CN86107935A - 噻吨酮衍生物 - Google Patents
噻吨酮衍生物 Download PDFInfo
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- CN86107935A CN86107935A CN86107935.3A CN86107935A CN86107935A CN 86107935 A CN86107935 A CN 86107935A CN 86107935 A CN86107935 A CN 86107935A CN 86107935 A CN86107935 A CN 86107935A
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
- 239000000470 constituent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- OEZKDMYTQDZSAZ-UHFFFAOYSA-N 1-hydroxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O OEZKDMYTQDZSAZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 17
- 150000001450 anions Chemical class 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 235000019441 ethanol Nutrition 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 238000010992 reflux Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
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- 229910052708 sodium Inorganic materials 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- -1 dichromate compound Chemical class 0.000 description 3
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 3
- SYZJDGAOLGLIDX-UHFFFAOYSA-N 1-hydroxyazocane Chemical compound ON1CCCCCCC1 SYZJDGAOLGLIDX-UHFFFAOYSA-N 0.000 description 2
- MNZDVSVZUSIPCU-UHFFFAOYSA-N Cl.C(C1CO1)CN(C)C Chemical compound Cl.C(C1CO1)CN(C)C MNZDVSVZUSIPCU-UHFFFAOYSA-N 0.000 description 2
- 235000007466 Corylus avellana Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 125000002228 disulfide group Chemical group 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- CSPHGSFZFWKVDL-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-trimethylazanium;chloride Chemical class [Cl-].C[N+](C)(C)CC(O)CCl CSPHGSFZFWKVDL-UHFFFAOYSA-M 0.000 description 1
- NHJNEVDNUSFTSG-UHFFFAOYSA-N 1,5-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CC(C)(O)C1 NHJNEVDNUSFTSG-UHFFFAOYSA-N 0.000 description 1
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 description 1
- LHXGLTZNCXCSKG-UHFFFAOYSA-N 2-hydroxy-4-methylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C)=CC(O)=C2 LHXGLTZNCXCSKG-UHFFFAOYSA-N 0.000 description 1
