CA1054839A - Stabilization of photosensitive recording material - Google Patents
Stabilization of photosensitive recording materialInfo
- Publication number
- CA1054839A CA1054839A CA209,478A CA209478A CA1054839A CA 1054839 A CA1054839 A CA 1054839A CA 209478 A CA209478 A CA 209478A CA 1054839 A CA1054839 A CA 1054839A
- Authority
- CA
- Canada
- Prior art keywords
- group
- compound
- layer
- recording
- photosensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A recording process including image stabilization com-prising the steps of :
(1) image-wise exposing to active electromagnetic radia-tion of a recording material containing in a recording layer a aye precursor compound and at least one photosensitive organic polyhalogen compound capable of producing photoradi-cals and a dyestuff with said dye precursor compound when exposed with ultraviolet radiation and/or visible light, and (2) heating the photoexposed recording material thereby transforming the non-decomposed polyhalogen compound into a non-photosensitive substance by reaction with at least one stabilizing substance selected from the group consisting of triphenylamine.
a soft base containing an element of the group consisting of phosphorus, arsenic, antimony, bismuth, selenium, and tellu-rium, and an .alpha.,.beta.-ethylenically unsaturated compound in which at least the .alpha.-carbon atom of at least one ethylene group is linked to cyano, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group or an aryl group, said stabilizing substance(s) being available in a layer adjacent to the recording layer for allowing on heating the reaction with non-photo-decomposed polyhalogen compound.
A recording process including image stabilization com-prising the steps of :
(1) image-wise exposing to active electromagnetic radia-tion of a recording material containing in a recording layer a aye precursor compound and at least one photosensitive organic polyhalogen compound capable of producing photoradi-cals and a dyestuff with said dye precursor compound when exposed with ultraviolet radiation and/or visible light, and (2) heating the photoexposed recording material thereby transforming the non-decomposed polyhalogen compound into a non-photosensitive substance by reaction with at least one stabilizing substance selected from the group consisting of triphenylamine.
a soft base containing an element of the group consisting of phosphorus, arsenic, antimony, bismuth, selenium, and tellu-rium, and an .alpha.,.beta.-ethylenically unsaturated compound in which at least the .alpha.-carbon atom of at least one ethylene group is linked to cyano, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group or an aryl group, said stabilizing substance(s) being available in a layer adjacent to the recording layer for allowing on heating the reaction with non-photo-decomposed polyhalogen compound.
Description
1~54839 The present invention is directed to a recording method for forming a permanent or stabilized image resulting from the information-wise exposure of a free radical photo-sensitive aterial as hereinafter defined, wherein said method includes the inactivation of the photosensitivity of the compound pro-ducing the free radical.
By the term "free radical photosensitive material"
employed in the present description is meant a photosensitive material in which at least one of the photosensitive ingredients is an ultraviolet and/or visible light sensitive organic poly-halogen compound producing photoradicals on exposure with said radiation.
Photographic dye-forming systems based on the use of said polyhalogen compound and a dye precursor compound have been des-cribed, e.g. by R.A. Fotland in J. Phot. Sci., 18 (1970), 33-37, in the United States Patents 3,102,810 and 3,377,167, the United Kingdom Patents 1,151578 and 1,073,345 and in the Belgian Patents 771,848 - 786,973 - 787,339 and 790,340 corresponding with the published German applicatlons Nos. 2,142,966; 2,241,563;
By the term "free radical photosensitive material"
employed in the present description is meant a photosensitive material in which at least one of the photosensitive ingredients is an ultraviolet and/or visible light sensitive organic poly-halogen compound producing photoradicals on exposure with said radiation.
Photographic dye-forming systems based on the use of said polyhalogen compound and a dye precursor compound have been des-cribed, e.g. by R.A. Fotland in J. Phot. Sci., 18 (1970), 33-37, in the United States Patents 3,102,810 and 3,377,167, the United Kingdom Patents 1,151578 and 1,073,345 and in the Belgian Patents 771,848 - 786,973 - 787,339 and 790,340 corresponding with the published German applicatlons Nos. 2,142,966; 2,241,563;
2,244,783; and 2,251,105, respectively.
In all these dye-forming systems carbon tetrabromide and/
or iodoform are the most commonly used photoradical-generating compounds because these compounds excel in photosensitivity when compared with other representatives of the class of photosensitive organic polyhalogen compounds.
One of the presently known stabilization techniques makes use of the volatility of the carbon tetrabromide, which can be ~OSW39 removed from the non-exposed portions of the recording mate-rial relatively easily by evaporation. A suitable stabiliza-tion temperature is, e.g., in the range of 100 to 150C.
~ he evaporation of carbon tetrabromide in the environment of the operating personel poses, however, a problem since the compound is physiologically not inert and classified as being toxic (see I. ~ax, Dangerous Properties of Industrial Mate-rials (1968)).
~ he toxicity problem still remains when applying another commonly used stabilization technique that is based on the extraction of the photosensitive polyhalogen compound.
In the known extraction-stabilization technique a solvent for the photosensitive polyhalogen compound is used, which solvent does not affect or only weakly affects the binding agent of the recording layer. Some solvents such as diethyl ether, although being excellent extraction agents cannot be used for the risk of explosion. Other suitable extraction solvents belonging to the class of liquid halogenated aliphatic hydro-carbons are not miscible with water and must not be drained off in the sewer.
Now a recording process has been found including image stabilization comprising the steps of :
(1) image-wise exposing to active electromagnetic radio-tion a recording material containing in a recording layer a dye precursor compound and at least one photosensitive organic polyha~ogen compound capable of producing photoradicals and GV.781 PCT - 2 -lOS4839 a dyestuff with said dye precursor compound when exposed with ultraviolet radiation and/or visible light, and (2) by heating transforming the non-decomposed poly-halogen compound into a non-photosensitive substance by reac-tion with at least one stabilising substance selected from the group consisting of triphenylamine, a "soft-base" containing an element of the group consisting of phosphorus, arsenic, antimony, bismuth, selenium and tellurium, and an ~,~ -ethylenically unsaturated compound in which at least the ~-carbon atom of at least one ethylene group is linked to cyano, a cyanomethyl group, an aGyl group, an acyl-oxy group, an alkoxycarbonyl group, a carbamoyl group or an aryl group, said stabilizing substance(s) being available in a layer adjacent to the recording layer for allowing the reaction with non-photo-decomposed polyhalogen compound on heating.
