Reversible photochromic material

Abstract

To provide a reversible photochromic material that enables development of a yellow to orange color when irradiated with light, shows superior density in the colored state, and allows control of color-change sensitivity.SOLUTION: A reversible photochromic material comprising a naphthopyran-based photochromic compound having a specific structure and an oligomer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a reversible photochromic material. [Background technology]

[0002] Conventionally, photochromic materials that have improved light resistance and density in a colored state have been disclosed that consist of a photochromic compound selected from spirooxazine derivatives or spiropyran derivatives and a styrene-based oligomer having a weight-average molecular weight of 200 to 6000 (see, for example, Patent Document 1). Furthermore, as a photochromic material having a high density in the colored state and capable of adjusting the decolorization sensitivity, a photochromic material consisting of a photochromic compound selected from spirooxazine derivatives or spiropyran derivatives and an acrylic oligomer having a weight-average molecular weight of 12,000 or less has been disclosed (see, for example, Patent Document 2). Furthermore, as a photochromic composition capable of adjusting the color change sensitivity, a photochromic composition consisting of a chromene-based photochromic compound having a specific structure and a styrene-based oligomer or terpene-based oligomer having a weight-average molecular weight of 250 to 4000 has been disclosed (see, for example, Patent Document 3). Furthermore, a photochromic coloring material comprising a photochromic compound and a terpene phenol resin has been disclosed as a photochromic coloring material that has little residual color in a decolorized state and high density in a colored state (see, for example, Patent Document 4). The above Patent Documents 1 to 4 are inventions that can improve light resistance and density in a colored state, as well as adjust color change sensitivity and can be applied to various fields such as toys, writing implements, education, medicine, interior design, decoration, and printing. However, they do not disclose the application of naphthopyran-based photochromic compounds with specific structures. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-48159 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-231573 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-180396 [Patent Document 4] International Publication No. 2015 / 111744 Brochure Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention aims to provide a reversible photochromic material comprising a specific naphthopyran-based photochromic compound and an oligomer, which develops a yellow to orange color upon irradiation with light, has adjustable color change sensitivity, and exhibits excellent density in the colored state. [Means for solving the problem]

[0005] The present invention relates to a reversible photochromic material comprising a photochromic compound represented by the following general formula (1) and an oligomer. [ka] (In general formula (1), R 11A and R 11B each independently represents a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent; R 12A and R 12B each independently represents a hydrogen atom, an optionally substituted linear, branched, or cyclic alkoxy group, or an optionally substituted aryloxy group; R 13A , R 14A , R 15A , R 13B , R 14B , and R 15Bare each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched, or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched, or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched, or cyclic alkyl group, or an optionally substituted aryl group, X A and X B represent, independently of each other, an oxygen atom or a sulfur atom. Also, R 12A and R 12B are each independently a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms; R 12A and R 12B is a hydrogen atom, R 11A and R 11B are each independently a linear or branched alkyl group having 1 to 8 carbon atoms; R 13A , R 14A , R 15A , R 13B , R 14B , and R 15B are each independently a hydrogen atom, a halogen atom, or a linear, branched, or cyclic alkoxy group which may have a substituent; X A and X B is an oxygen atom; the oligomer is selected from the group consisting of a styrene-based oligomer, an acrylic-based oligomer, a terpene-based oligomer, and a terpene-phenol-based oligomer; and the photochromic compound is a reversibly photochromic microcapsule pigment containing the photochromic compound and the oligomer, or a reversibly photochromic resin particle containing the photochromic compound and the oligomer dispersed in a thermoplastic resin or a thermosetting resin. Furthermore, the present invention requires a reversibly photochromic liquid composition comprising the reversibly photochromic material and a vehicle. Furthermore, the present invention provides a reversibly photochromic solid writing material or a reversibly photochromic solid cosmetic comprising the reversibly photochromic material and an excipient. Furthermore, the present invention requires a reversibly photochromic molding resin composition comprising the reversibly photochromic material and a molding resin. Furthermore, the present invention requires a reversibly photochromic laminate comprising a support and a reversibly photochromic layer containing the reversibly photochromic material. [Effects of the Invention]

[0006] The present invention provides a reversible photochromic material that comprises a specific naphthopyran-based photochromic compound and an oligomer, and that changes color to yellow or orange when irradiated with light. The reversible photochromic material has excellent density in the colored state and adjustable color change sensitivity. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a graph showing the relationship between wavelength and absorbance of a photochromic compound. DETAILED DESCRIPTION OF THE INVENTION

[0008] The reversibly photochromic material according to the present invention comprises a specific naphthopyran-based photochromic compound (hereinafter sometimes referred to as "photochromic compound"). Photochromic compounds have a reversible photochromic function (hereinafter sometimes referred to as "reversible photochromic function"), whereby they develop color when irradiated with light and lose color when the light irradiation is stopped. That is, depending on whether or not light is irradiated, photochromic compounds reversibly change from a decolorized state (hereinafter sometimes referred to as "decolorized state") to a colored state (hereinafter sometimes referred to as "colored state"). They also have the characteristic of decolorizing when heated after developing color due to light irradiation. The reversible photochromic material containing this photochromic compound has the same characteristics, and reversibly changes color depending on whether or not it is irradiated with light. Each component constituting the reversibly photochromic material of the present invention will be described below.

[0009] The naphthopyran-based photochromic compound of the present invention is a compound represented by formula (1), which develops a yellow to orange color when irradiated with light and has excellent density in the colored state (hereinafter sometimes referred to as "color density"). [ka] (In general formula (1), R 11A and R 11B each independently represents a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent; R 12A and R 12B each independently represents a hydrogen atom, an optionally substituted linear, branched, or cyclic alkoxy group, or an optionally substituted aryloxy group; R 13A , R 14A , R 15A , R 13B , R 14B , and R 15B are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched, or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched, or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched, or cyclic alkyl group, or an optionally substituted aryl group, X A and X B represent, independently of each other, an oxygen atom or a sulfur atom.

[0010] In general formula (1), R 11A and R 11Brepresent, independently of each other, a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0011] R 11A and R 11B Examples of the linear, branched, or cyclic alkyl group which may have a substituent include linear, branched, or cyclic alkyl groups which have 1 to 20 carbon atoms and may have a substituent. In this specification, the number of carbon atoms in a group which may have a substituent refers to the number of carbon atoms in the entire group including the substituent. The substituent is not particularly limited, and examples thereof include monocyclic or polycyclic aromatic groups having 6 to 10 carbon atoms, such as phenyl or naphthyl; linear, branched, or cyclic alkoxy groups having 1 to 8 carbon atoms; amino groups; mono- or di-alkylamino groups (where the alkyl has 1 to 8 carbon atoms); halogen atoms; cyano groups; hydroxy groups; nitro groups; carboxy groups; alkoxycarbonyl groups having 1 to 8 carbon atoms; acyl groups having 2 to 10 carbon atoms; acyloxy groups having 2 to 10 carbon atoms; and alkenyl groups having 2 to 10 carbon atoms. Substituents in cyclic alkyl groups that may have a substituent include linear or branched alkyl groups having 1 to 10 carbon atoms. When an alkyl group has two or more substituents, the respective substituents may be the same or different. The substituent is preferably a halogen atom; a linear, branched, or cyclic alkoxy group having 1 to 8 carbon atoms, a hydroxy group, or a monocyclic or polycyclic aromatic group having 6 to 10 carbon atoms. Examples of the linear, branched, or cyclic alkyl group having the above substituent include a fluoromethyl group, a chloromethyl group, a bromobutyl group, a methoxymethyl group, a methoxyethyl group, a hydroxyethyl group, and a benzyl group.

[0012] R 11A and R 11BExamples of the aryl group which may have a substituent include an aryl group having 6 to 20 carbon atoms which may have a substituent. Examples of the aryl group include monocyclic aromatic hydrocarbon groups such as a phenyl group, and polycyclic aromatic hydrocarbon groups such as a naphthyl group. The substituent is not particularly limited, and examples thereof include a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; an amino group; a mono- or di-alkylamino group (wherein the alkyl has 1 to 8 carbon atoms); a halogen atom; a cyano group; a hydroxy group; a nitro group; a halogenated hydrocarbon group having 1 to 8 carbon atoms; a carboxy group; an alkoxycarbonyl group having 1 to 8 carbon atoms; and a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms. When the aryl group has two or more substituents, the respective substituents may be the same or different. The substituent is preferably a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, or a halogen atom. Examples of the aryl group having the above substituent include a nitrophenyl group, a cyanophenyl group, a hydroxyphenyl group, a carboxyphenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a methoxyphenyl group, an ethoxyphenyl group, a trifluoromethylphenyl group, an N,N-dimethylaminophenyl group, a nitronaphthyl group, a cyanonaphthyl group, a hydroxynaphthyl group, a methylnaphthyl group, a fluoronaphthyl group, a chloronaphthyl group, a bromonaphthyl group, a trifluoromethylnaphthyl group, a phenoxyphenyl group, and a biphenyl group.

