text:
A photo-sensitive and heat-sensitive composition consisting essentially of a leuco-pigment; a hydrogen donator; a photo-reductant which, when exposed to a visible light, produces a reducing agent by the action of said hydrogen donator coexisting therewith; a photooxidant which, when exposed to an ultraviolet ray, causes said leuco-pigment coexisting therewith to generate color and simultaneously, when reacted with said reducing agent, is deprived of its own oxidizing ability; and a cobalt complex which reacts with the reducing agent in amplifying manner to thereby suppress the reaction of a color-forming system, and a recording element using the same.
1. A photo-sensitive, heat-sensitive composition, consisting essentially of:
a color-generating system consisting essentially of a mixture of: photooxidant capable of producing an oxidizing substance when irradiated with ultraviolet radiation, and leuco pigment capable of being oxidized by said oxidizing substance to generate a visible color; and
a fixing system consisting essentially of a mixture of:
photoreductant, hydrogen donator capable of supplying hydrogen to said photoreductant, said photoreductant being capable of producing a reducing substance, in the presence of said hydrogen donator, when irradiated with visible light, and
cobalt (III) complex capable, when heated, of reacting with said reducing substance so that said cobalt complex is reduced and produces ammonia or an amine which is effective to suppress the reaction between said leuco pigment and said oxidizing substance in the area irradiated with visible light.
2. A composition according to claim 1 wherein the amount of said photooxidant is 0.1-10 moles per mole of said leuco pigment, the amount of said cobalt (III) complex is in the range of 0.1-10 moles per mole of said photoreductant, the amount of said hydrogen donator is in excess per mole of said photoreductant, and the molar ratio of said leuco pigment to said photoreductant is 1:1-20 moles.
3. A composition according to claim 1 containing from 30 to 90 wt. % of a binder resin.
4. A composition according to claim 1 in which said color-generating system contains from 1-10 moles of an acid per mole of said leuco pigment.
5. A recording element comprising a support and a photosensitive, heat-sensitive layer superposed on said support, said layer consisting essentially of a mixture of:
photooxidant capable of producing an oxidizing substance when irradiated with ultraviolet radiation, leuco pigment capable of being oxidized by said oxidizing substance to generate a visible color, photoreductant, hydrogen donator capable of supplying hydrogen to said photoreductant, said photoreductant being capable of producing a reducing substance, in the presence of said hydrogen donator, when irradiated with visible light, and
cobalt (III) complex capable, when heated, of reacting with said reducing substance so that said cobalt complex is reduced and produces ammonia or an amine which is effective to suppress the reaction between said leuco pigment and said oxidizing substance in the area irradiated with visible light.
6. A recording element according to claim 5 wherein the amount of said photooxidant is 0.1-10 moles per mole of said leuco pigment, the amount of said cobalt (III) complex is in the range of 0.1-10 moles per mole of said photoreductant, the amount of said hydrogen donator is in excess per mole of said photoreductant, and the molar ratio of said leuco pigment to said photoreductant is 1:1-20 moles.
7. A recording element according to claim 5 wherein said layer contains from 30 to 90 wt. % of binder resin.
8. A recording element according to claim 5 wherein said layer contains from 1-10 moles of an acid per mole of said leuco pigment.
9. A recording element according to claim 5 wherein the thickness of said photo-sensitive and heat-sensitive layer is 5-40 μm.
10. A recording element according to claim 5 wherein said support is paper or a plastic film.
11. A photo-sensitive, heat-sensitive recording element comprising a support, a fixing layer superposed on said support, said fixing layer consisting essentially of a mixture of:
photoreductant, hydrogen donator capable of supplying hydrogen to said photoreductant, said photoreductant being capable of producing a reducing substance, in the presence of said hydrogen donator, when irradiated with visible light, and cobalt (III) complex capable, when heated, of reacting with said reducing substance so that said cobalt complex is reduced and produces ammonia or an amine, and a color-generating layer superposed on said fixing layer, said color-generating layer consisting essentially of a mixture of:
photooxidant capable of producing an oxidizing substance when irradiated with ultraviolet radiation, and leuco pigment capable of being oxidized by said oxidizing substance to generate a visible color, said ammonia or amine being effective to suppress the reaction between said leuco pigment and said oxidizing substance in the area irradiated by visible light.
12. A recording element according to claim 11 wherein the amount of said photooxidant is 0.1-10 moles per mole of said leuco pigment, the amount of said cobalt (III) complex is in the range of 0.1-10 moles per mole of said photoreductant, the amount of said hydrogen donator is in excess per mole of said photoreductant, and the molar ratio of said leuco pigment to said photoreductant is 1:1-20 moles.
13. A recording element according to claim 11 wherein the fixing and color-generating layers contain from 30 to 90 wt. % of binder resin.
14. A recording element according to claim 11 wherein said color-generating layer contains from 1-10 moles of acid, per mole of said leuco pigment.
15. A recording element according to claim 11 wherein the thickness of said fixing layer is 5-20 μm and the thickness of said color-generating layer is 1-20 μm.
16. A recording element according to claim 11 wherein a 1-10 μm-thick intermediate layer is interposed between said fixing layer and said color-generating layer.
17. A recording element according to claim 16 wherein the intermediate layer is made of a resin material.
(a) Field of the Invention
This invention is directed to a photo-sensitive and heat-sensitive composition which is devised to be fixed when irradiated with visible light and generate color when irradiated with ultraviolet radiation to thereby produce a high quality image, and a recording element comprising a support and a layer of said composition superposed thereon.
(b) Description of the Prior Art
A considerably large number of photo-sensitive compositions, photo-sensitive and heat-sensitive compositions and image-forming recording elements using said compositions have been widely utilized or proposed up to now. As typical examples, there can be enumerated, for instance, diazo copying materials using alkali media as developers, photographic films using silver salts, etc. However, the above-mentioned photo-sensitive compositions and recording elements are defective in the fact that developers and fixers must be used in order to obtain an image in practice.
As an attempt to eliminate the foregoing defect, accordingly, public attention has been attracted to dry photochemical photo-sensitive compositions and recording elements capable of forming images only with light as described in Japanese Patent Publications Nos. 19161/1968, 40150/1970, 17855/1972, Japanese Laid Open Patent Application No. 12879/1972, etc. For instance, the photo-sensitive composition as described in Japanese Patent Publication No. 19161/1968 comprises (a) a photooxidant such as hexaarylbiimidazole, tetraarylhydrazine or the like, (b) a color-generator such as leuco-pigment, hydrazone or the like and (c) a binary system redox couple comprising an oxidant component such as quinone, ketone or the like and a reductant component such as alcohol, ester or the like or a one component system redox couple such as 1,4-bis (2-methoxyethyl)anthraquinone or the like. The said photo-sensitive composition generates color by light of specific wavelength such as ultraviolet radiation (the color generating reaction is performed by the action of photooxidant and color-generator, and the originally generated color is deactivated permanently, that is, fixed by light of a different wavelength such as visible light (the fixing reaction is performed by the action of said redox couple). The use of the photo-sensitive composition of this type, accordingly, can obtain both positive image and negative image by selecting the sequence of irradiation of ultraviolet radiation and visible light, but is defective in that the fixing sensitivity (non-color-forming sensitivity) is still low. Accordingly, in order to obtain high contrast and clear-cut copies by using the conventional photo-sensitive components there was inevitably needed a long time period of exposure.
It is an object of this invention to provide a photo-sensitive and heat-sensitive composition capable of producing a copy which is exceedingly superior in both ultraviolet color-generating sensitivity and visible light non-color-forming (fixing) sensitivity and consequently clear-cut to a high extent.
In other words, the photo-sensitive and heat-sensitive composition according to this invention is characterized by consisting essentially of (a) a photooxidant capable of producing an oxidizing substance by irradiation of ultraviolet radiation, (b) a leuco-pigment generating color by the action of said oxidizing substance produced by ultraviolet radiation, (c) a photoreductant capable of producing a reducing substance by irradiation of visible light, (d) a hydrogen donator operable to supply hydrogen to said photoreductant and (e) a cobalt complex which reacts with said reducing substance in amplifying manner to thereby produce a substance acting to suppress the reaction of the color-generating system (for instance, NH3 or the like).
In the composition according to this invention, the aforesaid two components (a) and (b) are a color-generating system and the aforesaid three components (c), (d) and (e) are a fixing system, but the composition per se is photo-sensitive in nature. Due to this, it is the general practice to prepare a mono-layer recording element comprising a support such as paper, plastic film or the like and a photo-sensitive and heat-sensitive layer which is formed by applying the composition onto the support so as to have a dry thickness of about 5-40 μm. Further, by the use of the composition of this invention there may be prepared a two-layer recording element having an about 5-20 μm-thick fixing layer and an about 1-20 μm-thick color-generating layer by the steps of dividing the composition into two systems, i.e., the fixing system and the color-generating system, applying onto a support the fixing system and the color-generating system in that order and drying. According to a similar application method, still further, there may be prepared a three-layer recording element comprising the provision of an about 1-10 μm-thick binder intermediate layer between the fixing layer and the color-generating layer for the purpose of enhancing mainly the color-forming sensitivity. In this case there can be employed a solvent and a binder in combination with the composition, that is, the color-generating system and/or fixing system, in order to facilitate the applying (coating) operation and improving the dispersion and adhesion of the respective elements used.
Next, reference will be made to the respective elements used in this invention.
The photooxidant used in this invention is a compound operable to produce an oxidizing substance by irradiation of ultraviolet radiation and oxidize a color-generator (leuco-pigment) with said oxidizing substance for color generating purposes, said compound comprising two types, that is, one is a compound operating as an initiator and the other is a compound operating as an acceptor. The initiator type photooxidants suitably used in this invention include hexaarylbiimidazoles and tetraarylhydrazines, and the acceptor type photooxidants suitably used in this invention include tetraacylhydrazines, diacylaminobenzotriazoles, benzothiazoledisulfides, triacylhydroxylamines, diacylaminotriazoles, alkylidene-2,5-cyclohexadiene-1-ones, a certain copolymer, diacylaminopyrazoles, bibenzotriazoles, etc. Their typical examples are enumerated as follows:
2,8'-bis(p-cyanophenyl)-4,4',5,5'-tetrakis(p-methoxyphenyl) biimidazole,
2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl) biimidazole,
2,2'-bis(o-chlorophenyl)-4,4'-bis(p-methoxyphenyl)-5,5'-diphenylbiimidazole, and
tetra-p-tolylhydrazine, and
tetraformylhydrazine, and
1-diacetylaminobenzotriazole, and
bis(2-benzothiazolyl) disulfide, and
bis(6-methoxy-2-benzothiazolyl) disulfide.
N,N,O-tribenzoylhydroxylamine, and
1-dipropionylamino-3,5-diphenyl-1H-1,2,4,-triazole, and
1-diacetylaminopyrazole, and
5,5'-dichloro-1,1'-bibenzotriazole, and
As the other photooxidants can be enumerated halogen compounds.
carbon tetraiodide (initiator type)
Iodoform (the same as above)
carbon tetrabromide (acceptor type)
1,2,3,4-tetrachlorobenzene (the same as above)
1,2,3,4-tetrabromobutane (the same as above)
Hexachloroethane (the same as above)
Of the above mentioned photooxidants, the hexaarylbiimidazoles can be represented by the formula ##STR1## (wherein A, B and D stand for aryl radicals. The B and D groups normally carry 0-3 substituents, the A groups 0-4 substituents.) The aryl groups include one- and two-ring aryls, such as phenyl, biphenyl, naphthyl, pyridyl, furyl, thienyl and the like. The substituents may be halogen, cyano, lower hydrocarbyl (including alkyl, halo alkyl, cyanoalkyl, hydroxyalkyl, aryl and the like), lower alkoxy, aryloxy, lower alkylthio, arylthio, sulfo, alkylsulfonyl, nitro, lower alkylcarbonyl and the like. The alkyl groups are preferably of 1-6 carbon atoms, while aryl groups are preferably of 6-10 carbon atoms. And, preferable hexaarylbiimidazoles include 2,2',4,4',5,5'-hexaphenylbiimidazole bearing chlorine, bromine, fluorine, C1 -C6 alkoxy or C1 -C6 alkyl group at the ortho-position of the 2- and 2'-phenyl rings, most preferably 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.