- ANHLDZMOXDYFMQ-UHFFFAOYSA-N 2-hydroxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(O)=CC=C3SC2=C1 ANHLDZMOXDYFMQ-UHFFFAOYSA-N 0.000 description 1
- MFSNBWUXJDADAB-UHFFFAOYSA-N 4-hydroxy-1-methylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2C MFSNBWUXJDADAB-UHFFFAOYSA-N 0.000 description 1
- MFZQDMVFXIZESQ-UHFFFAOYSA-N 4-hydroxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2 MFZQDMVFXIZESQ-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000007582 Corylus avellana Species 0.000 description 1
- 240000003211 Corylus maxima Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000005236 alkanoylamino group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000005191 hydroxyalkylamino group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000005075 thioxanthenes Chemical class 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
- G03F7/12—Production of screen printing forms or similar printing forms, e.g. stencils
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Steroid Compounds (AREA)
- Pyrane Compounds (AREA)
Abstract
本发明提供通式(I)的噻吨酮衍生物,在式(I)中,R2、R3和R4中有一个是式(II)基团,在式(II)中,R5、R6和R7中有一个是烷基或苄基,其余则是烷基,A-代表一种阴离子,R1和R2、R3及R4中的其余两个各自独立地选自氢原子、烷基和烷氧基。这种衍生物可以用作光引发剂,尤其是用作制造丝网漏印板用的含水光聚合组成物中的光引发剂。
Description
本发明涉及噻吨酮衍生物、其制备方法、含有这种衍生物的光聚合组成物、这种组成物在制造丝印漏印板方面的应用、涂有该组织物的丝印板以及这种衍生物作光引发剂的应用。
丝印制板主要采用三种感光材料体系,按其用法,通常称为直接法、间接法和直接/间接法。先有技术的光引发剂包括某些重铬酸盐化合物、聚合的重氮盐以及某种靛蓝或硫靛染料的无色硫酸酯。当这些光引发剂用于任何一种丝印制板法时,都有不易溶于水的缺点,这样,就必需添加某种过氧化物的溶液,或使用大量的湿润剂,或者采用双组合体系。
为了克服这些困难,欧洲专利EP-A-81280揭示:某些含有诸如羧酸或磺酸基这类阴离子基团的噻吨酮,在pH合适的水中,有好的溶解性,可用作丝印制版的光引发剂。这些噻吨酮有如下的化学式,并包括它们的水溶性盐类:
其中,R1是卤素、烷基、烷氧基、烷硫基、硝基、氨基、烷基氨基、二烷基氨基、羟烷基氨基、链烷酰基氨基、苯甲酰氨基、N-链烷酰基-N-苯甲酰氨基、氨磺酰基或乙酰基,R2是碳原子数为1-4的亚烷基,n为0、1或2,m为1或2,A是-COOH、-SO3H-、-OSO3H或-OCO-X-COOH(这里X要使HOOC-X-COOH成为碳原子数最多可达8的二元或三元羧酸;上述的烷基、烷氧基以及链烯基各含有四个以下的碳原子。
现已发现,一些新的噻吨衍生物在很宽的pH范围内都具有非常好的水溶性。
本发明提供以下通式的噻吨酮生物:
式中,R2、R3和R4中有一个是化学式如下的基团:
Ⅱ式中的R5、R6和R7中有一个是烷基或苄基,其余则是烷基,A-代表一种阴离子;R1与R2、R3和R4三个基团中的其余两个都各自独立地选自氢原子、烷基和烷氧基。
烷基或烷氧基R1、R2、R3或R4最好是C1-6烷基或C1-6烷氧基,以C1-4烷基或C1-4烷氧基(如甲氧基)为更佳。在本发明的推荐实施方案里,R1与所说的R2、R3和R4三个基团中的其余两个都各自独立地选自氢原子和甲基。
最好是,R5、R6和R7中有一个是C1-20烷基(如十六烷基)或苄基,其余则是C1-6烷基,最好是C1-4烷基。在本发明的推荐实施方案中,R5、R6和R7都是甲基。
A-可以代表半个二价阴离子,如1/2 SO2- 4,但最好是一个单价阴离子,如卤离子。A最好代表一个氯或溴原子,以氯原子最为适宜。
式(Ⅰ)的噻吨酮衍生物以R2或R4代表式(Ⅱ)基团的为佳。
