Camera toy set

Abstract

To provide a toy camera set comprising a photochromic printed matter including a reversible photochromic image, and a toy camera including an opening part for taking in and out the photochromic printed matter and a light source for discoloring the reversible photochromic image, when the photochromic printed matter is inserted or stored in the toy camera, appearing an image on the photochromic printed matter, making a user feel as if taking a photograph using a real camera, and allowing the user to easily play therewith.SOLUTION: A toy camera set comprises, on a support body, a photochromic printed matter including a reversible photochromic material composed of at least a photochromic compound, and a toy camera imitating an external appearance of a camera. The toy camera includes an opening part in a camera body for taking in and out the photochromic printed matter, and a light source inside the camera body.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a toy camera set, and more particularly to a toy camera set capable of causing an image such as a photograph or a picture to appear on a printed matter inserted or housed in the toy camera by a light source provided in the toy camera. [Background technology]

[0002] Conventionally, a toy camera has been disclosed in which a camera body has an opening for inserting and removing a base plate having water-colored paper attached thereto, the base plate comprising a water-permeable colored layer carrying a predetermined picture on top of a water-permeable background color layer that contains a low refractive index pigment and has a different hue from the colored layer, and further the camera body is fitted with a water-retaining member that comes into contact with the water-colored paper and wets it (see, for example, Patent Document 1). The above-mentioned camera toy is a toy that allows a user to feel as if he or she is using an instant camera in which a photographed picture is instantly developed and comes out, by placing a plain water-colored paper on a base plate and pushing it in, and thus allows a user to feel as if he or she is using an instant camera when the picture is instantly developed and comes out when the base plate is pulled out. However, since a real camera does not use water, the above-mentioned camera toy is easily devoid of the feeling of using a real camera and lacks realism. In addition, every time the water in the water-containing member runs out, it is necessary to remove the water-containing member from the camera body and allow the water-containing member to absorb water, which makes playing with the above-mentioned camera toy troublesome. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Microfilm of Jikkai No. 55-27567 Summary of the Invention [Problem to be solved by the invention]

[0004] To provide a toy camera set comprising a photochromic print having a reversible photochromic image, an opening for inserting and removing the photochromic print, and a toy camera having a light source for discoloring the reversible photochromic image. [Means for solving the problem]

[0005] The present invention comprises a photochromic printed matter having a reversible photochromic image formed on a support and containing a reversible photochromic material at least consisting of a photochromic compound, and a toy camera imitating the appearance of a camera, the toy camera having an opening in the camera body for inserting and removing the photochromic printed matter, and a light source provided inside the camera body. The reversible photochromic image is an image formed by process printing using at least three colors of photochromic printing inks, each of which is prepared by dispersing the reversible photochromic materials, which develop colors of cyan, magenta, and yellow when irradiated with light, in a vehicle. The requirement is that the toy camera set be Furthermore, the light source has a peak wavelength in the range of 400 to 495 nm; a power source is further provided in the camera body or inside the camera body, and the power source and the light source are connected by wires; the camera body is further provided with a switch that is pressed to energize, and the switch, the power source, and the light source are connected by wires; and the reversible photochromic material further contains an oligomer. ,before The photochromic compound in the reversible photochromic material is a spirooxazine compound for cyan and a naphtha compound for magenta. J It is a pyran compound, and the yellow color is naphtho. J It is a pyran compound. The photochromic compound in the reversibly photochromic material is a compound represented by the following general formula (1) for cyan, a compound represented by the following general formulas (2) to (4) for magenta, and a compound represented by the following general formula (6) or (7) for yellow: The requirements are as follows. [ka] (In the formula, R 1 、R 2 Each represents an alkyl group having 1 to 3 carbon atoms, and R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, a mono-, di-, or tri-substituted phenyl group, or an alkoxy group; R 4 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, a mono-, di-, or tri-substituted phenyl group, an alkoxy group, a morpholino group, an alkoxycarbonyl group, or a cyano group, and A represents =CH- or =N-. [ka] [In the formula, R 5 ~R 8 represents the following general formula (5), and R 11 ~R 14 represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; R15 indicates an alkyl group having 3 or more carbon atoms, and * indicates the bonding site with the pyran skeleton. [ka] [ka] [In the formula, R 9 ~R 12 represents the following general formula (8), and R 21 ~R 24 represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; R 25 indicates a hydrogen atom, a methoxy group, or an ethoxy group, and * indicates the bonding site with the pyran skeleton. [ka] Effect of the Invention

[0006] The present invention provides a camera toy set that is highly playful and easy to play with, comprising a photochromic printed material with a reversible photochromic image, an opening for inserting and removing the photochromic printed material, and a camera toy equipped with a light source that discolors the reversible photochromic image, and when the photochromic printed material is inserted or stored in the camera toy, an image such as a photograph or picture appears on the photochromic printed material, allowing the user to experience the feeling of having taken a photograph using a real camera. [Brief description of the drawings]

[0007] [Figure 1] 1 is a perspective view of an embodiment of a camera toy set of the present invention; [Diagram 2] 2 is a perspective view illustrating a state in which a photochromic printed matter is inserted into the toy camera in the toy camera set of FIG. 1. FIG. [Diagram 3] FIG. 1 is a longitudinal sectional view of an embodiment of a photochromic printed matter used in the present invention. [Figure 4] FIG. 4 is a vertical cross-sectional view of another embodiment of a photochromic printed matter used in the present invention. [Diagram 5] FIG. 4 is a vertical cross-sectional view of another embodiment of a photochromic printed matter used in the present invention. [Figure 6]1 is a plan view of an embodiment of a camera toy used in the present invention. [Figure 7] 7 is a plan view showing the internal structure of the camera toy of FIG. 6. [Figure 8] FIG. 13 is a plan view of another embodiment of a camera toy used in the present invention. [Figure 9] 9 is a plan view showing the internal structure of the camera toy of FIG. 8. [Figure 10] FIG. 11 is a perspective view of another embodiment of a camera toy set of the present invention. [Figure 11] 11 is a perspective view showing a state in which a photochromic printed material and a non-photochromic printed material are inserted into the camera toy set of FIG. 10. FIG. [Figure 12] FIG. 1 is a longitudinal sectional view of an embodiment of a non-discoloring printed matter used in the present invention. [Figure 13] FIG. 11 is a perspective view showing the internal structure of another embodiment of a camera toy used in the present invention. [Figure 14] FIG. 14 is a perspective view showing the internal structure of the toy camera in FIG. 13 with a photochromic printed matter inserted therein. [Figure 15] FIG. 11 is a perspective view showing the internal structure of another embodiment of a camera toy used in the present invention. [Figure 16] 16 is a perspective view showing the internal structure of the camera toy of FIG. 15 in a state in which a photochromic printed material and a non-photochromic printed material are inserted. FIG. [Figure 17] FIG. 2 is a perspective view showing the internal structure of the erasing tool used in the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The toy camera set of the present invention comprises a photochromic printed matter (hereinafter sometimes referred to as "printed matter") having a reversible photochromic image comprising a reversible photochromic material consisting at least of a photochromic compound (hereinafter sometimes referred to as "compound") provided on a support, and a toy camera imitating the appearance of a camera (see Figure 1).

[0009] The support applicable to the present invention is not particularly limited, and examples thereof include paper, synthetic paper, fabrics such as fibers, knitted fabrics, woven fabrics, and nonwoven fabrics, synthetic leather, leather, plastics, glass, elastomers, rubber, ceramics, metals, wood, stone, etc., and paper, synthetic paper, and plastics are preferred because of their excellent durability and ease of handling. In addition, the form of the support is preferably a flat, sheet, or film shape.

[0010] The reversible photochromic material used in the present invention is composed of at least a photochromic compound, such as a spirooxazine derivative, a spiropyran derivative, or a naphthopyran derivative.

[0011] Examples of the spirooxazine derivative include indolinospirobenzoxazine compounds, indolinospironaphthoxazine compounds, indolinospirophenanthrooxazine compounds, and indolinospiroquinolinoxazine compounds.

[0012] Examples of indolinospirobenzoxazine compounds include: 1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 6′-chloro-5-fluoro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 3,3-Dimethyl-1-ethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5,7-difluoro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-cyano-3,3-dimethyl-1-(methoxycarbonyl)methyl spiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 1′-Methyldispiro[cyclohexane-1,3′-[3H]indole-2′(1′H),3″-[3H]pyrido[4,3-f][1,4]benzoxazine], 1′-Methyl-5′-nitrodispiro[cyclopentane-1,3′-[3H]-indole-2′(1′H),3″-[3H]pyrido[4,3-f][1,4]benzoxazine], 1,3,3,5′-tetramethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 6′-fluoro-1′-methyldispiro[cyclohexane-1,3′-[3H]indole-2′(1′H),3″-[3H]pyrido[4,3-f][1,4]benzoxazine], 1-benzyl-6′-chloro-3,3-dimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 6′-Methoxy-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-chloro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-Bromo-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-iodo-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-trifluoromethyl-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 3,3-diethyl-1-methylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 1,3,3,6′-tetramethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 6-chloro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5′-fluoro-1′-methyldispiro[cyclohexane-1,3′-[3H]indole-2′(1′H),3″-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-cyano-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-ethoxycarbonyl-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 4′,6′-difluoro-1′-methyldispiro[cyclohexane-1,3′-[3H]indole-2′(1′H),3″-[3H]pyrido[4,3-f][1,4]benzoxazine], 3,3-Dimethyl-1-(methoxycarbonyl)methylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 3,3-Dimethyl-1-phenylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 5-Methoxy-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 1,3,3,5-tetramethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 7′-chloro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 1,3,3,7′-tetramethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 7′-Methoxy-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine], 1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 6′-chloro-5-fluoro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 5-chloro-1,3-dimethyl-3-ethyl-5′-methoxyspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 3,3-diethyl-1-methyl-5-nitrospiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 1′,6′-dimethylspiro[cyclohexane-1,3′-[3H]indole-2′(1′H),3″-[3H]pyrido[2,3-f][1,4]benzoxazine], 9″-Bromo-1′-methoxycarbonylmethyl-5′-trifluoromethyldispiro[cyclopentane-1,3′-[3H]-indole-2′[1′H],3″-[3H]pyrido[2,3-f][1,4]benzoxazine], 1-benzyl-3,3-di-n-butyl-7′-ethyl-5-methoxyspiro[2H-indole-1,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 1′-n-Butyl-6′-iododispiro[cycloheptane-1,3′-[3H]-indole-2′(1′H),3″-[3H]pyrido[2,3-f][1,4]benzoxazine], 3,3-Dimethyl-9′-iodo-1-naphthylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 4'-cyano-1'-[2-(methoxycarbonyl)ethyl]dispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3"-[3H]pyrido[2,3-f][1,4]benzoxazine], 7-Methoxycarbonyl-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 4-bromo-3,3-diethyl-9′-ethoxy-1-(2-phenyl)ethyl spiro[2H-indole-2,3′-[2,3-f][1,4]benzoxazine], 1′-Methyldispiro[cyclohexane-1,3′-[3H]-indole-2′(1′H),3″-[3H]pyrido[2,3-f][1,4]benzoxazine], 6-fluoro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 5-ethyl-9-fluoro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 1′-benzyl-6″-iododispiro[cyclopentane-1,3′-[3H]-indole-2′(1′H),3″-[3H]pyrido[2,3-f][1,4]benzoxazine], 5-ethoxy-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 1′-Methyl-5′-trichloromethyldispiro[cyclohexane-1,3′-[3H]-indole-2′(1′H),3″-[3H]pyrido[2,3-f][1,4]benzoxazine], 1,3-diethyl-3-methylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine], 1'-Methoxycarbonylmethyldispiro[cyclohexane-1,3'-[3H]-indole-2'(1'H)-[3H]pyrido[2,3-f][1,4]benzoxazine] and the like, and examples of the substituents such as halogen atoms, methyl groups, ethyl groups, methylene groups, ethylene groups, and hydroxyl groups on the indole ring and benzene ring of indolinospirobenzoxazine.

