CN1051251A - 用于全息摄影的光聚合物薄膜 - Google Patents
用于全息摄影的光聚合物薄膜 Download PDFInfo
- Publication number
- CN1051251A CN1051251A CN90108849A CN90108849A CN1051251A CN 1051251 A CN1051251 A CN 1051251A CN 90108849 A CN90108849 A CN 90108849A CN 90108849 A CN90108849 A CN 90108849A CN 1051251 A CN1051251 A CN 1051251A
- Authority
- CN
- China
- Prior art keywords
- film
- ester
- acrylic acid
- monomer
- composition
- 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
- 239000000178 monomer Substances 0.000 claims abstract description 49
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002769 thiazolinyl group Chemical group 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 7
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- -1 chlorobenzene ester Chemical class 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003384 imaging method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 6
- 239000007767 bonding agent Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 125000004494 ethyl ester group Chemical group 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- UAGIUNHUUPYKPA-UHFFFAOYSA-N phenol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC1=CC=CC=C1 UAGIUNHUUPYKPA-UHFFFAOYSA-N 0.000 claims description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 239000010408 film Substances 0.000 description 79
- 239000007788 liquid Substances 0.000 description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- 238000009792 diffusion process Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000005855 radiation Effects 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 230000001427 coherent effect Effects 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229940106691 bisphenol a Drugs 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 238000007046 ethoxylation reaction Methods 0.000 description 4
- 239000000852 hydrogen donor Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- GMIUUCWUOPOETN-UHFFFAOYSA-N 2,4,5-triphenyl-1-(2,4,5-triphenylimidazol-2-yl)imidazole Chemical compound C1=CC=CC=C1C1=NC(N2C(=C(N=C2C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC=CC=2)(C=2C=CC=CC=2)N=C1C1=CC=CC=C1 GMIUUCWUOPOETN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005076 polymer ester Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KWQJKAHZHOILKK-UHFFFAOYSA-N (2,3,4,5,6-pentachlorophenyl) prop-2-enoate Chemical compound ClC1=C(Cl)C(Cl)=C(OC(=O)C=C)C(Cl)=C1Cl KWQJKAHZHOILKK-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- CVYRINMMHSLKTL-UHFFFAOYSA-N 1-bromo-9-ethenylcarbazole Chemical compound C=CN1C2=CC=CC=C2C2=C1C(Br)=CC=C2 CVYRINMMHSLKTL-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- DHLRWIMLMIMZEH-UHFFFAOYSA-N 2-[(4-methoxyphenyl)methyl]-1h-imidazole Chemical class C1=CC(OC)=CC=C1CC1=NC=CN1 DHLRWIMLMIMZEH-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical group C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- NKYDKCVZNMNZCM-UHFFFAOYSA-N 5-chloro-3h-1,3-benzothiazole-2-thione Chemical compound ClC1=CC=C2SC(S)=NC2=C1 NKYDKCVZNMNZCM-UHFFFAOYSA-N 0.000 description 1