本发明还提供制备一种如上面定义的式(Ⅰ)所代表的噻吨酮衍生物的方法,该方法包括:使与式(Ⅰ)相对应、只不过其中的式(Ⅱ)基团被羟基所代替的羟基噻吨酮在碱存在下与式(Ⅲ)化合物反应,
上式中,R5、R6、R7和A-的定义都和对式(Ⅱ)中的相应基团规定的相同,R8是羟基,R9是一个离去基团,或者R8与R9合在一起代表一个氧原子。
离去基团R9一般可以是卤原子。R8是-OH基时,R9最好是氯原子。
与式(Ⅰ)相对应、但其中式(Ⅱ)基团被羟基所代替的这类羟基噻吨酮,或者是可用已知方法制得的已知化合物,或者是可用已知方法的类似方法制得的化合物。本领域的熟练技术人员参照文献资料,很容易找到合适的制备方法,这些资料是,例如:欧洲专利EP-A-81280;东德专利DE-A-2504642;捷克斯洛伐克专利145,016;印度化学学会杂志J.Ind.Chem.Soc.,1929,6,273(作者:R.N.Sen和S.C.Sen Guppta);化学学会杂志J.C.S.1911,99,2050-1(作者:H.Christopher和S.Smiles);以及美国化学学会杂志J.A.C.S.,1957,79,2227-8(作者:A.Mustafa和O.H.Hishmat)。
羟基噻吨酮与式(Ⅲ)化合物的反应适于这样进行:一般可采用链烷醇,如C1-3链烷醇,通常是用乙醇,作溶剂,或者采用一种极性的质子惰性溶剂,诸如N,N-二甲基甲酰胺作溶剂,反应温度在60℃到回流温度范围内。在回流温度下进行反应非常方便。常用的碱有碱金属(如钠或钾)的烷氧化物和氢氧化物。
另外,本发明还提供一种可光聚合的含水组成物,其中含有至少一种光聚合单体的水分散液或溶液,以及作为光引发剂的一种式(Ⅰ)的噻吨酮衍生物。本发明内容还包括这种组成物用于制造丝印漏印板的用途,以及把这种组成物涂布在丝网上并干燥后制得的丝印板。
合乎使用要求的这种含水的可光聚合组成物,也包括欧洲专利EP-A-81280中所述的组成物,但采用式(Ⅰ)的噻吨酮衍生物代替其噻吨酮光引发剂。所以通过引用该专利也将其公开内容合并于此。
本发明内容也包括把(Ⅰ)的衍生物用作光引发剂。
式(Ⅰ)化合物具有容易吸收泼长在330毫微米以上的光化学光的性质。它们除了可以如前所述在光聚合组成物里用作光引发剂以外,还可以用来制造水基紫外光固化油墨。
参照下面的实施例,对本发明内容会有深一步的了解,其中实施例1-6涉及式(Ⅰ)化合物的制备,而实施例7则证实了该化合物作为光引发剂的效能。
实施例1
氯化2-羟基-3-(9-氧代-9H-噻吨-4-基氧基)-N,N,N-三甲基-1-丙铵
将5.7克4-羟基噻吨酮(熔点284.5-286.5℃,制备方法和东德专利DE-A-2504642和捷克专利145,016的方法相似)和5.44克含量为70%的缩水甘油基三甲胺盐酸盐与95毫升无水乙醇混合在一起搅拌,升温至回流温度,随后加入几滴乙醇钠溶液(3%重量/体积)把pH调节到大约9。回流四分钟后,得到透明溶液,继续回流三小时,出现结晶状固体。再回流3.5小时后,加入7毫升水,用几滴当量浓度为2的氯化氢异丙醇溶液把pH调节到大约3。趁热过滤,随后用冰浴冷却滤液,从中过滤出粗的标题化合物,经异丙醇洗涤,用普通烘箱在60℃干燥。得8.58克暗淡绿色固体(熔点267-268℃),经乙醇(90毫升)和水(7毫升)的混合液重结晶,用乙醇洗涤,再干燥后,得到7.03克(87.8%)标题化合物的亮绿色结晶体,熔点268.5-269.2℃。
元素分析:
C19H22ClNO3S∶0.25H2O;
计算值:C59.36;H5.90;N3.64;C19.22;S8.34
实测值:C59.53;H5.76;N3.63;C19.48;S8.40
该化合物的水溶液在波长391毫微米处有最大吸收峰,其消光系数E(浓度1%;1厘米吸收池)为149。
实施例2
氯化2-羟基-3-(1-甲基-9-氧代-9H-噻吨-4-基氧基)-N,N,N-三甲基-1-丙铵
将6.05克4-羟基-1-甲基噻吨酮(采用R.N.Sen和S.C.Sen Guppta在J.Ind.Chem.Soc.,1929,6,2730上所发表方法的类似方法制得)和5.44克含量为70%的缩水甘油基三甲胺盐酸盐与60毫升无水乙醇混合在一起搅拌,升温到回流温度,随后加入几滴乙醇钠的乙醇溶液(3%重量/体积)把pH调节到大约9,回流2分钟后,得到透明溶液,继续回流2小时,出现结晶状固体。加入13毫升水,使固体重新溶解,继续回流另外4小时。用几滴当量浓度为2的氯化氢异丙醇溶液把pH调节到大约4,趁热过滤,随后用冰浴冷却滤液,并从中过滤出粗的标题化合物,经乙醚洗涤,真空干燥之。
黄色固体(6.37克;熔点269-270.5℃)用含有少量水的乙醇重结晶,经乙醇洗涤,用普通烘箱在70℃干燥,得到4.5克(45.6%)黄色结晶状标题化合物,熔点271-272℃。
元素分析:
C20H24ClNO3S:
计算值:C60.98;H6.14;N3.56;C19.00;S8.14
实测值:C60.70;H6.15;N3.48;C19.01;S8.13
该化合物的水溶液在波长390毫微米处有最大吸收峰,其消光系数E(浓度1%;1厘米吸收池)为134.5。
