KR100285777B1 - Photochromic recording material - Google Patents

Abstract

Photochromic recording material comprising a boron compound represented by the following general formula (I) and a color dye having absorbance in the visible ray region

Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently alkyl, aryl, allyl, aralkyl, alkenyl, alkynyl, silyl, heterocyclic, substituted alkyl, substituted aryl, substituted allyl , Substituted aralkyl, substituted alkenyl, substituted alkynyl or substituted silyl group, Z ⁺ represents quaternary ammonium, quaternary pyridinium, quaternary quinolinium or phosphonium cation).

Description

[Name of invention]

Photochromic recording material

Detailed description of the invention

[Background of invention]

[Field of Invention]

The present invention is excellently stable to fluorescent lamp light, a toner or a toner comprising a photobleaching recording material which is discolored when exposed to visible radiation and a colorant of the photobleaching recording material. Relates to ink.

[Description of Prior Art]

In technical fields such as printing and copying, the environmental resistance of recording materials such as light fastness and moisture resistance, solvent resistance and heat resistance has drawn attention from the industry. The physical properties of recording materials have been improved extensively. In particular, there has been extensive development in the fields of electronic photographic recording and electrostatic recording. For example, US Pat. 2297691 Specification and Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. Many methods, such as those disclosed in 43-24748, are known and in accordance with these methods generally form an electrical latent image on a light-sensitive material by a variety of means using photoconductive materials. The latent image thus formed is subsequently developed with toner to be converted into a visible image, the toner image is transferred to a moving material such as paper, and, if necessary, fixed by heating and pressurization to obtain a copied image. In addition, various developing methods of electrostatic latent image visualizing with toner are known (for example, US Pat. No. 2874063, US Pat. No. 2618552, and US Pat. No. 2221776). The toner used in the heat fixing method is uniformly dispersed by melt mixing a colorant such as carbon black and an additive such as an electric charge regulator with a thermoplastic resin such as styrene-butyl acrylate copolymer, After cooling the mixture, the obtained mixture can generally be prepared by pulverizing to a desired size by a pulverizing mill or a dispersing machine. In addition, in fields such as printing and copying, coloring materials have recently been widely distributed and improvement of physical properties such as colorants and charge control agents has been extensively performed (for example, Japanese Patent Laid-Open No. 57-130046 and No. 57-191650). . Further, in the printing field, for example, the use of impact printers and non-impact printers, such as offset printing, relief printing, photogravure, hole print printing ) Or various printing methods of special printing and electronic printing such as flexo graphic printing, metal printing, plastic printing, glass printing, transfer printing, etc., and the inks used in these printing methods Mainly consists of carriers such as binders and colorants such as dyes or pigments.

Furthermore, the development of ultraviolet curing inks to prevent environmental pollution by using no solvent in the ink, to improve productivity by rapid curing, or to improve the physical properties of the cured coat has recently been widely developed. (For example, Japanese Patent Laid-Open No. 1-229084, Japanese Patent Laid-Open No. 1-271469, and Japanese Patent Laid-Open No. 2-22370).

Nevertheless, the toners and printing inks of the electrophotographic recording have the drawback that they cannot completely discolor the printed image after printing. Therefore, when printed on the printing top once again, the printed image is duplicated and difficult to read, and thus the recording paper to be printed could not be reduced.

[Summary of invention]

An object of the present invention is to solve the problem that the set and printed recording portions can be discolored by visible light, resetting and reprinting on the same portions, and provide an excellently stable recording material for fluorescent lamp light.

In order to solve the above problem, a wide range of color dyes and boron compounds absorbing visible light in the range of 400 to 780 nm have been studied extensively. A photobleachable material was obtained, thereby completing the present invention.

That is, in the photochromic recording material obtained according to the present invention, the coloring dye does not disappear until light containing visible light is irradiated, and the colored coloring material disappears by using a combination of a boron compound having Formula (1). , Dyes have absorption in the visible range.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are alkyl, aryl, allyl, aralkyl, alkenyl, alkynyl, silyl, heterocyclic, substituted alkyl, substituted aryl, substituted allyl, substituted Aralkyl, substituted alkenyl, substituted alkynyl or substituted silyl groups, Z ⁺ represents quaternary ammonium cation, quaternary pyridinium cation, quaternary quinolinium cation, or phosphonium cation.

In addition, the photochromic recording material of the present invention is stable even when exposed to light such as a fluorescent lamp, and thus has practical stability.

[Description of Preferred Embodiment]

Although the photochromic recording material according to the present invention is discolored by radiation having visible wavelength region wavelength, it is possible to provide a stable photochromic composition for fluorescent lamps and the like.

The boron compound used in the present invention is represented by the general formula (1), wherein the groups of R ₁ , R ₂ , R ₃ and R ₄ are alkyl, or aryl, allyl, aralkyl, alkenyl, alkynyl, silyl, hetero Cyclic, substituted alkyl, substituted aryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, substituted silyl group, and the like, examples of the preferred groups among the above groups are phenyl, an Yarn, ethoxyphenyl, toluyl, t-butylphenyl, fluorophenyl, chlorophenyl, diethylaminophenyl, xylyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Dodecyl, cyclohexyl, cyclohexenyl, methoxymethyl, methoxyethyl, vinyl, allyl, triphenylsilyl, dimethylphenylsilyl, dibutylphenylsilyl, trimethylsilyl, piperidyl, thienyl, furyl group And so on. Specific examples of the anion include n-methyltriphenyl borate, n-ethyltriphenyl borate, n-butyltriphenyl borate, n-octyltriphenyl borate, n-dodecyltriphenyl borate, n- Methyltri-p-tolyl borate, n-ethyltri-p-tolyl borate,

n-butyltri-p-tolyl borate, n-octyltri-p-tolyl borate, n-dodecyltri-p-tolyl borate, n-methyltrianisyl borate, n-ethyltrianisyl borate, n- Butyltrianisyl borate, n-octyltrianisyl borate, n-dodecyltrianisyl borate, dimethyldiphenyl borate, diethyldiphenyl borate, di-n-butyldiphenyl borate, di-n-octyldi Phenyl borate, di-n-dodecyldiphenyl borate, dimethyldi-p-tolyl borate, diethyl-p-tolyl borate, di-n-butyldi-p-tolyl borate, di-n-octyl di-p-tolyl Borate, di-n-dodecyl di-p-tolyl borate, dimethyl dianisyl borate, diethyl dianisyl borate, di-n-butyl dianisyl borate, di-n-octyl dianisyl borate, di- n-dodecyl dianisyl borate, tetraphenyl borate, tetraanisyl borate, tetra-p-tolyl borate, triphenyl Fyl borate, tri-p-tolylnaphthyl borate, tetrabutyl borate, tri-n-butyl (triphenylsilyl) borate, tri-n-butyl (dimethyl phenylsilyl) borate, n-octyldimethyl (di-n-butyl Phenylsilyl) borate, dimethylphenyl (trimethylsilyl) borate ion, and the like can be mentioned.

Also mentioned as cations (Z ⁺ ) are quaternary ammonium cations, quaternary pyridinium cations, quaternary quinolinium cations and phosphonium cations.

