CN101001923A - 具有高存储密度的光记录材料 - Google Patents
具有高存储密度的光记录材料 Download PDFInfo
- Publication number
- CN101001923A CN101001923A CNA200580027018XA CN200580027018A CN101001923A CN 101001923 A CN101001923 A CN 101001923A CN A200580027018X A CNA200580027018X A CN A200580027018XA CN 200580027018 A CN200580027018 A CN 200580027018A CN 101001923 A CN101001923 A CN 101001923A
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- China
- Prior art keywords
- sub
- unsubstituted
- group
- replace
- alkyl
- 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.)
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- 230000003287 optical effect Effects 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims description 38
- 238000003860 storage Methods 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- -1 nitro, formyl Chemical group 0.000 claims description 55
- 150000003254 radicals Chemical class 0.000 claims description 35
- 229910052736 halogen Inorganic materials 0.000 claims description 29
- 150000002367 halogens Chemical class 0.000 claims description 29
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 16
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 8
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 150000003053 piperidines Chemical class 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000002310 reflectometry Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 4
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- 108091074834 12 family Proteins 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
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- 239000010410 layer Substances 0.000 description 74
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- 150000002500 ions Chemical class 0.000 description 19
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
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- 238000000576 coating method Methods 0.000 description 10
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- 229920000515 polycarbonate Polymers 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 125000002524 organometallic group Chemical group 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 150000003839 salts Chemical class 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
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- 230000035945 sensitivity Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000002769 thiazolinyl group Chemical group 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
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- 238000013375 chromatographic separation Methods 0.000 description 3
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- 150000004696 coordination complex Chemical class 0.000 description 3
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- 229910052731 fluorine Inorganic materials 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- BNDRWEVUODOUDW-UHFFFAOYSA-N 3-Hydroxy-3-methylbutan-2-one Chemical compound CC(=O)C(C)(C)O BNDRWEVUODOUDW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 150000003851 azoles Chemical class 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000013500 data storage Methods 0.000 description 2
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- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
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- 238000009998 heat setting Methods 0.000 description 2
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- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
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- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
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- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 2
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Classifications
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- G—PHYSICS
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Abstract