实施例3
氯化2-羟基-3-(9-氧代-9H-噻吨-4-基氧基)-N,N,N-三甲基丙铵
1.36克金属钠与120毫升无水乙醇反应,同时加入11.4克2-羟基噻吨酮(采用H.Christopher和S.Smiles在J.C.S.,1911,99,2050-2051上所发表方法的类似方法制得)。在搅拌下的回流混合物里,加入10.7克(3-氯-2-羟丙基)三甲基氯化铵,混合物回流过夜。用几滴当量浓度为2的氯化氢异丙醇溶液,把pH调节到大约4,趁热过滤,随后用冰浴冷却滤液,并从中过滤出粗的标题化合物,经甲醇洗涤,真空干燥之。
黄色固体(15.3克;熔点245-246.5℃)用乙醇(150毫升)和甲醇(40毫升)的混合物重结晶,经乙醇洗涤,真空干燥,得到14.5克(72.8%)黄色结晶状标题化合物,熔点245-246.5℃。
元素分析:
C19H22ClNO3S∶1H2O:
计算值:C57.35;H6.08;N3.52;Cl8.91;S8.06
实测值:C57.73;H6.01;N3.40;Cl8.77;S8.02
实施例4
氯化2-羟基-3-(4-甲基-9-氧代-9H-噻吨-2-基氧基)-N,N,N-三甲基丙铵
将6.5克2-羟基-4-甲基噻吨酮(采用A.Mustafa和O.H.Hishmat在J.A.C.S.1957,79,2227-8上所发表方法的类似方法制得)和5.12克含量为80%的缩水甘油基三甲基氯化铵同70毫升无水乙醇混合在一起搅拌,升温到回流温度,随后加入几滴乙醇钠溶液(3%重量/体积)把pH调节到大约9。回流2小时后,得到透明溶液,继续回流18小时后,出现结晶状固体。加入70毫升甲醇,接着加入2毫升水,使固体溶解,将混合物回流过夜。用几滴当量浓度为2的氯化氢异丙醇溶液把pH调节到大约4,趁热过滤,随后用冰浴冷却滤液,并从中过滤出粗的标题化合物,用乙醚洗涤二次,真空干燥之。
黄色固体(9.6克;熔点247-253℃)用甲醇(60毫升)、乙醇(60毫升)和水(6毫升)三者的混合液重结晶,经乙醇洗涤、真空干燥,得到8.0克(77.7%)黄色结晶状标题化合物,熔点253.3-255℃。
元素分析:
C20H24ClNO3S∶1H2O:
计算值:C58.33;H6.36;N3.40;Cl8.61;S7.78
实测值:C58.65;H6.54;N3.27;Cl8.57;S7.73
该化合物的水溶液在波长404毫微米处有最大吸收峰,其消光系数E(浓度1%;1厘米吸收池)为144。
实施例5
氯化2-羟基-3-(3,4-二甲基-9-氧代-9H-噻吨-2-基氧基)-N,N,N-三甲基-1-丙铵
制备2-羟基-3,4-二甲基噻吨酮(用70%体积比的二甲基甲酰胺/水混合溶剂重结晶后,其熔点为309-310℃;微量分析:C15H12O2S计算值:C70.30;H4.72;S12.51;实测值:C70.22;H4.73;S12.37);的方法如下:将24.4克2,3-二甲基苯酚在搅拌下,在两小时内加到2,2′-亚二硫基二苯甲酸(2,2′-dithiobisbenzoic acid)(15.5克)与浓硫酸(150毫升)的混合物中,同时用水冰浴冷却,使反应温度保持在15±5℃。继而将温度升高到65℃,并在65±5℃保持1小时,此后将混合物冷却16小时,然后将其倾入500毫升温度为95±5℃的水中,随后搅拌30分钟,再过滤之。滤渣用水洗两次,然后在加入的250毫升70℃的水里调成浆状,并慢慢加入44克碳酸氢钠,直到pH值达到8。将混合物煮沸10分钟后过滤,滤渣用水洗三次,再用异丙醇洗一次。在60℃普通烘箱里干燥,得到18.59克2-羟基-3,4-二甲基噻吨酮粗产物,为暗黄色结晶状固体,熔点298-302℃。
在104℃,将6.4克上述粗产物溶解在40毫升二甲基甲酰胺中,趁热过滤。在100℃的滤液里,加入5.44克含量为70%的缩水甘油基三甲基氯化铵(用10毫升二甲基甲酰胺调成浆状)。用几滴氢氧化钠的乙醇溶液(3%重量/体积)将pH调节至大约9,在100℃搅拌12分钟,便出现结晶状固体。继续在100℃搅拌6小时,用几滴当量浓度为2的氯化氢异丙醇溶液调节pH至大约6,然后用冰浴冷却混合物。过滤后得到的滤渣用二甲基甲酰胺洗一次,再用异丙醇洗三次,在70℃空气干燥,得到7.57克(72.4%)标题化合物,为淡黄色固体,熔点271.5-273.5℃。
元素分析:
C21H26ClNO3∶0.75H2O:
计算值:C59.82;H6.58;N3.36;Cl8.41;S7.61
实测值:C59.90;H6.55;N3.23;Cl8.53;S7.69
该化合物的水溶液在波长402毫微米处有最大吸收峰,其消光系数E(浓度1%;1厘米吸收池)为115。
实施例6
氯化2-羟基-3-(1,3,4-三甲基-9-氧代-9H-噻吨-2-基氧基)-N,N,N-三甲基-1-丙铵