[0013] In general formula (1), R 11A and R 11B are each independently preferably a linear or branched alkyl group of 1 to 8 carbon atoms which may have a substituent, more preferably a linear or branched alkyl group of 1 to 6 carbon atoms which may have a substituent, still more preferably a linear or branched alkyl group of 1 to 5 carbon atoms which may have a substituent, and particularly preferably a linear or branched alkyl group of 1 to 4 carbon atoms which may have a substituent. The linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, is preferably a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, and more preferably a methyl group, an ethyl group, or a sec-butyl group. R 11A and R 11B are preferably the same.

[0014] In general formula (1), R 12A and R 12B represent, independently of each other, a hydrogen atom, an optionally substituted linear, branched, or cyclic alkoxy group, or an optionally substituted aryloxy group.

[0015] R 12A and R 12B The optionally substituted linear, branched, or cyclic alkoxy group in the above formula includes an optionally substituted linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms. The substituent is not particularly limited, and examples thereof include a halogen atom, a hydroxy group, a linear, branched, or cyclic alkoxy group having 1 to 18 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 16 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an amino group, and a mono- or di-alkylamino group (wherein the alkyl group has 1 to 8 carbon atoms). Some or all of the hydrogen atoms in the alkoxy group may be substituted with halogen atoms.

[0016] R 12A and R 12B The aryloxy group in the formula (I) may have a substituent, and may be a monocyclic or polycyclic aryloxy group having 6 to 20 carbon atoms and may have a substituent. The substituent is not particularly limited, and examples thereof include a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms; a linear, branched, or cyclic alkoxy group having 1 to 8 carbon atoms; an amino group; a mono- or di-alkylamino group (the alkyl group has 1 to 8 carbon atoms); a halogen atom; a cyano group; a hydroxy group; a nitro group; and an aryloxy group having 6 to 14 carbon atoms. The substituent is preferably a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, or a halogen atom. Examples of the aryloxy group having the above substituent include a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-tert-butylphenoxy group, a 2-methoxyphenoxy group, a 4-isopropylphenoxy group, and a phenoxyphenoxy group.

[0017] In general formula (1), R 12A and R 12B are each independently preferably a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or a linear or branched alkoxy group having 1 to 4 carbon atoms which may have a substituent, still more preferably a hydrogen atom or a linear or branched alkoxy group having 3 or 4 carbon atoms which may have a substituent, and particularly preferably a hydrogen atom. The linear or branched alkoxy group having 1 to 4 carbon atoms, which may have a substituent, is preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, or a tert-butoxy group, more preferably an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, or a tert-butoxy group, and still more preferably a sec-butoxy group. R 12A and R 12B are preferably the same.

[0018] In general formula (1), R 13A , R 14A , R 15A , R 13B , R 14B, and R 15B are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched, or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched, or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 Represents. R 21 represents a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent. 21 is preferably a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0019] R 13A , R 14A , R 15A , R 13B , R 14B , and R 15B In the above, the optionally substituted linear, branched, or cyclic alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, which may have a substituent. The optionally substituted aryl group is preferably an aryl group having 6 to 12 carbon atoms, which may have a substituent. The optionally substituted linear, branched, or cyclic alkoxy group is preferably an optionally substituted linear, branched, or cyclic alkoxy group having 1 to 12 carbon atoms, which may have a substituent. The optionally substituted aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms, which may have a substituent. R 13A and R 13B , R 14A and R 14B , and R 15A and R 15B are preferably the same.

[0020] In general formula (1), R 13A , R 14A , R 15A , R 13B , R14B , and R 15B are each independently preferably a hydrogen atom, a halogen atom, or a linear, branched, or cyclic alkoxy group which may have a substituent, more preferably a hydrogen atom, a halogen atom, or a linear or branched alkoxy group which has 1 to 12 carbon atoms and may have a substituent, still more preferably a hydrogen atom, a halogen atom, or a linear or branched alkoxy group which has 1 to 12 carbon atoms, and particularly preferably a hydrogen atom. As the halogen atom, a fluorine atom or a chlorine atom is preferred.

[0021] In general formula (1), X A and X B X each independently represents an oxygen atom or a sulfur atom. A and X B is preferably an oxygen atom.

[0022] The naphthopyran-based photochromic compound according to the present invention is a compound represented by the general formula (1) below: 11A and R 11B are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and R 12A and R 12B are each independently a hydrogen atom or a linear or branched alkoxy group having 1 to 4 carbon atoms which may have a substituent, and R 13A , R 14A , R 15A , R 13B , R 14B , and R 15B is a hydrogen atom, and X A and X B is preferably an oxygen atom, and in general formula (1), R 11A and R 11B are, independently of one another, a methyl group, an ethyl group, or a sec-butyl group; R 12A and R 12B are each independently a hydrogen atom or a sec-butoxy group, and R 13A , R 14A , R 15A , R 13B , R 14B , and R 15Bis a hydrogen atom, and X A and X B is more preferably an oxygen atom.

[0023] The naphthopyran-based photochromic compound according to the present invention has excellent light resistance and rapidly changes from a colored state to a colorless state. 11A and R 11B are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and R 12A and R 12B is a hydrogen atom, and R 13A , R 14A , R 15A , R 13B , R 14B , and R 15B is a hydrogen atom, and X A and X B is preferably an oxygen atom. Furthermore, since the color density is even more excellent, the naphthopyran-based photochromic compound according to the present invention is preferably a compound represented by the general formula (1) where R 11A and R 11B are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and R 12A and R 12B are each independently a linear or branched alkoxy group having 1 to 4 carbon atoms, and R 13A , R 14A , R 15A , R 13B , R 14B , and R 15B is a hydrogen atom, and X A and X B is an oxygen atom, and R 11A and R 12A , and R 11B and R 12B More preferred are compounds in which the total number of carbon atoms in each of the above is 2 to 8 (preferably 3 to 7, more preferably 4 to 6).

[0024] Specific examples of the naphthopyran-based photochromic compound according to the present invention include the following compounds. 3,10-bis(4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-n-propoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-isopropoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-n-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-isobutoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-n-pentyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-n-hexyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-n-heptyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(4-n-octyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2,4-dimethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-ethoxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-propoxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isopropoxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-butoxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isobutoxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-sec-butoxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-hexyloxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-octyloxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-methoxy-4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane 3,10-bis(2-n-propoxy-4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isopropoxy-4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-butoxy-4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isobutoxy-4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-sec-butoxy-4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-methoxy-4-n-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-propoxy-4-n-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isopropoxy-4-n-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2,4-di-n-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isobutoxy-4-n-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-sec-butoxy-4-n-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-methoxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-ethoxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-propoxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isopropoxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-butoxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-isobutoxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2,4-di-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-hexyloxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-n-octyloxy-4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b']-dipyrane, 3,10-bis(2-methoxy-4-n-hexyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b']-dipyrane, 3,10-bis(2-ethoxy-4-n-hexyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-sec-butoxy-4-n-hexyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-methoxy-4-n-octyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-bis(2-ethoxy-4-n-octyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane, 3,10-Bis(2-sec-butoxy-4-n-octyloxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane

[0025] The method for producing the naphthopyran-based photochromic compound according to the present invention is not particularly limited, and can be obtained, for example, by reacting 2,7-dihydroxynaphthalene with a compound represented by the following general formula (2A) (hereinafter sometimes referred to as "compound (2A)") and a compound represented by the following general formula (2B) (hereinafter sometimes referred to as "compound (2B)"). When carrying out the reaction described below, functional groups other than those at the relevant sites may be protected in advance with appropriate protecting groups as necessary, and these may be deprotected at an appropriate stage.

[0026] [ka]

[0027] R in the above general formula (2A) 11A , R 12A , R 13A , R 14A , R 15A , and X A are R in general formula (1), 11A , R 12A , R 13A , R 14A , R 15A , and X A R in general formula (2A) 11A , R 12A , R 13A , R 14A , R 15A , and X A Preferred substituents are R 11A , R 12A , R 13A , R 14A , R 15A , and X A The preferred substituents are the same as those of the above.

[0028] R in the above general formula (2B)11B , R 12B , R 13B , R 14B , R 15B , and X B are R in general formula (1), 11B , R 12B , R 13B , R 14B , R 15B , and X B R in general formula (2B) 11B , R 12B , R 13B , R 14B , R 15B , and X B Preferred substituents are R 11B , R 12B , R 13B , R 14B , R 15B , and X B The preferred substituents are the same as those of the above.

[0029] Compound (2A) and compound (2B) may be the same compound or different compounds, but are preferably the same compound.

[0030] The conditions for reacting 2,7-dihydroxynaphthalene with compound (2A) and compound (2B) are not particularly limited, but the reaction is usually carried out in a solvent in the presence of an acid catalyst.

[0031] The acid catalyst is not particularly limited, and examples thereof include organic acids such as p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, and pyridinium p-toluenesulfonate.

[0032] The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include dichloroethane, toluene, xylene, ethanol, isopropyl alcohol, and acetonitrile.

[0033] The reaction temperature can be set to 20 to 100°C, preferably 30 to 70°C. The reaction time can be set to 1 to 24 hours, preferably 1.5 to 5 hours. The reaction efficiency can be improved by adding a dehydrating agent such as trimethyl orthoformate to the reaction system.

