JP3196252B2 - Photo-decolorable recording material - Google Patents

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 capable of being erased by visible light and a toner or ink containing the photo-erasable recording material as a colorant.

[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 preservation properties such as heat resistance, and improvements in physical properties of dyes and pigments have been actively carried out. In particular, development has been actively carried out in fields such as thermal transfer recording, electrophotographic recording, and electrostatic recording. For example, Japanese Patent Application Laid-Open No. 50-75991 discloses a thermochromic material using a color former mainly composed of a leuco dye and a phenolic hydroxyl group-containing compound as a developer. Similarly, many studies have been made in the fields of electrophotographic recording, electrostatic recording, and printing and printer inks. For example, in electrophotographic recording, U.S. Pat. No. 2,297,691;
JP-B-42-23910 and JP-B-43-24748
Although many methods are known as described in Japanese Patent Application Laid-Open Publication No. H10-163, generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. Is developed with toner to form a visible image, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating pressure or the like to obtain a copy.

There are also various known developing methods for visualizing an electrostatic latent image using toner. For example, a magnetic brush method described in U.S. Pat. No. 2,870,063, a cascade developing method described in U.S. Pat. No. 2,618,552, a powder cloud method described in U.S. Pat. Many developing methods such as a developing method and a liquid developing method are known. Various magnetic recording methods for forming a magnetic latent image and developing with a magnetic toner are also known. The developed toner image is transferred and fixed to a transfer material such as paper as necessary.However, as a fixing method of the toner image, the toner is heated and melted by a heater or a heat roller to be fused to the support. How to solidify,
There are known a method of softening or dissolving a binder resin of a toner with an organic solvent to fix the toner on a support, a method of fixing the toner to the support by pressurization, and the like.

The toner used in the above-described heat roller fixing method generally comprises a thermoplastic resin such as a styrene-butyl acrylate copolymer and an additive such as a colorant such as carbon black and a charge controlling agent. After being melt-mixed and uniformly dispersed, the mixture is cooled and then finely pulverized to a desired particle size by a fine pulverizer or disperser, and adjusted. Further, recently, colorization has been advanced in fields such as printing and copying, and physical properties such as colorants and charge control agents have been actively improved. (For example,
JP-A-57-130046, JP-A-57-19165
0)

In the field of printing, offset printing,
There are various printing methods such as letterpress printing, gravure printing, stencil printing, or special printing such as flexographic printing, metal printing, plastic printing, glass printing and transfer paper printing, and electronic printing using printers such as impact printers and non-impact printers. However, the inks used therein mainly consist of a vehicle as a binder and a coloring agent such as a dye or a pigment. Furthermore, recently, ultraviolet light curable inks have been actively developed for the purpose of preventing pollution by eliminating the solvent of printing inks, improving productivity by rapid curing, or improving physical properties of cured films.
(For example, Japanese Patent Application Laid-Open Nos. 1-229084 and 1-271
469 and JP-A-2-22370). However, a thermochromic material such as a leuco dye, a toner for electrophotographic recording or a printing ink cannot erase a printed image after printing. Furthermore, it is not possible to reprint the recorded portion or reuse the recording paper, or there is a problem in maintaining confidentiality accompanying the disposal of the recording paper.

[0006]

SUMMARY OF THE INVENTION The present invention has a sensitivity to visible light so that a recorded portion can be reprinted, and the printed and printed recording material is decolorized by visible light and is re-printed on the same portion. It is an object to provide a recordable recording material.

[0007]

According to the present invention, a recording material using a dye having absorption in the visible light region and a boron-based compound has been intensively studied in order to solve this problem. The inventors have found that a decolorable recording material can be obtained, and have completed the present invention. That is, according to the present invention, the boron compound represented by the general formula (1) and the general formula (1); Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, silyl, alicyclic and saturated or unsaturated heterocyclic groups or Substituted alkyl, substituted aryl,
Substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl and substituted silyl are shown. R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom,
Alkyl, aryl, allyl, alkaryl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups or substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl Show. 3.) A photo-decolorable recording material comprising a sensitizing dye having absorption in the visible light region and decoloring by irradiation with visible light of 400 to 700 nm is obtained.

The photo-decolorizable recording material according to the present invention has sensitivity in the visible light region by being contained in a support material such as wax or resin, and can be decolorized by irradiating light in this region. However, a stable photo-decolorable composition can be obtained with light from a fluorescent lamp or the like.

