC1(CC)COC1)(COCC1(CC)COC1)COCC1(CC)COC1 HPINXYMPRYQBGF-UHFFFAOYSA-N 0.000 description 1
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- IXAUCVOJRVFRBJ-UHFFFAOYSA-N 4-(trichloromethyl)triazine Chemical class ClC(Cl)(Cl)C1=CC=NN=N1 IXAUCVOJRVFRBJ-UHFFFAOYSA-N 0.000 description 1
- SDJOUGYEUFYPLL-UHFFFAOYSA-N 4-azidobenzaldehyde Chemical compound [N-]=[N+]=NC1=CC=C(C=O)C=C1 SDJOUGYEUFYPLL-UHFFFAOYSA-N 0.000 description 1
- PQXPAFTXDVNANI-UHFFFAOYSA-N 4-azidobenzoic acid Chemical compound OC(=O)C1=CC=C(N=[N+]=[N-])C=C1 PQXPAFTXDVNANI-UHFFFAOYSA-N 0.000 description 1
- OHIMQTXUHLZGPH-UHFFFAOYSA-N 4-diazo-n,n-dimethylcyclohexa-1,5-dien-1-amine;hydrochloride Chemical compound Cl.CN(C)C1=CCC(=[N+]=[N-])C=C1 OHIMQTXUHLZGPH-UHFFFAOYSA-N 0.000 description 1
- ULPDSNLBZMHGPI-UHFFFAOYSA-N 4-methyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C)CCC2OC21 ULPDSNLBZMHGPI-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- KYUGRJLPPCDMOH-UHFFFAOYSA-N 6-(7-oxabicyclo[4.1.0]heptan-3-ylmethoxy)-6-oxohexanoic acid Chemical compound C1C(COC(=O)CCCCC(=O)O)CCC2OC21 KYUGRJLPPCDMOH-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 1
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- RUDMETXSMVJPSS-UHFFFAOYSA-N C1=CC=CC1[Ti](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1C=CC=C1 Chemical compound C1=CC=CC1[Ti](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1C=CC=C1 RUDMETXSMVJPSS-UHFFFAOYSA-N 0.000 description 1
- HIYZSAWILSSWMJ-UHFFFAOYSA-N CC1(C=CC=C1)[Ti](C1=C(C(=C(C(=C1F)F)F)F)F)(C1=C(C(=C(C(=C1F)F)F)F)F)C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Ti](C1=C(C(=C(C(=C1F)F)F)F)F)(C1=C(C(=C(C(=C1F)F)F)F)F)C1(C=CC=C1)C HIYZSAWILSSWMJ-UHFFFAOYSA-N 0.000 description 1
- XTWDIHZQOPTRRD-UHFFFAOYSA-N CC1(C=CC=C1)[Ti](C1=C(C=CC=C1F)F)(C1=C(C=CC=C1F)F)C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Ti](C1=C(C=CC=C1F)F)(C1=C(C=CC=C1F)F)C1(C=CC=C1)C XTWDIHZQOPTRRD-UHFFFAOYSA-N 0.000 description 1
- ZBZXIGONWYKEMZ-UHFFFAOYSA-N CCO[Ti] Chemical compound CCO[Ti] ZBZXIGONWYKEMZ-UHFFFAOYSA-N 0.000 description 1
- FLTYUJMFMHOICO-UHFFFAOYSA-N CO[Ti] Chemical compound CO[Ti] FLTYUJMFMHOICO-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UQCCYKOPWCMQGP-UHFFFAOYSA-N FC1=CC(F)=C(F)C([Ti]C2=C(F)C(F)=CC(F)=C2F)=C1F Chemical compound FC1=CC(F)=C(F)C([Ti]C2=C(F)C(F)=CC(F)=C2F)=C1F UQCCYKOPWCMQGP-UHFFFAOYSA-N 0.000 description 1
- SLXAQTAKXHEFEK-UHFFFAOYSA-N Fc1c(F)c(F)c(c(F)c1F)[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)c(F)c(F)c(F)c1F Chemical compound Fc1c(F)c(F)c(c(F)c1F)[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)c(F)c(F)c(F)c1F SLXAQTAKXHEFEK-UHFFFAOYSA-N 0.000 description 1
- GDZYQNNNCWVNRM-UHFFFAOYSA-N Fc1cc(F)c(F)c(c1F)[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)c(F)cc(F)c1F Chemical compound Fc1cc(F)c(F)c(c1F)[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)c(F)cc(F)c1F GDZYQNNNCWVNRM-UHFFFAOYSA-N 0.000 description 1
- OXKJNFIZXAAMQB-UHFFFAOYSA-N Fc1cc(F)c(c(F)c1)[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)cc(F)cc1F Chemical compound Fc1cc(F)c(c(F)c1)[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)cc(F)cc1F OXKJNFIZXAAMQB-UHFFFAOYSA-N 0.000 description 1
- HTOTWKSXJYHNJF-UHFFFAOYSA-N Fc1ccc(c(F)c1)[Ti](C1C=CC=C1)(C1C=CC=C1)c1ccc(F)cc1F Chemical compound Fc1ccc(c(F)c1)[Ti](C1C=CC=C1)(C1C=CC=C1)c1ccc(F)cc1F HTOTWKSXJYHNJF-UHFFFAOYSA-N 0.000 description 1
- NINDQYVXCNRUFR-UHFFFAOYSA-N Fc1cccc(F)c1[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)cccc1F Chemical compound Fc1cccc(F)c1[Ti](C1C=CC=C1)(C1C=CC=C1)c1c(F)cccc1F NINDQYVXCNRUFR-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- HSZUHSXXAOWGQY-UHFFFAOYSA-N [2-methyl-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)COC(=O)C=C HSZUHSXXAOWGQY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- PIPBVABVQJZSAB-UHFFFAOYSA-N bis(ethenyl) benzene-1,2-dicarboxylate Chemical group C=COC(=O)C1=CC=CC=C1C(=O)OC=C PIPBVABVQJZSAB-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- OSQDBLDITWKSLT-UHFFFAOYSA-N bis[2-(1,4,5,6-tetrahydropyrimidin-2-yl)propan-2-yl]diazene;hydrochloride Chemical compound Cl.N=1CCCNC=1C(C)(C)N=NC(C)(C)C1=NCCCN1 OSQDBLDITWKSLT-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 1
- WYFGBFHRZGNGAU-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;hydrochloride Chemical compound Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 WYFGBFHRZGNGAU-UHFFFAOYSA-N 0.000 description 1
- ZJZDQLCRNFFYFY-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;sulfuric acid Chemical compound OS(O)(=O)=O.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 ZJZDQLCRNFFYFY-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- XKLWATAZDMHTSH-UHFFFAOYSA-L cyclopentane;dichlorotitanium Chemical compound Cl[Ti]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 XKLWATAZDMHTSH-UHFFFAOYSA-L 0.000 description 1
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- IQIJRJNHZYUQSD-UHFFFAOYSA-N ethenyl(phenyl)diazene Chemical compound C=CN=NC1=CC=CC=C1 IQIJRJNHZYUQSD-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- JPZYWLWSLROXQG-UHFFFAOYSA-N ethyl 2-prop-2-enoylperoxycarbonylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OOC(=O)C=C JPZYWLWSLROXQG-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229960004667 ethyl cellulose Drugs 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- SJNXJRVDSTZUFB-UHFFFAOYSA-N naphthalen-2-yl(phenyl)methanone Chemical compound C=1C=C2C=CC=CC2=CC=1C(=O)C1=CC=CC=C1 SJNXJRVDSTZUFB-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- WUKMCKCDYKBLBG-UHFFFAOYSA-N tris(4-methoxyphenyl)sulfanium Chemical compound C1=CC(OC)=CC=C1[S+](C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 WUKMCKCDYKBLBG-UHFFFAOYSA-N 0.000 description 1
- QKFJVDSYTSWPII-UHFFFAOYSA-N tris(4-methylphenyl)sulfanium Chemical compound C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 QKFJVDSYTSWPII-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/001—Phase modulating patterns, e.g. refractive index patterns
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/0005—Adaptation of holography to specific applications
- G03H1/0011—Adaptation of holography to specific applications for security or authentication
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/328—Diffraction gratings; Holograms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
- G03H2001/0264—Organic recording material
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2250/00—Laminate comprising a hologram layer
- G03H2250/43—One layer having dispersed particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/12—Photopolymer
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Computer Security & Cryptography (AREA)
- Holo Graphy (AREA)
- Credit Cards Or The Like (AREA)
Abstract
【課題】干渉パターンを記録層内部の重合物と無機微粒子間の屈折率差で記録する体積ホログラム向けの感光性組成物であって、特にその種のホログラム記録の偽造変造を有効に防止すべく改良された偽造防止ホログラム用感光性組成物及びそれから得られる偽造防止ホログラム媒体の提供。【解決手段】(a)25℃において粘度が5mPa・s以上10,000mPa・s以下である液状重合性化合物、(b)光重合開始剤、(c)無機微粒子を含み、前記重合性化合物(a)と無機微粒子(c)の屈折率差が0.005以上0.1以下である偽造防止ホログラム用感光性組成物。【選択図】なしA photosensitive composition for a volume hologram that records an interference pattern with a refractive index difference between a polymer inside a recording layer and inorganic fine particles, and in particular to effectively prevent forgery and alteration of that type of hologram recording. An improved anti-counterfeit hologram photosensitive composition and an anti-counterfeit hologram medium obtained therefrom. (A) A liquid polymerizable compound having a viscosity of 5 mPa · s or more and 10,000 mPa · s or less at 25 ° C., (b) a photopolymerization initiator, (c) inorganic fine particles, and the polymerizable compound ( A photosensitive composition for anti-counterfeit hologram, wherein a difference in refractive index between a) and inorganic fine particles (c) is 0.005 or more and 0.1 or less. [Selection figure] None
Description
本発明は、偽造防止ホログラム用感光性組成物及び偽造防止ホログラム媒体に関する。詳細には、干渉パターンを記録層内部の重合物と無機微粒子間の屈折率差で記録する体積ホログラム向けの感光性組成物であって、特にその種のホログラム記録の偽造変造を有効に防止すべく改良された偽造防止ホログラム用感光性組成物及びそれから得られる偽造防止ホログラム媒体に関する。 The present invention relates to a photosensitive composition for anti-counterfeit hologram and an anti-counterfeit hologram medium. Specifically, it is a photosensitive composition for volume holograms that records an interference pattern with a refractive index difference between a polymer inside the recording layer and inorganic fine particles, and effectively prevents counterfeiting and alteration of that type of hologram recording. The present invention relates to a forgery-preventing hologram photosensitive composition and a forgery-preventing hologram medium obtained therefrom.