The color-generator (leuco-pigment) is a substantially colorless compound which generates color upon undergoing the oxidizing action of an oxidizing substance coming from the photooxidant. And it, when contained in the composition, is naturally required to be stable under normal storage conditions. Such exemplary color-generators are enumerated as follows:
bis(p-dimethylaminophenyl)(p-sec. butylethylaminophenyl)methane
bis[4-ethyl(2-hydroxyethyl)amino-m-tolyl](p-diethyl aminophenyl)methane
5-[bis(4-diethylamino-o-tolyl)methyl]-2,3-cresotic acid
4-[bis(4-diethylamino-o-tolyl)-methyl]-benzoic acid
4-[bis(4-diethylamino-o-tolyl)-methyl]-diphenyl sulfone
4-[bis(4-diethylamino-o-tolyl)-methyl]-phenylmethyl sulfone
bis(4-diethylamino-o-tolyl)-p-nitrophenyl methane
In addition to the above enumerated aminotriarylmethanes there can be employed leucatriphenylmethane dyes bearing CI numbers 42000B, 42005, 42010, 42025, 42030, 42035, 42036, 42040, 42500, 42505, 42510B, 42515, 52520, 42555B, 42556, 42563B, 42600, 42605, 42705, 42760, 42785, 43500.
In addition to the above enumerated aminoxanthenes there can be employed leuco forms of xanthene dyes bearing CI Numbers 45000, 45005, 45010, 45015, 45050, 45070, 45090, 45095, 45100, 45105, 45150.
In addition thereto there can also be enumerated the leuco forms of acridine dyes bearing CI numbers 46000, 46005B, 46010, 46015, 46020, 46025, 46030, 36035, 36040, 46055, 46060, 46065, 46070, 46075, 46080.
and leuco forms of phenoxazine dyes bearing CI numbers 51000, 51180, 51185, 51190, and 51195 (for instance, 5-benzylamino-9-diethylamino-benzo[a]phenoxadine)
3,7-bis(benzylamino)phenothiazine and leuco forms of phenothiazine dyes bearing CI numbers 52000, 52010, 52015, 52020, 52025, 52030, 52035, 52050 (for instance, 3,7-bis(dimethylamino)-4-nitrophenothiazine, 3,7-bis[N-ethyl-N(m-sulfobenzyl)amino]phenothiazine, monosodium salt, 3-7-diaminophenothiazine)
In addition thereto there can be enumerated leuco forms of phenazine dyes bearing CI numbers 50035, 50040, 50045, 50200, 50205, 50206, 50210, 50216, 50220, 50225, 20235, 50240.
bis(p-diethylaminophenyl) (p-cloroanilino)methane
bis(p-diethylaminophenyl) (2,4-dichloroanilino)methane
bis(p-diethylaminophenyl) (methylamino)methane
bis(p-diethylaminophenyl) (octadecylamino)methane
and leuco forms of indoamine and indophenol dyes bearing CI numbers 49400, 49405, 49410, 49700.
4-amino-α,β-dicyanohydrocinnamic acid, methyl ester
4-anilino-α,β-dicyanohydrocinnamic acid, methyl ester
4-(p-chloroanilino)-α,β-dicyanohydrocinnamic acid, methyl ester
α-cyano-4-dimethylaminohydrocinnamic acid, methyl ester
α,β-dicyano-4-diethylaminohydrocinnamic acid, methyl ester
α,β-dicyano-4-dimethylaminohydrocinnamic acid, methyl ester
α,β-dicyano-4-dimethylaminohydrocinnamic acid
α,β-dicyano-4-dimethylaminohydrocinnamic acid, hexyl ester
α,β-dicyano-4-ethylaminohydrocinnamic acid, methyl ester
α,β-dicyano-4-hexylaminohydrocinnamic acid, methyl ester
α,β-dicyano-4-methylaminocinnamic acid, methyl ester
and substituted hydrocinnamic acids, namely leuco-pigments comprising dyes bearing CI numbers 48000, 48001, and 48005.
The leuco forms of indigoid dyes having CI numbers 73000, 73015, 73025, 73030, 73035, 73040, 73045, 73050, 73055, 73060, 73065, 73070, 73085, 73090, 73110, 73300, 73305, 73310, 73315, 73320, 73325, 73335, 73340, 73345, 73350, 73360.
and leuco forms of dyes bearing CI numbers 61100, 61105, 61107, 61116, 61120, 61140, 61500, 61505, 61510, 61515, 61520, 61525, 61530, 61535, 61540, 61545, 61565, 61650 [for instance, 1-amino-4-methoxyanilino-2,3-dihydroanthraquinone, 1-p-(2-hydroxyethylamino)anilino-4-methylamino-2,3-dihydroanthraquinone].
An acid is needed for enhancing color generation. In other words, most color-generators perform best when an acid is present. Color-generators which contain amino radicals can bind the acid by salt formation. The quantity of acid used is suitably in the range of 1-10 moles per mole of each color-generator.
As the concrete examples of said acids there can be enumerated organic and inorganic acids such as maleic acid, p-toluene sulfonic acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid and additionally Lewis acids such as zinc chloride, zinc bromide, ferric chloride and the like.
The cobalt complexes used in the present invention (in particular, it is preferable to use cobalt (III) complex substances), when heated, are subjected to reduction so as to produce basic substances such as ammonia, amine, etc., thereby accelerating the speed of fixing reaction, i.e., the fixing sensitivity. As typical examples of said complexes can be enumerated the following compounds:
(1) hexa-ammine cobalt (III) perchlorate
(2) hexa-ammine cobalt (III) acetate
(3) hexa-ammine cobalt (III) thiocyanate
(4) hexa-ammine cobalt (III) trifluoroacetate
(5) hexa-ammine cobalt (III) benzirate
(6) chloropenta-ammine cobalt (III) bromide
(7) chloropenta-ammine cobalt (III) perchlorate
(8) bromopenta-ammine cobalt (III) bromide
(9) bromopenta-amine cobalt (III) perchlorate
(10) aquopenta-ammine cobalt (III) nitrate
(11) aquopenta-ammine cobalt (III) perchlorate
(12) bis(ethylenediamine)di-ammine cobalt (III) perchlorate
(13) bis(ethylenediamine)diazido cobalt (III) perchlorate
(14) bis(ethylenediamine)diacetate cobalt (III) chloride
(15) bis(ethylenediamine)diacetate cobalt (III) trifluoroacetate
(16) triethylenetetradichloro cobalt (III) acetate
(17) triethylenetetraamine dichloro cobalt (III) trifluoroacetate
(18) bis(methylamine)tetra-ammine cobalt (III) hexafluorophosphate
(19) aquopenta(methylamine) cobalt (III) nitrate
(20) chloropenta(ethylamine) cobalt (III) chloride
(21) chloropenta(ethylamine) cobalt (III) perfluorobutanoate
(22)trinitrotris-amine cobalt (III)
(23) trinitrotris(methylamine) cobalt (III)
(24) tris(ethylenediamine) cobalt (III) acetate
(25) tris(ethylenediamine) cobalt (III) perchlorate
(26) tris(1,3propanediamine) cobalt (III) trifluoroacetate
(27) bis(dimethylglyoxime)bispyridine cobalt (III) trichloroacetate
(28) N,N'-ethylenebis(salicylideneimine)bisammine cobalt (III) bromide
(29) N,N'-ethylenebis(salicylideneimine)bisammine cobalt (III) perchlorate
(30) bis(dimethylglyoxime)ethylaquo cobalt (III)
(31) μ-superoxodeca-ammine dicobalt (III) perchlorate
(32) sodium dichloro ethylenediaminediaceto cobalt (III)
(33) penta-ammine carbonate cobalt (III) nitrite
(34) penta-ammine carbonato cobalt (III) perchlorate
(35) tris(glycinato) cobalt (III)
(36) trans[bis(ethylenediamine)chlorothiocyanato cobalt (III)]sulfite
(37) trans[bis(ethylenediamine)chlorothiocyanato cobalt (III)]perchlorate
(38) trans[bis(ethylenediamine)diazido cobalt (III)]chloride
(39) trans[bis(ethylenediamine)diazido cobalt (III)]thiocyanato
(40) cis[bis(ethylenediamine)ammine diazido cobalt (III)]trifluoroacetate
(41) tris(ethylenediamine) cobalt (III) chloride
(42) tris(ethylenediamine) cobalt (III) benzilate
(43) trans[bis(ethylenediamine)dichloro salt (III)]chloride
(44) trans[bis(ethylenediamine)dichloro cobalt (III)]perchlorate
(45) bis(ethylenediamine)dithiocyanato cobalt (III) fluoride
(46) bis(ethylenediamine)dithiocyanato cobalt (III) perfluorobenzoate
(47) triethylenetetramine dinitro cobalt (III) iodide
(48) triethylenetetramine dinitro cobalt (III) dichloroacetate
(49) tris(ethylenediamine) cobalt (III) 2-pyridylcarboxylate
(50) tris(ethylenediamine) cobalt (III) salicylate
(51) tris(2,2'-dipyridyl) cobalt (III) perchlorate
(52) bis(dimethylglyoxime) (chloropyridime) cobalt (III)
(53) bis(dimethylglyoxime)thiocyanatopyridine cobalt (III)
Further, the photoreductants suitably used in the present invention, when irradiated with visible light, produced reducing substances in the presence of hydrogen donators, which, when heated, are capable of instantaneously reducing the cobalt (III) complex compounds. As the typical examples of aforegoing photoreductants can be enumerated quinone, disulfide, diazo anthrone, diazonium salt, diazo phenanthrone, aromatic azide, acyloin, aromatic ketone, aromatic carbazide, aromatic diazo sulfonate, etc. Above all, those capable of exhibiting strong absorption to the visible region are preferably used in the present invention.
The specific, exemplary disulfide, diazo anthrone, diazo phenanthrone, aromatic carbazide, aromatic azide, diazonium salt, and aromatic sulfonate will be given below:
(1) 1-naphthyl disulfide
(2) β-naphthyl disulfide
(3) 9-anthryl disulfide
(4) cyclohexyl 2-naphthyl disulfide
(5) diphenylmethyl 2-naphthyl disulfide
(6) 2-dodecyl 1'-naphthyl disulfide
(7) thioctic acid
(8) 2,2'-bis(hydroxymethyl)diphenyl disulfide
(9) 10-diazoanthrone
(10) 2-methoxy-10-diazoanthrone
(11) 3-nitro-10-diazoanthrone
(12) 3,6-diethoxy-10-diazoanthrone
(13) 3-chloro-10-diazoanthrone
(14) 4-ethoxy-10-diazoanthrone
(15) 4-(1-hydroxyethyl)-10-diazoanthrone
(16) 2,7-diethyl-10-diazoanthrone
(17) 9-diazo-10-phenanthrone
(18) 3,6-dimethyl-9-diazo-10-phenanthrone
(19) 2,7-dimethyl-9-diazo-10-phenanthrone
(20) 4-azidobenzoic acid
(21) 4-nitrophenyl azide
(22) 4-dimethylaminophenyl azide
(23) 2,6-di-4-azidobenzylidene-4-methylcyclohexanone
(24) 2-azido-1-octylcarbamoyl-benzimidazole
(25) 2,5-bis(4-azidophenyl)-1,3,4-oxadiazole
(26) 1-azido-4-methoxynaphthalene
(27) 2-carbazido-1-naphthol
(28) benzophenone
(29) 2-nitrobenzophenone
(30) diaminobenzophenone
(31) phthalophenone
(32) phenyl(1-methoxybenzyl)ketone
(33) phenyl-1-(1-phenoxy)benzylketone
(34) phenyl-1-(2-chlorophenoxy)benzylketone
(35) phenyl-1-(4-chlorophenoxy)benzylketone
(36) phenyl-1-(2-bromophenoxy)benzylketone
(37) phenyl-1-(2-iodinephenoxy)benzylketone
(38) phenyl-1-(4-phenoxy)benzylketone
(39) phenyl-1-(4-benzylphenoxy)benzylketone
(40) 4-(diamylamino)benzenediazonium tetrafluoroborate
(41) 2-methyl-4-diethylaminobenzenediazonium tetrafluoroborate
(42) 4-(oxazolidino)benzenediazonium tetrafluoroborate
(43) 4-(cyclohexylamino)benzenediazonium tetrafluoroborate
(44) 2-nitro-4-morpholinobenzenediazonium hexafluorophosphate
(45) 4-(9-carbazolyl)benzenediazonium hexafluorophosphate
(46) 4-(dihydroxyethylamino)-3-methylbenzenediazonium hexafluorophosphate
(47) 4-diethylaminobenzenediazonium hexachlorostannate
(48) 4-dimethylamino-3-methylbenzenediazonium hexachlorostannate
(49) 2-methyl-4-(N-methyl-N-hydroxypropylamino)benzenediazonium hexachlorostannate
(50) 4-dimethylaminobenzenediazonium tetrachlorozincate
(51) 4-dimethylamino-3-ethoxybenzenediazonium chlorozincate
(52) 4-diethylaminobenzenediazonium tetrachlorozincate
(53) 4-diethylaminobenzenediazonium hexafluorophosphate
(54) 2-carboxy-4-dimethylaminobenzenediazonium hexafluorophosphate
(55) 3-(2-hydroxyethoxy)-4-pyrrolidinobenzenediazonium hexafluorophosphate
(56) 4-methoxybenzenediazonium hexafluorophosphate
(57) 2,5-diethoxy-4-acetamidobenzenediazonium hexafluorophosphate
(58) 4-methylamino-3-ethoxy-6-chlorobenzenediazonium hexafluorophosphate
(59) 3-methoxy-4-diethylaminobenzenediazonium hexafluorophosphate
(60) di(1-naphthyl)acyloin
(61) di(2-naphthyl)acyloin
(62) benzoin
(63) benzoin acetate
(64) benzoin methylether
(65) benzoin phenylether
(66) benzoin 2-bromophenylether
(67) benzoin 4-chlorophenylether
(68) benzoin 4-phenoxyphenyl ether
(69) benzoin 4-benzoylphenyl ether
(70) benzoin 2-iodinephenyl ether
(71) benzoin 2-chlorophenyl ether
(72) 2-phenylbenzoin
(73) 2-(1-naphthol)benzoin
(74) 2-n-butylbenzoin
(75) 2-hydroxymethyl benzoin
(76) 2-(2-cyanomethyl)benzoin
(77) 2-(5-benzinyl)benzoin
(78) potassium 4-(N-ethyl-N-hydroxyethylamino)-benzenediazosulfonate
(79) sodium 4-(diethylamino)benzenediazosulfonate
(80) potassium 2-chloro-4-morpholinobenzenediazosulfonate
(81) tetramethylammonium 3-methoxy-4-piperidinobenzenediazosulfonate
In addition to the above mentioned substances, those obtained by subjecting the under mentioned amino compounds to diazotization may also be employed effectively as diazonium salts in the present invention. As the counter ions therefor there may be enumerated Cl-, ZnCl-, SO4 2-, BF4 -, CF3 COO-, etc.