- HOASVNMVYBSLSU-UHFFFAOYSA-N 6-ethoxy-3h-1,3-benzothiazole-2-thione Chemical compound CCOC1=CC=C2N=C(S)SC2=C1 HOASVNMVYBSLSU-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- FXEDRSGUZBCDMO-PHEQNACWSA-N [(e)-3-phenylprop-2-enoyl] (e)-3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1/C=C/C(=O)OC(=O)\C=C\C1=CC=CC=C1 FXEDRSGUZBCDMO-PHEQNACWSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- FXEDRSGUZBCDMO-UHFFFAOYSA-N cinnamic acid anhydride Natural products C=1C=CC=CC=1C=CC(=O)OC(=O)C=CC1=CC=CC=C1 FXEDRSGUZBCDMO-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical group O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- LBXQUCHUHCBNTC-UHFFFAOYSA-N dibutyl octanedioate Chemical compound CCCCOC(=O)CCCCCCC(=O)OCCCC LBXQUCHUHCBNTC-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IZXGMKHVTNJFAA-UHFFFAOYSA-N n-methyl-n-phenylprop-2-enamide Chemical compound C=CC(=O)N(C)C1=CC=CC=C1 IZXGMKHVTNJFAA-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
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
- G03H1/024—Hologram nature or properties
- G03H1/0248—Volume holograms
-
- 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
- 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
- G03H2001/0268—Inorganic recording material, e.g. photorefractive crystal [PRC]
-
- 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
- G03H1/04—Processes or apparatus for producing holograms
- G03H1/0402—Recording geometries or arrangements
- G03H2001/0415—Recording geometries or arrangements for recording reflection holograms
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/11—Vinyl alcohol polymer or derivative
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/111—Polymer of unsaturated acid or ester
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Holo Graphy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
通过在其中加入丙烯酸酐的方法,改善了含有聚
乙酸乙烯酯粘合剂和烯基不饱和单体的全息光聚合
物膜的膜速度。
Description
本发明涉及折射率成像(全息摄影),更确切地说,涉及一种光聚合物薄膜,该薄膜对用来记录影像的辐射线有良好的响应性能。
能够记录相位全息图,尤其是反射全息图的一些材料,因其各种各样的应用而在最近得到了重视,这些应用如图表技术,光学偶合装置,平视显示装置,陷波滤波器,等等。由于其高的折射率调制值(即高的衍射效率)和宽的带宽响应,重铬酸化的明胶一直是制备全息图所选择的材料。然而,重铬酸化的明胶具有较短的贮存寿命,以及在该材料被成像而含有全息图后,需要用湿法加工。由于重铬酸化的明胶较差的贮存寿命,它须在成像前的短时间内制备,或使用预坚膜的明胶,但这又会降低影像效率。
光聚合物薄膜已被建议用作重铬酸化的明胶的替代物,例如,Haugh的美国专利3,658,526公开了由可光聚合的薄膜通过对相干光源曝光而制备稳定的,具有高解像力的全息图。然而,Haugh公开的材料仅提供了对可见光辐射有限的影像响应,并且其应用仅限于透过全息图,即只有通过使光线透过该材料才能看到全息图。这种材料具有很小或根本没有反射效率,因此,在需要利用反射全息图的一些重要用途上,它不适用。