[0013] Examples of the indolinospironaphthoxazine compounds include: 1,3,3-trimethyl-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-chloro-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-bromo-spiroindolinonaphthoxazine, 1,3,3,5-tetramethyl-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-n-propyl-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-isobutyl-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-methoxy-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-n-propoxy-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-cyano-spiroindolinonaphthoxazine, 1-n-propyl-3,3-dimethyl-spiroindolinonaphthoxazine, 1-isobutyl-3,3-dimethyl-spiroindolinonaphthoxazine, 1-n-octyl-3,3-dimethyl-spiroindolinonaphthoxazine, 1-n-octadecyl-3,3-dimethyl-spiroindolinonaphthoxazine, Sodium 1,3,3-trimethyl-8′-sulfonate-spiroindolinonaphthoxazine, 1,3,3-trimethyl-9′-methoxy-spiroindolinonaphthoxazine, 1,3,3-trimethyl-8′-cyano-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5-trifluoro-spiroindolinonaphthoxazine, 1-(4′-methylphenyl)-3,3-dimethyl-spiroindolinonaphthoxazine, 1,3,3-trimethyl-6′-(2,3-dihydro-1-indolino)-spiroindolinonaphthoxazine, 1,3,3-trimethyl-6′-(1-piperidinyl)-spiroindolinonaphthoxazine, 1,3,3-trimethyl-6′-(1-morpholino)-spiroindolinonaphthoxazine, 1-ethyl-3,3-dimethyl-6-trifluoromethyl-6′-(1-morpholino)-spiroindolinonaphthoxazine, 1,3,3-trimethyl-6-trifluoromethyl-6′-(1-piperidinyl)-spiroindolinonaphthoxazine, 1-benzyl-3,3-dimethyl-spiroindolinonaphthoxazine, 1-(4-methoxybenzyl)-3,3-dimethyl-spiroindolinonaphthoxazine, 1-(4-chlorobenzyl)-3,3-dimethyl-spiroindolinonaphthoxazine, 1-ethyl-3,3-dimethyl-spiroindolinonaphthoxazine, 1-isopropyl-3,3-dimethyl-spiroindolinonaphthoxazine, 1-(2-phenoxyethyl)-3,3-dimethyl-spiroindolinonaphthoxazine, 1,3-dimethyl-3-ethyl-spiroindolinonaphthoxazine, 1,3,3-trimethyl-9′-hydroxy-spiroindolinonaphthoxazine, 1,3-dimethyl-3-ethyl-8′-hydroxy-spiroindolinonaphthoxazine, 1,3,3,5-tetramethyl-9′-methoxy-spiroindolinonaphthoxazine, 1,3,3,5,6-pentamethyl-9′-methoxy-spiroindolinonaphthoxazine, 1,3,3-trimethyl-4-trifluoromethyl-5′-methoxy-spiroindolinonaphthoxazine, 1,3,3-trimethyl-5′-methoxy-6′-trifluoromethyl-spiroindolinonaphthoxazine, 1,3,3-trimethyl-4-trifluoromethyl-9′-methoxy-spiroindolinonaphthoxazine, 1,3,5,6-tetramethyl-3-ethyl-spiroindolinonaphthoxazine, 1,3,3,5,6-pentamethyl-spiroindolinonaphthoxazine, 1-methyl-3,3-diphenyl-spiroindolinonaphthoxazine, 1-(4-methoxybenzyl)-3,3-dimethyl-spiroindolinonaphthoxazine, 1-(3,5-dimethylbenzyl)-3,3-dimethyl-spiroindolinonaphthoxazine, 1-(2-Fluorobenzyl)-3,3-dimethyl-spiroindolinonaphthoxazine and the like, and examples of the substituents such as halogen atoms, methyl groups, ethyl groups, methylene groups, ethylene groups, and hydroxyl groups on the indole ring and benzene ring of indolinospironaphthoxazine.

[0014] Examples of the indolinospirophenanthrooxazine compounds include: 1,3,3-trimethyl-spiroindolinophenanthrooxazine, 1,3,3-trimethyl-5-chloro-spiroindolinophenanthrooxazine and the like, and examples of the substituents such as halogen atoms, methyl groups, ethyl groups, methylene groups, ethylene groups and hydroxyl groups on the indole ring and benzene ring of indolinospirophenanthrooxazine.

[0015] Examples of the indolinospiroquinolinoxazine compounds include: 1,3,3-trimethyl-spiroindolinoquinolinoxazine and the like, and examples of the substituents such as halogen atoms, methyl groups, ethyl groups, methylene groups, ethylene groups, and hydroxyl groups on the indole ring and benzene ring of indolinospiroquinolinoxazine.

[0016] Examples of the spiropyran derivative include 1,3,3-trimethyl-indolinobenzopyrilospiran, 1,3,3-trimethylindolino-6′-bromobenzopyrilospiran, 1,3,3-trimethylindolino-8′-methoxybenzopyrilospiran, 1,3,3-trimethylindolino-β-naphthopyrilospiran, 1,3,3-Trimethylindolino-6'-nitrobenzopyrilospiran Examples include:

[0017] Examples of naphthopyran derivatives include 3,3,9,9-tetraphenyl-3H,9H-naphtho[2,1-b:6,5-b′]dipyrane, 3,3,10,10-tetraphenyl-3H,10H-naphtho[2,1-b:7,8-b′]dipyrane, 3,3,9,9-tetraphenyl-3H,9H-naphtho[4,3-b:8,7-b′]dipyrane, 3,3-diphenyl-9-methoxy-3H-naphtho[4,3-b]pyran, 3,3-diphenyl-10-methyl-3H-naphtho[2,1-b:5,6-b′]dipyran-8-one, 3,3,9,9-tetra(4′-methoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]dipyrane, 3,3-diphenyl-8-[2-(4-dimethylamino)phenyl]ethene-3H-naphtho[4,3-b]pyran, 3,3-diphenyl-5-acetoxy-3H-naphtho[4,3-b]pyran, 3,3-Diphenyl-8-(1H-benzotriazol-1-yl)carbonyl-3H-naphtho[4,3-b]pyran Examples include:

[0018] As the photochromic compound, a compound having a photomemory property (color memory photochromic property) can be used. As the photochromic compound having a photomemory property, a diarylethene derivative or the like can be mentioned.

[0019] Examples of diarylethene derivatives include 1-(1,2-dimethyl-3-indolyl)-2-(2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1-(2-methyl-5-phenyl-3-thienyl)-2-(5-methyl-2-phenyl-4-thiazolyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2-methoxy-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2-methoxy-5-methyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2-methyl-6-nitro-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(6-amino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(6-amino-2-ethyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2-methyl-6-(1-pyrrolidino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(6-diethylamino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(6-acetylamino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2-methyl-6-(1-piperidino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(6-dibenzylamino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2-butyl-6-(1-piperidino)-3-benzofuranyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2-methyl-6-(1-morpholino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(3-methoxy-2-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2-methyl-6-nitro-3-benzofuranyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(3-methyl-2-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(3-methyl-2-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1-(2-methyl-3-benzothienyl)-2-(3-methyl-2-benzofuranyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1-(2-methyl-5-phenyl-3-thienyl)-2-(3-methyl-2-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2-butyl-6-nitro-3-benzofuranyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2-methyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1-(5-phenyl-2-methyl-3-thienyl)-2-(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2,4-dimethyl-5-(4-methoxyphenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[5-(4-dimethylaminophenyl)-2-methyl-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1-[2-methyl-5-(4-methylphenyl)-3-thienyl]-2-[2,4-dimethyl-5-(4-methylphenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1-[2-methyl-5-(4-methoxyphenyl)-3-thienyl]-2-[2,4-dimethyl-5-(4-methoxyphenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1-[2-methyl-5-(4-methylphenyl)-3-thienyl]-2-[2,4-dimethyl-5-(4-methoxyphenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2,4-dimethyl-5-(4-dimethylaminophenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2,4-dimethyl-5-(2-phenylethenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2,4-dimethyl-5-(4-aminophenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1-(2,4-dimethyl-5-phenyl-3-thienyl)-2-[2,4-dimethyl-5-(2-phenylethenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(2-ethyl-6-nitro-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2-ethyl-6-(5-methyl-2-thienyl)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis[2-ethyl-6-(1-piperidino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-bis(6-dibenzylamino-2-ethyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene, 1,2-Bis[2-ethyl-6-(1-morpholino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene Examples include:

[0020] When a diarylethene-based photochromic compound is used as the photochromic compound, the compound maintains its colored state when it is colored by a light source with a peak wavelength in the range of 400 to 495 nm. Therefore, a photochromic printed matter using a diarylethene-based photochromic compound as a reversible photochromic material can maintain the image displayed by irradiating it with light from a light source. Furthermore, the image that appears on the printed matter can be erased by using an erasing tool that erases the colored diarylethene photochromic compound. Examples of the decolorizing device include a decolorizing device equipped with a light source whose main light emission region is in the visible light region of 500 nm or more, and a decolorizing device which contains a light-shielding pigment and / or dye that blocks light with a wavelength of less than 500 nm, including ultraviolet light, and optionally an ultraviolet absorber, and which cuts out light with a wavelength of less than 500 nm, including ultraviolet light, and decolorizes a diarylethene photochromic compound in a colored state by irradiating it with visible light with a wavelength of 500 nm or more, thereby shifting the compound to the decolorized state and maintaining it there. It may also be a molded product in the form of a sheet, filament, or any other shape obtained by integrally blending a general-purpose ultraviolet absorbing agent, a light-shielding pigment, and / or a dye with a thermoplastic plastic. It may also be a printed or coated layer (including an image) in which a light-shielding pigment and / or a dye that blocks light with a wavelength of less than 500 nm, including ultraviolet rays, and optionally an ultraviolet absorbing agent are fixed in a dissolved or dispersed state in a vehicle containing a binder resin on a support made of a transparent or semi-transparent sheet or an optionally shaped object. It may also be a plastic or fluid form such as a paste or gel containing a light-shielding pigment and / or a dye that blocks light with a wavelength of less than 500 nm, including ultraviolet rays, and optionally an ultraviolet absorbing agent. When a light-shielding pigment and / or dye that blocks light with a wavelength of less than 500 nm, including ultraviolet light, and an ultraviolet absorber, if necessary, are blended into a vehicle containing a binder resin, the blending ratio is 0.05% by mass to 40% by mass, preferably 0.1% by mass to 30% by mass, relative to the binder resin, which makes it easier to exert the effect of blocking light with a wavelength of less than 500 nm, including ultraviolet light. The decolorizer uses a spectrophotometer (manufactured by Gretag Macbeth, product name: Spectro Eye) to measure the reflectance spectrum when irradiated with light based on the reflectance spectrum when not irradiated, and converts the spectral difference at each wavelength into a rate to obtain intensity.It is preferable that the light intensity at each wavelength below 500 nm is 5% or less of the maximum light intensity at the peak wavelength above 500 nm, and has excellent function of decolorizing diarylethene-based photochromic compounds.

[0021] In addition, the reversible photochromic material may be a reversible photochromic composition prepared by dissolving the above-mentioned photochromic compound in various oligomers, such as styrene-based oligomers, acrylic-based oligomers, terpene-based oligomers, and terpene phenol-based oligomers. By dissolving the photochromic compound in various oligomers, it is possible to improve the light resistance as well as the color density, and further to adjust the color change sensitivity.