Specific examples of the boron compound used in the present invention include tetramethylammonium n-butyltriphenylboron, tetramethylammonium n-butyltrianisylboron, tetramethylammonium n
-Octyltriphenylboron, tetramethylammonium n-octyltrianisylboron, tetraethylammonium n-butyltriphenylboron, tetraethylammonium n-butyltrianisylboron, trimethylhydrogenammonium n-butyltriphenylboron, triethylhydrogenammonium n-butyl Triphenyl boron, tetrahydrogen ammonium n-butyl triphenyl boron, tetramethyl ammonium tetraphenyl boron, tetraethyl ammonium tetraphenyl boron, tetrabutyl ammonium tetraphenyl boron, tetramethyl ammonium tetraanisyl boron, tetraethyl ammonium tetraanisyl boron, tetra Butyl ammonium tetraanisyl boron, tetrame Le ammonium triphenyl naphthyl boron, tetraethylammonium triphenyl naphthyl boron, tetrabutylammonium triphenyl naphthyl boron, tetramethylammonium tetrabutyl borate, tetraethylammonium tetrabutyl borate,

[0010] Tetramethylammonium tri-n-butyl (
(Triphenylsilyl) boron, tetraethylammonium tri-n-butyl (triphenylsilyl) boron, tetrabutylammonium tri-n-butyl (triphenylsilyl) boron, tetramethylammonium tri-n-butyl (
Dimethylphenylsilyl) boron, tetraethylammonium tri-n-butyl (dimethylphenylsilyl) boron, tetrabutylammonium tri-n-butyl (dimethylphenylsilyl) boron, tetramethylammonium n-
Octyl diphenyl (di-n-butylphenylsilyl) boron, tetraethyl ammonium n-octyl diphenyl (
Di-n-butylphenylsilyl) boron, tetrabutylammonium n-octyldiphenyl (di-n-butylphenylsilyl) boron, tetramethylammonium dimethylphenyl (trimethylsilyl) boron, tetraethylammonium dimethylphenyl (trimethylsilyl) boron,
And tetrabutylammonium dimethylphenyl (trimethylsilyl) boron.

The sensitizing dye having an absorption in the visible light region used in the present invention includes merocyanine dyes, coumarin dyes, xanthene dyes, thioxanthene dyes, indigo dyes, aromatic amine dyes, phthalocyanine dyes. , Oxazine dyes, thiazine dyes, azo dyes,
Examples include quinone dyes, cyanine dyes, diphenylmethane dyes, triphenylmethane dyes, pyrylium dyes, and squarylium dyes. Typical examples include those shown in Table 1.

[0012]

[Table 1]

In Table 1, 1) Me represents a methyl group. 2) Et represents an ethyl group. 3) Bu represents an n-butyl group. 4) Pr represents an n-propyl group. 5) tBu represents a t-butyl group. 6) cHex represents a cyclohexyl group. 7) Oct represents an n-octyl group. 8) Ph represents a phenyl group. 9) MeO represents a methoxy group. 10) All represents an allyl group. 11) Bz represents a benzyl group. 12) Tol represents a p-methylphenyl group.

Wax in the support material that can be used in the present invention is generally used for thermal transfer sheets and inks. Examples of the wax include plant carbana wax and wood wax, animal waxes such as beeswax and wool wax, and mineral wax. Paraffin wax and microcrystalline wax, synthetic waxes such as polyethylene wax, polypropylene wax, PTTE, chlorinated paraffin, and fatty acid amide. The resin used in the present invention includes all conventional resins, for example, brushing, spray coating,
Immersion painting, gravure painting, doctor painting, roll painting,
Room temperature dry / curable paint resin, moisture curable paint resin, thermosetting paint resin, etc. that can be used for electrostatic coating, powder coating, transfer, printing, etc.Specifically, oil varnish, boil oil , Cerac, cellulosic resin, phenolic resin,
Alkyd resin, amino resin, xylene resin, toluene resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polystyrene resin, vinyl butyral resin, acrylic resin, methacrylic resin, diallyl phthalate resin, epoxy Resin, urethane resin,
Examples include polyester-based resins, polyether-based resins, aniline-based resins, furan-based resins, polyimide-based resins, silicon-based resins, and fluorine-based resins.