ホログラフィック回折格子(ホログラム)は光の明暗(干渉)パターンを感光材料等に屈折率あるいは吸収率のパターンとして記録したものであり、光波の波面を記録・操作できることから回折光学素子、ホログラフィック光メモリ、狭帯域波長フィルター、フォトニック結晶、光導波路結合器、光インターコネクション、立体画像ディスプレイ、ヘッドアップディスプレイなど、フォトニクスや情報ディスプレイ等の幅広い分野において数多くの応用が報告されている。
従来、セキュリティ分野への応用では、クレジットカード等で見られる表面レリーフ型(エンボス型)ホログラムの使用が主流であるが、近年、ホログラム記録材料の入手が容易になったことや印刷機が普及したことでホログラム記録の偽造品の製造が容易となり、偽造ホログラム記録体が高級ブランド品や部品、著作権を伴うDVDやCDなどに貼られて市場に出回っていることが問題になっている。そのため、偽造品の発生防止に有効なICチップ等の開発も進んでいるが、ICチップから情報を読み出す装置が必要であり、また装置導入による相当のコスト負担もあることから、その場で視認判断できる安価な次世代の偽造防止ラベルの提供が要求されている。ここで体積ホログラムはICチップと異なりその場で視認判断が可能であり、またエンボス型ホログラムと異なりレーザ等高度な生産設備や作成技術が必要とされるため、偽造が困難であり、偽造防止ラベルの用途に有利である。A holographic diffraction grating (hologram) is a light-dark (interference) pattern recorded on a photosensitive material as a pattern of refractive index or absorptivity. Since the wavefront of a light wave can be recorded and manipulated, it is a diffractive optical element, holographic optical memory. Many applications have been reported in a wide range of fields such as photonics and information displays, such as narrowband wavelength filters, photonic crystals, optical waveguide couplers, optical interconnections, stereoscopic image displays, and head-up displays.
Conventionally, the use of surface relief type (embossed type) holograms found on credit cards and the like has been the mainstream for security applications, but in recent years it has become easier to obtain hologram recording materials and printers have become popular. This makes it easy to manufacture counterfeit hologram recordings, and it has become a problem that counterfeit hologram recording bodies are put on high-end brand products and parts, DVDs and CDs with copyrights, and the like. For this reason, development of IC chips and the like effective in preventing the generation of counterfeit products is progressing, but a device that reads information from the IC chip is necessary, and there is a considerable cost burden due to the introduction of the device. There is a demand for providing a cheap next-generation anti-counterfeit label that can be judged. Here, volume holograms can be visually recognized on the spot unlike IC chips, and unlike embossed holograms, advanced production equipment such as lasers and production techniques are required, so counterfeiting is difficult. This is advantageous for use.
一般に偽造防止のために使用されるホログラム層は、それを剥がそうとすると容易に破壊され、それにより画像の貼り替え等の偽造を有効に防止することができるようにするために、高い脆弱性並びに透明性を持つことが求められる。
偽造防止ホログラムに関する提案として、例えば特許文献1及び2には、2種の重合物の屈折率差を利用して光干渉パターンを記録する方式の体積ホログラム記録用感光性組成物において、体積ホログラム層に脆弱性を与えるための微粒子をさらに含有した組成物が記載されている。
一方、これら特許文献1及び2に記載されるホログラム記録とは異なる簡単な方式により体積ホログラムを記録する技術として、特許文献3には、1種の重合性モノマーと無機微粒子を含み、重合時に無機微粒子を移動させて生じる重合体と無機微粒子との屈折率差を利用して光干渉パターンを記録する方式の体積ホログラム記録用感光性組成物が記載されている。
As a proposal for forgery prevention holograms, for example, Patent Documents 1 and 2 disclose a volume hologram layer in a volume hologram recording photosensitive composition that records a light interference pattern using a difference in refractive index between two kinds of polymers. A composition further containing fine particles for imparting brittleness is described.
On the other hand, as a technique for recording a volume hologram by a simple method different from the hologram recording described in Patent Documents 1 and 2, Patent Document 3 includes one kind of polymerizable monomer and inorganic fine particles, and is inorganic during polymerization. There is described a photosensitive composition for volume hologram recording in which a light interference pattern is recorded using a difference in refractive index between a polymer produced by moving fine particles and inorganic fine particles.
しかし、上記特許文献1及び2に記載の感光性組成物は、回折格子形成に関与しない微粒子を含有するものであるため、ホログラムの屈折率変調(ダイナミックレンジ)が低下するという問題がある。
一方、特許文献3には、その種のホログラム記録において偽造防止のための脆弱性及び透明性の改良について記載も示唆も為されていない。しかも、特許文献3に記載の感光性組成物は、露光後にホログラム層が白濁化し、明瞭なホログラム記録が得られないことがある。However, since the photosensitive compositions described in Patent Documents 1 and 2 contain fine particles that do not participate in diffraction grating formation, there is a problem that the refractive index modulation (dynamic range) of the hologram is reduced.
On the other hand, Patent Document 3 neither describes nor suggests improvement of vulnerability and transparency for preventing forgery in such hologram recording. Moreover, in the photosensitive composition described in Patent Document 3, the hologram layer becomes clouded after exposure, and clear hologram recording may not be obtained.
そこで本発明者らは、鋭意検討した結果、1種の重合性モノマーと無機微粒子とを含み、重合時、該微粒子の移動により生じる屈折率差を利用して干渉パターンを記録する方式の体積ホログラム記録用感光性組成物において、適度な粘度の液状重合性化合物、光重合開始剤、無機微粒子を含み、前記重合性化合物と無機微粒子の屈折率差を調節した感光性組成物を用いることによって、形成するホログラムが十分に高い回折効率を有するだけでなく、該組成物から得られるホログラム層が偽造防止用として必要な高い脆弱性及び透明性を有することを見出し、本発明を完成した。
すなわち、本発明は、
第1観点として、(a)25℃において粘度が5mPa・s以上10,000mPa・s以下である液状重合性化合物、(b)光重合開始剤、(c)無機微粒子を含み、前記重合性化合物(a)と無機微粒子(c)の屈折率差が0.005以上0.1以下である偽造防止ホログラム用感光性組成物に関する。
第2観点として、前記無機微粒子(c)の平均粒径が1nm以上、100nm以下である、第1観点に記載の偽造防止ホログラム用感光性組成物に関する。
第3観点として、前記重合性化合物(a)、光重合開始剤(b)及び無機微粒子(c)の合計体積に占める無機微粒子(c)の体積の割合が3体積%乃至50体積%である、第1観点又は第2観点に記載の偽造防止ホログラム用感光性組成物に関する。
第4観点として、前記重合性化合物(a)が、エチレン性不飽和結合を有する重合性化合物である、第1観点乃至第3観点のうちいずれか1つの偽造防止ホログラム用感光性組成物に関する。
第5観点として、前記重合性化合物(a)が、分子内に平均で3個以上20個以下の炭素原子数2乃至6のオキシアルキレン基を有する重合性化合物である、第1観点乃至第4観点のうちいずれか1つの偽造防止ホログラム用感光性組成物に関する。
第6観点として、前記重合性化合物(a)が、カチオン重合性の部位を有する化合物であり、前記光重合開始剤が光酸発生剤である、第1観点、第2観点、第3観点及び第5観点のうちいずれか1つの偽造防止ホログラム用感光性組成物に関する。
第7観点として、第1観点乃至第6観点のうちいずれか1つの感光性組成物から得られる偽造防止ホログラム層に関する。
第8観点として、第7観点の偽造防止ホログラム層が支持体上に形成され、該ホログラム層が保護材で覆われている偽造防止ホログラム媒体に関する。Accordingly, the present inventors have intensively studied and, as a result, a volume hologram of a system that includes one kind of polymerizable monomer and inorganic fine particles, and records an interference pattern by utilizing a refractive index difference caused by movement of the fine particles during polymerization. In the photosensitive composition for recording, by using a photosensitive composition containing a liquid polymerizable compound having an appropriate viscosity, a photopolymerization initiator, inorganic fine particles, and adjusting the refractive index difference between the polymerizable compound and the inorganic fine particles, The inventors have found that the hologram to be formed not only has a sufficiently high diffraction efficiency, but also that the hologram layer obtained from the composition has high brittleness and transparency necessary for anti-counterfeiting, thereby completing the present invention.
That is, the present invention
As a first aspect, the polymerizable compound includes (a) a liquid polymerizable compound having a viscosity of 5 mPa · s to 10,000 mPa · s at 25 ° C., (b) a photopolymerization initiator, and (c) inorganic fine particles. The present invention relates to a photosensitive composition for anti-counterfeit hologram, in which the difference in refractive index between (a) and inorganic fine particles (c) is 0.005 or more and 0.1 or less.
As a second aspect, the present invention relates to the anti-counterfeit hologram photosensitive composition according to the first aspect, wherein the inorganic fine particles (c) have an average particle size of 1 nm or more and 100 nm or less.
As a third aspect, the ratio of the volume of the inorganic fine particles (c) to the total volume of the polymerizable compound (a), the photopolymerization initiator (b) and the inorganic fine particles (c) is 3% by volume to 50% by volume. The invention relates to a forgery-preventing photosensitive composition according to the first aspect or the second aspect.
As a 4th viewpoint, the said polymeric compound (a) is related with the photosensitive composition for anti-counterfeit hologram among any one of the 1st viewpoint thru | or the 3rd viewpoint which is a polymeric compound which has an ethylenically unsaturated bond.
As a fifth aspect, the polymerizable compound (a) is a polymerizable compound having an oxyalkylene group having 2 to 6 carbon atoms having an average of 3 to 20 in the molecule. It relates to the photosensitive composition for anti-counterfeit holograms in any one of viewpoints.
As a sixth aspect, the polymerizable compound (a) is a compound having a cationic polymerizable moiety, and the photopolymerization initiator is a photoacid generator, the first aspect, the second aspect, the third aspect, and The present invention relates to any one of the fifth aspects of the photosensitive composition for anti-counterfeit hologram.
As a seventh aspect, the present invention relates to a forgery-preventing hologram layer obtained from any one of the first to sixth aspects of the photosensitive composition.
As an eighth aspect, the present invention relates to a forgery-preventing hologram medium in which the forgery-preventing hologram layer of the seventh aspect is formed on a support and the hologram layer is covered with a protective material.
本発明においては、感光性組成物が、25℃において粘度が5mPa・s以上10,000mPa・s以下である液状重合性化合物と無機微粒子とを含み、且つ、前記重合性化合物と無機微粒子の屈折率差が0.005以上0.1以下であるという構成を有する。これらの構成を有することにより、十分に高い回折効率を有するホログラムを形成することができるだけでなく、該感光性組成物から形成した偽造防止ホログラム層が偽造防止用として必要な高い脆弱性及び透明性を有するものになるという効果が得られる。さらには、重合性化合物が液状で且つ5mPa・s以上10,000mPa・s以下という粘度を有するものであるため、支持体への塗布などの操作性がよいという利点を有する他、パターン露光の際の無機微粒子の移動が円滑となり(屈折率差がより明瞭に生じるものとなり)、鮮明な画像が得られ、高感度のホログラム記録が可能となる。
従って本発明の感光性組成物又はホログラム媒体によれば、高い回折効率、高い感度、高い脆弱性及び透明性を有する偽造防止ホログラムラベルを提供することができる。
また、本発明の組成物により得られるホログラムでは、他の光学的な機能性を付与することが可能である。該ホログラムは光波の波面操作や記録を行う光学素子として、回折光学素子、ホログラフィック光メモリ、狭帯域波長フィルター、フォトニック結晶、光導波路結合器、光インターコネクション、立体画像ディスプレイ、ヘッドアップディスプレイなど、フォトニクスや情報ディスプレイ、並びにその他の幅広い分野への応用が可能である。In the present invention, the photosensitive composition contains a liquid polymerizable compound having a viscosity of 5 mPa · s to 10,000 mPa · s at 25 ° C. and inorganic fine particles, and the refractive index of the polymerizable compound and the inorganic fine particles. The ratio difference is 0.005 or more and 0.1 or less. By having these configurations, not only can a hologram having a sufficiently high diffraction efficiency be formed, but also the anti-counterfeit hologram layer formed from the photosensitive composition has high vulnerability and transparency required for anti-counterfeiting. The effect that it becomes what has is obtained. Furthermore, since the polymerizable compound is liquid and has a viscosity of 5 mPa · s or more and 10,000 mPa · s or less, it has the advantage of good operability such as application to a support, and also during pattern exposure. The inorganic fine particles can move smoothly (the difference in refractive index is more clearly generated), a clear image can be obtained, and high-sensitivity hologram recording can be performed.
