JPH07325428A - Decolorable toner and its production - Google Patents

Abstract

PURPOSE:To facilitate the control of the extent of electrostatic charge of a decolorable toner and to prevent the fading of a dye due to kneading at the time of production of the toner by dispersing a bonding resin blended with a visible radiation-near IR absorbing dye in a bonding resin and blending one of the resins with a decoloring agent. CONSTITUTION:A bonding resin (A) blended with a visible radiationnear IR absorbing dye is dispersed in a bonding resin (B) and one of the resins A and B is blended with a decoloring agent. When the extent of electrostatic charge of the resultant decolorable toner is controlled by blending the resin B with an electrostatic charge controlling agent, the control is facilitated because the controlling agent is hardly affected by the high positive chargeability of the dye. In the case where resins incompatible with each other are used as the resins A and B, they are dispersed in a sea-island structure at the time of melting by heating and kneading but the high positive chargeability of the dye is hardly exhibited at the surface because of incompatibility.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decolorizable toner and a method for producing the same. More specifically, the present invention relates to a decolorizable toner capable of visualizing an electric latent image and an electric signal in electrophotography, an electrostatic recording material and the like, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, the reuse and recycling of used paper has been reviewed for the purpose of nature protection, particularly forest resource protection and waste reduction in urban areas. As part of this, the reuse of waste paper such as used copy paper, printed matter, and facsimile paper that has become unnecessary in the office of a company is being considered.

However, since most of these waste papers are company confidential documents which are generally regarded as trade secrets, it is not possible to collect and recycle these waste papers at a paper manufacturing company outside the company. It is extremely difficult, and since the recorded and printed parts of printed matter and copied materials cannot be easily erased, they must be incinerated or crushed for disposal, and such papers can be reused. Was considered virtually impossible. In addition, some studies have been conducted on the recycling of waste paper crushed by shredders, etc. However, since the strength of recycled paper manufactured using such crushed waste paper is generally small, for example, information paper, etc. There was a drawback that it could not withstand use as.

Therefore, as a method of easily and safely recycling these waste papers, copying is carried out by using a decolorizable toner in which a binding resin contains a decolorizable dye having a property of decoloring by near infrared rays. After printing, it is proposed to erase the decolorizable toner by irradiating it with near infrared rays (Japanese Patent Laid-Open No. 4-362935).
JP-A-5-119520).

However, the decolorizable toner contains
(A) It is difficult to control the amount of charge of the obtained decolorizable toner because the decolorizable dye exhibits strong positive chargeability.
(B) Due to the interaction between the decolorizable dye and the toner property-imparting agent such as the charge control agent, the decolorizable dye is decolored during the production of the toner, or the decolorizing property and the image of the toner are produced after the production of the toner. There was a quality problem.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, in which the charge amount of the decolorizable toner obtained can be easily adjusted, and a dye is obtained by kneading during the production of the toner. It is an object of the present invention to provide a method for producing a color-erasable toner that is hard to fade, and to provide a color-erasable toner that can be rapidly color-erased during erasing.

[0007]

The present invention relates to (1) a visible light to near infrared ray, a decolorizable toner containing a dye, a decoloring agent and a binder resin as main components, the visible ray to near infrared ray. A decolorizable toner characterized in that a binding resin A containing an absorptive dye is dispersed in a binding resin B, and a decoloring agent is blended in at least one of the binding resin A and the binding resin B. (2) A method for producing a decolorizable toner containing a visible ray to near infrared ray absorbing dye, a decoloring agent and a binder resin as main components, the method including a visible ray to near infrared ray absorbing dye and a decoloring agent. Binder resin A and binder resin B are heated and melt-kneaded, cooled, and then pulverized, and (3) a visible light to near-infrared absorptive dye, and a erasable dye. Method for producing decolorizable toner mainly composed of colorant and binder resin A decolorizable toner characterized in that a binding resin A containing a visible light to near infrared ray absorbing dye, a binding resin B and a decolorizing agent are melted and kneaded by heating, cooled and then pulverized. Manufacturing method.

[0008]

Functions and Examples The decolorizable toner of the present invention is mainly composed of a visible light to near infrared absorbing dye, a decolorizing agent and a binder resin, and the visible light to near infrared absorbing dye is blended. The binding resin A thus dispersed is dispersed in the binding resin B,
The decoloring agent is blended with at least one of the binder resin A and the binder resin B.

According to the production method of the present invention, (A) a binder resin A containing a visible light to near infrared ray absorbing dye and a decoloring agent, and a binder resin B are melted and kneaded by heating and then cooled. By crushing (hereinafter referred to as production method invention I),
Alternatively, (B) a binder resin A containing a visible light to near-infrared absorptive dye, a binder resin B and a decoloring agent are heated and melt-kneaded, and after cooling, crushed (hereinafter,
Manufacturing method invention II), a decolorizable toner is obtained.

According to the above Inventions I to II, the visible light to near infrared absorbing dye exhibiting a strong positive charging property is contained in the binder resin A, and the visible light to near infrared absorbing dye is contained. Since the binder resin A is dispersed in the binder resin B, for example, by blending a charge control agent or the like in the binder resin B, it is possible to control the amount of visible light to Since the near-infrared absorbing dye is unlikely to be affected by the strong positive charging property, it becomes easy to control the charge amount of the decolorizable toner. Further, as described above, the visible light to near-infrared absorptive dye is contained in the binder resin A and is difficult to come into contact with the toner property imparting agent such as the charge control agent, which is compounded in the binder resin B. Therefore, the problem that the color erasability of the obtained color erasable toner is deteriorated or the image quality is deteriorated due to the interaction between the two is solved.