[0015] Alternatively, light and electron beam curable resins, such as polyvinyl cinnamate resin, polyvinyl benzal acetophenone resin, polyvinyl styryl pyridine resin, polyvinyl anthral resin,
Unsaturated polyester resin, acrylated oil, acrylated alkyd resin, acrylated polyester resin, acrylated polyether resin, acrylated epoxy resin, acrylated polyurethane resin, acrylated resin,
Macromonomers, oligomers, and monomers of acrylated spirane-based resins, acrylated silicon-based resins, acrylated fluorine-based resins, polythiol-based resins, and cation-polymerized epoxy resins are exemplified. Alternatively, it is a monomer or oligomer of a light or chemical polymerization type, specifically an ethylenically unsaturated compound, containing an acrylate or methacrylate or 4- (meth) acryloxyl group of a monohydric alcohol or a polyhydric alcohol. Examples include aromatic polycarboxylic acids and acid anhydrides thereof.

These can be used alone or in combination of two or more. When a monomer is used as a support material, the effect is not affected even if the photo-decolorable recording material is dissolved in the monomer and subjected to chemical polymerization, ultraviolet light polymerization or near-infrared light polymerization. Further, the support material according to the present invention is not limited to these, but may be any as long as it can be mixed by dissolution or dispersion.

The sensitizing dye having absorption in the visible light region constituting the photo-decolorable recording material of the present invention is added to the support material by 0.01
The boron compound of the general formula (1) constituting the photobleachable recording material of the present invention is a solution of the boron compound in a range of 0.01 to 20% by weight based on 1% by weight of the sensitizing dye. Can be formed by melt-mixing or melt-mixing. However, in the photo-decolorable recording material of the present invention, the same effect can be obtained even if the recording material itself is dissolved in a solvent and coated or printed. Further, if necessary, general coloring dyes and pigments can be added. In this case, after the photo-decolorable recording material has been decolorized by irradiation with visible light, the color of the coloring dye and pigment is changed. Can be left. Further, the photo-decolorable recording material of the present invention is used in combination with a recording material that decolors with near-infrared light of 700 nm or more, thereby decolorizing the color of the photo-decolorable recording material of the present invention, The color of the recording material that can be erased by external light can be left.

The photobleachable recording material of the present invention can be used not only alone but also in combination of a plurality of photobleachable recording materials. The photo-decolorable recording material of the present invention is 400 to 700 n.
m, the composition is sensitive to visible light, but can be mixed with a support material as described above to obtain a composition that is stable under light such as fluorescent lamps, and the composition can be printed or printed on paper, plastic, metal, etc. After printing, it can irradiate visible light from a visible light source such as a halogen lamp, a light emitting diode and a semiconductor laser to decolor the printed part and the printed part,
Further, printing or printing can be performed again on the decolored portion.

The photo-decolorizable recording material of the present invention can be used as a toner for electrophotographic recording or electrostatic recording or as a coloring agent for printing and sublimation or melt transfer printer inks, as well as inks for serial printers and inks. -Can be used as ink for jets, writing implements for stationery such as ballpoint pens, markers, and magic, or coloring agents for UV curable inks and paints. However, usable applications are not limited to these.

Hereinafter, a specific example of use will be described. The decolorizable toner for electrophotography according to the present invention comprises a photo-decolorable recording material in a support material such as a binder resin for a toner, and a charge control agent and other additives such as titanium white and calcium carbonate as necessary. The filler is adjusted by melting or kneading or dispersing in a solution. At this time, if an ultraviolet absorber is added, the storage stability is further improved.

As the charge control agent, any of the positively or negatively chargeable charge control agents conventionally used for color toners can be used. For example, as the positively chargeable charge control agent, a quaternary charge control agent can be used. Examples of negatively charged charge control agents such as ammonium salts, alkylamides, and hydrophobic silicas include diaminoanthraquinone, chlorinated polyolefins,
Examples include chlorinated polyesters, metal salts of naphthenic acids, metal salts of fatty acids, and the like. Fillers include titanium white, talc, kaolin, silica, alumina, calcium carbonate,
White fillers such as aluminum sulfate, barium sulfate, calcium sulfate, titanium oxide, and calcium phosphate can be used, and the whiteness after decoloring can be adjusted by adding the filler. Further, as the ultraviolet absorber, a conventional ultraviolet absorber can be used.

