JPH06236000A - Light decoloring recording material - Google Patents

Abstract

PURPOSE:To provide a recording material decolored with a typed or printed record portion via the visible light, made readable when typed or printed again on the same portion, and excellent in stability against the light of a fluorescent lamp by combining a specific decolorant and a specific cation dye having an absorbing capability in the visible light area. CONSTITUTION:A cation dye expressed in the formula I or the formula II and a declorant expressed by the formula III are concurrently used. In the formula I, II, D<+> indicates the cation having an absorbing capability in the visible light area, R1, R2, R3, R4 independently indicate the alkyl group and allyl group. A<-> indicates the anion selected from halogen ion, perchloric acid ion, PR<->6, BF<->4, SbF<->6, and sulfonic acid ion. In the formula III, R5, R6, R7, R8 independently indicate the alkyl group and allyl group, and Z<+> indicates quaternary pyridinium cation, quaternary quinolinium cation, or phosphonium cation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-erasable recording material which is erased by exposing it to visible light and which is excellent in stability against light from fluorescent lamps. .

[0002]

2. Description of the Related Art Conventionally, in the fields of printing and copying, the environmental resistance of recording materials, that is, light resistance, moisture resistance, solvent resistance,
Attention has been paid to storability such as heat resistance, and physical properties have been actively improved. Particularly in the fields of electrophotographic recording, electrostatic recording and the like, development has been actively promoted. For example, in electrophotographic recording, US Pat. No. 2,297,691 specification, Japanese Patent Publication No.
Although a number of methods are known as described in JP-A-2-23910 and JP-B-43-24748,
Generally, a photoconductive substance is used to form an electrical latent image on a photoconductor by various means, and then the latent image is developed with toner to form a visible image, and if necessary, transfer to paper or the like. After the toner image is transferred onto the material, it is fixed by heating or pressure to obtain a copy.

Various developing methods are known in which an electrostatic latent image is visualized with toner. (For example, US Pat. No. 2874063, US Pat. No. 2,618,552.
The toner used in the heat fixing method as described above generally comprises a coloring agent such as carbon black and a coloring agent such as carbon black in a thermoplastic resin such as styrene-butyl acrylate copolymer. An additive such as a charge control agent is melt-mixed and uniformly dispersed, and after cooling, finely pulverized and adjusted to a desired particle size by a fine pulverizer and a disperser. Further, recently, colorization has progressed in fields such as printing and copying, and physical properties of colorants, charge control agents and the like have been actively improved. (For example, JP-A-57-13004
6, JP-A-57-191650) In the field of printing, offset printing, letterpress printing, gravure printing, stencil printing, or flexographic printing, metal printing, plastic printing, glass printing, transfer paper printing and other special printing, impact printing. There are various printing methods such as electronic printing using a printer such as a printer and a non-impact printer, and the ink used for these mainly comprises a vehicle as a binder and a colorant such as a dye or a pigment.

Furthermore, recently, the prevention of pollution by making printing ink solvent-free, the improvement of productivity by rapid curing, or
Development of UV-curable inks has also been actively pursued for the purpose of improving the physical properties of cured films. (For example, JP-A-1-
229084, Japanese Patent Application Laid-Open No. 1-271469, and Japanese Patent Application Laid-Open No. 2-
22370). However, the electrophotographic recording toner or printing ink cannot erase the printed image portion after printing. Therefore, when printing is performed again on the erased image portion, the printed portions are overlapped and it is difficult to read the printed image, and the printed recording paper cannot be reused.

[0005]

DISCLOSURE OF THE INVENTION According to the present invention, the printed and printed recording portion is erased by visible light, and when printed and printed again on the same portion, it is readable and stable to the light of a fluorescent lamp. The purpose is to provide a recording material having excellent properties.

[0006]

In the present invention, in order to solve this problem, a cation dye having absorption in the visible light region of 400 to 780 nm and a boron-based compound as a decoloring agent were intensively studied, and as a result, fluorescence was obtained. They have found that a photobleachable recording material that is sufficiently stable in room light such as a lamp and that is erased by applying visible light is obtained, and has completed the present invention.

That is, according to the present invention, a cationic dye represented by the general formula (1) or (2) is represented by the general formula (1);

[Chemical 3]

(Wherein D ⁺ is a cation having absorption in the visible light region, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group, an aryl group, an allyl group, an aralkyl group, Alkenyl group, alkynyl group, silyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted allyl group,
Indicates a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group)

General formula (2); D ⁺ · A ⁻

(In the formula, D ⁺ is a cation having absorption in the visible light region, and A ⁻ is selected from halogen ion, perchlorate ion, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ and sulfonate ion. Shows anions that have been spilled)

And a decolorizing agent represented by the general formula (3):

[Chemical 4]

(Wherein R ₅ , R ₆ , R ₇ and R ₈ are each independently an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group or a substituted alkyl group. Group, a substituted aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, Z ⁺ represents a quaternary pyridinium cation, a quaternary quinolinium cation or a phosphonium cation)

The photobleaching property is such that the absorption of the cationic dyes of the general formulas (1) and (2) in the visible light region disappears and the color is erased only by irradiating with light including visible light. A recording material is obtained. This photobleachable recording material is stable even when exposed to the light of a fluorescent lamp or the like, and practical stability is obtained. The photo-bleachable recording material according to the present invention is contained in a supporting material such as a wax, a resin and a solvent so as to be erased when irradiated with light in the visible light region, but stable with respect to light such as a fluorescent lamp. A sex composition is obtained.