[0034] The method for producing Compound (2A) and Compound (2B) is not particularly limited, and they can be produced by the methods described in, for example, JP-A No. 2012-501326 and CN103936793A.

[0035] The naphthopyran-based photochromic compound according to the present invention can be made to develop color by irradiation with sunlight or light containing ultraviolet rays such as ultraviolet light, but it can also be made to develop color using a light irradiator equipped with a light source for irradiating light. The light source is preferably one that irradiates purple to blue light with a peak emission wavelength in the range of 400 to 495 nm. Light sources with a peak emission wavelength of around 350 to 390 nm contain ultraviolet rays (particularly UVA) like sunlight and ultraviolet light, and can cause conventional photochromic compounds to develop color well, but UVA may penetrate deep into human skin and affect the skin. On the other hand, light sources that irradiate purple to blue light with a peak emission wavelength in the range of 400 to 495 nm have little effect on the human body and are highly safe, so light irradiators equipped with such light sources are preferably used.

[0036] The light source is not particularly limited as long as it has a peak emission wavelength in the above range, but a violet to blue light emitting diode (LED) is preferred. Examples of such light emitting diodes include purple light emitting diodes and blue light emitting diodes available from Nichia Corporation, Kyo Semiconductor Corporation, OPTOSUPPLY, Optocode Corporation, and the like.

[0037] The naphthopyran-based photochromic compound has an integrated absorbance value (x) in the range from the wavelength showing the maximum absorbance at less than 400 nm to a wavelength of 400 nm, and an integrated absorbance value (y) in the wavelength range of 400 nm to 700 nm that satisfies the following formula (3) (see Figure 1). y / x≧0.02 (3) By satisfying formula (3), the photochromic compound exhibits a reversible photochromic function when exposed to a light source with a peak emission wavelength in the range of 400 to 495 nm, and shows a visible color density when exposed to light. If y / x is less than 0.02, the photochromic compound will not develop color even when exposed to light using a light irradiator, or will develop very little color, resulting in insufficient color density and making it difficult for the user to visually recognize the color change. The ratio y / x is preferably 0.025 or more, and more preferably 0.03 or more.

[0038] The reversible photochromic material according to the present invention comprises an oligomer. As the reversible photochromic material, a reversible photochromic composition in which the above photochromic compound is dissolved in an oligomer can be used. By dissolving the photochromic compound in the oligomer, it is possible to improve both the light resistance and color density of the photochromic compound, and further to adjust the color change sensitivity of the photochromic compound. The oligomer is at least one selected from the group consisting of styrene-based oligomers, acrylic-based oligomers, terpene-based oligomers, and terpene-phenol-based oligomers. The oligomers can be used alone or in combination of two or more.

[0039] The styrene-based oligomer preferably has a mass-average molecular weight of 200 to 6000, more preferably 200 to 4000. If the mass-average molecular weight exceeds 6000, color retention is likely to occur upon light irradiation, the color density is likely to be low, and it becomes difficult to adjust the color change sensitivity. On the other hand, if the mass-average molecular weight is less than 200, the amount of contained monomer increases, resulting in a lack of stability and a tendency to impair light resistance. 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.

[0040] The acrylic oligomer preferably has a mass-average molecular weight of 12,000 or less, more preferably 1,000 to 8,000, and even more preferably 1,500 to 6,000. If the mass-average molecular weight exceeds 12,000, it becomes difficult to adjust the discoloration sensitivity. On the other hand, if the mass-average molecular weight is less than 1,000, the amount of contained monomer increases, resulting in a lack of stability, which tends to result in a low color density and a loss of lightfastness. Examples of the acrylic oligomer include acrylic acid ester copolymers.

[0041] The terpene oligomer preferably has a mass-average molecular weight of 250 to 4000, more preferably 300 to 4000. If the mass-average molecular weight exceeds 4000, color retention is likely to occur upon light irradiation, the color density is likely to be low, and it becomes difficult to adjust the color change sensitivity. On the other hand, if the mass-average molecular weight is less than 250, the amount of contained monomer increases, resulting in a lack of stability and a tendency to impair lightfastness. Terpene oligomers are compounds having a terpene skeleton, and examples thereof include α-pinene polymers, β-pinene polymers, and d-limonene polymers.

[0042] The terpene phenol oligomer preferably has a mass-average molecular weight of 200 to 2000, more preferably 500 to 1200. If the mass-average molecular weight 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, resulting in a lack of stability and a tendency for the color density to decrease. The terpene phenol oligomer is a compound obtained by copolymerizing a cyclic terpene monomer with a phenol, or a hydrogenated product thereof, and an example thereof is an α-pinene-phenol copolymer.

[0043] The mass average molecular weights of the styrene-based oligomer, acrylic-based oligomer, terpene-based oligomer, and terpene-phenol-based oligomer are values ​​measured by GPC (gel permeation chromatography).

[0044] In the reversibly photochromic composition, the mass ratio of the photochromic compound to the styrene-based oligomer or the photochromic compound to the acrylic oligomer is preferably 1:1 to 1:10000, more preferably 1:5 to 1:500. In the reversibly photochromic composition, the mass ratio of the photochromic compound to the terpene oligomer is preferably 1:1 to 1:5000, more preferably 1:5 to 1:500. In the reversibly photochromic composition, the mass ratio of the photochromic compound to the terpene phenol oligomer is preferably 1:1 to 1:50, more preferably 1:2 to 1:30. When the mass ratio of the photochromic compound to the oligomer is within the above range, the reversible photochromic function of the photochromic compound can be more easily maintained, and sufficient color density can be easily exhibited.

[0045] The reversibly photochromic material of the present invention may also contain various additives such as antioxidants, dissolving agents, preservatives, and antifungal agents, as long as they do not affect its functions. The reversible photochromic material can also be blended with a non-color-changing colorant such as a common dye and / or pigment to cause the reversible photochromic material to undergo an alternating color change from a first color to a second color.

[0046] The light resistance of the reversibly photochromic material of the present invention can be improved by incorporating an ultraviolet absorber therein. Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, anilide oxalate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers.

[0047] It is preferable to use a hindered amine light stabilizer in combination with the reversibly photochromic material containing an ultraviolet absorber, which can further improve the light resistance. The hindered amine light stabilizer is preferably a compound represented by the following general formula (4). [ka] (In the formula, R1 represents an alkyl group having 1 to 30 carbon atoms, R2, R3, R4, and R5 each represent an alkyl group having 1 to 5 carbon atoms, n represents an integer of 1 or more, and R6 represents an n-valent organic residue.) The ultraviolet absorber to be used in combination with the hindered amine light stabilizer is preferably a benzotriazole ultraviolet absorber or a triazine ultraviolet absorber.

[0048] As the reversible photochromic material according to the present invention, a reversible photochromic composition in which the above-mentioned photochromic compound is dissolved in an oligomer can be used. However, it is also possible to use a reversible photochromic material in the form of a reversible photochromic microcapsule pigment (hereinafter sometimes referred to as a "microcapsule pigment") encapsulating the above-mentioned photochromic compound and oligomer, or a reversible photochromic resin particle (hereinafter sometimes referred to as a "resin particle") in which the above-mentioned photochromic compound and oligomer are dispersed in a thermoplastic resin or a thermosetting resin. The reversible photochromic material is preferably a reversible photochromic microcapsule pigment containing a reversible photochromic composition encapsulated therein. By encapsulating the reversible photochromic composition in microcapsules, a chemically and physically stable pigment can be formed, and the reversible photochromic composition can maintain the same composition under various conditions of use, thereby achieving the same effects.

[0049] The reversibly photochromic microcapsule pigment comprises an inclusion (including a reversibly photochromic composition) and a wall film encapsulating the core substance. Examples of materials for the wall film include epoxy resin, urea resin, urethane resin, urea-urethane resin, and isocyanate resin. The reversible photochromic microcapsule pigment preferably has a mass ratio of inclusions to wall film of 7:1 to 1:1. By keeping the mass ratio of inclusions to wall film within the above range, it is possible to prevent a decrease in color density and clarity during color development. More preferably, the mass ratio of inclusions to wall film is 6:1 to 1:1.

[0050] Microencapsulation of the microcapsule pigment can be carried out by a conventionally known method such as an isocyanate-based interfacial polymerization method, an in situ polymerization method such as a melamine-formalin-based method, a liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melting dispersion cooling method, an air suspension coating method, or a spray drying method, and an appropriate method can be selected depending on the application. Furthermore, depending on the purpose, a secondary resin film may be provided on the surface of the microcapsules to impart durability or modify the surface properties for practical use.

[0051] During microencapsulation, non-color-changing colorants such as common dyes and / or pigments can be incorporated to cause the microencapsulated pigment to undergo an antacroid color change from a first color to a second color.

[0052] The average particle size of the reversibly photochromic microencapsulated pigment or resin particles is not particularly limited, but is preferably 0.5 to 100 μm, more preferably 0.5 to 50 μm, even more preferably 1 to 30 μm, and particularly preferably 1 to 10 μm. If the average particle size exceeds 100 μm, dispersion stability and processability tend to be poor when blended into ink, paint, or resin. On the other hand, if the average particle size is less than 0.5 μm, it becomes difficult to achieve high-concentration color development. When the microencapsulated pigment or resin particles according to the present invention are used in the ink for a writing instrument described below, the average particle size is preferably 0.01 to 5 μm, more preferably 0.05 to 4 μm, even more preferably 0.1 to 3 μm, and particularly preferably 0.5 to 3 μm. If the average particle size exceeds 5 μm, it becomes difficult to obtain good ink dischargeability when used in a writing instrument. On the other hand, if the average particle size is less than 0.01 μm, it becomes difficult to obtain high-density color development in handwriting.

[0053] The average particle diameter was measured by determining the particle area using image analysis particle size distribution measurement software (manufactured by Mountec Co., Ltd., product name: MacView), calculating the diameter equivalent to a circle with a projected area (Heywood diameter) from the area of ​​the particle area, and measuring the average particle diameter of particles equivalent to a sphere of equal volume using this value. If the particle size of all or the majority of particles exceeds 0.2 μm, it is also possible to measure the average particle size of particles equivalent to an equal volume sphere using the Coulter method using a particle size distribution analyzer (Beckman Coulter, Inc., product name: Multisizer 4e). 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-960V2) based on values ​​measured using the above software or a measuring device using the Coulter method.

[0054] The reversible photochromic material according to the present invention is dispersed as a reversible photochromic colorant in a vehicle containing at least one of water and an organic solvent and, if necessary, various additives to form an ink composition (hereinafter, sometimes referred to as "ink"), It can be used as a liquid composition such as printing ink used in screen printing, offset printing, process printing, gravure printing, coater printing, pad printing, etc.; paint used in brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc.; inkjet ink; ultraviolet-curing ink; ink for writing instruments such as marking pens, ballpoint pens, fountain pens, and brush pens; ink for applicators; ink for stamps; paints; cosmetics; and coloring liquid for textiles.

[0055] The liquid composition may contain various additives. Examples of additives include resins, crosslinking agents, curing agents, drying agents, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, anti-settling agents, smoothing agents, gelling agents, antifoaming agents, matting agents, penetrating agents, pH adjusters, foaming agents, coupling agents, moisturizing agents, antifungal agents, preservatives, and rust inhibitors. The liquid composition can also be formulated with a non-color-changing colorant such as a common dye and / or pigment to provide an enantiotropic color change from a first color to a second color.

[0056] The ink composition according to the present invention can be used as an ink for a writing instrument. Examples of writing vehicle used in writing ink include oil-based vehicles containing an organic solvent, and aqueous vehicles containing water and, if necessary, an organic solvent. When the vehicle is an aqueous vehicle, the writing instrument ink may contain a water-soluble organic solvent that is compatible with water, which has the effect of suppressing water evaporation from the ink and preventing fluctuations in the specific gravity of the vehicle, thereby stably dispersing the reversibly photochromic colorant in the ink.

[0057] When the writing instrument ink contains a water-soluble organic solvent, the content of the water-soluble organic solvent relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 1 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 10 to 25 mass%.

[0058] A thickener can be blended into the writing ink, which can suppress aggregation and / or sedimentation of the reversibly photochromic colorant and can also suppress bleeding of handwriting, allowing for the formation of good handwriting. As the thickener, any known substance can be used, but it is preferable to use a substance that can impart shear thinning properties to the ink composition (shear thinning agent). Inks containing shear thinning agents (shear thinning inks) are highly viscous and difficult to flow when left at rest or under low stress, but easily become less viscous when external stress is applied. This prevents ink leakage, separation, or backflow when not writing, and facilitates good ink ejection stability from the pen tip when writing. In particular, when such an ink composition is used in a writing instrument (ballpoint pen) equipped with a ballpoint tip as the pen tip, the ink composition is stably retained in the ballpoint pen because it has a high viscosity when left standing without shear stress. Therefore, during writing, a strong shear stress is applied to the ink composition due to the rotation of the ball, which makes it easier for the viscosity of the ink composition in the vicinity of the ball to decrease, thereby improving the ink ejection stability.

[0059] If the writing ink contains a thickener, the content of the thickener relative to the total mass of the ink composition is Although there are no particular limitations, the range is preferably 0.1 to 20% by mass.

[0060] A polymeric flocculant can be blended into the ink for the writing instrument. In the ink containing the polymeric flocculant (flocculating ink), the reversible photochromic colorant forms loose aggregates via the polymeric flocculant, which prevents the reversible photochromic colorants from coming into contact with each other and aggregating, thereby improving the dispersibility of the reversible photochromic colorant. When the writing ink contains a polymer flocculant, the reversible photochromic colorant is preferably a reversible photochromic microcapsule pigment.

[0061] When the writing instrument ink contains a polymer flocculant, the content of the polymer flocculant relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 0.1 to 1 mass%, more preferably 0.3 to 0.5 mass%. When the content is within the above range, the reversibly photochromic colorant forms loose aggregates, and the effect of improving the dispersibility of the reversibly photochromic colorant can be fully exerted.

[0062] A dispersant can be blended into the writing instrument ink to improve the dispersibility of the reversible photochromic colorant. A polymer flocculant and a dispersant can also be used in combination. The combined use of these two agents improves the dispersibility of the reversible photochromic colorant and further improves the dispersibility of loose aggregates of the reversible photochromic colorant formed by the polymer flocculant.

[0063] When a writing instrument ink contains a dispersant, the content of the dispersant relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 0.01 to 2 mass%, more preferably 0.1 to 1.5 mass%. If the content exceeds 2 mass%, the reversibly photochromic colorant is likely to settle or float when subjected to external vibrations, etc. On the other hand, if the content is less than 0.01 mass%, the effect of improving dispersibility is unlikely to be achieved.

[0064] If necessary, the writing instrument ink may also contain additives such as water-soluble resins, specific gravity adjusters, surfactants, pH adjusters, wetting agents, resin particles, rust inhibitors, lubricants, humectants, antifoaming agents, viscosity adjusters, preservatives or antifungal agents, bubble absorbers, antioxidants, and ultraviolet absorbers.

[0065] In the ink for writing instruments, the content of the reversibly photochromic colorant relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 5 to 40 mass%, more preferably 10 to 40 mass%, and even more preferably 10 to 30 mass%. By having the content within the above range, the desired color density can be obtained and a decrease in ink outflow properties can be prevented.

[0066] The ink composition can be produced by any conventionally known method. Specifically, the ink composition can be produced by mixing the required amounts of the above-mentioned components and stirring them with a stirrer such as a propeller stirrer, a homodisper, or a homomixer, or by dispersing them with a disperser such as a bead mill.

[0067] Examples of writing implements that can accommodate writing implement ink include ballpoint pens, marking pens, fountain pens, brush pens, calligraphy pens, and other writing implements.

[0068] When the writing instrument ink is used in a ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited, and the ink may be used by filling it into, for example, a ballpoint pen refill or ballpoint pen equipped with a ballpoint pen tip and an ink filling mechanism.

[0069] A ballpoint pen tip consists of a tip body and a ball attached to the front end of the tip body. Examples of ballpoint pen tips include a tip formed by deforming a metal pipe tip body near the tip end by pressing the ball inward from the outer surface to hold the ball in a ball-holding portion, a tip formed by cutting a metal tip body with a drill or the like to hold the ball in a ball-holding portion, a tip with a metal or plastic tip body provided with a resin ball receiving seat, and a tip in which the ball held in the tip is biased forward by a spring. The material of the tip body and the ball is not particularly limited, and examples thereof include cemented carbide (super hard), stainless steel, ruby, ceramic, resin, rubber, etc. Furthermore, the ball may be subjected to a surface treatment such as a DLC coating. The diameter of the ball is generally in the range of 0.2 to 3 mm, preferably 0.2 to 2 mm, more preferably 0.2 to 1.5 mm, and even more preferably 0.2 to 1 mm.

[0070] An example of the ink filling mechanism is an ink reservoir that can be directly filled with ink. A ballpoint pen refill (hereinafter sometimes referred to as "refill") can be formed by connecting a ballpoint pen tip to an ink reservoir directly or via a connecting member and directly filling the ink reservoir with ink. A ballpoint pen can be formed by storing this refill in a barrel.

[0071] The ink reservoir is filled with an ink backflow preventive body at the rear end of the ink. Examples of the ink backflow preventive body include a liquid stopper made of a non-volatile liquid and / or a hardly volatile liquid, and a solid stopper. The liquid stopper and the solid stopper may be used in combination. It is preferable to add a thickener to the non-volatile liquid and / or the hardly-volatile liquid to thicken it to a suitable viscosity.

[0072] In addition, by using the barrel itself as the ink filling mechanism, filling ink directly into the barrel, and attaching a ballpoint pen tip to the front end of the barrel, it is possible to form a ballpoint pen equipped with a ballpoint pen tip and an ink filling mechanism.

[0073] If the ink filled in the ink filling mechanism has a low viscosity, a ballpoint pen equipped with a ballpoint pen tip and an ink filling mechanism may further include an ink supply mechanism for supplying the ink filled in the ink filling mechanism to the pen tip. The ink supply mechanism is not particularly limited, and examples include: (1) a mechanism that has an ink guide core made of a fiber bundle or the like as an ink flow rate regulator and supplies ink to the pen tip through this; (2) a mechanism that has a comb-shaped ink flow rate regulator and supplies ink to the pen tip through this; and (3) a mechanism that supplies ink to the pen tip through a pen core consisting of multiple disks arranged in parallel with comb-shaped intervals, with slit-shaped ink guide grooves running axially through the disks and wider air vent grooves than the grooves, and an ink guide core arranged in the axis center to guide ink from the ink filling mechanism to the pen tip.

[0074] Specific examples of the configuration of a ballpoint pen that contains ink for a writing instrument include: (1) a ballpoint pen that has an ink reservoir filled with ink within the barrel, to which a ballpoint pen tip is connected either directly or via a connecting member, and in which an ink backflow prevention body is filled at the end face of the ink reservoir; (2) a ballpoint pen in which ink is directly filled within the barrel, and a mechanism is provided for supplying ink to the pen tip via an ink flow regulator such as a comb-shaped ink flow regulator or an ink guide core made of a fiber bundle; and (3) a ballpoint pen in which ink is directly filled within the barrel, and a mechanism is provided for supplying ink to the pen tip via the above-mentioned pen core.

[0075] When the writing instrument ink is used in a marking pen, the structure and shape of the marking pen itself are not particularly limited, and the ink may be used by filling it into, for example, a marking pen refill or a marking pen equipped with a marking pen tip and an ink filling mechanism.

[0076] Examples of marking pen tips include conventional porous members with interconnected pores, such as resin-processed fibers, fused heat-fusible fibers, and felt, which have a porosity selected from a range of approximately 30 to 70%, or extrusion-molded synthetic resin bodies with multiple ink outlet holes extending in the axial direction, and one end of which can be processed into a shape appropriate for the purpose, such as a bullet shape, a rectangle, or a chisel shape, for practical use.

[0077] An example of the ink filling mechanism is an ink occlusion body that can be filled with ink. The ink occlusion body is a fiber bundle formed by bundling crimped fibers in the longitudinal direction, and is contained within a plastic cylinder or a covering such as a film, with the porosity adjusted to a range of approximately 40 to 90%. A marking pen can be formed by housing an ink-impregnated ink reservoir inside the barrel and connecting the marking pen tip to the barrel directly or via a connecting member so that it is connected to the ink reservoir.

[0078] A marking pen refill (hereinafter sometimes referred to as a "refill") can be formed by housing an ink-impregnated ink reservoir in an ink reservoir and connecting a marking pen tip to the ink reservoir directly or via a connecting member. A marking pen can be formed by housing this refill in a barrel.

[0079] A marking pen having a marking pen tip and an ink filling mechanism may further include an ink supply mechanism for supplying the ink filled in the ink filling mechanism to the pen tip.

[0080] The ink supply mechanism is not particularly limited, and examples thereof include, in addition to the ink supply mechanism provided in the ballpoint pen described above, (4) a mechanism provided with an ink flow rate regulator using a valve mechanism, which supplies ink to the pen tip by opening the valve. The valve mechanism can be a conventional, general-purpose pumping type that opens when the tip is pressed, and is preferably set to a spring pressure that can be pressed and opened by the pressure of the writing pen.

[0081] When the marking pen is provided with an ink supply mechanism, the ink filling mechanism may be an ink reservoir that can be directly filled with ink, in addition to the ink occlusion body described above. Also, the barrel itself may serve as the ink filling mechanism, allowing ink to be directly filled.

[0082] Specific examples of the configuration of a marking pen that contains ink for a writing instrument include: (1) a marking pen in which an ink reservoir made of a fiber bundle impregnated with ink is contained within the barrel, and a marking pen tip made of a fiber processed body or a resin molded body with capillary gaps formed therein is connected to the barrel directly or via a connecting member so that the ink reservoir and the tip are connected; (2) a marking pen in which ink is directly filled into the barrel, and a mechanism is provided for supplying ink to the pen tip using a comb-shaped ink flow regulator or an ink guide core made of a fiber bundle or the like as an ink flow regulator; (3) a marking pen in which ink is directly filled into the barrel, and a mechanism is provided for supplying ink to the pen tip via the above-mentioned pen core; and (4) a marking pen in which the tip and ink reservoir are connected via a valve mechanism that opens when the tip is pressed, and ink is directly filled into the ink reservoir.

[0083] When the ballpoint pen or marking pen according to the present invention is one in which ink is directly filled, an agitator such as an agitating ball for agitating the ink can be built into the ink reservoir or barrel into which the ink is filled, in order to facilitate redispersion of the reversibly photochromic colorant.

[0084] The writing instrument such as a ballpoint pen or a marking pen according to the present invention may have a detachable ink cartridge structure. In this case, after the ink contained in the ink cartridge of the writing instrument is used up, the writing instrument can be used again by replacing it with a new ink cartridge. The ink cartridges used may be those that double as the barrel that constitutes the writing instrument when connected to the writing instrument body, or those that cover and protect the barrel (rear barrel) after being connected to the writing instrument body. In the latter case, the ink cartridge may be used alone, or may be one in which the writing instrument body and ink cartridge are connected in the writing instrument before use, or one that is stored in the barrel in a disconnected state so that the user of the writing instrument can connect the ink cartridge in the barrel when using it to start use.

[0085] A writing instrument such as a ballpoint pen or marking pen according to the present invention can be made into a cap-type writing instrument by providing a cap that is attached to cover the pen tip (writing tip), thereby preventing the writing tip from being contaminated or damaged. Furthermore, writing instruments such as ballpoint pens or marking pens that contain a refill inside the barrel can be made into retractable writing instruments by providing a retraction mechanism inside the barrel that allows the writing tip to protrude and retract from the barrel, thereby preventing the writing tip from becoming contaminated or damaged.

[0086] Any retractable writing instrument can be used as long as the writing tip is housed within a barrel and exposed to the outside air, and the writing tip protrudes from the barrel opening when the retractable mechanism is activated. It may also be a composite type retractable writing instrument in which a plurality of refills are housed in the barrel, and the writing tip of one of the refills is caused to protrude and retract from the barrel opening by the operation of the retraction mechanism.

[0087] The form of the ballpoint pen or marking pen is not limited to the configuration described above, and it may be equipped with tips of different shapes, or with tips that dispense ink of different tones or hues, or it may be a composite writing instrument (double-headed, retractable tip, etc.) that is equipped with tips of different shapes and dispenses ink of different tones or hues.

[0088] The writing implements described above can be used to form handwriting on various surfaces. Furthermore, handwriting formed on a surface using a writing implement containing writing implement ink can be colored by irradiation with sunlight or ultraviolet light, or by irradiation with light using a light irradiator.

[0089] The light irradiator is preferably one equipped with a light source that irradiates purple to blue light having a peak emission wavelength in the range of 400 to 495 nm, and for example, a purple to blue light emitting diode is preferred. The light irradiator may be separate from the writing instrument, but by providing it in the writing instrument, the writing instrument can be made more portable. Also, the writing instrument and the light irradiator can be combined to form a writing instrument set. The location where the light irradiator is provided is not particularly limited. For example, it is preferable to provide it near the barrel opening of a writing instrument equipped with a retractable mechanism. When using the writing instrument of the present invention indoors, the photochromic compound in the ink is in a decolorized state, making it impossible to see the handwriting during writing, and it may be difficult to determine whether the writing is being done properly while writing. However, by providing a light irradiator near the barrel opening and irradiating it with light while writing, the handwriting becomes visible during writing, making it possible to confirm whether the writing is being done properly while writing.

[0090] The ink composition according to the present invention can be used as an ink for stamps. Examples of stamp vehicles used in stamp inks include oil-based vehicles containing an organic solvent, and aqueous vehicles containing water and, if necessary, an organic solvent. When the vehicle is an aqueous vehicle, the stamp ink may contain a water-soluble organic solvent that is compatible with water. The water-soluble organic solvent suppresses evaporation of the ink and prevents fluctuations in the specific gravity of the vehicle, thereby stably dispersing the reversibly photochromic colorant in the ink.

[0091] When the stamp ink contains a water-soluble organic solvent, the content of the water-soluble organic solvent relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 30 to 60 mass%, more preferably 30 to 55 mass%, and even more preferably 40 to 50 mass%.

[0092] The ink for stamps can be blended with a thickener, which can suppress aggregation and / or sedimentation of the reversibly photochromic colorant and also suppress bleeding of the printed image, thereby allowing the formation of a clear printed image.

[0093] Stamp ink can be blended with a binder resin to improve the adhesion of the print and adjust the viscosity.

[0094] The stamp ink may also contain other additives, such as surfactants, pH adjusters, wetting agents, resin particles, rust inhibitors, humectants, antifoaming agents, viscosity adjusters, preservatives or antifungal agents, bubble absorbers, antioxidants, and ultraviolet absorbers, as needed.

[0095] In the ink for stamps, the content of the reversible photochromic colorant relative to the total mass of the ink composition is not particularly limited, but is preferably in the range of 10 to 40 mass%, more preferably 10 to 35 mass%, and even more preferably 10 to 30 mass%. If the content exceeds 40 mass%, the dispersion stability of the reversible photochromic colorant in the ink tends to decrease. On the other hand, if the content is less than 10 mass%, the color density tends to decrease.

[0096] The ink for stamps can be used as ink for stamp pads and ink for stamps provided with a stamp material having continuous pores. For example, a stamp pad can be impregnated with ink to obtain a stamp pad that supplies ink to the printing surface of a stamp that comes into contact with it.Also, a stamp can be obtained by impregnating ink into a stamp material having continuous pores.

[0097] The stamp described above can form an image on various surfaces. Furthermore, the image formed on the surface using the stamp containing the stamp ink can be colored by irradiation with sunlight or ultraviolet light, or by light irradiation using a light irradiator. The light irradiator is preferably the aforementioned purple to blue light emitting diode. The light irradiator may be separate from the stamp, but by providing it on the stamp, it becomes possible to improve portability. Also, a stamp and a light irradiator can be combined to obtain a stamp set.

[0098] When the ink composition according to the present invention is used by printing or coating, the material of the substrate to be printed or coated is not particularly limited and all materials are effective, and examples thereof include paper, synthetic paper, fiber, fabric, synthetic leather, leather, plastic, glass, ceramic material, metal, wood, stone, etc. The shape of the support is not limited to a flat surface, but may be uneven.

[0099] A reversibly photochromic laminate (reversibly photochromic printed matter) can be obtained by providing a reversibly photochromic layer on a support using the liquid composition of the present invention. This laminate (printed matter) reversibly changes color depending on the presence or absence of light irradiation. Furthermore, in the case of a support on which a non-color-changing colored layer (non-color-changing colored image) is already formed, by providing a reversible photochromic layer on the non-color-changing colored layer, the non-color-changing colored layer (non-color-changing colored image) can be made to appear or disappear by the reversible photochromic layer depending on whether or not light is irradiated, thereby further diversifying the manner of change.

[0100] The reversibly photochromic material of the present invention can be melt-blended as a reversibly photochromic colorant with an excipient and molded into a solid molded article for application, which can be used as a solid writing material or solid cosmetic. Examples of solid writing materials include crayons, pencil leads, mechanical pencil leads, solid gel markers, and the like. Examples of solid cosmetics include foundation, eyeliner, eyebrow pencil, eyeshadow, lipstick, etc.

[0101] The content of the excipient relative to the total mass of the solid molding for application is not particularly limited, but is preferably in the range of 0.2 to 70 mass%, more preferably 0.5 to 40 mass%. When the content is within the above range, the shape of the solid molding for application can be easily obtained, and in the case of a solid writing material, it is easy to increase the writing density.

[0102] The solid molding for coating may also contain other additives, such as fillers, binder resins, viscosity modifiers, preservatives or antifungal agents, antibacterial agents, antioxidants, ultraviolet inhibitors, lubricants, and fragrances, as needed. By blending a non-color-changing colorant such as a common dye and / or pigment into the solid molded product for application, it is possible to cause the solid molded product for application to undergo an alternating color change from a first color to a second color.

[0103] The solid molding for application may be used alone, or may be used as an inner core with an outer shell covering the outer periphery to form a core-sheath structure (double core).

[0104] The solid writing material can be used to write on various surfaces. Furthermore, the writing marks formed on the surface using the solid writing material can be colored by irradiation with sunlight or ultraviolet light, or by light irradiation using a light irradiator. The light irradiator is preferably the aforementioned purple or blue light-emitting diode. The light irradiator may be separate from the solid writing body or the exterior of a solid writing implement in which the solid writing body is housed in an exterior container, but by providing it on the exterior of the solid writing body or solid writing implement, excellent portability can be achieved. Also, a solid writing body set or solid writing implement set can be obtained by combining the solid writing body or solid writing implement with the light irradiator.

[0105] The reversibly photochromic material according to the present invention can be melt-blended as a reversibly photochromic colorant with thermoplastic resins, thermosetting resins, waxes, etc. to form pellets, powder, or paste, and used as a molding resin composition. Using the above-mentioned molding resin composition, molded articles in the form of three-dimensional objects of any shape, films, sheets, plates, filaments, rods, pipes, etc. can be obtained by general-purpose means such as injection molding, extrusion molding, blow molding, cast molding, etc. By blending a non-discoloring colorant such as a common dye and / or pigment into the molding resin composition, the molding resin composition can also be made to undergo an alternating color change from a first color to a second color.

[0106] It can also be melt blended with thermoplastic resins to obtain toners or powder coatings.

[0107] Specific examples of products using the reversible photochromic material of the present invention include the following. (1)Toys Dolls and animal-shaped toys; hair for dolls and animal-shaped toys; doll houses and furniture, doll accessories such as clothing, hats, bags, shoes, etc.; accessory toys; stuffed toys; drawing toys; toy picture books; puzzle toys such as jigsaw puzzles; building block toys; block toys; clay toys; fluid toys; tops; kites; musical instrument toys; cooking toys; gun toys; capture toys; background toys; mask toys; toys imitating vehicles, animals, plants, buildings, food, etc. (2) Clothing Clothing such as T-shirts, sweatshirts, blouses, dresses, swimwear, raincoats, skiwear, etc.; footwear such as shoes; shoelaces; shoe components such as insoles, outsoles, and midsoles; cloth personal items such as handkerchiefs, towels, and wrapping cloths; gloves; ties; hats; sportswear, etc. (3) Indoor decorations Carpets, curtains, curtain strings, tablecloths, rugs, cushions, seat cushions, chair upholstery, seats, mats, picture frames, artificial flowers, photo frames, etc. (4) Furniture Bedding such as futons, pillows, mattresses, etc.; chairs; floor chairs; sofas; lighting equipment; heating and cooling equipment, etc. (5) Ornaments Rings, bracelets, tiaras, necklaces, earrings, hair clips, false nails, ribbons, scarves, watches, glasses, sunglasses, key chains, etc. (6) Stationery Writing implements, stamps, erasers, writing pads, rulers, planners, notebooks, adhesive tape, etc. (7)Daily necessities Toiletries such as disposable diapers; bath products; toothbrushes; cooling or heat-retaining bags; hand warmers; thermometers; watering cans; buckets; cleaning tools; cosmetics such as lipstick, eye shadow, foundation, eyeliner, eyebrow pencil, nail polish, hair dye, and false nail paint, etc. (8) Kitchen utensils Cookware, lunch boxes, water bottles, cups, plates, chopsticks, spoons, forks, pots, frying pans, coasters, trivets, placemats, etc. (9) Other Calendars, labels, cards, recording materials, various printed materials for preventing counterfeiting; picture books and other books; sports equipment such as gloves, protectors, nets, etc.; bags; packaging containers; embroidery thread; fishing tackle; musical instruments; ice packs; bags such as wallets; umbrellas; vehicles; buildings; temperature detection indicators; teaching aids such as picture books and maps; pet supplies: medical or nursing care products such as supports, bandages, and adhesive plasters, electronic devices such as smartphones, earphones, and speakers, etc.; optical filters for display materials or eyewear; display materials; agricultural films. [Example]

[0108] Examples are shown below. Unless otherwise specified, "parts" in the examples refer to "parts by mass."

[0109] Example 101 Preparation of reversible photochromic material (reversible photochromic composition) A reversible photochromic composition was obtained by uniformly dissolving 1 part of 3,10-bis(4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b']-dipyrran as a photochromic compound in 50 parts of styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., product name: Picolastic A-5 (mass average molecular weight: 317)) as an oligomer with heating.

[0110] Examples 102 to 105 and Comparative Example 101 A reversibly photochromic composition was obtained in the same manner as in Example 101, except that the types and amounts of the photochromic compound and oligomer were changed to those shown in Table 1 below.

[0111] Example 201 Preparation of reversible photochromic materials (reversible photochromic microencapsulated pigments) A reversible photochromic composition was prepared by warming and dissolving 1 part of 3,10-bis(4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b']-dipyrane as a photochromic compound in 50 parts of a styrene-α-methylstyrene copolymer (Eastman Chemical Company, product name: Picolastic A-5 (weight average molecular weight: 317)) as an oligomer. This reversible photochromic composition was then added to a mixed solution consisting of 20 parts of an aromatic isocyanate prepolymer as a wall material and 20 parts of ethyl acetate. The mixture was then emulsified and dispersed in a 15% gelatin solution and stirred under heating to prepare a microcapsule dispersion. A reversible photochromic microcapsule pigment was obtained from the microcapsule dispersion by centrifugation.

[0112] Examples 202 to 206 and Comparative Examples 201 and 202 A reversible photochromic microcapsule pigment was obtained in the same manner as in Example 201, except that the types and amounts of the photochromic compound and oligomer were changed to those shown in Table 2 below.

[0113] Example 207 Preparation of reversible photochromic materials (reversible photochromic microencapsulated pigments) The photochromic compound was 1 part of 3,10-bis(4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b']-dipyrane, the benzotriazole-based ultraviolet absorber was 6 parts of 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole (manufactured by BASF, product name: T-928), and the hindered amine-based light stabilizer was 2 parts of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (manufactured by BASF, product name: T-765). A reversible photochromic composition was prepared by uniformly dissolving 21 parts of a styrene-α-methylstyrene copolymer (Eastman Chemical Co., product name: Picolastic A-5 (mass average molecular weight: 317)) and 21 parts of a styrene-α-methylstyrene copolymer (Eastman Chemical Co., product name: Picolastic A-75 (mass average molecular weight: 917)) in a heated mixture. The resulting mixture was then added to a mixed solution of 20 parts of an aromatic isocyanate prepolymer and 20 parts of ethyl acetate as a wall film material. The mixture was then emulsified and dispersed in a 15% gelatin solution, and the mixture was heated and stirred to prepare a microcapsule dispersion. A reversible photochromic microcapsule pigment was obtained from the microcapsule dispersion by centrifugation.

[0114] [Preparation of test samples] 50 parts of each of the reversible photochromic compositions of Examples 101 to 105 and Comparative Example 101 was dissolved in 100 parts of methyl ethyl ketone, and the solution was uniformly coated on white fine paper using a bar coater to a wet film thickness of 90 μm, and then dried to prepare test samples. A reversible photochromic ink was prepared by mixing 40 parts of each of the microcapsule pigments of Examples 201 to 207 and Comparative Examples 201 and 202, 52 parts of an ethylene-vinyl acetate copolymer resin emulsion, 5 parts of a thickener, and 3 parts of a leveling agent. A solid pattern was formed on white fine paper by screen printing, and the ink was dried to prepare a test sample.

[0115] [Color confirmation test] Each test sample was placed 10cm away from the light source of a light irradiator (Optocord Co., Ltd., product name: Select 100 LED Stand Light), and irradiated with ultraviolet light at a wavelength of 375nm for 1 minute, after which the color tone of the reversibly photochromic material was visually confirmed by ultraviolet light. Next, each test sample was decolorized, and the light source was changed to purple light at a wavelength of 405nm, and irradiated with light for 1 minute under the same conditions as above, after which the color tone of the reversibly photochromic material was visually confirmed by purple light. The results obtained are shown in Tables 1 and 2 below.

[0116] [Brightness value test] Each test sample was placed 10 cm apart from the light source of the light irradiator, and irradiated with ultraviolet light having a wavelength of 375 nm for 1 minute, after which the brightness of the reversibly photochromic material that had developed a color due to the ultraviolet light was measured using a color difference meter (product name: TC-3600, manufactured by Tokyo Denshoku Co., Ltd.). Next, each test sample was decolorized, and the light source was changed to purple light having a wavelength of 405 nm, and irradiated with light for 1 minute under the same conditions as above, after which the brightness of the reversibly photochromic material that had developed a color due to the purple light was measured using the color difference meter. The results obtained are shown in Tables 1 and 2 below. The brightness value is a value converted from the Z value, and a larger value indicates a lower color density of the reversibly photochromic material, and a smaller value indicates a higher color density of the reversibly photochromic material.

[0117] [Lightfastness test] Using a xenon light resistance tester (manufactured by Suga Test Instruments Co., Ltd., product name: Table Sun XL750L), the test was carried out at 170 w / m 2 Each test sample was continuously irradiated with light at an irradiance of 10 ... The results obtained are shown in Tables 1 and 2 below.

[0118] [Decolorization speed test] Each test sample was placed so that the distance between the light source of the light irradiator and each test sample was 10 cm, and a violet light with a wavelength of 405 nm was used as the light source to irradiate the test sample for 1 minute, causing each test sample to develop color, and then the time it took for each test sample to become discolored (the state before light irradiation) was measured. The discoloration speed test was continued for 10 minutes. The results obtained are shown in Tables 1 and 2 below.

[0119] The units of the values ​​for the photochromic compounds and oligomers in the table are "parts by mass," the units of the values ​​for lightfastness are "hours," and the units of the values ​​for decolorization speed are "seconds."

[0120] [Table 1]

[0121] [Table 2]

[0122] The photochromic compounds and oligomers in the table are the compounds shown below. Aa-1 3,10-bis(4-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane Aa-2 3,10-bis(2,4-di-sec-butoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane (R 11A and R 12A , and R 11B and R 12B The total number of carbon atoms in each of these is 8.) Aa-3 3,10-bis(2-sec-butoxy-4-methoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane (R 11A and R 12A , and R 11B and R 12B The total number of carbon atoms in each of these is 5.) Aa-4 3,10-bis(4-ethoxyphenyl)-3,10-diphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane Ab-1 3,3,10,10-tetraphenyl-3H,10H-naphtho[2,1-b:7,8-b′]-dipyrane Ba-1: Styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Company, product name: Picolastic A-5 (mass average molecular weight: 317)) Ba-2: Styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Company, product name: Picolastic A-75 (mass average molecular weight: 917)) Bb-1 α-pinene polymer (manufactured by Eastman Chemical Company, product name: Picolite A115 (mass average molecular weight: 833)) Bc-1 α-pinene-phenol copolymer [Yasuhara Chemical Co., Ltd., product name: YS Polystar T145 (mass average molecular weight: 1050)] Bc-2 α-pinene-phenol copolymer [Yasuhara Chemical Co., Ltd., product name: YS Polystar T130 (mass average molecular weight: 900)] Bd-1 Acrylic ester copolymer [manufactured by Toagosei Co., Ltd., product name: ARUFON UP-1170 (mass average molecular weight: 8000)] C-1 2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benzotriazole (BASF, product name: T-928) C-2 Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (BASF, product name: T-765)

[0123] Among the photochromic compounds in the table, Aa-1, Aa-2, Aa-3, and Aa-4 are compounds represented by the general formula (1) above, where R 13A , R 14A , R 15A , R 13B , R 14B , and R 15B is a hydrogen atom, and X A and X B is an oxygen atom, and R 11A , R 12A , R 11B , and R 12B is a compound having the substituents shown in the following Table 3. In the substituents shown in Table 3, * indicates the bonding site with general formula (1). Ab-1 is a compound represented by the following formula (1'-1).

[0124] [Table 3]

[0125] [ka]

[0126] Application example 1 Fabrication of reversible photochromic display A reversible photochromic liquid composition was prepared by mixing 10 parts of the reversible photochromic composition of Example 101 and 10 parts of toluene. The liquid composition was uniformly coated on a transparent polypropylene sheet using a wire coater to a wet film thickness of 90 μm, and then dried to provide a reversible photochromic layer. A white paper sheet was then attached to the coated sheet to prepare a reversible photochromic display. When viewed from the transparent polypropylene sheet side, the reversible photochromic display was white before being exposed to sunlight, but turned yellow when exposed to sunlight. After being left indoors for a while, it returned to its original white color. This color change was reversible.

[0127] Application example 2 Fabrication of a reversible photochromic writing implement (reversible photochromic ballpoint pen) A reversible photochromic liquid composition serving as an ink for a writing instrument was prepared by mixing 25 parts of the reversible photochromic microcapsule pigment of Example 202, 0.3 parts of a shear-thinning agent (xanthan gum), 10 parts of urea, 10 parts of glycerin, 0.5 parts of a nonionic penetrant (manufactured by San Nopco Ltd., product name: Nopco SW-WET-366), 0.1 parts of a modified silicone antifoaming agent (manufactured by San Nopco Ltd., product name: Nopco 8034), 0.5 parts of a phosphate ester surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name: Plysurf AL), 0.5 parts of a pH adjuster (triethanolamine), 0.2 parts of a preservative (manufactured by Arcsada Japan Co., Ltd., product name: Proxel XL-2(S)), and 52.9 parts of water. The above-mentioned writing instrument ink was sucked and filled into an ink reservoir tube made of polypropylene pipe, and then connected to a ballpoint pen tip having a 0.5 mm diameter carbide ball at its tip via a resin holder. Next, a viscoelastic ink backflow preventive material (liquid stopper) mainly composed of polybutene was filled into the rear end of the ink reservoir tube to prepare a ballpoint pen refill. The above-mentioned refill was incorporated into the barrel to prepare a retractable reversible photochromic writing instrument (reversible photochromic ballpoint pen). The above-mentioned ballpoint pen has a tip provided in a ballpoint pen refill stored in a barrel while being exposed to the outside air, and is provided with a rear-end knock-type protruding / retracting structure in which the tip protrudes from the front end opening of the barrel by pressing forward an operating part provided at the rear end of the barrel. When the above ballpoint pen was used to write on paper indoors, the handwriting was colorless and invisible, but when the written area was exposed to sunlight, yellow handwriting became visible. After leaving the pen indoors for a while, the handwriting returned to its colorless state and became invisible again. This color change was reversible. The ballpoint pen described above did not cause writing defects such as skipped lines, and had high writing performance as a ballpoint pen.

[0128] Application example 3 Fabrication of a reversible photochromic writing implement (reversible photochromic marking pen) A reversible photochromic liquid composition, which is an ink for a writing instrument, was prepared by mixing 25 parts of the reversible photochromic microcapsule pigment of Example 202, 0.4 parts of hydroxyethyl cellulose, 10 parts of glycerin, 5 parts of polyvinyl alcohol, 0.2 parts of a preservative (manufactured by Arcsada Japan Co., Ltd., product name: Proxel XL-2(S)), and 59.4 parts of water. The above-mentioned writing instrument ink was impregnated into an ink reservoir made of polyester sliver covered with a synthetic resin film, and housed in a barrel made of polypropylene resin. A resin-processed polyester fiber pen body (chisel type) was attached to the tip of the barrel, and connected via a resin holder. A cap was then attached to produce a cap-type reversible photochromic writing instrument (reversible photochromic marking pen). When the marking pen was used to write on paper indoors, the handwriting was colorless and invisible. However, when light was shone on the written area using a light emitting device with a purple LED (peak emission wavelength: 405 nm) attached to the tip, yellow handwriting became visible. After that, when the light irradiation was stopped and the pen was left indoors for a while, the handwriting returned to colorless and was no longer visible. This color change was reversible. The markings were free of writing defects such as smearing, and the marking pen had high writing performance.

[0129] Application example 4 Fabrication of a reversible photochromic toy (reversible photochromic miniature car) A reversible photochromic liquid composition, which is a paint used for spray coating, was prepared by stirring and mixing 15 parts of the reversible photochromic microcapsule pigment of Example 203 and 0.1 parts of a blue general pigment in a vehicle consisting of 40 parts of an acrylic resin / xylene solution, 20 parts of xylene, 20 parts of methyl isobutyl ketone, and 5 parts of a polyisocyanate-based curing agent. The entire body of a white miniature car made by injection molding ABS resin as a support was spray-painted with the above paint and dried to form a reversible photochromic layer, producing a reversible photochromic toy (reversible photochromic miniature car). The miniature car shown above was blue before being exposed to sunlight, but turned green when exposed to sunlight. After being left indoors for a while, it returned to its original blue color. This color change was reversible. When the above miniature car was irradiated with light indoors using a light irradiator with a purple LED (peak emission wavelength: 405 nm) attached to the tip as the light source, the irradiated area changed from blue to green. After that, when the light irradiation was stopped and the car was left indoors for a while, the car returned to its original blue color. This color change was reversible. Because the above light source irradiates purple light with a peak emission wavelength of 405 nm, it has little effect on the human body, making the reversible photochromic miniature car highly safe.

[0130] Application example 5 Fabrication of reversible photochromic flock (reversible photochromic animal-shaped toy) Seven parts of the reversibly photochromic microcapsules of Example 204, two parts of a dispersant, and 91 parts of nylon 12 with a melting point of 180°C were melt-mixed in an extruder at 200°C to prepare a reversibly photochromic molding resin composition in pellet form. The pellets were fed into an extruder, spun from 32 discharge holes at 200°C, and wound up at a draw ratio of 2 to obtain a drawn yarn of 224 denier / 32 filaments. The obtained filaments were further bundled and spun, then cut into a cut length of 1.5 mm using a pile cutter, and further subjected to electrodeposition treatment and drying to obtain a reversibly photochromic pile. The above-mentioned reversibly photochromic pile was implanted using an electrostatic flocking device onto a vinyl chloride rabbit-shaped animal-shaped toy (hereinafter sometimes referred to as a "rabbit toy") that had been pre-coated with adhesive, and then dried to produce a reversibly photochromic flocked body (reversibly photochromic animal-shaped toy). When the above rabbit toy was irradiated with light indoors using a light irradiator with a purple LED (peak emission wavelength: 405 nm) attached to the tip as the light source, the irradiated area changed from white to yellow. After that, when the light irradiation was stopped and the toy was left indoors for a while, it returned to its original white color. This color change was reversible. Because the above light source irradiates purple light with a peak emission wavelength of 405 nm, it has little effect on the human body, and the reversible photochromic animal-shaped toy was highly safe.

[0131] Application example 5 Fabrication of a doll toy with hair using reversibly photochromic composite fibers Five parts of the reversibly photochromic microcapsule pigment of Example 205, 0.1 parts of a red general pigment, 1 part of a dispersant, and 94 parts of a polypropylene-ethylene copolymer with a melting point of 135°C were melt-mixed in an extruder at 200°C to prepare a reversibly photochromic molding resin composition in pellet form for the core. The above pellets were fed into an extruder for forming the core, and 6-12 copolymer nylon natural pellets with a melting point of 145°C were fed into an extruder for forming the sheath. Using a composite fiber spinning device, the fibers were spun at 200°C through 18 discharge holes so that the core:sheath volume ratio was 6:4, yielding a reversibly photochromic composite fiber consisting of 18 single filaments with an outer diameter of 90 μm. Furthermore, the reversible photochromic composite fiber was implanted on the head of a doll by a conventional method (for example, using a hair implantation sewing machine) to produce a doll toy with hair made of the reversible photochromic composite fiber. When light was shone onto the hair of the doll toy indoors using a light emitting device with a purple LED (peak emission wavelength: 405 nm) attached to the tip as a light source, the irradiated area changed from red to orange. After that, when the light irradiation was stopped and the device was left indoors for a while, the hair returned to its original red color. This color change was reversible. Because the light source irradiates purple light with a peak emission wavelength of 405 nm, it has little effect on the human body, and the doll toy was highly safe.

[0132] Application example 6 Preparation of reversible photochromic prints A reversible photochromic liquid composition serving as a printing ink was prepared by mixing 40 parts of the reversible photochromic microcapsule pigment of Example 206, 52 parts of an ethylene-vinyl acetate copolymer resin emulsion, 5 parts of a thickener, and 3 parts of a leveling agent. The above printing ink was screen printed on an aluminum foil substrate and dried to provide a reversibly photochromic layer with a star pattern, thereby producing a reversibly photochromic printed matter. The printed matter above was silver before being exposed to sunlight, but when it was exposed to sunlight, a yellow star pattern appeared. After leaving it indoors for a while, the star pattern disappeared and it returned to its original silver color. This color change was reversible.

Claims

1. A photochromic compound represented by the following general formula (1), Oligomers and A reversible photochromic material comprising: 【Chemical 1】 (In general formula (1), R １１Ａ and R １１Ｂ each independently represents a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent; R １２Ａ and R １２Ｂ each independently represents a hydrogen atom, an optionally substituted linear, branched, or cyclic alkoxy group, or an optionally substituted aryloxy group; R １３Ａ , R １４Ａ , R １５Ａ , R １３Ｂ , R １４Ｂ , and R １５Ｂ are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched, or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched, or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or —CO ２ R ２１ represents R ２１ represents an optionally substituted linear, branched, or cyclic alkyl group, or an optionally substituted aryl group, X Ａ and X Ｂ each independently represents an oxygen atom or a sulfur atom.

2. R １２Ａ and R １２Ｂ and each independently represent a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms.

3. R １２Ａ and R １２Ｂ The reversible photochromic material according to claim 1 or 2, wherein is a hydrogen atom.

4. R １１Ａ and R １１Ｂ and each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms.

5. R １３Ａ , R １４Ａ , R １５Ａ , R １３Ｂ , R １４Ｂ , and R １５Ｂ and each independently represent a hydrogen atom, a halogen atom, or a linear, branched, or cyclic alkoxy group which may have a substituent.

6. X Ａ and X Ｂ The reversible photochromic material according to claim 1 , wherein is an oxygen atom.

7. 7. The reversibly photochromic material according to claim 1, wherein the oligomer is selected from the group consisting of a styrene-based oligomer, an acrylic-based oligomer, a terpene-based oligomer, and a terpene-phenol-based oligomer.

8. 8. The reversible photochromic material according to claim 1, which is a reversible photochromic microcapsule pigment encapsulating the photochromic compound and the oligomer, or a reversible photochromic resin particle in which the photochromic compound and the oligomer are dispersed in a thermoplastic resin or a thermosetting resin.

9. A reversibly photochromic liquid composition comprising the reversibly photochromic material according to any one of claims 1 to 8 and a vehicle.

10. 10. The reversibly photochromic liquid composition according to claim 9, which is selected from the group consisting of printing ink, writing ink, applicator ink, stamp ink, inkjet ink, paint, ultraviolet-curable ink, pigment, cosmetic, and textile coloring liquid.

11. A reversibly photochromic solid writing material or a reversibly photochromic solid cosmetic comprising the reversibly photochromic material according to any one of claims 1 to 8 and an excipient.

12. A reversibly photochromic molding resin composition comprising the reversibly photochromic material according to any one of claims 1 to 8 and a molding resin.

13. A reversibly photochromic molded article obtained by molding the reversibly photochromic molding resin composition according to claim 12.

14. A reversibly photochromic laminate comprising a support and a reversibly photochromic layer comprising the reversibly photochromic material according to any one of claims 1 to 8.

Images