The binder resin for the toner of the present invention includes polystyrene resin, acrylic resin, styrene (meth) acrylate copolymer, vinyl chloride resin, ethylene-vinyl acetate copolymer, rosin-modified maleic resin, and phenol resin. , Epoxy resin, polyester resin, low molecular weight polystyrene, low molecular weight polypropylene,
Thermoplastic resins such as ionomer resins, polyurethane resins, silicone resins, ketone resins, xylene resins, and polyvinyl butyral resins are used.For example, polystyrene resins include polystyrene homopolymer, hydrogenated polystyrene, styrene-propylene copolymer, and styrene-
Isobutylene copolymer, styrene-butadiene copolymer, styrene-allyl alcohol copolymer, styrene-
Maleic ester copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-styrene-acrylic ester terpolymer, styrene-acrylonitrile copolymer, acrylonitrile-acryl For acrylic resins such as rubber-styrene terpolymer, acrylonitrile-chlorinated polyethylene-styrene terpolymer, etc., polymethyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, fluorine-containing acrylate, methylene methacrylate-butyl Styrene (meth) acrylate copolymers such as methacrylate copolymer and ethyl acrylate-acrylic acid copolymer include styrene-acrylic acid copolymer and styrene-butadiene-a Lylic acid ester terpolymer, styrene-methyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-diethylaminoethyl methacrylate copolymer, styrene-methyl methacrylate-butyl acrylate terpolymer, styrene-glycidyl Methacrylate copolymer, styrene-butadiene-dimethylaminoethyl methacrylate terpolymer, styrene-acrylate-maleate terpolymer, styrene-butyl acrylate-
Acrylic acid terpolymers and the like can be mentioned.

Further, in order to improve the compatibility and decoloring speed between the photo-decolorable recording material and the binder for toner, a plasticizer generally used for modifying a resin or an ink used for a heat-sensitive recording paper or the like is used. Sensitizers and waxes can be used. Specific examples of the sensitizer include dibutyl phthalate, dioctyl phthalate, dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate,
Dioctyl adipate, dioctyl azelate, tricyl citrate, tributyl acetyl citrate, dibutyl sebacate, dioctyl sebacate, methyl stearate, ethyl stearate, butyl stearate, methyl ester of hydrogenated rosin, chlorinated paraffin, etc. .

The sensitizing dye having absorption in the visible light region, which constitutes the photo-decolorable recording material of the present invention, which is a colorant of the decolorizable toner, is prepared by adding a solvent to the above-mentioned binder for toner to obtain a sensitizing dye.
It can be mixed at a ratio of about 90 to 90% by weight, and particularly preferably at a rate of 0.5 to 20% by weight. Further, the boron-based compound of the general formula (1) constituting the photo-decolorable recording material of the present invention includes:
It can be added in the range of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on 1% by weight of the sensitizing dye.

The charge control agent can be added in an amount sufficient to adjust the charge amount of the toner.
-20% by weight can be added. Also, a filler can be added in an amount of 0.1 to 20% by weight, particularly 0.1 to 5% by weight, based on the toner binder.
It is preferred to add. The ultraviolet absorber can be added in an amount of 0.1 to 20% by weight based on the binder for the toner.

As a method for adjusting the decolorizable toner, there are a solution method and a melting method. With the solution method, the photo-decolorable recording material of the present invention is dissolved and kneaded in a binder for a toner with an organic solvent, and further, in some cases, a charge control agent, an ultraviolet absorber, etc. are added and kneaded. For the filler, the mixed resin is adjusted by dispersing with a paint conditioner, etc., and after removing the organic solvent of the mixed resin obtained therefrom, coarsely pulverized by a hammer mill or a cutter mill,
The toner is adjusted through fine grinding by a jet mill.
Further, the melting method is to melt-knead the photo-decolorable recording material of the present invention into a binder for a toner, and further, in some cases,
The mixed resin is adjusted by melting and kneading the charge control agent, the ultraviolet absorber, and the filler, and the mixed resin is pulverized in the same manner as in the solution method to adjust the toner. The decolorizable toner obtained as described above can be used not only as a two-component toner but also as a one-component toner.