5-amino-2-diethylamino-p-anisic acid, methyl ester
N2, N2 -dimethyl-1,2-naphthalenediamine
2-methyl-N1 -phenyl-1,4-naphthalenediamine
N1, N1 -diethyl-4-methyl-m-phenylenediamine
4-methoxy-N3,N3 -dimethyl-m-phenylenediamine
N1, N1 -diethyl-4-methyl-o-phenylenediamine
2-chloro-5-methoxy-N1,N1 -dimethyl-p-phenylenediamine
N1 -cyclohexyl-2-methoxy-p-phenylenediamine
N-(2-hydroxyethyl)-N-ethyl p-phenylenediamine
2-phenyl-N4,N4 -dimethyl-p-phenylenediamine
N2,N2 -dimethyltoluene-2,5-diamine
As previously stated, quinones can be effectively used as photoreductants. And the quinones preferably used in the present invention include O- or p-benzoquinone, O- or p-naphthoquinone, phenanthrenequinone and anthraquinone. These quinones can be divided into the external hydrogen source type quinones which produce reducing agents in the manner of drawing their hydrogen sources (active hydrogen atoms) out of different compounds (hydrogen donators) and the internal hydrogen source type quinones which include the hydrogen sources of their own. The internal hydrogen source type quinones per se can exhibit a photoreducing property with ease but with little efficiency. Therefore, it is preferable that they should be used in combination with the hydrogen donators.
As the concrete examples of the aforesaid external hydrogen source type quinones there can be enumerated the following substances:
(1) 2,5-dimethyl-1,4-benzoquinone
(2) 2,6-dimethyl-1,4-benzoquinone
(3) duroquinone
(4) 2-(1-formyl-1-methylethyl)-5-methyl-1,4-benzoquinone
(5) 2-methyl-1,4-benzoquinone
(6) 2-phenyl-1,4-benzoquinone
(7) 2,5-dimethyl-6-(1-formylethyl)-1,4-benzoquinone
(8) 2-(2-cyclohexanonyl)-3,6-dimethyl-1,4-benzoquinone
(9) 1,4-naphthoquinone
(10) 2-methyl-1,4-naphthoquinone
(11) 2,3-dimethyl-1,4-naphthoquinone
(12) 2,3-dichloro-1,4-naphthoquinone
(13) 2-thiomethyl-1,4-naphthoquinone
(14) 2-(1-formyl-2-propyl)-1,4-naphthoquinone
(15) 2-(2-benzoylethyl)-1,4-naphthoquinone
(16) 9,10-phenanthrenequinone
(17) 2-tert-butyl-9,10-anthraquinone
(18) 2-methyl-1,4-anthraquinone
(19) 2-methyl-9,10-anthraquinone
(20) 1,8-pyrenequinone
(21) 1,6-pyrenequinone
On the other hand, as the concrete examples of the aforesaid internal hydrogen source type quinones there can be enumerated the following substances:
(1) 5,8-dihydro-1,4-naphthoquinone
(2) 5,8-dihydro-2,5,8-trimethyl-1,4-naphthoquinone
(3) 2,5-bis(dimethylamino)-1,4-benzoquinone
(4) 2,5-dimethyl-3,6-bis(dimethylamino)-1,4-benzoquinone
(5) 2,5-dimethyl-3,6-bispyrrolidino-1,4-benzoquinone
(6) 2-ethoxy-5-methyl-1,4-benzoquinone
(7) 2,6-dimethoxy-1,4benzoquinone
(8) 2,5-dimethoxy-1,4-benzoquinone
(9) 2,6-diethoxy-1,4-benzoquinone
(10) 2,5-diethoxy-1,4-benzoquinone
(11) 2,5-bis(2-methoxyethoxy)-1,4-benzoquinone
(12) 2,5-bis(β-phenoxyethoxy)-1,4-benzoquinone
(13) 2,5-diphenethoxy-1,4-benzoquinone
(14) 2,5-di-n-propoxy-1,4-benzoquinone
(15) 2,5-di-isopropoxy-1,4-benzoquinone
(16) 2,5-di-n-butoxy-1,4-benzoquinone
(17) 2,5-di-sec-butoxy-1,4-benzoquinone
(18) 1,1'-bis(5-methyl-1,4-benzoquinone-2-yl)-diethyl ether
(19) 2-methyl-5-morpholinomethyl-1,4-benzoquinone
(20) 2,3,5-trimethyl-6-morpholinomethyl-1,4-benzoquinone
(21) 2,5-bis(morpholinomethyl)-1,4-benzoquinone
(22) 2-hydroxymethyl-3,5,6-trimethyl-1,4-benzoquinone
(23) 2-(1-hydroxyethyl)-5-methyl-1,4-benzoquinone
(24) 2-(1-hydroxy-n-propyl)-5-methyl-1,4-benzoquinone
(25) 2-(1-hydroxy-2-methyl-n-propyl)-5-methyl-1,4-benzoquinone
(26) 2-(1,1-dimethyl-2-hydroxyethyl)-5-methyl-1,4-benzoquinone
(27) 2-(1-acetoxyethyl)-5-methyl-1,4-benzoquinone
(28) 2-(1-methoxyethyl)-5-methyl-1,4-benzoquinone
(29) 2-(2-hydroxyethyl)-3,5,6-trimethyl-1,4-benzoquinone
(30) 2-ethoxy-5-phenyl-1,4-benzoquinone
(31) 2-i-propoxy-5-phenyl-1,4-benzoquinone
(32) 1,4-dihydro-1,4-dimethyl-9,10-anthraquinone
(33) 2-dimethylamino-1,4-naphthoquinone
(34) 2-methoxy-1,4-naphthoquinone
(35) 2-benzyloxy-1,4-naphthoquinone
(36) 2-methoxy-3-chloro-1,4-naphthoquinone
(37) 2,3-dimethoxy-1,4-naphthoquinone
(38) 2,3-diethoxy-1,4-naphthoquinone
(39) 2-ethoxy-1,4-naphthoquinone
(40) 2-phenethoxy-1,4-naphtoquinone
(41) 2-(2-methoxyethoxy)-1,4-naphthoquinone
(42) 2-(2-ethoxyethoxy)-1,4-naphthoquinone
(43) 2-(2-phenoxy)ethoxy-1,4-naphthoquinone
(44) 2-ethoxy-5-methoxy-1,4-naphthoquinone
(45) 2-ethoxy-6-methoxy-1,4-naphthoquinone
(46) 2-ethoxy-7-methoxy-1,4-naphthoquinone
(47) 2-n-propoxy-1,4-naphthoquinone
(48) 2-(3-hydroxypropoxy)-1,4-naphthoquinone
(49) 2-isopropoxy-1,4-naphthoquinone
(50) 7-methoxy-2-isopropoxy-1,4-naphthoquinone
(51) 2-n-butoxy-1,4-naphthoquinone
(52) 2-sec-butoxy-1,4-naphthoquinone
(53) 2-n-pentoxy-1,4-naphthoquinone
(54) 2-n-hexoxy-1,4-naphthoquinone
(55) 2-n-heptoxy-1,4-naphthoquinone
(56) 2-acetoxymethyl-3-methyl-1,4-naphthoquinone
(57) 2-methoxymethyl-3-methyl-1,4-naphthoquinone
(58) 2-(β-acetoxyethyl)-1,4-naphthoquinone
(59) 2-N,N-bis-(cyanomethyl)aminomethyl-3-methyl-1,4-naphthoquinone
(60) 2-methyl-3-morpholinomethyl-1,4-naphthoquinone
(61) 2-hydroxymethyl-1,4-naphthoquinone
(62) 2-hydroxymethyl-3-methyl-1,4-naphthoquinone
(63) 2-(1-hydroxyethyl)-1,4-naphthoquinone
(64) 2-(2-hydroxyethyl)-1,4-naphthoquinone
(65) 2-(1,1-dimethyl-2-hydroxyethyl)-1,4-naphthoquinone
(66) 2-bromo-3-isopropoxy-1,4-naphthoquinone
(67) 2-ethoxy-3-methyl-1,4-naphthoquinone
(68) 2-chloro-3-piperidino-1,4-naphthoquinone
(69) 2-morpholino-1,4-naphthoquinone
(70) 2,3-dipiperidino-1,4-naphthoquinone
(71) 2-dibenzylamino-3-chloro-1,4-naphthoquinone
(72) 2-methyloxycarbonylmethoxy-1,4-naphthoquinone
(73) 2-(N-ethyl-N-benzylamino)-3-chloro-1,4-naphthoquinone
(74) 2-morpholino-3-chloro-1,4-naphthoquinone
(75) 2-pyrrolidino-3-chloro-1,4-naphthoquinone
(76) 2-diethylamino-3-chloro-1,4-naphthoquinone
(77) 2-diethylamino-1,4-naphthoquinone
(78) 2-piperidino-1,4-naphthoquinone
(79) 2-pyrrolidino-1,4-naphthoquinone
(80) 2-(2-hexyloxy)-1,4-naphthoquinone
(81) 2-neo-pentyloxy-1,4-naphthoquinone
(82) 2-(2-n-pentyloxy)-1,4-naphthoquinone
(83) 2-(3-methyl-n-butoxy)-1,4-naphthoquinone
(84) 2-(6-hydroxy-n-hexoxy)-1,4-naphthoquinone
(85) 2-ethoxy-3-chloro-1,4-naphthoquinone
(86) 2-di(phenyl)methoxy-1,4-naphthoquinone
(87) 2-(2-hydroxyethoxy)-3-chloro-1,4-naphthoquinone
(88) 2-methyl-3-(1-hydroxymethyl)ethyl-1,4-naphthoquinone
(89) 2-azetidino-3-chloro-1,4-naphthoquinone
(90) 2-(2-hyroxyethyl)-3-bromo-1,4-naphthoquinone
(91) 2,3-dimorpholino-1,4-naphthoquinone
(92) 2-ethylamino-3-piperidino-1,4-naphthoquinone
(93) 2-ethoxymethyl-1,4-naphthoquinone
(94) 2-phenoxymethyl-1,4-naphthoquinone
In addition, 2H-benzimidazoles may be used as photoreductants, which, when irradiated with active radiant ray, produce reducing agents, dihyrobenzimidazoles, in the presence of unstable hydrogen atoms.