可以用来用记录透过和反射全息图的优良的光聚合物薄膜,最近在已出版的欧洲专利局专利申请89100495.4和89100498.8中已有公开。这些光聚合物薄膜可用通常的方式通过对相干光源曝光而成像,随后用加热或光泛射的方法使全息影像定影。用前述专利申请公开的各种技术可提高成像薄膜的效率。
已经发现,特定的光聚合物薄膜的膜速度,可以通过向该膜组合物中加入丙烯酸酐而增大。这里应用的“膜速度”这个术语的意思是指,在热加工后,能够得到记录全息图的反射效率大于90%所需要的能量。较高的膜速度不仅可以使生产速度提高,而且还能减少影像加工中,由于仪器的振动而产生带有缺陷的全息图的趋势。因此,本发明提供了一种用于折射率成像的光聚合物薄膜,它的基本组成如下:
(a)大约25%到90%的聚乙酸乙烯酯粘合剂;
(b)具有能够有效地提高膜速度需要量的丙烯酸酐;
(c)大约5%到60%的烯基不饱和单体;
(d)大约0到25%的增塑剂;和
(e)大约0.1%到10%的光引发剂;
其中所述的百分比是以膜的总重量而计算的重量百分比。
光聚合物薄膜通常是固态的,透明的,同时还需要有足够的柔软性,以便它能够紧密地与表面相接触(例如,风挡玻璃,头盔上的观望器或玻璃层),而这些表面最终要被粘上一层这种光聚合物薄膜。该膜的组份包括,聚乙酸乙烯酯粘合剂,烯基不饱和单体,丙烯酸酐,任意的增塑剂和其它通常用于光聚合物薄膜物体系中的组份,以及光引发体系。在如下所描述的对相干光曝光之后,单体聚合形成较高分子量的聚合物,与膜的未曝光区域相比,曝光部分具有不同的折射率和流变学特性。虽然膜通常是固态的,但在对相干光源曝光之前,之中,之后其组分都可扩散转移,直到最后用均一地对光化辐射曝光或用升高温度进行热处理的方法来使其定影为止。这种膜通常代表性的具有大约1-100微米的厚度。较薄的膜一般不能获得有用的反射效率。
这种薄膜反射的辐射线(例如光)具有一个光谱的和角度的带宽,这种带宽是由该膜的厚度和折射率调制值决定的。因此,膜的厚度必须与实际应用以及光学体系的光学要求相匹配,光学要求就是在实际应用中(“显示源”)用来照射全息图的光的带宽。一般地,相对较厚的薄膜将被选用在窄带宽的应用场合,相对较薄的薄膜将被选用在宽带宽的应用场合。聚乙酸乙烯酯粘合剂可以是均聚物,或含有共聚单体,例如乙基乙烯醚,它可调变薄膜的化学及机械性能,例如溶解性,混溶性,粘附性,柔软性,或坚硬性。
从结果来看,丙烯酸酐在一些组合物中可用来增加膜速度,但其原因还不得了解。采用丙酸酐或不饱和酸酐如甲基丙烯酸酐和肉桂酸酐还没有取得过相似的结果。同样,当用聚乙烯醇缩丁醛作为粘合剂而向组合物中加入丙烯酸酐时,也没有观察到膜速度有任何改善。
这种薄膜含有至少一种烯基不饱和单体。此单体能够进行自由基引发的加成聚合反应,具有高于100℃的沸点,能够与涂覆溶剂以及选择的粘合剂混溶。该单体通常将在末端位置上含有不饱和基团。一般是选择液态单体,但固态单体也可被选择以增加其优越性,通常是与一种或多种液态单体结合使用,只要固态单体在通常的固体膜组合物中能够扩散转移。
用于本发明的组合物的一类优选的单体是液态的,能够进行加成聚合反应的且具有高于100℃的沸点的烯基不饱和化合物,它含有选自组成下列基团的一个或多个部分:取代的或未取代的苯基,二苯基,苯氧基,萘基,萘氧基,含有至多3个芳香环的杂环芳香基团;氯;和溴。这种单体可以含有至少一个这种部分,并可含有二个或多个相同的或不同的这种基团部分。只要该单体能够保持液态。可以存在下述取代基团,如低级烷基,烷氧基,苯基,苯氧基,羧基,羰基,氰基,氯,溴,或它们的结合,只要单体能够保持液态并且在可光聚合的层中可扩散。代表性的液态单体包括:丙烯酸-2-苯氧基乙酯,甲基丙烯酸-2-苯氧乙酯,苯酚乙氧基化合物单丙烯酸酯,丙烯酸-2-(对氯苯氧基)乙酯,丙烯酸对氯苯酯,丙烯酸苯酯,丙烯酸2-苯基乙酯,丙烯酸-2-(1-萘氧基)乙酯,甲基丙烯酸邻二苯酯,丙烯酸邻二苯酯、及其混合物。
虽然在本发明中使用的大多数单体是液态的,但它们可以与一种或多种烯基不饱和固态单体一起混合使用,例如在H.Kamogawa等著的Journal of Polymer Science:Polymer Chemistry Edition,第18卷(1979),9-18页中公开的烯基不饱和咔唑单体;丙烯酸-2-萘酯,丙烯酸五氯苯酯,丙烯酸-2-,4,6-三溴苯酯;丙烯酸-2-(2-萘氧基)乙酯;N-苯基马来酰亚胺,甲基丙烯酸对二苯酯,2-乙烯基萘,甲基丙烯酸-2-萘酯,N-苯基甲基丙烯酰胺,甲基丙烯酸叔丁苯酯。
含有接到咔唑部分的氮原子上的乙烯基的烯基不饱和咔唑单体一般为固体。这类合适的单体包括,N-乙烯基咔唑和3,6-二溴-9-乙烯基咔唑。特别优选的烯基不饱和单体的混合物含有N-乙烯基咔唑与一种或多种上述液态单体的结合,特别是与丙烯酸-2-苯氧乙酯,苯酚乙氧基化物单丙烯酸酯,乙氧基化的双酚A的二丙烯酸酯,或其混合物。
如果希望光聚合物交联,高至约5%的重量百分比的至少一种多官能团单体可被结合到组合物中,这种多官能团单体含有2个或多个终端烯基不饱和基团。多官能团的单体必须能与组合物的其它组份相混溶,且优选的是液体的。适合的多官能团单体包括:双酚A的二-(2-丙烯酰氧乙基)醚,乙氧基化的双酚A的二丙烯酸酯,二丙烯酸三甘醇酯,三羟甲基丙烷的三丙酸酯,等等。本发明的组合物中使用的一种优选的交联是乙氧基化的双酚A的二丙烯酸酯。
引发剂体系含有一种或多种化合物,它们在光化辐射激化时,可直接提供自由基。光化辐射的意思是指这样一种辐射,它能够产生引发单体材料聚合反应所需要的自由基。它也可含有多种化合物,其中的一种化合物在被另一种化合物作用后能够产生自由基,这另一种化合物也可称作为敏化剂,它能被光化辐射激活。在实施本发明的过程中使用的光引发剂体系将典型地含有一种光引发剂和一种敏化剂,这种敏化剂可将光谱响应扩展到近紫外,可见光,和/或近红外光谱区域。
优选的引发剂体系是2,4,5-三苯基咪唑基双聚体,和链转移剂或氢授体,及其混合物,由可见光敏化剂敏化。优选的2,4,5-三苯基咪唑基二聚体包括:CDM-HABI,即2-(邻-氯苯基)-4,5-双(间-甲氧苯基)-咪唑二聚体;邻-氯HABI,即1,1'-二咪唑,2,2'-双(邻-氯苯基)-4,4'5,5'-四苯基-;和TCTM-HABI,即1H-咪唑,2,5-双(邻-氯苯基)-4-[3,4-二甲氧苯基]-,二聚体,每种通常都与氢授体共用。