After the decolorizing toner is printed and fixed on paper or an OHP film or the like, visible light can be irradiated from a visible light source such as a halogen lamp, a light emitting diode or a semiconductor laser to decolor the printed portion. Further, the decolored portion can be overprinted again. The decoloring ink for printing according to the present invention is prepared by mixing and kneading the photo-decolorable recording material as a colorant with a vehicle for fixing to the surface of a printing substrate. If necessary, fillers such as titanium white, calcium carbonate and the like as other additives are dispersed and kneaded for adjustment. At this time, if an ultraviolet absorber is added, the storage stability is further improved. The vehicle used for the decoloring ink for printing is composed of a drying oil that dries relatively quickly when left in the air, a resin for improving drying, gloss, transferability, etc., and a solvent for providing the necessary viscosity and fluidity. If necessary, a plasticizer or the like can be added to impart flexibility and flexibility to the dried film of the ink.

Here, examples of the drying oil include linseed oil, radish oil, soybean oil, castor oil and the like. Examples of the resin include a natural resin such as rosin or cerac, a cured resin, a rosin ester, a natural resin derivative such as a maleic acid resin or a fumaric acid resin, a phenol resin, a xylene resin, a urea-melamine resin, a ketone resin, and a polystyrene resin. Vinyl chloride, vinyl chloride-vinyl acetate copolymer resin, butyral resin, styrene-maleic acid resin,
Synthetic resins such as chlorinated polypropylene, acrylic resin, polyester resin, alkyd resin, polyamide resin, epoxy resin, polyurethane, nitrocellulose and the like can be mentioned.

As the solvent, hexane, heptane,
Aliphatic hydrocarbons such as rubber volatile oil, aromatic hydrocarbons such as toluene and xylene, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, cyclohexyl alcohol, diethylene glycol, diethylene glycol Propylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycols such as glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether,
Glycol derivatives such as diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, esters such as ethyl acetate, isopropyl acetate, and butyl acetate, acetone, and methyl ethyl ketone ,
Ketones such as methyl isobutyl ketone and cyclohexanone are exemplified. As the plasticizer, the same as the above-described electrophotographic decolorizing toner is used.

As the filler, the same filler as that used in the above-described electrophotographic toner can be used.
In addition, a common ultraviolet absorber can be used as the ultraviolet absorber. Further, in order to improve the decoloring speed of the decolorizable ink, a plasticizer used for resin modification or a sensitizer or wax used for heat-sensitive recording paper or the like is used as in the case of the decolorizable toner. be able to. The sensitizing dye having absorption in the visible light region, which constitutes the photo-decolorable recording material of the present invention, which is a colorant of the decoloring ink for printing, is added to the vehicle described above.
The general formula (1) in an amount of 0.01 to 90% by weight, particularly 0.5 to 20% by weight, and which constitutes the near-infrared light decolorable recording material of the present invention.
The boron compound 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 sensitizing dye. The resin can be mixed in an appropriate amount according to the printing method.

The filler can also be added in an amount of 0.1 to 20% by weight, particularly preferably 0.1 to 5% by weight, based on the vehicle. The ultraviolet absorber can be added in an amount of 0.1 to 20% by weight based on the drying oil. The method for adjusting the decolorable ink for printing is adjusted by kneading the photo-decolorable recording material of the present invention in a drying oil, and, if necessary, adding and kneading an ultraviolet absorber, a filler and the like. .

This decoloring ink for printing is used for offset printing,
Printing by various printing methods such as letterpress printing, gravure printing, stencil printing, or special printing such as flexographic printing, metal printing, plastic printing, glass printing and transfer paper printing, and electronic printing using printers such as impact printers and non-impact printers. After that, visible light can be irradiated from a visible light source such as a halogen lamp, a light emitting diode, and a semiconductor laser to decolor the printed portion. Further, the decolored portion can be overprinted again. Further, as an example of use of the hot-melt transfer sheet, a transfer film obtained by kneading this photo-decolorable recording material as a binder with paraffin wax, a softening agent xylene resin, and other calcium carbonate and applying the mixture on a PET film is recorded. The paper is brought into close contact with paper and transferred and printed with a heating head.
This printed portion can be erased by irradiating it with visible light.