[0022] The styrene oligomer has a mass average molecular weight of 200 to 6000, preferably 200 to 4000. If the mass average molecular weight of the styrene oligomer exceeds 6000, color retention occurs due to light irradiation, and the color density tends to be low, and it tends to be difficult to adjust the discoloration sensitivity. On the other hand, if the mass average molecular weight is less than 200, the amount of contained monomer increases, resulting in lack of stability, and therefore light resistance tends to be impaired. The styrene oligomer is a compound having a styrene skeleton or a hydrogenated product thereof, and examples thereof include low molecular weight polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene polymer, and copolymer of α-methylstyrene and vinyltoluene. Specific examples of low molecular weight polystyrene include Sanyo Chemical Industries, Ltd.'s product names: Hymer SB-75 (mass average molecular weight: 2000) and ST-95 (mass average molecular weight: 4000). Specific examples of styrene-α-methylstyrene copolymers include Eastman Chemical Company's product names: Picolastic A-5 (mass average molecular weight: 317) and A-75 (mass average molecular weight: 917). Specific examples of α-methylstyrene polymers include those manufactured by Eastman Chemical Company, product names: Crystallex 3085 (mass average molecular weight: 664), 3100 (mass average molecular weight: 1020), and 1120 (mass average molecular weight: 2420). Specific examples of the copolymer of α-methylstyrene and vinyltoluene include Eastman Chemical Company's product names: Picotex LC (mass average molecular weight: 950) and Picotex 100 (mass average molecular weight: 1740).

[0023] The acrylic oligomer has a mass average molecular weight of 12000 or less, preferably 1000 to 8000, and more preferably 1500 to 6000. If the mass average molecular weight of the acrylic oligomer exceeds 12000, it becomes difficult to adjust the discoloration sensitivity. On the other hand, if the mass average molecular weight is less than 1000, the amount of contained monomer increases and the stability is lacking, so that the color density tends to be low and the light resistance is easily impaired. The acrylic oligomer may, for example, be an acrylic acid ester copolymer. Specific examples of acrylic acid ester copolymers include those manufactured by Toa Gosei Co., Ltd., product names: ARUFON UP-1170 (mass average molecular weight: 8000), ARUFON 1080 (mass average molecular weight: 6000), ARUFON 1000 (mass average molecular weight: 3000), ARUFON 1020 (mass average molecular weight: 2000), ARUFON 1010 (mass average molecular weight: 1700), UH-2000 (mass average molecular weight: 11000), US-6100 (mass average molecular weight: 2500), and UC-3510 (mass average molecular weight: 2000).

[0024] The terpene oligomer has a mass average molecular weight of 250 to 4000, preferably 300 to 4000. If the mass average molecular weight of the terpene oligomer exceeds 4000, color retention occurs due to light irradiation, and the color density tends to be low, and it tends to be difficult to adjust the discoloration sensitivity. On the other hand, if the mass average molecular weight is less than 250, the amount of monomer contained increases, resulting in lack of stability, and therefore, light resistance tends to be impaired. The terpene oligomer is a compound having a terpene skeleton, and examples thereof include α-pinene polymer, β-pinene polymer, and d-limonene polymer. A specific example of the α-pinene polymer is Piccolite A115 (product name: mass average molecular weight: 833) manufactured by Eastman Chemical Company. A specific example of the β-pinene polymer is Piccolite S115 (product name: mass average molecular weight: 1710) manufactured by Eastman Chemical Company. A specific example of the d-limonene polymer is Piccolite C115 (mass average molecular weight: 902), a product name manufactured by Eastman Chemical Company.

[0025] The terpene phenol oligomer has a mass average molecular weight of 200 to 2000, preferably 500 to 1200. If the mass average molecular weight of the terpene phenol oligomer exceeds 2000, it becomes difficult to adjust the discoloration sensitivity. On the other hand, if the mass average molecular weight is less than 200, the amount of contained monomer increases and the stability is lacked, so that the color density tends to be low. The terpene phenol oligomer is a compound obtained by copolymerizing a cyclic terpene monomer with a phenol or a hydrogenated product thereof, and examples thereof include an α-pinene-phenol copolymer. Specific examples of α-pinene-phenol copolymers include those manufactured by Yasuhara Chemical Co., Ltd., product names: YS Polystar T145 (mass average molecular weight: 1050), T130 (mass average molecular weight: 900), T500 (mass average molecular weight: 500), and S145 (mass average molecular weight: 1050).

[0026] The mass average molecular weights of the above-mentioned styrene-based oligomers, acrylic-based oligomers, terpene-based oligomers, and terpene phenol-based oligomers are values ​​measured by GPC (gel permeation chromatography). The above oligomers may be used alone or in combination of two or more kinds.

[0027] In the reversible photochromic composition, the mass ratio of the photochromic compound to the styrene-based oligomer or the acrylic-based oligomer is preferably 1:1 to 1:10000, and more preferably 1:5 to 1:500. The mass ratio of the photochromic compound to the terpene oligomer is preferably 1:1 to 1:5000, and more preferably 1:5 to 1:500. The mass ratio of the photochromic compound to the terpene phenol oligomer is preferably 1:1 to 1:50, and more preferably 1:2 to 1:30. When the mass ratio of the photochromic compound to the oligomer is within the above range, the photochromic compound satisfies the color developing and decoloring functions, and a sufficient color density is easily exhibited.

[0028] The above-mentioned reversible photochromic composition can be encapsulated in a microcapsule to form a reversible photochromic microcapsule pigment (hereinafter sometimes referred to as "microcapsule pigment"), or dispersed in a thermoplastic resin or thermosetting resin to form reversible photochromic resin particles and used as a reversible photochromic material, but it is preferable to encapsulate the reversible photochromic composition in a microcapsule to use it as a microcapsule pigment. This is because by encapsulating the reversible photochromic composition in a microcapsule, a chemically and physically stable pigment can be formed, and the reversible photochromic composition can be maintained in the same composition under various conditions of use, and can exhibit the same action and effect.

[0029] Microencapsulation can be appropriately selected according to the application, from known methods such as isocyanate-based interfacial polymerization, melamine-formaldehyde-based in situ polymerization, liquid curing coating, phase separation from an aqueous solution, phase separation from an organic solvent, melt dispersion cooling, air suspension coating, spray drying, etc. Furthermore, a secondary resin film can be provided on the surface of the microcapsules according to the purpose to impart durability or modify the surface properties for practical use. The mass ratio of the inclusions to the wall film of the microcapsule pigment is preferably 7:1 to 1:1, and by having the mass ratio of the inclusions to the wall film within the above range, a decrease in color density and clarity during color development is prevented.The mass ratio of the inclusions to the wall film is more preferably 6:1 to 1:1. In addition, by blending a non-discolorable colorant such as a general dye or pigment during microencapsulation, it is possible to bring about an alternating color change from color (1) to color (2).

[0030] The average particle size of the reversible photochromic microencapsulated pigment is 0.5 to 10 μm, preferably 0.5 to 5 μm, and more preferably 1 to 3 μm, which is practical. If the average particle size exceeds 10 μm, the pigment tends to lack dispersion stability and processing suitability when blended into ink, paint, or resin. On the other hand, if the average particle size is less than 0.5 μm, the pigment tends to be difficult to exhibit high-concentration color development. The average particle size was determined by determining the particle region using image analysis particle size distribution measurement software (manufactured by Mountec Co., Ltd., product name: MacView), calculating the projected area equivalent circle diameter (Heywood diameter) from the area of ​​the particle region, and measuring the average particle size of particles equivalent to a sphere of equal volume using this value. In addition, when the particle size of all or the majority of the particles exceeds 0.2 μm, it is also possible to measure the average particle size of particles equivalent to an equal volume sphere by the Coulter method using a particle size distribution analyzer (product name: Multisizer 4e, manufactured by Beckman Coulter, Inc.). Furthermore, the volumetric particle size and average particle size may be measured using a calibrated laser diffraction / scattering particle size distribution analyzer (manufactured by HORIBA, Ltd., product name: LA-300) based on values ​​measured using the above software or a measuring device using the Coulter method.

[0031] If necessary, additives such as ultraviolet absorbers, light stabilizers, and antioxidants may be blended into the above-mentioned reversibly photochromic composition to improve light resistance. The above-mentioned additives for improving light resistance may be used alone or in combination of two or more kinds.

[0032] Examples of ultraviolet absorbents include: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-octyloxybenzophenone, Bis-(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)-benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-Hydroxy-4-benzyloxybenzophenone Benzophenone-based ultraviolet absorbers such as Phenyl salicylate, para-tert-butylphenyl salicylate, Paraoctylphenyl salicylate, 2,4-di-tert-butylphenyl-4-hydroxybenzoate, 1-hydroxybenzoate, 1-hydroxy-3-tert-butyl benzoate, 1-hydroxy-3-tert-octyl benzoate, Resorcinol Monobenzoate Salicylic acid-based ultraviolet absorbers such as Ethyl-2-cyano-3,3′-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, 2-Ethylhexyl-2-cyano-3-phenylcinnamate Cyanoacrylate-based ultraviolet absorbers such as 2-(5-tert-butyl-2-hydroxyphenyl)-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)-benzotriazole, 2-[2-hydroxy-3,5-bis(a,a-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-benzotriazole, 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-propyloctylate-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl)-benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)-benzotriazole, 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]-benzotriazole Benzotriazole-based ultraviolet absorbers such as Ethanediamide-N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl), 2,2,4,4-Tetramethyl-20-(β-lauryloxycarbonyl)-ethyl-7-oxa-3,20-diazodispiro(5,1,11,2)heneicoic acid-21-one oxalic acid anilide-based ultraviolet absorbers such as 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-pentyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-[2-hydroxy-4-(2-butoxyethoxy)phenyl]-1,3,5-triazine, 2,4-di-p-trail-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-di-p-trail-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-di-p-trail-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-di-p-trail-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-di-p-trail-6-(2-hydroxy-4-pentyloxyphenyl)-1,3,5-triazine, 2,4-di-p-trail-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-di-p-trail-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4-di-p-trail-6-[2-hydroxy-4-(2-hexyloxyethoxy)phenyl]-1,3,5-triazine, 2-{4-[2-hydroxy-3-(dodecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-{4-[2-hydroxy-3-(tridecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-{4-[2-hydroxy-3-(2′-ethyl)hexyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, A mixture of 2-{4-[2-hydroxy-3-(tridecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-{4-[2-hydroxy-3-(dodecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazine, 2-{2-hydroxy-4-[(1-octyloxycarbonylethoxy)phenyl]}-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, Tris(3-methylanilino)triazine Triazine-based UV absorbers such as Examples include:

[0033] Examples of light stabilizers include: Dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, Poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2-4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]}hexamethylene, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentapetyl-4-piperidyl), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentapetyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, Bis(1,2,2,6,6-pentamethyl-4-piperidylsebacic acid), 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione Examples of the hindered amine light stabilizer include:

[0034] Examples of antioxidants include: 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-ethylphenol, Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2-methylenebis(4-methyl-6-tert-butylphenol), 4,4-thiobis(2-methyl-6-tert-butylphenol), 2,2-thiobis(4-methyl-6-tert-butylphenol), 4,4-butylidenebis(3-methyl-6-tert-butylphenol), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}, 2,4,8,10-tetraoxaspiro[5,5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2,2-ethylenebis(4,6-di-tert-butylphenol), Bis[3,3-bis-(4′-hydroxy-3′-tert-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3′,5′-di-tert-butyl-4′-hydroxybenzyl)-S-triazine-2,4,6-[1H,3H,5H]-trione, Tocopherol, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, Pentaerythritol tetrakis(3-laurylthiopropionate), Triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexadiol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thioethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-tert-butyl-4-hydroxy-hydrocinnamamide), Tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,2,4-trimethyl-1,2-hydroquinone, Styryl phenol, 2,5-di-tert-butylhydroquinone, Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate Phenolic antioxidants such as Dilauryl-3,3′-thiodipropionate, Dimyristyl-3,3′-thiodipropionate, Distearyl-3,3′-thiodipropionate, Stearyl Thiopropylamide Sulfur-based antioxidants such as Tris(2,4-di-tert-butylphenyl)phosphite, Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzylphosphanate-diethyl ester, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl isodecyl phosphite, 4,4′-butylidene-bis(3-methyl-6-tert-butylphenylditridecyl)phosphite, Octadecyl phosphite, Tris(nonylphenyl)phosphite, Diisodecyl pentaerythritol diphosphite, 9,10-dihydroxy-9-oxa-10-phosphaphenanthrene, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydroxy-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydroxy-9-oxa-10-phosphaphenanthrene, Cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl)phosphite, Cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenyl)phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, Octylated Diphenylamine Phosphate-based antioxidants such as Examples include:

[0035] A reversible photochromic image is formed on a support by using a liquid composition such as a printing ink or paint prepared by dispersing a reversibly photochromic material in a vehicle, by a printing method such as screen printing, offset printing, process printing, gravure printing, inkjet printing, coater, and transfer printing, or by a coating method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating. Note that a reversible photochromic image is formed by volatilization of volatile components such as a solvent in the liquid composition and the remaining components.