Specific examples of such boron compounds are as follows;

Tetramethylammonium methyltriphenyl borate,

Tetramethylammonium n-butyltriphenyl borate,

Tetramethylammonium n-octyltriphenyl borate,

Tetramethylammonium n-dodecyltriphenyl borate,

Tetramethylammonium methyltri-p-tolyl borate,

Tetramethylammonium n-butyltri-p-tolyl borate,

Tetramethylammonium n-octyltri-p-tolyl borate,

Tetramethylammonium n-dodecyltri-p-tolyl borate,

Tetramethylammonium methyltrianisyl borate,

Tetramethylammonium n-butyltrianisyl borate,

Tetramethylammonium n-octyltrianisyl borate,

Tetramethylammonium n-dodecyltrianisyl borate,

Tetraethylammonium methyltriphenyl borate,

Tetraethylammonium n-butyltriphenyl borate,

Tetraethylammonium n-octyltriphenyl borate,

Tetraethylammonium n-dodecyltriphenyl borate,

Tetraethylammonium methyltri-p-tolyl borate,

Tetraethylammonium n-butyltri-p-tolyl borate,

Tetraethylammonium n-octyltri-p-tolyl borate,

Tetraethylammonium n-dodecyltri-p-tolyl borate,

Tetraethylammonium methyltrianisyl borate,

Tetraethylammonium n-butyltrianisyl borate,

Tetraethylammonium n-octyltrianisyl borate,

Tetraethylammonium n-dodecyltrianisyl borate,

Tetrabutylammonium methyltriphenyl borate,

Tetrabutylammonium n-butyltriphenyl borate,

Tetrabutylammonium n-octyltriphenyl borate,

Tetrabutylammonium n-dodecyltriphenyl borate,

Tetrabutylammonium methyltri-p-tolyl borate,

Tetrabutylammonium n-butyltri-p-tolyl borate,

Tetrabutylammonium n-octyltri-p-tolyl borate,

Tetrabutylammonium n-dodecyltri-p-tolyl borate,

Tetrabutylammonium methyltrianisyl borate,

Tetrabutylammonium n-butyltrianisyl borate,

Tetrabutylammonium n-octyltrianisyl borate,

Tetrabutylammonium n-dodecyltrianisyl borate,

Tetraoctylammonium methyltriphenyl borate,

Tetraoctylammonium n-butyltriphenyl borate,

Tetraoctylammonium n-octyltriphenyl borate,

Tetraoctylammonium n-dodecyltriphenyl borate,

Tetraoctylammonium methyltri-p-tolyl borate,

Tetraoctylammonium n-butyltri-p-tolyl borate,

Tetraoctylammonium n-octyltri-p-tolyl borate,

Tetraoctylammonium n-dodecyltri-p-tolyl borate,

Tetraoctylammonium methyltrianisyl borate,

Tetraoctylammonium n-butyltrianisyl borate,

Tetraoctylammonium n-octyltrianisyl borate,

Tetraoctylammonium n-dodecyltrianisyl borate,

Tetramethylammonium dimethyldiphenyl borate,

Tetramethylammonium di-n-butyldiphenyl borate,

Tetramethylammonium di-n-octyldiphenyl borate,

Tetramethylammonium di-n-dodecyldiphenyl borate,

Tetramethylammonium dimethyldi-p-tolyl borate,

Tetramethylammonium di-n-butyldi-p-tolyl borate,

Tetramethylammonium di-n-octyldi-p-tolyl borate,

Tetramethylammonium di-n-dodecyldi-p-tolyl borate,

Tetramethylammonium dimethyl dianisyl borate,

Tetramethylammonium di-n-butyldianisyl borate,

Tetramethylammonium di-n-octyldianisyl borate,

Tetramethylammonium di-n-dodecyl- dianisyl borate,

Tetraethylammonium dimethyldiphenyl borate,

Tetraethylammonium di-n-butyldiphenyl borate,

Tetraethylammonium di-n-octyldiphenyl borate,

Tetraethylammonium di-n-dodecyldiphenyl borate,

Tetraethylammonium dimethyldi-p-tolyl borate,

Tetraethylammonium di-n-butyldi-p-tolyl borate,

Tetraethylammonium di-n-octyldi-p-tolyl borate,

Tetraethylammonium di-n-dodecyldi-p-tolyl borate,

Tetraethylammonium dimethyl dianisyl borate,

Tetraethylammonium di-butyldianisyl borate,

Tetraethylammonium di-n-octyldianisyl borate,

Tetraethylammonium di-n-dodecyldiazinyl borate,

Tetrabutylammonium dimethyldiphenyl borate,

Tetrabutylammonium di-n-butyldiphenyl borate,

Tetrabutylammonium di-n-octyldiphenyl borate,

Tetrabutylammonium di-n-dodecyldiphenyl borate,

Tetrabutylammonium dimethyldi-p-tolyl borate,

Tetrabutylammonium di-n-butyldi-p-tolyl borate,

Tetrabutylammonium di-n-octyldi-p-tolyl borate,

Tetrabutylammonium di-n-dodecyldi-p-tolyl borate,

Tetrabutylammonium dimethyl dianisyl borate,

Tetrabutylammonium di-n-butyldianisyl borate,

Tetrabutylammonium di-n-octyldianisyl borate,

Tetrabutylammonium di-n-dodecyldiazinyl borate,

Tetraoctylammonium dimethyldiphenyl borate,

Tetraoctylammonium di-n-butyldiphenyl borate,

Tetraoctylammonium di-n-octyldiphenyl borate,

Tetraoctylammonium di-n-dodecyldiphenyl borate,

Tetraoctylammonium dimethyl-di-p-tolyl borate,

Tetraoctylammonium di-n-butyl-di-p-tolyl borate,

Tetraoctylammonium di-n-octyldi-p-tolyl borate,

Tetraoctylammonium di-n-dodecyldi-p-tolyl borate,

Tetraoctylammonium dimethyl dianisyl borate,

Tetraoctylammonium di-n-butyldianisyl borate,

Tetraoctylammonium di-n-octyldianisyl borate,

Tetraoctylammonium di-n-dodecyldiazinyl borate,

Tetramethylammonium tetraphenyl borate,

Tetraethylammonium tetraphenyl borate,

Tetrabutylammonium tetraphenyl borate,

Tetraoctylammonium tetraphenyl borate,

Tetramethylammonium tetra-p-tolyl borate,

Tetraethylammonium tetra-p-tolyl borate,

Tetrabutylammonium tetra-p-tolyl borate,

Tetraoctylammonium tetra-p-tolyl borate,

Tetramethylammonium tetraanisyl borate,

Tetraethylammonium tetraanisyl borate,

Tetrabutylammonium tetraanisyl borate,

Tetraoctylammonium tetraanisyl borate,

Tetramethylammonium triphenylnaphthyl borate,

Tetraethylammonium triphenylnaphthyl borate,

Tetrabutylammonium triphenylnaphthyl borate,

Tetramethylammonium tri-p-tolylnaphthyl borate,

Tetraethylammonium tri-p-tolylnaphthyl borate,

Tetrabutylammonium tri-p-tolylnaphthyl borate,

Tetramethylammonium tetrabutyl borate,

Tetraethylammonium tetrabutyl borate,

Tetrabutylammonium tetrabutyl borate,

Trimethylhydrogenammonium n-butyltriphenyl borate,

Triethylhydrogenammonium n-butyltriphenyl borate,

Trimethylhydrogenammonium n-butyltrianisyl borate,

Triethylhydrogenammonium n-butyltrianisyl borate,

Tetrahydrogenammonium n-butyltriphenyl borate,

Tetrahydrogenammonium n-butyltrianisyl borate,

Tetramethylammonium tri-n-butyl (triphenylsilyl) borate,

Tetraethylammonium tri-n-butyl (triphenylsilyl) borate,