As the cationic dye used here,
Although represented by the general formula (1) or the general formula (2),
The types of anions (A ⁻ ) that compose the general formula (2) include halogen ions, perchlorate ions, PF ₆ ⁻ , and B.
Anions such as F ₄ ⁻ , SbF ₆ ⁻ and sulfonate ion. Here, examples of the halogen ion include fluorine ion, chlorine ion, bromine ion and iodine ion, and examples of the sulfonate ion include CH ₃
SO ₃ ^- methyl sulfonic acid ion such as, FCH ₂ S
O 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 sulfonate ion such as, C ₆ H ₅ SO ₃ ^- phenyl sulfonate ion such _{as, CH 3 C 6 H4 SO 3} -, (CH 3) _{2
^{C 6 H 3 SO 3 -,}} (CH 3) 3 C 6 H 2 SO 3 -,

[0015] ^{_{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 4}} 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 S
Substituted phenyl sulfonate ions such as O ₃ ⁻ and (CH ₃ ) ₂ NC ₆ H ₄ SO ₃ ⁻ can be used.

In the general formula (1), R ₁ ,
Specific examples of R ₂ , R ₃ and R ₄ include an alkyl group,
Aryl group, allyl group, aralkyl group, alkenyl group,
Alkynyl group, silyl group, heterocyclic group, substituted alkyl group,
Examples thereof include a substituted aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group and a substituted silyl group. Among these, the preferable ones are
Phenyl group, anisyl group, ethoxyphenyl group, toluyl group, t-butylphenyl group, fluorophenyl group, chlorophenyl group, diethylaminophenyl group, xylyl group, n-butyl group, n-pentyl group, n-hexyl group,
n-heptyl group, n-octyl group, n-dodecyl group,

Cyclohexyl group, cyclohexenyl group,
Methoxymethyl group, methoxyethyl group, vinyl group, allyl group, triphenylsilyl group, dimethylphenylsilyl group, dibutylphenylsilyl group, trimethylsilyl group,
Examples include piperidyl group, thienyl group, furyl group,

Specific examples of the anion include n-methyltriphenylboron ion, n-ethyltriphenylboron ion, n-butyltriphenylboron ion,
n-octyltriphenylboron ion, n-dodecyltriphenylboron ion, n-methyltrianisylboron ion, n-ethyltrianisylboron ion, n
-Butyltrianisylboron ion, n-octyltrianisylboron ion, n-dodecyltrianisylboron ion,

N-methyltritoluylboron ion, n
-Ethyltritoluylboron ion, n-butyltritoluylboron ion, n-octyllittletoluylboron ion, n-dodecyltritoluylboron ion, di-n
-Methyldiphenylboron ion, din-ethyldiphenylboron ion, din-butyldiphenylboron ion, din-octyldiphenylboron ion, din-dodecyldiphenylboron ion, din-methyldianisylboron ion, din- Ethyldianisylboron ion, di-n-butyldianisylboron ion,

Di-n-octyldianisyl boron ion,
Di n-dodecyl dianisyl boron ion, di n-methyl ditoluyl boron ion, di n-ethyl ditoluyl boron ion, di n-butyl ditoluyl boron ion, di n
-Octylditoluylboron ion, di-n-dodecylditoluylboron ion, tetraphenylboron ion,
Tetraanisylboron ion, tetratoluylboron ion, triphenylnaphthylboron ion, tritoluylnaphthylboron ion, tetrabutylboron ion,
Tri-n-butyl (triphenylsilyl) boron ion, tri-n-butyl (dimethylphenylsilyl) boron ion,
Examples thereof include n-octyldiphenyl (din-butylphenylsilyl) boron ion and dimethylphenyl (trimethylsilyl) boron ion.

Preferred examples of the cation (D ⁺ ) having absorption in the visible light region of the general formulas (1) and (2) include, for example, cyanine, xanthene, oxazine, thiazine, diallylmethane and triallyl. methane,
Examples include cations of pyrylium-based cation dyes. Typical examples of such cationic dyes are shown in Table 1 below.
Some of them are shown in.

[0022]

[Table 1]

[0023]

[Table 1]

[0024]

[Table 1]

[0025]

[Table 1]

[0026]

[Table 1]

[0027]

[Table 1]

[0028]

[Table 1]

[0029]

[Table 1]

[0030]

[Table 1]

[0031]

[Table 1]

[0032]

[Table 1]

[0033]

[Table 1]

[0034]

[Table 1]

[0035]

[Table 1]

[0036]

[Table 1]

[0037]

[Table 1]

[0038]

[Table 1]

In Table 1, 1) Me represents a methyl group. 2) Et represents an ethyl group. 3) n-Bu represents an n-butyl group. 4) n-Hex represents an n-hexyl group. 5) c-Hex represents a cyclohexyl group. 6) n-Hep represents an n-heptyl group. 7) n-Oct represents an n-octyl group. 8) All represents an allyl group. 9) Ph represents a phenyl group. 10) Bz represents a benzyl group. 11) Tol represents a toluyl group. 12) Anisyl represents an anisyl group. 13) OMe represents a methoxy group.