一组优选的敏化剂包括:在Baum和Henry的美国专利3,652,275中公开的双(对-二烷基氨基苯亚甲基)酮,和Dueber的美国专利4,162,162中公开的亚芳基芳基酮。特别优选的敏化剂包括下列一些:DEAW,即环戊酮,2,5-双[4-(二乙基氨基)苯基-亚甲基]-;和JAW,即环戊酮2,5-双[(2,3,6,7-四氢-1H,5H-苯并[i,j]喹嗪-1-基)亚甲基]-。其它特别有用的敏化剂是环戊酮,2,5-双[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-亚基)亚乙基],CAS27713-85-5;和环戊酮,2,5-双-(-2-乙基萘并[1,2-d]噻唑-2(1H)-亚基)亚乙基],CAS27714-25-6。
适宜的氢授体包括:2-巯基苯并恶唑,2-巯基苯并噻唑,4-甲基-4H-1,2,4-三唑-3-硫醇,等等。对于含有N-乙烯基咔唑单体的组合物特别优选的其它适宜的氢授体化合物,是5-氯-2-巯基苯并噻唑,2-巯基苯并噻唑;1H-1,2,4-三唑-3-硫醇;6-乙氧基-2-巯基苯并噻唑;4-甲基-4H-1,2,4,-三唑-3硫醇;1-十二烷硫醇,及其混合物。
也可以存在其它的通常加入到光聚合物组合物中的组份,以便调整膜的物理性质。这样的组份包括:增塑剂,热稳定剂,光学增白(亮)剂,紫外辐射稳定剂,粘附调节剂,涂覆助剂,剥离剂。
可以存在一种增塑剂,用通常的方式来调节膜的粘附性能,柔软性,坚硬性,以及其它机械性能。待选的增塑剂包括:三甘醇二辛酸酯,三甘醇-二(2-乙基己酸酯),四甘醇二庚酸酯,癸二酸二乙酯,辛二酸二丁酯,其它的能产生相同结果的增塑剂对于本领域熟练的技术人员是很明显的。如果增塑剂和固体单体的混合物可以采用,那将更好,只要增塑剂和单体的混合物保持液态即可。
通常要存在一种热聚合反应抑制剂,以便改善组合物的存贮稳定性,使用的热稳定剂包括:氢醌,苯醌,对-甲氧基苯酚,烷基和芳基取代的氢醌和醌,叔丁基儿茶酚,焦培酚,β-萘酚,2,6-二叔丁基-对-甲苯酚,吩噻嗪和氯醌。因为单体中通常由其制造者加入了热聚合反应抑制剂,所以没有必要再加额外的抑制剂。
有用的光学增白(亮)剂包括那些在Held的美国专利3,854,950中公开的。一种代表性的光学增白(亮)剂是7-(4'-氯-6'-二乙基氨基-1',3',5'-三嗪-4'-基)氨基 3-苯基香豆素。在本发明中使用的紫外辐射吸收材料也在Held的美国专利3,854,950中公开。
光聚合物组合物中各组份的比例一般地将落在下列的百分比范围之内,百分数依据整个组合物的重量计算:聚乙酸乙烯酯粘合剂,25%到90%,优选的是45%到75%;丙烯酸酐,0.5%到5%,优选的是2%到4%;单体,5%到60%,优选的是15%到50%;增塑剂0到25%,优选的是0到15%;光引发剂体系,0.1%到10%,优选的是1%到7%;以及任选的组份,0到5%,典型的是1%到4%。如果粘合剂的量低于大约25%,或单体的量超过大约60%,那么组合物将没有足够的粘度以形成固体膜。粘合剂的存在量应限制在大约90%以内,因为在加入过多量时,其作用丧失很大。导致膜具有很小的折射率调制值。同样,所用的单体的量应至少大约5%,因为较低的量将不会产生具有实用的折射率调制值的膜。
在实施本发明的过程中,光敏组合物首先被涂布,分层,或更优选的是,旋转涂布到一个透明的支撑体上,该支撑体(在这里指一层膜)在加工过程中为组合物提供了结构完整性。因为光敏膜一般地只有1-100微米厚,所以必须有一个支撑体以防止在加工过程中膜的破裂或任何拉伸,否则将会影响到在膜中产生的用来形成全息图的干涉条纹的空间间隔。透明支撑体必须具有足够的光学质量,使其在形成全息图时不过多地吸附或散射经过它的相干光。同样,支撑体一般地将具有足够的柔软性,以便在它与将要被膜永久地裱贴的表面接触时不致从膜上脱离下来。如一个弯曲的基层(例如风挡玻璃或头盔观望镜),如果永久裱贴的表面是平面的如玻璃板,那么便需要很小的柔软性则可。具有一定优点的可选择的代表性透明支撑体包括:聚对苯二酸乙烯酯膜,聚甲基丙烯酸甲酯膜,聚碳酸酯,和三乙酸纤维素酯。
在一些应用场合,可能希望保持支撑体为光聚合物膜的永久性覆盖层或保护层,在这种情况下,支撑体和光聚合物膜可以永久地结合在一起。被支撑起的光聚合物膜的另一侧可以有一个暂时性的保护层,如聚乙烯或聚丙烯膜,可剥离地粘附其上。通常的中间层或涂层可以用于使粘附和/或剥离容易的特性,这些特性在一些特殊用途的场合是所希望的。
在光聚合物薄膜成像含有反射全息图之后,采用本领域熟知技术,一般地要将该薄膜加热到高于50℃的温度,优选的是在80到160℃之间,以提高其效果。可很容易地使折射率调制值得到2倍到3倍的改善。可以在影像定影之前或之后完成热增强处理过程,影像的定影是如前面描述的那样,用光化辐射泛射薄膜来完成,但一般情况下是在定影步骤之后完成的。热处理过程可同时用硬化的方法或聚合全息图中的可光聚合材料的方法来定影增强的全息图。热增强的速度和热硬化的速度都随温度的增加而增加,大多数的效益是在早期的处理阶段中获取的。例如,当使用100℃的增强温度时,大多数的增强作用是在前5到10分钟内发生的,而在随后的一个小时内只有很小的改善。
同时也发现了,全息图的光学性质,如衍射和反射效率,在降解了一段时间后趋于稳定,但前提是在反射全息图形成之后,用-含有液态单体的溶液来处理该膜。在这处理过程中,通过浸泡,喷雾,或其它相似的技术,使该薄膜的表面暴露于液体单体溶液之中,从而使单体被吸收到膜之中。单体可以是与薄膜组合物中所含有的单体相同的,或是不同的液体单体。然后将膜干燥,被吸收的单体通过将膜对光化辐射如紫外或可见光曝光而聚合。这一处理过程不仅具有对光学性质的稳定作用,而且还影响干涉条纹平面之间的空间间隔,进而使全息镜能够反射较长波长的光。同时,反射效率也受到影响。因此,通过选择特定的液体单体,负载溶剂,聚合反应前的浸湿时间,可以永久地调变薄膜的光学性质。
如需要,在成像步骤中,薄膜中还可含有一种相对挥发性的溶剂,它可在成像之后被除去。在这样的实例中,当该试剂被去除之后,全息镜的条纹间隔会减小,从而使膜反射波长比用来形成全息镜的波长更短的辐射。这一效果可通过选择能和所选择的膜组合物混溶的溶剂或增塑剂来完成,而这些溶剂或增塑剂又可用蒸发或在膜的热加工过程中除去。