Tetrabutylammonium tri-n-butyl (triphenylsilyl) borate,

Tetramethylammonium tri-n-butyl (dimethylphenylsilyl) borate,

Tetraethylammonium tri-n-butyl (dimethylphenylsilyl) borate,

Tetrabutylammonium tri-n-butyl (dimethylphenylsilyl) borate,

Tetramethylammonium n-octyldiphenyl (di-n-butylphenylsilyl) borate,

Tetraethylammonium n-octyldiphenyl (di-n-butylphenylsilyl) borate,

Tetramethylammonium dimethylphenyl (trimethylsilyl) borate,

Tetraethylammonium dimethylphenyl (trimethylsilyl) borate,

Tetrabutylammonium dimethylphenyl (trimethylsilyl) borate,

Methylpyridinium n-butyltriphenyl borate,

Methylpyridinium n-octyltriphenyl borate,

Methylpyridinium n-dodecyltriphenyl borate,

Ethylpyridinium n-butyltriphenyl borate,

Ethylpyridinium n-octyltriphenyl borate,

Ethylpyridinium n-dodecyltriphenyl borate,

n-butylpyridinium n-butyltriphenyl borate,

n-butylpyridinium n-octyltriphenyl borate,

n-butylpyridinium n-dodecyltriphenyl borate,

n-octylpyridinium n-butyltriphenyl borate,

n-octylpyridinium n-octyltriphenyl borate,

n-octylpyridinium n-dodecyltriphenyl borate,

Methylpyridinium n-butyltri-p-tolyl borate,

Methylpyridinium n-octyltri-p-tolyl borate,

Methylpyridinium n-dodecyltri-p-tolyl borate,

Ethylpyridinium n-butyltri-p-tolyl borate,

Ethylpyridinium n-octyltri-p-tolyl borate,

Ethylpyridinium n-dodecyltri-p-tolyl borate,

n-butylpyridinium n-butyltri-p-tolyl borate,

n-butylpyridinium n-octyltri-p-tolyl borate,

n-butylpyridinium n-dodecyltri-p-tolyl borate,

n-octylpyridinium n-butyltri-p-tolyl borate,

n-octylpyridinium n-octyltri-p-tolyl borate,

n-octylpyridinium n-dodecyltri-p-tolyl borate,

Methylpyridinium n-butyltrianisyl borate,

Methylpyridinium n-octyltrianisyl borate,

Methylpyridinium n-dodecyltrianisyl borate,

Ethylpyridinium n-butyltrianisyl borate,

Ethylpyridinium n-octyltrianisyl borate,

Ethylpyridinium n-dodecyltrianisyl borate,

n-butylpyridinium n-butyltrianisyl borate,

n-butylpyridinium n-octyltrianisyl borate,

n-butylpyridinium n-dodecyltrianisyl borate,

n-octylpyridinium n-butyltrianisyl borate,

n-octylpyridinium n-octyltrianisyl borate,

n-octylpyridinium n-dodecyltrianisyl borate,

Methylquinolinium n-butyltriphenyl borate,

Methylquinolinium n-octyltriphenyl borate,

Methylquinolinium n-dodecyltriphenyl borate,

Ethylquinolinium n-butyltriphenyl borate,

Ethylquinolinium n-octyltriphenyl borate,

Ethylquinolinium n-dodecyltriphenyl borate,

n-butylquinolinium n-butyltriphenyl borate,

n-butylquinolinium n-octyltriphenyl borate,

n-butylquinolinium n-dodecyltriphenyl borate,

n-octylquinolinium n-butyltriphenyl borate,

n-octylquinolinium n-octyltriphenyl borate,

n-octylquinolinium n-dodecyltriphenyl borate,

Methylquinolinium n-butyl tri-p-tolyl borate,

Methylquinolinium n-octyl tri-p-tolyl borate,

Methylquinolinium n-dodecyl tri-p-tolyl borate,

Ethylquinolinium n-butyl tri-p-tolyl borate,

Ethylquinolinium n-octyl tri-p-tolyl borate,

Ethylquinolinium n-dodecyl tri-p-tolyl borate,

n-butylquinolinium n-butyl tri-p-tolyl borate,

n-butylquinolinium n-octyl tri-p-tolyl borate,

n-butylquinolinium n-dodecyl tri-p-tolyl borate,

n-octylquinolinium n-butyl tri-p-tolyl borate,

n-octylquinolinium n-octyl tri-p-tolyl borate,

n-octylquinolinium n-dodecyl tri-p-tolyl borate,

Methylquinolinium n-butyl trianisyl borate,

Methylquinolinium n-octyl trianisyl borate,

Methylquinolinium n-dodecyl trianisyl borate,

Ethylquinolinium n-butyl trianisyl borate,

Ethylquinolinium n-octyl trianisyl borate,

Ethylquinolinium n-dodecyl trianisyl borate,

n-butylquinolinium n-butyl trianisyl borate,

n-butylquinolinium n-octyl trianisyl borate,

n-butylquinolinium n-dodecyl trianisyl borate,

n-octylquinolinium n-butyl trianisyl borate,

n-octylquinolinium n-octyl trianisyl borate,

n-octylquinolinium n-dodecyl trianisyl borate,

Methylpyridinium di-n-butyldiphenyl borate,

Ethylpyridinium di-n-octyldiphenyl borate

n-butylpyridinium di-n-dodecyldiphenyl borate,

n-octylpyridinium di-n-butyldiphenyl borate,

Methylpyridinium di-n-butyl di-p-tolyl borate,

Ethylpyridinium di-n-octyl di-p-tolyl borate,

n-butylpyridinium di-n-dodecyl di-p-tolyl borate,

n-octylpyridinium di-n-butyl di-p-tolyl borate,

Methylpyridinium di-n-octyl dianisyl borate,

Ethylpyridinium di-n-octyl dianisyl borate,

n-butylpyridinium di-n-dodecyl dianisyl borate,

n-octylpyridinium di-n-butyl dianisyl borate,

Methylquinolinium di-n-butyldiphenyl borate,

Ethylquinolinium di-n-octyldiphenyl borate,

n-butylquinolinium di-n-dodecyldiphenyl borate,

n-octylquinolinium di-n-butyldiphenyl borate,

Methylquinolinium di-n-butyl di-p-tolyl borate,

Ethylquinolinium di-n-octyl di-p-tolyl borate,

n-butylquinolinium di-n-dodecyl di-p-tolyl borate,

n-octylquinolinium di-n-butyl di-p-tolyl borate,

Methylquinolinium di-n-butyl dianisyl borate,

Ethylquinolinium di-n-octyl dianisyl borate,

n-butylquinolinium di-n-dodecyl dianisyl borate,

n octylquinolinium di-n-butyl dianisyl borate,

Methylpyridinium tetra-n-butyl borate,

Ethylpyridinium tetra-n-butyl borate,

n-butylpyridinium tetra-n-butyl borate,

n-octylpyridinium tetra-n-butyl borate,

Methylquinolinium tetra-n-butyl borate,

Ethylquinolinium tetra-n-butyl borate,

n-butylquinolinium tetra-n-butyl borate,

n-octylquinolinium tetra-n-butyl borate,

Methyl pyridinium tetra-n-octyl borate,

Ethyl pyridinium tetra-n-octyl borate,

n-butyl pyridinium tetra-n-octyl borate,

n-octyl pyridinium tetra-n-octyl borate,

Methylquinolinium tetra-n-octyl borate,

Ethylquinolinium tetra-n-octyl borate,

n-butylquinolinium tetra-n-octyl borate,

n-octylquinolinium tetra-n-octyl borate,

Tetramethylphosphonium n-butyltriphenyl borate,

Tetraethylphosphonium n-butyltriphenyl borate,

Tetra n-butylphosphonium n-butyltriphenyl borate,

Tetra n-octylphosphonium n-butyltriphenyl borate,