By the wording "soft base" is understood in the present invention a substance whose logarithm of the reaction rate constant of the reaction of the base with the trans-Pt (C5H5N)2Cl2 complex is larger than 3. Soft bases having that property are described in Science 151, 172-7 (1966) and in J.Chem.~duc. 45, 581-587 (1968) more particularly in Table of the article "Acids and Bases, HSAB" by Ralph G.Pearson.
The present invention includes further an integral copy material containing the photosensitive polyhalogen compound and stabilizing agent out of direct chemical contact from each GV.781 PCl - ~ -lOS4839 other at room temperature (20-30C) but in such a condition that reactive contact is effected through heating of the mate-rial at a temperature above 60C.
In the integral copy material system different techniques of keeping the polyhalogen compound and the "soft base" and/or sterically hindered phenol out of reactive chemical contact below 60C may be applied. For example, the reactants are kept out of direct chemical contact by enveloping at least one of the reactants in a capsule or droplet that contains a shell or envelope of a material, normally a polymeric mate-rial or wax that prevents the direct contact with the other reactant. ~he capsule shell or droplet envelope is ruptured or softened by heating, as a result of which the reactants enter into reactive contact.
Preferred integral copy materials applied in the present invention contain the photosensitive organic polyhalogen com-pound and stabilizing substance out of chemical reactive con-tact at least below 60C in apart binder layers in which the layer containing the stabilizing substance is a layer adjacent to the layer containing the polyhalogen compound and is applied from a solution in a volatile liquid, which is a non-solvent for the polyhalogen compound and the binder con-tained in the imaging layer comprising the polyhalogen com-pound and dye precursor compound. Premature reaction is avoided effectively when in a first layer on the support, e.g. resin support, of the recording material a vinyl car-bazole homopolymer or copolymer binder containing the dye GV.781 PCT _ 4 _ 1054~39 precursor compound, e.g. a spiropyran compound and polyhalogen compound and being insoluble or poorly soluble in ethanol or methanol, is coated and the stabilizing substance is app:Lied in a polymeric binder that is highly soluble in ethanol. Preferred binders for the covering layer are cel-lulose nitrate, polyvinyl acetate, ethylcellulose and poly-vinylbutyral.
If coated on a removable carrier, the very vinyicarbazole polymer or copolymer film containing the dye precursor com-pound and polyhalogen compound may serve as the support butpreferably it is permanently supported on a separate heat-resistant film, e.g. a polyester resin film, preferably a polyethylene terephthalate film. ~he ratio of vinyl carba-zole, homopolymer or copolymer to dye precursor compound in the integral sheet system material may be in the range of about 20 to 2 parts by weight of polymer to 1 part by weight of dye precursor compound.
~ he triphenylamine and "soft base" stabilizing agent are preferably present in the recording material at least in equimolar amount with respect to the photosensitive poly-halogen compound.
~ he molar amount of ,~ -ethylenically unsaturated compound is preferably at least 2 times as large as the molar amount of the photosensitive polyhalogen compound in the recording material.
If plasticizers are used in the layer containing the triphenylamine, "soft base" and/or ~,~ -ethylenicalIy unsatu-GV.781 PC~ - 5 -:
1 1~54839 rated compound preference is given to those that do not opa-cify the recording material, in other words those that are compatible with the binder, e.g. cellulose nitrate. The plasticizer should therefore be soluble in the same solvent as the binder. It should be essentially non-volatile in normal storage conditions. Suitable plasticizers for cellu-lo~e nitrate are polyalkylene glycol and camphor.
Particularly useful stabilizing agents of the "soft base"
type of the elements phosphorus, arsenic, antimony or bismuth correspond to the following structural formula :
r - Ar ~ Ar wh~rein :
X is phosphorus, arsenic, antimony or bismuth, and Ar is an aryl group e.g. a phenyl group.
~he use of such triaryl compounds in a photosensitive mixture containing a leuco dye compound and a photosensitive organic halogen compound has been described already in the United Kingdom Patent Specification 1,161,058.
Preferred stabilizing agents of the "soft base" type are given in the following ~able 1 with their structural formula, melting point and reference to their preparation.
GV.781 PCT - 6 -1054~39 q!able 1 , . . _ _ .
No.Structural formula point or Preparation Boiling ref.
,~ point (C) ll 1 ( ~ )3 74-76 P.Pfeiffer, Ber.
37, 4620 (190~) 2 (HO-~ )3P.H20 200 O.Neunhoeffer!, Ber., 94, 2515 (1961~
In all these dye-forming systems carbon tetrabromide and/
or iodoform are the most commonly used photoradical-generating compounds because these compounds excel in photosensitivity when compared with other representatives of the class of photosensitive organic polyhalogen compounds.
One of the presently known stabilization techniques makes use of the volatility of the carbon tetrabromide, which can be ~OSW39 removed from the non-exposed portions of the recording mate-rial relatively easily by evaporation. A suitable stabiliza-tion temperature is, e.g., in the range of 100 to 150C.
~ he evaporation of carbon tetrabromide in the environment of the operating personel poses, however, a problem since the compound is physiologically not inert and classified as being toxic (see I. ~ax, Dangerous Properties of Industrial Mate-rials (1968)).
~ he toxicity problem still remains when applying another commonly used stabilization technique that is based on the extraction of the photosensitive polyhalogen compound.
In the known extraction-stabilization technique a solvent for the photosensitive polyhalogen compound is used, which solvent does not affect or only weakly affects the binding agent of the recording layer. Some solvents such as diethyl ether, although being excellent extraction agents cannot be used for the risk of explosion. Other suitable extraction solvents belonging to the class of liquid halogenated aliphatic hydro-carbons are not miscible with water and must not be drained off in the sewer.
Now a recording process has been found including image stabilization comprising the steps of :
(1) image-wise exposing to active electromagnetic radio-tion a recording material containing in a recording layer a dye precursor compound and at least one photosensitive organic polyha~ogen compound capable of producing photoradicals and GV.781 PCT - 2 -lOS4839 a dyestuff with said dye precursor compound when exposed with ultraviolet radiation and/or visible light, and (2) by heating transforming the non-decomposed poly-halogen compound into a non-photosensitive substance by reac-tion with at least one stabilising substance selected from the group consisting of triphenylamine, a "soft-base" containing an element of the group consisting of phosphorus, arsenic, antimony, bismuth, selenium and tellurium, and an ~,~ -ethylenically unsaturated compound in which at least the ~-carbon atom of at least one ethylene group is linked to cyano, a cyanomethyl group, an aGyl group, an acyl-oxy group, an alkoxycarbonyl group, a carbamoyl group or an aryl group, said stabilizing substance(s) being available in a layer adjacent to the recording layer for allowing the reaction with non-photo-decomposed polyhalogen compound on heating.