The decoloring agent is represented by the general formula (3). Specific examples of R ₅ , R ₆ , R ₇ and R _{8 in} the formula are R ₁ and R in the general formula (1). _{The same as 2} , R ₃ and R ₄ can be mentioned.

Examples of the cation (Z ⁺ ) include a quaternary pyridinium cation, a quaternary quinolinium cation, and a phosphonium cation. Specific examples of the decolorizing agent include methylpyridinium n-butyltriphenylboron and methyl. Pyridinium n-octyltriphenylboron, methylpyridinium n-dodecyltriphenylboron, ethylpyridinium n-butyltriphenylboron, ethylpyridinium n-octyltriphenylboron, ethylpyridinium n-dodecyltriphenylboron, n-butylpyridinium n- Butyltriphenylboron, n-butylpyridinium n-octyltriphenylboron, n-butylpyridinium n-dodecyltriphenylboron, n
-Octylpyridinium n-butyltriphenylboron,

N-octylpyridinium n-octyltriphenylboron, n-octylpyridinium n-dodecyltriphenylboron, methylpyridinium n-butyltri-p-tolylboron, methylpyridinium n-octyltri-p-tolylboron, methylpyridiniumn
-Dodecyltri-p-tolylboron ethylpyridinium n-butyltri-p-tolylboron, ethylpyridinium n-octyltri-p-tolylboron, ethylpyridinium n-dodecyltri-p-tolylboron, n-butylpyridinium n-butyltri-p- Triryl boron, n
-Butylpyridinium n-octyltri-p-tolylboron, n-butylpyridinium n-dodecyltri-p-
Triryl boron,

N-octylpyridinium n-butyltri-p-tolylboron, n-octylpyridinium n-octyltri-p-tolylboron, n-octylpyridinium n-dodecyltri-p-tolylboron, methylpyridinium n-butyltrianisylboron , Methylpyridinium n-octyltrianisylboron, methylpyridinium n-dodecyltrianisylboron, ethylpyridinium n-butyltrianisylboron, ethylpyridinium n-octyltrianisylboron, ethylpyridinium n-dodecyltrianisylboron, n-butylpyridinium n-butyltrianisylboron, n-butylpyridinium n-octyltrianisylboron, n-butylpyridinium n-dodecyltrianisylboron,

N-octylpyridinium n-butyltrianisylboron, n-octylpyridinium n-octyltrianisylboron, n-octylpyridinium n-
Dodecyltrianisylboron, methylquinolinium n-
Butyltriphenylboron, methylquinolinium n-octyltriphenylboron, methylquinolinium n-dodecyltriphenylboron, ethylquinolinium n-butyltriphenylboron, ethylquinolinium n-octyltriphenylboron, ethyl Quinolinium n-dodecyltriphenylboron, n-butylquinolinium n-
Butyltriphenylboron, n-butylquinolinium n
-Octyltriphenylboron, n-butylquinolinium n-dodecyltriphenylboron, n-octylquinolinium n-butyltriphenylboron,

N-octylquinolinium n-octyltriphenylboron, n-octylquinolinium n-dodecyltriphenylboron, methylquinolinium n-butyltri-p-tolylboron, methylquinolinium n-octyltriphenyl- p-tolylboron, methylquinolinium n
-Dodecyltri-p-tolylboron ethylquinolinium n-butyltri-p-tolylboron, ethylquinolinium n-octyltri-p-tolylboron, ethylquinolinium n-dodecyltri-p-tolylboron, n-butylquinol Norinium n-butyltri-p-tolylboron, n
-Butylquinolinium n-octyltri-p-tolylboron, n-butylquinolinium n-dodecyltri-p-
Triryl boron,

N-octylquinolinium n-butyltri-p-tolylboron, n-octylquinolinium n-octyltri-p-tolylboron, n-octylquinolinium n-dodecyltri-p-tolylboron, methylquinone Norinium n-butyltrianisylboron, methylquinolinium n-octyltrianisylboron, methylquinolinium n-dodecyltrianisylboron, ethylquinolinium n-butyltrianisylboron, ethylquinolinium n-octyltria Nisil boron,

Ethylquinolinium n-dodecyltrianisylboron, n-butylquinolinium n-butyltrianisylboron, n-butylquinolinium n-octyltrianisylboron, n-butylquinolinium n-dodecyltria Nisylboron, n-octylquinolinium n-
Butyltrianisylboron, n-octylquinolinium n-octyltrianisylboron, n-octylquinolinium n-dodecyltrianisylboron, methylpyridiniumdi-n-butyldiphenylboron, ethylpyridiniumdi-n-octyldiphenylboron,

N-butylpyridiniumdin-dodecyldiphenylboron, n-octylpyridiniumdin-butyldiphenylboron, methylpyridiniumdin-butyldi-p-tolylboron, ethylpyridiniumdin-octyldi-p-tolylboron, n -Butylpyridinium din-dodecyldi-p-tolylboron, n-octylpyridinium di-n-butyldi-p-tolylboron, methylpyridiniumdi-n-butyldianisylboron, ethylpyridiniumdi-n-octyldianisylboron, n-butyl Pyridinium di-n-dodecyl dianisyl boron, n-octyl pyridinium di-n-butyl dianisyl boron,