制备2-羟基-1,3,4-三甲基噻吨酮的方法如下:在30.6克2,2′-亚二硫基二苯甲酸与300毫升浓硫酸的混合物里,在搅拌下,在两小时内加入18.6克2,3,6-三甲基苯酚,同时用冰浴冷却,使温度保持在12.5±2.5℃。将混合物在75±5℃加热1小时后冷却到50℃,然后在搅拌下倒入2升热水中。过滤后用水洗涤,用普通烘箱在70℃干燥,粗产物从二甲基甲酰胺(140毫升)和水(60毫升)的混合物中重结晶出来,过滤后用水洗,在70℃干燥,制得38.4克(71.1%)2-羟基-1,3,4-三甲基噻吨酮产物,为黄褐色结晶体,熔点201-204℃。
将6.75克上述产物和6.44克含量为70%的缩水甘油基三甲基氯化铵与60毫升无水乙醇放在一起搅拌,升温到回流温度,随后加入几滴乙醇钠的乙醇溶液(3%重量/体积)把pH调节到大约9。回流1小时后,得到透明溶液。将混合物继续回流16小时,加入30毫升甲醇和2毫升水,使反应均匀。用几滴当量浓度为2的氯化氢异丙醇溶液把pH调节到大约3,趁热过滤,滤液用冰浴冷却,经过滤,得到粗制的标题化合物,用乙醇洗三次,真空干燥之。淡褐色固体(9.21克;熔点258.5-260.5℃)用甲醇(90毫升)和乙醇(75毫升)的混合物重结晶,经乙醇洗和真空干燥,得到6.5克(61.0%)标题化合物,为淡褐色结晶体,熔点264.5-265.5℃。
元素分析:
C22H28Cl NO3S∶0.25H2O:
计算值:C61.94;H6.74;N3.28;Cl8.30;S7.52
实测值:C62.26;H6.76;N3.23;Cl8.17;S7.42
该化合物的水溶液在波长309毫微米处有最大吸收峰,其消光系数E(浓度1%;1厘米吸收池)为111。
实施例7
实施例1-6制得的化合物作水溶性光引发剂的效果评定
前面实施例中叙述的每种化合物按下列方法进行试验。将0.33克样品溶于0.8毫升水中,加入0.7毫升N,N-二甲氨基乙醇。将得到的溶液搅拌,并加到30克“Azcol S”(商标名)乳液中,随后加入1克N,N′-亚甲基双丙烯酰胺。搅拌5分钟后,混合物放置16小时,便可涂布于橙色的聚酯丝网(110线/厘米),在丝网正面涂布两次,反而涂布一次。涂有感光胶的丝网用空气干燥,辐射光先通过一块平板玻璃(5厘米厚),再透过一块带正像的薄膜,照射到丝网上。丝网、薄膜和玻璃以夹心式结构紧贴在一起,其位置正好在两盏375瓦摄影灯的下方,灯的底面距玻璃片顶面的距离为35厘米。光照一定时间后,将丝网用流动的冷水慢慢冲洗,直至开始形成影像,然后再继续冲洗两分钟。空气干燥丝网,并对制得的丝印漏印板进行检定。采用逐步延长曝光时间的方法,测定出要得到质量合格的漏印板所需要的最少曝光时间,其结果列于下表。由比较起见,按制造商的规程配制一种标准的、敏化了的“Azocol S”乳液,并按上述方法加工,随后测定出它的最少曝光时间。为比较效果,还按上述方法测试了2-(3-硫代丙氧基)噻吨酮的钠盐(EP-A-81280的实施例2)一“比较例A”。
测定结果
化合物实例号 曝光时间(秒)
1 4
2 2
3 8
4 2
5 4
6 8
标准化合物 30
“比较例A” 8
这些结果证实了本发明化合物作水溶性光引发剂的效果。
“Azocol”乳液是一种部分水解的聚醋酸乙烯酯在水中的乳液。推荐使用的光敏剂是对苯二胺/甲醛交联聚合物的重氮盐。
Claims (10)
2、按照权利要求1的一种衍生物,其中R1与所说的R2、R3和R4中的其余两个都各自独立地选自氢原子和甲基。
3、按照权利要求1或2的一种衍生物,其中R5、R6和R7都是甲基。
4、按照权利要求1、2或3的一种衍生物,其中A代表氯原子或溴原子。
5、按照权利要求1-4中任何一项的一种衍生物,其中R或R代表式(Ⅱ)基团。
7、按照权利要求6的方法,其中当R8是-OH基时,R9是氯原子。
8、一种含水的光聚合组成物,它包含至少一种光聚合单体的水分散液或溶液以及作为光引发剂的一种噻吨酮衍生物,这种衍生物具有权利要求1-5中任何一项中所示的式(Ⅰ)结构。
9、按照权利要求8的一种组成物用于制造丝印漏印板。
10、用按照权利要求8的一种组成物涤布后进行干燥而得到的丝印版。
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TW466256B (en) | 1995-11-24 | 2001-12-01 | Ciba Sc Holding Ag | Borate photoinitiator compounds and compositions comprising the same |
EP0791859B1 (en) * | 1996-02-20 | 2001-05-30 | Asahi Kasei Kabushiki Kaisha | Process for producing photosensitive resin printing plate |
US6025408A (en) * | 1997-03-27 | 2000-02-15 | First Chemical Corporation | Liquid thioxanthone photoinitiators |