As the typical examples of 2H-benzimidazoles there can be enumerated the following substances:
(1) 2,2-dimethyl-2H-benzimidazole
(2) 2,2-diethyl-2H-benzimidazole
(3) 2,2-di-n-hexyl-2H-benzimidazole
(4) spiro(2H-benzimidazole-2,1'-cyclohexan)
(5) dispiro(2H-benzimidazole-2,1'-cyclohexan-4,2'-2H-benzimidazole)
(6) 2,2-benzyl-2H-benzimidazole
(7) 2,2-diphenyl-2H-benzimidazole
(8) 2,2-dimethyl-4-n-butyl-2H-benzimidazole
(9) 2,2-diphenyl-5-n-hexyl-2H-benzimidazole
(10) 2'-methyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(11) 3'-methyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(12) 4'-methyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(13) 2',6'-dimethyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(14) 5-methyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(15) 5,6-dimethyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(16) 5,5"-dimethyl dispiro(2H-benzimidazole-2,1'-cyclohexan-4',2"-2H-benzimidazole)
(17) 5,6,5",6"-tetramethyl spiro(2H-benzimidazole-2,1'-cyclohexan-4',2"-2H-benzimidazole-2,1'-cyclohexan-4',2"-2H-benzimidazole)
(18) 4-bromo-2,2-dimethyl-2H-benzimidazole
(19) 5-iodine-2,2-dimethyl-2H-benzimidazole
(20) 5-chloro spiro(2H-benzimidazole-2,1'-cyclohexan)
(21) 4-chloro spiro(2H-benzimidazole-2,1'-cyclohexan)
(22) 2,2-diethyl-4-trichloromethyl-2H-benzimidazole
(23) 2,2-diphenyl-4-trifluoromethyl-2H-benzimidazole
(24) 2',3',4',5',6'-pentachloro spiro(2H-benzimidazole-2,1'-cyclohexan)
(25) 5-trifluoromethyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(26) 2,2-dibenzyl-4-methoxy-2H-benzimidazole
(27) 2,2-diethyl-4-isopropoxy-2H-benzimidazole
(28) 2,2-diethyl-5-ethoxy-2H-benzimidazole
(29) 5-methoxy spiro(2H-benzimidazole-2,1'-cyclohexan)
(30) 4-ethoxy spiro(2H-benzimidazole-2,1'-cyclohexan)
(31) 5-isopropoxy spiro(2H-benzimidazole-2,1'-cyclohexan)
(32) 2'-methoxy spiro(2H-benzimidazole-2,1'-cyclohexan)
(33)3'-neopentoxy spiro(2H-benzimidazole-2,1'-cyclohexan)
(34) 4,4'-dimethoxy dispiro(2H-benzimidazole-2,1'-cyclohexan-4',2"-2H-benzimidazole)
(35) 5,5"-diisopropoxy-2'-methoxy dispiro (2H-benzimidazole-2,1'-cyclohexan-4',2"-2H-benzimidazole)
(36) 2,2-dimethyl-4-amino-2H-benzimidazole
(37) 2,2-dimethyl-4-(N,N-dimethylamino)-2H-benzimidazole
(38) 2,2-dimethyl-5-(N-phenylamino)-2H-benzimidazole
(39) 2,2-dimethyl-5-(N-tolylamino)-2H-benzimidazole
(40) 4-(N,N-diphenylamino)spiro(2H-benzimidazole-2,1'-cyclohexan)
(41) 4-(N-phenylamino)spiro(2H-benzimidazole-2,1'-cyclohexan)
(42) 2'-morpholino spiro(2H-benzimidazole-2,1'-cyclohexan)
(43) 2,2-diphenyl-4-pipridino-2H-benzimidazole
(44) 2,2-diphenyl-5-methylazo-2H-benzimidazole
(45) 2'-methylazo spiro(2H-benzimidazole-2,1'-cyclohexan)
(46) 2,2-dimethyl-5-styryl-2H-benzimidazole
(47) 2,2-dimethyl-4-vinyl-2H-benzimidazole
(48) 5-vinyl spiro(2H-benzimidazole-2,1'-cyclohexan)
(49) 2,2-diphenyl-5-nitro-2H-benzimidazole
(50) 5-carbomethoxy spiro(2H-benzimidazole-2,1'-cyclohexan)
And, 1,3-diazabicyclo[3,1,0]hexy-3-en compounds can also be used as photoreductants which, when exposed to active radiant ray and heat, are capable of producing the precursory substances or reducing agents and the reducing agents per se continuously. The exemplary 1,3-biazabicyclo[3,1,0]hexy-3-en compounds can be defined as those represented by the formula ##STR2## [wherein R1 and R2 are selected from hydrogen, alkyl (including cycloalkyl), aralkyl, alkaryl and aryl substituents; or R1 and R2 couple to form alkylene substituent, preferably 5 or 6 rings; R3 is aryl radical or electron attractive radical such as cyano radical, carboxyl radical, nitro radical or carbonyl-containing radical; and R4 is aryl or allyl radical]
The exemplary 1,3-diazabicyclo[3,1,0]hexy-3-en forms of photoreductants are enumerated as follows:
(1) 4,6-diphenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(2) 4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(3) 2,4,6-triphenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(4) 2,4-diphenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(5) 2,2-dicyclopropyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(6) 2,6-diphenyl-4-cyano-1,3-diazabicyclo[3,1,0]hexy-3-en
(7) 2-(1-naphthyl)-4,6-di(chlorophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(8) 2-methyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(9) 2-n-propyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(10) 2-isopropyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(11) 2,2-dimethyl-4,6-diphenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(12) 2,2-dimethyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(13) 2,2-dimethyl-4-(4-nitrophenyl)-6-phenyl-1,3-diazabicyclo [3,1,0]hexy-3-en
(14) 2,2-dimethyl-4-phenyl-6-(4-cyclophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(15) 2-methyl-2-ethyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(16) 2-methyl-2-n-propyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(17) 2-methyl-2-t-butyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(18) 2,4-diphenyl-2-methyl-6-(4-nitrophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(19) 2,2-dimethyl-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(20) 2,2-diethyl-4-phenyl-6-(3-nitrophenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(21) 2,2-di-n-hexyl-4,6-diphenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(22) spiro{cyclopentane-1,2'[4'-phenyl-6'-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en]}
(23) spiro{cyclohexan-1,2'-[4'-phenyl-6'-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en]}
(24) spiro{cycloheptane-1,2'-[4'-phenyl-6'-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en]}
(25) spiro{cyclooctane-1,2'-[4'-phenyl-6'-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en]}
(26) spiro{1-methylcyclohexan-2,2'-[4'-phenyl-6'-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en]}
(27) spiro{1-methylcyclohexan-4,2'-[4'-phenyl-6'-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en]}
(28) 2-(4-ethoxycarbonylphenyl)-4,6-diphenyl-1,3-diazabicyclo [3,1,0]hexy-3-en
(29) 2,4-diphenyl-6-(benzoyloxyphenyl)-1,3-diazabicyclo [3,1,0]hexy-3-en
(30) 2,6-di(1-naphthyl)-4-nitro-1,3-diazabicyclo[3,1,0]hexy-3-en
(31) 2,6-di(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(32) 2,4-diphenyl-6-(3-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(33) 2,6-diphenyl-4-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(34) 2-(4-tolyl)-4-phenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(35) 2,6-di(4-tolyl)-4-phenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(36) 2,4,6-tri(2-aminophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(37) 2-(4-diethylaminophenyl)-4,6-diphenyl-1,3diazabicyclo[3,1,0]hexy-3-en
(38) 2,4-diphenyl-6-(4-morpholinophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(39) 2-benzyl-4-nitro-6-phenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(40) 2,4-diphenyl-4-nitro-6-phenyl-1,3-diazabicyclo[3,1,0]hexy-3-en
(41) 2,4-diphenyl-6-(4-nitrophenyl)-1,3-diazabicyclo[3,1,0]hexy-3-en
(42) 1-azonia-4,6-diphenyl-1-methyl-3-azabicyclo[3,1,0]hexy-3-en.tetrafluoroborate
(43) 1-azonia-4,6-diphenyl-1,2,2-trimethyl-3-azabicyclo[3,1,0]hexy-3-en.hexafluoroborate
(44) 1-azonia-4-phenyl-6-(4-nitrophenyl)-1,2,2-trimethyl-3-azabicyclo[3,1,0]hexy-3-en.tetrafluoroborate
(45) 1-azonia-4-nitro-2,6-diphenyl-3-azabicyclo[3,1,0]hexy-3-en.chloride
(46) 4,6-diphenyl-1,3-diazabicyclo[3,1,0]hexy-3-en-1-oxide
(47) 2,2-dimethyl-6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3,1,0]hexy-3-en-1-oxide
(48) spiro{cyclopentane-1,2'-[4'-phenyl-6'-(4-nitrophenyl)-1',3'-diazabicyclo[3,1,0]hexy-3-en-1-oxide]}
(49) spiro{1-methylcyclohexane-4,2'-[2',4',6'-triphenyl-1',3'-diazabicyclo[3,1,0]hexy-3-en-1-oxide]}
(50) spiro{1-cycloheptane-1,2'-[2',2'-dicyclopropyl-4',6'-di(4-nitrophenyl)-1',3'-diazabicycl[3,1,0]hexy-3-en-oxide]}
The hydrogen donators suitably used in the present invention, when exposed to light, supply active hydrogen atoms to photoreductants for converting the latter into reducing substances. The exemplary examples thereof are as follows:
(1) poly(ethylene glycol)
(2) phenyl-1,2-ethanediol
(3) nitrilotriacetonitrile
(4) triethylnitrilotriacetate
(5) poly(vinyl butyral)
(6) poly(vinyl acetal)
(7) 1,4-benzenedimethanol
(8) methyl cellulose
(9) cellulose acetate butyrate
(10) 2,2-bis-(hydroxymethyl)-propionic acid
(11) 1,3-bis-(hydroxymethyl)-urea
(12) 4-nitrobenzyl alcohol
(13) 4-methoxybenzyl alcohol
(14) 2,4-dimethoxybenzyl alcohol
(15) 3,4-dichlorophenylglycol
(16) N-(hydroxymethyl)-benzamide
(17) N-(hydroxymethyl)-phthalimide
(18) 5-(hydroxymethyl)-uracil hemihydrate
(19) nitrilotriacetic acid
(20) 2,2',2"-triethylnitrilotripropionate
(21) 2,2',2"-nitrilotriacetophenone
(22) poly(vinyl acetate)
(23) poly(vinyl alcohol)
(24) ethyl cellulose
(25) carboxymethyl cellulose
(26) poly(vinyl formal)
(27) triethanolamine triacetate
(28)triethanolamine triopropionate
(29) triethanolamine tributyrate
(30) triethanolamine trivalerate
The hydrogen donators suitably used in the present invention actually perform plural functions. For instance, the polymers of the above enumerated hydrogen donators also function as binders, and especially the substances such as polyethylene glycol and alcohol, when the fluidity of each element of the composition is enhanced, function as color generating assistants, too.
The composition (color-developing system and/or fixing system) according to the present invention can be added with binders and solvents in addition to the aforegoing components. The binders suitably used in the present invention include a wide variety of natural or synthetic polymers. It is more preferable to use selectively from among them linear film-forming polymers, for instance, such as gelatin; celluloses, for instance, such as ethylcellulose, butylcellulose, cellulose acetate, cellulose triacetate, cellulose butyrate, etc.; vinyl polymers, for instance, such as polyvinyl acetate and polyvinylidene chloride; polyvinylacetals, for instance, such as polyvinylbutyral, poly(vinylchloride-vinylacetate), polystyrene, polybutadiene, polyvinylpyrrolidone, and polymer or copolymer of esters of acrylic acid or methacrylic acid or both; and polyesters, for instance, such as poly(ethylene glycol-isophthalic acid-cyclohexylenebismethanol), poly(p-cyclohexanedicarbonic acid-2,2,4,4-tetramethylcyclobutane-1,3-diol). The condensate of epichlorohydrin and bisphenol is usefully employed as binder, too. In this connection, it should be noted that these binders can also be utilized for the formation of an intermediate layer.