本发明涉及式(I)、(II)、(III)或(IV)的新化合物和其在光记录介质的记录层中的用途,光记录介质包括基材、记录层和任选的一个或多个反射层。本化合物具有式(1)、式(2)式(3)或式(4):或其互变异构体,其中G1和G2各自独立的是式(Ⅴ);X1和X2各自相互独立地是直接键或由1至8个成员组成的链,每个成员独立地选自下列基团:CR12=CR13,C=CR12R13,CR12R13,C=O,C=S,C=N(R14),N(R14),O或S,优选直接键或由1、2、3或4个成员组成的链,最优选直接键或下列链:CR12R13,C=O,C=S,C=N(R14),N(R14),O或S;A1,A2和A3是CR15R16,[见式(Ⅵ)],N(R14),O,S,Se,N=C(R18)或CR19=CR20,且A4是O,S或Se;M1是9至12族的过渡金属,优选Co,Cu,Ni,Pd或Zn,特别是Co,Cu或Ni,或是SiR21R22,GeR21R22,PR21R22或AlR21;且Q1和Q2各自独立的是C(R23),N或P。对于进一步取代基的详细定义,参见说明书。记录和播放特别在从350至500nm波长处得以实施,例如使用蓝色激光。记录和播放品质是出色的、并容许高存储密度。
Description
本发明涉及新的光记录材料,其具有出色的记录和播放品质,特别是在350-500nm波长处。在相同波长处,可以非常有利地、高灵敏度地实现记录和播放,并且可实现的存储密度比已知材料显著地提高。此外,按照本发明的材料在记录前和后、甚至在特别苛刻条件、例如暴露于目光或荧光照明、加热和/或高湿度下也具有很好的贮存性能。此外,其制备简单,并且使用通常的涂层方法例如旋转-涂敷可以很容易地再生。
JP-A-11/34500,JP-A-11/92479和EP-A-0 903 733公开了下式色料(colorants)的金属和硼复合物
和
其可以在从520至690nm处使用,用于光记录材料,例如CD-R或DVD-R。然而,到目前为止,为可能存在的最高存储密度所必需的光学性质、特别是在UV范围或接近UV范围的光谱性能和单位表面积的信息密度不能满足所希望的最高需要。单位表面积的信息密度远比所希望的信息密度低。
WO 02/082438公开了离子盐、包括那些具有金属络合物阴离子的盐在光记录材料中的用途。那些色料总是在氮原子上被烷基、烯基、芳基或杂芳基取代。然而它们的光学性质没有完全满足增加的需求。尤其是,在固体中的折射率以及在其长波长侧翼(flank)上的吸收谱带的吸收和陡度还有些地方不能令人满意。
因此,常规的光记录材料仅仅在某种程度上能够满足更高的要求,或没有同时满足所有的要求至完全令人满意的程度。
另一方面,J.Org.Chem.
67/16,5753-5772[2002]描述了很多双(o-氮杂杂芳基)甲烷的合成和它们相对于二价过渡金属的配位性能,杂芳基是1,3-吖唑-2-基,1,3-氮茚-2-基和吖嗪基,过渡金属是Zn,Cu,Co,Ni,Hg和Pd。尤其是公开了双(苯并噻唑-2-基)甲烷和双(苯并唑-2-基)甲烷与氯化铜(II)和硫酸镍(II)、和氯化钴(II)和硝酸钯(II)的2∶1盐复合物,而双(噻唑-2-基)甲烷用脱质子化获得与Zn(II)、Cu(II)、Ni(II)和Co(II)的中性2∶1螯合物。所有物质是强显色的。
WO 04/079732是按照EPC条款54(3)和PCT细则64.3的专利申请,其涉及包括两个独立配体的复合物。
本发明的目标是具有高信息密度、灵敏度和数据可靠性的光记录介质。这种记录介质应该是坚固的(robust)、耐用的和易于使用的。而且,作为大量生产的产品,它应该便宜,并且应该需要尽可能小和便宜的装置。
X1和X2各自相互独立地是直接键或由1至8个成员组成的链,每个成员独立地选自下列基团:CR12=CR13,C=CR12R13,CR12R13,C=O,C=S,C=N(R14),N(R14),O或S,优选直接键或由1、2、3或4个成员组成的链,最优选直接键或下列链:CR12R13,C=O,C=S,C=N(R14),N(R14),O或S;
M1是第9至12族的过渡金属,优选Co,Cu,Ni,Pd或Zn,特别是Co,Cu或Ni,或是SiR21R22,GeR21R22,PR21R22或AlR21;
Q1和Q2各自独立的是C(R23),N或P;
R1,R2,R3,R4,R5,R6,R7,R8,R19和R20各自独立的是氢,R10,或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;或
R5或R6,优选R6,是式(I)或(III)中的X1位置,或式(IV)中的X2位置,条件是,当X1或X2是直接键或具有小于3个原子长度的链时,其在G1或G2处的位置不是R5;
R9、R14和R18各自独立的是:C1-C24烷基,C3-C24环烷基,C2-C24烯基,C3-C24环烯基,C1-C4烷基-[O-C1-C4亚烷基]m或C1-C4烷基-[NH-C1-C4亚烷基]m,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R24取代;或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;
或R9是式(I)或(III)中的X1位置,或式(IV)中的X2位置;和/或R14是COR9,COOR9,CONR12R13,C(R9)=NR18,C(OR9)=NR18或C(NR12R13)=NR18;
或R1和R2、R3和R4、R5和R6、R5和R18、R5和R19、式(II)或(IV)中的R1和R3、式(I)中的R3和R5、式(III)或(IV)中的G1的R5与G2的R5、和/或式(III)或(IV)中的G1的R6与G2的R6,一起成对地是C3-C6亚烷基或C3-C6亚烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24和/或R32取代,并且可以是不间断的或被O、S或N(R14)或1,4-丁-1,3-亚二烯基、
或
所间隔,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R10取代,其中1或2个碳原子可以被氮替代;
R10和R11各自独立的是C(R23)=NR25,C(R23)=NR26或R28;或R10是式(I)或(III)中的X1位置,或式(IV)中的X2位置;
R12和R13各自独立地是氢,R10,或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;或
R12和R13一起构成C2-C7亚烷基或C2-C7亚烯基,优选C3-C6亚烷基或C3-C6亚烯基,最优选C4-C5亚烷基或C4-C5亚烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24和/或R32取代;
R15和R16各自独立地选自C1-C5烷基,其是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代,
R17是C2-C7亚烷基,优选C4-C5亚烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代,并且可以是不间断的或被O、S或N(R14)间隔,
R21和R22各自独立的是羟基,C1-C12烷氧基,C3-C12环烷氧基,C1-C12烷硫基,C1-C12烷基,C3-C12环烷基,C2-C12烯基,C3-C12环烯基,C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;
R23是氢,氰基,羟基,C1-C12烷氧基,C3-C12环烷氧基,C1-C12烷硫基,C3-C12环烷基硫基,氨基,NHR29,NR30R31,R32,卤素,硝基,甲酰基,N=N-R32,C(R33)=CR26R27,C(R33)=NR25,COO-R30,羧基,氨基甲酰基,CONH-R30,CONR30R31,N=CR25R34,或C1-C12烷基,C3-C12环烷基,C2-C12烯基或C3-C12环烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;
R24是卤素,羟基,O-R30,O-CO-R30,S-R30,NH2,NH-R30,NR30R31,NH3 +,NH2R30 +,NHR30R31 +,NR29R30R31 +,NR30-CO-R29,NR30COOR29,氰基,甲酰基,COO-R30,羧基,氨基甲酰基,CONH-R30,CONR30R31,脲基,NH-CO-NHR29,NR30-CO-NHR29,磷酸根合(phosphato),PR30R29,POR30OR29,P(=O)OR30OR29,OPR30R29,OPR30OR29,OP(=O)R30OR29,OPO3R30,OP(=O)OR30OR29,SO2R30,硫酸根合(sulfato),磺基或C1-C12烷氧基或C1-C12环烷氧基,每个是未取代的或被卤素单或多取代;
R26和R27各自独立的是NR30R31,CN,CONH2,CONHR25,CONR25R34或COOR34;