By the wording "soft base" is understood in the present invention a substance whose logarithm of the reaction rate constant of the reaction of the base with the trans-Pt (C5H5N)2Cl2 complex is larger than 3. Soft bases having that property are described in Science 151, 172-7 (1966) and in J.Chem.~duc. 45, 581-587 (1968) more particularly in Table of the article "Acids and Bases, HSAB" by Ralph G.Pearson.
The present invention includes further an integral copy material containing the photosensitive polyhalogen compound and stabilizing agent out of direct chemical contact from each GV.781 PCl - ~ -lOS4839 other at room temperature (20-30C) but in such a condition that reactive contact is effected through heating of the mate-rial at a temperature above 60C.
In the integral copy material system different techniques of keeping the polyhalogen compound and the "soft base" and/or sterically hindered phenol out of reactive chemical contact below 60C may be applied. For example, the reactants are kept out of direct chemical contact by enveloping at least one of the reactants in a capsule or droplet that contains a shell or envelope of a material, normally a polymeric mate-rial or wax that prevents the direct contact with the other reactant. ~he capsule shell or droplet envelope is ruptured or softened by heating, as a result of which the reactants enter into reactive contact.
Preferred integral copy materials applied in the present invention contain the photosensitive organic polyhalogen com-pound and stabilizing substance out of chemical reactive con-tact at least below 60C in apart binder layers in which the layer containing the stabilizing substance is a layer adjacent to the layer containing the polyhalogen compound and is applied from a solution in a volatile liquid, which is a non-solvent for the polyhalogen compound and the binder con-tained in the imaging layer comprising the polyhalogen com-pound and dye precursor compound. Premature reaction is avoided effectively when in a first layer on the support, e.g. resin support, of the recording material a vinyl car-bazole homopolymer or copolymer binder containing the dye GV.781 PCT _ 4 _ 1054~39 precursor compound, e.g. a spiropyran compound and polyhalogen compound and being insoluble or poorly soluble in ethanol or methanol, is coated and the stabilizing substance is app:Lied in a polymeric binder that is highly soluble in ethanol. Preferred binders for the covering layer are cel-lulose nitrate, polyvinyl acetate, ethylcellulose and poly-vinylbutyral.
If coated on a removable carrier, the very vinyicarbazole polymer or copolymer film containing the dye precursor com-pound and polyhalogen compound may serve as the support butpreferably it is permanently supported on a separate heat-resistant film, e.g. a polyester resin film, preferably a polyethylene terephthalate film. ~he ratio of vinyl carba-zole, homopolymer or copolymer to dye precursor compound in the integral sheet system material may be in the range of about 20 to 2 parts by weight of polymer to 1 part by weight of dye precursor compound.
~ he triphenylamine and "soft base" stabilizing agent are preferably present in the recording material at least in equimolar amount with respect to the photosensitive poly-halogen compound.
~ he molar amount of ,~ -ethylenically unsaturated compound is preferably at least 2 times as large as the molar amount of the photosensitive polyhalogen compound in the recording material.
If plasticizers are used in the layer containing the triphenylamine, "soft base" and/or ~,~ -ethylenicalIy unsatu-GV.781 PC~ - 5 -:
1 1~54839 rated compound preference is given to those that do not opa-cify the recording material, in other words those that are compatible with the binder, e.g. cellulose nitrate. The plasticizer should therefore be soluble in the same solvent as the binder. It should be essentially non-volatile in normal storage conditions. Suitable plasticizers for cellu-lo~e nitrate are polyalkylene glycol and camphor.
Particularly useful stabilizing agents of the "soft base"
type of the elements phosphorus, arsenic, antimony or bismuth correspond to the following structural formula :
r - Ar ~ Ar wh~rein :
X is phosphorus, arsenic, antimony or bismuth, and Ar is an aryl group e.g. a phenyl group.
~he use of such triaryl compounds in a photosensitive mixture containing a leuco dye compound and a photosensitive organic halogen compound has been described already in the United Kingdom Patent Specification 1,161,058.
Preferred stabilizing agents of the "soft base" type are given in the following ~able 1 with their structural formula, melting point and reference to their preparation.
GV.781 PCT - 6 -1054~39 q!able 1 , . . _ _ .
No.Structural formula point or Preparation Boiling ref.
,~ point (C) ll 1 ( ~ )3 74-76 P.Pfeiffer, Ber.
37, 4620 (190~) 2 (HO-~ )3P.H20 200 O.Neunhoeffer!, Ber., 94, 2515 (1961~
3 (cH3-cH2-cH2-cH2)3p b.p. W. Davies, J.Chem.
(50 mm Soc., 1929, 33 l Hg)
(50 mm Soc., 1929, 33 l Hg)
4 ( ~ )3Sb 50 G.Hiers, Org.Synth.
Coll.Vol.1, 535 (CH3- ~3 )3Sb 127 !I~.~alalaevce, J.Gen.Chem.
(i946;
6 ( ~ )2Se b.p. H. Leicester,-165 Org.Synth.Coll.
Hg) Vol. II, 238 !
a "~-Ethylenically unsaturated compounds for use as sta-bilizing agents according to the present invel~tion correspond to the following general formula:
X- (CH=CH-)nY
wherein:
X represents an aryl group e.g. phenyl, CN, -CH2CN,,an acyl group e.g. banzoyl, an acyloxy group, an alkoxycarbonyl GVo 781 PCT - 7 ' iO54839 group, an aryloxycarbonyl group or a carbamoyl group, Y represents hydrogen or one of the groups mentioned under X, and n is 1 or 2.
Preferred unsaturated compounds are given in the following q~able 2 with their structural formula, melting point and reference to their preparation.
q!able 2 .,.. ____ .
No. Structural formula Boiling Preparation ref.
point (bp or melt-_ (ng)p(ooc)t 1 CH2=CH-CN (bp) i8 C.Monreu, Bull.Soc.
Chim.France (4) 27, 903 2 CX3-11-0-CX=CH2 (bp) 72 1 ( 954)R., 24, 459 3 CH2=CH-CX2CN (bp) 118 P.Bruylants, BulI.
Soc.Chim.Belge, 31, 4 ~3-CH=CH-~3 (mp) 125 Beilsteirl, E II
Vol. 5 (1943), 537 ~ -CH=CH-CH=CH- G~> (mp) 147 Beilstein, E II
Vol.5 (1943), 589 6 ~3-CH=CH-C~ (mp) 59 Beilstein, E II
_ Vol.7 (1948), 423 ~ he above mentioned stabilizing agents that are parti-cularly advantageously used in conjunction with carbon tetra-bromide are also effective in the stabilization of photo-GV.781 PC~ - 8 lOS4~39 sensitive materials containing photosensitive organic poly-halogen compounds other than carbon tetrabromide.
Photosensitive organic polyhalogen compounds that ob-tain reduced photosensitivity by reaction with the mentioned stabilizing agents are within the scope of the following géneral formula that includes carbon tetrabromide : -C
B/ \Y
wherein :
each of A, B, X and Y is a halogen atom of the group of chlorine, bromine or iodine, or wherein one of said radicals A, B, X or Y represents an alkyl group, including a substituted alkyl group, e.g.
a halogen-substituted alkyl radical, a hydroxy-alkyl radical or an aralkyl radical, e.g. benzyl, a quinoxaline group, an aryl group, a substituted aryl group, an aroyl group or an aryl sulphonyl group and the other radicals chlorine, bromine or iodine, or wherein two of said radicals A, B, 2 or Y represent an aromatic acyl group, e.g. benzoyl, and the other radicals chlorine, bromine or iodine.
Particularly suitable representatives falling within the scope of that general formula are organic halides such as carbon tetrabromide, bromoform, iodoform, hexachloro-ethane, hexabromoethane, pentabromoethane, 1,1,2,2-tetra-bromoethane, ~,q,~-tribromoacetophenone,~ ,a,-tribromo-GV.781 PCT - 9 -methylsulphonylbenzene, and its chlorine- or nitro-substi-tuted derivatives, tribromoethanol and the 2-tribromomethyl-guinoxaline compounds described in ~elgian Patent 757,145.
The following examples illustrate the present inven-tion without, however, limiting it thereto. ~he parts, per-centages and ratios are by weight, unless otherwise indicated.
~xam~eae_1 24 parts of carbon tetrabromide, 24 parts of iodoform, 24 parts of 3-methyl-di- ~-naphtospiropyran, 100 parts of poly-N-vinylcarbazole, 2 parts of silicone oil dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride were used for the coating of the imaging layer A on a polyethylene terephthalate support of a coverage of 95 ml per sq.m.
~he stabilizing layer B was coated on top of layer A
in a ratio of 38 ml per sq.m with the following composition :
50 ml of a 5 % solution of cellulose nitrate in ethanol and 50 ml of a 10 % solution of triphenylstibine in ethylene glycol monomethyl ether.
After drying, this material was exposed for 20 s to ultraviolet radiation in an Actina SH (trade name) diazo copier containing an U.V. lamp of 1000 W and heated for 8 s at 130C. A light-stable image was obtained.
Example 2 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 76 ml per sq.m GV.781 PC~ - 10 -with the following composition : 50 ml of a 10 % ethylcellu-lose solution in dioxan and 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether.
After drying, this material was exposed to U.V. radiation, as described in Example 1, heated for ~0 s at 130C (or for 90 s at ~20C). A light-stable image was obtained.
Example 3 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 76 ml per sq.m with the following composition : 50 ml of a 10 % polyvinyl butyral solution in ethanol and 50 ml of a 7 % triphenylstibine solution in ethylene glycol monomethyl ether.
After drying, this material was image-wise exposed as described in Example 1, and heated for 6 s at 1~0a.
light-stable image was obtained.
ExamPle 4 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 20 % polyvinyl acetate solution in methanol and 50 ml of a 12 % tritolylsti-bine solution-in benzene.
~ fter drying, this material was image-wise exposed as described in Example 1 and heated for 40 s at 130C. A stable image was obtained.
Example 5 On the same imaging layer as described in Example 1 a GV.781 PC~
stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 20 % cellulose nitrate solution in methanol and 50 ml of a 10 % diphenyl-selenide solution in methanol.
After drying, this material was image-wise exposed as described in Example 1 and heated for 40 s at 130C. A
light-stable image was obtained.
Exampl~ 6 On the same imaging layer as described in ~xample 1 a stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 30 % ethylcellu-lose solution in ethanol and 50 ml of a 12 % propene-3-nitrile solution in ethanol.
After drying, this materlal was ima~e-wise exposed as described in Example 1 and heated for 40 s at 130C. A
light-stable image was obtained.
_xample 7 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 20 % polyvinyl acetate solution in ethanol and 50 ml of a 10 % triphenyl-phosphine solu-tion in methanol.
After drying, this material was image-wise exposed to U.V. radiation and heated for 40 s at 130C. A stable image was obtained.
xample 8 A polyethylene terephthalate support of a thickness of GV.781 PC~ - 12 -1i354B39 0.10 mm was coated in a ratio of 76 ml per sq.m with the fol-lowing composition : 50 ml of a 10 % phenolic resin solu-tion in methanol and 50 ml of a 8 % triphenylstibine solution in e~thylene glycol monomethyl ether. On this stabilizing layer a light-sensitive layer of the composition of ~ayer A of Exa~ple 1 was coated but in a ratio of 152 ml per sq.m.
After drying, this material was exposed to~U.V. radiation and heated at 130C for 2 min. A stable image was obtained.
ExamPle 9 A polyethylene terephthalate support of a thickness of 0.10 mm was coated in a ratio of 152 ml per sq.m with the following composition : 12 parts of ~,d,~-tribromoquinoxa-line-2, 12 parts of 3-methyl-di-~ -naphthospiropyran, 50 parts of poly-N-vinylcarbazole, 1 pa~t of silicone oil, dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride.
On top of this imaging layer a stabilizing layer was coated in a ratio of 76 ml per sq.m. with the following compo-sition : 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10 % ethylcellulose solution in methanol.
After drying, this material was exposed to U.V. radiation and heated for 4 s at 140C. A light-stable image was obtained.
Example 10 A polyethylene terephthalate support of a thickness of 0.10 mm was coated in a ratio of 152 ml per sq.m with the GV.781 PC~ - 13 -following composition : 15 parts of carbon tetrabromide, 15 parts of iodoform, 15 parts of 3-methyl-di-~-naphthospiropy-ran as dye precursor, 1.5 part of Michler's ketone, 50 parts of polystyrene, dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride.
On top of this imaging layer a stabilizing layer was coated in a ratio of 76 ml per sq.m with the following com-position : 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10 %iethyl-cellulose solution in methanol.
After drying, this material was exposed to U.V. radia-tion and heated for 3Q s at 130C. A light-stable image was obtained.
A polyethylene teréphthalate support of a thick~ess of 0.10 mm was coated in a ratio of 152 ml per sq.m with the following composition : 20 parts of carbon tetrabromide, 25 parts of 4-p-dimethylaminostyrylquinoline as dye precur-sor, 50 parts of polystyrene, dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride.
On top of this imaging layer a stabilizing layer was coated in a ratio of 76 ml per sq.m with the following com-position : 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10 % ethyl-cellulose solution in methanol.
After drying, this material was exposed to U.V. radi-ation and heated for 1 min at 130C. A light-stable image was obtained.
GN.781 PCl - 14 -Example 12 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 50 ml per sq.m with the following composition : 35 ml of a 10 % pol~vinyl-butyral solution in methanol, 10 ml of ethylene glycol mono-méthyl ether and 35 ml of a 5 % by weight solution in toluol of compound * of Table 2.
After drying, this material was exposed to U.V. radia-tion, as described in Example 1, and heated for 60 s at 130C. A light-stable image was obtained.
Example 13 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 76 ml per sq.m with the fol~owing composition : 40 ml of a 10 % polyvinyl-butyral solution in methanol, and 40 ml of a 5 % by weight solution in toluol of triphenylamine.
After drying, this material was exposed to U.V. radia-tion, as described in Example 1, and heated for 60 s at 130C. A light-stable image was obtained.
Example 14 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 50 ml per sq.m with the following composition : 40 ml of a 10 % polyvinyl-butyral solution in methanol, and 40 ml of a 5 % by weight solution in ethylene glycol monomethyl ether of compound 6 of ~able 2.
GV.781 PCT - 15 -~054839 After drying, this material was exposed to U.V. radia-tion, as described in Example 1, heated for 45 s at 130C.
A light-stable image was obtained.
GV.781 PCT - 16 -
Coll.Vol.1, 535 (CH3- ~3 )3Sb 127 !I~.~alalaevce, J.Gen.Chem.
(i946;
6 ( ~ )2Se b.p. H. Leicester,-165 Org.Synth.Coll.
Hg) Vol. II, 238 !
a "~-Ethylenically unsaturated compounds for use as sta-bilizing agents according to the present invel~tion correspond to the following general formula:
X- (CH=CH-)nY
wherein:
X represents an aryl group e.g. phenyl, CN, -CH2CN,,an acyl group e.g. banzoyl, an acyloxy group, an alkoxycarbonyl GVo 781 PCT - 7 ' iO54839 group, an aryloxycarbonyl group or a carbamoyl group, Y represents hydrogen or one of the groups mentioned under X, and n is 1 or 2.
Preferred unsaturated compounds are given in the following q~able 2 with their structural formula, melting point and reference to their preparation.
q!able 2 .,.. ____ .
No. Structural formula Boiling Preparation ref.
point (bp or melt-_ (ng)p(ooc)t 1 CH2=CH-CN (bp) i8 C.Monreu, Bull.Soc.
Chim.France (4) 27, 903 2 CX3-11-0-CX=CH2 (bp) 72 1 ( 954)R., 24, 459 3 CH2=CH-CX2CN (bp) 118 P.Bruylants, BulI.
Soc.Chim.Belge, 31, 4 ~3-CH=CH-~3 (mp) 125 Beilsteirl, E II
Vol. 5 (1943), 537 ~ -CH=CH-CH=CH- G~> (mp) 147 Beilstein, E II
Vol.5 (1943), 589 6 ~3-CH=CH-C~ (mp) 59 Beilstein, E II
_ Vol.7 (1948), 423 ~ he above mentioned stabilizing agents that are parti-cularly advantageously used in conjunction with carbon tetra-bromide are also effective in the stabilization of photo-GV.781 PC~ - 8 lOS4~39 sensitive materials containing photosensitive organic poly-halogen compounds other than carbon tetrabromide.
Photosensitive organic polyhalogen compounds that ob-tain reduced photosensitivity by reaction with the mentioned stabilizing agents are within the scope of the following géneral formula that includes carbon tetrabromide : -C
B/ \Y
wherein :
each of A, B, X and Y is a halogen atom of the group of chlorine, bromine or iodine, or wherein one of said radicals A, B, X or Y represents an alkyl group, including a substituted alkyl group, e.g.
a halogen-substituted alkyl radical, a hydroxy-alkyl radical or an aralkyl radical, e.g. benzyl, a quinoxaline group, an aryl group, a substituted aryl group, an aroyl group or an aryl sulphonyl group and the other radicals chlorine, bromine or iodine, or wherein two of said radicals A, B, 2 or Y represent an aromatic acyl group, e.g. benzoyl, and the other radicals chlorine, bromine or iodine.
Particularly suitable representatives falling within the scope of that general formula are organic halides such as carbon tetrabromide, bromoform, iodoform, hexachloro-ethane, hexabromoethane, pentabromoethane, 1,1,2,2-tetra-bromoethane, ~,q,~-tribromoacetophenone,~ ,a,-tribromo-GV.781 PCT - 9 -methylsulphonylbenzene, and its chlorine- or nitro-substi-tuted derivatives, tribromoethanol and the 2-tribromomethyl-guinoxaline compounds described in ~elgian Patent 757,145.
The following examples illustrate the present inven-tion without, however, limiting it thereto. ~he parts, per-centages and ratios are by weight, unless otherwise indicated.
~xam~eae_1 24 parts of carbon tetrabromide, 24 parts of iodoform, 24 parts of 3-methyl-di- ~-naphtospiropyran, 100 parts of poly-N-vinylcarbazole, 2 parts of silicone oil dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride were used for the coating of the imaging layer A on a polyethylene terephthalate support of a coverage of 95 ml per sq.m.
~he stabilizing layer B was coated on top of layer A
in a ratio of 38 ml per sq.m with the following composition :
50 ml of a 5 % solution of cellulose nitrate in ethanol and 50 ml of a 10 % solution of triphenylstibine in ethylene glycol monomethyl ether.
After drying, this material was exposed for 20 s to ultraviolet radiation in an Actina SH (trade name) diazo copier containing an U.V. lamp of 1000 W and heated for 8 s at 130C. A light-stable image was obtained.
Example 2 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 76 ml per sq.m GV.781 PC~ - 10 -with the following composition : 50 ml of a 10 % ethylcellu-lose solution in dioxan and 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether.
After drying, this material was exposed to U.V. radiation, as described in Example 1, heated for ~0 s at 130C (or for 90 s at ~20C). A light-stable image was obtained.
Example 3 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 76 ml per sq.m with the following composition : 50 ml of a 10 % polyvinyl butyral solution in ethanol and 50 ml of a 7 % triphenylstibine solution in ethylene glycol monomethyl ether.