响应的波长可以通过扩散一种非挥发性的增塑剂或单体到已成像和加工的全息图中而改变。这一过程可以很方便地通过层压一扩散组份到含有已成像和加工过的全息图的膜上的方法来完成,扩散组份中含有粘合剂和单体和/或增塑剂,并使其发生扩散作用。该扩散组份可以是一片未曝光的膜或它可以含有单体和/或增塑剂,被层压的膜和扩散组份在扩散过程中可被加热,或者扩散作用在室温下完成。为了停止扩散,可以在扩散后将扩散组份移去,或者,如需要,扩散可以一直进行到平衡,在适当的时候移去。如果扩散组份中含有单体,那么可以用加热层压层和/或将其对光化辐射曝光而使扩散作用停止。
本发明的光聚合物薄膜可被用于多种应用全息图可被用于显示,如在广告和包装上,在保密应用场合,如在信用卡,银行汇票,彩票等等;亦可用于信息贮存,平视显示器等。
本发明将用下面的实施例作参考来进一步说明,其中共聚物组合物将以重量百分比给出。
AA 丙烯酸酐
DEAW 环戊酮,2,5-双{[4-(二乙基胺基)
-2-甲苯基]亚甲基}-;CAS1111
4-17-3
氟代脂肪族的聚合物酯;CAS11114
-17-3;3M公司
50%的氟代脂肪族的聚合物酯的乙酸乙酯
溶液;3M公司
JAW 环戊酮,2,5-双{[2,3,6,7]-四氢
-1H,5H-苯并[i,j]喹嗪-1-基)亚
甲基}-
MMT 4-甲基-4H-1,2,4-三
唑-3-硫醇;CAS24854-43-1
NVC N-乙烯基咔唑;9-乙烯基咔唑;CAS
1484-13-5
10-Cl-HABI 1,1'-二咪唑,2,2'-双[邻-氯苯基]
-4,4',5,5'-四苯基-;CAS
1707-68-2
Photomer 4039 单丙烯酸苯酚乙氧基化物酯;CAS 56641-
05-5;Henkel Process化学公司
Sartomer 349 乙氧基化的双酚A的二丙烯酸酯;CAS
24447-78-7;Sartomer公司,
West Chester,PA.
Vinac B-100 聚(乙酸乙烯酯);M.W.350,000;
CAS9003-20-7;Air Produets;
膜的制备
在琥珀瓶中,在黄灯或红灯下,加入各种组份到溶剂中,同时用机械搅拌器混合,直到完全溶解,制得没有敏化染料的涂布溶液。所有的组份都不需进一步纯化,直接由供应商处获得使用。敏化染料,DEAW和JAW,在红灯下加入,所有随后的溶液操作和其膜的形成都仅在红灯下完成。可以理解“整个固体”指的是组合物中的所有非挥发组份,虽然它们中的某些组份可能是非挥发性液体,而不是固体。
在Talboy涂布机上装上一把250微米的手术刀,3.7M的干燥机装置,在40-50℃,用层压机将溶液涂布到100微米厚的透明的聚对苯二酸乙烯酯支撑体上(Mylar 聚对苯二酸乙烯酯膜)。当涂层物从干燥机中出来时,用一张23微米厚的聚对苯二酸乙烯酯覆盖层层压到涂层上。使用之前,涂层样品都在室温下贮存于黑色的聚乙烯袋中。
样品评价:
涂布好的膜连同膜支撑体和覆盖层一起被切成10×13cm的部分,然后将其夹在-透明玻璃板和铝镜的正面之间。用-薄层二甲苯来光学偶合玻璃板和铝镜到膜上。通过用-垂直于膜表面的平行的488nm氩离子激光束曝光而将全息镜记录在膜之中,这样激光束穿过玻璃板,二甲苯,聚对苯二酸乙烯酯覆盖层,涂层,和聚对苯二酸乙烯酯支撑体,二甲苯,然后被铝镜反射回来,再经过二甲苯,聚对苯二酸乙烯酯支撑体,涂层,聚对苯二酸乙烯酯覆盖层。二甲苯和玻璃板。在所有情况下,激光束的强度都是10mw/cm2,直径为2-3cm。改变曝光时间,每一层形成16个影像。
在激光曝光后,将玻璃板和铝镜拿掉,用Theimer-Strahler#5027汞弧光聚合物灯的输出光(Exposure System公司,Bridgeport CT),该灯安置在Douthitt DCOP-x曝光器上(Douthitt公司,Detroit,MI),将膜对紫外和可见光进行全部曝光。在一吹风通风炉中将涂层在100℃下热加工30分钟。
用Perkin Elmer Lambda-9型光度计,于400-700nm的范围内记录每一种全息影像的透射光谱,从透射光谱上确定最大反射效率。膜速度的定义为:在热加工后,获得大于90%的反射效率所需要的能量。
实施例1-5
这些实施例给出了丙烯酸酐对膜速度的影响。
表1和2中给出的组合物被涂布到聚对苯二酸乙烯酯上,然后曝光,加工,再用在一般步骤中描述的方法来评价。加工后的反射效率,作为曝光量的函数列于表3和表4中。
FC-430 0.056(0.2) 0.057(0.2) 0.056(0.2)
DEAW 0.0077(0.03) 0.0078(0.03) 0.0077(0.03)
溶剂(mL)
二氯甲烷 114 116 114
甲醇 3.5 3.6 3.5
厚度(微米) 28.5 30.1 29.8
a%以组合物中整个固体的重量计算
表2
组份(gm) 实施例
(%以重量计)a 4 5
AA 0.82 (3.1) 0.99 (3.8)
Photomer 4039 4.26 (16.3) 4.26 (16.3)
NVC 1.99 (7.6) 1.98 (7.6)
Sartomer 349 0.76 (2.9) 0.76 (2.9)
MMT 0.54 (0.21) 0.53 (2.0)
o-Cl HABI 0.93 (3.6) 0.93 (3.6)
FC-430 0.056 (0.22) 0.055 (0.2)
DEAW 0.0078 (0.03) 0.0074 (0.03)
溶剂(mL)
二氯甲烷 115 115
甲醇 3.6 3.6
厚度(微米) 31.1 30.4
a%以组合物中整个固体的重量计算
表3
反射效率(%)
曝光量(mJ/cm2) 实施例1 实施例2 实施例3
@488nm (0% AA) (1.0% AA) (2.0% AA)
11 13 56 52
15 41 72 71
19 62 84 90
25 76 92 92
32 75 96 96
42 88 -a -
55 96 - -
271 98.7 99.3 96.1
a- 指示出该值没有被测定
表4
反射效率(%)
曝光量(mJ/cm2) 实施例4 实施例5