R28是卤素,硝基,氰基,硫氰酸根合,羟基,O-R25,O-CO-R25,S-R25,CHO,COR34,CHOR25OR35,CR34OR25OR35,R36,N=N-R36,N=CR25R34,N=CR26R27,NH2,NH-R25,NR25R34,NH3 +,NH2R25 +,NHR25R34 +,NR25R34R35 +,CONH2,CONHR25,CONR25R34,SO2R25,SO2NH2,SO2NHR25,SO2NR25R34,COOH,COOR25,OCOOR25,NHCOR25,NR25COR35,NHCOOR25,NR25COOR35,脲基,NR25-CO-NHR35,B(OH)2,B(OH)(OR25),B(OR25)OR35,磷酸根合,PR25R35,POR25OR35,P(=O)OR25OR35,OPR25R35,OPR25OR35,OP(=O)R25OR35,OP(=O)OR25OR35,OPO3R25,硫酸根合(sulfato),磺基(sulfo),或C1-C12烷基,C3-C12环烷基,C2-C12烯基,C3-C12环烯基,C1-C12烷硫基,C3-C12环烷基硫基,C2-C12链烯基硫基,C3-C12环烯基硫基,C1-C12烷氧基,C3-C12环烷氧基C2-C12链烯氧基或C3-C12环烯基氧基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代;
R29,R30和R31各自独立的是C1-C12烷基,C3-C12环烷基,C2-C12烯基,C3-C12环烯基,C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基;或
R30和R31与共用的氮一起构成吡咯烷,哌啶,哌嗪或吗啉,每个是未取代的或被C1-C4烷基单至四取代;
R32是C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R28取代;
R33是氢,R28,或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R28取代;
R25、R34和R35各自独立的是R36,或C1-C12烷基,C3-C12环烷基,C2-C12烯基或C3-C12环烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;或
R19和R25一起,R23和R25一起和/或R25和R35一起构成C2-C12亚烷基,C3-C12环亚烷基,C2-C12亚烯基或C3-C12环亚烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;或
R25和R34与共用的氮一起是吡咯烷,哌啶,哌嗪或吗啉,每个是未取代的或被C1-C4烷基单至四取代;或咔唑(carbazole),吩嗪或吩噻嗪,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R37取代;
R36是C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R37取代;
R37是硝基,SO2NHR30,SO2NR30R31,或C1-C12烷基,C3-C12环烷基,C1-C12烷硫基,C3-C12环烷基硫基,C1-C12烷氧基或C3-C12环烷氧基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代;和
m是从1至10的数值。
当R5与R6形成桥接时,优选R5不与R18或R19同时形成桥接。
应理解,酸性基团例如羧基、磺基、硫酸根合和磷酸根合,可以是盐的形式,例如碱金属、碱土金属、铵或盐,例如Li+,Na+,K+,Mg2+,Ca2+,Cu2+,Ni2+,Fe2+,Co2+,Zn2+,Sn2+,La3+,铵,甲基铵,乙基铵,异丙基铵,TMPrimene 81-R,TMRosin Amine D,五癸基铵,TMPrimeneJM-T,二环己基铵,四甲基铵,四乙基铵,四丁基胺,苄基三甲基铵,苄基三乙基铵,甲基三辛基铵,三(十二烷基)甲基铵,四丁基磷,四苯基磷,丁基三苯基磷或乙基三苯基磷,或US-6225024中提到的任何阳离子B-1至B-169,这里明确对其中各个引用加以引用。
卤素是氯、溴、氟或碘,优选氟或氯,特别是烷基上的氟(例如三氟甲基,α,α,α-三氟乙基或全氟化烷基,例如七氟丙基)和芳基、杂芳基上或芳烷基的芳基部分上、或杂芳烷基的杂芳基部分上的氯。
烷基、环烷基、烯基或环烯基可以是直链或分支的,或单环或多环的。烷基是例如甲基,直链C2-C24烷基或优选分支的C3-C24烷基。烯基是例如直链C2-C20烯基或优选分支的C3-C24烯基,尤其是乙烯基,烯丙基,C(R23)=CHR27或C(R23)=CR26R27。因此本发明还特别涉及含有分支的C3-C24烷基或分支的C3-C24烯基的式(I)、(II)、(III)或(IV)的化合物,以及涉及包括这种化合物的光记录材料。C1-C24烷基因此是例如甲基,乙基,正丙基,异丙基,正丁基,仲丁基,异丁基,叔丁基,正戊基,2-戊基,3-戊基,2,2-二甲基丙基,正己基,正辛基,1,1,3,3-四甲基丁基,2-乙基己基,壬基,癸基,十二烷基,十四烷基,十六烷基,十八烷基,二十烷基,二十一烷基,二十二烷基或二十四烷基。C3-C24环烷基是例如环丙基,环丁基,环戊基,环己基,三甲环乙烷,薄荷基,苧基(thujyl),冰片基,1-金刚烷基或2-金刚烷基。
C2-C20烯基和C3-C20环烯基是单或多不饱和的C2-C20烷基和C3-C20环烷基,其中两个或多个双键可以分离或共轭,例如乙烯基,烯丙基,2-丙烯-2-基,2-丁烯-1-基,3-丁烯-1-基,1,3-丁二烯-2-基,2-环丁烯-1-基,2-戊烯-1-基,3-戊烯-2-基,2-甲基-1-丁烯-3-基,2-甲基-3-丁烯-2-基,3-甲基-2-丁烯-1-基,1,4-戊二烯-3-基,2-环戊烯-1-基,2-环己烯-1-基,3-环己烯-1-基,2,4-环己二烯-1-基,1-对-孟烯(menthen)-8-基,4(10)-苧烯-10-基,2-降冰片烯-1-基,2,5-降冰片二烯-1-基,7,7-二甲基-2,4-降蒈二烯-3-基或下列的各种异构体:己烯基,辛烯基,壬烯基,癸烯基,十二碳烯基,十四碳烯基,十六碳烯基,十八碳烯基,二十碳烯基,二十一碳烯基,二十二碳烯基,二十四碳烯基,己二烯基,辛二烯基,壬二烯基,癸二烯基,十二碳二烯基,十四碳二烯基,十六碳二烯基,十八碳二烯基或二十碳二烯基。
C7-C12芳烷基是例如,苄基,2-苄基-2-丙基,β-苯基-乙基,9-芴基,α,α-二甲苄基,ω苯基-丁基或ω-苯基-己基。当C7-C12芳烷基是取代的时,芳烷基的烷基部分和芳基部分两者可以是取代的,后者是优选的。
C6-C12芳基是例如苯基,萘基,联苯基或2-芴基。
C4-C12杂芳基是不饱和的或具有4n+2共轭π电子的芳基,例如2-噻吩基,2-呋喃基,2-吡啶基,2-噻唑基,2-唑基,2-咪唑基,异噻唑基,三唑基或由噻吩、呋喃、吡啶、噻唑、唑、咪唑、异噻唑、三唑、吡啶和苯环组成的任何其它环系,并且是未取代的或被1至6个乙基、甲基、亚乙基和/或亚甲基取代基取代,例如苯并三唑基,和如果合适的话,还可以是在N-杂环情况下的其N-氧化物形式。
C5-C12杂芳烷基是例如被C4-C11杂芳基取代的C1-C8烷基。
优选过渡金属M1是双重带正电荷的阳离子形式,例如Co2+,Cu2+,Ni2+,Pd2+或Zn2+,特别是Co2+,Cu2+或Ni2+。
式(I)、(II)、(III)或(IV)的化合物还可以是用无机、有机或有机金属阴离子中和的阳离子,例如当存在一个或多个铵基团或当过渡金属具有一个或多个过量正电荷时,例如Co3+。无机、有机或有机金属阴离子可以是例如无机酸的阴离子、有机酸共轭碱的阴离子(例如醇化物阴离子,苯酚盐阴离子,羰酸根,磺酸根或磷酸根)或有机金属络合物阴离子,例如氟离子,氯离子,溴离子,碘离子,高氯酸根,高碘酸根,硝酸根,碳酸氢根,碳酸根,硫酸根,C1-C4烷基硫酸根,硫酸氢根,磷酸根,磷酸氢根,磷酸二氢根,1/2C1-C4烷烃磷酸根,C1-C4烷烃-C1-C12烷基磷酸根,二-C1-C4烷基亚膦酸根,四氟硼酸根,六氟磷酸根,六氟锑酸根,乙酸根,三氟乙酸根,七氟丁酸根,草酸根,甲磺酸根,三氟甲磺酸根,苯磺酸根,甲苯磺酸根,对-氯苯磺酸根,对硝基苯磺酸根,苯酚盐阴离子,苯甲酸根或带负电荷的金属络合物。
本领域技术人员很容易认识到,也可以使用他所熟悉的其它阴离子。不言自明,1/x的具有x个负电荷的无机、有机或有机金属阴离子,例如·SO4 2-,是多重带电的阴离子,该阴离子中和几个具有x电荷的独自带电的阳离子,视情况而定。
酚盐阴离子或羰酸根是例如下式:
或
(其中R38、R39和R40各自独立的是氢,R28,或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R28取代,例如C1-C12烷基化,特别是叔C4-C8烷基化的酚和苯甲酸的阴离子,例如
或
优选式(I)、(II)、(III)或(IV)的化合物,其中
A1和A2各自独立的是N(R14)、O、S或Se,A3是C(C1-C5烷基)2、C(C4-C5亚烷基)、N(R14)、O、S、Se,N=C(R18)或未取代的或R19-取代的CH=CH,特别是其中A1、A2和A3各自独立的是O、S或N(R14)和/或Q1和Q2是C(R23)或N;
