KR100226246B1 - Near infrared ray-decolorizable recording material - Google Patents

Abstract

According to the present invention, there is provided a near infrared decolorizing recording material containing a near infrared ray-absorbing cationic dye-borate anion complex of the following general formula (I).

Among these, D ⁺ is a cationic dye having absorbency in the near infrared region; R ₁ , R ₂ , R ₃ and R ₄ are each alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, silyl, alicyclic, or saturated or unsaturated heterocyclic groups, substituted alkyl, Substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, or substituted silyl, provided that at least _{one of} R ₁ , R ₂ , R ₃ and R ₄ is C _1-8 An alkyl group of.

Description

Near Infrared-Bleaching Recording Material

The present invention relates to a near-infrared-decolorable recording material which can be discolored by near-infrared light, an ink and a toner containing the near-infrared-decolorable recording material as a colorant.

For example, in the field of printing and copying, the durability of recording materials has become increasingly important in terms of environmental resistance, such as light resistance, moisture resistance, solvent resistance, and heat resistance, and thus, attempts to improve the physical properties of dyes and pigments have been made. A lot has been done. In particular, much progress has been made in the fields of electrophotographic recording, electrostatic recording, and heat transfer-ink recording. In recent years, as the amount of information available has increased, repeat printing has been required, and photochromic materials and thermochromic materials have been developed for recording materials for multiple recording systems or rewritable recording materials (e.g., Japanese Unexamined Patent Publication). Kokai) No. 60-155179, Japanese Unexamined Patent Publication (Kokai) No. 50-75991, and Japanese Unexamined Patent Publication (Kokai) No. 50-105555).

Japanese Unexamined Patent Publication (Kokai) No. 60-155179 discloses a liquid compound which appears blue under ultraviolet light and transparent under white light, and is disclosed in Japanese Unexamined Patent Publication (Kokai) No. 50-75991 discloses thermally decolorizing substances containing a binder mainly composed of white dyes and a phenolic hydroxyl group-containing compound as developer. However, these rewritable recording materials are not only prone to be reversibly discolored and colored or cause color change by visible light or ultraviolet light, but also suffer from problems in terms of storage stability under visible light and durability to repeat recording.

Moreover, many similar studies have been conducted in the fields of electrophotographic recording, electrostatic recording, printing inks or printer inks, for example in US Pat. 2297691, Japanese Patent Publication No. (Kokoku) No. 42-23910, and Japanese Patent Publication (Kokoku) No. Many electrophotographic printing methods are known, as described in 43-24748. Generally, an electrical latent image is formed on a sensitive material in various ways by using a photoconductive material, and then the latent image is developed using a toner to form a visible image, and optionally, the toner image is a paper-like material. After being transferred to, a copy is obtained by fixing the image by applying heat and pressure. In addition, many development methods for obtaining an electrostatic image by using toner are known. For example, U.S. Patent No. Magnetic brush method disclosed in 2874063, US Patent No. Various development methods are known, such as the powder-cloud method, fur brush development method, liquid development method, and the like disclosed in 2618552. Various magnetic recording methods are also known in which magnetic latent images are formed and then developed with magnetic toner. When the toner image is developed, it is randomly transferred to a material such as paper and then fixed. As a method of developing a toner image, a method of heating a toner, melting it by a heater or a heated roller and fusing it to a base material, and then solidifying or softening or dissolving the binder resin of the toner on the base material A method of fixing and a method of fixing the toner to the base material by applying pressure are known.

As described above, the toner used in the fixing process by using a heating roller is generally melt mixed, and then additives such as colorants such as carbon black and additives such as charge control agents are uniformly dispersed in a thermoplastic resin such as styrene-butyl acrylate copolymer. The mixture is cooled and the solidified product is finely ground to a desired particle size by a mill or dispersion machine. Also, nowadays, efforts have been made to improve the physical properties of colorants and charge control agents by performing coloring under development in printing and radiation fields (for example, Japanese Unexamined Patent Publication (Kokai) No. 57-130046 and Japanese Unexamined). Patent Publication (Kokai) No. 57-191650).