Therefore, according to the photosensitive composition or hologram medium of the present invention, a forgery-preventing hologram label having high diffraction efficiency, high sensitivity, high vulnerability and transparency can be provided.
Further, the hologram obtained by the composition of the present invention can be provided with other optical functionalities. The hologram is an optical element that performs wavefront manipulation and recording of light waves, diffractive optical elements, holographic optical memories, narrowband wavelength filters, photonic crystals, optical waveguide couplers, optical interconnections, stereoscopic image displays, head-up displays, etc. It can be applied to photonics, information display, and other wide fields.
偽造防止のためには明瞭なホログラム像の形成が求められ、このためには、回折格子形成に関与しない希釈用重合性化合物を用いない材料で透明な重合体を形成し得るという観点より、液体状の重合性化合物を用いるのが望ましい。また、一般に、用いられる重合性化合物と無機微粒子との屈折率差が小さすぎると、該微粒子の移動に伴い生じる露光部と非露光部との屈折率差が殆ど無いものとなりホログラムそれ自体が形成されなくなる。逆に屈折率差が大きすぎると、透明な系の露光部と非露光部との屈折率差が相当大きなものとなり、光散乱による偽造防止ホログラム層の白濁化が目立つようになり、明瞭なホログラムの形成の点で望ましくない。また、重合性化合物の粘度が低すぎると、感光性組成物を支持体に塗布するとき、ホログラム層の形成に必要な厚さの組成物層を均一に支持体上に形成することが難しくなる。逆に重合性化合物の粘度が高すぎると、感光性組成物を支持体上に円滑且つ均一に塗布することが難しくなり、またパターン露光の際に無機微粒子の移動が阻害され、高感度のホログラム記録、鮮明なホログラム像の形成が達成されなくなる。
以上の観点より、本発明の偽造防止ホログラム用感光性組成物は、25℃において液状且つ粘度が5mPa・s以上10,000mPa・s以下という物性を有する重合性化合物及び無機微粒子を含み、且つ該重合性化合物と該無機微粒子の屈折率差が0.005以上0.1以下であるという構成を備えるものとなっている。In order to prevent counterfeiting, it is necessary to form a clear hologram image. To this end, liquids can be formed from the viewpoint that a transparent polymer can be formed with a material that does not use a polymerizable compound for dilution that does not participate in diffraction grating formation. It is desirable to use a polymerizable compound in the form of a solid. In general, if the difference in refractive index between the polymerizable compound used and the inorganic fine particles is too small, there is almost no difference in the refractive index between the exposed portion and the non-exposed portion caused by the movement of the fine particles, and the hologram itself is formed. It will not be done. On the other hand, if the difference in refractive index is too large, the difference in refractive index between the exposed and unexposed areas in the transparent system will be considerably large, and the whitening of the anti-counterfeit hologram layer due to light scattering will become conspicuous, resulting in a clear hologram. It is not desirable in terms of formation. If the viscosity of the polymerizable compound is too low, it is difficult to uniformly form a composition layer having a thickness necessary for forming a hologram layer on the support when the photosensitive composition is applied to the support. . Conversely, when the viscosity of the polymerizable compound is too high, it becomes difficult to apply the photosensitive composition smoothly and uniformly on the support, and the movement of inorganic fine particles is inhibited during pattern exposure, resulting in a highly sensitive hologram. Recording and formation of a clear hologram image cannot be achieved.
From the above viewpoints, the photosensitive composition for anti-counterfeit hologram of the present invention contains a polymerizable compound and inorganic fine particles that are liquid at 25 ° C. and have physical properties of a viscosity of 5 mPa · s to 10,000 mPa · s, and The refractive index difference between the polymerizable compound and the inorganic fine particles is 0.005 or more and 0.1 or less.
次に、本発明の感光性組成物の成分である、(a)重合性化合物、(b)光重合開始剤、(c)無機微粒子について説明する。 Next, (a) a polymerizable compound, (b) a photopolymerization initiator, and (c) inorganic fine particles that are components of the photosensitive composition of the present invention will be described.
(a)重合性化合物
本発明における重合性化合物は、25℃において粘度が5mPa・s以上10,000mPa・s以下の液状であって、光重合開始剤の作用によって重合する重合性の部位を分子内に一個以上、好ましくは一個乃至六個有する化合物であれば特に制限はない。重合性の部位としては、ラジカル重合性の部位とカチオン重合性の部位とがあり、重合性化合物が双方の部位を有するものであってもよい。
なお、本発明における重合性化合物の意味するところは、所謂高分子物質でない化合物である。従って、狭義の単量体化合物だけでなく、二量体、三量体、オリゴマーや反応性高分子をも包含するものである。そのような重合性化合物としては、ラジカル重合性の部位、例えばエチレン性不飽和結合を有する重合性化合物、並びに、カチオン重合性の部位、例えばビニルエーテル構造、ビニルチオエーテル構造、エポキシ環又はオキセタン環といった環状エーテル構造を有する重合性化合物が挙げられる。(A) Polymerizable compound The polymerizable compound in the present invention is a liquid having a viscosity of 5 mPa · s or more and 10,000 mPa · s or less at 25 ° C., and the polymerizable portion is polymerized by the action of a photopolymerization initiator. There is no particular limitation as long as it is a compound having one or more, preferably one to six in it. As a polymerizable site, there are a radical polymerizable site and a cationic polymerizable site, and the polymerizable compound may have both sites.
The meaning of the polymerizable compound in the present invention is a compound that is not a so-called polymer substance. Therefore, it includes not only a narrowly-defined monomer compound but also a dimer, trimer, oligomer or reactive polymer. Such polymerizable compounds include radically polymerizable moieties such as polymerizable compounds having an ethylenically unsaturated bond, and cationic polymerizable moieties such as cyclic rings such as vinyl ether structures, vinyl thioether structures, epoxy rings or oxetane rings. Examples thereof include polymerizable compounds having an ether structure.
ラジカル重合性の部位を有する重合性化合物としては、エチレン性不飽和結合を有する重合性化合物、例えば、不飽和カルボン酸、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物、脂環族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物、芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物、脂肪族ポリヒドロキシ化合物及び脂環族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物、脂肪族ポリヒドロキシ化合物及び芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と不飽和カルボン酸及び多価カルボン酸とのエステル化合物、脂肪族ポリアミン化合物と不飽和カルボン酸とのアミド化合物等を挙げることができる。
このうち、好ましくは、不飽和カルボン酸、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物、脂環族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物、及び芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物が挙げられる。
また、より好ましくは、エチレン性不飽和結合を有する重合性化合物であって、分子内に3個以上20個以下の炭素原子数2乃至6のオキシアルキレン基をさらに有する重合性化合物が挙げられる。炭素原子数2乃至6のオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基、オキシブチレン基等が挙げられ、それらは未置換であっても、またヒドロキシ基、ハロゲン原子等で置換されていても良い。Examples of the polymerizable compound having a radical polymerizable moiety include a polymerizable compound having an ethylenically unsaturated bond, such as an unsaturated carboxylic acid, an ester compound of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an alicyclic poly Ester compound of hydroxy compound and unsaturated carboxylic acid, ester compound of aromatic polyhydroxy compound and unsaturated carboxylic acid, aliphatic polyhydroxy compound and ester compound of alicyclic polyhydroxy compound and unsaturated carboxylic acid, fat And ester compounds of polyhydric hydroxy compounds such as aromatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids, and amide compounds of aliphatic polyamine compounds and unsaturated carboxylic acids. .
Of these, an unsaturated carboxylic acid, an ester compound of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester compound of an alicyclic polyhydroxy compound and an unsaturated carboxylic acid, and an aromatic polyhydroxy compound and an unsaturated compound are preferred. Examples include ester compounds with saturated carboxylic acids.
More preferably, it is a polymerizable compound having an ethylenically unsaturated bond, and further having a oxyalkylene group having 2 to 6 carbon atoms in the molecule and having 2 to 6 carbon atoms. Examples of the oxyalkylene group having 2 to 6 carbon atoms include an oxyethylene group, an oxypropylene group, an oxybutylene group, etc., which may be unsubstituted or substituted with a hydroxy group, a halogen atom, or the like. Also good.
上記の不飽和カルボン酸としては、アクリル酸、メタクリル酸、2−アクリロイロキシエチルスクシネート、又は2−アクリロイロキシエチルフタレート等が挙げられる。また、これらのアクリル酸エステル化合物のアクリレート部分をメタクリレートに代えたメタクリル酸エステル化合物、同様にイタコネートに代えたイタコン酸エステル化合物、クロトネートに代えたクロトン酸エステル化合物、マレエートに代えたマレイン酸エステル化合物等も挙げられる。 Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinate, and 2-acryloyloxyethyl phthalate. In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylate, itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, maleic acid ester compounds in place of maleate, etc. Also mentioned.
脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物としては、トリプロピレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ジトリメチロールプロパンテトラアクリレート、1,6−ヘキサンジオールジアクリレート、ポリブタンジオールジアクリレート、2−ヒドロキシ−3−フェノキシプロピルアクリレート、3−クロロ−2−ヒドロキシプロピルアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、グリセロールアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、4,7−ジオキサ−5−メチル−1,2,9,10−デカンテトラオール−1,10−ジアクリレート等が挙げられる。
より好ましくは、これら脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物のアルコキシ変性物(1分子内のアルコキシ基の平均付加数は1乃至20、好ましくは3乃至20、より好ましくは3乃至10)を挙げることができる。このようなエステル化合物のアルコキシ変性物として、例えば、エトキシ変性ペンタエリスリトールテトラアクリレート(下記の式(1)化合物)、プロポキシ変性ペンタエリスリトールテトラアクリレート(下記の式(2)化合物)、エトキシ変性トリメチロールプロパントリアクリレート(下記の式(3)化合物)を挙げることができる。また、これらのアクリル酸エステル化合物のアクリレート部分をメタクリレートに代えたメタクリル酸エステル化合物、同様にイタコネートに代えたイタコン酸エステル化合物、クロトネートに代えたクロトン酸エステル化合物、マレエートに代えたマレイン酸エステル化合物等も挙げられる。Examples of ester compounds of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include tripropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, ditrimethylolpropane tetraacrylate, 1,6-hexanediol diacrylate, Polybutanediol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-chloro-2-hydroxypropyl acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerol acrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, 4,7-dioxa-5-methyl-1, , 9,10 decane tetraol-1,10-di acrylate.