[0036] The vehicle in which the reversible photochromic material is dispersed is composed of a solvent, a binder resin, and various additives that are blended as necessary, and is not particularly limited as long as it does not affect the color development / erasing function, color change function, sensitivity, etc. of the reversible photochromic material. In addition, by blending a non-color-changing colorant such as a general dye or pigment in the vehicle together with the reversibly photochromic material, it is possible to bring about an alternating color change from color (1) to color (2) in the reversibly photochromic image.

[0037] The solvent may be water or various organic solvents. Examples of organic solvents include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-octane, isooctane, n-heptane, methylcyclohexane, ethylcyclohexane, toluene, xylene, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

[0038] Examples of the binder resin include ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinyl acetate resin, vinyl chloride resin, vinylidene chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinyl chloride ethylene copolymer resin, chlorinated polyethylene, chlorinated polypropylene, polyamide resin, polycarbonate, polybutadiene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, high impact polystyrene, styrene-maleic acid copolymer resin, acrylic-styrene copolymer resin, polypropylene, polymethylstyrene, acrylic ester resin, polymethyl methacrylate, epoxy acrylate resin, alkylphenol resin, rosin modified phenolic resin, rosin modified alkyd resin, phenolic resin modified alkyd resin, styrene modified Alkyd resin, epoxy resin modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, butyral resin, urethane resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, alkyd resin, styrene-butadiene copolymer resin, unsaturated polyester resin, saturated polyester resin, vinyl chloride-acrylic copolymer resin, polyisobutylene, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether, fluororesin, silicon resin, phenolic resin, petroleum-based hydrocarbon resin, ketone resin, toluene resin, xylene resin, melamine resin, urea resin, Benzoguanamine resin, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylates, polymethacrylates, acrylate emulsions, methacrylate emulsions, vinyl acetate-acrylate copolymer resin emulsions, ethylene-vinyl acetate copolymer resin emulsions, styrene-acrylate copolymer resin emulsions, vinyl chloride emulsions, vinylidene chloride emulsions, polyvinyl acetate emulsions,Synthetic resins such as polyolefin emulsions, rosin ester emulsions, epoxy resin emulsions, polyurethane emulsions, synthetic rubber latex, low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene, coumarone plastics, polybutene, phenoxy plastics, liquid polybutadiene, liquid rubber, petroleum-based hydrocarbon resins, and cyclopentadiene-based petroleum resins; Examples include natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubber, shellac, agar, casein, glue, gelatin, and polyterpene.

[0039] Examples of additives include crosslinking agents, curing agents, drying agents, plasticizers, viscosity modifiers, dispersants, UV absorbers, antioxidants, light stabilizers, anti-settling agents, smoothing agents, gelling agents, defoaming agents, matting agents, penetrating agents, pH adjusters, foaming agents, coupling agents, moisturizing agents, lubricants, antifungal agents, preservatives, and rust inhibitors.

[0040] The reversible photochromic material is blended in the binder resin at a ratio of 0.1 to 40% by mass, preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass. If the blending ratio of the reversible photochromic material exceeds 40% by mass, the material is likely to lack dispersion stability and processability when dispersed in the binder resin, and it is difficult to achieve a significant improvement in color density, and it is also likely to leave residual color in the decolorized state. On the other hand, if the blending ratio is less than 0.1% by mass, it is difficult to achieve the desired color density and to fully fulfill the color-changing function.

[0041] The reversible photochromic image is not particularly limited, but photographs or pictures of people, animals, plants, food, dishes, vehicles, buildings, heavenly bodies, landscapes, etc. taken with a real camera are preferred. The camera toy set of the present invention allows a user to experience the feeling of using a real camera, but in order to further enhance this feeling, it is preferable that the image on the printed matter be detailed and clear. It is preferable that the reversible photochromic image be formed using process printing, as this allows for excellent reproducibility of the colors and shades of the image and allows for the formation of detailed and clear images.

[0042] Process printing is a method of printing original images such as pictures and photographs using printing inks of four colors, cyan (C), magenta (M), yellow (Y), and black (K), with plates made by four-color photographic separation, and is a printing method capable of reproducing colors and shades with a high degree of precision. When forming a reversibly photochromic image by process printing, at least three colors of photochromic printing inks are used, in which reversibly photochromic materials that turn cyan, magenta, and yellow when exposed to light are dispersed in a vehicle. As the black printing ink, a black photochromic printing ink obtained by mixing the above three color photochromic printing inks can be used. Photochromic printed matter is produced by process printing using four photochromic printing inks of cyan, magenta, yellow, and black. Before being irradiated with light, no image is visible. However, when light is irradiated to change the color of the reversible photochromic image, a fine and clear image becomes visible on the printed matter, making it possible to create a toy camera set that gives the user a greater sense of realism as if they were using a real camera.

[0043] As the photochromic compound that develops a cyan color when irradiated with light, a spirooxazine-based compound is preferable, and a benzoindolinospirooxazine-based compound represented by the following general formula (1) is more preferable. [ka] (In the formula, R1 and R2 each represent an alkyl group having 1 to 3 carbon atoms; R3 represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, a mono-, di-, or tri-substituted phenyl group, or an alkoxy group; R4 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, a mono-, di-, or tri-substituted phenyl group, an alkoxy group, a morpholino group, an alkoxycarbonyl group, or a cyano group; and A represents =CH- or =N-.)

[0044] Examples of the compound represented by the general formula (1) include 1,3,3-trimethyl-spiro[benzo[e]indoline-2,3′[3H]naphtho[2,1-b][1,4]oxazine], 1,3,3-trimethyl-8′-cyano-spiro[benzo[e]indoline-2,3′[3H]naphtho[2,1-b][1,4]oxazine], 1,3,3-trimethyl-8′-methoxycarbonyl-spiro[benzo[e]indoline-2,3′[3H]naphtho[2,1-b][1,4]oxazine], 3,3-Dimethyl-1-ethyl-spiro[benzo[e]indoline-2,3′[3H]naphtho[2,1-b][1,4]oxazine], 1,3,3-trimethyl-9′-methoxy-spiro[benzo[e]indoline-2,3′[3H]naphtho[2,1-b][1,4]oxazine], 1,3,3-trimethyl-8′-bromo-spiro[benzo[e]indoline-2,3′[3H]naphtho[2,1-b][1,4]oxazine], 3,3-Dimethyl-1-ethyl-8′-cyano-spiro[benzo[e]indoline-2,3′[3H]naphtho[2,1-b][1,4]oxazine], 1,3,3-Trimethyl-spiro[benzo[e]indoline-2,3′[3H]quinolino[6,5-b][1,4]oxazine] Examples include:

[0045] As the photochromic compound that develops a magenta color when irradiated with light, naphthopyran-based compounds are preferred, and naphthopyran-based compounds represented by the following general formulas (2) to (4) are more preferred. [ka] [wherein R5 to R8 represent the following general formula (5), R 11 ~R 14 represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; R 15indicates an alkyl group having 3 or more carbon atoms, and * indicates the bonding site with the pyran skeleton. [ka]

[0046] Examples of the compounds represented by the general formulas (2) to (4) include: 2,2,8,8-tetra(4′-n-propoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b′]-dipyrane, 2,2,8,8-tetra(3′-chloro-4′-n-butoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b′]-dipyrane, 2,2,8,8-tetra(4′-sec-butoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b′]-dipyrane, 2,2,8,8-tetra(4′-tert-butoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b′]-dipyrane, 2,2,8,8-tetra(3′-cyano-4′-n-hexyloxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b′]-dipyrane, 2,2,8,8-tetra(4′-n-octyloxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b′]-dipyrane, 3,3,8,8-tetra(2′-methyl-4′-n-propoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b′]-dipyrane, 3,3,8,8-tetra(2′-methoxy-4′-n-butoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b′]-dipyrane, 3,3,8,8-tetra(4′-isobutoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b′]-dipyrane, 3,3,8,8-tetra(4′-sec-butoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b′]-dipyrane, 3,3,8,8-tetra(2′-hydroxy-4′-tert-butoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b′]-dipyrane, 3,3,8,8-tetra(4′-n-hexyloxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b′]-dipyrane, 3,3,8,8-tetra(3′-bromo-4′-n-octyloxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b′]-dipyrane, 3,3,9,9-tetra(4′-n-propoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane, 3,3,9,9-tetra(4′-isopropoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane, 3,3,9,9-tetra(2′-cyano-4′-n-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane, 3,3,9,9-tetra(2′-hydroxy-4′-isobutoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane, 3,3,9,9-tetra(4′-sec-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane, 3,3,9,9-tetra(4′-tert-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane, 3,3,9,9-tetra(2′-ethoxy-4′-n-hexyloxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane, 3,3,9,9-Tetra(4′-n-octyloxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b′]-dipyrane Examples include:

[0047] As the photochromic compound that develops a yellow color when irradiated with light, a naphthopyran-based compound is preferable, and a naphthopyran-based compound represented by the following general formula (6) or (7) is more preferable. [ka] [In the formula, R9 to R 12 represents the following general formula (8), and R 21 ~R 24represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; R 25 indicates a hydrogen atom, a methoxy group, or an ethoxy group, and * indicates the bonding site with the pyran skeleton. [ka]

[0048] Examples of the compound represented by the general formula (6) or (7) include 3,3,10,10-tetraphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,3,10,10-tetra(4′-methoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,3,10,10-Tetra(2'-cyano-4'-ethoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']-dipyrane 3,3,6,6-tetraphenyl-3H,6H-naphtho[2,1-b:3,4-b′]-dipyrane, Examples include 3,3,6,6-tetra(2'-chlorophenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dipyrane.

[0049] The above-mentioned photochromic compounds have a high density in the colored state and little residual color in the decolorized state. When the above-mentioned compounds are used as photochromic compounds that develop cyan, magenta, or yellow colors when exposed to light, photochromic printed matter produced by process printing has an image that is difficult to see before light exposure, but after light exposure, a fine, clear, and highly dense image is visible on the support, and the reproducibility of the image that appears on the printed matter is even better, thereby further increasing the commercial value of the camera toy set.