Tetramethylphosphonium n-butyl tri-p-tolyl borate,

Tetraethylphosphonium n-butyl tri-p-tolyl borate,

Tetra n-butylphosphonium n-butyl tri-p-tolyl borate,

Tetra n-octylphosphonium n-butyl tri-p-tolyl borate,

Tetramethylphosphonium N-butyltrianisyl borate,

Tetraethylphosphonium N-butyltrianisyl borate,

Tetra n-butylphosphonium N-butyltrianisyl borate,

Tetra n-octylphosphonium N-butyltrianisyl borate,

Tetramethylphosphonium N-octyl triphenyl borate,

Tetraethylphosphonium N-octyl triphenyl borate,

Tetra n-butylphosphonium n-octyl triphenyl borate,

Tetra n-octylphosphonium n-octyl triphenyl borate,

Tetramethylphosphonium n-octyl tri-p-tolyl borate,

Tetraethylphosphonium n-octyl tri-p-tolyl borate,

Tetra n-butylphosphonium n-octyl tri-p-tolyl borate,

Tetra n-octylphosphonium n-octyl tri-p-tolyl borate,

Tetramethylphosphonium n-octyl trianisyl borate,

Tetraethylphosphonium n-octyl trianisyl borate,

Tetra n-butylphosphonium n-octyl trianisyl borate,

Tetra n-octylphosphonium n-octyl trianisyl borate,

Tetramethylphosphonium n-dodecyl triphenyl borate,

Tetraethylphosphonium n-dodecyl triphenyl borate,

Tetra n-butylphosphonium n-dodecyl triphenyl borate,

Tetra n-octylphosphonium n-dodecyl triphenyl borate,

Tetramethylphosphonium n-dodecyltri-p-tolyl borate,

Tetraethylphosphonium n-dodecyltri-p-tolyl borate,

Tetra n-butylphosphonium n-dodecyltri-p-tolyl borate,

Tetra n-octylphosphonium n-dodecyltri-p-tolyl borate,

Tetramethylphosphonium n-dodecyltrianisyl borate,

Tetraethylphosphonium n-dodecyltrianisyl borate,

Tetra n-butylphosphonium n-dodecyltrianisyl borate,

Tetra n-octylphosphonium n-dodecyltrianisyl borate,

Tetramethylphosphonium di-n-butyldiphenyl borate,

Tetraethylphosphonium di-n-butyldiphenyl borate,

Tetra n-butylphosphonium di-n-butyldiphenyl borate,

Tetra n-octylphosphonium di-n-butyldiphenyl borate,

Tetramethylphosphonium di-n-butyl di-p-tolyl borate,

Tetraethylphosphonium di-n-butyl di-p-tolyl borate,

Tetra n-butylphosphonium di-n-butyl di-p-tolyl borate,

Tetra n-octylphosphonium di-n-butyl di-p-tolyl borate,

Tetramethylphosphonium n-butyldianisyl borate,

Tetraethylphosphonium di-n-butyldianisyl borate,

Tetra n-butylphosphonium di-n-butyldianisyl borate,

Tetra n-octylphosphonium di-n-butyldianisyl borate,

Tetramethylphosphonium di-n-octyldiphenyl borate,

Tetraethylphosphonium di-n-octyldiphenyl borate,

Tetra n-butylphosphonium di-n-octyldiphenyl borate,

Tetra n-octylphosphonium di-n-octyldiphenyl borate,

Tetramethylphosphonium di-n-octyl di-p-tolyl borate,

Tetraethylphosphonium di-n-octyl di-p-tolyl borate,

Tetra n-butylphosphonium di-n-octyl di-p-tolyl borate,

Tetra n-octylphosphonium di-n-octyl di-p-tolyl borate,

Tetramethylphosphonium di-n-octyldianisyl borate,

Tetraethylphosphonium di-n-octyldianisyl borate,

Tetra n-butylphosphonium di-n-octyldianisyl borate,

Tetra n-octylphosphonium di-n-octyldianisyl borate,

Tetraphenylphosphonium n-butyltriphenyl borate,

Tetraanisylphosphonium n-butyltriphenyl borate,

Tetraphenylphosphonium n-butyltri-p-tolyl borate,

Tetraanisylphosphonium n-butyltri-p-tolyl borate,

Tetraphenylphosphonium n-butyltrianisyl borate,

Tetraanisylphosphonium n-butyltrianisyl borate,

Tetraphenylphosphonium n-butyldiphenyl borate,

Tetraanisylphosphonium di-n-butyldiphenyl borate,

Tetraphenylphosphonium di-n-butyldi-p-tolyl borate,

Tetraanisylphosphonium di-n-butyldi-p-tolyl borate,

Tetraphenylphosphonium di-n-butyldianisyl borate,

Tetraanisylphosphonium di-n-butyldianisyl borate and the like.

In the present invention, the colored dye absorbing the wavelength of the visible region is an electric neutral dye having no ionic bond in the molecule or a cationic dye having ionic bond in the molecule, and is represented by the general formulas (2) and (3). Representative examples of coloring dyes include merocyanine dyes, xanthene dyes, thioxanthene dyes, indigo dyes, aromatic amine dyes, phthalocyanine dyes, oxazine dyes, thiazine dyes, azo dyes, quinone dyes, cyanine dyes and diarylmethanes. Dyes, triarylmethane dyes, pyryllium dyes, squarylium dyes and the like.

General formula (2)

Wherein D ⁺ is a cation that absorbs the wavelength of the visible region, and R ₅ , R ₆ , R ₇ and R ₈ are each independently alkyl, aryl, allyl, aralkyl, alkenyl, alkynyl, silyl, heterocy Click, substituted alkyl, substituted aryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl or substituted silyl group.

General formula (3)

D ⁺ · A ^-

In the above formula, D ⁺ is a cation that absorbs the wavelength of the visible region and A ⁻ represents an anion.

As the groups R ₅ , R ₆ , R ₇ and R ₈ of the general formula (2), the same groups as the groups R ₁ , R ₂ , R ₃ and R ₄ of the general formula (1) may be mentioned.

Examples of the anion (A ⁻ ) constituting the cationic dye of the general formula (3) include anion represented by halogen ion, perchlorate ion, PF ₆ ⁻ , BF ₄ ⁻ , S b F ₆ ⁻ , sulfonic acid ion, and the like. . Specific examples of the anion include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, and sulfonic acid ions such as methyl sulfonic acid ion such as CH ₃ SO ₃ ⁻ , FCH ₂ SO ₃ ⁻ , F ₂ CHSO _{3 ^{-, F 3 CSO 3 -,}} ClCH 2 SO 3 -, Cl 2 CHSO 3 -, Cl 3 CSO 3 -, CH 3 OCH 2 SO 3 -, (CH 3) 2 NCH 2 SO 3 - substituted methyl such etc. acid ion, C ₆ H ₅ SO ₃ ^- phenyl sulfonic acid ions _{etc., CH 3 C 6 H 4 SO} 3 -, (CH 3) 2 C 6 H 3 SO 3 -, (CH 3) 3 C 6 H 2 SO 3 _{^{-, HOC 6 H 4 SO 3}} -, (HO) 2 C 6 H 3 SO 3 -, (HO) 3 C 6 H 2 SO 3 -, CH 3 OC 6 H 4 SO 3 -, C 6 H 6 ClSO 3 _{^{-, C 6 H 3 Cl 2}} SO 3 -, C 6 H 2 Cl 3 SO 3 -, C 6 HCl 4 SO 3 -, C 6 Cl 5 SO 3 -, C 6 H 4 FSO 3 -, C 6 H 3 _{^{F 2 SO 3 -, C 6}} H 2 F 3 SO 3 -, C 6 HF 4 SO 3 -, C 6 F 5 SO 3 -, (CH 3) 2 NC 6 H 4 SO 3 - , such as phenyl substituted in etc. Sulfonic acid ions. Representative examples of such colored dyes include those listed in Table 1.