More preferably, an alkoxy-modified product of an ester compound of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid (the average addition number of alkoxy groups in one molecule is 1 to 20, preferably 3 to 20, more preferably 3 to 10). Examples of such alkoxy-modified products of ester compounds include ethoxy-modified pentaerythritol tetraacrylate (the following formula (1) compound), propoxy-modified pentaerythritol tetraacrylate (the following formula (2) compound), ethoxy-modified trimethylolpropane. A triacrylate (compound of the following formula (3)) can be mentioned. In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylate, itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, maleic acid ester compounds in place of maleate, etc. Also mentioned.
脂環族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物としては、例えばトリシクロデカンジメタノールジアクリレートが挙げられる。
より好ましくは、これら脂環族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物のアルコキシ変性物(1分子内のアルコキシ基の平均付加数は1乃至20、好ましくは3乃至20、より好ましくは3乃至10)、例えば、エトキシ変性水添ビスフェノールAジアクリレート(下記の式(4)化合物)を挙げることができる。また、これらのアクリル酸エステル化合物のアクリレート部分をメタクリレートに代えたメタクリル酸エステル化合物、同様にイタコネートに代えたイタコン酸エステル化合物、クロトネートに代えたクロトン酸エステル化合物、マレエートに代えたマレイン酸エステル化合物等も挙げられる。Examples of the ester compound of an alicyclic polyhydroxy compound and an unsaturated carboxylic acid include tricyclodecane dimethanol diacrylate.
More preferably, these alkoxy-modified products of ester compounds of alicyclic polyhydroxy compounds and unsaturated carboxylic acids (the average number of alkoxy groups added in one molecule is 1 to 20, preferably 3 to 20, more preferably 3 To 10), for example, ethoxy-modified hydrogenated bisphenol A diacrylate (compound of formula (4) below). In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylate, itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, maleic acid ester compounds in place of maleate, etc. Also mentioned.
芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物としては、ビスフェノールAジアクリレート、ビスフェノールFジアクリレート、ヒドロキノンジアクリレート、レゾルシンジアクリレート、ピロガロールトリアクリレート等が挙げられる。
より好ましくは、これら芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物のアルコキシ変性物(1分子内のアルコキシ基の平均付加数は1乃至20、好ましくは4乃至20、より好ましくは6乃至20)を挙げることができる。このようなエステル化合物のアルコキシ変性物として、例えば、エトキシ変性ビスフェノールAジアクリレート(下記の式(5)化合物)、プロポキシ変性ビスフェノールAジアクリレート(下記の式(6)化合物)、エトキシ−プロポキシ変性ビスフェノールAジアクリレート(下記の式(7)化合物)、エトキシ変性ビスフェノールFジアクリレート(下記の式(8)化合物)、プロポキシ変性ビスフェノールFジアクリレート(下記の式(9)化合物)、エトキシ−プロポキシ変性ビスフェノールFジアクリレート(下記の式(10)化合物)等が挙げられる。また、これらのアクリル酸エステル化合物のアクリレート部分をメタクリレートに代えたメタクリル酸エステル化合物、同様にイタコネートに代えたイタコン酸エステル化合物、クロトネートに代えたクロトン酸エステル化合物、マレエートに代えたマレイン酸エステル化合物等も挙げられる。Examples of the ester compound of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include bisphenol A diacrylate, bisphenol F diacrylate, hydroquinone diacrylate, resorcin diacrylate, and pyrogallol triacrylate.
More preferably, an alkoxy modified product of an ester compound of these aromatic polyhydroxy compound and unsaturated carboxylic acid (the average addition number of alkoxy groups in one molecule is 1 to 20, preferably 4 to 20, more preferably 6 to 20). Examples of such alkoxy-modified products of ester compounds include ethoxy-modified bisphenol A diacrylate (compound of formula (5) below), propoxy-modified bisphenol A diacrylate (compound of formula (6) below), and ethoxy-propoxy-modified bisphenol. A diacrylate (compound of formula (7) below), ethoxy modified bisphenol F diacrylate (compound of formula (8) below), propoxy modified bisphenol F diacrylate (compound of formula (9) below), ethoxy-propoxy modified bisphenol F diacrylate (the following formula (10) compound) etc. are mentioned. In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylate, itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, maleic acid ester compounds in place of maleate, etc. Also mentioned.
脂肪族ポリヒドロキシ化合物及び芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と不飽和カルボン酸及び多価カルボン酸とのエステル化合物としては、必ずしも単一物では無いが代表的な具体例を挙げれば、アクリル酸及びフタル酸とエチレングリコールの縮合物、アクリル酸及びマレイン酸とジエチレングリコールの縮合物、アクリル酸及び安息香酸とトリメチロールプロパンの縮合物、アクリル酸及びテレフタル酸とペンタエリスリトール及びジペンタエリスリトールの縮合物、アクリル酸及びアジピン酸とブタンジオール及びグリセリンの縮合物等が挙げられる。 As an ester compound of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound and an unsaturated carboxylic acid and a polyvalent carboxylic acid, although not necessarily a single substance, a typical example is given, Condensates of acrylic acid and phthalic acid with ethylene glycol, condensates of acrylic acid and maleic acid with diethylene glycol, condensates of acrylic acid and benzoic acid with trimethylolpropane, condensation of acrylic acid and terephthalic acid with pentaerythritol and dipentaerythritol And condensates of acrylic acid and adipic acid with butanediol and glycerin.
エチレン性不飽和結合を有する重合性化合物のその他の例としては、多価イソシアネートとヒドロキシアルキル不飽和カルボン酸エステルとの反応によって得ることができるウレタン化合物、多価エポキシ化合物とヒドロキシアルキル不飽和カルボン酸エステルとの反応によって得ることができる化合物、リン酸基を有する多価アクリレート及びメタクリレートを挙げることができる。
本発明に用いられるエチレン性不飽和結合を有する重合性化合物のさらに他の例としては、また、例えば、エチレンビスアクリルアミド等のアクリルアミド化合物、フタル酸ジアリル等のアリルエステル化合物、ジビニルフタレート等のビニル基含有化合物等が有用である。Other examples of the polymerizable compound having an ethylenically unsaturated bond include a urethane compound, a polyvalent epoxy compound and a hydroxyalkyl unsaturated carboxylic acid which can be obtained by a reaction between a polyvalent isocyanate and a hydroxyalkyl unsaturated carboxylic acid ester. Mention may be made of compounds obtainable by reaction with esters, polyvalent acrylates and methacrylates having a phosphate group.
Still other examples of the polymerizable compound having an ethylenically unsaturated bond used in the present invention include, for example, acrylamide compounds such as ethylene bisacrylamide, allyl ester compounds such as diallyl phthalate, and vinyl groups such as divinyl phthalate. Containing compounds and the like are useful.
本発明においては、エチレン性不飽和結合を有する重合性化合物としては、アクリル酸エステル化合物またはメタクリル酸エステル化合物が特に好ましい。
これらのエチレン性不飽和結合を有する重合性化合物は単独で用いてもよいし、必要に応じて二種以上を混合して用いてもよい。
以下、式中のacryloylはアクリロイル基を表し、methacryloylはメタクリロイル基を表す。また、式中のw、x、y及びzは、1分子内の各部分(鎖)のオキシアルキレン基の付加モル数を表し、w+x+y+z、x+y+z、x+yの各数値は1分子内のオキシアルキレン基の平均付加モル数を表す。
These polymerizable compounds having an ethylenically unsaturated bond may be used alone or as a mixture of two or more thereof as necessary.
Hereinafter, acryloyl in the formula represents an acryloyl group, and methacryloyl represents a methacryloyl group. In addition, w, x, y and z in the formula represent the number of added moles of oxyalkylene groups in each part (chain) in one molecule, and each numerical value of w + x + y + z, x + y + z and x + y represents an oxyalkylene group in one molecule. Represents the average number of moles added.
一方、カチオン重合性の部位を有する化合物のうち、ビニルエーテル構造を有する化合物としては、例えば、ビニル−2−クロロエチルエーテル、ビニル−n−ブチルエーテル、トリエチレングリコールジビニルエーテル、1,4−シクロヘキサンジメタノールジビニルエーテル、トリメチロールエタントリビニルエーテル、ビニルグリシジルエーテル等を挙げることができる。 On the other hand, among the compounds having a cationically polymerizable moiety, examples of the compound having a vinyl ether structure include vinyl-2-chloroethyl ether, vinyl-n-butyl ether, triethylene glycol divinyl ether, and 1,4-cyclohexanedimethanol. Examples thereof include divinyl ether, trimethylol ethane trivinyl ether, vinyl glycidyl ether and the like.
エポキシ環を有する化合物としては、例えば、ジグリセロールポリジグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、1,4−ビス(2,3−エポキシプロポキシパーフルオロイソプロピル)シクロヘキサン、ソルビトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、レゾルシンジグリシジルエーテル、1,6−へキサンジオールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、フェニルグリシジルエーテル、p−tert−ブチルフェニルグリシジルエーテル、アジピン酸ジグリシジルエーテル、o−フタル酸ジグリシジルエーテル、ジブロモフェニルグリシジルエーテル、1,2,7,8−ジエポキシオクタン、1,6−ジメチロールパーフルオロヘキサンジグリシジルエーテル、4,4’−ビス(2,3−エポキシプロポキシパーフルオロイソプロピル)ジフェニルエーテル、2,2−ビス(4−グリシジルオキシフェニル)プロパン、3,4−エポキシシクロヘキシルメチル−3’,4’−エポキシシクロヘキサンカルボキシレート、3,4−エポキシシクロヘキシルオキシラン、2−(3,4−エポキシシクロヘキシル)−3’,4’−エポキシ−1,3−ジオキサン−5−スピロシクロヘキサン、1,2−エチレンジオキシビス(3,4−エポキシシクロヘキシルメタン)、4’,5’−エポキシ−2’−メチルシクロヘキシルメチル−4,5−エポキシ−2−メチルシクロヘキサンカルボキシレート、エチレングリコールビス(3,4−エポキシシクロヘキサンカルボキシレート)、ビス(3,4−エポキシシクロヘキシルメチル)アジペート、ジ−2,3−エポキシシクロペンチルエーテル等を挙げることができる。 Examples of the compound having an epoxy ring include diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl. Ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether , Dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perfluorohexane Glycidyl ether, 4,4′-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl-3 ′, 4′- Epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 2- (3,4-epoxycyclohexyl) -3 ′, 4′-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy Bis (3,4-epoxycyclohexylmethane), 4 ′, 5′-epoxy-2′-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol bis (3,4-epoxycyclohexanecarboxy) Rate), bi (3,4-epoxycyclohexylmethyl) adipate, and di-2,3-epoxy cyclopentyl ether or the like.