Offset press printing, letterpress printing, gravure printing, transfer press printing, or electroprinting by printers such as flexure printing, metal printing, plastic printing, and glass printers are known in the printing arts and are mainly carriers, binders. And inks made of colorants such as dyes and pigments. In recent years, a method of developing an ultraviolet curing ink to prevent contamination without using a solvent to improve productivity by rapid curing or to improve the physical properties of the cured coat has been proposed (eg, Japan). Unexamined Patent Publication No. 1-229084, Japanese Unexamined Patent Publication (Kokai) No. 1-271469 and Japan Unexamined Patent Publication (Kokai) No. 2-22370).

Nevertheless, the above-mentioned photochromic materials and thermochromic materials such as white dyes have low image stability under visible light. In addition, since the toner for electrophotographic recording and printing ink is set, the set image is not discolored and the recording portion cannot be set again, so that not only the recording paper cannot be reused, but also the processing paper Problems also arise from the non-disclosure point of view regarding incidental processing capacity.

One object of the present invention is stable under visible light, which is sensitive to light in the near infrared region, stabilizes the recorded portion, decolorizes the set and printed recording material with near infrared, and can write back to the same portion. To provide the record material.

In order to solve the above problems, as a result of studying a specific near-infrared-absorbing cationic dye-borate anion complex, the present invention was completed as it was found that a near-infrared decolorable recording material that can be discolored by near-infrared can be obtained.

According to the present invention, a near-infrared-absorbing cationic dye-borate anion complex having the following general formula (I) is absorbable in the near-infrared region, and can be decomposed and discolored by irradiating near-infrared wavelengths with a wavelength of 700 nm or more, but stable near infrared- Decolorant recording materials are provided.

Wherein D ⁺ is a cationic dye having absorbency in the near infrared region; R ₁ , R ₂ , R ₃ and R ₄ are each alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkanyl, silyl, alicyclic, or saturated or unsaturated heterocyclic groups, substituted alkyl, Substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, or substituted silyl, wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is C ₁ The alkyl group of _-8 is shown.

The near-infrared recording material according to the present invention can be made into a near-infrared sensitive photo-decoloring composition which can be discolored by incorporating it into a base such as wax or resin and irradiating light in the near infrared wavelength range.

Particular examples of the cationic dyes constituting the near-infrared-absorbing cationic dye-borate anion complex used in the present invention include cyanine, triarylmethane, ammonium, and dimonium dyes having absorbency in the near infrared region. R ₁ , R ₂ , R ₃ and R ₄ in the borate anion are alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, silyl, alicyclic, or saturated or unsaturated hetercyclic, respectively. Groups, substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, or substituted silyl, wherein R ₁ , R ₂ , R ₃ and R ₄ are At least one is an alkyl group of C _1-8 . Examples of the substituent in the above-described substituents include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, cyclohexyl, cyclohexenyl, methoxymethyl, methoxyethyl, dimethylaminoethyl, phenyl , Anylyl, ethoxyphenyl, methylphenyl, tert-butylphenyl, fluorophenyl, chlorophenyl, dimethylaminophenyl, diethylaminophenyl, vinyl, allyl, triphenylsilyl, dimethylphenylsilyl, dibutylphenylsilyl, trimethyl Silyl, piperidyl, thienyl, furyl, pyrrolyl and the like.

Examples of complexes particularly available in the present invention are shown in Table 1 below.

Footnote λ: absorption wavelength

TMPT: Trimethylolpropane trimethacrylate

Ph: phenyl group

Base waxes usable in the present invention include, for example, carbana waxes and Japanese waxes, which are vegetable waxes; Beeswax and wool grease which are animal waxes; Paraffin waxes and microcrystalline waxes that are mineral waxes; Synthetic waxes such as polyethylene wax, PTTE, chlorinated paraffin, fatty acid amides, and the like that are commonly used in heat transfer sheets and inks.