Methyl quinolinium di-n-butyl diphenyl boron, ethyl quinolinium di-n-octyl diphenyl boron, n-butyl quinolinium di-n-dodecyl diphenyl boron, n-octyl quinolinium di-n-butyl diphenyl boron , Methylquinolinium di-n-butyldi-p-tolylboron, ethylquinolinium di-n-octyldi-p-tolylboron, n-butylquinoliniumdi-n
-Dodecyldi-p-tolylboron, n-octylquinolinium di-n-butyldi-p-tolylboron, methylquinolinium di-n-butyldianisylboron, ethylquinolinium di-n-octyldianisylboron, n- Butylquinolinium di-n-dodecyldianisyl boron,

N-octylquinolinium di-n-butyldianisyl boron, methylpyridinium tetra-n-butylboron, ethylpyridinium tetra-n-butylboron,
n-butylpyridinium tetra n-butylboron, n-
Octyl pyridinium tetra n-butyl boron, methyl quinolinium tetra n-butyl boron, ethyl quinolinium tetra n-butyl boron, n-butyl quinolinium tetra n-butyl boron, n-octyl quinolinium tetra n-butyl Boron, methylpyridinium tetra n-
Octylboron, ethylpyridinium tetra n-octylboron, n-butylpyridinium tetra n-octylboron, n-octylpyridinium tetra n-octylboron,

Methylquinolinium tetra-n-octyl boron, ethylquinolinium tetra-n-octyl boron,
n-butylquinolinium tetra n-octyl boron, n
-Octylquinolinium tetra n-octyl boron, tetramethylphosphonium n-butyl triphenyl boron, tetraethyl phosphonium n-butyl triphenyl boron, tetra n-butyl phosphonium n-butyl triphenyl boron, tetra n-octyl phosphonium n-
Butyltriphenylboron,

Tetramethylphosphonium n-butyltri-p-tolylboron, tetraethylphosphonium n-butyltri-p-tolylboron, tetra-n-butylphosphonium n-butyltri-p-tolylboron, tetra-n-
Octylphosphonium n-butyltri-p-tolylboron, tetramethylphosphonium n-butyltrianisylboron, tetraethylphosphonium n-butyltrianisylboron, tetran-butylphosphonium n-butyltrianisylboron, tetran-octylphosphonium n-butyl Trianisylboron, tetramethylphosphonium n-octyltriphenylboron, tetraethylphosphonium n-octyltriphenylboron,

Tetra n-butylphosphonium n-octyltriphenylboron, tetra n-octylphosphonium n-octyltriphenylboron, tetramethylphosphonium n-octyltri-p-tolylboron, tetraethylphosphonium n-octyltri-p-tolylboron, Tetra n-butylphosphonium n-octyl tri-
p-tolylboron, tetra-n-octylphosphonium n
-Octyltri-p-tolylboron, tetramethylphosphonium n-octyltrianisylboron,

Tetraethylphosphonium n-octyltrianisyl boron, tetra n-butylphosphonium n-
Octyl trianisyl boron, tetra n-octyl phosphonium n-octyl trianisyl boron, tetramethyl phosphonium n-dodecyl triphenyl boron, tetraethyl phosphonium n-dodecyl triphenyl boron, tetra n-butyl phosphonium n-dodecyl triphenyl boron, tetra n -Octylphosphonium n-dodecyltriphenylboron,

Tetramethylphosphonium n-dodecyltri-p-tolylboron, tetraethylphosphonium n-
Dodecyl tri-p-tolyl boron, tetra n-butyl phosphonium n-dodecyl tri-p-tolyl boron, tetra n-octyl phosphonium n-dodecyl tri-p-tolyl boron, tetramethylphosphonium n-dodecyl trianisyl boron, tetraethyl phosphonium n-dodecyl Trianisyl boron, tetra n-butyl phosphonium n-dodecyl trianisyl boron, tetra n-octyl phosphonium n-dodecyl trianisyl boron, tetramethylphosphonium di n-butyl diphenyl boron,
Tetraethylphosphonium di-n-butyldiphenylboron,

Tetra n-butyl phosphonium di n-butyl diphenyl boron, tetra n-octyl phosphonium di n-butyl diphenyl boron, tetramethyl phosphonium di n-butyl di-p-tolyl boron, tetraethyl phosphonium di n-butyl di-p-tolyl Boron, tetra n-butyl phosphonium di n-butyl di-p-tolyl boron, tetra n-octyl phosphonium di n-butyl di-p-tolyl boron, tetramethyl phosphonium di n
-Butyldianisylboron, tetraethylphosphonium di-n-butyldianisylboron, tetra-n-butylphosphonium di-n-butyldianisylboron, tetra-n-octylphosphonium di-n-butyldianisylboron, tetramethylphosphonium-di-n-octyldiphenyl Boron, tetraethylphosphonium di-n-octyldiphenyl boron, tetra-n-butylphosphonium di-n-octyldiphenyl boron, tetra-n-octylphosphonium di-n-octyldiphenylboron, tetramethylphosphonium di-n-octyldi-p-tolylboron, tetraethylphosphonium Di-n-octyldi-p-tolylboron,

Tetra n-butyl phosphonium di n-octyl di-p-tolyl boron, tetra n-octyl phosphonium di n-octyl di-p-tolyl boron, tetramethyl phosphonium di n-octyl dianisyl boron, tetraethyl phosphonium di n-octyl Dianisyl boron,