オキセタン環を有する化合物としては、例えば、オキセタン環を一つ有する化合物、3−エチル−3−ヒドロキシメチルオキセタン、3−エチル−3−(フェノキシメチル)オキセタン、3,3−ジエチルオキセタン、3−エチル−3−(2−エチルヘキシルオキシメチル)オキセタン、オキセタン環を二つ以上有する化合物、1,4−ビス{[(3−エチル−3−オキセタニル)メトキシ]メチル}ベンゼン、ジ(1−エチル(3−オキセタニル))メチルエーテル、ペンタエリスリトールテトラキス(3−エチル−3−オキセタニルメチル)エーテル等を挙げることができる。 Examples of the compound having an oxetane ring include a compound having one oxetane ring, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3,3-diethyloxetane, and 3-ethyl. -3- (2-ethylhexyloxymethyl) oxetane, a compound having two or more oxetane rings, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di (1-ethyl (3 -Oxetanyl)) methyl ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and the like.
(b)光重合開始剤
本発明における光重合開始剤としては、パターン露光によって前記重合性化合物の重合を開始することができる機能を有する化合物であれば特に限定はない。パターン露光の方法としては、フォトマスク露光、フェーズマスク露光、及び干渉露光等が挙げられる。これらのうち体積ホログラム記録を行う場合には干渉露光が好ましい。干渉露光の光源としては、一般に干渉性の高いレーザー光であり、光重合開始剤に高感度であればよく、例えばアルゴンイオンレーザー(458nm、488nm、514.5nm)、クリプトンイオンレーザー(647.1nm)、Nd:YAGレーザー(532nm)、Nd:YVO4レーザー(532nm)、InGaNレーザー(405nm)、He−Cdレーザー(325nm、442nm)等が使用される。(B) Photopolymerization initiator The photopolymerization initiator in the present invention is not particularly limited as long as it is a compound having a function capable of initiating polymerization of the polymerizable compound by pattern exposure. Examples of the pattern exposure method include photomask exposure, phase mask exposure, and interference exposure. Among these, when performing volume hologram recording, interference exposure is preferable. The light source for the interference exposure is generally a laser beam having high coherence, and it is sufficient if it has high sensitivity to the photopolymerization initiator. For example, an argon ion laser (458 nm, 488 nm, 514.5 nm), a krypton ion laser (647.1 nm). ), Nd: YAG laser (532 nm), Nd: YVO 4 laser (532 nm), InGaN laser (405 nm), He—Cd laser (325 nm, 442 nm) and the like are used.
重合性化合物として前記のエチレン性不飽和結合を有する重合性化合物が使用された場合、光重合開始剤としてはパターン露光時に活性ラジカルを生成する光ラジカル重合開始剤が好ましい。
重合性化合物として前記のカチオン重合性の部位を有する化合物、例えばビニルエーテル構造、エポキシ環またはオキセタン環を有する化合物が使用された場合、光重合開始剤としては干渉露光時にルイス酸あるいはブレンステッド酸を生成する光酸発生剤が好ましい。When the above-described polymerizable compound having an ethylenically unsaturated bond is used as the polymerizable compound, the photopolymerization initiator is preferably a photoradical polymerization initiator that generates active radicals during pattern exposure.
When a compound having the above-mentioned cationically polymerizable moiety, such as a compound having a vinyl ether structure, an epoxy ring or an oxetane ring, is used as the polymerizable compound, a Lewis acid or Bronsted acid is generated as a photopolymerization initiator during interference exposure. A photoacid generator is preferred.
光ラジカル重合開始剤としては、パターン露光時に活性ラジカルを生成する化合物であれば特に限定されないが、例えば、ベンゾイン系化合物、α−アミノアルキルフェノン系化合物、チオキサントン系化合物、アゾ系化合物、アジド系化合物、ジアゾ系化合物、o−キノンジアジド系化合物、アシルホスフィンオキサイド系化合物、オキシムエステル系化合物、有機過酸化物、ベンゾフェノン類、ビスクマリン、ビスイミダゾール化合物、チタノセン化合物、チオール化合物、ハロゲン化炭化水素化合物、トリクロロメチルトリアジン化合物、あるいはヨードニウム塩化合物、スルホニウム塩化合物などのオニウム塩化合物等が用いられる。これらのうち、チタノセン化合物が好ましい。光ラジカル重合開始剤は単独で用いてもよいし、必要に応じて二種以上を混合して用いてもよい。 The radical photopolymerization initiator is not particularly limited as long as it is a compound that generates an active radical at the time of pattern exposure. , Diazo compounds, o-quinonediazide compounds, acylphosphine oxide compounds, oxime ester compounds, organic peroxides, benzophenones, biscoumarins, bisimidazole compounds, titanocene compounds, thiol compounds, halogenated hydrocarbon compounds, trichloro Methyltriazine compounds or onium salt compounds such as iodonium salt compounds and sulfonium salt compounds are used. Of these, titanocene compounds are preferred. A radical photopolymerization initiator may be used alone or in combination of two or more as required.
チタノセン化合物は、特に限定はされないが、具体的には、ビス(シクロペンタジエニル)ジクロロチタニウム、ビス(シクロペンタジエニル)ジフェニルチタニウム、ビス(シクロペンタジエニル)ビス(2,3,4,5,6−ペンタフルオロフェニル)チタニウム、ビス(シクロペンタジエニル)ビス(2,3,5,6−テトラフルオロフェニル)チタニウム、ビス(シクロペンタジエニル)ビス(2,4,6−トリフルオロフェニル)チタニウム、ビス(シクロペンタジエニル)ビス(2,6−ジフルオロフェニル)チタニウム、ビス(シクロペンタジエニル)ビス(2,4−ジフルオロフェニル)チタニウム、ビス(メチルシクロペンタジエニル)ビス(2,3,4,5,6−ペンタフルオロフェニル)チタニウム、ビス(メチルシクロペンタジエニル)ビス(2,3,5,6−テトラフルオロフェニル)チタニウム、ビス(2,6−ジフルオロフェニル)ビス(メチルシクロペンタジエニル)チタニウム、ビス(シクロペンタジエニル)ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)フェニル)チタニウム等を挙げることができる。 The titanocene compound is not particularly limited. Specifically, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) bis (2,3,4, 5,6-pentafluorophenyl) titanium, bis (cyclopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4,6-trifluoro Phenyl) titanium, bis (cyclopentadienyl) bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis ( 2,3,4,5,6-pentafluorophenyl) titanium, bis (methylsilane) Lopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (2,6-difluorophenyl) bis (methylcyclopentadienyl) titanium, bis (cyclopentadienyl) bis (2,6- And difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.
ベンゾイン系化合物としては、例えばベンゾインエチルエーテル、2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン、1−ヒドロキシシクロヘキシルフェニルケトン、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン等を挙げることができる。 Examples of benzoin compounds include benzoin ethyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON etc. can be mentioned.
α−アミノアルキルフェノン系化合物としては、例えば2−メチル−1−(4−(メチルチオ)フェニル)−2−モルフォリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)ブタン−1−オン等を挙げることができる。 Examples of the α-aminoalkylphenone compounds include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one and the like.
チオキサントン系化合物としては、例えばチオキサントン、1−クロロチオキサントン、2−クロロチオキサントン、1−クロロ−4−プロポキシチオキサントン、2−メチルチオキサントン、2−イソプロピルチオキサントン、2,4−ジエチルチオキサントン等を挙げることができる。 Examples of the thioxanthone compound include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone. .
アゾ系化合物としては、2,2’−アゾビス(2−アミノジプロパン)塩酸塩、4,4’−アゾビス(4−シアノ吉草酸)、2,2’−アゾビス〔N−(2−カルボキシエチル)−2−メチルプロピオンアミジン〕、ジメチル2,2’−アゾビスイソブチレート、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2−メチルブチロニトリル)、1,1’−アゾビス(シクロヘキサン−1−カルボニトリル)、2,2’−アゾビス{2−メチル−N−〔2−(1−ヒドロキシブチル)〕プロピオンアミド}、2,2’−アゾビス〔2−メチル−N−(2−ヒドロキシエチル)−プロピオンアミド〕、2,2’−アゾビス〔2−(5−メチル−2−イミダゾリン−2−イル)プロパン〕塩酸塩、2,2’−アゾビス〔2−(2−イミダゾリン−2−イル)プロパン〕塩酸塩、2,2’−アゾビス〔2−(2−イミダゾリン−2−イル)プロパン〕硫酸塩、2,2’−アゾビス〔2−(3,4,5,6−テトラヒドロピリミジン−2−イル)プロパン〕塩酸塩、2,2’−アゾビス{2−〔1−(2−ヒドロキシエチル)−2−イミダゾリン−2−イル〕プロパン}塩酸塩、2,2’−アゾビス〔2−(2−イミダゾリン−2−イル)プロパン〕等を挙げることができる。 Examples of the azo compound include 2,2′-azobis (2-aminodipropane) hydrochloride, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxyethyl). ) -2-methylpropionamidine], dimethyl 2,2′-azobisisobutyrate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl) )] Propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azobis [2- (5-methyl-2-imidazoline-2- I ) Propane] hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] sulfuric acid Salt, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] hydrochloride, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and the like.
アジド系化合物としては、例えばp−アジドベンズアルデヒド、p−アジドアセトフェノン、p−アジド安息香酸、p−アジドベンザルアセトフェノン、4,4’−ジアジドカルコン、4,4’−ジアジドジフェニルスルフィド、2,6−ビス(4’−アジドベンザル)−4−メチルシクロヘキサノン、4,4’−ジアジドスチルベン等を挙げることができる。 Examples of the azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidodiphenyl sulfide, 2 , 6-bis (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidostilbene, and the like.
ジアゾ系化合物としては、例えば1−ジアゾ−2,5−ジエトキシ−4−p−トリルメルカプトベンゼンボロフルオリド、1−ジアゾ−4−(ジメチルアミノ)ベンゼンクロリド、1−ジアゾ−4−(ジエチルアミノ)ベンゼンボロフルオリド等を挙げることができる。 Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4- (dimethylamino) benzene chloride, 1-diazo-4- (diethylamino). Examples thereof include benzeneborofluoride.
o−キノンジアジド系化合物としては、例えば1,2−ナフトキノンジアジド(2)−4−スルホン酸ナトリウム塩、1,2−ナフトキノンジアジド(2)−5−スルホン酸エステル、1,2−ナフトキノンジアジド(2)−4−スルホニルクロリド等を挙げることができる。 Examples of the o-quinonediazide compounds include 1,2-naphthoquinonediazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinonediazide (2) -5-sulfonic acid ester, 1,2-naphthoquinonediazide (2 ) -4-sulfonyl chloride and the like.
アシルホスフィンオキサイド系化合物としては、例えばビス(2,4,6−トリメチルベンゾイル)フェニルホスフィンオキサイド、2,4,6−トリメチルベンゾイルジフェニルホスフィンオキサイド等を挙げることができる。 Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
オキシムエステル系化合物としては、例えば2−(O−ベンゾイルオキシム)−1−[4−(フェニルチオ)フェニル]−1,2−オクタンジオン、1−(O−アセチルオキシム)−1−[9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル]エタノン等を挙げることが出来る。 Examples of oxime ester compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl. And -6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.