The solvents used in the present invention include amides such as formamide, dimethylformamide, dimethylacetoamide, hexaneamide, etc.; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, polyethylene glycol, etc. and esters such as ethyl acetate, ethyl benzoate, etc.; aromatic compounds such as benzene, o-dichlorobenzene, toluene, etc.; ketones such as acetone, methylethyl ketone, 3-pentanone, etc.; chlorinated hydrocarbons such as methylene chloride, chloroform, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethylene, etc.; dimethylsulfoxide; pyridine; tetrahydrofuran; dioxane; dicyanocyclobutane; 1-methyl-2-oxohexamethyleneimine, etc. In addition, water may be used if circumstances require.
In the actual preparation of the composition according to the present invention the ratios of the respective components may be selected suitably. However, in the case of the composition of color-forming system the quantity of photooxidant used preferably is in the range of 0.1-10 moles per mole of the color-developer (leuco-pigment). In the composition of non-color-forming system the quantity of cobalt complex used preferably is in the range of 0.1-10 moles per mole of the photoreductant, while the hydrogen donator may be used in excess moles per mole of the photoreductant. And, the ratio of color developer to photoreductant is suitable to be about 1:1-20 (mole). The quantity of binder is about 30-90% of the weight of each layer.
The recording element prepared by applying the said composition onto the support as stated above is applicable to photography, printing, pattern layout for metal working and so forth. Furthermore, in view of the fact that the composition according to the present invention, when incorporated as a component in a film which is liable to inactivation without being irradiated or subjected to heat- or chemical-treatment, permits said film to have a superior resolving power, said composition is also utilizable in the manufacture of microfilms.
Next, the image-forming method utilizing the composition according to the present invention will be explained with reference to the example of a mono-layer recording element.
First, reference will be made to the formation of a positive image. When the surface layer of said recording element is irradiated imagewise with visible light, the photoreductant, for instance, such as quinone, present in the exposed area of said surface layer absorbs this visible light and draws the hydrogen from the coexisting hydrogen donator, thereby forming hydroquinone, i.e., reducing agent. Next, when the surface layer is heated to a temperature of about 80�-150� C., cobalt (III) complex is reduced, thereby producing a basic substance such as NH3 or the like in a chain reaction manner. This basic substance immediately functions to neutralize the acid present in the exposed area or trap the photooxidant such as hexaarylbiimidazole or the like present in the exposed area for inactivation or fixing. When the overall surface layer under such conditions is irradiated with ultraviolet ray, in the image area which has not been exposed to visible light, for instance, the hexaarylbiimidazole produces an imidazole radical which is operable to oxidize the color generator, for instance, leuco-pigment in cooperation with the action of the acid present in the image area and thus lead to color generation. And, the basic substance generated in a chain reaction manner in the above image forming method acts upon the color-forming system (that is, photooxidant, color generator and acid) so as to prevent the color generator from being oxidized.
The formation of a negative image, on the other hand, may be achieved by replacing the visible light used at the time of imagewise exposure in the aforesaid positive image forming method by ultraviolet ray, then irradiating the overall surface with visible light prior to heating treatment, and thereafter heating the same.
The photo-sensitive composition according to the present invention, which has employed, as its one component, cobalt complex (preferably, cobalt (III) complex), can react with the reducing agent produced by visible light irradiation in an amplifying manner so that the reaction of photooxidant may be suppressed, whereby a more clear-cut image can be obtained. In case of necessity, furthermore, the said photo-sensitive composition may contain a chelating agent capable of causing the aforegoing amplifying reaction, a photosensitizer capable of inducing the reducing agent production owing to visible light irradiation, etc. in addition to the previously mentioned acids.
The exemplary chelating agents which are effectively used in the present invention and capable of forming a bidentate ligand with Co (III) include for instance nitroso-arol, dithiooxiamide, formazan, aromatic azo-compound, hydrazone, Schiff's base.
______________________________________[Co(NH3)6 ](CF3 COO)3 200 mgAcetone 9 mlIsopropanol 1 mlParabenzoquinone 60 mg9,10-phenanthrenequinone 10 mgPolyethylene glycol 500 mg2,2'-bis(o-chlorophenyl)-4,4'5,5'-tetraphenylbiimidazole 132 mgTris(4-diethylamino-o-tolyl)methane 50 mgP-toluenesulfonic acid monohydrate 40 mg______________________________________
A solution was prepared by adding the aforegoing components in the above mentioned order. A filter paper was impregnated with this solution and dried at 30� C. A part of the treated paper was exposed through a filter (UV39) to visible light of 50,000 luxes from a tungsten lamp repeatedly while changing the exposure times variously such as 4, 8.5, 12.5, 30 and 40 seconds. This sample was next passed through a pair of heating rollers heated to 130� C., and thereafter was subjected to a 5 seconds' overall ultraviolet ray exposure with a 20 W ultraviolet ray from a distance of 4 cm.
As a result of this, the areas exposed to visible light more than 12.5 seconds did not generate color even when irradiated with ultraviolet ray for 5 seconds, while the area not exposed to visible light was observed to generate a blue color having a density of more than 0.8.
For comparison sake, a filter paper was impregnated with the solution of the same composition except for the use of the cobalt complex. The thus treated paper was measured in respect of color generation through the same procedure except for the heat treatment at 130� C., which showed that it took 30 seconds or more until the image was fixed by exposure to a visible light.
______________________________________Acetone 9 mlIsopropanol 1 ml2,2'-bis(o-chlorophenyl)-4,4'5,5'-tetraphenylbiimidazole 132 mgtris(4-diethylamino-o-tryl)methane 50 mgParabenzoquinone 60 mg9,10-phenanthrequinone 10 mgPolyethylene glycol 480 mgP-toluenesulfonic acid monohydrate 40 mg[Co(NH)6 ](CF3 COO)3 200 mgEthyl cellulose 600 mg______________________________________
A solution was prepared by adding the aforegoing components in the above mentioned order. This solution was applied onto a 75 μm-thick polyethyleneterephthalate film using a 50 μm spacer and a 4 mill brade. The thus treated film was then allowed to air-dry to thereby obtain a photo-sensitive film having thereon an about 16 μm-thick photosensitive layer.
A positive image was superposed on this film, and the same was given a 15 second exposure with a tungsten lamp source. Then, it was passed through a pair of heating rollers heated to 130� C. and thereafter was given an overall ultraviolet ray irradiation identical with Example 1, thereby obtaining a blue colored positive image.
For comparison sake, a control photo-sensitive film was prepared by using the solution having the same composition as described above except for the use of the cobalt complex and was subjected to the same test procedure to find that it took 60 seconds until said control film produced the same image with a visible light exposure.
The addition of 5 mg of 1-(2-pyridylazo)-2-naphthol to the composition according to Example 2 showed that the time required for visible light exposure was reduced to seconds.
______________________________________[Co(NH)6 ](CF3 COO)3 13.5 mgAcetone-butanol(volume ratio 9:1) 1 mlmixed solventPolyethylene glycol 44 mgParabenzoquinone 5.7 mg2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazol 0.5 mgBis(4-diethylamino-o-tryl)-4-diethylaminophenylmethane 0.6 mg______________________________________
A solution was prepared by adding the aforegoing components in the above mentioned order. A filter paper was impregnated with this solution and dried at 30� C. The treated paper was subjected to the same test procedure as Example 1. At the time of heating it to 130� C., however, a commercially available diazo photo-sensitive paper incorporated therein a coupler was superposed thereon for the purpose of investigating the occurrence of ammonia gas. As a result, it was observed that the portion of the diazo photo-sensitive paper opposite to the visible light-exposed area of the filter paper generated color while in the visible light-exposed area of the filter paper ammonia was generated by decomposition of the cobalt complex.
______________________________________Acetone-isopropanol(volume ratio 9:1 10 mlmixed solventCellulose acetate butyrate 1 g2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole 132 mgBis(4-diethylamino-o-tolil)-4-diethylaminophenylmethane 50 mgP-toluene sulfonic acid monohydride 20 mgPolyethylene glycol 0.5 g9,10-phenonthrequinone 20 mgCo(III)complex (which see Table-1) 1 m mole______________________________________
A mixed solution having the above composition was applied onto a 100 μm-thick polyethylene terephthalate film by means of a 4 mill doctor blade. The thus coated film was dried at 50� C. for 20 minutes to thereby form a 13 μm-thick photo-sensitive layer.
The thus obtained mono-layer recording element was given a 60 second imagewise exposure with a visible light having a spectral energy distribution of 400-500 nm and an intensity of 400 μW/cm2, was thermally treated for 30 seconds on a stainless plate heated to 90� C., and successively was given a 2 minutes' overall irradiation with ultraviolet radiation having an intensity of 150 μW/cm2, whereby a superior positive-positive cyan image was formed. The observed results are set forth below in Table-1.
TABLE - 1______________________________________ Back- Image ground area areaExample Co(III) complex density density______________________________________5 Hexaammine cobalt (III) 0.9 0.3 trifluoroacetate6 Bis(ethylenediamine)diammine 0.9 0.4 cobalt (III) perchlorate7 Bis(ethylenediamine)diacetate 0.8 0.3 cobalt (III) trifluoroacetate8 Tris(ethylenediamine)cobalt 0.9 0.3 (III) acetate9 Tris(1,3-propanediamine)cobalt 1.1 0.3 (III) trifluoroacetate______________________________________
______________________________________Acetone˜isopropanol(volume ratio 9:1) 10 mlmixed solventPolyvinyl butyral 1 gHexaammine cobalt(III) trifluoroacetate 500 mgPhotoreductant (which see Table-2) Proper quantity (which see Table-2)______________________________________
A mixed solution having the above composition was applied onto a 100 μm-thick polyethylene terephthalate film by means of a 2 mill doctor blade. The thus coated film was air-dried, thereby forming a 6 μm-thick fixing layer. Next, a mixed solution having the following composition was applied onto said fixing layer by means of a 4 mill doctor blade and a 23 μm spacer and was air-dried to thereby form a 8 μm-thick color generating layer.
______________________________________Acetone 10 mlCellulose acetate butyrate 1 g2,2'-bis(o-chlorophenyl)-4,4',5,5'- 132 mgtetraphenylbiimidazoleBis(4-diethylamino-o-tolil)-4- 50 mgdiethylaminophenylmethanep-toluene sulfonic acid 40 mgPolyethylene glycol 0.5 g______________________________________
The same image forming method as disclosed in Example 5-9 was applied repeatedly to the thus prepared double-layer recording element, thereby obtaining a positive-positive cyan image. The observed results are set forth below in Table-2.
TABLE 2______________________________________ Back- Quantity Image ground added area areaExample Photoreductant (m mole) density density______________________________________10 1,6- and 1,8- 0.3 1.1 0.3 pyrenequinone11 Diphenylmethyl 4.0 0.9 0.5 2-naphthyldisulfide12 Phenyl-1- 5.0 0.9 0.3 (1-phenoxy)benzil ketone13 2-isopropoxy- 5.0 0.8 0.4 1,4-naphthoquinone14 2,2-diphenyl- 7.0 0.9 0.3 2H-benziimidazole______________________________________
______________________________________Acetone˜isopropanol(volume ratio 9:1) 10 mlmixed solventPolyvinyl butyral 1 gHexaammine cobalt(III) trifluoroacetate 500 mg9,10-phenanthrequinone 60 mg______________________________________
A mixed solution having the above composition was applied onto a 100 μm-thick polyethylene terephthalate film by means of a 2 mill doctor blade and the same was air-dried to thereby form a 6 μm-thick fixing layer. Subsequently, a 10 wt% aqueous solution of polyvinyl alcohol was applied onto said layer by means of a 2 mill doctor blade and a 23 μ spacer and then the same was dried at 50� C. for 20 minutes to thereby form a 4 μm-thick intermediate layer thereon. Still further, a mixed solution having the following composition was applied onto said layer by means of a 3 mill doctor blade and a 23 μm spacer and the same was air-dried to form a 6 μm-thick color generating layer.
______________________________________Acetone 10 mlCellulose acetate butyrate 1 g2,2'-bis(o-chlorophenyl)4,4',5,5'- 132 mgtetraphenylbiimidazolep-toluene sulfonic acid Proper quantity(which see Table-3) (which see Table-3)Color generator (leuco-pigment) 0.1 m mole(which see Table-3)Polyethylene glycol 0.5 g______________________________________
The obtained three-layer recording material was given a 1 minute's imagewise exposure with ultraviolet radiation having an intensity of 150 μW/cm2, succeedingly was given a 20 seconds' overall irradiation with a visible light having a spectral energy distribution of 400-500 nm and an intensity of 400 μW/cm2 and further was thermally treated for 60 seconds on a stainless plate heated to 120� C., whereby a satisfactory negative-positive image was formed, the background area of which is light yellow. The observed results are set forth below in Table-3.