@488nm (3.1% AA) (3.8% AA)
11 81 74
15 91 87
19 96 95
25 97 97
32 97 96
271 98.0 98.2
实施例6-7
这些实施例说明了采用JAW作为含有丙烯酸酐的组合物的敏化剂。制备表5中的溶液,然后按一般步骤中所描述的方法来涂布和曝光,但不同的是用200微米的手术刀来涂布膜,用来成像的激光的波长是514nm而不是488nm。除去覆盖层,把膜层压到一块10×13cm的玻璃板上。用一薄层二甲苯来光学偶合膜到镜上。将膜用垂直于其表面平行的514nm的氩离子激光束曝光,从而使全息镜记录在膜中,这样光束便穿过了玻璃板,涂层,PET支撑体,二甲苯,然后被镜子反射回来,再穿过二甲苯,PET支撑体,涂层,和玻璃板。作为曝光量的函数的反射效率列于表6中。
表5
组份(gm) 实施例
(%以重量计)a 6 7
AA 0 (0) 1.20 (2.91)
JAW 0.032 (0.08) 0.032 (0.08)
FC-431 0.16 (0.40) 0.16 (0.39)
MMT 1.20 (2.99) 1.20 (2.91)
o-CL HABI 1.20 (2.99) 1.20 (2.91)
′Sartomer 349 1.20 (2.99) 1.20 (2.91)
NVC 3.60 (8.98) 3.60 (8.72)
Vinac B-100 25.9 (64.60) 25.9 (62.72)
溶剂(mL)
甲醇 8.0 8.0
二氯甲烷 152.0 152.0
a%以组合物中整个固体的重量计;用一把8密耳的刀(200微米)涂布组合物,得到一厚度为25±2微米的膜
表6
反射效率(%)a
曝光量(mJ/cm2) 实施例6 实施例7
@514nm (0% AA) (2.9% AA)
4 46.6 87.4
5 79.1 90.5
6 90.8 97.5
8 92.0 96.4
11 95.3 99.4
14 98.8 99.2
18 99.5 99.3
24 99.9 97.3
41 98.7 98.5
118 98.7 99.8
a 成像前膜被层压到玻璃上
Claims (4)
1、一种用于折射率成像的光聚合物膜,其基本组成为。
(a)约25%到90%的聚乙酸乙烯酯粘合剂;
(b)能有效地增加膜速度的量的丙烯酸酐;
(c)约5%至60%的烯基不饱和单体。
(d)约0到25%的增塑剂;和
(e)约0.1%到10%的光引发剂;
其中,所述的百分比是以整个膜的重量而计的重量百分比。
2、权利要求1所述的膜,其中含有约0.5%到5%重量的丙烯酸酐。
3、权利要求2所述的光聚合物膜,其中粘合剂是聚乙酸乙烯酯均聚物
4、权利要求2所述的光聚合物膜,其中所述的单体是选自构成如下一组物质:丙烯酸-2-苯氧乙酯,甲基丙烯酸-2-苯氧乙酯,单丙烯酸苯酚乙氧基化物酯,丙烯酸-2-(对-氯苯氧基)乙酯,丙烯酸对-氯苯酯,丙烯酸苯酯,丙烯酸-2-苯基乙酯,丙烯酸-2-(1-萘氧基)乙酯,甲基丙烯酸邻-二苯酯,丙烯酸邻二苯酯,及其混合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/414,419 US5013632A (en) | 1989-09-29 | 1989-09-29 | Photopolymer film for holography |
US414,419 | 1989-09-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1051251A true CN1051251A (zh) | 1991-05-08 |
Family
ID=23641378
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN90108849A Pending CN1051251A (zh) | 1989-09-29 | 1990-09-29 | 用于全息摄影的光聚合物薄膜 |
Country Status (8)
Country | Link |
---|---|
US (1) | US5013632A (zh) |
EP (1) | EP0420225B1 (zh) |
JP (1) | JPH03192289A (zh) |
KR (1) | KR910006771A (zh) |
CN (1) | CN1051251A (zh) |
AU (1) | AU613280B2 (zh) |
CA (1) | CA2026230A1 (zh) |
DE (1) | DE69000967D1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101034257B (zh) * | 2007-04-06 | 2010-09-08 | 上海复旦天臣新技术有限公司 | 用于全息记录的感光薄膜及其制备方法 |
CN107533318A (zh) * | 2015-04-27 | 2018-01-02 | 索尼公司 | 全息记录组合物、全息记录介质和全息记录介质的制造方法 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4942112A (en) * | 1988-01-15 | 1990-07-17 | E. I. Du Pont De Nemours And Company | Photopolymerizable compositions and elements for refractive index imaging |
US5464690A (en) * | 1994-04-04 | 1995-11-07 | Novavision, Inc. | Holographic document and method for forming |
EP0780731B1 (en) * | 1995-12-22 | 2002-04-17 | Mitsubishi Chemical Corporation | Photopolymerizable composition for a color filter, color filter and liquid crystal display device |
US5786127A (en) * | 1996-08-15 | 1998-07-28 | Western Litho Plate & Supply Co. | Photosensitive element having an overcoat which increases photo-speed and is substantially impermeable to oxygen |
US6638386B2 (en) | 2000-04-19 | 2003-10-28 | Novavision, Inc. | Method for making holographic foil |
US6497778B1 (en) | 2000-04-19 | 2002-12-24 | Novavision, Inc. | Method for making holographic foil |
US6775839B1 (en) | 2002-03-15 | 2004-08-10 | O'brien Patrick J. | Optical storage device with print layer surface feature |
DE102008009332A1 (de) | 2008-02-14 | 2009-08-20 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Optische Elemente mit Gradientenstruktur |
GB2476275A (en) | 2009-12-17 | 2011-06-22 | Dublin Inst Of Technology | Photosensitive holographic recording medium comprising glycerol |
US8703363B2 (en) | 2011-02-16 | 2014-04-22 | Sabic Innovative Plastic Ip B.V. | Reflection hologram storage method |
US20130003151A1 (en) | 2011-06-29 | 2013-01-03 | Sabic Innovative Plastics Ip B.V. | Holographic storage method and article |
US20130004887A1 (en) | 2011-06-29 | 2013-01-03 | Sabic Innovative Plastics Ip B.V. | Holographic recording medium |
US20130038916A1 (en) | 2011-08-11 | 2013-02-14 | Sabic Innovative Plastics Ip B.V. | Method of making multiplexed transmission holograms |
US20130071773A1 (en) | 2011-09-16 | 2013-03-21 | Sabic Innovative Plastics Ip B.V. | Holographic storage medium |
EP2979126B1 (en) * | 2013-03-28 | 2022-11-30 | Snap Inc. | Improvements in and relating to displays |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3144905A1 (de) * | 1981-11-12 | 1983-05-19 | Basf Ag, 6700 Ludwigshafen | Zur herstellung von druck- und reliefformen geeignetes lichtempfindliches auszeichnungsmaterial und verfahren zur herstellung von druck- und reliefformen mittels dieses aufzeichnungsmaterials |
US4535052A (en) * | 1983-05-02 | 1985-08-13 | E. I. Du Pont De Nemours And Company | Constrained n-alkylamino aryl ketones as sensitizers for photopolymer compositions |
US4942112A (en) * | 1988-01-15 | 1990-07-17 | E. I. Du Pont De Nemours And Company | Photopolymerizable compositions and elements for refractive index imaging |
US4942102A (en) * | 1988-01-15 | 1990-07-17 | E. I. Du Pont De Nemours And Company | Holographic optical elements having a reflection hologram formed in a photopolymer |
US4950567A (en) * | 1988-01-15 | 1990-08-21 | E. I. Du Pont De Nemours And Company | Holographic optical combiners for head-up displays |
BR8900132A (pt) * | 1988-01-15 | 1989-09-12 | Du Pont | Processo para a formacao de um halograma de reflexao;processo para a formacao e a intensificacao de um halograma de reflexao em um meio de registro fotopolimerizavel substancialmente solido;e projecao de um feixe do objeto com a mesma radiacao actinica coerente aproximadamente na direcao oposta a do feixe de referencia |
