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
  • G03C1/00—Photosensitive materials
  • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
  • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
• • 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
  • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
  • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
  • G03C1/732—Leuco dyes

Definitions

• the present invention relates to a photosensitive composition in which color is developed by irradiation of light.
• One photosensitive composition is an irreversible photosensitive composition in which color developed by light irradiation does not change upon interruption of light irradiation
• another photosensitive composition is a reversible photosensitive composition in which color developed by light irradiation gradually disappears upon interruption of light irradiation.
• the former irreversible photosensitive composition known is such a composition that is made up of a combination of an electron donative chromatic organic compound and a photoactivator.
• the electron donative chromatic organic compound known is the use of, for example, those compounds described in KAMIPAGIKYOHSHI, Vol. 30, p. 411 (1976), SHIKIZAI, Vol. 54, p. 355 (1981), KINOHSEISHIKISO NO KAGAKU (published by CMC Co. of Japan), pp. 189-210 (1981), and U.S. Patent 4,028,118, and as the photoactivator, known is the use of, for example, organic halides (described in U.S.
• Patents 3,042,515, 3,042,516, 3,042,517, 3,042,518 and 3,042,519 and Japanese Patent Publication No. 373/65 quinone diazides (described in Japanese Patent Publication No. 30885/70), and diazonium salts (described in Japanese Patent Publication No. 521/74).
• reversible photosensitive composition known are such an inorganic photosensitive composition that silver halides are dispersed into grass and an organic photosensitive composition such as azobenzene, N-salicylidene anilin, spiropyran, bis(triphenylimidazole), thionine, viologen, furgide, or the like.
• organic photosensitive composition such as azobenzene, N-salicylidene anilin, spiropyran, bis(triphenylimidazole), thionine, viologen, furgide, or the like.
• both compositions have at least one of such disadvantages that gas bubbles may be often produced owing to the generation of gases at the time of light irradiation, an odious smell is strong, a variety of colors developed is poor, durability and long-term preservation property are poor due to lack of stability against heat and humidity, and so on.
• the reversible photosensitive composition has at least one of such disadvantages, in addition to the above-mentioned disadvantages, as poor color disappearing property at the time of interruption of light irradiation, poor durability in repeated use, difficulties in availability of materials, difficulties in work onto materials and so on. Accordingly, there has no photosensitive composition satisfactory for the multi-purpose use in industrial viewpoint yet.
• the photosensitive composition is required to have properties of color sensitivity in which color is rapidly developed by light irradiation, a variety of colors developed, high color density, no odious smell, no generation of gases at the time of light irradiation, high durability against heat and humidity, stability in long-term preservation, abundant variety of colors, easiness in availability of materials, easiness in work onto materials, and so on.
• the inventors have found that in the case where a salt selected from the group consisting of an aromatic halonium salt, an aromatic onium salt of elements belonging to Group VIa in the periodic table and an aromatic onium salt of elements belonging to Group Va in the periodic table is used in combination with an electron donative chromatic organic compound, the foregoing salt releases rapidly color forming components such as Br ⁇ nstead acid, Lewis acid, and the like so as to immediately cause the electron donative chromatic organic compound to color without producing gas bubbles even if irradiated with light.
• the foregoing salt is an extremely superior photoactivator in that the foregoing salt per se has no odious smell and has high durability as well as a long-term preservation property are good due to stability against heat and humidity.
• the compositions in which the foregoing photoactivator is combined with an electron donative chromatic organic compound are superior novel photosensitive compositions in which the disadvantages in the prior art are completely eliminated. This point is the most significant feature of the present invention.
• the photosensitive composition in which a compound having alcoholic hydroxyl groups coexists with the foregoing photosensitive composition (1) could have improvement in color sensitivity without deteriorating the performance of the photosensitive composition (1). This point is a significant feature of the invention.
• the photosensitive composition in which at least one of a compound having oxyethylene groups and basic fine powder coexists with the photosensitive composition (1) could have a property of color disappearance owing to interruption of light irradiation with respect to a coloring matter having color developed owing to light irradiation, that is, a so-called photochromic property, without deteriorating the performance of the photosensitive composition (1). Also this point is a significant feature of the invention.
• the photosensitive composition in which a compound having alcoholic hydroxyl groups coexists with the photosensitive composition (3) could have improvement in color sensitivity without deteriorating the performance of the photosensitive composition (3), and more, could have a property of color disappearance owing to interruption of light irradiation with respect to a coloring matter having color developed owing to light irradiation, that is, a so-called photochromic property. Also this point is a significant feature of the invention.
• color forming components such as Bronstead acid, Lewis acid, and the like, to color sensitively the electron donative chromatic organic compound are released from the photoactivator and then the electron donative chromatic organic compound is colored by these color forming components.
• the photosensitive composition exhibits superior properties in which the electron donative chromatic organic compound is colored in a moment of light irradiation. That is, it is to be supposed that the color forming components such as Br ⁇ nstead acid, Lewis acid, and the like are rapidly produced by the interaction between the photoactivator and the compound having alcoholic hydroxyl groups, so that the electron donative chromatic organic compound donates electrons to the color forming components and color is developed in a moment.
• the electron donative chromatic organic compound is colored by the color forming components such as Bronstead acid, Lewis acid, and the like, released from the photoactivator owing to light irradiation.
• the releasing of the color forming components such as Bronstead acid, Lewis acid, and the like, from the photoactivator is stopped and at the same time at least one of the compound having oxyethylene groups and basic fine powder begins to absorb the color forming components such as Brpnstead acid, Lewis acid, and the like, so that the electron donative chromatic organic compound is decolored.
• the photosensitive composition comprising at least one of the compound having oxyethylene groups and basic fine powder according to the present invention, it is to be supposed that the electron donative chromatic organic compound donates and accepts electrons corresponding to the presence of light, so that color is developed or disappears. That is, the photosensitive composition can be that having so-called photochromic property.
• the electron donative chromatic organic compound used according to the present invention is generally colorless or light-colored, and has the property of color developed by the donation of electrons owing to the action of the color forming components such as Bronstead acid, Lewis acid, and the like.
• the compound to be used triphenylmethane- phthalides, fluorans, phenothiazines, indolylphthalides, leucoauramines, rhodamine lactams, rhodamine lactones, indolines, triphonylmethanes, azaphthalides, chromenoindols, triazenes, etc., are preferable, and triphenylmethanephtha- lides, fluorans, indolylphthalides, leucoauramines, rhodamine lactams, triphenylmethanes, azaphthalides, etc., are more preferable.
• the compound may be used in the combination of two or more compounds
• the photoactivator used according to the present invention that is, the photoactivator selected from the group consisting of an aromatic halonium salt, an aromatic onium salt of elements belonging to Group VIa in the periodic table and an aromatic onium salt of elements belonging to Group Va in the periodic table is a compound being colorless or light-colored, and having the property of releasing the color forming components such as Bronstead acid, Lewis acid, and the like owing to light irradiation, so that the electron donative chromatic organic compound is colored.
• the compound preferably used as the photoactivator is an aromatic halonium salt (a salt of an aromatic halonium and a halogen-containing complex ion of Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, B, P and As); a salt of an aromatic onium of element belonging to Group VIa in the periodic table (O, S, Se, and Te) and a halogen containing complex ion of Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, B, P and As; a salt of an aromatic onium of elements belonging to Group Va in the periodic table (N, P, As, Sb and Bi) and a halogen-containing complex ion of Sb, Fe, Sn, Bi, A1, Ga, In, Ti, Zr, B, P, and As; and a salt of an aromatic onium and a perchloric acid.
• aromatic halonium salt a salt of an aromatic halonium and a halogen-containing complex
• the more preferable compound is aromatic iodonium salt (a salt of an aromatic iodonium and a halogen-containing complex ion of Sb, B, P and As); a salt of an aromatic onium of element belonging to Group VIa in the periodic table (S) and a halogen-containing complex ion of Sb, B, P, and As; a salt of an aromatic onium of elements belonging to Group Va in the periodic table (N and P) and a halogen-containing complex ion of Sb, B, P, and As; and a salt of an aromatic onium and a perchloric acid.
• aromatic iodonium salt a salt of an aromatic iodonium and a halogen-containing complex ion of Sb, B, P and As
• the further preferable compound is a salt of an aromatic iodonium and BF . ; a salt of an aromatic iodonium and PF 6 - ; a salt of an aromatic sulfonium and BF 4 - ; and a salt of an aromatic sulfonium and PF 6 - .
• Aromatic halonium salts :
• Aromatic onium salts of elements belonging to Group VIa in the periodic table are aromatic onium salts of elements belonging to Group VIa in the periodic table:
• the compound having alcoholic hydroxyl groups used in the invention is colorless or light-colored liquid or solid, and has the property of improving a coloring speed at the time of light irradiation as long as it coexists with the electron donative chromatic organic compound and the photoactivator.
• the compound preferably used as the compound having alcoholic hydroxyl groups is an aliphatic alcohol of 6 or more carbon atoms, having a boiling point of 150°C or more; a polyhydric alcohol of 6 or more carbon atoms, having a boiling point of 150°C or more; an aromatic alcohol of 7 or more carbon atoms, having a boiling point of 150°C or more; and a macromolecular alcohol of from about 10,000 through about 300,000 molecular weight.
• the more preferable compound is an aliphatic alcohol of 9 or more carbon atoms, having a boiling point of 200°C or more; an aromatic alcohol of 7 or more carbon atoms, having a boiling point of 200°C or more; a polyhydric alcohol of 6 or more carbon atoms, having a boiling point of 200°C or more; and a macromolecular alcohol of from about 10,000 through about 300,000 in molecular weight.
• Such compounds include an aliphatic alcohol such as hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, docosyl alcohol, melissyl alcohol, oleyl alcohol, cyclohexanol, cyclopentanol, etc.; an aromatic alcohol such as benzyl alcohol, S -phenylethyl alcohol, cinnamyl alcohol, triphenylcarbinol, etc.; a polyhydric alcohol such as ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol, propylene glycol monobutyl ether, propylene glycol monoacrylate, propylene glycol monophenyl ether, butylene glycol, hexylene glycol
• the compound having oxyethylene groups used in the invention is colorless or light-colored liquid or solid, and although it is desired that the compound is miscible with the electron donative chromatic organic compound and the photoactivator, also the compound immiscible therewith can be used.
• the preferable compound is a compound of 100 or more in molecular weight, having 3 or more oxyethylene groups in a molecule, and the more preferable compound is a compound of 190 or more in molecular weight, having 6 or more oxyethylene groups in a molecule.
• Such compounds include diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol dioctyl ether, tetraethylene glycol, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether acetate, polyethylene glycol, oxyethylene-oxypropylene block copolymer, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monoolate, polyoxyethylene sorbitan triolate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene steary
• the compound having alcoholic hydroxyl groups and oxyethylene groups in one molecule has both the property of improving a coloring speed and the property of decoloring color developed by light irradiation.
• the basic fine powder used in the invention is colorless or light-colored and immiscible with the electron donative chromatic organic compound or the photoactivator, having the average particle diameter of about 0.01 U m through about 100 ⁇ m, preferably about 0.1 ⁇ m through about 10 ⁇ m, and pH of 8 through 13.
• the words "immiscible with the electron donative chromatic organic compound or the photoactivator” means that solubility is 1% or less at room temperature.
• Examples of the basic fine powder are generally a hydroxide of alkali metals such as lithium, sodium, potassium, etc., and alkaline-earth metals such as magnesium, calcium, barium, etc., and the carbonate thereof.
• alkali-processed fine powder such as basic fine powder silica, basic montmorillonite, basic talc, basic lead sulfate, basic lead carbonate, etc. can be used.
• the electron donative chromatic organic compound, the compound having alcoholic hydroxyl groups, the compound having oxyethylene groups, and the basic fine powder are available on the market as manufacturing products. Being hard to obtain (although sometimes available on the market), the photoactivator was synthesized on the basis of the above-mentioned literatures.
• the weight proportion of the photoactivator to the electron donative chromatic organic compound is from 0.01 to 100 parts to 1 part, preferably from 0.1 to 10 parts to 1 part, and most preferably from 0.5 to 10 parts to 1 part.
• the weight proportion of the compound having oxyethylene groups to the electron donative chromatic organic compound is from 0.01 to 100 parts to 1 part, preferably from 0.1 to 10 parts to 1 part, and most preferably from 0.5 to 5 parts to 1 part.
• the weight proportion of the basic fine powder to electron donative chromatic organic compound is from 0.01 to 100 parts to 1 part, preferably from 0.1 to 100 parts to 1 part, and most preferably from 0.1 to 10 parts to 1 part.
• the weight proportion of the compound having alcoholic hydroxyl groups to the photoactivator is from 0.01 to 200 parts to 1 part, preferably from 0.1 to 100 parts to 1 part, and most preferably from 0.1 to 20 parts to 1 part.
• the photosensitive composition according to the present invention can be used in its original condition, and can be used also in various conditions in which a support material is coated, printed, or kneaded with it.
• the photosensitive composition (1), (2), (3) or (4) according to the invention can be used in the condition through the steps of: adding essential components and necessary additional components to proper solvent; dissolving or dispersing them at a temperature within a range from room temperature to about 100°C by using a stirrer, disperser, or the like, for the purpose of obtaining photosensitive composition solution; and enclosing the solution in a suitable vessel, printing with the solution on a support material, coating the solution on a support material, impregnating a support material with the solution, or the like, by the use of a printing machine, a writing instrument, etc., or the photosensitive composition according to the invention can be used in the condition through the steps of: kneading essential components and necessary components with being heated and fused; and cooling there up to room temperature.
• the photosensitive composition can be used with various additional components added thereto in accordance with these various modes of use.
• binders such as natural resin, synthetic resin, etc., sensitizers to improve color sensitivity
• masking agent such as titanium white, alumina, etc.
• thickeners such as silica powder, etc.
• pH adjusters such as acid, alkali, etc.
• color tone adjusters such as a dye, a pigment, etc.
• plasticizers various stabilizers, and the like
• the foregoing photosensitive compositions (1), (2), (3) and (4) can be obtained by application of additives at need, by dissolution or dispersion thereof in suitable solvent, or by evaporation of the solvent thereafter.
• the photosensitive compositions obtained as described above are colored by ultraviolet radiation of 400 nm or less wavelength, and particularly, effectively colored by ultraviolet radiation of 250 to 350 nm wavelength.
• Sunlight, mercury-lamp light, black light, xenon-lamp light, ultraviolet laser light, and the like are suitable as a light source.
• the compositions are spectrally sensitized by suitable sensitizers such as, for example, dye such as Acridine Orange (C.I. 46005), Acridine Yellow (C.I. 46025), Phosphine R (C.I. 46045), Benzoflavin (C.I. 46065), Setoflavin T (C.I.
• compositions become colored by visible radiation (sunlight, or tungsten light) of 400 nm or more wavelength. There is no deterioration in properties even after long-term preservation for one year or more.
• the photosensitive composition according to the invention can overcome all the disadvantages of the conventional photosensitive composition, and it can be used under the conditions that it is applied onto paper, plastic sheet, metallic foil, various fiber, glass, ceramic, and the like, by being coated, printed, or impregnated thereon, and under the conditions that it is inserted between two support'materials, or kneaded in support materials such as plastic, wax, or the like, and moreover, it can be produced in the form of ink to thereby use as ink or paint having a photosensitive property. Consequently, the photosensitive composition according to the invention is applicable widely to various industrial materials, recording materials, indicating media, ornamental materials, printing matters, daily necessaries, clothes, writing materials, toys, and so on.
• the color-producing paper was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the paper was superior in color sensitivity and color density.
• the color-producing paper was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the paper was superior in color sensitivity and color density.
• the holographs with this ink were odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the holographs were superior in color sensitivity and color density.
• the film was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the film was superior in color sensitivity and color density.
• the sheet was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the film was superior in color sensitivity and color density.
• a sheet having a photosensitive composition was obtained by the same way as in Example 1. When the sheet was exposed to sunlight for 20 seconds, the exposed portion thereof became red-colored.
• the sheet was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the film was superior in color sensitivity and color density.
• a sheet having a photosensitive composition was obtained by the same way as in Example l. When the sheet was exposed to sunlight for 20 seconds, the exposed portion thereof became orange-colored.
• the sheet was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at time of exposure, and the film was superior in color sensitivity and color density.
• the label was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at time of exposure, and the film was superior in color sensitivity and color density.
• Sheet having a photosensitive composition was obtained in the same way as in Example 1. When the sheet was exposed to sunlight for 20 seconds, the exposed portion thereof became blue-colored.
• the sheet was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at time of exposure, and the film was superior in color sensitivity and color density.
• Sheet having a photosensitive composition was obtained in the same way as in Example 1.
• the sheet was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the film was superior in color sensitivity and color density.
• Sheet having a photosensitive composition was obtained in the same way as in Example 1. When the sheet was exposed to sunlight for 20 seconds, the exposed portion thereof became orange-colored.
• the sheet was odorless, and superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the film was superior in color sensitivity and color density.
• the label was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• a sheet having photochromic property was obtained in the same way as in Example 26.
• the exposed portion became blue-colored.
• the sheet was left with interruption of light irradiation at room temperature for 24 hours thereafter, the sheet was returned to an original white color. Although the appearance and disappearance of color were repeated 20 times, little deterioration in the property was seen.
• a sheet having photochromic property was obtained in the same way as in Example 27.
• the exposed portion became black-colored.
• the sheet was left with interruption of light irradiation at room temperature for 12 hours thereafter, the sheet was returned to an original white color. Although the appearance and disappearance of color were repeated 20 times, little deterioration in the property was seen.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• a colorless crayon was obtained in the same way as in Example 32, except that Pergascript Red I-6B was used instead of S-205.
• a colorless crayon was obtained in the same way as in Example 32, except that Green 24P was used instead of S-205.
• a colorless crayon was obtained in the same way as in Example 32, except that NBP-1 was used instead of S-205.
• a colorless crayon was obtained in the same way as in Example 32, except that OR-55 was used instead of S-205.
• the label was superior in heat-proof, humidity-proof, and preservation properties.
• a yellow sheet having photochromic property was obtained in the same way as in Example 37.
• the exposed portion became green-colored.
• the sheet was left with interruption of light irradiation at room temperature for 24 hours thereafter, the sheet was returned to an original yellow color. Although the appearance and disappearance of color were repeated 10 times, little deterioration in the property was seen.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the paper was superior in color sensitivity and color strength.
• the sheet was superior in heat-proof, humidity-proof, and preservation properties. Moreover, gases or air bubbles were not generated at the time of exposure, and the paper was superior in color sensitivity and color density.
• the photosensitive compositions according to the present invention have abundant kinds of color productions, are superior in heat-proof, humidity-proof, and preservation properties, and can be used as a useful material in a wide field.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Materials For Photolithography (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Cited By (6)

• 1985
  • 1985-09-06 DE DE198585111294T patent/DE175238T1/de active Pending
  • 1985-09-06 AU AU47154/85A patent/AU4715485A/en not_active Abandoned
  • 1985-09-06 NO NO853494A patent/NO853494L/no unknown
  • 1985-09-06 EP EP85111294A patent/EP0175238A2/de not_active Withdrawn

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