TABLE 3______________________________________ p-tlueneEx- sulfonic Colorample Color generator (leuco-pigment) acid tone______________________________________15 Bis(4-diethylamino-o-tolil)-4-diethyl- 30 mg blue aminophenyl methane16 Tris(p-hydroxyphenyl)methane 30 mg red17 3,6-bis(diethylamino)- 0 red 9-(o-ethoxycarbonyl phenyl)-xanthene zinc chloride double salt18 9,10-dihydro-3,6-bis(diethylamino)-9- 0 red phenylacridine zinc chloride double salt19 Phenothiazine 35 mg bluish green______________________________________
______________________________________Acetone˜isopropanol(volume ratio 9:1) 10 mlmixed solventPolyvinyl butyral 1 gHexaammine cobalt(III) trifluoroacetate 500 mg9,10-phenanthrequinone 60 mg______________________________________
A mixed solution having the above composition was applied onto a 100 μm-thick polyethylene terephthalate film by means of a 2 mill doctor blade and the same was air-dried to thereby form a 6 μm-thick fixing layer. Subsequently, a 10 wt.% aqueous solution of polyvinyl alcohol was applied onto said layer by means of a 2 mill doctor blade and a 23 μm spacer and then the same was dried at 50� C. for 20 minutes to thereby form a 4 μm-thick intermediate layer. Still further, a mixed solution having the following composition was applied onto said layer by means of a 4 mill doctor blade and a 23 μm spacer and the same was air-dried, thereby forming a 8 μm-thick color generating layer.
______________________________________Acetone-isopropanol(volume ratio 9:1) 10 mlPolyvinyl butyral 1 gBis(4-diethylamino-o-tolil)-4-diethylaminophenylmethane 50 mgp-toluene 30 mgPolyethylene glycol 0.5 gPhotooxidant (which see Table-4) Proper quantity (which see Table-4)______________________________________
The obtained three-layer recording element was given a 60 seconds' imagewise exposure with the same visible light source as employed in Example 5-9, then was subjected to a ten seconds' thermal treatment on a iron plate heated to 90� C., and successively was given a 2 minutes' overall irradiation with ultraviolet radiation, whereby a satisfactory positive-positive image was formed. The observed results are set forth below in Table-4.
TABLE 4______________________________________ Back- Image groundEx- Quantity area areaample Photooxidant added density density______________________________________20 1-diacetylaminobenzotriazole 1.0 1.2 0.321 Carbon tetrabromide 2.0 1.0 0.322 2,6-dimethyl-4- 5.0 1.0 0.3 (1,1,3,3-tetrafluoro- 1,3-dichloroisopropylidene)- 2,5-cyclohexadiene23 tetracetylhydrozine 0.4 1.4 0.324 N,N,O-triacetyl- 1.0 1.0 0.3 hydroxylamine______________________________________
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Forum Post: What about that Defensive Game Plan???
Posted 12/01/2009 03:10:23 EST
We blitzed this qb, but not manning?? Why not keep the same frame of scheme against these guys? They love the deep ball so we give them one on one match ups with average cover guys? No rush is one more »
Forum Post: Who would you rather see play on Thanksgiving?
Posted 11/25/2009 12:37:42 EST
As much as life changes....it is good to have traditions. more »
Forum Post: THAT was the last loss of the season: guaranteed.
Posted 11/18/2009 05:56:54 EST
Can not compare scores and think we are better based on how they played against another opponent. It is all about match-ups. How do we match up with the Saints compared to the Colts?? Each game has more »
Forum Post: BRADY'S inaccuracy cost us the GAME!
Posted 11/18/2009 10:21:25 EST
If you look at the replay and angles......the ball looked as if it were meant for Moss on a quick hitch....if Faulk clears, Moss looks to have the ball for a first down??
Forum Post: Brady calls out Tedy?
Posted 11/17/2009 01:40:50 EST
You can not stop being aggressive with your game plan. Last 2 drives we did not play to win or stop them, but rather we played to not lose. Notice on 2 TD throws Manning is able to slide to his left more »
Forum Post: He should take a knee
Posted 11/16/2009 04:04:16 EST
BB was questioned in our super bowl win over the rams for not playing for overtime. It is a game, one of chances..... We were all happy when those close games went in our favor in 2007 and look what more »
Forum Post: New left tackle = Running the ball?
Posted 10/12/2009 11:10:59 EDT
What ever happened to the BB idea of we move on when someone goes down....the next guy has to be ready to play? Light goes down and we then run the ball for the next 2 possions? Not that is why we l more »
Forum Post: Pats old uniforms should be brought back for good.
Posted 10/02/2009 11:29:05 EDT
Need the blue strip on the helmet along with the red ones.....like the Grogan days! more »
Forum Post: the big picture..........
Posted 09/25/2009 11:27:36 EDT
Remember last year.......we went to NY early and won......then when it mattered later in the season, we lost a close one at home against the same JETS... Week 2 does not make or break your season. Mo more »
Forum Post: Players love to say it is a business when...
Posted 09/08/2009 03:31:11 EDT
Funny how players state that hold outs for new contracts are a "business decision", but when they get cut, traded, etc., then it is more personal?! Can not have it both ways.........if you hold out f more »
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2016 Campaign Checklist: Who's Doing What
This is the season of cultivation for people who might run for president in 2016.
It's a time to get to know donors, to get the public to know you on TV and social media, to visit big primary states, network with the activists and ideologues, produce a vanity book, polish a record, deflect personal baggage, take a stand, develop a world view and scout for advisers and political organizations that can power up a campaign team.
All this, for the season of harvest to come. And all while sounding coy about running.
Here's a look at the hoops that people interested in the presidency must generally jump through to prepare for a campaign - whether they end up running or not - and who's doing what.
The main players: For the Democrats, Vice President Joe Biden, former Secretary of State Hillary Rodham Clinton, New York Gov. Andrew Cuomo and Maryland Gov. Martin O'Malley; and for the Republicans, former Florida Gov. Jeb Bush, New Jersey Gov. Chris Christie, Louisiana Gov. Bobby Jindal; Kentucky Sen. Rand Paul, Florida Sen. Marco Rubio, Wisconsin Rep. Paul Ryan and Wisconsin Gov. Scott Walker.
The non-denial denial: "I can die a happy man never having been president of the United States of America. But it doesn't mean I won't run." GQ interview, July.
Book: Not lately. Could be time for a sequel to "Promises to Keep" from '07.
Iowa: Yes, in 2012 campaign. Schmoozed with Iowa power-brokers during 2013 inauguration week in Washington. (Poor Iowa caucuses showing knocked him out of the 2008 presidential race.)
New Hampshire: Yes, in 2012 campaign, and 2013 summer fundraiser planned in Maine for New Hampshire governor.
South Carolina: Yes. Headlined annual fundraising dinner in May for South Carolina Democratic Party, a speculation-stoker in big primary state. Appeared at prominent South Carolina Dem Rep. James Clyburn's annual fish-fry. Spent Easter weekend this year with wife at South Carolina's Kiawah Island, near Charleston. Vacationed there for a week in 2009 as well.
Foreign travel: You bet. Frequent foreign travel and plenty of foreign policy experience by former chairman of Senate Foreign Relations Committee. Countless trips to Iraq and Afghanistan during President Barack Obama's first term. Already been to India, Singapore, Rome, Brazil, Trinidad and Tobago, and Colombia in second term.
Meet the money: Regularly schmoozes Dem contributors at private receptions.
Networking: And how. Cozied up to key players during inauguration week, including reception for activists from New Hampshire, Iowa and South Carolina among other states; dropped into the Iowa ball, met environmental and Hispanic activists. Also, keynote speech at Michigan Democratic Party dinner. Making calls for House Democrats' campaign organization, assisting in recruitment of candidates to run next year. Speech to South Carolina Dems. Raising money for Democrats. Campaigned for new Massachusetts Sen. Ed Markey. Speaks regularly to special interests. One week in May: Monday, spoke to religious leaders at the White House; Tuesday, voting rights talk with African Americans; Wednesday; immigration talk with Asian Americans; Thursday meeting with firefighters about Boston bombing. And on the fifth day, he rested.
Hog the TV: No, not lately.
Do something: Point man on gun control, which failed. Lots with foreign policy. Point man on Violence Against Women Act. Credited with pushing Obama to embrace gay marriage. Called upon by the administration to be a go-between with the Senate. Negotiated fiscal cliff deal.
Take a stand: Guns. Violence against women. Gay rights. Veterans. He's touched on everything as senator and vice president.
Baggage: Age, flubs, fibs. White-haired Biden would be 74 by Inauguration Day 2017. His deflection: unfailing enthusiasm and a busy schedule. Habit of ad libbing and wandering off reservation is a turnoff to some; endearing to others. Biden's response: "I am who I am." A tendency to embellish a good story dates to first run for president, when he appropriated material from the life story of a British politician, sometimes without attribution. Despite policy gravitas, Pew Research polling recently found public perceives him as not so bright, clownish. Those who like him in polling say he's honest and good.
Shadow campaign: Maintains close contact with his political advisers past and present. Creating a shadow campaign would be difficult early in Obama's second term as the public perception could hasten Obama's lame duck status.
Social media: Not active on Facebook, occasional contributor to his office's Twitter account. Narrates "Being Biden" photo series showing him behind the scenes. Episodes include a meeting with actress Julia Louis-Dreyfuss, who plays VP on the HBO show "Veep."
(Contributor: Josh Lederman)
Non-denial denial: "I have absolutely no plans to run. ... I don't know everything I'll be doing. I'll be working on behalf of women and girls, and hopefully be writing and speaking. Those are the things that I am planning to do right now. ... I'm looking forward to this next chapter in my life, whatever it is." CNN, January. Also: "TBD." Part of her self-description on Twitter after joining in June.
Book: Yes - again. Previously published author has a new book expected in 2014.
Iowa: No. (Third-place shocker in 2008 caucuses won by Barack Obama portended scrappy nomination fight to come.)
New Hampshire: No. (Beat Obama in 2008 primary to regain traction in nomination contest.)
South Carolina: No. (Distant second to Obama in 2008 primary.)
Foreign travel: Do birds fly? Former secretary of state doesn't need to globe-trot any time soon. Spent 401 days overseas and nearly three months in the air, covering nearly 1 million miles. Recent speech in Canada.
Meet the money: No, but can tap deep well of Dem and activist money. Supporters launched a super PAC, Ready for Hillary, in January to support another presidential run and are raising money at rapid clip.
Networking: After a respite, kicking it into gear on the speech circuit: several paid speeches since April to trade groups, conferences about the lives of women around the globe. Much more coming. In September, will be presented with Liberty Medal by former Florida Gov. Jeb Bush at Philadelphia ceremony sponsored by National Constitution Center, chaired by the potential 2016 Republican presidential candidate. In October: speeches to college students at three upstate New York universities, bringing her back to communities where she campaigned and served in the Senate.
Hog the TV: No. But stay tuned for "Hillary," an NBC miniseries hatched with the expectation she'll run. Diane Lane will play her.
Do something: For now, a record to be judged on as secretary of state, senator and first lady.
Take a stand: You name it, she's had something to say about it in her varied political life. Recent speeches have focused on the economy, housing, opportunities for women and finance. Obama objected to her proposed individual mandate for health insurance in 2008 campaign - a contentious idea then and now - only to adopt it in office.
Baggage: Age, Benghazi, politics. She would be 69 on Inauguration Day. She lived through some grueling days as secretary of state. She counters with a serious spunk factor and memories of her energetic schedule as top diplomat. Republicans would love to pin blame on her for last year's deadly assault on the U.S. diplomatic mission in Benghazi, Libya. She does just fine politically - until she gets political. Then her old enemies come out of the woodwork.
Shadow campaign: Keeping a traditional shadow campaign at arm's length for now. Ready for Hillary super PAC has received endorsements from Democrats such as Missouri Sen. Claire McCaskill and former Michigan Gov. Jennifer Granholm; several old Clinton hands are advising the group, including Craig T. Smith and Harold Ickes. The group is encouraging Clinton to run and trying to lay a foundation of grassroots supporters for a campaign if Clinton chooses to pursue one.
Social media: Twitter: Huge throng of followers, over 600,000, but few tweets. Her tweeted congrats and advice to British royal family for the new baby: "It Takes a (Royal) Village!" Not active on Facebook.
(Contributor: Ken Thomas)
Non-denial denial: "To the extent that I'm focusing on politics, it's my (governor's) race next year."