After drying, this material was image-wise exposed as described in Example 1, and heated for 6 s at 1~0a.
light-stable image was obtained.
ExamPle 4 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 20 % polyvinyl acetate solution in methanol and 50 ml of a 12 % tritolylsti-bine solution-in benzene.
~ fter drying, this material was image-wise exposed as described in Example 1 and heated for 40 s at 130C. A stable image was obtained.
Example 5 On the same imaging layer as described in Example 1 a GV.781 PC~
stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 20 % cellulose nitrate solution in methanol and 50 ml of a 10 % diphenyl-selenide solution in methanol.
After drying, this material was image-wise exposed as described in Example 1 and heated for 40 s at 130C. A
light-stable image was obtained.
Exampl~ 6 On the same imaging layer as described in ~xample 1 a stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 30 % ethylcellu-lose solution in ethanol and 50 ml of a 12 % propene-3-nitrile solution in ethanol.
After drying, this materlal was ima~e-wise exposed as described in Example 1 and heated for 40 s at 130C. A
light-stable image was obtained.
_xample 7 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 152 ml per sq.m with the following composition : 50 ml of a 20 % polyvinyl acetate solution in ethanol and 50 ml of a 10 % triphenyl-phosphine solu-tion in methanol.
After drying, this material was image-wise exposed to U.V. radiation and heated for 40 s at 130C. A stable image was obtained.
xample 8 A polyethylene terephthalate support of a thickness of GV.781 PC~ - 12 -1i354B39 0.10 mm was coated in a ratio of 76 ml per sq.m with the fol-lowing composition : 50 ml of a 10 % phenolic resin solu-tion in methanol and 50 ml of a 8 % triphenylstibine solution in e~thylene glycol monomethyl ether. On this stabilizing layer a light-sensitive layer of the composition of ~ayer A of Exa~ple 1 was coated but in a ratio of 152 ml per sq.m.
After drying, this material was exposed to~U.V. radiation and heated at 130C for 2 min. A stable image was obtained.
ExamPle 9 A polyethylene terephthalate support of a thickness of 0.10 mm was coated in a ratio of 152 ml per sq.m with the following composition : 12 parts of ~,d,~-tribromoquinoxa-line-2, 12 parts of 3-methyl-di-~ -naphthospiropyran, 50 parts of poly-N-vinylcarbazole, 1 pa~t of silicone oil, dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride.
On top of this imaging layer a stabilizing layer was coated in a ratio of 76 ml per sq.m. with the following compo-sition : 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10 % ethylcellulose solution in methanol.
After drying, this material was exposed to U.V. radiation and heated for 4 s at 140C. A light-stable image was obtained.
Example 10 A polyethylene terephthalate support of a thickness of 0.10 mm was coated in a ratio of 152 ml per sq.m with the GV.781 PC~ - 13 -following composition : 15 parts of carbon tetrabromide, 15 parts of iodoform, 15 parts of 3-methyl-di-~-naphthospiropy-ran as dye precursor, 1.5 part of Michler's ketone, 50 parts of polystyrene, dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride.
On top of this imaging layer a stabilizing layer was coated in a ratio of 76 ml per sq.m with the following com-position : 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10 %iethyl-cellulose solution in methanol.
After drying, this material was exposed to U.V. radia-tion and heated for 3Q s at 130C. A light-stable image was obtained.
A polyethylene teréphthalate support of a thick~ess of 0.10 mm was coated in a ratio of 152 ml per sq.m with the following composition : 20 parts of carbon tetrabromide, 25 parts of 4-p-dimethylaminostyrylquinoline as dye precur-sor, 50 parts of polystyrene, dissolved in 1446 parts of trichloroethylene and 1336 parts of methylene chloride.
On top of this imaging layer a stabilizing layer was coated in a ratio of 76 ml per sq.m with the following com-position : 50 ml of a 10 % triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10 % ethyl-cellulose solution in methanol.
After drying, this material was exposed to U.V. radi-ation and heated for 1 min at 130C. A light-stable image was obtained.
GN.781 PCl - 14 -Example 12 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 50 ml per sq.m with the following composition : 35 ml of a 10 % pol~vinyl-butyral solution in methanol, 10 ml of ethylene glycol mono-méthyl ether and 35 ml of a 5 % by weight solution in toluol of compound * of Table 2.
After drying, this material was exposed to U.V. radia-tion, as described in Example 1, and heated for 60 s at 130C. A light-stable image was obtained.
Example 13 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 76 ml per sq.m with the fol~owing composition : 40 ml of a 10 % polyvinyl-butyral solution in methanol, and 40 ml of a 5 % by weight solution in toluol of triphenylamine.
After drying, this material was exposed to U.V. radia-tion, as described in Example 1, and heated for 60 s at 130C. A light-stable image was obtained.
Example 14 On the same imaging layer as described in Example 1 a stabilizing layer was coated in a ratio of 50 ml per sq.m with the following composition : 40 ml of a 10 % polyvinyl-butyral solution in methanol, and 40 ml of a 5 % by weight solution in ethylene glycol monomethyl ether of compound 6 of ~able 2.
GV.781 PCT - 15 -~054839 After drying, this material was exposed to U.V. radia-tion, as described in Example 1, heated for 45 s at 130C.
A light-stable image was obtained.
GV.781 PCT - 16 -
Claims (13)
1. A recording process including image stabilization comprising the steps of :
1. image-wise exposing to active electromagnetic radiation of a recording material containing in a recording layer a dye precursor compound and at least one photosensitive organic polyhalogen compound capable of producing photoradicals and a dyestuff with said dye precursor compound when ex-posed with ultraviolet radiation and/or visible light, and 2. heating the photoexposed recording material at a temperature above 60°C while said recording layer is in contact with an adjacent layer containing a molar excess of at least one stabilizing substance selected from the group contain-ing of (1) triphenylamine, (2) a phenylselenide compound, and (3) an .alpha.,.beta.-ethylenically unsaturated compound having the structural formula :
X-(CH=CH-)Yn wherein :
X represents cyano, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxy-carbonal group, a carbamoyl group or an aryl group, Y represents hydrogen or a group represented by X, and n is 1 or 2, whereby the nondecomposed polyhalogen compound is transformed by reaction with such stabili-zing substance into a non-photosensitive substance, and the aforesaid polyhalogen compound has the struc-tural formula :
wherein :
each of A, B, X and Y is a halogen atom of the group of chlorine, bromine or iodine, or wherein one of said radicals A, B, X or Y represents an alkyl group, including a substituted alkyl group, a quinoxaline group, an aryl group, a substituted aryl group, an aroyl group or an aryl sulphonyl group and the other radicals chlorine, bromine or iodine, or wherein two of said radicals A, B, X or Y represent an aromatic acyl group, and the other radicals chlorine, bromine or iodine.
X-(CH=CH-)Yn wherein :
X represents cyano, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxy-carbonal group, a carbamoyl group or an aryl group, Y represents hydrogen or a group represented by X, and n is 1 or 2, whereby the nondecomposed polyhalogen compound is transformed by reaction with such stabili-zing substance into a non-photosensitive substance, and the aforesaid polyhalogen compound has the struc-tural formula :
wherein :
each of A, B, X and Y is a halogen atom of the group of chlorine, bromine or iodine, or wherein one of said radicals A, B, X or Y represents an alkyl group, including a substituted alkyl group, a quinoxaline group, an aryl group, a substituted aryl group, an aroyl group or an aryl sulphonyl group and the other radicals chlorine, bromine or iodine, or wherein two of said radicals A, B, X or Y represent an aromatic acyl group, and the other radicals chlorine, bromine or iodine.
2. A recording process according to claim 1, wherein the stabilizing agent is available for the stabilization in an integral copy sheet in which the stabilizing agent is present in a binder layer adjacent to the recording layer.
3. A recording process according to claim 1, wherein the recording material contains on a support a first layer com-prising in a binder being a vinylcarbazole homopolymer or copolymer the photosensitive polyhalogen compound and a dye precursor compound, and the stabilizing agent or a mixture of stabilizing agents is contained in a polymeric binder in a covering layer applied to said first layer from a solvent that is non-solvent for the binder of said first layer.
4. A recording process according to claim 3, wherein the binder of the covering layer is cellulose nitrate.
5. A recording process according to claim 1, wherein the dye precursor compound is a spiropyran compound.
6. A recording process according to claim 1, wherein the at least one photosensitive organic polyhalogen compound contains carbon tetrabromide or a mixture of carbon tetra-bromide and iodoform.
7. A recording process according to claim 1, wherein the .alpha.,.beta.-ethylenically unsaturated compound is available in the recording material in a molar amount being at least 2 times as large as the molar amount of the photosensitive polyhalo-gen compound.
8. An integral copy material containing a dye precursor compound, at least one photosensitive organic polyhalogen compound and a molar excess relative to said polyhalogen com-pound of a stabilizing agent or mixture of stabilizing agents, said polyhalogen compound and stabilizing agent being kept out of direct chemical contact with each other at a room tem-perature below 60°C in separate and adjacent polymeric binder layers but in such condition that reactive contact is effec-table through heating of the material at a temperature above 60°C, and the stabilizing agent is selected from the group consisting of (1) triphenylamine, (2) a phenylselenide com-pound, and (3) an .alpha.,.beta.-ethylenically unsaturated compound having the structural formula :
X-(CH=CH-)nY
wherein :
X represents cyano, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbonyl group or an aryl group, Y represents hydrogen or a group represented by X, and n is 1 or 2, and the aforesaid polyhalogen compound has the structural formula :
wherein :
each of A, B, X and Y is a halogen atom of the group of chlorine, bromine or iodine, or wherein one of said radicals A, B, X or Y represents an alkyl group, including a substituted alkyl group, a quinoxa-line group, an aryl group, a substituted aryl group, an aroyl group or an aryl sulphonyl group and the other ra-dicals chlorine, bromine or iodine, or wherein two of said radicals A, B, X or Y represent an aromatic acyl group, and the other radicals chlorine, bromine or iodine.
X-(CH=CH-)nY
wherein :
X represents cyano, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbonyl group or an aryl group, Y represents hydrogen or a group represented by X, and n is 1 or 2, and the aforesaid polyhalogen compound has the structural formula :
wherein :
each of A, B, X and Y is a halogen atom of the group of chlorine, bromine or iodine, or wherein one of said radicals A, B, X or Y represents an alkyl group, including a substituted alkyl group, a quinoxa-line group, an aryl group, a substituted aryl group, an aroyl group or an aryl sulphonyl group and the other ra-dicals chlorine, bromine or iodine, or wherein two of said radicals A, B, X or Y represent an aromatic acyl group, and the other radicals chlorine, bromine or iodine.
9. An integral copy material according to claim 8, wherein the polyhalogen compound and stabilizing agent(s) are contained out of chemical contact below 60°C in apart polymeric binder layers in which the layer comprising the stabilizing agent is a layer adjacent to the layer containing the photosensitive polyhalogen compound and is applied from a solution in a volatile liquid, which liquid is a non-solvent for the polyhalogen compound and for the binder of the layer containing said polyhalogen compound and the dye precursor compound.
10. An integral copy material according to claim 9, wherein the recording material contains on a support in a first layer a vinylcarbazole homopolymer or copolymer binder containing the dye precursor compound and photosensitive polyhalogen compound, and in a covering layer applied to said first layer the stabilizing agent in a polymeric binder that is applied from a solvent containing ethanol.
11. An integral copy material according to claim 10, wherein the covering layer contains a polymeric binder selec-ted from the group comprising cellulose nitrate, polyvinyl acetate, ethylcellulose and polyvinylbutyral.
12. An integral copy material according to claim 8, wherein the .alpha.,.beta.-ethylenically unsaturated compound is pre-sent in said material in a molar amount being at least 2 times as large as the molar amount of the photosensitive polyhalogen compound.