When binder resins A and B which are incompatible with each other are used as the binder resins A and B, both binder resins A and B are not melted when heated and melted and kneaded. -Dispersed in an island structure but not compatible with each other, so that the surface of the resulting decolorizable toner is unlikely to exhibit a strong positive charging property of a visible light to near infrared absorbing dye. Further, when the binding resin B contains a substance having an electrostatic property, for example, a charge control agent, the binding resin A and the binding resin B containing the charging substance are different from each other. Since it exhibits compatibility, it prevents direct contact between the visible light to near-infrared absorptive dye and decoloring agent and the electrifying substance, and therefore, when kneading during production of the decolorizable toner, the electrifying property is improved. The fading of the visible light to near infrared absorbing dye due to the substance is prevented, and the chargeable substance is not much affected by the strong positive charging property of the visible light to near infrared absorbing dye. It becomes easy to adjust the triboelectric charge amount of the toner to a predetermined value.

Further, as the binding resin A, 8 to 30 is used.
When the one having an acid value of mgKOH / g is used, discoloration during the production of the decolorizable toner is prevented, and the light fastness of the obtained decolorizable toner is enhanced.

Further, generally, the binding resin has an essentially light color, but among them, as the binding resin A in particular, L * measured by a color difference meter in a 30% ethyl acetate solution is used.
When the b * value in the a * b color coordinate is 20 or less, an image is formed on a copy sheet by using the obtained decolorizable toner, and then the formed image is irradiated with visible rays to near infrared rays. When the image is subjected to the color erasing process by irradiating with, the image subjected to the color erasing process hardly becomes yellowish, so that the reusability of the copy paper is further enhanced.

In Process Invention I, the visible to near-infrared absorbing dye, the decolorizing agent and the binder resin A are dissolved in an organic solvent and mixed or kneaded. When a binder resin A containing an infrared absorbing dye and a decoloring agent is prepared, or in the production method II, the visible light to near infrared absorbing dye and the binder resin A are dissolved in an organic solvent and mixed or not mixed. After kneading, when the organic solvent is removed to prepare a binder resin A containing a visible light to near-infrared absorbing dye, as in the case of heat melting kneading without using an organic solvent, The visible-near-infrared absorbing dye hardly causes discoloration, fading or decoloration during heat-melt kneading.

Specific examples of the binder resin A and the binder resin B include, for example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, and substitution products thereof, styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene- Octyl methacrylate copolymer, styrene-α
-Styrene-acrylic copolymers such as methyl chloromethacrylate copolymer, styrene-hydroxyethyl acrylate copolymer, styrene-acrylic acid ester-hydroxyethyl acrylate copolymer, styrene-hydroxypropyl acrylate copolymer, styrene -Styrene-acrylonitrile copolymers such as acrylonitrile copolymer, styrene-acrylic rubber-acrylonitrile copolymer, styrene-EPDM-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-chlorinated polyethylene-acrylonitrile copolymer Copolymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-vinyl copolymer Methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-malein Acid copolymer, other styrene-based copolymers such as styrene-maleic acid ester copolymer, polyacrylic acid, polymethyl methacrylate, polybutyl methacrylate, polyhydroxymethyl acrylate, polyhydroxyethyl acrylate, polyhydroxypropyl acrylate, (Meth) acrylic resin represented by polyhydroxymethylmethacrylate, polyhydroxyethylmethacrylate, polyhydroxypropylmethacrylate, etc., saturated polyester, unsaturated polyester Typical examples include polyester resins, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate copolymers such as modified ethylene-vinyl acetate copolymers, olefin resins such as polyethylene and polypropylene, epoxy resins, vinyl chloride Resin, silicone resin, fluororesin, polyamide resin, polyvinyl alcohol resin, polyurethane resin, polyvinyl butyral, rosin, modified rosin, rosin modified phenol formaldehyde resin, phenol formaldehyde resin, phenolic resin, vinyl acetate resin, terpene Examples thereof include resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin wax, and carnauba wax, but the present invention is not limited to these examples. The binding resin A and the binding resin B may be the same or different. These binder resins are usually used alone or in admixture of two or more. Among the specific examples of these binding resins, the polarity of the binding resin itself is large, for example, polyester resin, epoxy resin,
(Meth) acrylic resin, polyamide resin, polyvinyl alcohol resin, polyurethane resin, polyacrylonitrile resin, polyvinyl acetate resin, phenol resin, styrene-acryl copolymer, styrene-acrylonitrile copolymer , Ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and the like, a binder resin having a large polarity having at least one group selected from a hydroxyl group, a cyano group, a carboxyl group and a carbonyl group in the molecule, Further, since it imparts excellent anti-fading property, it can be particularly suitably used as the binding resin A in the present invention.

In the present invention, the binder resin A and the binder resin B are preferably incompatible with each other. As described above, when the binder resin A and the binder resin B are incompatible with each other, as described above, the strong positive charging property of the visible light to near infrared absorbing dye can be obtained. It becomes difficult to appear on the surface of the color toner, and when the binding resin B contains a charge substance such as a charge control agent, when the decolorizable toner is kneaded during production, the charge substance may be Visible light to near infrared absorbing dyes are prevented from fading and discoloring, and are not affected by the strong positive charging property of visible light to near infrared absorbing dyes.
There is an advantage that it becomes easy to adjust the triboelectric charge amount of the obtained decolorizable toner to a predetermined value.

Among the specific examples of the binder resin A and the binder resin B, the styrene-acrylic acid ester copolymer and the binder resin A and the binder resin B are incompatible with each other. The polyester resin is particularly preferably used.

Although there are various scales of incompatibility between the binder resin A and the binder resin B, in the present invention, 0.2 g of each of the two binder resins whose compatibility is to be evaluated is taken, Each of them is dissolved in a solvent capable of dissolving both binder resins, for example, about 20 ml of tetrahydrofuran or dichloromethane, 10 ml of each binder resin solution is mixed, and then stirred to obtain a uniform composition. When the resulting mixed solution is cast on a glass plate such as a slide glass, air-dried to remove the solvent, and the degree of turbidity of the formed film having a thickness of about 100 μm on the glass plate is visually observed. The presence of white turbidity is a measure of incompatibility.
When a binder resin which is hardly soluble or insoluble in an organic solvent is used, two kinds of binder resins are respectively melted by heating, mixed to obtain a uniform composition, and then cooled to form a film. The formation of the above is recognized as a phase-separated structure of these binder resins by microscopic observation, which is a measure of incompatibility.