Tetra-n-butylphosphonium di-n-octyldianisyl boron, tetra-n-octylphosphonium di-n-octyldianisyl boron, tetraphenylphosphonium n-butyltriphenylboron, tetraanisylphosphonium n-butyltriphenylboron, Tetraphenylphosphonium n-butyltri-p-tolylboron, tetraanisylphosphonium n-butyltri-p
-Tolylboron, tetraphenylphosphonium n-butyltrianisylboron, tetraanisylphosphonium n
-Butyltrianisylboron, tetraphenylphosphonium di-n-butyldiphenylboron,

Tetraanisylphosphonium di-n-butyldiphenylboron Tetraphenylphosphonium di-n-butyldi-p-tolylboron, tetraanisylphosphonium di-n-butyldi-p-tolylboron, tetraphenylphosphoniumdi-n-butyldianisylboron , Tetraanisylphosphonium di-n-butyldianisylboron and the like.

These cationic dyes and decolorizing agents may be used alone or in admixture of two or more. The wax in the support material usable in the present invention is generally used for heat-sensitive transfer sheets and inks, and examples thereof include a plant wax, a wax wax, a wax wax, a wax wax, a wax wax and a paraffin wax. Examples thereof include wax, microcrystalline wax, synthetic wax such as polyethylene wax, polypropylene wax, chlorinated paraffin and fatty acid amide.

The resins which can be used in the present invention include all conventional resins such as brush coating, spray coating, dip coating, gravure coating, doctor coating, roll coating, electrostatic coating, powder coating, transfer and printing. Possible room temperature drying / curable coating resin, moisture curable coating resin, thermosetting coating resin, toner resin, etc., specifically oil varnish,
Boil oil, shellac, cellulose resin, phenol resin, alkyd resin, amino resin, xylene resin,
Toluene resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polystyrene resin typified by polystyrene, polyolefin resin, polyvinyl butyral resin, (meth) acrylic resin typified by polymethylmethacrylate, etc. , Polyester resin represented by diallyl phthalate resin, epoxy resin, polyurethane resin, unsaturated polyester, polyether resin, polyvinyl alcohol resin, aniline resin, furan resin, polyamide resin, silicone resin, Fluorine-based resins and the like are included.

These resins can be used alone or in admixture of two or more. Further, the support material according to the present invention is not limited to these, and may be any material as long as the photobleachable recording material of the present invention can be mixed by dissolution or dispersion. The cationic dye having absorption in the visible light region, which constitutes the photobleachable recording material of the present invention, can be added to the support material as described above.
It can be compounded in the range of 01 to 90% by weight, and particularly preferably in the range of 0.5 to 50% by weight. The decoloring agent may be added in an amount of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on 1% by weight of the cationic dye.

These photo-bleachable recording materials can be used by melt-mixing or by melt-mixing the support material with a solvent. However, the photobleachable recording material of the present invention can obtain the same effect even if it is dissolved or dispersed in a solvent and applied or printed. Further, if necessary, general coloring dyes and pigments can be blended. In this case, after the photobleachable recording material is erased by irradiation with visible light, only the colors of the coloring dyes and pigments are left. be able to.

The cationic dye and the decolorizing agent used in the photobleachable recording material of the present invention can be used not only alone but also in combination of two or more. The cationic dye constituting the photo-bleachable recording material of the present invention is sensitive to visible light, but when mixed with the above-mentioned supporting material, a composition which is stable in light including visible light such as a fluorescent lamp can be obtained. Obtained, after printing or printing the composition on paper, plastic, metal, etc., the printed or printed portion is first irradiated with light including visible light from a light source such as a halogen lamp, a xenon lamp, a light emitting diode and a laser. The printed or printed portion can be erased, and the erased portion can be printed again or printed again.

When the photobleachable recording material of the present invention is irradiated with visible light to be erased, heating at the time of erasing can reduce the speed of erasing. Further, in the photo-bleachable recording material of the present invention, the cationic dye and the decolorizing agent which compose it can be used separately. That is, a composition in which a support material is mixed with a cationic dye and a composition in which a support material is mixed with a decolorizing agent are separately prepared, and after printing or printing with the composition containing a cationic dye, the decolorizing agent is added. Even if the mixed composition is applied to a printed portion or a printed portion and irradiated with visible light, the same effect as described above can be obtained.

The photobleachable recording material of the present invention can be used as toner for electrophotographic recording or electrostatic recording or ink for printing and sublimation or melt transfer printer, ink for serial printer, ink ribbon. It can also be used for inks for inks, inks for ink and jets, ballpoint pens, markers, writing instruments for stationery such as magic and pencils, UV curable inks, and paints. However, the usable applications are not limited to these.

A specific example of use will be described below. The electrophotographic recording toner is a combination of the cationic dye of the general formula (1) or (2) and the decoloring agent of the general formula (3) in a supporting material such as a binder for toner. Depending on the case, other additives such as a charge control agent and a filler such as titanium white and calcium carbonate are adjusted by kneading or dispersing. At this time, if a UV absorber is added, the storage stability is further improved.