R1,R2,R3,R4,R5,R6,R7,R8和R19各自独立的是氢,R10,或C6-C12芳基,或C7-C12芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;
R9、R14和R18各自独立的是未取代的或R10-取代的C1-C8烷基;或
R9是式(I)或(III)中的X1位置,或式(IV)中的X2位置;
R10和R28各自独立的是卤素,硝基,氰基,O-R25,甲酰基,CH=C(CN)2,CH=C(CN)CONH2,CH=C(CN)CONHR25,CH=C(CN)CONR25R34,CH=C(CN)COOR25,CH=C(COOR25)COOR34,CONH2,CONHR25,CONR25R34,SO2C1-C12烷基,SO2NH2,SO2NHR25,SO2NR25R34,COOH,COOR25,NHCOR25,NR25COR35,NHCOOR25,NR25COOR35,脲基,P(=O)OR25OR35,磺基,或C1-C12烷基,C1-C12烷硫基或C1-C12烷氧基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代;
R23是氢,氰基,卤素,硝基,甲酰基,N=N-R32,C(R19)=CR26R27,C(R19)=NR25,COO-R30,羧基,氨基甲酰基,,CONH-R30,CONR30R31,或未取代的或被一个或多个卤素取代基取代的C1-C12烷基;
R24是卤素,羟基,,O-R30,氨基,NH-R30,NR30R31,NR30-CO-R29,NR30COOR29,氰基,COO-R30,羧基,CONH-R30,CONR30R31,硫酸根合,磺基,或未取代的或被卤素单或多取代的C1-C12烷氧基;
R25、R34和R35各自独立的是C1-C12烷基,其是未取代的或如果合适的话被一个或多个相同或不同的卤素、羟基或C1-C12烷氧基基团取代,或未取代的C6-C12芳基或C7-C12芳烷基;或
R25和R34与共用的氮一起构成吗啉,或被C1-C4烷基N-取代的哌啶;
R29、R30和R31各自独立的是C1-C12烷基,C2-C12烯基,C6-C12芳基或C7-C12芳烷基;或
R30和R31与共用的氮一起构成吗啉,或被C1-C4烷基N-取代的哌啶;
R36是未取代的或取代的C6-C12芳基或C7-C12芳烷基,特别是金属茂基基团;和/或
m是从1至4的数值,
或其互变体。
特别优选式(I)、(II)、(III)或(IV)的化合物,其中Q1和Q2是N或C(R23);G1和G2是
或
;A1、A2和A3是S或CR19=CH,特别是S,X1和X2是直接键或C1-C3亚烷基桥;
R5和R8相互独立地是氢或R28;
R2、R4和R6相互独立地是氢或未取代或取代的C1-C4烷基,尤其是未取代或取代的甲基或乙基;
R23是氢,氰基,COO-R30或C1-C12烷基;和
R28是未取代或取代的C1-C12烷基,O-R25或吸电子基团,特别是C1-C12烷基,其既可以是未取代的也可以被卤素、羟基或O-R25取代,例如CH2OH或CF3,CH=C(CN)2,COOR25,COR34,CHO,脲基,CONR30R31,SO2R30,P(=O)OR25OR35,卤素,硝基或氰基。
那些优选的含义可以独自和组合应用。式(I)、(II)、(III)或(IV)的化合物通常显现更优越的性能,它们具有更优选的独立特征。
其中C1-C4烷基是例如甲基,乙基,异丙基,2-丁基,异丁基或叔丁基,优选甲基。
记录层有利地包括式(I)、(II)、(III)或(IV)的化合物或这种化合物的混合物作为主要成分,例如至少30%重量,优选至少60%重量,特别是至少80%重量。进一步的常用组分是可能的,例如其它发色团(例如公开在WO 01/75873中的那些,或在从300至1000nm处具有最大吸收的其它组分),稳定剂,1O2-,三重态或荧光猝灭剂,熔点降低剂,分解促进剂或在光记录介质中已经描述的任何其它添加剂。如果需要的话,优选加入稳定剂或荧光猝灭剂。
当记录层包括进一步的发色团时,应该优选少量这种发色团,以使其在整个固体层吸收的最长波长侧翼的转化点波长处的吸收是在相同波长处的整个固体层中的式(I)、(II)、(III)或(IV)的纯化合物吸收的一部分,有利的是至多,优选至多1/5,特别是至多1/10。优选最大吸收比425nm高,特别是比500nm高。
稳定剂、1O2-、三重态或荧光-猝灭剂是例如含有N-或S-的烯醇化物、酚盐、双酚盐、硫醇盐或双硫醇盐或偶氮、甲亚胺(azomethine)或三苯基甲脂染料(formazan dyes)的金属复合物,例如双(4-二甲基氨基二硫基苯偶酰)镍[CAS No 38465-55-3],Irgalan Bordeaux EL,Cibafast N或类似的化合物,位阻酚和它们的衍生物(同样任选作为反离子X的形式),例如Cibafast AO,邻-羟基苯基-三唑或三嗪或其它UV吸收剂,例如Cibafast W或Cibafast P或位阻胺(TEMPO或HALS,同样以硝基氧化物或NOR-HALS的形式,也任选以反离子X的形式),也以阳离子二亚胺基(diimmonium)、ParaquatTM或OrthoquatTM盐的形式,例如Kayasorb IRG 022,Kayasorb IRG 040,也任选以基团离子的形式,例如N,N,N’,N’-四(4-二丁基氨基苯基)-对-亚苯基胺-铵六氟代磷酸盐,六氟代锑酸盐或高氯酸盐。后者得自于Organica(Wolfen/DE);Kayasorb牌号得自于Nippon Kayaku Co.Ltd.,Irgalan和Cibafast牌号得自于Ciba Spezialitten-chemie AG。
许多这种结构是已知的,它们中的一些也与光记录介质有关,例如得自于US-5219707,JP-A-06/199045,JP-A-07/76169,JP-A-07/262604或JP-A-2000/272241的那些。它们可以是例如上面公开的金属络合物阴离子与任何希望的阳离子,例如上面公开的阳离子的盐,或例如通过下式说明的金属复合物
或
本领域技术人员将会由其它光学信息介质知道或容易确定哪些添加剂、以什么浓度特别适合于哪些目的。基于式(I)、(II)、(III)或(IV)的记录介质,添加剂的合适浓度是例如从0.001至1000%重量,优选从1至50%重量。
按照本发明的光记录材料显现了固态无定形记录层的出色光谱性能。折射率非常高,在某些情况下甚至高于2.5。由于这种化合物在固体中的聚集趋势惊人地低,吸收谱带是狭窄和强烈的,吸收谱带在长波长端特别陡。意想不到地和非常有利地没有形成微晶体,或仅仅以可忽略程度地形成微晶体。在未写入状态,写入和读出波长范围内的层的反射率是很高的。
同先前已知的化合物比较起来,还惊人地提高了热稳定性。因此,对于低强度激光,由热或多重读出而意外改变数据的危险减到最小,而当使用高(写入)能量激光时,衰变作用(decomposition behaviour)保持了所需要的锐度,能够惊人有效地将标记记录下来。
由于那些出色的层性能,可以获得具有高灵敏度、高重现性和几何学非常精密标记界面的快速光学记录,基本上改变了折射率和反射率,得到高对比度。标记长度和间隔距离中的差异(“晃动(jitter)”)非常小,使用具有狭窄磁道间距(“间距(pitch)”)的相对薄的录音系统,其能够获得高存储密度。此外,播放所记录的数据,具有惊人低的误码率,使得纠错仅仅需要少量的存储空间。
由于包在在非极性溶剂中的完全出乎意外的极优溶解性,可以使用溶液,甚至以高浓度使用,没有麻烦的沉淀,例如在存储期间,使得可以基本上除去旋涂期间的问题。
记录和播放可以在相同波长处进行,因此优选要求具有优选从350至500nm,优选从370至450nm的单激光源的简单光学系统。特别优选的是370至390 nm的UV范围,特别是大约380nm,或特别在从390至430nm的可见区的边缘,更特别是大约405±5nm。在蓝色或紫色激光二极管(例如Nichia GaN 405nm)与高数值孔径光学系统的紧密结合方面,标记可以很小,因此记录槽可以很狭窄,在120mm圆盘上每个记录层可达到最多20至25Gb。在380nm处,可以使用掺杂铟的UV-VCSELs(
Vertical-
Cavity
Surface-
Emitting
Laser)(垂直-空腔表面-发射激光),这种激光源已经以模型机(prototype)形式存在[Jung Han等人,参见MRS Internet J.Nitride Semicond.Res.5S1,W6.2(2000)]。
本发明因此还涉及记录或播放数据的方法,其中在按照本发明的光记录介质上的数据,在350至500nm波长处记录或播放。
该记录介质基于已知记录介质的结构,并且是例如类似于如上所述的那些。它可以由例如透明基材、包括式(I)、(II)、(III)或(IV)化合物中的至少一种的记录层、反射层和覆盖层组成,读和写是通过基材实现的。
合适的基材是例如玻璃,矿物质,陶瓷和热固化和热塑性塑料。优选的载体是玻璃和均聚或共聚合塑料。合适的塑料是例如热塑性塑料聚碳酸酯,聚酰胺,聚酯,聚丙烯酸酯和聚甲基丙烯酸酯,聚氨酯,聚烯烃,聚氯乙烯,聚偏二氟乙烯,聚酰亚胺,热固化聚酯和环氧树脂。特别优选聚碳酸酯基材,其可以例如利用注塑的方式制造。基材可以是纯的形式或可以包括通常的添加剂,例如UV吸收剂或染料,如JP-A-04/167239所推荐的,作为记录层的光稳定作用。在后者情形中,在写入波长(激光的发射波长)范围内,加入到载体基材中的染料可以没有或仅仅极低的吸收,优选直到集中到记录层上的激光的约20%的最大值。