In the present invention, the binder resin A and the binder resin B are each selected from the binder resins exemplified above as long as they are incompatible with each other.
One kind or two or more kinds can be used.

As the binder resin A, JIS K is used in order to prevent discoloration during the production of the decolorizable toner and to improve the weather resistance of the decolorizable toner obtained and the storage stability of the formed image. Acid value determined according to 0070 (1992) is 8 mg KOH / g or more, especially 10 mg
It is preferable to use KOH / g or more. In addition,
If the acid value is too large, the moisture resistance and the decoloring property become poor, so 30 mgKOH / g
Hereafter, it is preferably 20 mgKOH / g or less.

Further, as the binder resin A, the image formed by using the obtained decolorizable toner is
B in the L * a * b color coordinates measured by a color difference meter with a 30% ethyl acetate solution of the binder resin in order to prevent the occurrence of color residue when irradiated with near infrared rays.
* It is desirable to use those having a value of 20 or less, preferably -20 to 20, and more preferably -5 to 20.

In the present invention, the L * value, the a * value and the b * value are all obtained by using a 30% ethyl acetate solution of a binder resin, a color difference meter "Z" manufactured by Nippon Denshoku Industries Co., Ltd. −Σ
90COLOR MEASURING SYSTEM "
Is a value obtained by measurement of transmitted light.

As the L * value increases, the lightness increases, and as the L * value decreases, the lightness decreases. As the a * value increases, it becomes green, and as it decreases, it becomes red. The b * value becomes yellow as it increases, becomes colorless as it approaches 0, and becomes blue as the negative value increases.

By the way, in the present invention, particularly b *
The value of 20 or less means that when the b * value is larger than 20, the binder resin is colored yellow, and the yellow coloring adversely affects the hue of the image after decolorization. Because it affects.

When the ratio of the binder resin A and the binder resin B (binder resin A / binder resin B: weight ratio) is too small, the coloring property of the obtained toner particles is deteriorated. 5/95 or more, especially 8
/ 92 or more, and when it is too large, the adhesive resins A and B tend to be difficult to phase-separate, so 50/50 or less, especially 45/5
It is preferably 5 or less.

When a decolorizable toner is prepared with such a ratio of the binder resin A and the binder resin B, the ratio of the binder resin A is relatively smaller than that of the binder resin B.
A decolorizable toner having a so-called "sea-island structure" in which the binding resin A constitutes "islands" and the binding resin B constitutes "sea" can be obtained. Therefore, the obtained decolorizable toner has a structure in which the visible light to near-infrared absorptive dye and the decolorizing agent are contained in the “island” made of the binding resin A, and the “island” is bound. Since it has a structure in which the wearing resin B is dispersed in the "sea", one kind of binding resin is used, and visible light to near-infrared absorbing dye is dispersed in the visible light to near The strong positive charging property of the infrared absorbing dye is less likely to appear on the surface of the obtained decolorizable toner.

In the present invention, the binder resin may be blended with wax such as polyolefin wax and paraffin wax, if necessary.

The amount of the above-mentioned wax is the total amount of the binder resin A and the binder resin B (hereinafter, the total amount of the binder resin) in order to sufficiently bring out the effect of adding such a wax, for example, the offset prevention effect. Called resin) 10
It is desirable that the amount is 0.1 part or more, preferably 0.5 part or more with respect to 0 part (part by weight, the same applies below). However, if the amount of the wax is too large, an electric latent image is formed. Since there is a tendency that a film is formed on the photoconductor to be formed, it is desirable that the amount is 20 parts or less, preferably 10 parts or less with respect to 100 parts of the total binding resin.

Examples of the visible light to near infrared ray absorbing dye used in the present invention include those represented by the general formula (I):

[0030]

[Chemical 1]

(In the formula, D ⁺ is a cation having absorption in the visible light region to the near infrared 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, 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, cationic dye or the formula represented by a substituted alkynyl group or substituted silyl ^{group) (II): D + ·} a - (II) ( wherein, D ⁺ is an absorption in the near infrared region from the visible light region Cation, A ^- is halogen ion, perchlorate ion,
Typical examples are cationic dyes represented by PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ or sulfonate ion).

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 SO
^{_{3 -, F 2 CHSO 3 -}} , F 3 CSO 3 -, ClCH 2
^{_{SO 3 -, Cl 2 CHSO 3}} -, Cl 3 CSO 3 -, C
^{_{H 3 OCH 2 SO 3 -,}} (CH 3) 2 NCH 2 SO 3 -
Substituted methyl sulfonate ion such as, C ₆ H ₅ SO ₃ ^-
Phenylsulfonate ion such as CH ₃ C ₆ H ₄ SO
^{_{3 -, (CH 3) 2}} C 6 H 3 SO 3 -, (CH 3) 3 C
^{_{6 H 2 SO 3 -, HOC}} 6 H 4 SO 3 -, (HO) 2 C
^{_{6 H 3 SO 3 -, (}} HO) 3 C 6 H 2 SO 3 -, CH 3
^{_{OC 6 H 4 SO 3 -,}} C 6 H 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 FS
^{_{O 3 -, C 6 H 3}} F 2 SO 3 -, C 6 H 2 F 3 S
^{_{O 3 -, C 6 HF 4}} SO 3 -, C 6 F 5 SO 3 -, (C
Substituted phenyl sulfonate ion such as H ₃ ) ₂ NC ₆ H ₄ SO ₃ ⁻ may be used.