[0050] A photochromic print has a reversible photochromic image on one side of a support (see Figure 3). A reversible photochromic image or a non-photochromic image can also be provided on the side of the support opposite to the side on which the reversible photochromic image is provided. For example, as shown in Fig. 4, a photochromic print having a reversible photochromic image (first reversible photochromic image) 22 formed on one side of a support 21 and a reversible photochromic image (second reversible photochromic image) 23, which is different from the first reversible photochromic image, formed on the other side of the support (the side of the support opposite to the side on which the reversible photochromic image is formed) can produce two different images with one print. Therefore, even with a small number of prints, a wide variety of images can be produced, making it possible to produce a toy camera set with excellent playability. Furthermore, as shown in Figure 5, a photochromic printed material having a reversible photochromic image 22 formed on one side of a support 21 and a non-colorable image 24, which is identical to the reversible photochromic image, on the other side of the support (the side of the support opposite to where the reversible photochromic image is formed), allows the type of reversible photochromic image to be determined in advance by checking the non-colorable image on the other side of the support even if the reversible photochromic image on one side of the support is not visible, making it easy to select a printed material on which a specific image is formed, and a user can play with a camera toy set using the desired photochromic printed material.

[0051] The camera toy is a toy that imitates the appearance of a camera, and has an opening in the camera body for inserting and removing photochromic printed matter (see FIG. 6). The appearance of the camera body is not particularly limited, and examples include digital single-lens reflex cameras, mirrorless single-lens cameras, compact digital cameras, single-lens reflex cameras, twin-lens reflex cameras, rangefinder cameras, spring cameras, toy cameras, film cameras with lenses, instant cameras, wearable cameras, etc. Among these, a camera body that imitates the appearance of an instant camera, into which film can be inserted or housed and into which a photograph can be viewed immediately after shooting, is preferable. In the toy camera used in the present invention, the direction in which the lens is located is the front.

[0052] The opening is provided in the camera body so that the photochromic printed matter can be freely inserted and removed from inside the camera body. The position where the opening is provided is not particularly limited, but it can be provided, for example, on the lower part of the front surface, the side surface, or the bottom surface of the camera body. The opening may be provided at a height that allows the photochromic printed materials to be inserted and removed one by one, but it is preferable that the opening be provided at a height that allows multiple printed materials to be freely inserted and removed from inside the camera body in a stacked state, so that printed materials with images appearing thereon can be obtained successively when playing with the camera toy set.

[0053] As shown in Figure 7, a light source 32 is provided inside the camera body for discoloring the reversible photochromic image of a photochromic printed matter. When light is irradiated from the light source onto a printed matter inserted or housed inside the camera body, the reversible photochromic image changes color, and an image such as a photograph or picture appears on the printed matter. The light source is positioned so that light is irradiated onto a reversible photochromic image of a photochromic print inserted or housed inside the camera body, and it is preferable that the light source be positioned at a vertical position on the side of the reversible photochromic image of the photochromic print.

[0054] The light source is not particularly limited as long as it can change the color of the photochromic compound in the reversible photochromic image, but one that has a peak emission wavelength in the range of 400 to 495 nm and mainly irradiates blue light is preferable because, unlike light sources that irradiate ultraviolet light having a peak emission wavelength in the vicinity of 350 to 390 nm, which is a light source that causes conventional photochromic compounds to develop color well, the light emitted is purple to blue light, which has little effect on the human body and is highly safe. As the light source, any light source having the above-mentioned peak emission wavelength can be used, but a blue light emitting diode is preferably used. Specific examples of light-emitting diodes include a blue LED manufactured by Nichia Corporation, product name: NSPB336CS (peak wavelength: 465 nm), a blue LED manufactured by Kyosemi Corporation, product name: KED471M53A (peak wavelength: 465 nm), a blue LED manufactured by Seiwa Electric Co., Ltd., product name: SDDB16001A1 (peak wavelength: 460 nm), a purple LED manufactured by Kyosemi Corporation, product name: KED405UH3 (peak wavelength: 405 nm), a purple LED manufactured by OPTOSUPPLY, product name: OSSV5111A (peak wavelength: 430 nm), and a purple LED manufactured by OPTOSUPPLY, product name: OSSV9131A (peak wavelength: 430 nm).

[0055] It is preferable to further provide a power source in or inside the camera body, and the light source and the power source are connected by a wire such as an electric cord. Although a household power source may be used as the power source, a solar cell, a dry cell, or a storage battery is preferable because the camera toy set can be freely carried around and there are fewer restrictions on where it can be played with. When a solar cell is used as a power source, the camera toy set can be used outdoors since light can be irradiated by sunlight. The solar cell is provided on the camera body so that sunlight is irradiated onto the solar cell. By using a storage battery together with the solar cell, electricity generated by sunlight can be charged into the storage battery to emit light, so that the camera toy set can be used both indoors and outdoors. When dry batteries or storage batteries are used as the power source, the camera toy set can be used both indoors and outdoors regardless of the weather, and it is preferable that the power source 33 is provided inside the camera body as shown in Fig. 7. The dry batteries can be either primary or secondary batteries.

[0056] As shown in FIG. 7, it is preferable that a camera toy equipped with a power source 33 further includes a switch 34 on the camera body 30 for turning on and off the emission of light from the light source, and the light source 32, power source 33, and switch 34 are connected by wires such as an electric cord. By providing the switch, the light source can be turned off when the camera toy is not in use, thereby reducing power consumption by the camera toy. The type of switch and the position of the switch on the camera body are not particularly limited, but it is preferable to provide a switch that energizes when pressed in a position where a shutter button is generally provided on a real camera. The camera toy configured as described above has an operational feel similar to the operation of pressing the shutter button on a real camera to take a picture, and when the switch is pressed, light is irradiated from a light source onto the photochromic printed matter, causing the reversible photochromic image to change color, and an image such as a photo or picture appears on the printed matter, so that the camera toy set can provide an enhanced sense of realism as if the real camera were being used. It is more preferable that the switch has a shape that imitates the shutter button. Examples of switches that are energized when pressed include a switch that turns on when pressed, irradiates light for a certain period of time, and turns off when the pressure is released, stopping the light emission; and a switch that turns on when pressed, irradiates light for a certain period of time, and turns off after the certain period of time has passed, automatically stopping the light emission. As this allows play with a feel that is close to that of a real camera, a switch that turns on when pressed, irradiates light for a certain period of time, and turns off after the certain period of time has passed, and automatically stops the light emission, is preferred.

[0057] 7, a mounting member (stage) 350 may be further provided inside the camera body so as to be connected to the opening 31, and the photochromic printed matter inserted from the opening can be placed on the mounting member and stably held inside the camera body. The mounting member is preferably further provided with a frame or fastener, which prevents the printed matter from moving inside the camera body due to vibrations of the toy camera, and prevents the inserted or housed printed matter from being unintentionally ejected from inside the camera body, allowing the printed matter to be stably held inside the camera body and light to be irradiated stably onto the reversible photochromic image.

[0058] In addition, a plate-like member on which a printed matter can be placed may be provided, and the photochromic printed matter may be placed on the plate-like member and inserted into or removed from the opening. Furthermore, a discharge mechanism may be provided to discharge the plate-like member inserted into the opening from the opening. An example of an ejection mechanism is one in which an elastic member such as a spring is provided inside the camera body, and a locking portion is provided on the camera body to hold the plate-like member inserted against the elastic member, and a release portion is provided on the camera body to release the locking portion, and when the locking portion is released by the release portion, the elastic force of the elastic member causes the plate-like member to be ejected from the opening.

[0059] Also, the camera body may be structured so that it can be separated into an upper and lower part, and the lower part of the camera body may be provided with a storage section for storing photochromic printed matter, and a discharge mechanism for discharging the printed matter from inside the camera body through an opening. In a toy camera set using the toy camera of the above configuration, when the printed matter before light irradiation is stored in the storage section at the lower part of the camera body, the upper and lower parts of the camera body are fitted together, the printed matter is irradiated with light from a light source, and then the discharge mechanism discharges the printed matter from the opening, an image appears on the printed matter, and a toy camera set can be provided that allows a user to experience the feeling of using an actual instant camera. Examples of the ejection mechanism include an ejection mechanism that uses a roller, or an ejection mechanism in which a storage section has an elastic member such as a spring and an engagement section for storing the printed matter against the elastic member, and a release section is provided on the camera body for releasing the engagement by the engagement section, and when the engagement section is released by the release section, the elastic force of the elastic member causes the printed matter to be ejected from the opening. In the above-described camera toy, the storage section is preferably capable of storing a plurality of stacked printed materials, and in this case, it is preferable to provide a discharge mechanism so that the printed materials are discharged one by one through the opening.

[0060] A camera toy having a switch that is energized when pressed may be provided with a window portion. By providing the window portion so that the light from the light source provided inside the camera body can be seen from outside the camera toy through the window portion, when the switch is pressed, the light from the light source can be seen from outside through the window portion, making it possible to create a camera toy that gives the user the feeling of taking pictures with a flash. The window portion is formed from a transparent material, and as the transparent material, a conventionally known transparent resin can be used. Furthermore, as shown in Fig. 8, a strobe light source 37 may be provided behind the window 36 in addition to the light source 32 that discolors the reversible photochromic image, and the strobe light source may be emitted in conjunction with the pressing of the switch 34, providing a toy camera that further enhances the sense of flash photography. It is preferable that the light from the light source that discolors the reversible photochromic image is not visible through the window in the toy camera configured as described above. It is also preferable to provide a power source for emitting the strobe light source, and a power source 33 connected to the light source 32 may be used, but as shown in Fig. 9, a power source 33' separate from the power source 33 may be provided. The strobe light source 37, the power source 33' (33), and the switch 34 are connected by wires such as electric cables.

[0061] As shown in Fig. 6, it is preferable to provide a viewfinder 38 in the toy camera, and the location of the viewfinder is not particularly limited as long as the front side of the camera body can be seen through the viewfinder from the rear side of the camera body. The toy camera configured as above allows a child to experience the feeling of taking pictures while looking through the viewfinder, which enhances the feeling of using a real camera. The finder is formed entirely or partially from a transparent material, and as the transparent material, a conventionally known transparent resin can be used. In addition, when the toy camera is provided with a viewfinder, it is preferable that the image seen through the viewfinder and the image that appears on the printed matter are the same, which further enhances the sense of using a real instant camera. A toy camera set using such a toy camera will be described with reference to Figures 10 to 12. The toy camera set 1 shown in Fig. 10 comprises a photochromic printed matter 2, a non-colorable printed matter 4, and a toy camera 3 further provided with an opening 31' for inserting and removing the non-colorable printed matter and a holder 39 for holding the non-colorable printed matter in a predetermined position. As shown in Fig. 12, the non-colorable printed matter 4 comprises a support 41 and a non-colorable image 42 provided thereon, and the non-colorable image and the reversible photochromic image are the same image. As shown in Figure 11, the above-mentioned camera toy set can be played with by inserting the non-color-changing printed material with the non-color-changing image side facing the viewfinder into opening 31', and inserting the photochromic printed material with the reversible photochromic image facing up into opening 31. The image made by the non-color-changing printed material is visible through the viewfinder, and when a switch is pressed, light is irradiated from the light source onto the photochromic printed material, causing the reversible photochromic image to change color. When the photochromic printed material is removed from opening 31, the same image as that seen through the viewfinder appears on the photochromic printed material, making it a highly valuable product that gives an even greater sense of realism as if it were using a real instant camera.

[0062] The toy camera may further include a sound generating device such as a speaker, and a circuit board for controlling electronic sounds for generating sounds such as a shutter sound from the sound generating device. EXAMPLES

[0063] The following examples are given, but the present invention is not limited thereto. In the examples, "parts" refers to parts by weight.