Book: Yes. Coming in 2014 from HarperCollins. "Profound moments" of the New York governor's first term in office plus "a full and frank account" of his private life.
Iowa: No. Has stayed close to home.
New Hampshire: No.
South Carolina: No.
Foreign travel: Yes, but not much lately. Visited Israel twice in 2002 when running for Democratic nomination for governor.
Meet the money: Facing little opposition in his re-election campaign in 2014, Cuomo had socked away a whopping $27.8 million in his campaign account through July.
Networking: Sparingly. Rarely leaves New York state. Did not appear at the Democratic National Convention in Charlotte last year, choosing instead to hold a side event for New York delegates at a Charlotte hotel.
Hog the TV: No.
Do something: Led New York's effort to legalize same-sex marriage in 2011. This year, pushed through the nation's first gun-control law after the Newtown, Conn., school massacre. Minimum wage boost, on-time budgets, teacher standards.
Take a stand: Environmentalists and the energy industry are closely watching his pending decision whether to allow fracking in some upstate New York counties near the Pennsylvania line.
Baggage: Trumpets "remarkable string of accomplishments" in the state but record-high poll numbers have sunk to lowest yet. State economy grew at slower pace than national rate in 2012. New York ranked 37th among all states for gross domestic product for last three years. Deflection: "I'm focusing on running this state and doing it the best I can. And that's all there is to that." Cuomo's first marriage to Kerry Kennedy, daughter of the late Sen. Robert F. Kennedy, ended in a public and bitter divorce in 2005. Cuomo lives with Food Network star Sandra Lee.
Shadow campaign: Overshadowed by Clinton's shadow campaign. Considered a likely contender if Clinton ends up not running.
Social media: Few if any personal tweets; Facebook also generated primarily by staff.
(Contributor: Ken Thomas)
Non-denial: "By the end of this year, we're on course to have a body of work that lays the framework of the candidacy for 2016." An acknowledgment of presidential ambition that is rare in the field.
Book: No.
Iowa: Yes, once in 2012. Last fall, headlined Iowa Sen. Tom Harkin's annual steak fry, a must-stop for many Democrats seeking to compete in the leadoff caucuses. In Maryland, attended June fundraiser for Iowa Senate candidate Bruce Braley.
New Hampshire: Yes, in 2012. Appeared at May fundraiser in Washington area for New Hampshire Sen. Jeanne Shaheen.
South Carolina: Yes, April speech to Democratic activists.
Foreign travel: Yes, considerable. Israel this year for a second time. Also Denmark, Ireland, France in 2013. Asia in 2011, Iraq in 2010.
Meet the money: Has many bases covered as one of the party's top fundraisers. Raised more than $1 million for Obama's re-election campaign and is finance chairman for Democratic Governors Association heading into 2014 mid-term elections.
Networking: Yes. Springtime speech to party activists in South Carolina, another key early primary state. Work for 2014 candidates will take him to important presidential campaign states late this summer and fall, among them Ohio, Pennsylvania, Florida and New Jersey.
Hog the TV: One Sunday talk-show appearance since 2012 election. Frequent Sunday sermonizing on those shows on behalf of Obama during 2012 campaign.
Do something: Has posted some victories as governor that appeal to liberals: Toughened gun laws, repealed the death penalty, saw voters approve gay marriage after he got behind legislation to approve it, set up a framework to develop offshore wind power.
Take a stand: Liberal checklist: increased spending on education, infrastructure, transportation; supports same-sex marriage, immigration reform, repealing death penalty, pushes environmental protections.
Baggage: A record of raising taxes that could be challenged by less liberal Democrats, never mind Republicans. Sales and corporate income taxes went up his first year as governor. Last year, people making more than $100,000 got hit and the state's "flush tax" on sewer bills doubled. This year he raised the gasoline tax. A shot across the bow from Maryland Republican Party chairwoman Diana Waterman: "Outrageously high taxes, a hostile regulatory environment, and thousands of people who are closing shop or leaving the state for greener pastures. This 'progress' he likes to boast about will be a tough sell to voters in Iowa and tax-wary New Hampshire." O'Malley's deflection: A vigorous defense of his record and the state's business climate. U.S. Chamber of Commerce rates Maryland No. 1 for entrepreneurship and innovation.
Shadow campaign: Set up PAC called O'Say Can You See and hired two people for fundraising and communications.
Social media: On Twitter, standard governor's fare but promotes rare appearances by his Celtic rock band, O'Malley's March, for which he sings and plays guitar and tin whistle. On Facebook, his PAC-generated page is more active than official governor's account.
(Contributor: Brian Witte, Annapolis)
Non-denial denial: "I'm not thinking about it." ''I'm not saying yes. I'm just not saying no." March 10 talk shows. "My thinking is not to think about it for a year," May 30.
Book: Yes. Co-authored "Immigration Wars: Forging an American Solution," which he promoted on all five Sunday morning TV talk shows March 10.
Iowa: Yes, in 2012, economic development meeting in Sioux City.
New Hampshire: No record of recent visits.
South Carolina: Yes, in April 2012. Spoke to Empower S.C. Education Reform meeting.
Foreign travel: Yes, a few times a year. Several visits to Israel, as governor (1999) and since then (private visit 2007). Also went there as Florida commerce secretary in 1980s.
Meet the money: Yes, and he's got longtime connections. Party this summer for his immigration book at the home of Woody Johnson, owner of the New York Jets and a leading Republican bundler.
Networking: Yes, keynote dinner speech at Conservative Political Action Conference in March in Washington. 2013 Faith and Freedom Coalition meeting. Speeches and meetings on education policy.
Hog the TV: 6 Sunday talk show appearances since 2012 election, including all five shows on March 10 to plug his book on immigration.
Do something: Staked a position on immigration to the right of Sen. Marco Rubio and some others. Strong job approval ratings as governor of swing-state Florida. Revamped state educational system, cut taxes, managed state through several hurricanes.
Take a stand: Active on education reform in addition to immigration. On the later, irked some Republicans by writing in his book that he did not support a pathway to citizenship for those living in the country illegally. Previously had expressed support for a pathway to citizenship, and later said he was open to the idea if it did not encourage illegal immigration.
Baggage: The Bush factor. Jeb is yet another Bush - a plus for many people but a huge negative for a big slice of the electorate that either didn't like Bush 41 and-or 43, or simply objects to the whole idea of a political dynasty. Even Barbara Bush, when asked about Jeb running, said in April: "We've had enough Bushes." Not much he can do to deflect this, other than show that he's his own man, and keep 41 and 43 at a distance.
Shadow campaign: He's a Bush - he's got connections. Statehouse lobbyist Sally Bradshaw, his chief of staff when he was governor, is his go-to political person.
Social media: Tweets many Wall Street Journal stories. On Facebook, promotes immigration book, education reform.
(Contributor: Tom Beaumont, Des Moines, Iowa)
Non-denial denial: "I'm nowhere near making that decision yet, at all. I mean, I think anybody who tries to plan in politics that far in advance is crazy. ... I love being governor and I want to stay as governor." Feb. 4, "Late Show with David Letterman."
Book: No.
Iowa: Yes, in 2012. New Jersey governor also visited in 2011 and 2012 to help Iowa Rep. Steve King raise money.
New Hampshire: Yes, three times in the 2012 campaign, endorsing Mitt Romney in a visit to the state, campaigning for him there in January 2012 and returning in September for Ovide Lamontagne, who was running for governor. Schmoozed with New Hampshire delegates at GOP convention.
South Carolina: Yes, visited in 2012 to help Romney raise money.
Foreign travel: Yes. First official trip overseas was in July 2012, to Israel, then Jordan. Visited Western Wall, met Prime Minister Benjamin Netanyahu, who told him Israel and New Jersey are similar in size and population but New Jersey probably has "better neighbors."
Meet the money: Yes, went on an aggressive national fundraising tour in early 2013, courting GOP donors in New York City, the Washington area, Boston and Miami. Also raised money this year in Ohio, Wisconsin, Texas and California, where Facebook CEO Mark Zuckerberg hosted an event at his Palo Alto home. Although he's raising money for his governor's race, these connections put him in a good place to finance a presidential campaign. Attended Romney's retreat in Utah in June, joining Paul and Ryan in hanging out with major GOP donors.
Networking: Yes, but not the usual conservative activist network. Broad outreach as keynote speaker at 2012 Republican National Convention and vice chairman of Republican Governors Association, a group he'll chair in 2014. At Aspen Institute in July, started spat with Paul from afar, criticizing libertarians in the party. Spoke to Conservative Political Action Conference in 2012 but not invited this year. Invited to speak to Ralph Reed's Faith and Freedom conference, but declined and instead appeared with Bill Clinton in Chicago to talk about disaster relief.
Hog the TV: Yes but not the usual sober circuit. Late-night guest with David Letterman, Jon Stewart and Jimmy Fallon, occasional news-show guest. Brief appearance on "Saturday Night Live" and will play himself on an episode of the new sitcom "The Michael J. Fox Show" this fall.
Do something: Led state's response to Superstorm Sandy. Agreed to expand state's Medicaid program under Obamacare while some other Republican governors have refused to do so. Vetoed a bill that would have legalized gay marriage, signed law increasing pension and health costs for public workers.
Take a stand: Bridges partisan divide. Christie showed in disaster response that pragmatism trumped party labels. That could be a strength in a presidential election, although a weakness in striving for his party's nomination, because accommodation is not what core constituencies of either party want to see. But he's pleased some conservatives by taking on labor unions, opposing gay marriage and opposing abortion rights except in case of rape, incest or to save the life of the woman.
Baggage: Fat factor. Man dates with Obama, Bill Clinton. Prickly relations with conservatives. Began to deflect weight problem by having a band surgically placed around stomach to restrict food intake. His praise of Obama during storm response and while Romney was trying to win the 2012 campaign turned some Republicans apoplectic. His deflection could be summed up by the title of Romney's book: "No Apology." Has a lot of making up to do with the right.
Shadow campaign: Building broad coalition of donors through his national fundraising tour this spring. There were also "draft Christie" movements in Iowa and South Carolina in 2011, where activists continue to support him. Hired senior Romney media mind Russ Schriefer in late spring.
Social media: More engaged in Twitter ("It was great to be able to visit with the owners of Rossi's Rent-A-Rama in Ortley today.") than Facebook.
(Contributor: Steve Peoples, Boston)


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Stephen Hayes reminds us that none other than Obama once warned us of the folly of raising taxes in a recession:
Barack Obama understands that it's bad economics to raise taxes in a recession. It's "the last thing you want to do," he said almost exactly one year ago. … Obama was blunt: "Well — first of all, he's right. Normally you don't raise taxes in a recession, which is why we haven't and why we've instead cut taxes. So I guess what I'd say to [Elkhart, Indiana resident] Scott [Ferguson] is — his economics are right. You don't raise taxes in a recession. We haven't raised taxes in a recession."
But the Obama team insists, contrary to much available evidence, that we're in the midst of a recovery — so we can tolerate the liberals' mischief-making:
When he was asked specifically about raising taxes on top income earners, as is scheduled to happen on January 1, 2011, [Tim] Geithner said, "The country can withstand that. The economy can withstand that. I think it's good policy."
It was an interesting word choice: "withstand" a tax hike? So the U.S. economy is strong enough to endure the additional constraints the Obama administration wants to place on it in pursuit of its redistributionist goals? This is the triumph of ideology over economics.
Obama and his brain trust not only ignore their own country's experience and struggling economy, but also turn a blind eye toward the counter-example in Germany, which resisted Obama's exhortations to get the government to spend (actually, borrow in order to spend) its nation out of the recession. Germany's economic recovery (on track for 9 percent annual growth) should serve as a lesson to those still enamored of Obamanomics:
Germany has sparred with its European partners over how to respond to the financial crisis, argued with the United States over the benefits of stimulus versus austerity, and defiantly pursued its own vision of how to keep its economy strong. … By paring unemployment benefits, easing rules for hiring and firing, and management and labor's working together to keep a lid on wages, Germany ensured that it could again export its way to growth with competitive, nimble companies producing the cars and machine tools the world's economies — emerging and developed alike — demanded.
When Paul Krugman comes out of hiding, I look forward to his explanation of this one.
Maybe some restraints on spending, some pro-growth and pro-job-creation policies, and a halt to tax increases might be in order. Nah, the Obami insist they have everything under control.


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Every Tuesday, Queens Library will introduce you to a great new book!
Our pick for #BookTuesday, August 4 is The Marriage of Opposites by Alice Hoffman.