ベンゾフェノン類としては、例えばベンゾフェノン、4,4’−ビス(ジエチルアミノ)ベンゾフェノン、1,4−ジベンゾイルベンゼン、10−ブチル−2−クロロアクリドン、2−ベンゾイルナフタレン、4−ベンゾイルビフェニル、4−ベンゾイルジフェニルエーテル、3,3’,4,4’−テトラ(t−ブチルパーオキシカルボニル)ベンゾフェノン等を挙げることができる。 Examples of benzophenones include benzophenone, 4,4′-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, and 4-benzoyl. Examples thereof include diphenyl ether, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.
ビスクマリンとしては、例えば3,3’−カルボニルビス(7−(ジエチルアミノ)−2H−クロメン−2−オン)等が挙げられ、これはみどり化学株式会社でBC(CAS[63226−13−1])として市販されている。 Biscumarins include, for example, 3,3′-carbonylbis (7- (diethylamino) -2H-chromen-2-one) and the like, which is a product of BC (CAS [63226-13-1] manufactured by Midori Chemical Co., Ltd. ).
ビスイミダゾール化合物としては、例えば2,2’−ビス(o−クロロフェニル)−4,4’,5,5’−テトラキス(3,4,5−トリメトキシフェニル)−1,2’−ビイミダゾール、2,2’−ビス(o−クロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール等を挙げることができる。 Examples of the bisimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) -1,2′-biimidazole, Examples include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.
光酸発生剤としては、パターン露光時にルイス酸あるいはブレンステッド酸を生成する化合物であれば特に限定されないが、例えば、ジアリールヨードニウム塩化合物、トリアリールスルホン酸塩化合物、ジアゾニウム塩化合物などのオニウム塩化合物、及び鉄アレーン錯体化合物等を挙げることができる。 The photoacid generator is not particularly limited as long as it is a compound that generates a Lewis acid or a Bronsted acid during pattern exposure. For example, an onium salt compound such as a diaryl iodonium salt compound, a triaryl sulfonate compound, or a diazonium salt compound. , And iron arene complex compounds.
ジアリールヨードニウム塩化合物としては、例えば、ジフェニルヨードニウム、4,4’−ジクロロジフェニルヨードニウム、4,4’−ジメトキシジフェニルヨードニウム、4,4’−ジ−tert−ブチルジフェニルヨードニウム、(4−メチルフェニル)[4−(2−メチルプロピル)フェニル]ヨードニウム、3,3’−ジニトロフェニルヨードニウム等のヨードニウムの、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアルセネート、ヘキサフルオロアンチモネート等が挙げられる。 Examples of the diaryliodonium salt compound include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-di-tert-butyldiphenyliodonium, (4-methylphenyl) [ Examples thereof include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like of iodonium such as 4- (2-methylpropyl) phenyl] iodonium and 3,3′-dinitrophenyliodonium.
トリアリールスルホン酸塩化合物としては、例えば、トリフェニルスルホニウム、4−tert−ブチルトリフェニルスルホニウム、トリス(4−メチルフェニル)スルホニウム、トリス(4−メトキシフェニル)スルホニウム、4−チオフェニルトリフェニルスルホニウム等のスルホニウムの、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアルセネート、ヘキサフルオロアンチモネート等を挙げることができる。 Examples of the triarylsulfonate compound include triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, 4-thiophenyltriphenylsulfonium, and the like. Examples of sulfonium include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like.
鉄アレーン錯体化合物としては、例えばビスシクロペンタジエニル−(η6−イソプロピルベンゼン)−鉄(II)ヘキサフルオロホスフェート等が挙げられる。光酸発生剤は単独で用いてもよいし、必要に応じて二種以上を混合して用いてもよい。Examples of the iron arene complex compound include biscyclopentadienyl- (η 6 -isopropylbenzene) -iron (II) hexafluorophosphate. A photo-acid generator may be used independently and may mix and use 2 or more types as needed.
本発明の感光性組成物において、重合性化合物としてラジカル重合性の部位であるエチレン性不飽和結合を有する化合物が使用された場合には、光重合開始剤としては、基本的には光ラジカル重合開始剤が用いられる。重合性化合物としてカチオン重合性の部位であるビニルエーテル構造、エポキシ環またはオキセタン環を有する化合物が使用された場合には、光重合開始剤としては、基本的には光酸発生剤が用いられる。光重合開始剤の含有量は、重合性化合物100質量部に対し0.01乃至10質量部であり、好ましくは0.05乃至5質量部である。 In the photosensitive composition of the present invention, when a compound having an ethylenically unsaturated bond, which is a radical polymerizable site, is used as the polymerizable compound, the photopolymerization initiator is basically a radical photopolymerization. An initiator is used. When a compound having a vinyl ether structure, an epoxy ring or an oxetane ring, which is a cationically polymerizable site, is used as the polymerizable compound, a photoacid generator is basically used as the photopolymerization initiator. Content of a photoinitiator is 0.01-10 mass parts with respect to 100 mass parts of polymeric compounds, Preferably it is 0.05-5 mass parts.
(c)無機微粒子
用いる無機微粒子としては、本発明の目的を達成することができる粒子であれば特に限定されないが、光散乱損失を低減させる必要があるため、平均粒径がなるべく小さなものが好ましい。この点から、無機微粒子は、平均粒径が100nm以下である微粒子が望ましい。より好ましくは、平均粒径が3nm乃至20nmの無機微粒子である。具体的にはシリカ、ジルコニア、チタニア等の無機酸化物微粒子が好ましい。(C) Inorganic fine particles The inorganic fine particles to be used are not particularly limited as long as they can achieve the object of the present invention. However, since it is necessary to reduce light scattering loss, it is preferable that the average particle size is as small as possible. . In this respect, the inorganic fine particles are desirably fine particles having an average particle diameter of 100 nm or less. More preferred are inorganic fine particles having an average particle diameter of 3 nm to 20 nm. Specifically, fine inorganic oxide particles such as silica, zirconia, and titania are preferable.
また、無機微粒子の含有量は、多すぎても少なすぎても高い回折効率のホログラムを得ることができない。また、高い脆弱性を有する偽造防止ホログラム層を得るには、無機微粒子の含有量がより多い方がよい。これらの観点から、無機微粒子の含有量は、用いられる重合性化合物の種類にもよるが、重合性化合物(a)、光重合開始剤(b)及び無機微粒子(c)の合計体積に占める無機微粒子(c)の体積の割合がおおむね3乃至50体積%となる量が好ましく、より好ましくは、回折効率と脆弱性のバランスが最も良好な10乃至45体積%となる量である。
また、重合性化合物(a)として、芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル化合物のアルコキシ変性物、例えばエトキシ又はプロポキシ変性物を用いる場合には、無機微粒子の含有量は重合性化合物(a)、光重合開始剤(b)及び無機微粒子(c)の合計体積に占める無機微粒子(c)の体積の割合が15乃至40体積%となる量が好ましい。Further, if the content of the inorganic fine particles is too much or too little, a hologram with high diffraction efficiency cannot be obtained. In order to obtain a forgery-preventing hologram layer having high vulnerability, it is better that the content of the inorganic fine particles is larger. From these viewpoints, the content of the inorganic fine particles depends on the type of the polymerizable compound used, but the inorganic occupies the total volume of the polymerizable compound (a), the photopolymerization initiator (b) and the inorganic fine particles (c). The amount by which the volume ratio of the fine particles (c) is about 3 to 50% by volume is preferable, and more preferably the amount is 10 to 45% by volume with the best balance between diffraction efficiency and brittleness.
In addition, when an alkoxy-modified product of an ester compound of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, for example, ethoxy or propoxy-modified product is used as the polymerizable compound (a), the content of the inorganic fine particles is determined by the polymerizable compound. An amount in which the volume ratio of the inorganic fine particles (c) to the total volume of (a), the photopolymerization initiator (b) and the inorganic fine particles (c) is 15 to 40% by volume is preferable.
用いられる無機微粒子の形態としては粉末状のものでも、水または有機溶媒に分散したゾルでもよいが、本発明の感光性組成物への分散性、安定性の面から有機溶媒に分散したゾルで用いるのが好ましい。有機溶媒としては、例えばメタノール、イソプロパノール、ブタノール、エチレングリコール、エチレングリコールモノプロピルエーテル、メチルエチルケトン、メチルイソブチルケトン、キシレン、ジメチルアセトアミド、トルエン等であり、重合性モノマーに均一に分散可能なものであれば、特に限定はされない。 The inorganic fine particles used may be in the form of a powder or a sol dispersed in water or an organic solvent. However, a sol dispersed in an organic solvent from the viewpoint of dispersibility and stability in the photosensitive composition of the present invention. It is preferable to use it. Examples of the organic solvent include methanol, isopropanol, butanol, ethylene glycol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, xylene, dimethylacetamide, toluene, and the like as long as they can be uniformly dispersed in the polymerizable monomer. There is no particular limitation.
また、本発明の無機微粒子はカプセル化、表面処理、ハイブリッド化などの手法を用いてモノマーへの分散性を高めることが好ましい。中でも表面処理剤を用いた修飾が工業的にも簡便なため好ましい。
表面処理剤としては無機微粒子表面と親和性があり、かつ重合性化合物中への分散性を高めるために表面官能基と疎水基を兼ね備えたものが好ましい。In addition, it is preferable that the inorganic fine particles of the present invention have high dispersibility in the monomer by using a method such as encapsulation, surface treatment, or hybridization. Among them, modification using a surface treatment agent is preferable because it is industrially simple.
As the surface treating agent, those having an affinity for the surface of the inorganic fine particles and having a surface functional group and a hydrophobic group in order to enhance dispersibility in the polymerizable compound are preferable.
表面反応性官能基としては、例えば、メチルシラン、エチルシランなどのアルキルシラン、メトキシシラン、エトキシシランなどのアルコキシシラン、クロロシランなどのハロゲン化シランに代表される反応性シラン化合物、メトキシチタン、エトキシチタンなどのアルコキシチタンや塩化チタンに代表される反応性チタン化合物、カルボキシル基、リン酸基、スルホン酸基、またはそのエステル等が挙げられる。 Examples of surface reactive functional groups include alkylsilanes such as methylsilane and ethylsilane, alkoxysilanes such as methoxysilane and ethoxysilane, and reactive silane compounds represented by halogenated silanes such as chlorosilane, methoxytitanium, ethoxytitanium, and the like. Examples thereof include reactive titanium compounds typified by alkoxy titanium and titanium chloride, carboxyl groups, phosphoric acid groups, sulfonic acid groups, or esters thereof.
本発明の偽造防止ホログラム媒体の偽造防止ホログラム層には、重合性化合物(a)、光重合開始剤(b)及び無機微粒子(c)の他、必要に応じて、増感剤、連鎖移動剤、可塑剤、着色剤等の添加剤が加えられていても良い。また、膜厚の均一性を持たせ、光照射での重合で形成されたホログラムを安定に存在させるためには結合材としてバインダー樹脂を加えても良い。 In the anti-counterfeit hologram layer of the anti-counterfeit hologram medium of the present invention, in addition to the polymerizable compound (a), the photopolymerization initiator (b) and the inorganic fine particles (c), if necessary, a sensitizer and a chain transfer agent Additives such as plasticizers and colorants may be added. In addition, a binder resin may be added as a binder in order to make the film thickness uniform and allow a hologram formed by polymerization by light irradiation to exist stably.