[0064] Preparation of reversible photochromic microencapsulated pigments A reversible photochromic composition was prepared by uniformly dissolving 1 part of 3,3-dimethyl-1-ethyl-8'-cyano-spiro[benzo[e]indoline-2,3'[3H]naphtho[2,1-b][1,4]oxazine] in 50 parts of styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., product name: Picolastic A-5) by heating, and encapsulating the resulting composition in a microcapsule pigment made of urethane resin to prepare a reversible photochromic microcapsule pigment (average particle size: 5 μm). The above microcapsule pigment was colorless before being irradiated with light, but changed to cyan when irradiated with light. After that, it was left to stand for a while indoors, and returned to colorless.

[0065] Preparation of reversible photochromic microencapsulated pigments A reversible photochromic microcapsule pigment (average particle size: 5 μm) was prepared by encapsulating a reversible photochromic composition prepared by uniformly dissolving 1 part of 3,3,9,9-tetra(4'-sec-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipyrane in 50 parts of styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., product name: Picolastic A-5) with heat in a microcapsule pigment made of urethane resin. The above microcapsule pigment was colorless before being irradiated with light, but changed to magenta when irradiated with light. After that, it returned to colorless when left for a while indoors.

[0066] Preparation of reversible photochromic microencapsulated pigments A reversible photochromic microencapsulated pigment (average particle size: 5 μm) was prepared by encapsulating a reversible photochromic composition prepared by uniformly dissolving 1 part of 3,3,10,10-tetraphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane in 50 parts of styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., product name: Picolastic A-5) with heat in a microencapsulated pigment made of urethane resin. The microencapsulated pigment was colorless before being irradiated with light, but turned yellow when irradiated with light. After that, it returned to colorless when left for a while indoors.

[0067] Preparation of photochromic printing inks Two parts of each of the above microcapsulated pigments were uniformly mixed in a vehicle consisting of 2.5 parts of a polyester medium (manufactured by Seiko Advance Co., Ltd., product name: PAL Matte 8) and 1 part of a dilution solvent (manufactured by Seiko Advance Co., Ltd., product name: T-995) to prepare three photochromic printing inks in cyan, magenta, and yellow for use in process printing. Next, the three colors of photochromic printing inks prepared were mixed to prepare a photochromic printing ink that turns black when exposed to light.

[0068] Example 1 Preparation of photochromic printed matter (see Figure 3) The four photochromic printing inks (cyan, magenta, yellow, and black) described above were used on white Kent paper as a support 21, and a reversible photochromic image 22 was formed by printing the original portrait photograph using a plate made by process photographic resolution in sequence onto the paper. Photochromic print 2 was then produced. The photochromic print was white before it was irradiated with light from a light source, but when it was irradiated with light, the reversible photochromic image changed color to reveal an image of a portrait. After that, when it was left indoors for a while, it returned to its original white color.

[0069] Making a toy camera (see Figure 13) An opening 31 was provided on the front of a camera body 30 that imitates the appearance of an instant camera having a viewfinder 38, a blue LED (peak wavelength: 430 nm) was attached as a light source 32, and a dry cell was attached as a power source 33 inside the camera body, a mounting member 350 with a frame 351 attached was provided so as to connect to the opening, and a switch 34 imitating a shutter button was further provided on the camera body to produce a toy camera 3. In the above toy camera, the light source is placed at the top inside the camera body so that light is irradiated onto the photochromic printed matter, and the light source, power source, and switch are connected by wires, and when the switch is pressed, the switch turns on and light is irradiated from the light source, and after a certain time has passed, the switch turns off and the light irradiation by the light source automatically stops.

[0070] Making a toy camera set (see Figure 1) The above-mentioned photochromic printed matter 2 and a toy camera 3 were combined to produce a toy camera set 1.

[0071] As shown in Figure 14, when the photochromic printed matter 2 before exposure to light is inserted into the opening 31 of the toy camera 3 with the reversible photochromic image 22 facing up and the switch is pressed, light is irradiated onto the printed matter for a certain period of time, causing the reversible photochromic image to change color. When the print is removed from the opening after the light irradiation is stopped, a print appears with an image of a portrait. The toy camera set described above allows a child to experience the sensation of actually using an instant camera, which produces a photo instantly when the child presses the shutter button, and is easy to play with, as the image appears on the printout simply by pressing the switch. In addition, the toy camera set can be used both indoors and outdoors, regardless of the weather, as the camera body is equipped with dry cell batteries as a power source. If the print was left indoors for a while after being exposed to light, the image would disappear and it would return to its original white state, so the same print could be played with repeatedly. In addition, the light source used in the above camera toy has a peak emission wavelength of 430 nm and emits blue light, so the camera toy set has little effect on the human body and is highly safe.

[0072] Example 2 Preparation of photochromic printed matter (see Figure 3) The four photochromic printing inks (cyan, magenta, yellow, and black) described above were used on white Kent paper as a support 21, and the original landscape photograph was printed in sequence using a plate made by process photographic resolution to form a reversible photochromic image 22, thereby producing a photochromic print 2. The photochromic print was white before it was irradiated with light from a light source, but when it was irradiated with light, the reversible photochromic image changed color, revealing the image of the landscape photograph. After that, when it was left indoors for a while, it returned to its original white color.

[0073] Making a toy camera (see Figure 13) An opening 31 was provided on the front of a camera body 30 that imitates the appearance of an instant camera having a viewfinder 38, a blue LED (peak wavelength: 430 nm) was attached as a light source 32, and a dry cell was attached as a power source 33 inside the camera body, a mounting member 350 with a frame 351 attached was provided so as to connect to the opening, and a switch 34 imitating a shutter button was further provided on the outside of the camera body to produce a camera toy 3. In the above camera toy, the light source is placed at the top inside the camera body so that light is irradiated onto the photochromic printed matter, and the light source, power source, and switch are connected by wires, so that while the switch is pressed, light is irradiated from the light source in the on state, and when the switch is released, the light source stops irradiating light by turning off the switch.

[0074] Making a toy camera set (see Figure 1) The above-mentioned photochromic printed matter 2 and a toy camera 3 were combined to produce a toy camera set 1.

[0075] As shown in Figure 14, when the photochromic print 2 before exposure to light is inserted into the opening 31 of the toy camera 3 with the reversible photochromic image 21 facing up and the switch is pressed and held down, the print is irradiated with light and the reversible photochromic image changes color. After a certain period of time has passed, the switch is released and the print is taken out of the opening, revealing a print with an image of a landscape photograph. The toy camera set described above allows children to play with it while experiencing the sensation of actually using an instant camera, which allows pictures to be taken instantly by pressing the shutter button, and is easy to play with because an image can be made to appear on the printout simply by pressing the switch. In addition, the camera set can be used both indoors and outdoors, regardless of the weather, because the camera body is equipped with dry cell batteries as a power source. If the print was left indoors for a while after being exposed to light, the image would disappear and it would return to its original white state, so the same print could be played with repeatedly. In addition, the light source used in the above camera toy has a peak emission wavelength of 430 nm and emits blue light, so the camera toy set has little effect on the human body and is highly safe.

[0076] Example 3 Preparation of photochromic printed matter (see Figure 4) The support 21 was a white Kent paper, and on one side thereof, a curry pattern was printed in sequence using the above-mentioned four photochromic printing inks (cyan, magenta, yellow, and black) with a plate made by process photographic separation to form a reversible photochromic image (first reversible photochromic image) 22. Next, on the other side of the support (the side of the support opposite to where the first reversible photochromic image is formed), a picture of an omelet rice was printed sequentially using the above-mentioned four photochromic printing inks, cyan, magenta, yellow, and black, with a plate made by process photoresolution, to form a reversible photochromic image (second reversible photochromic image) 23, thereby producing photochromic printed matter 2. The photochromic print was white before being irradiated with light from a light source, but when irradiated with light, the first or second reversible photochromic image changed color, revealing a picture of curry or omelet rice. After that, when left indoors for a while, the original white color returned.

[0077] Making a toy camera set (see Figure 1) The above-mentioned photochromic printed matter 2 was combined with the toy camera 3 of Example 1 to produce a toy camera set 1.

[0078] When the photochromic printed matter before light irradiation is inserted into the opening of the toy camera with the first reversible photochromic image facing up and a switch is pressed, the printed matter is irradiated with light for a certain period of time, causing the first reversible photochromic image to change color, and when the printed matter is removed from the opening after the light irradiation is stopped, a printed matter with a curry pattern image is obtained. Next, when the photochromic printed matter before light irradiation is inserted into the opening of the toy camera set with the second reversible photochromic image facing up and a switch is pressed, the printed matter is irradiated with light for a certain period of time, causing the second reversible photochromic image to change color, and when the printed matter is removed from the opening after the light irradiation is stopped, a printed matter with a omelet rice pattern image is obtained. The toy camera set described above allows children to play with it while experiencing the sensation of actually using an instant camera that takes a photo instantly by pressing the shutter button, because an image appears on the printed matter when the user presses the switch, and since an image appears on the printed matter by simply pressing the switch, it is easy to play with. In addition, since a dry cell battery is installed inside the camera body as a power source, the toy camera set can be used both indoors and outdoors regardless of the weather. If the print is left indoors after exposure to light for a while, the image disappears and returns to the original white print, so the same print can be played with repeatedly. Furthermore, since different reversible photochromic images are provided on one side and the other side of the support, a wide variety of images can be produced with a single photochromic print, providing excellent playability. In addition, the light source used in the above camera toy has a peak emission wavelength of 430 nm and emits blue light, so the camera toy set has little effect on the human body and is highly safe.

[0079] Example 4 Preparation of non-discoloring printing inks One part of cyan, magenta, yellow, or black general pigment (non-discoloring colorant) was uniformly mixed in a vehicle consisting of 2.5 parts of polyester medium (product name: PAL Matte 8, manufactured by Seiko Advance Corp.) and 1 part of dilution solvent (product name: T-995, manufactured by Seiko Advance Corp.) to prepare four non-discoloring printing inks for use in process printing: cyan, magenta, yellow, and black.

[0080] Preparation of photochromic printed matter (see Figure 5) The support 21 was a white Kent paper, and one side of it was printed with the above-mentioned four non-discoloring printing inks (cyan, magenta, yellow, and black) using a plate made by process photographic separation of an original portrait photograph to form a non-discoloring image 24. Next, the other side of the support (the side of the support opposite to where the non-color-changing image is formed) was printed sequentially using the above-mentioned four photochromic printing inks, cyan, magenta, yellow, and black, with a plate made by process photographic separation of the above-mentioned original portrait photograph, to form a reversible photochromic image 22, thereby producing a first photochromic print 2. The surface of the first photochromic print on which the reversible photochromic image was formed was white before it was irradiated with light from a light source, but when it was irradiated with light, the reversible photochromic image changed color to reveal an image of a portrait. After that, when it was left for a while indoors, it returned to its original white color. In addition, on one side of a sheet of white Kent paper used as the support 21', the above-mentioned four colors of non-discoloring printing inks (cyan, magenta, yellow, and black) were used to print in sequence using a plate made by process photographic separation of the original landscape photograph, thereby forming a non-discoloring image 24'. Next, the other side of the support (the side of the support opposite to where the non-color-changing image is provided) was printed sequentially using the above-mentioned four photochromic printing inks, cyan, magenta, yellow and black, with a plate made by process photographic resolution of the above-mentioned original landscape photograph, to form a reversible photochromic image 22', thereby producing a second photochromic print 2'. The surface of the second photochromic print on which the reversible photochromic image was formed was white before it was irradiated with light from a light source, but when it was irradiated with light, the reversible photochromic image changed color to reveal an image of a landscape photograph. After that, when it was left indoors for a while, it returned to its original white color.

[0081] Making a toy camera set The above first and second photochromic printed materials were combined with the toy camera of Example 1 to produce a toy camera set.