优选,基材在350至500nm范围的至少一部分处是透明的,以使其对例如至少80%的写入或读出波长的入射光是可透的。基材优选从10μm至2mm厚度,优选从100至1200μm厚度,特别是从600至1100μm厚度,优选在涂布面上具有螺旋导向槽(记录槽),从10至200nm,优选从80至150nm的槽深,从100至400nm,优选从150至250nm的槽宽,两个匝数的间距从200至600nm,优选从350至450nm。不同横截面形状的凹槽是已知的,例如矩形的,梯形的或V字形的。与已知的CD-R和DVD-R介质相类似,导向槽可以另外进行小周期或准周期的侧向偏离(摇摆(wobble)),以使转速和读头(提取(pick-cep))的绝对位置同步化变成可能。代替偏转或除了偏转之外,可通过在邻声槽(预凹槽(pre-pits))之间标记完成相同的功能。
在凹槽中,例如通过旋涂溶液来施加记录介质,目的是在表面上(“接合面(land)”)制备尽可能无定形的层,层的厚度优选从0至40nm,优选从1至20nm,特别是从2至10nm,取决于凹槽的几何形状,优选从20至150nm,优选从50至120nm,特别是从60至100nm。
适合于反射层的反射材料主要包括金属,其提供了用于记录和播放的激光照射的良好反射,例如元素周期表元素中的13-15主族金属和3-12副族金属。Al,In,Sn,Pb,Sb,Bi,Cu,Ag,Au,Zn,Cd,Hg,Sc,Y,La,Ti,Zr,HF,V,Nb,Ta,Cr,Mo,W,Fe,Co,Ni,Ru,Rh,Pd,Os,Ir,Pt和镧系元素金属Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb和Lu和其合金是特别合适的。由于制品的高反射和释放能力,特别优选铝、银、金或其合金(例如白金合金)的反射层,特别是铝,其具有经济性和生态学基础。反射层优选从5至200nm厚度,优选从10至100nm厚度,特别是从40至60nm厚度,但更大厚度的反射层,例如1mm厚度或甚至更大,也是可能的。
适合于覆盖层的材料主要包括塑料,其可以直接或借助于增粘剂来施加在反射层的薄层上。选择具有良好表面性质的机械性和热稳定塑料是有利的,可以对其进一步修饰,例如写入。塑料可以是热固性塑料和热塑性塑料。直接施加的覆盖层优选辐射硬化的(例如使用紫外辐射)涂层,这种制备方式特别简单和经济。多种辐射-可固化的材料是已知的。辐射-可固化单体和齐聚物的例子是二醇、三醇和四醇的丙烯酸酯和甲基丙烯酸酯,芳香四羧酸和在氨基的至少两个邻位上具有C1-C4烷基的芳族二胺的聚二酰亚胺,带有二烷基马来酰亚胺基例如二甲基马来酰亚胺基的齐聚物。对于使用增粘剂施加的覆盖层,优选使用与用于基材层的材料相同的材料,特别是聚碳酸酯。所使用的增粘剂同样优选可辐射-固化的单体和齐聚物。代替使用增粘剂施加的覆盖层,也可以使用包括记录和反射层的第二种基材,以使记录介质可以双面放音。优选,在反射端通过增粘剂直接相连或通过中间层相连在一起的两个部分是对称结构。
在这种结构中,覆盖层或封面材料的光学性质本身基本上不重要,条件是,如果合适的话,例如通过紫外辐射可实现其固化。覆盖层的功能是总体上保证记录介质的机械强度,并且如果需要的话,保证薄反射层的机械强度。如果记录介质充分稳固,例如当存在厚反射层时,甚至可以完全不用覆盖层。覆盖层的厚度取决于整个记录介质的厚度,优选最大约2mm厚度。覆盖层优选从10μm至1mm厚度。
按照本发明的记录介质也可以具有附加层,例如干扰层或阻挡层。构成具有大量(例如从两个至十个)记录层的记录介质也是可以的。本领域技术人员已知这种材料的结构和用途。如果存在,优选将干扰层布置在记录层和反射层之间、和/或记录层和基材之间,并由介电材料组成,例如EP-A-0353393中所述的TiO2、Si3N4、ZnS或硅树脂。
按照本发明的记录介质可以通过本身已知的方法制备,可以采用各种涂层方法,这取决于使用的材料和它们的功能。
合适的涂敷法是例如浸泡,倾注,刷涂-涂层,刮刀-应用和旋转-涂层,以及在高真空条件下进行的蒸法镀敷。当例如使用倾注方法时,通常采用有机溶剂中的溶液。当采用溶剂时,应该注意,所使用的载体应该对那些溶剂不敏感。合适的涂敷法和溶剂描述在例如EP-A-0401791中。
优选通过使用旋涂染料溶液来施加记录层,已经证明令人满意的溶剂特别是醇,例如2-甲氧基乙醇,异丙醇或正丁醇,羟基酮,例如双丙酮醇或3-羟基-3-甲基-2-丁酮,羟基酯,例如乳酸甲酯或异丁酸甲酯,或优选氟化醇,例如2,2,2-三氟乙醇或2,2,3,3-四氟-1-丙醇,和其混合物。其它合适的溶剂是本领域众所周知的,且公开在例如EP-A-0483387中。
金属反射层的应用,优选通过溅射或通过真空蒸法镀敷来实施。这种技术是已知的,并且描述在专业文献中(例如J.L.Vossen和W.Kern,″Thin Film Processes″,Academic Press,1978)。该操作可以优选连续进行,并达到金属反射层良好反射性和高粘合度。
通过利用在记录层表面上以恒定或变速引导的调节的、集中的激光束来写入固定或可变长度的凹点(标记),按照已知的方法进行记录。按照本身已知的方法、通过记录反射的变化、使用激光照射进行信息的读出,例如,如下所述″CD-Player und R-DAT Recorder″(ClausBiaesch-Wiepke,Vogel Buchverlag,Würzburg 1992)。本领域技术人员熟悉该要求。
按照本发明的含有信息的介质主要是WORM类型的光学信息资料。可以将其用于电脑中,例如类似于CD-R(可记录光盘)或DVD-R(数字视频可记录磁盘),也可以用作鉴别和安全卡片的存储材料,或衍射光学要素例如全息照相的存储材料。
然而,还有基本上不同于CD-R和DVD-R的记录介质,其中记录和播放不通过基材进行,但通过覆盖层进行(“在机械录音中(in-grooverecording)”)。因此,覆盖层和基材的相应作用,特别是几何形状和光学性质,与如上所述结构比较是相反的。对于与蓝色GaN激光二极管结合的数字式录象,在Proceedings SPIE-Int.Soc.Opt.Eng.1999,3864中描述了许多次类似的方案。对于这种记录介质,特别适合于高存储密度且具有相当小的标记(″凹点″)的记录介质,精密聚焦是重要的,以致基本上类似的制造工艺显得更加笨拙。
然而,按照本发明的式(I)、(II)、(III)或(IV)的化合物,惊人好地满足了相反层状结构的需求增加。因此优选具有基材、反射层、记录层和覆盖层的层序列的相反层状结构。记录层因此设置在反射层和覆盖层之间。大约从50至400μm厚的薄覆盖层是特别有利的(典型地100μm,0.85的数值孔径)。
在相反层状结构中的记录和反射层原则上具有如上所指出的相同功能。正如凹槽几何形状一样,它们因此通常具有如上所述范围内的尺寸。
相反层状结构要求特别高的标准,使用按照本发明的化合物可以非常令人惊奇地满足该标准,例如当记录层施加到金属反射层上时,特别是当覆盖层施加到记录层上时,要求覆盖层给记录层提供针对摩擦、光致氧化、指纹、水份及其它环境影响的充分保护,优选具有从0.01至0.5mm范围内的厚度,优选从0.05至0.2mm范围内,特别是从0.08至0.13mm的范围。
优选覆盖层由这种材料组成,该材料在激光的写入或读出波长处可以显现80%或高于80%的传导。覆盖层的合适材料包括例如如上所述的那些材料,但特别是聚碳酸酯(例如Pure Ace或Panlite,TeijinLtd),三乙酸纤维素(例如Fujitac,Fuji Photo Film)或聚对苯二甲酸乙二醇酯(例如Lumirror,Toray Industry),特别优选聚碳酸酯。特别是在直接施加的覆盖层的情况下,辐射硬化的涂层,例如如上所述的那些是有利的,例如SD347TM(Dainippon Ink)。
利用合适的增粘剂,覆盖层可以直接施加到固体记录层上。在另一个实施方案中,施加到固体记录层上的是金属的、交联有机金属或优选介电无机材料的附加的薄分离层,例如厚度从0.001至10μm,优选从0.005至1μm,特别是从0.01至0.1μm,例如在介电分离层情况下的从0.05至0.08μm和在金属分离层情况下的从0.01至0.03μm。分离层和相应的方法公开在WO02/082438中,本文对其明确进行了参考。如果需要的话,这种涂层可以例如以相同厚度、同样在载体材料和金属反射层之间或在金属反射层和光记录层之间施加。在某些情况下这种方式可以是有利的,例如当在记录层中使用银反射物与含硫添加剂的组合时。
在一个特别的变体中,施加到固体记录层上的是金属的、交联有机金属的或优选介电无机材料的附加的薄分离层,例如厚度从0.001至10μm,优选从0.005至1μm,特别是从0.01至0.1μm。由于它们的高反射性,金属分离层应该优选最大0.03μm厚度。分离层和相应的方法公开在WO02/082438中,本文对其明确进行了参考。
所使用的按照本发明的式(I)、(II)、(III)或(IV)的化合物是新的,但容易由已知的化合物、通过已知的方法制备,例如按照类似于下列的方式:J.Org.Chem.