[0033]

EXAMPLES The present invention will be further described below with reference to examples. Examples 1 to 4 20 parts by weight of polymethyl methacrylate were dissolved in 76 parts by weight of methyl ethyl ketone, and a sensitizing dye and a boron compound shown in Table 2 were dissolved and mixed in the amounts shown in Table 2 to obtain a composition.

Examples 5 to 8 20 parts by weight of polystyrene were dissolved in 70 parts by weight of toluene, and a sensitizing dye and a boron compound shown in Table 2 were dissolved and mixed in the amounts shown in Table 2 to obtain a composition.

Examples 9 to 12 In 70 parts by weight of paraffin wax (melting point 69 ° C.), Table 2 was used.
Sensitizing dye and boron compound described in Table 2, the amount described in Table 2,
The composition was heated and melted at 80 ° C. to obtain a composition.

Examples 13 to 14 45 parts by weight of trimethylolpropane triacrylate were mixed with the sensitizing dye shown in Table 2 and the boron compound in the amounts shown in Table 2 and further mixed with methyl o-benylbenzoate.
0 parts by weight and 5 parts by weight of triethanolamine were added to obtain a composition.

Examples 15 to 17 Styrene-butyl methacrylate copolymer (softening point 7
(2 ° C.) After dissolving and kneading 96 parts by weight of the sensitizing dye and boron compound shown in Table 2 with methylene chloride in the amounts shown in Table 2, methylene chloride was distilled off. The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Examples 18 to 19 In 96 parts by weight of hydrogenated polystyrene (softening point: 101 ° C.), the sensitizing dyes and boron compounds shown in Table 2 were dissolved and kneaded with methylene chloride in the amounts shown in Table 2, and then methylene chloride was added. Was distilled off. The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Examples 20 to 22 Styrene-butyl methacrylate copolymer (softening point 7
(2 ° C) The sensitizing dye, boron compound and charge control agent shown in Table 2 were dissolved and kneaded with 94 parts by weight of methylene chloride in the amounts shown in Table 2 and then methylene chloride was distilled off. The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Examples 23 to 25 Styrene-butyl methacrylate copolymer (softening point 7
(2 ° C.) After dissolving and kneading 89 parts by weight of the sensitizing dye, boron compound, charge control agent and plasticizer described in Table 2 with methylene chloride in the amounts shown in Table 2, methylene chloride was distilled off. The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Examples 26 to 27 Styrene-butyl methacrylate copolymer (softening point 7
2 ° C.) After melt-kneading 94 parts by weight of the sensitizing dye, boron compound and charge control agent described in Table 2 in the amounts described in Table 2,
The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Examples 28 to 29 The sensitizing dyes, boron compounds and charge control agents listed in Table 2 were added to 91 parts by weight of polymethyl methacrylate (softening point 78 ° C.) in the amounts shown in Table 2, and titanium white was used as an additive. After adding 3 parts by weight of a methylene chloride dispersion and dissolving and kneading, methylene chloride was distilled off. The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Example 30 Polymethylmethacrylate (softening point: 78 ° C.): 89 parts by weight of the sensitizing dye, boron compound and charge control agent shown in Table 2 in the amounts shown in Table 2, and an ultraviolet absorber (additive) as an additive. 2 parts by weight of Sumitomo Chemical Co., Ltd., and 3 parts by weight of titanium white were added to a methylene chloride dispersion, and the mixture was dissolved and kneaded.
The methylene chloride was distilled off. The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Examples 31 to 35 The sensitizing dyes and boron compounds described in Table 2 were dissolved in 50 parts by weight of linseed oil and 30 parts by weight of a styrene-maleic acid resin (softening point: 70 ° C.) in the amounts shown in Table 2 and dissolved. The mixture was kneaded to prepare an ink.

Examples 36-38 40 parts by weight of soybean oil, acrylic resin (softening point 65 ° C.) 3
The sensitizing dye, boron compound and solvent shown in Table 2 were kneaded in 0 parts by weight in the amounts shown in Table 2 to prepare an ink.

Examples 39-41 40 parts by weight of soybean oil, acrylic resin (softening point 65 ° C.) 2
Inks were prepared by kneading 5 parts by weight of the sensitizing dye, boron compound, solvent and plasticizer shown in Table 2 in the amounts shown in Table 2.

Example 42 A composition was prepared in the same manner as in Example 3. Example 43 A toner was prepared in the same manner as in Example 16. Example 44 An ink was prepared in the same manner as in Example 32.