US20050261390A1 (en) * | 2004-05-13 | 2005-11-24 | Jean-Marc Frances | Stable cationically crosslinkable/polymerizable dental composition with a high filler content |
DE602005013513D1 (de) * | 2004-05-13 | 2009-05-07 | Bluestar Silicones France | Fotopolymerisierbare dentale zusammensetzungen |
FR2872409B1 (fr) * | 2004-06-30 | 2007-02-09 | Rhodia Chimie Sa | Composition dentaire photopolymerisable |
US7893130B2 (en) * | 2004-05-13 | 2011-02-22 | Bluestar Silicones France Sas | Photocurable dental composition |
US20060150847A1 (en) * | 2004-10-12 | 2006-07-13 | Presstek, Inc. | Inkjet-imageable lithographic printing members and methods of preparing and imaging them |
US7589083B2 (en) * | 2005-09-12 | 2009-09-15 | Cancure Laboratories, Llc | Compounds and compositions to control abnormal cell growth |
US20070154518A1 (en) * | 2005-12-29 | 2007-07-05 | Robert Falotico | Photoactive biocompatible coating composition |
US20080114055A1 (en) * | 2006-11-10 | 2008-05-15 | Zoltan Laboratories Llc | Thioxanthone Compounds to Reverse Weight Loss |
US20080207738A1 (en) * | 2007-02-28 | 2008-08-28 | Cancure Laboratories, Llc | Drug combinations to treat drug resistant tumors |
FR3067030B1 (fr) * | 2017-06-02 | 2019-07-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Dispositif et procede de realisation d'un objet |
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GB1434486A (en) * | 1974-02-04 | 1976-05-05 | Ici Ltd | Thioxanthene derivatives |
CH640849A5 (de) * | 1979-05-18 | 1984-01-31 | Ciba Geigy Ag | Thioxanthoncarbonsaeureester, -thioester und -amide. |
US4418138A (en) * | 1981-11-03 | 1983-11-29 | Sericol Group Limited | Photopolymerizable materials for use in producing stencils for screen printing |
GB2108487B (en) * | 1981-11-03 | 1985-07-31 | Sericol Group Ltd | Water soluble thioxanthone photoinitiators |
US4602097A (en) * | 1984-06-11 | 1986-07-22 | Ulano Corporation | Water soluble photoinitiator benzophenone and thioxanthenone ethoxy-ether derivatives |
-
1985
- 1985-11-29 GB GB858529448A patent/GB8529448D0/en active Pending
-
1986
- 1986-11-05 US US06/927,018 patent/US4791213A/en not_active Expired - Fee Related
- 1986-11-06 CA CA000522382A patent/CA1277328C/en not_active Expired - Fee Related