In the general formula (I), R ¹ ,
Specific examples of R ² , R ³ and R ⁴ include, for example, hydrogen atom, alkyl group, aryl group, allyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, substituted alkyl group and substituted aryl group. , A substituted allyl group,
Examples thereof include a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group, and a substituted silyl group. Among these, preferred are, for example, hydrogen atom, 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, tri Examples thereof include phenylsilyl group, dimethylphenylsilyl group, dibutylphenylsilyl group, trimethylsilyl group, piperidyl group, thienyl group and furyl group. In addition, R ¹ , R ² , R
^At least one of ³ and R ⁴ has 1 to 12 carbon atoms.
It is preferable that the alkyl group is, but among these alkyl groups, more preferable one is, for example, n-
Examples thereof include alkyl groups having 4 to 12 carbon atoms such as butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-dodecyl group. Specific examples of the anion include, for example, n-methyltriphenylboron ion, n-ethyltriphenylboron ion, n-butyltriphenylboron ion, n-octyltriphenylboron ion, n-dodecyltriphenylboron ion, n. -Methyltri-p-tolylboron ion, n-ethyltri-p-tolylboron ion, n-butyltri-
p-tolylboron ion, n-octyltri-p-tolylboron ion, n-dodecyltri-p-tolylboron ion, n-methyltrianisylboron ion, n-ethyltrianisylboron ion, n-butyltrianisylboron ion, n-octyltrianisylboron ion, n-dodecyltrianisylboron ion, di-n-methyldiphenylboron ion, di-n-ethyldiphenylboron ion, di-n-butyldiphenylboron ion,
Din-octyldiphenylboron ion, din-dodecyldiphenylboron ion, din-methyldi-p-tolylboron ion, din-ethyldi-p-tolylboron ion, din-butyldi-p-tolylboron ion, di n
-Octyldi-p-tolylboron ion, di-n-dodecyldi-p-tolylboron ion, di-n-methyldianisylboron ion, di-n-ethyldianisylboron ion, di-n-butyldianisylboron ion, di-n- Octyldianisylboron ion, di-n-dodecyldianisylboron ion, tetraphenylboron ion, tetraanisylboron ion, tetra-p-tolylboron ion, triphenylnaphthylboron ion, tri-p-tolylnaphthylboron ion, tetra Butylboron ion, tri-n-butyl (triphenylsilyl) boron ion, tri-n-butyl (dimethylphenylsilyl) boron ion, n-octyldiphenyl (di-n-butylphenylsilyl) boron ion, dimethylphenyl (trimethylsilyl) boron ion And the like.

Further, in the visible light to near infrared absorbing dye represented by the general formula (I), the cation (D ⁺ )
Preferred examples include cyanine, triarylmethane, aminium, diimmonium, thiazine, xanthene, thiazine, oxazine, diallylmethane, triallylmethane, styryl, pyrylium and thiopyrylium cationic dyes. Typical examples of such cationic dyes include those listed in Table 1.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

[Table 9]

[0044]

[Table 10]

[0045]

[Table 11]

[0046]

[Table 12]

[0047]

[Table 13]

[0048]

[Table 14]

[0049]

[Table 15]

[0050]

[Table 16]

[0051]

[Table 17]

[0052]

[Table 18]

[0053]

[Table 19]

[0054]

[Table 20]

[0055]

[Table 21]

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) Ar represents an aryl 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.

(14) Xylyl represents a xylyl group.

The visible light to near infrared ray absorbing dye is mixed with the binder resin A.

The visible light to near infrared ray absorbing dye is blended in an amount of 0.01 parts by weight or more, based on 100 parts by weight of the total binder resin, in order to impart sufficient coloring to the resulting decolorizable toner. The amount is preferably 0.1 part or more, and in order not to adversely affect the triboelectric charge amount inherent in the resulting decolorizable toner, 25 parts or less, especially 15 parts, based on 100 parts of the total binding resin. It is preferably not more than a part.

In the present invention, examples of the decolorizing agent include those represented by the general formula (III):

[0073]

[Chemical 2]

(In the formula, 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,
Multiple ring groups, substituted alkyl groups, substituted aryl groups, substituted allyl groups, substituted aralkyl groups, substituted alkenyl groups, substituted alkynyl groups or substituted silyl groups, Z ⁺ is a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium A decolorizer represented by a cation or a phosphonium cation) is a typical example.