バインダー樹脂は重合性化合物と相溶性の良いものが好ましく、その具体例としては塩素化ポリエチレン、ポリメチルメタクリレート、メチルメタクリレートと他の(メタ)アクリル酸アルキルエステルの共重合体、ポリスチレン、塩化ビニルとアクリロニトリルの共重合体、ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルピロリドン、エチルセルロース、アセチルセルロース、セルロースアセテートブチレート等が挙げられる。ここで、(メタ)アクリル酸の表記は、アクリル酸、メタアクリル酸の双方を表す。 The binder resin preferably has good compatibility with the polymerizable compound. Specific examples thereof include chlorinated polyethylene, polymethyl methacrylate, copolymers of methyl methacrylate and other alkyl (meth) acrylates, polystyrene, and vinyl chloride. Examples include acrylonitrile copolymer, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, ethyl cellulose, acetyl cellulose, and cellulose acetate butyrate. Here, the notation of (meth) acrylic acid represents both acrylic acid and methacrylic acid.
本発明の体積位相型の偽造防止ホログラム用感光性組成物から体積位相型の偽造防止ホログラム媒体を作るには、例えば以下のように行われる。重合性化合物、無機微粒子及び光重合開始剤を、必要に応じて溶剤、増感剤、バインダー樹脂又は添加剤とともに混合することにより、偽造防止ホログラム用感光性組成物を得た後、該組成物を支持体上に塗布し、その後乾燥させることにより偽造防止ホログラム層を形成する。そしてさらに、必要に応じて偽造防止ホログラム層を保護材で覆うことによって、偽造防止ホログラム媒体を得ることができる。
偽造防止ホログラム層の厚さは、おおむね、1乃至1,000μmであり、好ましくは10乃至500μmであり、より好ましくは15乃至200μmである。
また、用いられる支持体や保護層は、体積ホログラムを記録及び再生するために光を透過させる場合には、透明な物質である必要がある。To produce a volume phase type anti-counterfeit hologram medium from the volume phase type anti-counterfeit photosensitive composition of the present invention, for example, the following procedure is performed. After obtaining a photosensitive composition for anti-counterfeit hologram by mixing a polymerizable compound, inorganic fine particles and a photopolymerization initiator together with a solvent, a sensitizer, a binder resin or an additive as necessary, the composition Is applied on a support and then dried to form a forgery-preventing hologram layer. Further, a forgery prevention hologram medium can be obtained by covering the forgery prevention hologram layer with a protective material as necessary.
The thickness of the anti-counterfeit hologram layer is generally 1 to 1,000 μm, preferably 10 to 500 μm, more preferably 15 to 200 μm.
In addition, the support and the protective layer to be used need to be a transparent material when transmitting light for recording and reproducing a volume hologram.
このような透明支持体としては、透明なガラス板、アクリル板、ポリエチレンテレフタレートフィルム、ポリエチレンフィルムなどが用いられる。透明な樹脂フィルムとして、ポリエチレンテレフタレートフィルム、ポリエチレンフィルムなどが用いられる。塗布方法としては、直接滴下する方法に加え、従来公知の方法、例えば、回転塗布、ワイヤーバー塗布、ディップ塗布、エアーナイフ塗布、ロール塗布、ブレード塗布、及びカーテン塗布等を用いることができる。 As such a transparent support, a transparent glass plate, an acrylic plate, a polyethylene terephthalate film, a polyethylene film, or the like is used. As the transparent resin film, a polyethylene terephthalate film, a polyethylene film, or the like is used. As a coating method, in addition to the direct dropping method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used.
保護層としては、酸素による感度低下や保存安定性の劣化等の悪影響を防止するための公知技術、例えば、水溶性ポリマー等の塗布を用いることもできる。水溶性ポリマーとしては、透明な樹脂フィルムを形成する水溶性ポリマー等が挙げられる。また、保護層として前記透明支持体を用いることもできる。 As the protective layer, a known technique for preventing adverse effects such as a decrease in sensitivity due to oxygen and deterioration in storage stability, for example, application of a water-soluble polymer or the like can be used. Examples of the water-soluble polymer include a water-soluble polymer that forms a transparent resin film. Moreover, the said transparent support body can also be used as a protective layer.
そして、本発明の偽造防止ホログラム用感光性組成物よりパターンを形成するには、感光性組成物から上記のようにして得られた偽造防止ホログラム媒体のホログラム層に対して、パターン露光することにより行われる。パターン露光は、パターンを形成することのできる露光方法であれば特に制限はない。パターン露光としては、例えば干渉露光が挙げられる。また、パターン露光としては、適当なマスクを通して露光する方法(フォトマスク露光及びフェーズマスク露光等)が挙げられる。
本発明の感光性組成物は重合性化合物、光重合開始剤、無機微粒子を含んでいる。そのため、例えば、マスクを通して露光が行われると、露光された部分において重合性化合物の重合反応が起こり重合体となる。その結果、露光部分において重合性化合物の化学ポテンシャルが減少し、それを補うように非露光部から露光部へ重合性化合物の移動が起こる。一方、露光部では重合性化合物の減少とともに、光重合に関与しない無機微粒子の化学ポテンシャルが増加するため、それを抑えるように無機微粒子は露光部から非露光部へと移動をする。こうした各成分の移動は光重合が完了するまで本質的に継続する。結果として、無機微粒子の空間分布は固定され、露光部と非露光部での成分と屈折率差によってパターンが形成される。すなわち、本発明の感光性組成物より形成されるパターンは、パターン露光によって組成物中の各成分の相互拡散が起こった結果、生じた各成分の空間分布の差を利用したものである。And in order to form a pattern from the photosensitive composition for forgery prevention hologram of this invention, pattern exposure is carried out with respect to the hologram layer of the forgery prevention hologram medium obtained as mentioned above from the photosensitive composition. Done. The pattern exposure is not particularly limited as long as it is an exposure method capable of forming a pattern. Examples of pattern exposure include interference exposure. Moreover, as pattern exposure, the method (Photomask exposure, phase mask exposure, etc.) of exposing through an appropriate mask is mentioned.
The photosensitive composition of the present invention contains a polymerizable compound, a photopolymerization initiator, and inorganic fine particles. Therefore, for example, when exposure is performed through a mask, a polymerization reaction of the polymerizable compound occurs in the exposed portion to form a polymer. As a result, the chemical potential of the polymerizable compound decreases in the exposed portion, and the polymerizable compound moves from the non-exposed portion to the exposed portion so as to compensate for it. On the other hand, since the chemical potential of the inorganic fine particles not participating in photopolymerization increases with the decrease in the polymerizable compound in the exposed portion, the inorganic fine particles move from the exposed portion to the non-exposed portion so as to suppress it. These movements of each component essentially continue until the photopolymerization is complete. As a result, the spatial distribution of the inorganic fine particles is fixed, and a pattern is formed by the component and refractive index difference between the exposed part and the non-exposed part. That is, the pattern formed from the photosensitive composition of the present invention utilizes a difference in spatial distribution of each component generated as a result of mutual diffusion of each component in the composition by pattern exposure.
次に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these.
実施例1
シリカゾル(メチルエチルケトン分散、微粒子濃度30質量%)(日産化学工業株式会社製、商品名MEK−ST)1.40gに光重合開始剤であるビス(η5−2,4−シク
ロペンタジエン−1−イル)−ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)−フェニル)チタニウム(チバ・ジャパン株式会社製、商品名Irgacure784)0.01gを溶解した分散液に、下記式(11)の構造(オキシプロピレン基の平均付加モル数:4)を有する重合性モノマーのプロポキシ化ペンタエリスリトールテトラアクリレート(新中村化学工業株式会社製、商品名ATM−4P、25℃における粘度:230mPa・s):
この偽造防止ホログラム媒体に対し、図1に示す装置によって、二光束干渉露光を行い体積ホログラムの記録を試みた。偽造防止ホログラム媒体に対し、波長532nmのNd:YVO4レーザーを用いて、露光パワー密度100mW/cm2で二光束干渉露光(格子間隔1μm)を行った。Nd:YVO4レーザーから出射した光はハーフミラーで2本に分割され、それぞれミラーを経て偽造防止ホログラム媒体に照射され、両光の干渉縞が記録されホログラムが形成される。
同時に、偽造防止ホログラム媒体が感光しない波長632.8nmのヘリウムネオン(He−Ne)レーザーを偽造防止ホログラム媒体に照射し回折光を光検出器で検出することによりホログラム形成過程をモニターし、回折効率(=回折光強度/入射光強度)を評価した。また、露光後の偽造防止ホログラム媒体のホログラム層の透明性を目視にて3段階で評価した。結果を表1に示す。Example 1
1.40 g of silica sol (methyl ethyl ketone dispersion, fine particle concentration: 30% by mass) (trade name MEK-ST, manufactured by Nissan Chemical Industries, Ltd.) is bis (η 5 -2,4-cyclopentadien-1-yl as a photopolymerization initiator. ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (manufactured by Ciba Japan Co., Ltd., trade name Irgacure 784) was dissolved in a dispersion of the following formula ( 11) propoxylated pentaerythritol tetraacrylate (trade name: ATM-4P, trade name: ATM-4P, manufactured by Shin-Nakamura Chemical Co., Ltd.), a polymerizable monomer having the structure (average number of moles of oxypropylene group added: 4): 230 mPa · s):
The forgery-preventing hologram medium was subjected to two-beam interference exposure using the apparatus shown in FIG. The anti-counterfeit hologram medium was subjected to two- beam interference exposure (lattice spacing 1 μm) at an exposure power density of 100 mW / cm 2 using an Nd: YVO 4 laser having a wavelength of 532 nm. The light emitted from the Nd: YVO 4 laser is divided into two by a half mirror and irradiated to the anti-counterfeit hologram medium through each mirror, and interference fringes of both lights are recorded to form a hologram.
At the same time, the hologram formation process is monitored by irradiating the anti-counterfeit hologram medium with a helium-neon (He-Ne) laser with a wavelength of 632.8 nm, which is not exposed to the anti-counterfeit hologram medium, and detecting the diffracted light with a photodetector. (= Diffracted light intensity / incident light intensity) was evaluated. Further, the transparency of the hologram layer of the forgery-preventing hologram medium after exposure was visually evaluated in three stages. The results are shown in Table 1.