Resins usable in the present invention are all conventional resins and include, for example, resins that dry and cure at a normal temperature for coating, moisture curable resins for coating, and thermosetting resins for coating, which are brushed, spray coated , Dip coating, gravure coating, doctor coating, roll coating, electrostatic coating, powder coating, transferring, printing and the like. Specific examples include oil varnish, kerosene, shellac, cellulose resin, phenol resin, alkyd resin, amino resin, xylene resin, toluene resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polystyrene resin, vinyl-butyral resin And acrylic resins, methacryl resins, diallyl phthalate resins, epoxy resins, urethane resins, polyester resins, polyether resins, aniline resins, furan resins, polyimide resins, silicone resins, and fluoroplastics. In addition, these resins may be photo- and electro-photo-curing resins, and specific examples thereof include cinnamic acid polyvinyl resin, polyvinylbenzal-acetophenone resin, polyvinylstyrylpyridine resin, polyvinyl anthral resin, unsaturated polyester Resins, acrylated oils, acrylated alkyd resins, acrylated polyester resins, acrylated polyether resins, acrylated epoxy resins, acrylated polyurethane resins, acrylic resins, acrylated spiran resins, acrylated silicone resins, acrylated fluoroplastics, polythiol resins, and And macromonomers, oligomers, and monomers of cationic polymerizable epoxy resins. The base may also be light- and chemical-polymerizable monomers and oligomers, in particular ethylenically unsaturated compounds. Specific examples include acrylic or methacrylic esters of monohydric or polyhydric alcohols, and (meth) acryloxy group-containing aromatic polycarboxylic acids and their anhydrides. These may be used alone or as a combination of two or more components. When a monomer is used as the base, even if the near-infrared-coloring recording material is dissolved in the monomer and the mixture is chemically polymerized or photo-polymerized, little effect is felt. The base according to the present invention is not limited thereto, and any base may be mixed with the near-infrared-coloring recording material by dissolution or dispersion.

The near infrared decolorizing recording material of the present invention can be prepared by dissolving or melting with a solvent and then mixing the base with the base in a ratio of 0.01 to 90% by weight, especially 0.1 to 50% by weight. It is noted here that the near infrared decolorizing recording material of the present invention can produce a desired effect even when the near infrared decolorizing recording material itself is dissolved in a solvent and then coated or set.

Decolorization of the near-infrared-coloring recording material of the present invention can be further performed by adding a quaternary ammonium-borate complex having the following general formula (II) as a plasticizer:

Wherein R ₅ , R ₆ , R ₇ and R ₈ are alkyl, aryl, allyl, alkaryl, aralkyl, alkenyl, alkynyl, silyl, alicyclic, or saturated or unsaturated heterocyclic groups, respectively. , Substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, or substituted silyl, provided that at least one of R ₅ , R ₆ , R ₇ and R ₈ Is an alkyl group of C _1-8 ; R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent hydrogen, alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, or unsaturated or saturated heterocyclic group, substituted alkyl, substituted aryl, substituted Alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, or substituted alkynyl. Examples of this substituent are methyl, ethyl, n-propyl, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl, methoxymethyl, methoxyethyl, dimethylaminoethyl, phenyl, anylyl, ethoxyphenyl, methylphenyl Tert-butylphenyl, fluorophenyl, chlorophenyl, dimethylaminophenyl, diethylaminophenyl, vinyl, allyl, triphenylsilyl, dimethylphenylsilyl, dibutylphenylsilyl, trimethylsilyl, hydrogen, piperidyl, tier Nil, furyl, pyrrolyl and the like.

Typical examples include tetramethylammonium n-butyltriphenyl borate, tetramethyl ammonium n-butyltrianisyl borate, tetramethylammonium n-octyltriphenyl borate, tetramethylammonium n-octyltrianisyl borate, tetraethylammonium n-butyltriphenyl borate, tetraethylammonium n-butyltrianisyl borate, trimethylhydrogen ammonium n-butyltriphenyl borate, triethylhydrogenammonium n-butyltriphenyl borate, tetrahydrogenammonium n-butyltriphenyl Borate, tetramethylammonium tetrabutyl borate, tetraethylammonium tetrabutyl borate, tetramethylammonium tri-n-butyl (triphenylsilyl) borate, tetraethylammonium tri-n-butyl (triphenylsilyl) borate, tetrabutylammonium tri -n-butyl (triphenylsilyl) borate, tetramethylammonium t-n-butyl (dimethylphenylsilyl) borate, tetraethyl ammonium tri-n -Butyl (dimethylphenylsilyl) borate, tetrabutylammonium tri-n-butyl (dimethylphenylsilyl) borate, tetramethylammonium n-octyldiphenyl (di-n-butylphenylsilyl) borate, tetraethylammonium n-octyldi Phenyl (di-n-butylphenylsilyl) borate, tetrabutylammonium n-octyldiphenyl (di-n-butylphenylsilyl) borate, tetramethylammonium dimethylphenyl (trimethylsilyl) borate, tetraethylammonium dimethylphenyl (trimethylsilyl ) Borate, tetrabutylammonium dimethylphenyl (trimethylsilyl) borate, etc. are mentioned. Moreover, general coloring dye and pigment can also be added. In this case, the color of the dye or pigment may remain even after the near-infrared-coloring recording material is discolored by irradiation of near-infrared.