- 1986-11-26 CN CN86107935A patent/CN1020454C/zh not_active Expired - Fee Related
- 1986-11-26 EG EG737/86A patent/EG18427A/xx active
- 1986-11-27 DE DE8686202118T patent/DE3664469D1/de not_active Expired
- 1986-11-27 JP JP61280932A patent/JPH0788377B2/ja not_active Expired - Lifetime
- 1986-11-27 AU AU65751/86A patent/AU586051B2/en not_active Ceased
- 1986-11-27 ZA ZA868979A patent/ZA868979B/xx unknown
- 1986-11-27 HU HU864918A patent/HU205104B/hu not_active IP Right Cessation
- 1986-11-27 IE IE312686A patent/IE59500B1/en not_active IP Right Cessation
- 1986-11-27 ES ES86202118T patent/ES2009785B3/es not_active Expired
- 1986-11-27 EP EP86202118A patent/EP0224967B1/en not_active Expired
- 1986-11-27 DK DK572186A patent/DK164320C/da not_active IP Right Cessation
- 1986-11-27 NZ NZ218425A patent/NZ218425A/xx unknown
- 1986-11-27 IL IL80800A patent/IL80800A0/xx not_active IP Right Cessation
- 1986-11-27 BR BR8605813A patent/BR8605813A/pt unknown
- 1986-11-27 PT PT83820A patent/PT83820B/pt not_active IP Right Cessation
-
1989
- 1989-09-20 GR GR89400177T patent/GR3000160T3/el unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101397424B (zh) * | 2007-09-28 | 2013-06-12 | 富士胶片株式会社 | 油墨组合物 |
Also Published As
Publication number | Publication date |
---|---|
DK572186D0 (da) | 1986-11-27 |
NZ218425A (en) | 1988-10-28 |
EG18427A (en) | 1993-02-28 |
AU586051B2 (en) | 1989-06-29 |
ZA868979B (en) | 1987-07-29 |
GR3000160T3 (en) | 1990-12-31 |
PT83820A (en) | 1986-12-01 |
US4791213A (en) | 1988-12-13 |
AU6575186A (en) | 1987-06-04 |
EP0224967B1 (en) | 1989-07-19 |
IE59500B1 (en) | 1994-03-09 |
PT83820B (pt) | 1988-10-14 |
IE863126L (en) | 1987-05-29 |
ES2009785B3 (es) | 1989-10-16 |
CA1277328C (en) | 1990-12-04 |
CN1020454C (zh) | 1993-05-05 |
DE3664469D1 (en) | 1989-08-24 |
DK164320C (da) | 1992-11-02 |
HU205104B (en) | 1992-03-30 |
HUT44025A (en) | 1988-01-28 |
GB8529448D0 (en) | 1986-01-08 |
EP0224967A1 (en) | 1987-06-10 |
DK164320B (da) | 1992-06-09 |
IL80800A0 (en) | 1987-02-27 |
JPS62132880A (ja) | 1987-06-16 |
DK572186A (da) | 1987-05-30 |
BR8605813A (pt) | 1987-08-25 |
JPH0788377B2 (ja) | 1995-09-27 |
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