[0082] Before inserting the photochromic printed material into the opening of the toy camera, the non-discolored images of the first and second photochromic printed materials were confirmed, the first photochromic printed material depicting a portrait image was selected, the first photochromic printed material before light irradiation was inserted into the opening with the reversible photochromic image facing up and the switch was pressed, the printed material was irradiated with light for a certain period of time, causing the reversible photochromic image to discolor, and when the printed material was removed from the opening after the light irradiation was stopped, a printed material depicting a portrait image was obtained. Also, when the non-discolored images of the first and second photochromic printed materials were confirmed and the second photochromic printed material depicting a landscape image was selected, a printed material depicting a landscape image could be obtained by the same procedure. Therefore, in the first or second photochromic printed matter, the non-color-changing image formed on one side of the support and the reversible photochromic image formed on the other side of the support are identical, and even when the printed matter has not yet been exposed to light and the reversible photochromic image is not visible, the type of image that will appear on the photochromic printed matter can be determined in advance by checking the non-color-changing image, allowing the user to play around by selecting a printed matter that reveals the desired image. The toy camera set described above allows a child to experience the sensation of actually using an instant camera, where an image is visible on the printed matter when the child presses the shutter button, and allows the child to easily play with the set, since an image appears on the printed matter just by pressing the switch. In addition, the toy camera set can be used both indoors and outdoors, regardless of the weather, since the camera body is equipped with dry cell batteries as a power source. Furthermore, when the first and second photochromic printed materials before light irradiation are inserted into the opening of the toy camera with the reversible photochromic image facing up and the second photochromic printed material stacked on the first photochromic printed material and the switch is pressed, light is irradiated onto the second photochromic printed material for a certain period of time, causing the reversible photochromic image to change color, and when the second photochromic printed material is removed from the opening after the light irradiation is stopped, a printed material is obtained in which an image of a landscape photograph appears. Next, when the switch is pressed again, light is irradiated onto the first photochromic printed material for a certain period of time, causing the reversible photochromic image to change color, and when the first photochromic printed material is removed from the opening after the light irradiation is stopped, a printed material is obtained in which an image of a portrait appears. Therefore, the above-mentioned camera toy set can be played with by inserting multiple photochromic printed materials, which are stacked together, into the opening, allowing the child to take multiple pictures in succession, further enhancing the sense of using a real camera. If the print was left indoors for a while after being exposed to light, the image would disappear and it would return to its original white state, so the same print could be played with repeatedly. In addition, the light source used in the above camera toy has a peak emission wavelength of 430 nm and emits blue light, so the camera toy set has little effect on the human body and is highly safe.

[0083] Example 5 Preparation of photochromic printed matter (see Figure 3) The support 21 was made of white Kent paper, and one side of the support was printed in sequence with the above-mentioned four colors of photochromic printing inks, cyan, magenta, yellow, and black, using a plate made by process photo-resolution of a photograph of a building, to form a reversible photochromic image 22. Next, the lower center of the other side of the support (the side of the support opposite to the side on which the reversible photochromic image is formed) was offset printed with black non-color-changing offset printing ink, which was then dried and hardened to form the character "1," thereby producing a first photochromic printed matter 2. Also, on one side of a piece of white Kent paper used as the support 21', the above-mentioned four colors of photochromic printing inks (cyan, magenta, yellow, and black) were printed in sequence with a plate made by process photo-resolution of a landscape photograph to form a reversible photochromic image 22'. Next, the other side of the support (the side of the support opposite to the side on which the reversible photochromic image is formed) was offset printed in the lower center with black non-color-changing offset printing ink, which was then dried and hardened to form the character "2," thereby producing a second photochromic printed matter 2'. Furthermore, the support 21" was prepared by printing a food photograph on one side of white Kent paper in sequence using the above-mentioned four colors of photochromic printing inks (cyan, magenta, yellow and black) with a plate made by process photo resolution to form a reversible photochromic image 22". Next, the lower center of the other side of the support (the side of the support opposite to where the reversible photochromic image is formed) was offset printed using black non-color-changing offset printing ink, which was then dried and hardened to form the letter "3", thereby producing a third photochromic printed matter 2". Each of the above photochromic prints was white before being irradiated with light from a light source, but when irradiated with light, a reversible photochromic image changed color and an image of a building, landscape, or food appeared. After that, when left indoors for a while, the original white color returned.

[0084] Preparation of non-discoloring printed matter (see Figure 12) The support 41 was made of white Kent paper, and the building photographs used in producing the first photochromic printed matter were printed on one side of the support using the above-mentioned four colors of non-color-changing printing inks, cyan, magenta, yellow, and black, with plates made by process photo separation to form non-color-changing images 42. Next, the lower center of the other side of the support (the side of the support opposite to where the non-color-changing images are provided) was offset printed using black non-color-changing offset printing ink, which was then dried and hardened to form the character "1," thereby producing the first non-color-changing printed matter 4. Also, on one side of a piece of white Kent paper used as a support 41', the above-mentioned four colors of non-color-changing printing inks (cyan, magenta, yellow, and black) were printed in sequence with a plate made by process photo resolution of the landscape photograph used in producing the second photochromic printed matter, forming a non-color-changing image 42'. Next, the other side of the support (the side of the support opposite to the side on which the non-color-changing image is formed) was offset printed in the lower center with black non-color-changing offset printing ink, which was then dried and hardened to form the character "2," thereby producing a second non-color-changing printed matter 4'. Furthermore, the support 41" was prepared by printing the food photograph used in producing the third photochromic printed matter on one side of white Kent paper using the above-mentioned four colors of non-color-changing printing inks (cyan, magenta, yellow, and black) in sequence with a plate made by process photo separation to form a non-color-changing image 42". Next, the lower center of the other side of the support (the side of the support opposite to where the non-color-changing image is formed) was offset printed using black non-color-changing offset printing ink, which was then dried and hardened to form the letter "3", thereby producing a third non-color-changing printed matter 4".

[0085] Making a toy camera (see Figure 15) An opening 31' for inserting and removing a non-color-changing printed matter is provided at the top of a camera body 30 that imitates the appearance of an instant camera having a viewfinder 38, an opening 31 for inserting and removing a photochromic printed matter is provided at the front of the camera body, a blue LED (peak wavelength 430 nm) as a light source 32 and a dry cell as a power source 33 are attached inside the camera body, and a holder 39 for holding the non-color-changing printed matter in a predetermined position is provided, a mounting member 350 with a frame 351 attached is provided so as to connect to the opening 31, and a switch 34 imitating a shutter button is further provided on the camera body to produce a toy camera 3. In the toy camera described above, the light source is disposed at the top inside the camera body so that light is irradiated onto the photochromic printed matter, and the light source, power source, and switch are connected by wires, and when the switch is pressed, the switch turns on and light is irradiated from the light source, and after a certain time has passed, the switch turns off and the irradiation of light from the light source automatically stops.

[0086] Making a toy camera set Each of the above photochromic printed materials, each of the non-photochromic printed materials, and a toy camera were combined to create a toy camera set.

[0087] Before inserting the photochromic printed material and the non-color-changing printed material into the opening of the camera toy, a first photochromic printed material and a first non-color-changing printed material on which the letter "1" is printed are selected from the multiple photochromic printed materials and non-color-changing printed materials, respectively. The first non-color-changing printed material is inserted into the opening for inserting and removing the non-color-changing printed material with the non-color-changing image of the first non-color-changing printed material facing the viewfinder, and the first photochromic printed material before light irradiation is inserted into the opening for inserting and removing the photochromic printed material with the reversible photochromic image facing up. When this is done, an image of a building photograph made by the first non-color-changing printed material is visible through the viewfinder of the camera toy, and when a switch is pressed, light is irradiated onto the first photochromic printed material for a certain period of time, causing the reversible photochromic image to change color. When the first photochromic printed material is removed from the opening after the light irradiation is stopped, a printed material with the image of the building photograph revealed is obtained. Therefore, even if the photochromic printed matter is not yet irradiated with light and the image due to the reversible photochromic image is not visible, by selecting a photochromic printed matter and a non-color-changing printed matter with the same characters printed on the printed matter, the type of image that appears on the photochromic printed matter can be determined in advance from the non-color-changing printed matter, and the printed matter on which the desired image appears can be selected for play. Furthermore, it was easy to make the non-color-changing image visible through the viewfinder the same as the image that appears on the photochromic printed matter. Furthermore, when a second photochromic printed material and a second non-color-changing printed material with the letter "2" printed thereon, or a third photochromic printed material and a third non-color-changing printed material with the letter "3" printed thereon, were selected from among a plurality of photochromic printed materials and non-color-changing printed materials, a print appearing a landscape photograph or a food photograph could be obtained by following a similar procedure. The toy camera set described above allows a child to play with an instant camera that takes pictures instantly when the child presses the shutter button, making it possible to feel as if the child is actually using the camera. The same image as seen through the viewfinder is visible on the printed matter, making it even more realistic. Since the image can be made to appear on the printed matter by simply pressing the switch, the child can play with the camera easily. Furthermore, since a dry cell battery is installed inside the camera body as a power source, the toy camera set can be used both indoors and outdoors, regardless of the weather. Also, as shown in FIG. 16, the first non-color-changing printed material 4, the second non-color-changing printed material 4', and the third non-color-changing printed material 4" are stacked in order on the third non-color-changing printed material with the non-color-changing images (42, 42', 42") facing up, and the second non-color-changing printed material and the first non-color-changing printed material are inserted into the opening 31' with the non-color-changing image of the first non-color-changing printed material facing the viewfinder side. Furthermore, the first photochromic printed material 2, the second photochromic printed material 2', and the third photochromic printed material 2" before light irradiation are inserted into the opening 31'. The second photochromic printed material and the first photochromic printed material are layered in that order on top of the third photochromic printed material, with the reversible photochromic images (22, 22', 22") facing up, and when they are inserted into the opening 31 in this state, the image of a building photograph made by the first non-color-changing printed material is visible through the viewfinder. When a switch is pressed, light is irradiated onto the first photochromic printed material for a certain period of time, causing the reversible photochromic image to change color. After the light irradiation is stopped, the first photochromic printed material is removed from the opening 31, and a print in which the image of the building photograph appears is obtained. Next, when the first non-color-changing printed material is removed from the opening 31', an image of the landscape photograph made of the second non-color-changing printed material is visible through the viewfinder, and when a switch is pressed, light is irradiated onto the second photochromic printed material for a certain period of time, causing the reversible photochromic image to change color. After the light irradiation is stopped, the second photochromic printed material is removed from the opening, and a print showing the image of the landscape photograph is obtained. Next, when the second non-color-changing printed material is removed from the opening 31', an image of a food photo made of the third non-color-changing printed material is visible through the viewfinder, and when a switch is pressed, light is irradiated onto the third photochromic printed material for a certain period of time, causing the reversible photochromic image to change color.After the light irradiation is stopped, the third photochromic printed material is removed from the opening 31, and a print showing the image of the food photo is obtained. Therefore, the above-mentioned camera toy set can be played with by inserting a stack of multiple non-color-changing printed materials and photocolor-changing printed materials into the opening, allowing the child to take multiple pictures in succession, further enhancing the sense of using a real camera. If the print was left indoors for a while after being exposed to light, the image would disappear and it would return to its original white state, so the same print could be played with repeatedly. In addition, the light source used in the above camera toy has a peak emission wavelength of 430 nm and emits blue light, so the camera toy set has little effect on the human body and is highly safe.