Specific examples of the decoloring agent (boron-based compound) include, for example, tetramethylammonium n-methyltriphenylboron, tetramethylammonium n-butyltriphenylboron and tetramethylammoniumn.
-Octyltriphenylboron, tetramethylammonium n-dodecyltriphenylboron, tetramethylammonium n-methyltri-p-tolylboron, tetramethylammonium n-butyltri-p-tolylboron, tetramethylammonium n-octyltri-p-
Tolylboron, tetramethylammonium n-dodecyltri-p-tolylboron, tetramethylammonium n
-Methyltrianisyl boron, tetramethylammonium n-butyltrianisylboron, tetramethylammonium n-octyltrianisylboron, tetramethylammonium n-dodecyltrianisylboron, tetraethylammonium n-methyltriphenylboron, tetraethylammoniumn-butyl Triphenylboron, tetraethylammonium n-octyltriphenylboron, tetraethylammonium n-dodecyltriphenylboron, tetraethylammonium n-methyltri-p-tolylboron, tetraethylammoniumn
-Butyltri-p-tolylboron, tetraethylammonium n-octyltri-p-tolylboron, tetraethylammonium n-dodecyltri-p-tolylboron, tetraethylammonium n-methyltrianisylboron, tetraethylammonium n-butyltrianisylboron, tetraethylammonium n-octyltrianisylboron, tetraethylammonium n-dodecyltrianisylboron, tetrabutylammonium n
-Methyl triphenyl boron, tetrabutyl ammonium n-butyl triphenyl boron, tetrabutyl ammonium n-octyl triphenyl boron, tetrabutyl ammonium n-dodecyl triphenyl boron, tetrabutyl ammonium n-methyl tri-p-tolyl boron, tetrabutyl Ammonium n-butyltri-p-tolylboron, tetrabutylammonium n-octyltri-p-tolylboron, tetrabutylammonium n-
Dodecyl tri-p-tolyl boron, tetrabutyl ammonium n-methyl trianisyl boron, tetrabutyl ammonium n-butyl trianisyl boron, tetrabutyl ammonium n-octyl trianisyl boron, tetrabutyl ammonium n-dodecyl trianisyl boron, tetraoctyl ammonium n-Methyltriphenylboron, tetraoctylammonium n-butyltriphenylboron, tetraoctylammonium n-octyltriphenylboron, tetraoctylammonium n-dodecyltriphenylboron, tetraoctylammonium n-methyltri-p-tolylboron, tetra Octyl ammonium n-butyl tri-p-tolyl boron, tetraoctyl ammonium n-octyl tri-p
-Tolylboron, tetraoctylammonium n-dodecyltri-p-tolylboron, tetraoctylammonium n-methyltrianisylboron, tetraoctylammonium n-butyltrianisylboron, tetraoctylammonium n-octyltrianisylboron, tetraoctylammoniumn -Dodecyl trianisyl boron, tetramethyl ammonium di n-methyl diphenyl boron, tetramethyl ammonium di n-butyl diphenyl boron, tetramethyl ammonium di n-octyl diphenyl boron, tetramethyl ammonium di n-
Dodecyl diphenyl boron, tetramethyl ammonium di n-methyl di-p-tolyl boron, tetramethyl ammonium di n-butyl di-p-tolyl boron, tetramethyl ammonium di n-octyl di-p-tolyl boron, tetramethyl ammonium di n-dodecyl di -P-
Tolyl boron, tetramethyl ammonium di-n-methyl dianisyl boron, tetramethyl ammonium di-n-butyl dianisyl boron, tetramethyl ammonium di n
-Octyldianisylboron, tetramethylammonium di-n-dodecyldianisylboron, tetraethylammoniumdi-n-methyldiphenylboron, tetraethylammoniumdi-n-butyldiphenylboron, tetraethylammoniumdi-n-octyldiphenylboron, tetraethylammoniumdi-n-dodecyl Diphenylboron, tetraethylammonium di-n-methyldi-p-tolylboron, tetraethylammoniumdi-n-butyldi-p-tolylboron, tetraethylammoniumdi-n-
Octyldi-p-tolylboron, tetraethylammonium di-n-dodecyldi-p-tolylboron, tetraethylammoniumdi-n-methyldianisylboron, tetraethylammoniumdi-n-butyldianisylboron, tetraethylammoniumdi-n-octyldianisylboron, tetraethyl Ammonium di n-dodecyl dianisyl boron, tetrabutyl ammonium di n-methyl diphenyl boron, tetrabutyl ammonium di n-butyl diphenyl boron, tetrabutyl ammonium di n-octyl diphenyl boron, tetrabutyl ammonium di n-dodecyl diphenyl boron, tetra Butyl ammonium di-n-methyl di-p-tolyl boron, tetrabutyl ammonium di-n-butyl di-p-tolyl boron, tetrabutyl ammonium Muzi n- octyl di -p- Toriruhou arsenide, tetrabutylammonium di n- dodecyl di -p
-Tolylboron, tetrabutylammonium di-n-methyldianisylboron, tetrabutylammonium di-n-
Butyl dianisyl boron, tetrabutyl ammonium di n-octyl dianisyl boron, tetrabutyl ammonium di n-dodecyl dianisyl boron, tetraoctyl ammonium di n-methyl diphenyl boron, tetraoctyl ammonium di n-butyl diphenyl boron, tetraoctyl ammonium Di-n-octyl diphenyl boron, tetra-octyl ammonium di-n-dodecyl diphenyl boron, tetra-octyl ammonium di-n-methyl di-p-tolyl boron, tetra-octyl ammonium di-n-butyl di-p-tolyl boron, tetra-octyl ammonium di-n-octyl di -P-tolylboron, tetraoctylammonium di-n-dodecyldi-p-tolylboron, tetraoctylammonium di-n-methyldianisylboron, te La octyl ammonium di n- butyl Ziani sills borate, tetraoctylammonium di n
-Octyl dianisyl boron, tetraoctyl ammonium di-n-dodecyl dianisyl boron, tetramethyl ammonium tetraphenyl boron, tetraethyl ammonium tetraphenyl boron, tetrabutyl ammonium tetraphenyl boron, tetraoctyl ammonium tetraphenyl boron, tetramethyl ammonium tetra-p -Tolylboron, tetraethylammonium tetra-p-tolylboron, tetrabutylammonium tetra-p-tolylboron, tetraoctylammonium tetra-p-tolylboron, tetramethylammonium tetraanisylboron, tetraethylammoniumtetraanisylboron, tetrabutyl Ammonium tetraanisyl boron, tetraoctyl ammonium tetraanisyl boron, tetra Chill ammonium triphenyl naphthyl boron, tetraethylammonium triphenyl naphthyl boron, tetrabutylammonium triphenyl naphthyl boron, tetramethylammonium tri -p-
Trilylnaphthylboron, tetraethylammonium tri-p-tolylnaphthylboron, tetrabutylammonium tri-p-tolylnaphthylboron, tetramethylammoniumtetrabutylboron, tetraethylammoniumtetrabutylboron, tetrabutylammoniumtetrabutylboron, trimethylhydrogenammonium n- Butyl triphenyl boron, triethyl hydrogen ammonium n-butyl triphenyl boron, trimethyl hydrogen ammonium n-butyl trianisyl boron, triethyl hydrogen ammonium n-butyl trianisyl boron, tetrahydrogen ammonium n-butyl triphenyl boron, tetrahydrogen ammonium n- Butyltrianisylboron, tetramethylammonium Li-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-octyldiphenyl (di-n-butylphenylsilyl) boron, tetraethylammonium n-octyldiphenyl (din)
-Butylphenylsilyl) boron, tetrabutylammonium n-octyldiphenyl (di-n-butylphenylsilyl) boron, tetramethylammonium dimethylphenyl (trimethylsilyl) boron, tetraethylammonium dimethylphenyl (trimethylsilyl) boron, tetrabutylammonium dimethylphenyl (trimethylsilyl) ) Boron, methylpyridinium n-butyltriphenylboron, methylpyridinium n-octyltriphenylboron, methylpyridinium n-dodecyltriphenylboron, ethylpyridinium n-butyltriphenylboron, ethylpyridinium n-octyltriphenylboron, ethylpyridinium n-Dodecyltriphenylboron, n-butylpyridinium n-butyltriphenylboron n- butyl pyridinium n- octyl triphenyl boron, n- butyl pyridinium n-
Dodecyltriphenylboron, n-octylpyridinium n-butyltriphenylboron, n-octylpyridinium n-octyltriphenylboron, n-octylpyridinium n-dodecyltriphenylboron, methylpyridinium n-butyltri-p-tolylboron, methyl Pyridinium n-octyltri-p-tolylboron,
Methylpyridinium n-dodecyltri-p-tolylboron Ethylpyridinium n-butyltri-p-tolylboron, ethylpyridinium n-octyltri-p-tolylboron, ethylpyridinium n-dodecyltri-p-tolylboron, n-butylpyridinium n-butyltri −
p-tolylboron, n-butylpyridinium n-octyltri-p-tolylboron, n-butylpyridinium n
-Dodecyltri-p-tolylboron, n-octylpyridinium n-butyltri-p-tolylboron, n-octylpyridinium n-octyltri-p-tolylboron, n-octylpyridinium n-dodecyltri-p-
Triylboron, 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-butyl triphenyl boron, ethyl quinolinium n-octyl triphenyl boron, ethyl quinolinium n-dodecyl triphenyl boron, n-butyl quinolinium n-butyl triphenyl boron, n-butyl key Norinium 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-butylquinolinium n-butyltri-p-tolylboron, n-butylquinolinium n-octyltri-p-tolylboron, n-butylquinolinium n-dodecyltri-p-tolylboron,
n-octylquinolinium n-butyltri-p-tolylboron, n-octylquinolinium n-octyltri-
p-tolylboron, n-octylquinolinium n-dodecyltri-p-tolylboron, methylquinolinium n-
Butyltrianisylboron, methylquinolinium n-octyltrianisylboron, methylquinolinium n-dodecyltrianisylboron, ethylquinolinium n-butyltrianisylboron, ethylquinolinium n-octyltrianisylboron, ethyl Quinolinium n-dodecyl trianisyl boron, n-butyl quinolinium n-
Butyltrianisylboron, n-butylquinolinium n
-Octyl trianisyl boron, n-butyl quinolinium n-dodecyl trianisyl boron, n-octyl quinolinium n-butyl trianisyl boron, n-octyl quinolinium n-octyl trianisyl boron, n-octyl quinoli N-dodecyltrianisylboron,
Methylpyridinium di-n-butyldiphenylboron, ethylpyridiniumdi-n-octyldiphenylboron, n
-Butylpyridinium di-n-dodecyldiphenylboron, n-octylpyridiniumdi-n-butyldiphenylboron, methylpyridiniumdi-n-butyldi-p-tolylboron, ethylpyridiniumdi-n-octyldi-p-
Trilyboron, n-butylpyridinium din-dodecyldi-p-tolylboron, n-octylpyridinium din
-Butyldi-p-tolylboron, methylpyridiniumdi-n-butyldianisylboron, ethylpyridiniumdi-n
-Octyldianisylboron, n-butylpyridiniumdin-dodecyldianisylboron, n-octylpyridiniumdi-n-butyldianisylboron, methylquinoliniumdi-n-butyldiphenylboron, ethylquinoliniumdi-n-octyldiphenyl Boron, n-butylquinolinium di-n-dodecyldiphenyl boron, n-octylquinolinium di-n-butyldiphenyl boron, methylquinolinium di-n-butyldi-p-tolylboron, ethylquinolinium di-n-octyldi -P-tolylboron, n
-Butylquinolinium din-dodecyldi-p-tolylboron, n-octylquinolinium di-n-butyldi-p-
Tolylboron, methylquinolinium di-n-butyldianisylboron, ethylquinoliniumdi-n-octyldianisylboron, n-butylquinoliniumdi-n-dodecyldianisylboron, n-octylquinoliniumdi-n- Butyldianisyl boron, methylpyridinium tetra n-butylboron, ethylpyridinium tetra n-butylboron, n-butylpyridinium tetra n-butylboron,
n-octylpyridinium tetra-n-butylboron, methylquinolinium tetra-n-butylboron, ethylquinolinium tetra-n-butylboron, n-butylquinolinium tetra-n-butylboron, n-octylquinoliniumtetra-n -Butylboron, methylpyridinium tetra-n-octylboron, ethylpyridinium tetra-n-octylboron, n-butylpyridinium tetra-n-octylboron, n-octylpyridinium tetra-n-octylboron, methylquinolinium tetra-n-octylboron, 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, tetra-n-butylphosphonium n-butyltrianisylboron, tetra-n-octylphosphonium n-butyltrianisylboron, tetramethylphosphonium n-octyltriphenylboron,
Tetraethylphosphonium n-octyltriphenylboron, tetra n-butylphosphonium n-octyltriphenylboron, tetra n-octylphosphonium n-
Octyl triphenyl boron, tetramethylphosphonium n-octyl tri-p-tolyl boron, tetraethyl phosphonium n-octyl tri-p-tolyl boron, tetra n-butyl phosphonium n-octyl tri-p-tolyl boron, tetra n-octyl phosphonium n-octyl tri boron -P-tolylboron, tetramethylphosphonium n-octyltrianisylboron, tetraethylphosphonium n-octyltrianisylboron, tetra-n-
Butylphosphonium n-octyltrianisyl 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-octyl phosphonium n- Dodecyltriphenylboron, tetramethylphosphonium n-dodecyltri-p-tolylboron, tetraethylphosphonium n-dodecyltri-p
-Tolylboron, tetra-n-butylphosphonium n-dodecyltri-p-tolylboron, tetra-n-octylphosphonium n-dodecyltri-p-tolylboron, tetramethylphosphonium n-dodecyltrianisylboron, tetraethylphosphonium n-dodecyltrianisylboron , Tetra n-butyl phosphonium n-dodecyl trianisyl boron, tetra n-octyl phosphonium n-dodecyl trianisyl boron, tetramethyl phosphonium di n-butyl diphenyl boron, tetraethyl phosphonium di n-butyl diphenyl boron, tetra n-
Butylphosphonium di-n-butyldiphenyl boron, tetra-n-octylphosphonium di-n-butyldiphenyl boron, tetramethylphosphonium di-n-butyldi-p
-Tolylboron, tetraethylphosphonium di-n-butyldi-p-tolylboron, tetra-n-butylphosphonium di-n-butyldi-p-tolylboron, tetra-n-octylphosphonium di-n-butyldi-p-tolylboron,
Tetramethylphosphonium di-n-butyldianisyl boron, tetraethylphosphonium di-n-butyldianisyl boron, tetra-n-butylphosphonium di-n-butyldianisyl boron, tetra-n-octylphosphonium di-n
-Butyldianisylboron, tetramethylphosphonium di-n-octyldiphenylboron, tetraethylphosphonium di-n-octyldiphenylboron, tetra-n-butylphosphonium di-n-octyldiphenylboron, tetra-n-octylphosphoniumdi-n-octyldiphenylboron, tetra Methylphosphonium di-n-octyldi-p-tolylboron, tetraethylphosphonium di-n-
Octyldi-p-tolylboron, tetra-n-butylphosphonium di-n-octyldi-p-tolylboron, tetra-n-octylphosphonium di-n-octyldi-p-tolylboron, tetramethylphosphonium di-n-octyldianisylboron, tetraethylphosphonium Di-n-octyldianisyl 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, tetraanis Sylphosphonium di-n-butyldiphenylboron Tetraphenylphosphonium di-n-butyldi-p-tolylboron, tetraanisylphosphonium di-n-butyldi-
p-tolylboron, tetraphenylphosphonium din-
Examples thereof include butyldianisylboron and tetraanisylphosphonium di-n-butyldianisylboron. These decolorizers can be used alone or in admixture of two or more.

The decoloring agent is blended with at least one of the binder resin A and the binder resin B. In order to reduce the frequency of contact between the visible light to near infrared absorbing dye and the decoloring agent and prevent the visible light to near infrared absorbing dye from discoloring or fading, the decolorizing agent is the binder resin B. It is preferable to be blended in. Further, in order to prevent the charging characteristics of the toner particles from being deteriorated, it is preferable that the decoloring agent is mixed with the binder resin A.

The blending amount of the decoloring agent is set to 100 for the visible light to near infrared absorbing dye in order to increase the decoloring speed.
It is desirable that the amount is 1 part or more, preferably 5 parts or more, and the print formed using the decolorizable toner,
In order to improve the light resistance of an image and prevent discoloration or fading, the visible light to near-infrared absorbing dye 100 described above is used.
It is desirable that the amount is 2500 parts or less, preferably 1000 parts or less with respect to the parts.

When a decoloring agent is added to the binder resin A,
It is desirable that the content of the decoloring agent is 500 parts or less, preferably 300 parts or less, relative to 100 parts of the binding resin A in order to uniformly disperse the decoloring agent in the binding resin A. ..

When the decoloring agent is blended with the binder resin B, 100 parts or less, preferably 50 parts or less with respect to 100 parts of the binder resin B is added in order to uniformly disperse the decolorizing agent in the binder resin B. It is desirable that the number is not more than a part.

The amount of the decolorizer blended is 0.01 part or more, preferably 0. 0 part, based on 100 parts of the total binder resin in order to impart sufficient decolorability to the resulting decolorizable toner. It is preferably 1 part or more, and in order not to adversely affect the triboelectric charge amount peculiar to the resulting decolorizable toner, 80 parts or less, preferably 35 parts, relative to 100 parts of the total binder resin. The following is desirable.

In the present invention, when it is necessary to adjust the charge amount of the decolorizable toner obtained, a chargeable substance can be blended with the binder resin B. Among the chargeable substances, colorless, white or pale yellow, especially colorless or white chargeable substances that do not impair the hue of the toner and the hue of the image formed by the toner after the decoloring treatment can be preferably used.

As the binding resin, the incompatible binding resins A and B are used as the binding resin, and when a charging substance is mixed with the binding resin B, the binding resin A and the binding resin B are mixed. Since B is incompatible with each other, it is a resin for binding A
The direct contact between the plastic ray to the near-infrared absorbing dye and the decoloring agent and the charging substance is prevented, and the charging substance has a strong positive charging property of the visible to near-infrared absorbing dye. Since it is not affected so much, it becomes easy to adjust the triboelectric charge amount of the obtained decolorizable toner. Further, when kneading during the production of the toner, visible light due to a charging substance
The near-infrared absorbing dye is prevented from fading, and the resulting decolorizable toner has excellent decoloring properties.

Typical examples of the above-mentioned chargeable substances include charge control agents.

Examples of the charge control agent include positive charge control agents such as quaternary ammonium salt, alkylamide, and hydrophobic silica; diaminoanthraquinone, chlorinated polyolefin, chlorinated polyester, naphthenic acid metal salt, fatty acid metal salt. Examples include negatively charged charge control agents and the like.

The charge control agent is generally available as a commercial product, and a typical example of such a product is Bontron P-51 (Orient Chemistry), which is a positive charge control agent of a quaternary ammonium salt. Industry Co., Ltd.
), TP-415 (manufactured by Hodogaya Chemical Co., Ltd.), negative charge control agent Kayacharge N-3 (manufactured by Nippon Kayaku Co., Ltd.), and calixarene negative charge control agent. Bontron E-89 (Orient Chemical Industry Co., Ltd.)
Made) etc.

The blending amount of the above-mentioned chargeable substance may be appropriately adjusted according to the charge amount of the target decolorizable toner. In addition, when the amount of charging substance is too large,
Moisture resistance of the obtained decolorizable toner tends to be poor and image stability tends to be poor. Further, in order to impart a certain degree of chargeability, it is preferable that the amount of the chargeable substance is 0.3 part or more, especially 1 part or more, based on 100 parts of all the binder resin.

When the decolorizable toner of the present invention is preliminarily blended with an anti-fading agent, it is possible to prevent a decrease in the image density of the printed or copied image of the decolorizable toner. This is because reaction and decomposition of the visible light to near infrared absorbing dye in the decolorizable toner due to light and heat are suppressed.

The anti-fading agent used in the present invention has a function of preventing the visible light to near infrared absorbing dye from fading, discoloring or fading. In the present invention,
At least one selected from heat-resistant antioxidants, metal oxides and metal soaps can be used. Although the reason why the anti-fading agent used in the present invention exhibits such anti-fading action is not clear, it is likely that the heat-resistant antioxidant has a phenolic hydroxyl group and the metal oxide has a basic polar surface. It is considered that the groups are present and that the metallic soap is due to the presence of ionic polar groups such as carboxyl groups.

That is, visible light used in the present invention
The near-infrared absorbing dye is an ionic complex, and the presence of the polar group of the anti-fading agent stabilizes the ion pair of the dyeing complex, which makes the visible-near infrared absorbing dye stable against light and heat. It is thought that the sex will increase.
Therefore, due to this property, when the above-mentioned heat resistant antioxidant, metal oxide or metal soap is present at the same time as the visible light to near infrared absorbing dye used in the present invention, the visible light to near infrared absorbing dye is stable. Next, erasing, discoloring,
It is considered that fading is prevented.

Specific examples of the heat resistant anti-aging agent include:
For example, 2,5-di-t-amylhydroquinone, 2,5
-A hydroquinone derivative-based antiaging agent such as di-t-butylhydroquinone and hydroquinone monoethyl ether; p
-Methyl hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 3,4-hydroxyphenyl-P -Tolyl sulfone, methyl gallate, ethyl gallate, stearyl gallate, n-propyl gallate,
Lauryl gallate, resorcinol, 1-oxy-3-
Methyl-4-isopropylbenzene, 2,6-di-t-
Butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-sec-butylphenol, butylhydroxy Anisole, 2,6-
Anti-aging of alkylated phenols such as di-t-butyl-α-dimethylamino-p-cresol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, styrenated phenols, alkylated phenols and phenol derivative Agents: 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4,4'-butylidenebis- (3-methyl-6-t
-Butylphenol), 2,2-thiobis (4-methyl-6-t-butylphenol), n-octadecyl-3
-(4'-Hydroxy-3'-5'-di-t-butylphenylpropionate and other hindered phenolic antioxidants; tris (nonylphenyl) phosphite, tris (mixed mono- and di-nonylphenyl)) Phosphite, phenyldiisodecylphosphite, diphenylmono (2-ethylhexylphosphite, diphenylmonotridecylphosphite, diphenylisodecylphosphite, diphenylisooctylphosphite, triphenylphosphite, tris (tridecyl) phosphite, tetraphenyl Examples include phosphite-based antioxidants such as dipropylene glycol phosphite, etc. These heat-resistant antioxidants may be used alone or in combination of two or more. Then p-hid Methyl oxybenzoate, propyl p-hydroxybenzoate, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 3,4-hydroxyphenyl-p-tolylsulfone, methyl gallate, Ethyl gallate, stearyl gallate, n-propyl gallate, lauryl gallate, resorcinol and the like are preferable because they are excellent in transparency, whiteness and solubility in a binder resin.

The heat resistant anti-aging agent may be blended with either the binder resin A or the binder resin B, in order to impart sufficient color resistance to the visible light to near infrared ray absorbing dye. Is preferably added to the binder resin A in which the visible light to near infrared absorbing dye is added.

When the resin A for binding is blended with a heat resistant anti-aging agent, in order to fully exhibit the anti-fading property,
The blending amount of the heat resistant anti-aging agent is the resin A100 for binding.
It is desirable that the content is 0.02 part or more, preferably 0.3 part or more. Further, in order to uniformly disperse the heat resistant anti-aging agent in the binder resin A, the content of the heat resistant anti-aging agent is 200 parts or less, preferably 150 parts or less, relative to 100 parts of the binder resin A. Is desirable.

In order not to affect the triboelectric charge amount of the obtained decolorizable toner, the amount of the heat resistant anti-aging agent to be blended is 1 with respect to 100 parts of all the binder resin.
It is desirable that the content is 0 part or less, preferably 7 parts or less.

Specific examples of the metal oxide include, for example, MgO, Al ₂ O ₃ , SiO ₂ , Na ₂ O and SiO _2.
・ MgO, SiO ₂・ Al ₂ O ₃ , Al ₂ O ₃・ Na ₂
O · CO _2, such as _{MgO · Al 2 O 3 · CO} 2 and the like, these metal oxides may be used alone or in combination. Among these metal oxides, Mg
O, a mixture of MgO and SiO _2, a mixture of MgO and Al ₂ O ₃ , Na ₂ O, SiO ₂ · MgO, SiO ₂ · A
l ₂ O ