US3773508A - Imagewise exposing and heating a photosensitive composition containing a spiropyran compound and an organic peroxide - Google Patents
Imagewise exposing and heating a photosensitive composition containing a spiropyran compound and an organic peroxide Download PDFInfo
- Publication number
- US3773508A US3773508A US00199382A US3773508DA US3773508A US 3773508 A US3773508 A US 3773508A US 00199382 A US00199382 A US 00199382A US 3773508D A US3773508D A US 3773508DA US 3773508 A US3773508 A US 3773508A
- Authority
- US
- United States
- Prior art keywords
- group
- organic peroxide
- carbon atoms
- heating
- molecular weight
- 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 - Lifetime
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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
- G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/163—Radiation-chromic compound
Definitions
- ABSTRACT Permanent photochromic images are obtained by selectively exposing a photochromic compound and an organic peroxide in a resin binder to ultraviolet radiation and thereafter heating the element whereby a reaction occurs in the exposed areas to provide the permenent images.
- the present invention relates to a new process for forming images, In more detail, the present invention relates to a process for forming images which comprises reacting an organic compound which was altered by ultraviolet radiation absorption with another organic compound.
- Photochromic compound whose color varies upon absorption of ultraviolet rays are generally called photochromic compound. These compounds are usually in a stable colorless state when exciting rays such as ultraviolet rays are not applied thereto. However, when ultraviolet rays are applied thereto, they change into an unstable colored state which has a different absorption spectrum. It is believed that such a change is brought about by the state of the electrons in the molecule of the photochromic compound changing to an unstable high energy state from a stabel low energy state by absorption of the ultraviolet rays. By such a change the molecule isomerized and the colorless molecule changes into the colored state.
- the general image forming process of the present invention is as follows. A photochromic compound and an organic peroxide are subject to dissolution in a solution containing a high molecular weight compound. The solution is then applied to paper and dried. A photographic transparent negative film is put onto the resulting element. By applying ultraviolet rays thereto, a positive photochromic image is produced by coloring only the portion of the element through which the ray pass. By leaving the positive image element in the dark or by heating the resulting positive image element, the colored part selectively reacts with the organic peroxide to change into another color. The resulting image does not fade any longer and remains as apermanent image. In the prior light-coloring materials which do not contain an organic peroxide, the formed images automatically fade and return to their initial colorless state. Thus, it becomes possible in accordance with the present invention to obtain permanent images using a photochromic compound.
- the image recording process of the present invention has the advantage of being a dry treatment because development is not required and the image can be fixed by heating.
- the photochromic compound used in the present invention can be represented by the general formula
- Ra Rs 4/ xiqd 2 I N i Q 7 8 7 Rt R z lower alkyl group (carbon atoms: 1-5), substituted alkyl group (carbon atoms: l-5, substituent: carboxyl group, cyano group and ester group) or phenyl group; R and R lower alkyl group (carbon atoms: l-5), phenyl group, or R,+R CH (n 4 or 5);
- X hydrogen atom, nitro group, halogen atom, carboxyl group, alkoxycarbonyl group, lower alkyl group or alkoxy group, which prefered carbon atom range for the last three groups being l-5 carbon atoms, though higher carbon atom chains can be used.
- Y where m is l or 2 and Y is one or more nitro groups, halogen atoms, aldehyde groups or alkoxy groups, with preferred alkoxy groups having l-2 carbon atoms, though higher carbon atom chains can be used.
- Preferred Examples of Y are as follows:
- Such compounds can be formed in accordance with the teaching of U.S. Pat. No. 3,022,318 or No. 2,953,454.
- the photochromic compounds can be used solely or as a mixture of two or more thereof.
- organic peroxide used there are, for example, diacylperoxides, dialkylperoxides, hydroperoxide, ketoneperoxides and peroxyesters.
- Organic peroxides which are decomposed at l30C are preferred.
- the resin used as the medium of the layer containing the photochromic compound and the organic peroxide there can be used any synthetic high molecular weight compound which is soluble in common organic solvents, for example, polyvinyl acetate, polystyrene, polyvinylchloride, polyethylmethacrylate, polymethylmethacrylate, polymethylacrylate, and copolymers of the monomers of the above-mentioned polymers, cellulose butyrate acetate, polyvinylbutyral, cellulose acetate and polyvinylacetal.
- polyvinyl acetate polystyrene
- polyvinylchloride polyethylmethacrylate
- polymethylmethacrylate polymethylacrylate
- copolymers of the monomers of the above-mentioned polymers cellulose butyrate acetate, polyvinylbutyral, cellulose acetate and polyvinylacetal.
- the high molecular weight compound utilized should illustrate the following characteristics, i.e., the material should have a molecluar weight sufficient to maintain the photochromic compound in suspension, i.e., the resin binder is a solid, it should not be decomposed at heating temperature and it should be substantially transparent.
- a molecular weight of from about 10,000 to about 70,000 is preferred, with a most preferred molecular weight range being 40,000 to'60,000.
- Preferred organic solvents include acetone, benzene, toluene xylene, cyclohexanone, carbone tetand rachloride, buthyl acetate, ethyl acetate ester, methylethylketone, gamma-butyl lactone, cellosolve, methyl cellosolve, cellosolve acetate, methyl cellosolve acetate etc.
- a preferred amount of the photochromic compound is 0.1-l percent (by weight) based on the weight of the resin. Most preferably 2-5 percent.
- a preferred amount of the organic peroxide is 5-30 percent and especially about percent (by weight) based on the weight of the photochromic compound.
- a light-sensitive element is accordance with the present invention can be produced by applying a solution containing the above-mentioned photochromic compound, organic peroxide and resin dissolved in an organic solvent onto a support such as, paperand high molecular weight polymer films, and drying the same.
- the temperature of drying is not critical and is usually a room temperature to 80C.
- a dianegative is put onto the resulting element. After applying ultraviolet rays thereto, the element is heated to approximately 70-90C for about 5 to about 10 seconds, by which an image is easily obtained in which only the light-exposed part changes into a reddishorange color which is a permanent image.
- EXAMPLE 1 A solution composed of 1 part (hereinafter, all parts are by weight) of l,3,3-trimethyl-6'-nitro (indoline-2, 2'-2'H-chromene), 0.05 parts of benzoyl peroxide and 50 parts of a 20 percent benzene solution of polystyrene (m.w. 40,000) was applied to paper having a 80 p. thickness. The resulting element was colorless in the normal state. A dianegative was put on the element and ultraviolet rays were appled. Exposure to ultraviolet rays was carried out using an ultraviolet ray lamp (Toshiba SHL-IOO) as the light source for 30 seconds at a distance of approximately cm. In the following, examples, exposure was also carried out under the same conditions.
- an ultraviolet ray lamp Toshiba SHL-IOO
- EXAMPLE 2 A solution composed of 1 part of 1,3,3-trimethyl-5- methoxy-6'-nitro spiro(indoline-2,2'-2H-chromene), 0.5 parts of lauroyl peroxide and 50 parts of a percent ethyl acetate solution of polyvinyl acetate (m.w. 30,000) was applied to baryta paper and dried to provide a 5 11. thick layer. After ultraviolet rays were applied to the resulting element by the same procedure as in Example 1, the element was heated, by which a reddish orange permanent image was obtained.
- EXAMPLE 3 A solution composed of I part of l-gammaethoxycaronyl-ethyl-3,3-dimethyl-5-chloro-6'-nitro spiro (indoline-2,2'-2H-chromene), 0.1 parts of acetyl peroxide and 100 parts ofa 20 percent ethyl acetate solution of polyethylmethacrylate (m.w. 30,000) was applied to a polyethylene terephthalate film having a 80 1. thickness. A reddish-orange image was obtained by treating the resulting element by the same procedure as in Example I. The resulting image did not fade any longer by heating or by storage after image formation.
- EXAMPLE 4 A solution composed of 1 part of 1,3,3-trimethyl-5- ethoxycarbonyl-6-nitro-8-methoxy spiro(indoline- 2,2'-2'H-chromene), 0.2 parts of benzoyl peroxide and 50 parts of a 20 percent ethyl acetate solution of polyvinyl acetate was applied to a paper support. A reddish orange permanent image was obtained by treating the resulting element by the same procedure as in Example 1.
- a process for forming a permanent image which comprises selectively exposing to ultraviolet radiation a composition comprising a photochromic compound, an organic peroxide and a high molecular weight resin as a binder, and thereafter heating said exposed composition, in order to promote the reaction between said peroxide and said photochromic compound, whereby the exposed portion colors reddish-orange, said photochromic compound having the formula:
- R is a lower alkyl group, a substituted alkyl group or a phenyl group
- R and R are lower alkyl groups, a phenyl group or R and R, combine to form (Cl-l Where n is 4 or 5
- X is a hydrogen atom, nitro group, halogen atom, carboxyl group, alkoxy-carbonyl group, lower alkyl group or alkoxy group
- Ym is one or more member of nitro, halogen, aldehyde or alkoxy, where n is l or 2
- said composition comprises 0.1 to l0 percent by weight of said photochromic compound based on said resin and from 5 to 30 percent by weight of said organic peroxide based on said photochromic compound.
- organic peroxide is selected from the group consisting of diacyl peroxides, dialkyl peroxides, hydroperoxide, ketone peroxides and peroxyesters.