[0088] Example 6 Preparation of photochromic printed matter (see Figure 3) The four photochromic printing inks (cyan, magenta, yellow, and black) described above were used on white Kent paper as a support 21, and a reversible photochromic image 22 was formed by printing the original mountain landscape photograph using a plate made by process photographic resolution in sequence onto the paper, thereby producing a first photochromic print 2. The first photochromic print was white before it was irradiated with light from a light source, but when it was irradiated with light, the reversible photochromic image changed color to reveal a mountain landscape image. After that, when it was left indoors for a while, it returned to its original white color. In addition, a second photochromic print 2' was produced by printing a reversible photochromic image 22' on a transparent PET film as a support 21' using the above-mentioned four photochromic printing inks (cyan, magenta, yellow, and black) sequentially with a plate made by process photographic resolution of an original portrait photograph. In addition, a third photochromic print 2" was produced by printing a reversible photochromic image 22" on a transparent PET film as a support 21" using the above-mentioned four photochromic printing inks (cyan, magenta, yellow, and black) sequentially with plates made by process photographic resolution of original animal photographs. The second or third photochromic print was transparent before being irradiated with light from a light source, but when irradiated with light, the reversible photochromic image changed color to reveal an image of a person or an animal. After that, when left indoors for a while, the original white color returned.

[0089] Making a toy camera Each of the above photochromic printed materials was combined with the toy camera of Example 1 to create a toy camera set.

[0090] When the photochromic print before light irradiation was inserted into the opening of the toy camera with the reversible photochromic image facing up and a switch was pressed, the print was irradiated with light for a certain period of time, causing the reversible photochromic image to change color, and when the print was taken out of the opening after the light irradiation was stopped, a print in which an image of a mountain landscape appeared was obtained. Furthermore, the first and second photochromic printed materials before light irradiation are each placed with the reversible photochromic image facing up, with the second photochromic printed material layered on top of the first photochromic printed material, and when this state is inserted into the opening of the toy camera and the switch is pressed, light is irradiated onto the first and second photochromic printed materials for a certain period of time, causing each of the reversible photochromic images to change color, and when the first and second photochromic printed materials are removed from the opening in a layered state after the light irradiation is stopped, the mountain scenery photograph image made on the first photochromic printed material (reversible photochromic image 22) and the portrait image made on the second photochromic printed material (reversible photochromic image 22") are superimposed, resulting in the production of a print in which an image of a portrait against a mountain scenery background appears. Furthermore, the first and third photochromic printed materials before light irradiation are each placed with the reversible photochromic image facing up, and the third photochromic printed material is layered on the first photochromic printed material. When this state is inserted into the opening of the toy camera and the switch is pressed, light is irradiated onto the first and third photochromic printed materials for a certain period of time, causing each of the reversible photochromic images to change color. When the first and third photochromic printed materials are removed from the opening in a layered state after the light irradiation is stopped, the mountain scenery photo image made of the first photochromic printed material (reversible photochromic image 22) and the animal photo image made of the third photochromic printed material (reversible photochromic image 22") are superimposed, resulting in a print in which an animal photo image appears against a mountain scenery background. Thus, the above camera toy set allows the user to experience the feeling of using a real camera by irradiating light from a light source onto a reversible photochromic image provided on a photochromic printed matter (photochromic printed matter 2) using a non-light-transmitting support (white Kent paper) to cause the image to appear on the printed matter and discolor it, and in addition, when a photochromic printed matter (photochromic printed matter 2' or 2") using a light-transmitting support (transparent PET film) is layered on a photochromic printed matter using a non-light-transmitting support (white Kent paper) with the reversible photochromic image facing up, and the reversible photochromic images are layered on top of each other to cause the reversible photochromic images to overlap, causing a new image different from reversible photochromic image 22 to appear on the printed matter. Furthermore, by changing the type of photochromic printed matter using a light-transmitting support (transparent PET film) to be layered, the type of image that appears on the printed matter can be changed, and the variety of images that can be made to appear makes this a camera toy set with excellent playability. In addition, the camera toy set described above allows a child to experience the sensation of actually using an instant camera that takes a photo instantly by pressing the shutter button, making it easy to play with since an image can be made to appear on the printout simply by pressing the switch. Also, since a dry cell battery is installed inside the camera body as a power source, the camera toy set can be used both indoors and outdoors regardless of the weather. If the print was left indoors for a while after being exposed to light, the image would disappear and it would return to its original white state, so the same print could be played with repeatedly. In addition, the light source used in the above camera toy has a peak emission wavelength of 430 nm and emits blue light, so the camera toy set has little effect on the human body and is highly safe.

[0091] Example 7 Preparation of reversible photochromic microencapsulated pigments A reversible photochromic microcapsule pigment (average particle size: 5 μm) was prepared by encapsulating a reversible photochromic composition prepared by uniformly dissolving 1 part of 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene in 50 parts of butyl stearate with heating in a microcapsule pigment made of urethane resin. The above microcapsule pigment was colorless before being irradiated with light, but changed to blue when irradiated with light. After that, even if it was left for a while either indoors or in a dark place, the state of changing to blue was maintained.

[0092] Preparation of photochromic printing inks A blue photochromic screen printing ink was prepared by uniformly mixing 40 parts of the above microcapsule pigment in a vehicle consisting of 58 parts of ethylene-vinyl acetate copolymer resin emulsion, 3 parts of defoaming agent, 1 part of thickener, 3 parts of leveling agent, and 1 part of preservative.

[0093] Preparation of photochromic printed matter (see Figure 3) A reversible photochromic image 22 of a train design was formed by screen printing on a white Kent paper substrate 21 using the above-mentioned blue photochromic screen printing ink, to produce a photochromic print 2. The photochromic print was white before being irradiated with light from a light source, but when irradiated with light, the reversible photochromic image changed color and an image of a train appeared. After that, even if it was left indoors or in a dark place, the image remained visible without discoloration. The reversible photochromic image returned to its original white color by using the decolorizer described below.

[0094] Making a toy camera A toy camera was created by providing an opening on the side of a camera body that imitates the appearance of a rangefinder camera with a viewfinder, installing a blue LED (peak wavelength: 430 nm) as a light source and a dry cell as a power source inside the camera body, providing a mounting member with a fastener attached so as to connect to the opening, and further providing a switch imitating a shutter button on the camera body. In the above toy camera, the light source is placed at the front inside the camera body so that light is irradiated onto the photochromic printed matter, and the light source, power source, and switch are connected by wires, and when the switch is pressed, it turns on and light is irradiated from the light source, and after a certain time has passed it turns off and the light irradiation from the light source automatically stops.

[0095] Making a toy camera set The above photochromic printed matter was combined with a toy camera to create a toy camera set.

[0096] When the photochromic print before light irradiation was inserted into the opening of the toy camera with the reversible photochromic image facing the front of the camera body and a switch was pressed, the print was irradiated with light for a certain period of time, causing the reversible photochromic image to change color, and when the print was removed from the opening after the light irradiation was stopped, a blue image of a train appeared on the print. The toy camera set described above allows a child to play with the camera while experiencing the feeling of actually using the camera, since an image appears on the printed matter when the child presses a switch that resembles a shutter button, and the image that appears on the printed matter is blue, simulating a daylight photograph. Since the image appears on the printed matter by simply pressing a switch, the child can play with the camera easily, and since a dry cell battery is installed inside the camera body as a power source, the camera set can be used both indoors and outdoors, regardless of the weather. After exposure to light, the print will not revert to its original white color whether left indoors or in a dark place, and the image of the train can be preserved semi-permanently if stored in a dark place. In addition, the light source used in the above camera toy has a peak emission wavelength of 430 nm and emits blue light, so the camera toy set has little effect on the human body and is highly safe.

[0097] Making an erasing tool (see Figure 17) An opening 51 was provided on the side of a rectangular parallelepiped case 50 [width (W) 80 mm × depth (D) 50 mm × height (H) 50 mm], an LED (peak wavelength: 630 nm) was installed as a light source 52, and a dry cell was installed as a power source 53 inside the case, a mounting member 550 with a frame 551 attached was provided so as to connect to the opening, and a switch 54 was further provided on the case to produce the erasing tool 5. In the above erasing tool, the light source is placed at the top inside the case so that light is irradiated onto the photochromic printed matter, and the light source, power source, and switch are connected by wires, and when the switch is pressed, the switch turns on and light is irradiated from the light source, and after a certain time has passed, the switch turns off and the irradiation of light from the light source automatically stops.

[0098] When a photochromic print showing an image of a train was inserted into the opening of the erasing tool with the reversible photochromic image facing up and a switch was pressed, light was irradiated onto the print for a certain period of time, causing the reversible photochromic image to disappear, and when the print was removed from the opening after the light irradiation was stopped, the original white print was obtained. By using an erasing tool, the print would return to its original white color from the image of a train, allowing children to play with the same print repeatedly. [Explanation of symbols]

[0099] 1. Camera toy set 2, 2′, 2″ Photochromic prints 21, 21′, 21″ support 22, 22', 22" Reversible photochromic image (first reversible photochromic image) 23 Second reversible photochromic image 24, 24' Non-discolored images 3. Camera toys 30 Camera Body 31, 31′ Opening 32 light source 33, 33′ power supply 34 Switch 350 Mounting member (stage) 351 Frame 36 Window section 37 Strobe Light Source 38 Finder 39 Holding part 4, 4′, 4″ Non-discoloring print 41, 41′, 41″ support 42, 42′, 42″ Non-discolored images 5 Eraser 50 cases 51 Opening 52 Light source 53 Power supply 54 Switch 550 Mounting member (stage) 551 Frame

Claims

1. A camera toy set comprising a photochromic printed matter having a reversible photochromic image provided on a support, the reversible photochromic image comprising a reversible photochromic material at least consisting of a photochromic compound, and a camera toy imitating the appearance of a camera, the camera toy having an opening in the camera body for inserting and removing the photochromic printed matter and a light source inside the camera body, the reversible photochromic image being an image formed by process printing using at least three colors of photochromic printing inks in which the reversible photochromic material, which develops colors of cyan, magenta and yellow when irradiated with light, is dispersed in a vehicle, respectively.

2. 2. The toy camera set according to claim 1, wherein the light source has a peak wavelength in the range of 400 to 495 nm.

3. 3. The camera toy set according to claim 1, further comprising a power source provided on or within said camera body, said power source and said light source being connected by a wire.

4. 4. The camera toy set according to claim 3, further comprising a switch on said camera body which is energized when pressed, said switch being connected to said power source and said light source by wires.

5. 5. The camera toy set according to claim 1, wherein the reversible photochromic material further comprises an oligomer.

6. A camera toy set described in any one of claims 1 to 5, wherein the photochromic compound in the reversible photochromic material is a spirooxazine-based compound for cyan color, a naphthodipyrane-based compound for magenta color, and a naphthodipyrane-based compound for yellow color.

7. A camera toy set described in any one of claims 1 to 6, wherein the photochromic compound in the reversible photochromic material is a compound represented by the following general formula (1) for cyan, a compound represented by the following general formulas (2) to (4) for magenta, and a compound represented by the following general formula (6) or (7) for yellow. 【Chemistry 1】 (In the formula, R 1 and R 2 each represent an alkyl group having 1 to 3 carbon atoms; R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, a mono-, di-, or tri-substituted phenyl group, or an alkoxy group; R 4 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, a mono-, di-, or tri-substituted phenyl group, an alkoxy group, a morpholino group, an alkoxycarbonyl group, or a cyano group; and A represents =CH- or =N-.) 【Chemistry 2】 [wherein R 5 to R 8 represent the following general formula (5), R 11 to R 14 represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, R 15 represents an alkyl group having 3 or more carbon atoms, and * represents a bonding site with the pyran skeleton] 【Chemistry 3】 【Chemistry 4】 [In the formula, R 9 to R 12 represent the following general formula (8), R 21 to R 24 represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, R 25 represents a hydrogen atom, a methoxy group, or an ethoxy group, and * represents a bonding site with the pyran skeleton] 【Chemistry 5】

Images