As the charge control agent, any one of the positively charged or negatively charged charge control agents conventionally used for color toners can be used. For example, as a positive charge control agent, a quaternary ammonium salt, alkylamide, or hydrophobic silica, and as a negative charge control agent, diaminoanthraquinone, chlorinated polyolefin, chlorinated polyester, naphthenic acid metal salt, Examples thereof include fatty acid metal salts. As the filler, fillers such as titanium white, talc, kaolin, silica, alumina, calcium carbonate, aluminum sulfate, barium sulfate, calcium sulfate, titanium oxide, and calcium phosphate can be used. Can be adjusted. Further, as the ultraviolet absorber, a conventional ultraviolet absorber can be used.

As the toner binder of the present invention, polystyrene resin, acrylic resin, styrene (meth) acrylic acid ester copolymer, vinyl chloride resin, ethylene-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, Thermoplastic resins such as epoxy resin, polyester resin, low molecular weight polystyrene, low molecular weight polypropylene, ionomer resin, polyurethane resin, silicone resin, ketone resin, xylene resin, polyvinyl butyral resin are used,

For example, in the case of polystyrene resin, polystyrene homopolymer, hydrogenated polystyrene, styrene-propylene copolymer, styrene-isobutylene copolymer,
Styrene-butadiene copolymer, styrene-allyl alcohol copolymer, styrene-maleic acid ester copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-styrene-acrylic acid Ester terpolymer,
Styrene-acrylonitrile copolymer, acrylonitrile-acrylic rubber-styrene terpolymer,

Acrylonitrile-chlorinated polyethylene-
For acrylic resins such as styrene terpolymer, polymethylmethacrylate, ethylmethacrylate, butylmethacrylate, glycidylmethacrylate, fluorine-containing acrylate, methylenemethacrylate-butylmethacrylate copolymer, ethylacrylate-acrylic acid copolymer Such as styrene (meth) acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-
Butadiene-acrylic acid ester terpolymer, styrene-methylmethacrylate copolymer, styrene-butylmethacrylate copolymer, styrene-diethylaminoethylmethacrylate copolymer, styrene-methylmethacrylate-butylacrylate terpolymer, styrene -Glycidyl methacrylate copolymer, styrene-butadiene-dimethylaminoethyl methacrylate terpolymer, styrene-acrylic acid ester-maleic acid ester terpolymer, styrene-butyl acrylate-acrylic acid terpolymer, etc. can give.

The cationic dye constituting the photo-decolorizable recording material of the present invention, which is a colorant for the toner, can be compounded in the binder for the toner in an amount of 0.01 to 90% by weight, particularly 0.5 to
It is preferably blended in the range of 50% by weight. The decolorizing agent can be added in an amount of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on 1% by weight of the cationic dye. The charge control agent can be blended in an amount sufficient to adjust the toner charge amount, and is 0.1% relative to the toner binder.
Can be mixed up to 20% by weight. Further, the filler can be blended in the toner binder in an amount of 0.1 to 20% by weight, and particularly 0.1 to 5% by weight
It is preferable to mix them. The ultraviolet absorber can be added in an amount of 0.1 to 20% by weight based on the toner binder.

As a method for adjusting the decolorizable toner, there are a solution method and a melting method. The solution method is a method in which the cationic dye and the decoloring agent are dissolved and kneaded in a toner binder with an organic solvent, and if necessary, a charge control agent, an ultraviolet absorber, etc. are mixed and kneaded. Adjust the mixed resin by dispersing with a conditioner, etc., after removing the organic solvent of the mixed resin obtained from this, after roughly crushing with a hammer mill, a cutter mill, etc.,
For example, it is a method of finely pulverizing with a jet mill or the like to adjust the toner. Further, the melting method means that the cationic dye and the decoloring agent are melt-kneaded in a binder for toner, and if necessary, a charge control agent, an ultraviolet absorber, a filler and the like are mixed and kneaded and then cooled, and then the solution method. It is a method of finely pulverizing and adjusting the toner in the same manner as. The toner obtained as described above can be used not only as a two-component toner but also as a one-component toner.

After the toner is printed and fixed on paper or an OHP film, the printed portion is irradiated with light including visible light from a light source such as a halogen lamp, a xenon lamp, a light emitting diode and a laser, and the color of the cationic dye is changed. Can be erased and the printed part can be erased. Further, it is possible to print again with the toner or the conventional black toner on the decolored portion again. It is also possible to separately use the cationic dye and the decoloring agent which compose the toner in the toner. That is, a toner prepared by kneading only the cationic dye in the toner and a composition prepared by kneading the decoloring agent in the support material were separately prepared, and the decolorizing agent was kneaded after printing with the toner in which only the cationic dye was kneaded. Even if the composition is applied to the printed portion and irradiated with visible light, the same effect as above can be obtained.

The photobleachable recording material can also be used as ink. The ink is prepared by kneading the above-mentioned cationic dye and decoloring agent as a colorant into a support material for fixing on the surface to be printed, and if necessary, other additives such as titanium white and filler such as calcium carbonate. Disperse and knead to adjust. At this time, if an ultraviolet absorber is added, the storage stability is further improved. The supporting material used in this ink is composed of a drying oil which dries relatively quickly when left in the air, a resin for improving the drying property, luster, transferability, etc., and a solvent which gives necessary viscosity and fluidity. However, in some cases, the photobleachable recording material can be dissolved and used only in a solvent, or can be used by dispersing a cationic dye and a decolorizing agent in a poorly soluble solvent.