実施例2
シリカゾル(メチルエチルケトン分散、微粒子濃度30質量%)(日産化学工業株式会社製、商品名MEK−ST)1.35gに光重合開始剤であるビス(η5−2,4−シクロペンタジエン−1−イル)−ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)−フェニル)チタニウム(チバ・ジャパン株式会社製、商品名Irgacure784)0.01gを溶解した分散液に、重合性化合物として下記式(12)の構造を有するジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(Aldrich社製、25℃における粘度6,600mPa・s):
1.35 g of silica sol (methyl ethyl ketone dispersion, fine particle concentration: 30% by mass) (trade name MEK-ST, manufactured by Nissan Chemical Industries, Ltd.) is a photopolymerization initiator bis (η 5 -2,4-cyclopentadien-1-yl ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Ciba Japan Co., Ltd., trade name Irgacure 784) in a dispersion in which 0.01 g was dissolved, a polymerizable compound As a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate having the structure of the following formula (12) (manufactured by Aldrich, viscosity of 6,600 mPa · s at 25 ° C.):
実施例3
シリカゾル(メチルエチルケトン分散、微粒子濃度30質量%)(日産化学工業株式会社製、商品名MEK−ST)1.31gに光重合開始剤であるビス(η5−2,4−シクロペンタジエン−1−イル)−ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)−フェニル)チタニウム(チバ・ジャパン株式会社製、商品名Irgacure784)0.01gを溶解した分散液に、重合性化合物として下記式(13)の構造を有するプロピレングリコールジグリシジルエーテルのアクリル酸付加物(共栄社化学株式会社製、商品名エポキシエステル70PA、25℃における粘度1,400mPa・s):
Silica sol (methyl ethyl ketone dispersion, fine particle concentration 30% by mass) (Nissan Chemical Industry Co., Ltd., trade name MEK-ST) 1.31 g is a photopolymerization initiator bis (η 5 -2,4-cyclopentadien-1-yl ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Ciba Japan Co., Ltd., trade name Irgacure 784) in a dispersion in which 0.01 g was dissolved, a polymerizable compound As an acrylic acid adduct of propylene glycol diglycidyl ether having the structure of the following formula (13) (manufactured by Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 70PA, viscosity at 25 ° C .: 1,400 mPa · s):
実施例4
シリカゾル(メチルエチルケトン分散、微粒子濃度30質量%)(日産化学工業株式会社製、商品名MEK−ST)1.38gに光重合開始剤であるビス(η5−2,4−シクロペンタジエン−1−イル)−ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)−フェニル)チタニウム(チバ・ジャパン株式会社製、商品名Irgacure784)0.01gを溶解した分散液に、重合性化合物として下記式(14)の構造(オキシエチレン基の平均付加モル数:10)を有するエトキシ変性ビスフェノールAジアクリレート(新中村化学工業株式会社製、商品名NKエステルA−BPE−10、25℃における粘度550mPa・s):
また、この体積位相型の偽造防止ホログラム媒体にメタルハライドランプを15mW/cm2の照度で、30分間光照射を行い、光硬化した。硬化後に、スライドガラスの片側を剥離することで、偽造防止ホログラム層の脆弱性を測定し3段階で評価した。結果を表2に示す。
1.38 g of silica sol (methyl ethyl ketone dispersion, fine particle concentration: 30% by mass) (trade name MEK-ST, manufactured by Nissan Chemical Industries, Ltd.) is bis (η 5 -2,4-cyclopentadien-1-yl as a photopolymerization initiator. ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Ciba Japan Co., Ltd., trade name Irgacure 784) in a dispersion in which 0.01 g was dissolved, a polymerizable compound As an ethoxy-modified bisphenol A diacrylate having a structure of the following formula (14) (average number of added moles of oxyethylene group: 10) (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-BPE-10, at 25 ° C. (Viscosity 550 mPa · s):
Further, a metal halide lamp was irradiated on the volume phase type forgery-preventing hologram medium at an illuminance of 15 mW / cm 2 for 30 minutes for photocuring. After curing, one side of the slide glass was peeled to measure the vulnerability of the forgery-preventing hologram layer and evaluated in three stages. The results are shown in Table 2.
実施例5、6、7、8(最適シリカ微粒子濃度の評価)
シリカ微粒子の体積分率を20%(実施例5)、30%(実施例6)、40%(実施例7)、50%(実施例8)とした以外は、実施例4と同様にして体積位相型の偽造防止ホログラム媒体を作成し、回折効率と透明性を評価した。ホログラム記録時の回折効率の測定と透明性の評価は実施例1と同様の方法で行った。また、実施例4と同様にして、得られた偽造防止ホログラム層の脆弱性を測定し3段階で評価した。これら結果を表2に示す。Examples 5, 6, 7, and 8 (Evaluation of optimum silica fine particle concentration)
Except that the volume fraction of silica fine particles was 20% (Example 5), 30% (Example 6), 40% (Example 7), 50% (Example 8), the same as Example 4 Volume phase type anti-counterfeit hologram media were prepared, and diffraction efficiency and transparency were evaluated. Measurement of diffraction efficiency and evaluation of transparency during hologram recording were performed in the same manner as in Example 1. Further, in the same manner as in Example 4, the vulnerability of the obtained anti-counterfeit hologram layer was measured and evaluated in three stages. These results are shown in Table 2.
比較例1
シリカゾル(メチルエチルケトン分散、微粒子濃度30質量%)(日産化学工業株式会社製、商品名MEK−ST)6.38gに光重合開始剤であるビス(η5−2,4−シクロペンタジエン−1−イル)−ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)−フェニル)チタニウム(チバ・ジャパン株式会社製、商品名Irgacure784)0.02gを溶解した分散液に、重合性モノマーとして下記式(15)の構造を有するp−ビス(β−メタクリロイルオキシエチルチオ)キシリレン(25℃における粘度90mPa・s):
Bis (η 5 -2,4-cyclopentadien-1-yl) as a photopolymerization initiator is added to 6.38 g of silica sol (methyl ethyl ketone dispersion, fine particle concentration: 30% by mass) (trade name MEK-ST, manufactured by Nissan Chemical Industries, Ltd.) ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Ciba Japan Co., Ltd., trade name Irgacure 784) in a dispersion in which 0.02 g was dissolved in a polymerizable monomer P-bis (β-methacryloyloxyethylthio) xylylene (viscosity at 25 ° C. of 90 mPa · s) having the structure of the following formula (15):
1 ホログラム記録媒体 2Nd:YVO4レーザー 3 ビームエキスパンダ
4 He−Neレーザー 5,6,7,8,9,10,11 ミラー
12 ビームサンプラー 13 ハーフミラー 14,15 半波長板
16,17 偏光プリズム 18,19,20 光検出器
1 holographic recording medium 2Nd: YVO 4 laser 3 beam expander 4 the He-
Claims (8)
An anti-counterfeit hologram medium, wherein the anti-counterfeit hologram layer according to claim 7 is formed on a support, and the hologram layer is covered with a protective material.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008078896 | 2008-03-25 | ||
JP2008078896 | 2008-03-25 | ||
PCT/JP2009/055813 WO2009119576A1 (en) | 2008-03-25 | 2009-03-24 | Photosensitive composition for forgery preventive hologram and forgery preventive hologram medium |
Publications (1)
Publication Number | Publication Date |
---|---|
JPWO2009119576A1 true JPWO2009119576A1 (en) | 2011-07-28 |
Family
ID=41113768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010505671A Pending JPWO2009119576A1 (en) | 2008-03-25 | 2009-03-24 | Photosensitive composition for forgery prevention hologram and forgery prevention hologram medium |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2009119576A1 (en) |
TW (1) | TW200949443A (en) |
WO (1) | WO2009119576A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9091806B2 (en) * | 2012-04-05 | 2015-07-28 | Oracle International Corporation | Surface-normal optical coupling using a holographic recording material |
JP6303702B2 (en) * | 2014-03-28 | 2018-04-04 | 大日本印刷株式会社 | Scratch label |
JP7447816B2 (en) * | 2019-01-31 | 2024-03-12 | ソニーグループ株式会社 | Hologram recording composition, hologram recording medium, hologram, and optical devices and optical components using the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005321673A (en) * | 2004-05-11 | 2005-11-17 | Tdk Corp | Hologram recording material and hologram recording medium |
WO2006101003A1 (en) * | 2005-03-18 | 2006-09-28 | National University Corporation The University Of Electro-Communications | Photosensitive composition containing organic fine particles |
JP2007206704A (en) * | 2007-02-19 | 2007-08-16 | Yasuo Tomita | Volume hologram recording method |
JP2008503780A (en) * | 2004-06-22 | 2008-02-07 | クセトス・アーゲー | Photopolymerizable composition |
-
2009
- 2009-03-24 WO PCT/JP2009/055813 patent/WO2009119576A1/en active Application Filing
- 2009-03-24 JP JP2010505671A patent/JPWO2009119576A1/en active Pending
- 2009-03-25 TW TW098109753A patent/TW200949443A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005321673A (en) * | 2004-05-11 | 2005-11-17 | Tdk Corp | Hologram recording material and hologram recording medium |
JP2008503780A (en) * | 2004-06-22 | 2008-02-07 | クセトス・アーゲー | Photopolymerizable composition |
WO2006101003A1 (en) * | 2005-03-18 | 2006-09-28 | National University Corporation The University Of Electro-Communications | Photosensitive composition containing organic fine particles |
JP2007206704A (en) * | 2007-02-19 | 2007-08-16 | Yasuo Tomita | Volume hologram recording method |
Also Published As
Publication number | Publication date |
---|---|
TW200949443A (en) | 2009-12-01 |
WO2009119576A1 (en) | 2009-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5008080B2 (en) | Photosensitive composition containing organic fine particles | |
JP4461901B2 (en) | Hologram recording material and hologram recording medium | |
JP5568704B2 (en) | Holographic recording medium with control of photopolymerization and dark reaction | |
JP4893433B2 (en) | Volume hologram recording material and volume hologram recording medium | |
KR100714977B1 (en) | Composition of Organic-Inorganic Hybrid Photopolymer with Reduced Volume Shrinkage and Enhanced Diffraction Efficiency | |
JP2005321674A (en) | Hologram recording material and hologram recording medium | |
JP2005099612A (en) | Hologram recording material composition and hologram recording medium | |
JP5485548B2 (en) | Photosensitive composition containing organic-zirconia composite fine particles | |
WO2009119576A1 (en) | Photosensitive composition for forgery preventive hologram and forgery preventive hologram medium | |
JP2015079270A (en) | Composition for volume hologram recording material, and volume hologram recording medium | |
US20080176146A1 (en) | Photosensitive Composition Containing Organic Fine Particles | |
US20050036179A1 (en) | Holographic storage medium comprising metal-containing high refractive index region, and storage article containing same | |
JP4702814B2 (en) | Hologram recording medium and manufacturing method thereof | |
JP2006003388A (en) | Photosensitive composition for volume phase type hologram recording, hologram recording medium and method for manufacturing same, and hologram recording method | |
JP5408704B2 (en) | Photosensitive composition containing metal nanoparticle-dithiocarbamate group-containing polymer composite | |
JP2010260945A (en) | Vinylcyclopropane compound having low polymerization shrinkage and method for polymerizing the same | |
JP5284866B2 (en) | Photosensitive composition containing vinylcyclopropane compound | |
JP5729800B2 (en) | Photosensitive composition containing metal nanoparticle-ammonium group-containing branched polymer compound composite | |
JP6471390B2 (en) | Composition for volume hologram recording material containing hyperbranched polymer containing triazine ring | |
JP5826455B2 (en) | Composition for volume hologram recording material containing semiconductor fine particles | |
JP5344553B2 (en) | Two-photon absorption polymerizable composition and optical device | |
JP5286660B2 (en) | Hologram recording material and hologram recording medium | |
ES2955365T3 (en) | Light-curing composition | |
WO2020050321A1 (en) | Volume hologram-recording material composition containing triazine ring-containing hyperbranched polymer | |
Fimia et al. | A comparative review of silver halide photopolymerizable system and sol-gel holographic materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120223 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120223 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130501 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130701 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20140205 |