From the New York Times-bestselling author of The Dovekeepers and The Museum of Extraordinary Things ...
Join the action this summer and have a blast at the Summer Reading Program at Queens Library. This summer celebrate real-life and fictional heroes, cool books, popular fantasy and graphic novels to the latest in your favorite series.
Summer Reading 2015 begins Thursday, June 4.
Mayor de Blasio, Speaker Mark-Viverito, Finance Chair Ferreras, Majority Leader Van Bramer, outgoing Libraries Subcommittee Chair Constantinides, incoming Libraries Subcommittee Chair King and the New York City Council have made an historic investment in our city's libraries.
We're thanking them for their ...
Rockaways Summer of Health is a series of programs and events designed to educate and get the Rockaways fit and healthy. Participate in a variety of classes and workshops for a healthy lifestyle such as stress reduction, nutrition and exercise classes.
Get Fit! Get Healthy!
Visit the web page for more ...
Please join us during Saturdays in August, when Lincoln Center Local will bring free live concerts at 2:00 p.m. and 4:00 p.m. to select Queens Library locations.
These include performances by the Brazilian-American group Nation Beat, the New Orleans band Cha Wa, ...
Alicia Olatuja sings with a strong, lustrous tone, and mixes elements of classical, jazz, gospel, and pop into her fluid vocalism. She has played alongside giants like Chaka Khan, Christian McBride, and Bebe Winans.
Free tickets are available on Eventbrite
The Library Journal will honor the best self-published ebooks in the following genres: Romance, Mystery, Science Fiction, Fantasy. There will be a winner in each genre and each winner will receive $1,000.00 USD from Library Journal.
Visit our Self Publish page for more information.
Buscando libros para leer en español? Échale un vistazo a estos nuevos libros en español:
Amarres perros: Una autobiografía, de Jorge G. Castañeda
Hacer el bien, de Matt Sumell
Looking for books to read in Chinese? Check out these new arrivals!
新參者 / Xin can zhe, by 東野圭吾 Keigo Higashino
死亡通知单 / Si wang tong zhi dan, by 周浩晖 Zhou Haohui
Welcome to our brand-new publication!
Queens Library Magazine combines great library-themed feature stories and information about all our programs and special events, and it's available now at your neighborhood library or ...
Intermediate-Level Chess Club
Location: East Flushing
Registration: Not required
Our intermediate-level chess club meets on Thursday afternoons and is for adults and teens only.
Additional Program Dates/Locations
This is a recurring program. If registration is required, you must register individually.
Additional Dates
Free computer access is available at all the libraries.
The East Flushing Community Library has:
International Language Collections at the East Flushing Community Library include:
Special Interest/Noteworthy Collections at the East Flushing Community Library include:
| Child Care / Preschools
Community Board
Community Organizations & Services
Fire Department
Local Hospitals
Local Newspapers
| Parks and Playgrounds
Police Department
Post Office
Private / Parochial Schools
Public Elementary Schools
Public High Schools
| Public Intermediate / Junior High Schools
Senior Centers
Elected Officials
Special Services
|Child Care / Preschools
Crayon Box Preschool
4410 192nd Street
Flushing NY , 11358
phone: (718) 888-9341
Sensational Kids
4550 195th Street
Flushing NY , 11358
phone: (718) 631-5942
St. Nicholas Preschool
196-20 Northern Blvd.
Flushing NY , 11358
phone: (718)357-0800
|Community Board
Queens Community Board #11
46-21 Little Neck Parkway
Little Neck NY , 11377
phone: (718) 225-1054
fax: (718) 225-4514
|Community Organizations & Services
46 Avenue Beautification Comm
45-67 194th Street
Flushing NY , 11358
Auburndale Improv. Assoc
P.O. Box 331 – Station A
Flushing NY , 11358
|Fire Department
Engine 320/Ladder 167
36-18 Francis Lewis Blvd
Flushing NY , 11358
|Local Hospitals
Flushing Hospital Medical Center
4500 Parsons Blvd.
Flushing NY , 11355
|Local Newspapers
Queens Gazette
|Parks and Playgrounds
Kissena Park
Rose and Oak Avenues on the north, Kissena Boulev
P.S. 130 Playground
42nd Avenue & Francis Lewis Boulevard
|Police Department
111th Precinct
45-06 215th Street
Bayside NY , 11361
phone: (718) 279-5200
|Post Office
Station A
40-03 164th Street
Flushing NY , 11358
|Private / Parochial Schools
Holy Cross High School(9-12)
26-20 Francis Lewis Blvd.
Flushing NY , 11358
phone: (718) 886-7250
St. Kevin's School (PreK-8)
45-50 195th Street
Flushing NY , 11358
phone: (718) 357-8110
William Spyropoulos School (PreK-8)
196-10 Northern Blvd.
Flushing NY , 11358
phone: (718) 357-5583
|Public Elementary Schools
200-01 42nd Avenue
Bayside NY , 11361
phone: (718) 357-6606
200-01 42nd Avenue
Bayside NY , 11361
phone: (718) 224-0490
|Public High Schools
HS 495 Bayside High School (9-12)
208th Street & 32nd Avenue
Bayside NY , 11361
phone: (718) 229-7600
|Public Intermediate / Junior High Schools
IS 25 Adrien Block School (7-9)
34-65 192nd Street
Flushing NY , 11358
phone: (718) 961-3480
|Senior Centers
Self Help Clearview Senior Center
208-11 26th Avenue
Bayside NY , 11360
phone: (718) 224-7888
|Elected Officials
|NYC Council
Hon. Paul Vallone
District Office Address 42-40 Bell Boulevard, Suite 507
Bayside NY, 11361
phone: (718) 619-8611
fax: (718) 631-4100
Manhattan Office Address 250 Broadway, Suite 1841
New York NY, 10007
phone: 212-788-7250
fax: 212-788-1860
|NYS Assembly
Hon. Edward C. Braunstein
District Office 213-33 39th Avenue, Suite 238
Bayside NY, 11361
phone: (718) 357-3588
fax: (718) 357-5947
Albany Office LOB, Room 557
Albany NY , 12248
phone: (518) 455-5425
fax: (518) 455-4648
|NYS Senate
Hon. Tony Avella
District Office 38-50 Bell Boulevard, Suite C
Bayside NY, 11361
phone: (718) 357-3094
fax: (718) 357-3491
Albany Office Room 504, Legislative Office Building
Albany NY, 12247
phone: (518) 455-2210
fax: (518) 426-6736
|US Congress
Hon. Grace Meng
District Office Address 32-26 Union Street, Suite 1B
Flushing NY, 11354
phone: (718) 445-7860
fax: (718) 445-7868
Legislative Office 1317 Longworth House Office Building
Washington DC, 20515
phone: (202) 225-2601
fax: (202) 225-1589
|Boro President
Hon. Melinda Katz
Hon. Bill de Blasio
The Matinecock Indians sold Flushing to the Dutch Colonists in the 1620s at the rate of one ax per 50 acres. The Dutch named it "Vlissingen," after a port in Holland. It meant "flowing water."
In 1657, the document called the Flushing Remonstrance, was signed by the Dutch colonists giving the Quakers and others the right to worship as they chose. The principles stipulated in the Remonstrance foresaw the freedom of religion in the U.S. Constitution. The English began ruling in 1664 and changed the name to Flushing.
Because of the abundance of trees in Flushing, the first commercial nurseries in America were organized here in the 1700s. A town hall was built in 1864 and it has been used as an opera house, police station, jail, and a dinner theater.
There have been two World's Fairs in Flushing, one in 1939 and the other in 1964.
In the early to mid-1900s Irish, Germans and Italians resided in Flushing; but after 1965, Greeks, Chinese, Korean, and Hispanic immigrants started moving in. The formerly tree-lined pastoral town has become an important international residential and commercial center.
At first the new East Flushing Branch of the Queens Borough Public Library was set to open on November 1, 1975; but due to budget cuts it was unachievable to staff the additional branch. In 1977 a recent influx of federally financed CETA employees made it attainable for the East Flushing Branch to open for service on Monday, September 19, 1977 at 1:00pm. Previously this community had no library service, except for weekly visits by a bookmobile.


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Gear Review
Ready for the snow
So far so good. My husband has tried this helmet on several times just to make sure he still likes it! The fit is good, the style is very nice and he says its very comfortable. Now we're just waiting on the snow!
View More Details on Giro G10 MX Helmet


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The Crucible
by Arthur Miller
Elizabeth Proctor Timeline and Summary
- Proctor and his wife Elizabeth are having dinner in their house when Elizabeth lets him know that the town has gone crazy. Fourteen people have been arrested as witches.
- She urges her husband to go to the town and tell them that Abigail Williams's visions are a fraud.
- Elizabeth gets upset when she learns that Abigail told him about it when the two of them were alone. She claims she isn't judging him, but she is still sad and frustrated.
- Mary Warren returns home and tells them about the day's events. She gives Elizabeth a poppet (doll) that she made for Elizabeth, and then tells the Proctors that she saved Elizabeth's life today when Elizabeth's name got mentioned in court.
- When Mary leaves, Elizabeth says she has always suspected that her husband's affair would lead to nasty consequences. She again urges her husband talk to Abigail, to break the unspoken promise he made to her when they had sex.
- When Hale comes to find out what he can about Elizabeth, since she was mentioned, they discuss what is happening. Elizabeth says she cannot believe there are witches if she, or people like Rebecca, are to be sentenced as witches.
- She denies that the poppet is hers when the constable Cheever and Marshal Herrick come to arrest her, but she doesn't resist arrest. She asks her husband to come get her out of jail quickly.
- When the Salem court fetches her to ask her why she put Abigail out of the house, she hems and haws, explaining that she believed her husband had come to fancy Abigail.
- When asked directly if her husband is a lecher, she lies to protect his good name.
- On the day her husband is to die, Elizabeth is called in to plead with him to sign a confession and save his life. She doesn't do that, but she does say she won't judge him if he decides to confess to the false charge.
- She also tells him that she knows he's a good man, and that she now blames herself for his adultery – she was a cold wife.
- When he decides to go to the gallows, Hale urges her to go again and plead with him, but she says she cannot – he has regained his sense of goodness, and she won't take that away from him. That's the final line of the play.


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SHEPHERDSVILLE — Patrick Myers knows that his Apex physical therapy clinics are not associated with big-time medical companies.
SHEPHERDSVILLE — A former Shepherdsville city employee who was indicted for not returning property as required will not go to trial until August.
SHEPHERDSVILLE – After 90 minutes of discussion, Bullitt Fiscal Court appears ready to approve a 2012-13 budget next Thursday.
SHEPHERDSVILLE — Through two budget meetings, councilmembers voiced some concerns over the apparent turnaround in the financial status of the city of Shepherdsville.
SHEPHERDSVILLE - Let the lobbying begin once again.
SHEPHERDSVILLE — Clad in white shirts, residents concerned over a possible rezoning of 650 acres to light industrial could return home breathing a bit of relief.
SHEPHERDSVILLE - How much does Bullitt County's tourism industry contribute to the local economy?
SHEPHERDSVILLE - In the 13 years since its inception, Tony Hsieh has seen a whole lot of changes in the operations of Zappos.
Better Business Bureau is warning university and high school students looking for work this summer to be careful to avoid job scams.
Many Internet and newspaper ads have postings that claim: "summer job, make $300 a day!" or "last year our employees made $10,000 over the summer."
Here are 10 tip-offs that the "employment opportunity" could be a scam:
LEBANON JUNCTION - Richard Clark just retired after working as a maintenance instructor for a Fort Knox M1 tank in Bradley, Ky., for 37 years.
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The Pioneer News Online is your source for local news, sports, events and information in Bullitt County and Shepherdsville, KY, and the surrounding area.


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Anthony Edward Martelli 33, of Columbia City passed away unexpectedly Monday March 21, 2011 at his home.
He was born in Holyoke, Mass. Sept. 18, 1977 to Neil and Linda (Monroe) Martelli.
Surviving family include his fiancée, Tanya Boehly, son, Julian Anthony; mother, Linda Martelli; father, Neil Martelli; sisters: Traci Connors, Victoria Makuch, Nicole Martelli and Angelina Moran.
A memorial service will be held at a later date. Memorials can be made to Julian Martelli trust fund, c/o Hampden Bank, 19 Harrison Ave. Springfield, MA 01103
Local arrangements are by Smith and Sons Funeral Home, Columbia City. Condolences may be sent to www.smithandsonsfuneralhome.com.