Here, examples of the drying oil include linseed oil, shinai oil, soybean oil, castor oil and the like. As the resin, cured resin, natural resin derivative such as rosin ester, maleic acid resin or fumaric acid resin, phenol resin, urea-melamine resin, ketone resin, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resin, butyral resin , Styrene-maleic acid resin,
Examples thereof include synthetic resins such as styrene- (meth) acrylic acid ester copolymer resin, chlorinated polypropylene, acrylic resin, polyester resin, polyamide resin, epoxy resin, polyurethane resin and nitrocellulose.

As the solvent, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, cyclohexyl alcohol, Alcohols such as benzyl alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Dipropylene glycol, glycerin, polyalkylene glycol, hexylene glycol, glycols such as phenyl glycol, ethylene glycol monomethyl ether,

Ethylene glycol monoethyl ether,
Ethylene glycol monobutyl 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,

Glycol derivatives such as 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 ester, ethyl acetate, isopropyl acetate, acetic acid. Butyl, cesyl isooctanoate, sorbitan monostearate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, monooleic acid Polyoxyethylene sorbitan,
Examples thereof include esters such as ascorbic acid ester and castor oil fatty acid ester, phosphoric acid ester, waxes such as polyolefin wax, carnauba wax and paraffin wax, liquid paraffin, and water.

As the filler, the same filler as that used in the above electrophotographic recording toner can be used. Further, as the ultraviolet absorber, a conventional ultraviolet absorber can be used. The cationic dye used in this ink can be added to the above-mentioned supporting material in the range of 0.01 to 90% by weight, and particularly 0.5
It is preferably blended in the range of 50% by weight. The decolorizing agent can be added in an amount of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on 1% by weight of the cationic dye. The support material can be blended in an appropriate amount according to the printing method.

Also, the filler can be blended in the support material in an amount of 0.1 to 20% by weight, preferably 0.1 to 5% by weight. Further, the ultraviolet absorber can be added in an amount of 0.1 to 20% by weight based on the support material. The method for preparing this ink is prepared by kneading a cationic dye and a decoloring agent with a drying oil, and optionally mixing an ultraviolet absorber, a filler and the like and kneading. This ink can also be used for printing,
For example, offset printing, letterpress printing, gravure printing, stencil printing or special printing such as flexo printing, metal printing, plastic printing, glass printing and transfer paper printing, electronic printing with printers such as impact printers and non-impact printers, etc. After printing by printing method, halogen lamp, xenon lamp,
By irradiating light including visible light from a light source such as a light emitting diode and a laser, the color of the cationic dye can be erased and the printed portion can be erased. Further, it is possible to print again with this printing ink or a conventional printing ink on this decolored portion.

When used as an ink for an ink ribbon, the cationic dye and the decoloring agent are mixed with a support material, and the cationic dye and the decoloring agent are obtained by wet grinding with a roll mill, a ball mill or a paint shaker. Is crushed and dispersed in a solvent to prepare an ink. A ribbon made of synthetic fiber cloth such as nylon is impregnated with this adjusted ink and dried to prepare an ink ribbon. This ink ribbon is used to print on a paper with a printer, and the printed portion is irradiated with light including visible light from a light source such as a halogen lamp, a xenon lamp, a light emitting diode and a laser to erase the color of the cationic dye. Can be erased. Further, it is possible to print again with this printing ink or a conventional printing ink on this decolored portion. In addition, in the ink for the ink ribbon,
It is also possible to prepare the cationic dye and the decoloring agent constituting the same as separate inks and use them separately as in the toner.

[0083]

EXAMPLES The present invention will be further described below with reference to examples. Examples 1 to 6 Styrene-butylmethacrylate copolymer (softening point 72
C.) 40 parts by weight are dissolved in 50 parts by weight of dichloroethane, and the cationic dyes and decolorizers shown in Table 2 are added in Table 2.
A composition was obtained by dissolving and kneading the indicated amount.

Examples 7 to 12 40 parts by weight of phenol resin (softening point 110 ° C.) was dissolved in 50 parts by weight of veratrol, and the cationic dye and decoloring agent shown in Table 2 were dissolved and kneaded in the amounts shown in Table 2. A composition was obtained.

Examples 13 to 15 Polystyrene resin (softening point 92 ° C.)
After dissolving and kneading the cationic dye and the decoloring agent described in 1 above with methylene chloride in the amounts described in Table 2, methylene chloride was distilled off.
The kneaded resin was coarsely pulverized by a hammer mill or a cutter mill and then finely pulverized by a jet mill to prepare toner particles.

Examples 16 to 23 Styrene-butyl methacrylate copolymer (softening point 72
(° C) 96 parts by weight of the cationic dye and decoloring agent shown in Table 2 were dissolved and kneaded with acetone in the amounts shown in Table 2, and then acetone was distilled off. The kneaded resin was coarsely pulverized by a hammer mill or a cutter mill and then finely pulverized by a jet mill to prepare toner particles.

Examples 24 to 28 Styrene-butyl methacrylate copolymer (softening point 72
C.) 94 parts by weight of the cationic dye, the decoloring agent and the charge control agent shown in Table 2 were melt-kneaded in a twin-screw kneading extruder, and then the kneaded product was cooled. Next, the kneaded resin thus obtained was coarsely pulverized by a hammer mill or a cutter mill and then finely pulverized by a jet mill to prepare toner particles.