The near infrared decolorizing recording material of the present invention may be used alone or in combination with a plurality of near infrared decolorizing recording materials.

The near-infrared-coloring recording material of the present invention is mixed with such a base, and then set or printed on paper, plastic or metal, and then the set or printed portion is removed by near-infrared by a semiconductor laser, a halogen lamp, or a light emitting semiconductor diode. If soaked, it may discolor.

The near-infrared-decolorable recording material according to the present invention can be used as a toner for electrophotographic recording or electrostatic recording or as a colorant for printing ink and ink for sublimation or melt transfer printers, and also for serial printer ink and ink jet printer. It can also be used as stationery and writing instruments, such as ink for ballpoint pens, markers, and magic markers, and UV curing inks and colorants for paints. The scope of application of the near-infrared-coloring recording material is not limited to these examples.

Next, its detailed use will be explained.

The electrophotographic decolorable toner of the present invention melts, mixes or disperses a near infrared decolorizing recording material with a solvent in a base such as a binder resin for a toner, followed by titanium as a sensitizer and a charge control agent and other additives, if necessary. Prepared by kneading with fillers such as white and calcium carbonate. Storage stability can be further improved by adding ultraviolet absorbers.

The positive or negative charge control agents used so far as color toners can be used as charge control agents. Examples of positive charge control agents include quaternary ammonium salts, alkylamides, and hydrophobic silicas. Examples of negative charge control agents include diaminoanthraquinones, chlorinated polyolefins, chlorinated polyesters, metal salts of naphthenic acid, and metal salts of fatty acids.

Fillers may be white fillers such as titanium white, talc, kaolin, silica, alumina, calcium carbonate, aluminum sulfate, barium sulfate, calcium sulfate, titanium oxide and calcium phosphate. Adding fillers can control the whiteness after bleaching. What is necessary is just to use a normal ultraviolet absorber as a ultraviolet absorber.

As the binder resin for the toner of the present invention, polystyrene resin, acrylic resin and styrene- (meth) acrylate copolymer are used. Examples of polystyrene resins include polystyrene homopolymers, hydrogenated polystyrenes, styrene-propylene copolymers, styrene-isobutylene copolymers, styrene-butadiene copolymers, styrene-allyl alcohol copolymers, styrene-maleate copolymers, styrene- Maleic anhydride copolymer, acrylonitrile-butadiene-styrene terpolymer, acrylonitrile styrene-acrylate terpolymer, styrene-acrylonitrile copolymer, acrylonitrile-acrylic rubber-styrene terpolymer, acrylonitrile- And chlorine-added polyethylene-styrene terpolymers. Examples of acrylic resins include polymethyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, fluorine-containing acrylate, methylene methacrylate-butyl methacrylate copolymer, ethyl acrylate- Acrylic acid copolymer etc. are mentioned. Examples of styrene- (meth) acrylate copolymers include styrene-acrylic acid copolymers, styrene-butadiene-acrylate terpolymers, styrene-methyl methacrylate copolymers, styrene-butyl methacrylate copolymers, styrene-diethylamino Ethyl methacrylate copolymer, styrene-methyl methacrylate-butyl acrylate terpolymer, styrene-glycidyl methacrylate copolymer, styrene-butadiene-dimethylaminoethyl methacrylate terpolymer, styrene-acrylate-mali Eight terpolymer, styrene- butyl acrylate- acrylic acid terpolymer, etc. are mentioned.