67/16,5753-5772 [2002]。
本发明因此也涉及式(I)、(II)、(III)或(IV)的化合物。本发明涉及的式(I)、(II)、(III)或(IV)化合物的合适例子是下列物质,然而决不限于下列物质:
也可以使用其混合物代替纯化合物。
除了包括一或多种式(I)、(II)、(III)或(IV)的化合物和任选常用的添加剂之外,按照本发明的光记录介质也可以包括其它发色团,优选不含金属的发色团。如果需要的话,可以加入其它发色团,其量基于式(I)、(II)、(III)或(IV)的化合物的总数为从1至200%重量。基于式(I)、(II)、(III)或(IV)的化合物的总数,其它发色团的量优选从5至100%重量,特别是从10至50%重量。发色团可以是染料或UV吸收剂,优选在350至400nm或600至700nm,例如大约380或630nm处具有最大吸收。
特别优选的附加的不含金属的发色团是花青,氮杂菁,部花青和氧杂菁(oxonols)以及若丹明,例如在WO 04/006878、WO 02/082438或EP-A-1083555中公开的那些,以及
其中R49是C1-C24烷基或C2-C24烯基,每个可以是未取代或取代的,R50是任意取代基。R49可以是例如甲基,乙基,乙烯基,烯丙基,异丙基,正丁基,2-异丙基氧基-乙基,正戊基,3-甲基-丁基,3,3-二甲基-丁基,2-乙基-己基,2-氰基-乙基,呋喃-2-基-甲基或2-羟基-甲基;R50是例如,C6-C10芳基,C1-C24烷基或C2-C24烯基。
本发明化合物也可以有利地与WO04/079732中公开的化合物混合使用,特别是WO04/079732的式(II)、(III)、(IV)或(V)的那些化合物,以及在WO05/012228中公开的那些化合物。
本发明化合物能够高质量地记录,具有高灵敏度,特别是高调节性,具有良好的读出和光稳定性。很容易通过改变桥接X1和/或X2的长度和其它取代基来加强平面性或平面外变形,由此转换色彩(hue)和降低结晶的倾向。
下列实施例说明了本发明,但不限制其范围(除非另有陈述,“%”总是指%重量):
实施例1:a)在30分钟内,将12.72克溴小批量地加入到5.12克3,3-二甲基-2,4-戊二酮的30毫升乙酸溶液中,同时通过外部冷却保持温度在~10℃。搅拌6小时后,通过蒸馏从反应混合物中除去乙酸。将20毫升甲基叔丁基醚加入到得到的褐色液体中,并用K2CO3干燥该溶液。将溶剂蒸发,并将残余物在硅胶上色谱分离,用正己烷/乙酸乙酯(4∶1)作为洗脱液。获得1.88克1,5-二溴-3,3-二甲基-2,4-戊二酮褐色液体。
1H-NMR(δ,CDCl3):4.05(s,4H);1.36(s,6H)。
b)在回流条件下,将684毫克1,5-二溴-3,3-二甲基-2,4-戊二酮的5毫升乙醇溶液是加入到1.274克N-(2-噻唑基)硫脲的15毫升乙醇溶液中,并将该混合物回流3小时。冷却到0℃之后,将反应混合物用10%氢氧化钠水溶液中和。过滤沉淀(602mg),然后用乙酸乙酯提取有机层,并用无水硫酸钠干燥。将溶剂蒸发,并将残余物在硅胶上色谱分离,用正己烷/乙酸乙酯(2∶1)作为洗脱液。进一步得到148毫克下式的化合物
淡灰色固体(全部750毫克)。
1H-NMR(δ,DMSO-d6):7.29(d,2H);6.95(d,2H);6.58(s,2H);1.64(s,6H);12.01(宽峰,2H)。
c)在回流条件下,将98毫克醋酸铜的101的乙醇溶液逐滴加入到203毫克这种淡灰色固体的10毫升四氢呋喃溶液中,并将该混合物回流2小时。冷却到约23℃之后,在通过真空蒸发除去溶剂期间产生暗褐色固体沉淀,过滤收集固体(82毫克)。浓缩滤液,并将残余物在硅胶上色谱分离,用二氨甲烷/丙酮(20∶1)作为洗脱液,进一步得到70毫克金属络合物,产生全部152mg的下式的暗褐色粉末:
实施例2:a)将1.0克N-(2-吡啶基)硫脲溶于10毫升热乙醇中,然后加入0.80克1,4-二溴-2,3-丁二酮。将混合物加热至回流。搅拌1小时后,将乙酸钠的饱和水溶液加入到反应混合物中。过滤收集得到的白色固体,并用水和甲醇洗涤。干燥之后,获得0.80克粉红色固体。
1H-NMR(δ,DMSO-d6):11.41(s,2H),8.31(dd,2H),7.71(ddd,2H),7.15(s,2H),7.10(d,2H),6.93(ddd,2H)。
b)将85毫克Cu(OAc)2·H2O的7ml热乙醇溶液逐滴加入到150毫克这种粉红色固体在20毫升四氢呋喃和20毫升乙醇混合物的溶液中。加入完毕后,将混合物回流搅拌1.5小时。浓缩该混合物,随后用乙醇洗涤,产生0.18克下式的绿色固体:
实施例3:将0.31毫克按照实施例1的产物溶于50毫升二氯甲烷中。用分光光度计(U-3300TM,Hitachi)测定染料溶液的光谱。最大吸收(λmax)在346nm波长处。
实施例4:将12毫克按照实施例1的产物溶于1.00毫升2,2,3,3-四氟-1-丙醇中。然后在800rev/min下,在平的聚碳酸酯平皿(直径120毫米)上将染料溶液旋涂至1.2mm厚度;然后将转速增至2000rev/min,以甩出过量溶液,形成均匀固体层。使用光学测量系统(ETA-RTTM,STEAG ETA-Optik),测定层厚度和复合物折射率。在405nm处,染色层具有45nm的层厚度,1.909的折射率n和0.011的吸光系数k。使用脉冲染料激光器(15ns脉冲长度),在405nm波长和0.8kJ/m2的能量密度下,将较低反射性的标记写入到记录层中。
实施例5:将0.37毫克按照实施例2的产物溶于50毫升二氯甲烷中。用分光光度计(U-3300,Hitachi)测定染料溶液的光谱。最大吸收(λmax)在325nm波长处。
实施例6:将12毫克按照实施例2的化合物溶于1.00毫升2,2,3,3-四氟-1-丙醇中。然后在800rev/min下,在平的聚碳酸酯平皿(直径120毫米)上将染料溶液旋涂至1.2mm厚度;然后将转速增至2000rev/min,以甩出过量溶液,形成均匀固体层。使用光学测量系统(ETA-RTTM,STEAG ETA-Optik),测定层厚度和复合物折射率。在405nm处,染色层具有41nm的层厚度,1.986的折射率n和0.101的吸光系数k。使用脉冲染料激光器(15ns脉冲长度),在405nm波长和0.8kJ/m2的能量密度下,将较低反射性的标记写入到记录层中。
实施例7:在真空涂覆装置(TwisterTM,Balzers Unaxis)中,将30nm厚度银反射层施加到1.1mm厚度的开槽的聚碳酸酯磁盘(直径120mm,槽距400nm,槽深80nm,槽宽170nm)上。将0.12g的实施例1的产物溶于10ml的2,2,3,3-四氟-1-丙醇中,并通过0.2μm TeflonTM滤过器过滤。将染料溶液通过旋转涂敷法施加到反射层上,在70℃烘箱中干燥15分钟之后,形成均匀固体层。在真空涂覆装置(SprinterTM,Balzers Unaxis)中,通过RF-溅射,依次施加40nm厚度介质层(SiON)。将用压敏胶粘剂覆盖在单面的聚碳酸酯薄膜(总厚度100μm,LintecCorp.,Japan)最后结合到介质层上。使用基于407nm激光二极管和0.85数值孔径物镜的商用圆盘试验装置(ODU-1000TM,Blu-rayDisc,Pulstec,Japan),用5.28m/s的线速度和7mW的激光功率在磁盘上记录标记。然后用0.35mW激光功率回读记录的区域。
实施例8:用非常类似于实施例7的方式进行,不同的是,旋涂实施例2的化合物来代替旋涂实施例1的化合物。
实施例9-36:以非常类似于实施例1-5的方式,制备和测定下列化合物:
实施例37-53:将10毫克按照实施例12、13、14、15、16、19、20、21、22、23、24、25、26、30、33、35和36的化合物各自溶解在1.00ml的2,2,3,3-四氟-1-丙醇中。然后在800rev/min下,在平的聚碳酸酯平皿(直径120毫米)上将各个染料溶液旋涂至1.2mm厚度;然后将转速增至2000rev/min,以甩出过量溶液,形成均匀固体层。使用用于光数据存储器介质的静力试验-系统(MEDIA TEST-ITM,TOPTICAPhotonics),在399nm波长处、用写入激光(脉冲长度从25ns至300ns,激光功率从1至14mW)形成凹点标记。在422nm波长处、用读出激光测定凹点标记形成以前/之后的反射率变化。将调幅定义为凹点标记形成前后反射率(R)变化的比例:调幅[用%表示]=(R以前-R之后)/R以前。将灵敏度定义为:当调幅开始升高时的写入激光功率的阈值。
实施例54:将9毫克按照实施例20的化合物和1毫克的按照实施例33的化合物溶于1.00ml的2,2,3,3-四氟-1-丙醇中。然后在600rev/min下,在平的聚碳酸酯平皿(直径120毫米)上将混合染料溶液旋涂至1.2mm厚度;然后将转速增至2000rev/min,以甩出过量溶液,形成均匀固体层。形成凹点标记,并以与实施例37-53同样的方式、利用光数据存储器介质的静力试验-系统(MEDIA TEST-1TM,TOPTICAPhotonics)测定反射率。为了试验读出-稳定性,将读出-稳定性定义为激光照射前后反射率(R)变化的比例,然后在以低激光功率(波长399nm,激光功率0.5mW,脉冲持续时间1msec)激光照射期间也测定反射率变化:读出-稳定性[用%表示]=(R以前-R之后)/R以前。
实施例 | 染料 | 数量 | 灵敏度[mW] | 最大调幅[%] | 读出-稳定性[%] |
54 | 实施例20实施例33 | 90%10% | 4.0 | 45 | 9 |
进一步实施例:用非常类似于上述实施例的方式进行,不同的是,Zn或Cu相互替代,或分别被Co、Ni或Pd替代。还可以使用包括不同的两种或多种金属的化合物的混合物,例如Cu和Zn,Cu和Co,Cu和Ni,Cu和Pd,Co和Ni,Co和Pd,Co和Zn,Ni和Pd,Ni和Zn,或Cu、Co和Zn。
Claims (12)
或式(I)、(II)、(III)或(IV)的化合物的互变异构体,其中
X1和X2各自相互独立地是直接键或由1至8个成员组成的链,每个成员独立地选自下列基团:CR12=CR13,C=CR12R13,CR12R13,C=O,C=S,C=N(R14),N(R14),O或S,优选直接键或由1、2、3或4个成员组成的链,最优选直接键或下列链:CR12R13,C=O,C=S,C=N(R14),N(R14),O或S;
M1是第9至12族的过渡金属,优选Co,Cu,Ni,Pd或Zn,特别是Co,Cu或Ni,或是SiR21R22,GeR21R22,PR21R22或AlR21;
Q1和Q2各自独立的是C(R23),N或P;
R1,R2,R3,R4,R5,R6,R7,R8,R19和R20各自独立的是氢,R10,或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;或
R5或R6,优选R6,是式(I)或(III)中的X1位置,或式(IV)中的X2位置,条件是,当X1或X2是直接键或具有小于3个原子长度的链时,其在G1或G2处的位置不是R5;
R9、R14和R18各自独立的是:C1-C24烷基,C3-C24环烷基,C2-C24烯基,C3-C24环烯基,C1-C4烷基-[O-C1-C4亚烷基]m或C1-C4烷基-[NH-C1-C4亚烷基]m,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R24取代;或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;
或R9是式(I)或(III)中的X1位置,或式(IV)中的X2位置;和/或R14是COR9,COOR9,CONR12R13,C(R9)=NR18,C(OR9)=NR18或C(NR12R13)=NR18;
或R1和R2、R3和R4、R5和R6、R5和R18、R5和R19、式(II)或(IV)中的R1和R3、式(I)中的R3和R5、式(III)或(IV)中的G1的R5与G2的R5、和/或式(III)或(IV)中的G1的R6与G2的R6一起成对地是C3-C6亚烷基或C3-C6亚烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24和/或R32取代,并且可以是不间断的或被O、S或N(R14)或1,4-丁-1,3-亚二烯基、
或
间隔,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R10取代,其中1或2个碳原子可以被氮替代;
R10和R11各自独立的是C(R23)=NR25,C(R23)=NR26或R28;或R10是式(I)或(III)中的X1位置,或式(IV)中的X2位置;
R12和R13各自独立地是氢,R10,或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;或
R12和R13一起构成C2-C7亚烷基或C2-C7亚烯基,优选C3-C6亚烷基或C3-C6亚烯基,最优选C4-C5亚烷基或C4-C5亚烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24和/或R32取代;
R15和R16各自独立地选自C1-C5烷基,其是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代,
R17是C2-C7亚烷基,优选C4-C5亚烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代,并且可以是不间断的或被O、S或N(R14)间隔,
R21和R22各自独立的是羟基,C1-C12烷氧基,C3-C12环烷氧基,C1-C12烷硫基,C1-C12烷基,C3-C12环烷基,C2-C12烯基,C3-C12环烯基,C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;
R23是氢,氰基,羟基,C1-C12烷氧基,C3-C12环烷氧基,C1-C12烷硫基,C3-C12环烷基硫基,氨基,NHR29,NR30R31,R32,卤素,硝基,甲酰基,N=N-R32,C(R33)=CR26R27,C(R33)=NR25,COO-R30,羧基,氨基甲酰基,CONH-R30,CONR30R31,N=CR25R34,或C1-C12烷基,C3-C12环烷基,C2-C12烯基或C3-C12环烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;
R24是卤素,羟基,O-R30,O-CO-R30,S-R30,NH2,NH-R30,NR30R31,NH3 +,NH2R30 +,NHR30R31 +,NR29R30R31 +,NR30-CO-R29,NR30COOR29,氰基,甲酰基,COO-R30,羧基,氨基甲酰基,CONH-R30,CONR30R31,脲基,NH-CO-NHR29,NR30-CO-NHR29,磷酸根合,PR30R29,POR30OR29,P(=O)OR30OR29,OPR30R29,OPR30OR29,OP(=O)R30OR29,OPO3R30,OP(=O)OR30OR29,SO2R30,硫酸根合,磺基或C1-C12烷氧基或C1-C12环烷氧基,每个是未取代的或被卤素单或多取代;
R26和R27各自独立的是NR30R31,CN,CONH2,CONHR25,CONR25R34或COOR34;
R28是卤素,硝基,氰基,硫氰酸根合,羟基,O-R25,O-CO-R25,S-R25,CHO,COR34,CHOR25OR35,CR34OR25OR35,R36,N=N-R36,N=CR25R34,N=CR26R27,NH2,NH-R25,NR25R34,NH3 +,NH2R25 +,NHR25R34 +,NR25R34R35 +,CONH2,CONHR25,CONR25R34,SO2R25,SO2NH2,SO2NHR25,SO2NR25R34,COOH,COOR25,OCOOR25,NHCOR25,NR25COR35,NHCOOR25,NR25COOR35,脲基,NR25-CO-NHR35,B(OH)2,B(OH)(OR25),B(OR25)OR35,磷酸根合,PR25R35,POR25OR35,P(=O)OR25OR35,OPR25R35,OPR25OR35,OP(=O)R25OR35,OP(=O)OR25OR35,OPO3R25,硫酸根合,磺基,或C1-C12烷基,C3-C12环烷基,C2-C12烯基,C3-C12环烯基,C1-C12烷硫基,C3-C12环烷基硫基,C2-C12链烯基硫基,C3-C12环烯基硫基,C1-C12烷氧基,C3-C12环烷氧基C2-C12链烯氧基或C3-C12环烯基氧基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代;
R29,R30和R31各自独立的是C1-C12烷基,C3-C12环烷基,C2-C12烯基,C3-C12环烯基,C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基;或
R30和R31与共用的氮一起构成吡咯烷,哌啶,哌嗪或吗啉,每个是未取代的或被C1-C4烷基单至四取代;
R32是C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R28取代;
R33是氢,R28,或C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R28取代;
R25、R34和R35各自独立的是R36,或C1-C12烷基,C3-C12环烷基,C2-C12烯基或C3-C12环烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;或
R19和R25一起,R23和R25一起和/或R25和R35一起是C2-C12亚烷基,C3-C12环亚烷基,C2-C12亚烯基或C3-C12环亚烯基,每个是未取代的或如果合适的话,被一个或多个相同或不同的卤素、羟基、C1-C12烷氧基或C3-C12环烷氧基基团取代;或
R25和R34与共用的氮一起是吡咯烷,哌啶,哌嗪或吗啉,每个是未取代的或被C1-C4烷基单至四取代;或咔唑,吩嗪或吩噻嗪,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R37取代;
R36是C6-C12芳基,C4-C12杂芳基,C7-C12芳烷基或C5-C12杂芳烷基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R37取代;
R37是硝基,SO2NHR30,SO2NR30R31,或C1-C12烷基,C3-C12环烷基,C1-C12烷硫基,C3-C12环烷基硫基,C1-C12烷氧基或C3-C12环烷氧基,每个是未取代的或如果合适的话,被一个或多个相同或不同的基团R24取代;和
m是从1至10的数值。
2.按照权利要求1的光记录介质,其中X1和X2各自独立地是直接键或链CR12R13,C=O,C=S,C=N(R14),N(R14),O或S。
3.按照权利要求1或2的光记录介质,其中记录层包括式(I)、(II)、(III)或(IV)的化合物,其中
A1和A2各自独立的是N(R14),O,S或Se且A3是C(C1-C5烷基)2,C(C4-C5亚烷基),N(R14),O,S,Se,N=C(R18)或未取代或R19-取代的CH=CH,特别是其中A1、A2和A3各自独立的是O,S或N(R14)和/或Q1和Q2是C(R23)或N;
R1,R2,R3,R4,R5,R6,R7,R8和R19各自独立的是氢,R10,或C6-C12芳基,或C7-C12芳烷基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R10取代;
R9、R14和R18各自独立的是未取代的或R10-取代的C1-C8烷基;或
R9是式(I)或(III)中的X1位置,或式(IV)中的X2位置;
R10和R28各自独立的是卤素,硝基,氰基,O-R25,甲酰基,CH=C(CN)2,CH=C(CN)CONH2,CH=C(CN)CONHR25,CH=C(CN)CONR25R34,CH=C(CN)COOR25,CH=C(COOR25)COOR34,CONH2,CONHR25,CONR25R34,SO2C1-C12烷基,SO2NH2,SO2NHR25,SO2NR25R34,COOH,COOR25,NHCOR25,NR25COR35,NHCOOR25,NR25COOR35,脲基,P(=O)OR25OR35,磺基,或C1-C12烷基,C1-C12烷硫基或C1-C12烷氧基,每个是未取代的,或如果合适的话,被一个或多个相同或不同的基团R24取代;
R23是氢,氰基,卤素,硝基,甲酰基,N=N-R32,C(R19)=CR26R27,C(R19)=NR25,COO-R30,羧基,氨基甲酰基,CONH-R30,CONR30R31,或未取代的或被一个或多个卤素取代基取代的C1-C12烷基;
R24是卤素,羟基,O-R30,氨基,NH-R30,NR30R31,NR30-CO-R29,NR30COOR29,氰基,COO-R30,羧基,CONH-R30,CONR30R31,硫酸根合,磺基,或未取代的或被卤素单或多取代的C1-C12烷氧基;
R25、R34和R35各自独立的是C1-C12烷基,其是未取代的或如果合适的话被一个或多个相同或不同的卤素、羟基或C1-C12烷氧基基团取代,或未取代的C6-C12芳基或C7-C12芳烷基;或
R25和R34与共用的氮一起构成吗啉,或被C1-C4烷基N-取代的哌啶;
R29、R30和R31各自独立的是C1-C12烷基,C2-C12烯基,C6-C12芳基或C7-C12芳烷基;或
R30和R31与共用的氮一起构成吗啉,或被C1-C4烷基N-取代的哌啶;
R36是未取代的或取代的C6-C12芳基或C7-C12芳烷基,特别是金属茂基基团;和/或
m是从1至4的数值,
或其互变体。
5.按照权利要求1、2、3或4的光记录介质,其中记录层基本上是无定形的。
6.按照权利要求1、2、3、4或5的光记录介质,另外包括覆盖层,其中以基材、反射层、记录层和覆盖层的顺序布置。
7.按照权利要求1、2、3、4、5或6的光记录介质, 其除了包括式(I)的化合物之外,还包括不含金属的发色团。
8.一种记录或播放数据的方法,其中在按照权利要求1、2、3、4、5、6或7的光记录介质上的数据是用350至500nm波长的激光记录或播放的。
9.按照权利要求8的方法,其中数据是不同反射率的标记形式。
10.按照权利要求1的式(I)、(II)、(III)或(IV)的化合物或其互变异构体。
11.一种旋涂溶液,包括溶于溶剂中的按照权利要求10的式(I)、(II)、(III)或(IV)的化合物或其互变异构体。
12.按照权利要求1的式(I)、(II)、(III)或(IV)的化合物或其互变异构体、或按照权利要求10的旋涂溶液在制备光记录介质中的用途。
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