- said high molecular weight resin binder is a synthetic high molecular weight compounds suluble in organic solvents is selected from the group consisting of polyvinyl acetate, polystyrene, polyvinyl chloride, polymethylmethacrylate, polyethylmethacrylate, polymethylacrylate, copolymers of the monomers of the above compounds, cellulose acetate, cellulose butyrate acetate, polyvinyl butyral and polyvinyl acetal.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP45102198A JPS4923897B1 (cs) | 1970-11-19 | 1970-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3773508A true US3773508A (en) | 1973-11-20 |
Family
ID=14320947
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00199382A Expired - Lifetime US3773508A (en) | 1970-11-19 | 1971-11-16 | Imagewise exposing and heating a photosensitive composition containing a spiropyran compound and an organic peroxide |
Country Status (5)
Country | Link |
---|---|
US (1) | US3773508A (cs) |
JP (1) | JPS4923897B1 (cs) |
DE (1) | DE2157542A1 (cs) |
FR (1) | FR2114747A5 (cs) |
GB (1) | GB1356840A (cs) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4725527A (en) * | 1984-12-30 | 1988-02-16 | Richard L. Scully | Photosensitive compositions for direct positive color photography |
US5155230A (en) * | 1989-02-27 | 1992-10-13 | Matsushita Electric Industrial Co., Ltd. | Photochromic dinitrated spiropyrans |
US5501945A (en) * | 1994-08-30 | 1996-03-26 | The University Of Akron | Method of using multichromic polymers in packaging |
CN108148576A (zh) * | 2018-03-05 | 2018-06-12 | 天津孚信阳光科技有限公司 | 一种有色变无色光致变色化合物及其制备方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7604219A (nl) * | 1975-04-24 | 1976-10-26 | Cellophane Sa | Werkwijze voor het bereiden van gestabiliseerde fotochrome preparaten en registratiematerialen vervaardigd met behulp van deze preparaten. |
JP2722635B2 (ja) * | 1989-03-30 | 1998-03-04 | 松下電器産業株式会社 | フォトクロミック材料の製造方法 |
DE19646820C2 (de) * | 1996-11-13 | 2001-03-01 | Volker Bus | Optisch aktive Spiropyranverbindungen, Verfahren zu ihrer Herstellung und diese Spiropyrane enthaltende Materialien |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3320067A (en) * | 1963-09-03 | 1967-05-16 | Polaroid Corp | Composition and process utilizing photospirans |
US3355293A (en) * | 1964-02-26 | 1967-11-28 | Ncr Co | Conversion of benzo-indolinospiropyran image to fixed red image |
US3501410A (en) * | 1966-07-06 | 1970-03-17 | Eastman Kodak Co | Benzopyrylospiran photochrome containing an electron acceptor |
US3642479A (en) * | 1970-03-02 | 1972-02-15 | Eastman Kodak Co | Photographic element and process |
-
1970
- 1970-11-19 JP JP45102198A patent/JPS4923897B1/ja active Pending
-
1971
- 1971-11-16 FR FR7140953A patent/FR2114747A5/fr not_active Expired
- 1971-11-16 US US00199382A patent/US3773508A/en not_active Expired - Lifetime
- 1971-11-17 GB GB5346971A patent/GB1356840A/en not_active Expired
- 1971-11-19 DE DE19712157542 patent/DE2157542A1/de active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3320067A (en) * | 1963-09-03 | 1967-05-16 | Polaroid Corp | Composition and process utilizing photospirans |
US3355293A (en) * | 1964-02-26 | 1967-11-28 | Ncr Co | Conversion of benzo-indolinospiropyran image to fixed red image |
US3501410A (en) * | 1966-07-06 | 1970-03-17 | Eastman Kodak Co | Benzopyrylospiran photochrome containing an electron acceptor |
US3642479A (en) * | 1970-03-02 | 1972-02-15 | Eastman Kodak Co | Photographic element and process |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4725527A (en) * | 1984-12-30 | 1988-02-16 | Richard L. Scully | Photosensitive compositions for direct positive color photography |
US5155230A (en) * | 1989-02-27 | 1992-10-13 | Matsushita Electric Industrial Co., Ltd. | Photochromic dinitrated spiropyrans |
US5501945A (en) * | 1994-08-30 | 1996-03-26 | The University Of Akron | Method of using multichromic polymers in packaging |
CN108148576A (zh) * | 2018-03-05 | 2018-06-12 | 天津孚信阳光科技有限公司 | 一种有色变无色光致变色化合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE2157542A1 (de) | 1972-05-25 |
GB1356840A (en) | 1974-06-19 |
JPS4923897B1 (cs) | 1974-06-19 |
FR2114747A5 (cs) | 1972-06-30 |
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