Wax or sensitizers used in thermal recording papers, or resin modifications, in order to improve the compatibility of near-infrared-coloring recording materials, quaternary ammonium-borate complex sensitizers and toner binders, and to accelerate the decolorization rate. The plasticizer used can be used. As specific examples thereof, dibutyl phthalate, dioctyl phthalate, dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate, dioctyl adipate, dioctyl azelate, trioctyl citrate, tributyl acetyl citrate, dibutyl Sebacate, dioctyl sebacate, methyl stearate, ethyl stearate, butyl stearate, methyl ester of hydrogenated rosin, chlorinated paraffin and the like.

The near-infrared-coloring recording material, which is a colorant for toner which can be discolored, can be mixed with the above-mentioned toner binder by using a solvent in a ratio of 0.01 to 90% by weight, preferably 0.5 to 20% by weight. Decolorization rate is improved by adding 0.01 to 10% by weight, preferably 0.1 to 5% by weight of a quaternary ammonium-borate complex sensitizer based on 1% by weight of the near-infrared-bleachable recording material.

The amount of charge of the toner was 5 to 30 mu c / g. Charge control agents may be added in an amount sufficient to adjust the range, which may be added in an amount of 1 to 10% by weight based on the toner binder.

The filler may be added in an amount of 1 to 20% by weight, preferably 1 to 5% by weight, based on the toner binder. The ultraviolet absorbent may be added in an amount of 1 to 20% by weight based on the weight of the toner binder.

The manufacturing process of the decolorable toner includes a solution process and a melting process. In the solution process, the near-infrared-coloring recording material of the present invention is dissolved and kneaded with an organic solvent in a binder for toner, and if necessary, quaternary ammonium-borate complex sensitizer, charge control agent, ultraviolet absorber, etc. are added, dissolved, And kneading, if added, the filler is dispersed using a paint conditioner to obtain a mixed resin. After removing the organic solvent from the mixed resin thus obtained, the mixed resin is roughly pulverized using a hammer mill or a cutter mill, and then finely pulverized with a jet mill to prepare a toner. In the melting process, the near-infrared decolorable recording material of the present invention is melt kneaded in a toner binder, and if necessary, a quaternary ammonium-borate complex sensitizer, a charge control agent, an ultraviolet absorber and a filler are melt kneaded to prepare a mixed resin. The mixed resin thus obtained is pulverized in the same manner as in the above-described solution process to produce a toner. The decolorable toner obtained as described above can be used not only as a one-component type but also as a two-component type.

After the decolorizable toner is set or printed on paper or an OHP film, the set portion can be decolorized by irradiating near infrared rays with a semiconductor laser, a halogen lamp, or a light emitting semiconductor diode. Also, the discolored portion may be set repeatedly.

The decolorable printing ink of the present invention is prepared by mixing and kneading a near-infrared-coloring recording material as a colorant, a carrier for fixing a sensitizer to a surface to be printed, and, if necessary, titanium white and calcium carbonate as other additives. Prepared by dispersing and kneading the same filler. UV absorbers can be used to increase storage stability.

The carrier used in this decolorable printing ink consists of a drying oil which is relatively rapidly dried when left in air, a resin for improving drying, gloss, and transition characteristics, and a solvent which imparts a desired viscosity and fluidity. In addition, plasticizers may be added if necessary to give the dried ink coat flexibility and solubility.

Dry oils include linseed oil, kerosene oil, soybean oil and castor oil.

Examples of the resin include natural resins such as rosin and shellac; Natural resin derivatives such as cured resins, rosin esters, maleic acid resins and fumaric acid resins; Phenolic resin, xylene resin, urea-melamine resin, ketone resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, butyral resin, styrene-maleic acid resin, chlorinated polypropylene, acrylic resin, polyester resin, Synthetic resins such as alkyd resins, polyamide resins, epoxy resins, polyurethanes, and nitrocelluloses.

Solvents include aliphatic hydrocarbons such as hexane, heptane and rubber solvents; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and cyclohexyl alcohol; Glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and glycerin; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol mono Glycol derivatives such as ethyl ether acetate and diethylene glycol monobutyl ether acetate; Esters such as ethyl acetate, isopropyl acetate and butyl acetate; And ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. As the plasticizer, those mentioned in the above-mentioned decolorable toner for electrophotography can be used.