In Table 1

1) Me represents a methyl group,

2) Et represents an ethyl group,

3) n-Pr represents an n-propyl group,

4) n-Bu represents an n-butyl group,

5) t-Bu represents a t-butyl group,

6) n-Hex represents an n-hexyl group,

7) c-Hex represents a cyclohexyl group,

8) n-Hep represents an n-heptyl group,

9) n-Oct represents an n-octyl group,

10) All represents an allyl group,

11) Ph represents a phenyl group,

12) Bz represents a benzyl group,

13) Tol represents a toluyl group,

14) Anisy represents nosilyl,

15) OMe represents a methoxy group.

These colored dyes and boron compounds may be used separately or in combination of two or more thereof.

Among the base materials used in the present invention, the waxes are those generally used in heat transfer sheets and inks, for example, vegetable waxes such as carbana wax and Japan-ese wax, animal wax beeswax and wool. Paraffin wax and microcrystalline wax which are mineral wax; And synthetic waxes such as polyethylene wax, polypropylene wax, chlorinated paraffin, fatty acid amide, and the like.

The resins that can be used in the present invention are all conventional resins and include, for example, normal temperature drying and curing resins, coating curing resins, coating thermosetting resins, resins for toners, and the like. dip) coating, gravure coating, doctor coating, roll coating, electrostatic coating, powder coating, transfer, printing and the like. Specific examples thereof include polystyrene resins represented by oil varnish, voile oil, shellac, cellulose resin, phenol resin, alkyd resin, amino resin, xylene resin, toluene resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polystyrene, and the like. (Meth) acrylic resins represented by polyolefin resins, polyvinyl-butyral resins, polymethyl methacrylates, and the like; Polyester resins represented by diallyl phthalate resin, epoxy resin, polyurethane resin, unsaturated polyester and the like; Polyether resin, polyvinyl alcohol resin, aniline resin, furan resin, polyamide resin, silicone resin, fluorine resin and the like. These resins may be used alone or in mixture of two or more.

Further, the substrate according to the present invention is not limited to the above resins, and any one can be used as long as the photochromic recording material can be mixed by dissolution or dispersion.

In the photochromic recording material of the present invention, absorption of a colored dye having absorbance at a wavelength in the visible light region of 400 to 780 nm is used together with a boron compound to emit visible light so that absorption in the visible light region disappears and the colored dye is discolored. The reason is that the organic boron anion, which is an anion part of the boron compound, is photosensitized with a coloring dye, and the anion part is decomposed to generate radicals, and the radical reacts with the dye and the absorption of the coloring material disappears. When the colored dye is a cationic dye represented by the general formula (3), the anion of the colored dye and the anion of the boron compound undergo an ion exchange reaction by using the boron compound together with the boron represented by the general formula (2). Cationic dyes with anions are produced in the system.

The colored dyes having absorption in the visible light region constituting the photochromic recording material of the present invention can be mixed with the substrate in proportions of 0.01 to 90% by weight, preferably 0.5 to 50% by weight. Meanwhile, the boron compound may be mixed with the colored dye in a proportional amount of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on 1% by weight of the colored dye. These photochromic recording materials can be used in admixture with the substrate by dissolving it with a solvent or melting and mixing it. However, the photochromic recording material of the present invention can have the same effect even when the recording material itself is dissolved or dispersed in a solvent and the obtained solution is coated or set. Furthermore, if necessary, general dyes and pigments for coloring may be mixed, in which case only the color of the dyes and pigments for coloring may remain after the photochromic recording material is decolorized by the emission of visible light.

The coloring dyes and boron compounds used in the photochromic recording material may be used alone or in combination of two or more.

Although the coloring dye constituting the photochromic recording material of the present invention has sensitivity to visible light, a stable composition is obtained under visible light containing light such as a fluorescent lamp by mixing the recording material with the base material, and the obtained composition is made of paper, plastic, After being set or printed on a metal, etc., the part set or printed cannot be discolored until visible light is irradiated to this setting or printed part from light sources such as halogen lamps, xenon lamps, light emitting diodes and lasers. This can be done again on the bleaching site. Also, when visible light is irradiated to the photochromic recording material of the present invention to decolorize the recording material, the decolorization rate can be accelerated by heating it when the recording material is decolorized. Furthermore, in the photochromic recording material of the present invention, the coloring dyes and boron compounds constituting the recording material may likewise be used separately. That is, even when the composition obtained by mixing the coloring dye and the base material and the composition obtained by mixing the boron compound and the base material are separately prepared, and after the setting or printing with the composition in which the coloring dye is mixed, the boron compound is mixed. The present composition is applied to the setting or printed area and visible light is irradiated to this area and the same effect as described above can be obtained. The photochromic recording material of the present invention is not only used as an electrophotographic recording or electrostatic lock toner or ink for printing and sublimation or melt transfer printer, but also for serial printer ink, ink ribbon ink, ink jet printer, ballpoint pen, marker, magic It can be used for marker and pencil ink or UV curing ink and paint. However, the use of the photochromic recording material is not limited to these examples.

The toner for electrophotographic recording is a mixture of boron compound of the formula (1) and the coloring dye on a substrate such as a binder for toner, and if necessary, a filler such as titanium white, calcium carbonate and a charge control agent are kneaded or other additives. It is prepared by dispersing. The storage stability of the toner can be further improved when the ultraviolet absorbent is added. As the charge control agent, a positive or negative charge control agent which has been used as a color toner so far will be used. Examples of positive charge control agents include quaternary ammonium salts, acrylamides, hydrophobic silicas, and the like. Examples of negative charge control agents include diaminoanthraquinones, chloride polyolefins, chloride chlorides, metal salts of naphthenic acid, and metal salts of fatty acids.

White titanium, talc, kaolin, silica, alumina, calcium carbonate, aluminum sulfate, barium sulfate, calcium sulfate and calcium phosphate will be used as fillers. The addition of fillers allows control of whitening after bleaching. Conventional ultraviolet absorbers will be used as ultraviolet absorbers.

Polystyrene, acrylic resin, styrene- (meth) acrylic ester copolymer, vinyl chloride resin, ethylene acetate-butyl copolymer, rosine-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, low molecular weight polystyrene, low molecular weight Thermosetting resins such as polypropylene, ionomer resins, polyurethane resins, silicone resins, ketone resins, xylene resins, polyvinyl butyral resins, etc. will be used as the binder for the toner. Examples of polystyrene resins include polystyrene homopolymers, hydrogenated polystyrenes, styrene-propylene copolymers, styrene-isobutylene copolymers, styrene-butadiene copolymers, styrene-allyl alcohol copolymers, styrene-maleic acid ester copolymers, styrene-maleic anhydride Polymers, acrylonitrile-butadiene-styrene terpolymers, acrylonitrile-styrene-acrylic acid ester terpolymers, styrene-acrylonitrile copolymers, acrylonitrile-acrylic rubber-styrene copolymers, acrylonitrile-polyethylene-styrene Terpolymers and the like. Examples of the acrylic resin include polymethyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, fluorine-containing acrylate, methylene methacrylate-butyl methacrylate, and ethyl acrylate. Acrylic acid copolymers; Examples of styrene- (meth) acrylate copolymers include styrene-acrylic acid copolymers, styrene-butadiene-acrylic ester terpolymers, styrene-methacrylate methyl copolymers, styrene-methacrylate butyl copolymers, styrene-methacrylic acid Methyl-butyl butyl terpolymer, styrene-methacrylate glycidyl copolymer, styrene-butadiene-dimethyl aminoethyl methacrylate terpolymer, styrene-acrylic acid ester-maleic ester terpolymer, styrene-butyl acrylate-acrylic terpolymer There is this.

The coloring dye made of the photochromic recording material, which is the colorant for toner, may be mixed with the toner binder in a proportional amount of 0.01 to 90% by weight, preferably 0.5 to 50% by weight.

The boron compound will be mixed in proportional amounts of 0.01 to 20% by weight, preferably 0.1 to 10% by weight relative to 1% by weight of the dye salt.

The charge control agent may be added in an amount sufficient to control the amount of charge of the toner within the range of 0.1 to 20% by weight relative to the weight of the binder for the toner. The filler may be mixed in a proportional amount of 0.1 to 20% by weight, preferably 0.1 to 5% by weight relative to the weight of the binder for toner. The ultraviolet absorbent may be mixed in a proportional amount of 0.1 to 20% by weight based on the weight of the binder for toner.

The manufacturing method of the toner includes a dissolving method and a melting method. In the dissolution method, the colored dyes and boron compounds are dissolved and kneaded in a binder for toner together with an organic solvent, and, if necessary, charge control agents and ultraviolet absorbers are mixed in the organic solvent and the binder for toner, and dissolved. When kneaded and added, the filler is dispersed and kneaded by the paint conditioner to prepare a resin mixture, and after the organic solvent is removed from the resin mixture thus obtained, the resin mixture is roughened, such as a hammer mill and a cutter mill. It is pulverized and then pulverized by a jet mill to produce a toner. In the melting method, the colored dye and the boron compound are melted and kneaded in a binder for toner, and if necessary, the charge control agent, the ultraviolet absorber and the filler are mixed and kneaded and then cooled, and the obtained mixture is cooled in the same manner as the melting method. It is pulverized to produce a toner. The toner obtained as described above can be used not only as a one-component type toner but also as a two-component type toner.

After the toner is set or printed on paper or OHP film and fixed, the color of the colored dye is irradiated to the part where the visible-containing light from the light source such as halogen lamp, xenon lamp, light emitting diode and laser is set or printed. Thereby disappearing, and as a result, the setting or printed portion may be discolored. Moreover, the discolored portion can be repeatedly set or printed by the toner or a conventional black toner. In addition, it is possible in the toner to separately use the colored dye and the boron compound constituting the toner. That is, when the toner with only the toner and the kneading colored dye and the composition with only the substrate and the kneaded boron compound are prepared independently, and after printing is performed with the toner with only the dye and the kneaded colored dye, the substrate and the dough The composition having the boron compound thus obtained is applied to the printing site, and then visible light is irradiated thereon, thereby obtaining the same effect as above.

Moreover, the photochromic recording material of the present invention can also be used for ink. Inks can be prepared by kneading the above colored dyes and boron compounds as a colorant with a substrate which fixes them to the setting surface and, if necessary, dispersing and kneading fillers such as white titanium and calcium carbonate with other additives. Storage stability can be further improved when ultraviolet absorbers are added. Substrates used in these inks include dry oils that dry relatively quickly when placed in air, resins that improve drying properties, gloss, transition properties, and the like, and solvents that impart the required viscosity and flowability. However, if necessary, the photobleachable recording material of the present invention can be used only by dissolving in a solvent or in a state in which colored dyes and boron compounds are dispersed in a solvent having low solubility.

Dry oils include linseed oil, china wood oil, soybean oil and castor oil. Examples of the resin include natural resin derivatives such as cured rosin, rosin ester, maleic acid resin and fumaric acid resin; Phenolic resin, urea-melamine resin, kenon resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, butyral resin, styrene-maleic acid resin, styrene- (meth) acrylic acid ester copolymer resin, polypropylene chloride, acrylic acid resin, Synthetic resins such as polyester resins, polyamide resins, epoxy resins, polyurethane resins, and nitrocellulose.

The solvent includes aliphatic hydrocarbons such as hexane and heptane; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, cyclohexyl alcohol, and benzyl alcohol; Glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, polyalkylene glycol, hexylene glycol, and phenyl glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diphenyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol pentaerythritol fatty acid Glycol derivatives such as hotel; Ethyl acetate, isopropyl acetate, butyl acetate, cesyl isooctanoate, sorbitan monostearate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxy Esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, ascorbic acid ester, and castor oil fatty acid ester; Waxes such as polyolefin wax, carnauba wax, and paraffin wax; Liquid paraffin, water and the like.

Fillers similar to those useful for the toners used for electrophotographic recording will be used.

Conventional ultraviolet absorbers will be used as ultraviolet absorbers.

The colored dyes used in such inks will be mixed with the substrate in proportions of 0.01 to 90% by weight, preferably 0.5 to 50% by weight. The boron compound will be mixed in proportional amounts of 0.01 to 20% by weight, preferably 0.1 to 10% by weight relative to 1% by weight of the colored dye. The substrate will optionally be mixed according to the printing method.

The filler will also be mixed with the substrate in a proportional amount of 0.1 to 20% by weight, preferably 0.1 to 5% by weight. The ultraviolet absorbent will be mixed with the substrate in a proportional amount of 0.1 to 20% by weight.

This decolorizing ink is prepared by kneading colored dyes and boron compounds with dry oil and, if necessary, by adding and kneading ultraviolet absorbers, fillers and the like.

Such inks may also be used for printing, and may include offset press printing, letter press printing, gravure press printing, hole press printing, or printing as well as electro printing by printing presses such as impact or non-impact presses. Visible light from light sources such as halogen lamps, xenon lamps, light emitting diodes, and lasers, after being printed by various printing methods such as peculiar compression printing including flexo printing, metal printing, plastic printing, glass printing, mobile paper printing, and the like. When the containing light beam is irradiated to the printed portion, the color of the colored dye disappears, whereby the printed portion is discolored. Moreover, such discolored portions may be repeatedly printed with such a printing ink or a conventional printing ink.

Furthermore, when such inks are used as inks for ink ribbons, the colored dyes and boron compounds described above are mixed with a substrate and pulverized and dispersed in a solvent by wet grinding to prepare an ink. Ribbons made of synthetic fiber fabrics, such as nylon 66, are dried after injecting the ink so produced, thereby producing ink ribbons. When the visible-containing light from light sources such as halogen lamps, xenon lamps, light emitting diodes and lasers is irradiated on a piece of paper set or printed using a printing machine with the ink so produced, the color of the colored dye disappears. The setting or printed portion may be discolored. Furthermore, printing can be carried out on this discoloration portion repeatedly with such a printing ink and a conventional printing ink. In addition, in the above ink ribbon ink, it is possible to prepare colored dyes and boron compounds composed of such inks, which are independent inks as in the toner, and to use these inks independently.