-
1989
- 1989-09-29 US US07/414,419 patent/US5013632A/en not_active Expired - Fee Related
-
1990
- 1990-09-26 CA CA002026230A patent/CA2026230A1/en not_active Abandoned
- 1990-09-27 EP EP90118527A patent/EP0420225B1/en not_active Expired - Lifetime
- 1990-09-27 DE DE9090118527T patent/DE69000967D1/de not_active Expired - Lifetime
- 1990-09-28 AU AU63610/90A patent/AU613280B2/en not_active Ceased
- 1990-09-28 JP JP2257567A patent/JPH03192289A/ja active Pending
- 1990-09-28 KR KR1019900015571A patent/KR910006771A/ko not_active Application Discontinuation
- 1990-09-29 CN CN90108849A patent/CN1051251A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101034257B (zh) * | 2007-04-06 | 2010-09-08 | 上海复旦天臣新技术有限公司 | 用于全息记录的感光薄膜及其制备方法 |
CN107533318A (zh) * | 2015-04-27 | 2018-01-02 | 索尼公司 | 全息记录组合物、全息记录介质和全息记录介质的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0420225A3 (en) | 1991-07-17 |
AU613280B2 (en) | 1991-07-25 |
EP0420225B1 (en) | 1993-02-24 |
AU6361090A (en) | 1991-04-26 |
JPH03192289A (ja) | 1991-08-22 |
DE69000967D1 (en) | 1993-04-01 |
EP0420225A2 (en) | 1991-04-03 |
CA2026230A1 (en) | 1991-03-30 |
KR910006771A (ko) | 1991-04-30 |
US5013632A (en) | 1991-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1048756A (zh) | 为改变全息图波长响应的干性薄膜方法 | |
CN1051251A (zh) | 用于全息摄影的光聚合物薄膜 | |
CN1049564A (zh) | 改进的全息陷波滤波器 | |
JP2625028B2 (ja) | ホログラフ用ホトポリマ組成物および屈折率イメージングエレメント | |
JP2604172B2 (ja) | 印刷版,レリーフ版の製造に適した光重合可能の記録媒体 | |
JP3299274B2 (ja) | 光重合可能な組成物のための可視の光増感剤 | |
JP2988756B2 (ja) | 光重合開始剤およびこれを含有する光重合性組成物 | |
JPH0338684A (ja) | ヘッドアップ・ディスプレー用改良ホログラフィー光学コンバイナー | |
CN1043797A (zh) | 用于光聚合组合物的可见光增感剂 | |
JPH09506441A (ja) | 広帯域反射ホログラムとその乾式製造方法 | |
JPH0355587A (ja) | ホトポリマ中に形成された反射ホログラムを有するホログラフ光学エレメント | |
JPH1062986A (ja) | 感放射線性着色組成物 | |
CN86108826A (zh) | 含有离子染料化合物作为引发剂的光敏材料 | |
WO2008122226A1 (fr) | Membrane sensible pour réfléchir un enregistrement d'hologramme et son procédé de préparation | |
CN1292892A (zh) | 残留物含量降低的感光组合物连续液态加工法 | |
CN1645253A (zh) | 感光性树脂组合物,使用该组合物的感光性元件、保护层图案的制造法及印刷电路板的制造法 | |
CN1054324A (zh) | 对长波长可见光光化辐射敏感的光聚合组合物 | |
CN1055609A (zh) | 可用水加工的光敏元件 | |
FR2483637A1 (fr) | Materiau de formation d'une image a sec | |
JPH07210065A (ja) | ガラスへの改良された接着性を有する記録媒体 | |
JPH05239116A (ja) | 光重合性組成物用の可視域光増感剤 | |
FR2500467A1 (zh) | ||
JPH0962002A (ja) | 感放射線性組成物 | |
CN1035004A (zh) | 折射率成像用贮存稳定的光聚合材料 | |
CN1053846A (zh) | 用于记录体积透过型全息图的元件 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C01 | Deemed withdrawal of patent application (patent law 1993) | ||
WD01 | Invention patent application deemed withdrawn after publication |