A filler similar to that of the above-mentioned decolorable toner for electrophotography can be used, and a conventional ultraviolet absorber can be used as the ultraviolet absorber.

To accelerate the bleaching rate, as in the case of decolorable toner, a plasticizer or wax used in a sensitizer and a thermal recording paper may be used.

The near-infrared-coloring recording material, which is a colorant for decolorable printing ink, may be mixed with the carrier at a ratio of 0.01 to 90% by weight, preferably 0.5 to 20% by weight. If the quaternary ammonium-borate complex sensitizer is added in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on 1% by weight of the near infrared-white recording material, the decolorization rate is increased. You may mix resin in order to satisfy the requirement of a printing operation.

The filler may also be added in an amount of 1 to 20% by weight, preferably 1 to 5% by weight. The ultraviolet absorber may be added in an amount of 1 to 20% by weight based on the weight of dry oil.

This bleachable printing ink can be prepared by kneading the near-infrared-coloring recording material of the present invention with dry oil and, if necessary, adding and kneading quaternary ammonium-borate complex sensitizer, ultraviolet absorber, filler and the like.

For special press printing such as offset press printing, letterpress printing, gravure printing, transfer press printing and flexure printing, metal printing, plastic printing, and glass printing, as well as electrical printing by printers such as impact printers or non-impact printers. After being printed by various printing operations such as, the decolorable printing ink can be decolorized by irradiating near infrared rays with a semiconductor laser, a halogen lamp, or a light emitting semiconductor diode. Also, the discolored portion can be printed repeatedly.

In the application to the hot melt-transfer sheet, a transfer film made of paraffin wax as a binder and xylene resin as a softener coated on a PET film and a near-infrared-coloring recording material kneaded with the recording paper is brought into proximity with the recording paper and then transferred by a transfer and heating head. Print This set portion may be discolored by irradiation of near infrared rays.

According to the present invention, there is provided a near infrared decolorizing recording material, a decolorable toner and a decolorizable ink which can be decolorized by irradiating near infrared rays after being set and printed, repeatable in the same part, and stable under visible light.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1

20 parts by weight of polymethyl methacrylate was dissolved in 78 parts by weight of methyl ethyl ketone, and the near-infrared-coloring recording material of Table 2 was dissolved and mixed in the amounts shown in Table 2 to obtain a composition.

Example 2

20 parts by weight of polymethyl methacrylate was dissolved in 76 parts by weight of methyl ethyl ketone, and the near-infrared decolorable recording material of Table 2 and the sensitizer were dissolved and mixed in the amounts shown in Table 2 to obtain a composition.

Example 3

A composition was obtained by dissolving 20 parts by weight of polystyrene in 75 parts by weight of toluene and dissolving and mixing the near-infrared-coloring recording material shown in Table 2 in the amounts shown in Table 2.

Example 4

20 parts by weight of polystyrene was dissolved in 70 parts by weight of toluene, and the near-infrared-coloring recording material shown in Table 2 and the sensitizer were dissolved and mixed in the amounts shown in Table 2 to obtain a composition.

Example 5

20 parts by weight of polymethyl methacrylate was dissolved in 76 parts by weight of methyl ethyl ketone, and the amount shown in Table 2 of the near-infrared-degradable recording material shown in Table 2 and 2 parts by weight of SO Red 1 (Orient Chemical Industry) were mixed therein, A composition was obtained.

Example 6

20 parts by weight of polymethyl methacrylate was dissolved in 74 parts by weight of methyl ethyl ketone, and 2 parts by weight of oil yellow (provided by Orient Chemical Co., Ltd.) and oil yellow (provided by Orient Chemical Co., Ltd.) were dissolved and mixed therein. Got.

Example 7

80 parts by weight of paraffin wax (melting point: 69 ° C.) of the near-infrared-degradable recording material in an amount shown in Table 2 was thermally melted at 80 ° C. to obtain a composition.

Example 8

Paraffin wax (melting point: 69 DEG C) by 70 parts by weight of the near-infrared-decolorable recording material in an amount shown in Table 2 was thermally melted at 80 DEG C to obtain a composition.

Example 9

60 parts by weight of trimethylolpropane triacrylate was dissolved and mixed in the amount of the near-infrared-degradable recording material as shown in Table 2, and then 10 parts by weight of methyl o-benzylbenzoate and 5 parts by weight of triethanol amine were added. Got it.

Example 10

45 parts by weight of trimethylolpropane triacrylate was dissolved and mixed in the amount of the near-infrared-degradable recording material as shown in Table 2, and then 10 parts by weight of methyl o-benzylbenzoate and 5 parts by weight of triethanol amine were added to obtain a composition. .

[Examples 11 and 12]

98 parts by weight of hydrogenated polystyrene (softening point: 101 ° C.) was dissolved and kneaded in an amount of the near-infrared-coloring recording material as shown in Table 2 using methylene chloride, and then methylene chloride was removed. The obtained mixed resin was roughly pulverized using a hammer mill or cutter mill and finely pulverized using a jet mill to obtain a toner.

[Examples 13 to 17]

Styrene-butyl methacrylate copolymer (softening point: 72 ° C.) was dissolved and kneaded with methylene chloride in 96 parts by weight of the near-infrared-coloring recording material and the sensitizer in an amount as shown in Table 2, and then methylene chloride. Removed. The obtained mixed resin was roughly ground using a hammer mill or a cutter mill and finely ground using a jet mill to obtain a toner.

[Examples 18 to 20]

Styrene-butyl methacrylate copolymer (softening point: 72 ° C) After dissolving and kneading the near-infrared-coloring recording material, the sensitizer, the charge control agent and the plasticizer in an amount of 94 parts by weight using methylene chloride, And methylene chloride were removed. The obtained mixed resin was roughly ground using a hammer mill or a cutter mill, and then finely ground using a jet mill to obtain a toner.

[Examples 21 to 23]

Styrene-butyl methacrylate copolymer (softening point: 72 ° C) After dissolving and kneading the near-infrared-coloring recording material, the sensitizer, the charge control agent and the plasticizer in the amount shown in Table 2 by 89 parts by weight using methylene chloride And methylene chloride were removed. The obtained mixed resin was roughly ground using a hammer mill or a cutter mill, and then finely ground using a jet mill to obtain a toner.

Examples 24 and 25

Styrene-butyl methacrylate copolymer (softening point: 72 ° C.) After dissolving and kneading the near-infrared-coloring recording material, the sensitizer and the charge control agent in an amount of 94 parts by weight using methylene chloride, Methylene was removed. The obtained mixed resin was roughly ground using a hammer mill or a cutter mill, and then finely ground using a jet mill to obtain a toner.

Examples 26 and 27

Polymethyl methacrylate (softening point: 78 ° C.) Methylene chloride dispersion containing 3 parts by weight of titanium white as an additive and a near-infrared-degradable recording material, a sensitizer, and a charge control agent in an amount of 91 parts by weight as shown in Table 2. Was melted and kneaded and then methylene chloride was removed. The obtained mixed resin was roughly ground with a hammer mill or a cutter mill, and then finely ground with a jet mill to obtain a toner.

Example 28

Polymethyl methacrylate (softening point: 78 ° C) 2 parts by weight of an ultraviolet absorber (Sumitomo Chemical Co., SUMISORB 400) as 89 parts by weight of the near-infrared-degradable recording material, sensitizer and charge control agent and additives in the amounts shown in Table 2 And methylene chloride containing 3 parts by weight of titanium white were dissolved and kneaded, and then methylene chloride was removed. The obtained mixed resin was roughly ground using a hammer mill or a cutter mill, and then finely ground using a jet mill to obtain a toner.

Examples 29 and 30

Ink was prepared by dissolving and kneading the near-infrared-degradable recording material in the amount shown in Table 2 in 60 parts by weight of linseed oil and 30 parts by weight of styrene-maleic acid resin (softening point: 70 ° C).

[Examples 31 to 35]

Ink was prepared by dissolving and kneading the near-infrared-degradable recording material in the amount shown in Table 2 in 50 parts by weight of linseed oil and 30 parts by weight of styrene maleic acid resin (softening point: 70 ° C.).

[Examples 36 to 38]

Ink was prepared by kneading 40 parts by weight of soybean oil and 30 parts by weight of acrylic resin (softening point: 65 ° C.) by kneading the NIR-decoloring recording material, sensitizer and solvent in the amounts shown in Table 2.

[Examples 39 to 41]

Ink was prepared by kneading 40 parts by weight of soybean oil and 25 parts by weight of acrylic resin (softening point: 65 ° C.) in the amount of near-infrared-coloring recording material, sensitizer, solvent, and plasticizer as shown in Table 2.

[Evaluation Method of Discoloration Characteristics]

For the compositions of Examples 1-6, 05g of this composition was dropped on a carton paper using a RI tester to obtain a sample. The compositions of Examples 7 and 8 were coated on a 3.5 micron thick polyethylene terephthalate film using a wire rod to obtain a 4 micron thick film. The samples were obtained by transferring the sheets and setting them on a recording sheet using a thermal printer at an applied energy of 2.0 mj / dot. For the compositions of Examples 9 and 10, 0.5 g of this composition was dropped on a carton paper using a RI tester, and then cured by irradiating ultraviolet light for 1 minute using an 80 w / cm metal halogen lamp at a distance of 8 cm.

The toners obtained in Examples 11 to 28 were further surface treated with hydrophobic silica, and then the carrier was mixed therewith, and then set on the surface of the PPC using a copying machine for PPC (Casio, Model LCS-24). A sample was obtained.

The ink obtained in Examples 29 to 41 was dropped in an amount of 5 g on a carton using a RI tester to obtain a sample.

Decolorization was evaluated by irradiating the sample with near-infrared radiation generated from an aluminum-coated halogen lamp (2 W / cm 2) for 1 minute. The evaluation results are shown in Table 3.

Evaluation method for resistance to visible light

Samples were prepared in the same manner as in the evaluation method of decolorization characteristics. The sample was irradiated with a 2-color coated halogen lamp (2 W / cm 2) using an infrared cut filter for 1 minute to evaluate decolorization.

Footnote: TMAPB: Tetramethylammonium n-butyltriphenyl borate

TBAPB: tetrabutylmonium n-butyltriphenyl borate

TMHPB: Triethylhydrogen ammonium n-butyltriphenyl borate

TBABB: Tetrabutylammonium Tetra n-butyl Borate

Claims (3)

A near-infrared-decolorable recording material characterized by containing from 0.01 to 90% by weight of a near infrared ray-absorbing cationic dye-borate anion complex having the following general formula (I) and a sensitizer having the following general formula (II). [Formula I] Wherein D ⁺ is a cationic dye having absorbency in the near infrared region; R ₁ , R ₂ , R ₃ , and R ₄ are alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, silyl, alicyclic, or saturated or unsaturated heterocyclic groups, substituted alkyls, respectively. , Substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, or substituted silyl, provided that at least one of R ₁ , R ₂ , R ₃ , and R ₄ is C An alkyl group of _1-8 is represented; [Formula II] Wherein R ₅ , R ₆ , R ₇ , and R ₈ are each alkyl, aryl, allyl, alkaryl, aralkyl, alkenyl, alkynyl, silyl, arylcyclic, or saturated or unsaturated heterocyclic Group, substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, or substituted silyl, provided that R ₅ , R ₆ , R ₇ , and R ₈ At least one represents a C _1-8 alkyl group; Provided that R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are each hydrogen, alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, or saturated or unsaturated heterocyclic groups, substituted alkyl, substituted aryl , Substituted alkaryl, substituted aralkyl, substituted allyl, substituted aralkyl, substituted alkenyl, or substituted alkynyl. A decolorable toner for near-infrared dyes, characterized by containing 0.01 to 90% by weight of the near-infrared-coloring recording material according to claim 1 as a colorant, so that the set portion can be discolored by near-infrared. A decoloring ink for near-infrared dyes, characterized by containing 0.01 to 90% by weight of the near-infrared-coloring recording material according to claim 1 as a colorant, so that the set portion can be discolored by near-infrared.