Comparative Examples 1-2 Styrene-butyl methacrylate copolymer (softening point 7
(2 ° C.) 98 parts by weight of the sensitizing dye shown in Table 2 was dissolved and kneaded in the amount shown in Table 2 with methylene chloride, and then methylene chloride was distilled off. The mixed resin was subjected to coarse pulverization using a hammer mill or a cutter mill and fine pulverization using a jet mill to prepare a toner.

Decolorability Evaluation Method The compositions of Examples 1 to 8 and Example 42 were 0.5 g of the composition.
Was spread on Calton paper using an RI tester to obtain a sample. The compositions of Examples 9 to 12 were coated on a 3.5 micron thick polyethylene terephthalate film with a wire bar so as to have a thickness of 4.0 micron using a thermal printer.
The sample was transferred and printed on recording paper in a dot. The compositions of Examples 13 and 14 were prepared by applying 0.5 g of the composition to a carton paper using an RI tester, and irradiating ultraviolet rays for 1 second from a distance of 8 cm with an 80 W / cm metal halide lamp to obtain a sample.

The toners obtained in Examples 15 to 30 and Example 43 were subjected to a surface treatment with hydrophobic silica, mixed with a carrier, and then subjected to a PPC copier (manufactured by Casio, LC
In S-24), printing was performed on PPC paper to obtain a sample. Using the RI tester, 0.5 g of the ink obtained in Examples 31 to 41 and Example 44 was spread on carton paper to obtain samples. The toners obtained in Comparative Examples 1 and 2 were further surface-treated with hydrophobic silica and mixed with a carrier.
Printing was performed on PPC paper using a PC copier (LCS-24, manufactured by Casio) to obtain a sample.

The samples obtained in Examples 1 to 41 were irradiated with visible light for 1 second using an infrared cut filter with a dichroic coat type halogen lamp (2 W / cm ² ) to evaluate decoloration. Table 3 shows the evaluation results. The samples of Examples 42 to 44 were irradiated with light from a fluorescent lamp (50 mW / cm ² : 28 W eye white, manufactured by Iwasaki Electric Co., Ltd.) for 1 hour and evaluated for decoloration. No fading was observed.

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

According to the present invention, there is provided a photo-decolorable recording material, a decolorizable toner and a decolorable ink which can be decolored with visible light after printing and printing, and can be printed and printed on the same portion again. .

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 1]

[Table 2]

[Table 2]

[Table 2]

[Table 2]

Continuation of the front page (56) References JP-A-62-14163 (JP, A) JP-A-2-157768 (JP, A) JP-A-1-223446 (JP, A) JP-A-59-107350 (JP, A) JP-A-59-95534 (JP, A) JP-A-3-160461 (JP, A) JP-A-3-160462 (JP, A) JP-A-3-15076 (JP, A) 3-168757 (JP, A) JP-A-1-154162 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (8)

(57) [Claims] 1. A photo-decolorizable recording material comprising a boron-based compound represented by the general formula (1) and a sensitizing dye having absorption in the visible light region as a coloring agent, and a printed portion is erased by visible light. Decoloring toner that can be colored and recorded on the same part again . General formula (1); Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, silyl, alicyclic and saturated or unsaturated heterocyclic groups or Substituted alkyl, substituted aryl,
Substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, substituted silyl. R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom,
Alkyl, aryl, allyl, alkaryl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups or substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl Show. ) 2. A plasticizer containing a plasticizer.
2. The decolorizable toner according to item 1. 3. An agent comprising a charge control agent.
3. The decolorizable toner according to claim 1 or 2. 4. The method according to claim 1, further comprising a wax.
Item 4. The decolorizable toner according to any one of Items 1 to 3.
- 5. The method according to claim 1, further comprising an ultraviolet absorber.
The color erasing device according to claim 1.
Ner. 6. A process containing a white filler.
The decolorizable toner according to any one of claims 1 to 5.
- 7. The method of claim 1, wherein the weight of the sensitizing dye is 1% by weight.
0.01 to 20% by weight of the boron compound represented by (1)
% Or less in the range of
The decolorizable toner according to any one of Claims 6 to 10. 8. A decolorizable toner prepared by a solution method.
The method according to any one of claims 1 to 7, wherein
The decolorizable toner described in the above.