In an embodiment in which the recording material is applied to a thermal melting-transfer sheet, the transfer film composed of the above-mentioned colored dyes and boron compounds, calcium carbonate mixed with paraffin wax and other materials used as a binder is coated on a PET film. And is transferred and printed by the heated head in close contact with the recording paper. This setting site can be discolored in the same manner as the discoloration of the ink.

The invention will be explained in more detail with reference to the following non-limiting examples.

[Examples 1 to 4]

20 parts by weight of polymethyl methacrylate was dissolved in 76 parts by weight of methyl ethyl ketone, and the colored dyes and boron compounds listed in Table 2 were dissolved and mixed in the amounts shown in Table 2 to obtain a composition.

[Examples 5 to 10]

40 parts by weight of a styrene-methacrylate butyl copolymer (softening point: 72 ° C.) was dissolved in 50 parts by weight of dichloroethane, and the colored dyes and boron compounds listed in Table 2 were dissolved and kneaded in the amounts shown in Table 2 to obtain a composition. .

[Examples 11 to 14]

20 parts by weight of polystyrene was dissolved in 70 parts by weight of toluene, and the colored dyes and boron compounds listed in Table 2 were dissolved and kneaded in the amounts shown in Table 2 to obtain a composition.

[Examples 15 to 20]

40 parts by weight of phenol resin (softening point; 110 ° C.) was dissolved in 70 parts by weight of veratrol resin, and the colored dyes and boron compounds listed in Table 2 were dissolved and kneaded in the amounts shown in Table 2 to obtain a composition.

[Examples 21 to 24]

To 70 parts by weight of paraffin wax (melting point; 69 ° C.), the colored dyes and boron compounds listed in Table 2 were thermally melted at 80 ° C. in the amounts shown in Table 2 to obtain a composition.

[Examples 25 to 27]

96 parts by weight of the styrene-butyl methacrylate copolymer (softening point; 72 ° C.) was dissolved by kneading the colored dyes and boron compounds listed in Table 2 together with methylene chloride in the amounts shown in Table 2, followed by distillation of methylene chloride. Removed via The obtained resin mixture was roughly ground with a hammer mill or cutter mill and then finely ground with a jet mill to prepare toner particles.

[Examples 28 to 30]

The colored dyes and boron compounds listed in Table 2 were dissolved and kneaded together with methylene chloride in 96 parts of polystyrene (softening point; 92 ° C), and methylene chloride was removed by distillation. The obtained resin mixture was roughly ground with a hammer mill or cutter mill and then finely ground with a jet mill to prepare toner particles.

[Examples 31 to 32]

96 parts by weight of hydrogenated polystyrene (softening point; 101 ° C.) were dissolved and kneaded with methylene chloride in the amounts shown in Table 2 in the amounts shown in Table 2, and methylene chloride was removed by distillation. The obtained resin mixture was roughly ground with a hammer mill or cutter mill and then finely ground with a jet mill to prepare toner particles.

[Examples 33 and 40]

96 parts by weight of styrene-butyl methacrylate copolymer (softening point; 72 ° C.) was dissolved and kneaded with acetone and the coloring dyes and boron compounds listed in Table 2 in the amounts shown in Table 2, and acetone was removed by distillation. The obtained resin mixture was roughly ground with a hammer mill or cutter mill and finely ground with a jet mill to prepare toner particles.

[Examples 41 to 43]

Styrene-butyl methacrylate copolymer (softening point; 72 ° C.) was dissolved and kneaded with methylene chloride and colored dyes, boron compounds and charge control agents listed in Table 2 in the amounts shown in Table 2 in 94 parts by weight, and methylene chloride was distilled off. Removed by. The obtained resin mixture was roughly ground with a hammer mill or cutter mill and then finely ground with a jet mill to prepare toner particles.

[Examples 44 to 46]

Styrene-butyl methacrylate copolymer (softening point; 72 ° C.) was dissolved in 89 parts by weight of methylene chloride and the coloring dyes, boron compounds, and charge control agents listed in Table 2 in amounts shown in Table 2, and kneaded, and methylene chloride was distilled off. Removed by The obtained resin mixture was roughly ground with a hammer mill or a cutter mill and then finely ground with a jet mill to prepare toner particles.

[Examples 47 to 53]

The coloring dyes, boron compounds, and charge control agents listed in Table 2 were melted and kneaded in 94 parts by weight of a styrene-butyl methacrylate copolymer (softening point; 72 ° C.) by a biaxial kneader-molding machine. The dough mixture was then cooled. The obtained dough resin was roughly ground with a hammer mill or a cutter mill and then finely ground with a jet mill to prepare toner particles.

Examples 54 and 55

91 parts by weight of polymethyl methacrylate (softening point; 78 ° C.) was dissolved and kneaded with methylene chloride and the coloring dyes, boron compounds, and charge control agents listed in Table 2 in the amounts shown in Table 2, and additionally, 3 parts by weight of titanium bag. A portion of methylene chloride dispersion was dissolved and kneaded as filler, and methylene chloride was then removed by distillation. The obtained resin mixture was roughly ground with a hammer mill or cutter mill and then finely ground with a jet mill to prepare toner particles.

Examples 56 and 57

91 parts by weight of polymethyl methacrylate (softening point; 78 ° C.) was melted and kneaded with the coloring dyes, boron compounds, and charge control agents listed in Table 2 in the amounts shown in Table 2, and 3 parts by weight of titanium bags were biaxially formed. It was melted and kneaded as a filler by a kneader-molding machine and then the kneading mixture was cooled. Next, the obtained dough resin was roughly ground with a hammer mill or a cutter mill, and then pulverized with a jet mill to prepare toner particles.

Example 58

89 parts by weight of polymethyl methacrylate (softening point; 78 ° C.) was dissolved and kneaded with methylene chloride and the coloring dyes, boron compounds, and charge control agents listed in Table 2 in the amounts shown in Table 2, and further ultraviolet absorbers (Sumitomo 2 parts by weight of "Sumisorb 400" manufactured by Kagaku KK) and 3 parts by weight of titanium bag as a filler were dissolved and kneaded, and methylene chloride was then removed by distillation. Next, the obtained resin mixture was roughly ground with a hammer mill or a cutter mill and then finely ground with a jet mill to prepare toner particles.

[Examples 59 to 63]

50 parts by weight of linseed oil and 30 parts by weight of styrene-maleic acid resin (softening point; 70 ° C.) were dissolved and kneaded with the coloring dyes and boron compounds listed in Table 2 in the amounts shown in Table 2 to prepare an ink.

[Examples 64 to 67]

Ink was prepared by dissolving and kneading the colored dyes and boron compounds listed in Table 2 in 30 parts by weight of soybean oil and 50 parts by weight of styrene-maleic acid resin (softening point; 70 ° C.).

[Examples 68 to 70]

40 parts by weight of soybean oil and 30 parts by weight of an acrylic resin (softening point; 65 ° C.) were dissolved and kneaded with the coloring dyes and boron compounds listed in Table 2 in the amounts shown in Table 2 to prepare an ink.

[Examples 71 to 74]

An ink was prepared by kneading the colored dyes, boron compounds, and solvents listed in Table 2 in 60 parts by weight of an acrylic resin (softening point; 65 ° C).

[Examples 75 to 77]

Ink was prepared by kneading the coloring dyes, boron compounds, solvents and plasticizers listed in Table 2 in 40 parts by weight of soybean oil and 25 parts by weight of acrylic resin (softening point; 65 ° C).