Examples 29 to 30 In 91 parts by weight of polymethylmethacrylate (softening point 78 ° C.), the cationic dye, the decoloring agent and the charge control agent shown in Table 2 were added, and titanium white 3 was used as a filler. After the parts by weight were melt-kneaded by a twin-screw kneading extruder, the kneaded product was cooled. Next, the kneaded resin thus obtained was coarsely pulverized by a hammer mill or a cutter mill and then finely pulverized by a jet mill to prepare toner particles.

Examples 31 to 34 30 parts by weight of soybean oil and 50 parts by weight of styrene-maleic acid resin (softening point 70 ° C.) were dissolved and kneaded with the cationic dyes and decoloring agents shown in Table 2 in the amounts shown in Table 2. The ink was adjusted.

Examples 35 to 38 An ink was prepared by kneading 60 parts by weight of an acrylic resin (softening point: 65 ° C.) with the cationic dye, the decoloring agent and the solvent shown in Table 2 in the amounts shown in Table 2.

Examples 39 to 44 Liquid paraffin (Cristol 70, manufactured by Esso Oil Co., Ltd.)
60 parts by weight, 10 parts by weight of ethylene glycol and 10 parts by weight of Hirac 110 (ketone resin manufactured by Hitachi Chemical Co., Ltd.) were blended with the cationic dyes and decolorizers shown in Table 2 in the amounts shown in Table 2, and then ball milled. Was pulverized and dispersed to prepare an ink.

Comparative Examples 1-2 Styrene-butyl methacrylate copolymer (softening point 72
C.) 40 parts by weight was dissolved in 55 parts by weight of dichloroethane, and the cationic dyes shown in Table 2 were dissolved and kneaded in the amounts shown in Table 2 to obtain a composition.

[0093]

[Table 2]

[0094]

[Table 2]

[0095]

[Table 2]

[0096]

[Table 2]

[0097]

[Table 2]

(Preparation of Printed Sample) The compositions of Examples 1 to 12 were applied to a carton paper with a thickness of 10 using an RI tester.
The sample was obtained by spreading and drying so that the thickness became μm. Example 1
The toner particles obtained in 3 to 30 were further surface-treated with hydrophobic silica and mixed with a carrier, and then printed on PPC paper by a PPC copying machine (LCS-24 manufactured by Casio Co., Ltd.) to obtain a sample. . The inks obtained in Examples 31 to 38 were color-dried and dried on a carton paper using an RI tester so as to have a thickness of 5 μm to obtain samples. Examples 39-44
The ink obtained in 1. was impregnated into a ribbon made of nylon 66 so that the weight after drying was 13 g / m @ 2, put in a ribbon cassette for PC-201H manufactured by NEC Corporation, and
A sample was obtained by printing on paper using a C-201H printer. The compositions obtained in Comparative Examples 1 and 2 were spread and dried on a carton paper so as to have a thickness of 10 μm using an RI tester to obtain samples.

(Evaluation of Decoloring Property) These obtained samples of Examples 1 to 44 and Comparative Examples 1 and 2 were exposed to visible light for 2 seconds using a halogen lamp (0.5 W / cm 2) with an infrared cut filter. After irradiation, the image density of the sample was measured with a Macbeth reflection densitometer RD918 to evaluate the decoloring property.
The evaluation results are shown in Table 3.

[0100]

[Table 3]

[0101]

[Table 3]

[0102]

[Table 3]

(Evaluation of Image Stability) The samples of Examples 1 to 44 were irradiated with fluorescent light of 1100 lux having an illuminance about three times as high as that of a normal office for 24 hours, and the image density of the samples was Macbeth reflected. The stability of the image was evaluated by measuring with a densitometer RD918. The evaluation results are shown in Table 4.

[0104]

[Table 4]

[0105]

[Table 4]

[0106]

[Table 4]

[0107]

EFFECTS OF THE INVENTION According to the present invention, a photo-erasable recording which can be erased with visible light after being printed and printed, can be printed and printed again on the same portion, and has practical stability under a fluorescent lamp. Material is provided.

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Claims (3)

[Claims] 1. A cation dye represented by the general formula (1) or (2) having an absorption in the visible light region and a decolorizing agent represented by the general formula (3), and erased by visible light. Photo-erasable recording material. General formula (1); (In the formula, D ⁺ is a cation having absorption in a visible light region, and R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, An alkynyl group, a silyl group, a heterocyclic group, a substituted alkyl group, a substituted aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group) General formula (2); D ⁺ · A ^- (wherein, D ⁺ is a cation having an absorption in the visible light region, a ^- a halogen ion, perchlorate ion, PF ₆ ^-,
An anion selected from BF ₄ ⁻ , SbF ₆ ⁻ and a sulfonate ion is shown.) General formula (3); (In the formula, R ₅ , R ₆ , R ₇ and R ₈ are each independently an alkyl group, aryl group, allyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, substituted alkyl group, substituted An aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a quaternary pyridinium cation, a quaternary quinolinium cation or a phosphonium cation) 2. An erasable toner containing the light erasable recording material according to claim 1 as a colorant and erasing with visible light. 3. A decoloring ink containing the photobleachable recording material according to claim 1 as a colorant and capable of decoloring with visible light.