13. An integral copy material according to claim 8, wherein the dye precursor compound is a spiropyran compound.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4420073A GB1469641A (en) | 1973-09-20 | 1973-09-20 | Stabilization of photosensitive recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1054839A true CA1054839A (en) | 1979-05-22 |
Family
ID=10432220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA209,478A Expired CA1054839A (en) | 1973-09-20 | 1974-09-18 | Stabilization of photosensitive recording material |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5059028A (en) |
| BE (1) | BE819758A (en) |
| CA (1) | CA1054839A (en) |
| DE (1) | DE2444520A1 (en) |
| FR (1) | FR2245010B1 (en) |
| GB (1) | GB1469641A (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773182A (en) | 1993-08-05 | 1998-06-30 | Kimberly-Clark Worldwide, Inc. | Method of light stabilizing a colorant |
| US5733693A (en) | 1993-08-05 | 1998-03-31 | Kimberly-Clark Worldwide, Inc. | Method for improving the readability of data processing forms |
| US5865471A (en) | 1993-08-05 | 1999-02-02 | Kimberly-Clark Worldwide, Inc. | Photo-erasable data processing forms |
| US5681380A (en) | 1995-06-05 | 1997-10-28 | Kimberly-Clark Worldwide, Inc. | Ink for ink jet printers |
| US6017661A (en) | 1994-11-09 | 2000-01-25 | Kimberly-Clark Corporation | Temporary marking using photoerasable colorants |
| US5700850A (en) | 1993-08-05 | 1997-12-23 | Kimberly-Clark Worldwide | Colorant compositions and colorant stabilizers |
| US5645964A (en) | 1993-08-05 | 1997-07-08 | Kimberly-Clark Corporation | Digital information recording media and method of using same |
| US6017471A (en) | 1993-08-05 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Colorants and colorant modifiers |
| US6211383B1 (en) | 1993-08-05 | 2001-04-03 | Kimberly-Clark Worldwide, Inc. | Nohr-McDonald elimination reaction |
| US5721287A (en) | 1993-08-05 | 1998-02-24 | Kimberly-Clark Worldwide, Inc. | Method of mutating a colorant by irradiation |
| US6071979A (en) | 1994-06-30 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition method of generating a reactive species and applications therefor |
| US5685754A (en) | 1994-06-30 | 1997-11-11 | Kimberly-Clark Corporation | Method of generating a reactive species and polymer coating applications therefor |
| US6008268A (en) | 1994-10-21 | 1999-12-28 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition, method of generating a reactive species, and applications therefor |
| CO4560378A1 (en) * | 1995-01-17 | 1998-02-10 | Kimberly Clark Co | STABILIZING COMPOSITION FOR DYES AND METHOD FOR STABILIZING A DYE IN THE LIGHT |
| RU2170943C2 (en) | 1995-06-05 | 2001-07-20 | Кимберли-Кларк Уорлдвайд, Инк. | Recent precolors |
| US5786132A (en) | 1995-06-05 | 1998-07-28 | Kimberly-Clark Corporation | Pre-dyes, mutable dye compositions, and methods of developing a color |
| JP2000506550A (en) * | 1995-06-28 | 2000-05-30 | キンバリー クラーク ワールドワイド インコーポレイテッド | New colorants and colorant modifiers |
| US5782963A (en) | 1996-03-29 | 1998-07-21 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5855655A (en) | 1996-03-29 | 1999-01-05 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| CA2210480A1 (en) | 1995-11-28 | 1997-06-05 | Kimberly-Clark Worldwide, Inc. | Improved colorant stabilizers |
| US6099628A (en) | 1996-03-29 | 2000-08-08 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5891229A (en) | 1996-03-29 | 1999-04-06 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| BR9906513A (en) | 1998-06-03 | 2001-10-30 | Kimberly Clark Co | New photoinitiators and applications for the same |
| EP1062285A2 (en) | 1998-06-03 | 2000-12-27 | Kimberly-Clark Worldwide, Inc. | Neonanoplasts and microemulsion technology for inks and ink jet printing |
| US6228157B1 (en) | 1998-07-20 | 2001-05-08 | Ronald S. Nohr | Ink jet ink compositions |
| DE69930948T2 (en) | 1998-09-28 | 2006-09-07 | Kimberly-Clark Worldwide, Inc., Neenah | CHELATE WITH CHINOIDS GROUPS AS PHOTOINITIATORS |
| ATE238393T1 (en) | 1999-01-19 | 2003-05-15 | Kimberly Clark Co | DYES, DYE STABILIZERS, INK COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF |
| US6331056B1 (en) | 1999-02-25 | 2001-12-18 | Kimberly-Clark Worldwide, Inc. | Printing apparatus and applications therefor |
| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
| US6368395B1 (en) | 1999-05-24 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Subphthalocyanine colorants, ink compositions, and method of making the same |
| MXPA02012011A (en) | 2000-06-19 | 2003-04-22 | Kimberly Clark Co | Novel photoinitiators and applications therefor. |
-
1973
- 1973-09-20 GB GB4420073A patent/GB1469641A/en not_active Expired
-
1974
- 1974-09-10 BE BE1006175A patent/BE819758A/en unknown
- 1974-09-12 JP JP10586574A patent/JPS5059028A/ja active Pending
- 1974-09-13 FR FR7431462A patent/FR2245010B1/fr not_active Expired
- 1974-09-18 DE DE19742444520 patent/DE2444520A1/en active Pending
- 1974-09-18 CA CA209,478A patent/CA1054839A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2245010A1 (en) | 1975-04-18 |
| GB1469641A (en) | 1977-04-06 |
| FR2245010B1 (en) | 1978-07-21 |
| BE819758A (en) | 1975-03-10 |
| DE2444520A1 (en) | 1975-03-27 |
| JPS5059028A (en) | 1975-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1054839A (en) | Stabilization of photosensitive recording material | |
| US4039332A (en) | Stabilization of photosensitive recording material | |
| EP0537912B1 (en) | Positive-acting photothermographic materials | |
| JPS6266254A (en) | Light image forming composition | |
| GB2036352A (en) | Photosensitive composition containing a leuco dye and photosensitive elements containing such compositions | |
| US5389489A (en) | Image-forming material | |
| CH493006A (en) | Photographic material containing a photosensitizer | |
| US3510304A (en) | Dry working black image compositions comprising organic halogen compounds and ethylene compounds | |
| JPS6123543B2 (en) | ||
| US4060416A (en) | Stabilization of free-radical photosensitive materials | |
| US3484238A (en) | Photographic element and diffusion process | |
| CA1253513A (en) | Tellurium imaging composition including improved reductant precursor and method | |
| JPS6146816B2 (en) | ||
| CA1116917A (en) | Covering power photothermographic material containing a hydrazino thiourea nucleating agent | |
| EP0273590B1 (en) | Stabilization of ketazine dyes | |
| US3765895A (en) | Photographic print-out composition containing a colorless stable-free radical precursor and a photoactivator | |
| US3208850A (en) | Vesicular type photographic materials comprising a polyurethane resin containing light decomposable compounds | |
| CA1063855A (en) | Photosensitive composition containing cadmium iodide and cuprous iodide in a binder | |
| US3767399A (en) | Photosensitive composition containing an aldol naphthylamine as color former and a halogenated hydrocarbon as photoactivator | |
| GB2029038A (en) | Dry image forming material | |
| US4316984A (en) | Thermolabile acutance dyes | |
| US4308342A (en) | Dimensionally stabilized imaging element and method | |
| US4352872A (en) | Stabilization of latent images in photothermographic elements | |
| CA1094378A (en) | Tellurium (ii) materials and process | |
| US4347307A (en) | Dimensionally stabilized imaging element and method |