[Examples 78 to 83]

60 parts by weight of liquid paraffin ("Christol 70" [pronounced] manufactured by Esso Petroleum Oil Industries Incorporated), 10 parts by weight of ethylene glycol, and 10 parts by weight of "Hilac 110" (ketone resin manufactured by Hitachi Kasei KK) Part and the coloring dyes and boron compounds listed in Table 2 were mixed in the amounts shown in Table 2, and the obtained mixture was ground by a ball mill and dispersed to prepare an ink.

Comparative Examples 1 and 2

40 parts by weight of styrene-butyl methacrylate copolymer (softening point; 72 ° C.) was dissolved in 55 parts by weight of dichloroethane, and the colored dyes listed in Table 2 were dissolved and kneaded in the obtained mixture in the amounts shown in Table 2, and finally A composition was obtained.

Comparative Examples 3 and 4

Methylene chloride and the colored dyes listed in Table 2 were dissolved and kneaded in 98 parts by weight of styrene-butyl methacrylate copolymer (softening point; 72 ° C.), and methylene chloride was then removed by distillation. The obtained resin mixture was roughly ground with a hammer mill or a cutter mill and then finely ground with a jet mill to prepare toner particles.

[Production of Printed Sample]

The compositions of Examples 1-20 were developed on a cardboard with a thickness of 10 μm using a RI tester and dried to obtain a sample. For the compositions of Examples 21 to 24, a sheet obtained by applying each composition to a 3.5 μm thick polyethylene terephthalate film using a wire bar at a thickness of 4.0 μm was applied with an applied energy of 2.0mj / dot. A sample was obtained by transfer printing onto a recording sheet using a thermal printer at. The toner particles obtained in Examples 25 to 58 were further surface treated with hydrophobic silica, and then the carrier was mixed therein, and then PPC paper was used on a PPC copying machine ("LSC-24" by Casio Co., Ltd.). The toner was set to obtain a sample. The ink obtained in Examples 59 to 77 was absorbed and dried in a cardboard at a thickness of 5 탆 using a RI tester to obtain a sample. A ribbon made of nylon was infiltrated with the inks obtained in Examples 78 to 83 so that the ink weight after drying was 13 g / m 2, and Nippon Denki K.K. Each was put in the ribbon cassette for PC-201H which was produced, and it set to paper using the PC-201H printer, and obtained the sample.

The compositions obtained in Comparative Examples 1 and 2 were absorbed and dried on a cardboard with a thickness of 10 μm to obtain a sample. The toner particles obtained in Comparative Examples 3 and 4 were further surface treated with hydrophobic silica, and the carrier was mixed therein, and then these toners were copied to PLC by "LCS-24" manufactured by Casio Compu-ter Manufacturing Co., Ltd. Was printed on PPC paper to obtain a sample.

[Evaluation of the possibility of discoloration]

After irradiating visible light for 2 seconds to the sample obtained as a result of Examples 1 to 83 and Comparative Examples 1 to 4 using an infrared cut filter, the image density of the sample with a Macbeth reflection density meter RD 918 Was measured to evaluate the decolorization of these samples.

The results are shown in Table 3.

[Measurement of phase stability]

Fluorescent lamp light of 1100 lux corresponding to roughness intensity of about three times the normal office brightness was irradiated to the samples of Examples 1 to 83 for 24 hours, and the image density of these samples was measured using a Mévez reflection density meter RD918. The stability was evaluated.

The results are shown in Table 4.

From the results shown in Table 3, when the visible light is irradiated to the sample using a halogen lamp, it can be found that the Megves reflectance value shows that the print density is greatly reduced and the color of the sample is lost. It can also be seen from the results in Table 4 that even when the fluorescent lamp light is scanned into the sample at a much higher brightness than that of a typical office, the Mcbeth reflection density of the sample hardly changes, and thus the sample has substantial light stability.

According to the present invention there is provided a photochromic recording material, which can be discolored by visible light after setting and printing, and can set and print the setting and printing again, and substantially light stability under fluorescent lamp light. Have

Claims (9)

Recordable material decolorable by visible light except fluorescent lamps, including: (i) Boron compound represented by General formula (1). Wherein R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently alkyl, aryl, allyl, aralkyl, alkenyl, alkynyl, silyl, heterocyclic, substituted alkyl, substituted aryl , Substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl or substituted silyl group, Z ⁺ represents quaternary ammonium, quaternary pyridinium, quaternary quinolinium or phosphonium cation; and (Ii) absorbed in the visible range of 400 nm to 780 nm, selected from the group consisting of an electrically neutral dye having no ionic bond in the molecule represented by the formulas (2) and (3) and a cationic dye having an ionic bond in the molecule. Photochromic Dye Wherein D ⁺ represents a cation having absorbance in the visible region, and each of R ′ ₅ , R ′ ₆ , R ′ ₇ and R ′ ₈ independently represents alkyl, aryl, allyl, aralkyl, alkenyl, alkynyl , silyl, heterocyclic, represents substituted alkyl, substituted aryl, substituted allyl, substituted aralkyl, substituted alkenyl groups substituted alkynyl or substituted silyl a ^- is a halogen ion, perchloric acid ion, PF ^- ₆ , BF ^- ₄ , SbF ^- ₆ , and sulfonic acid ions), However, the coloring dye is not represented by one of the following formulas. (Wherein Ph represents a phenyl group, Ar and R represent a phenyl group and an n-butyl group, an anylyl and n-hexyl group, or a phenyl group and n-octyl group). The dye according to claim 1, wherein the coloring dye is merocyanine dye, xanthene dye, thioxanthene dye, indigo dye, aromatic amine dye, phthalocyanine dye, oxazine dye, thiazine dye, azo dye, quinone dye, cyanine dye, A photobleachable recording material, characterized in that it is selected from diarylmethane dyes, triarylmethane dyes, pyryllium dyes and squarylium dyes. The photochromic recording material according to claim 1 or 2, wherein the boron compound is present in an amount of 0.01 to 20 parts by weight based on 1 part by weight of the coloring dye. A toner decolorable by visible light except for fluorescent lamp light, comprising the photochromic recording material according to claim 1 as a colorant, wherein the setting portion is decolorized by visible light. The dye according to claim 4, wherein the coloring dye is merocyanine dye, xanthene dye, thioxanthene dye, indigo dye, aromatic amine dye, phthalocyanine dye, oxazine dye, thiazine dye, azo dye, quinone dye, cyanine dye, A decolorable toner, characterized in that it is selected from diarylmethane dyes, triarylmethane dyes, pyryllium dyes and squarylium dyes. The decolorable toner according to claim 4 or 5, wherein the boron compound is present in an amount of 0.01 to 20 parts by weight based on 1 part by weight of the coloring dye. An ink capable of being decolorized by visible light except for fluorescent lamp light, comprising the photochromic recording material according to claim 1 as a colorant, wherein the setting portion is decolorized by visible light. The dye according to claim 7, wherein the coloring dye is merocyanine dye, xanthene dye, thioxanthene dye, indigo dye, aromatic amine dye, phthalocyanine dye, oxazine dye, thiazine dye, azo dye, quinone dye, cyanine dye, A decolorable ink characterized in that it is selected from diarylmethane dyes, triarylmethane dyes, pyryllium dyes and squarylium dyes. The decolorable ink according to claim 7 or 8, wherein the boron compound is present in an amount of 0.01 to 20 parts by weight based on 1 part by weight of the coloring dye.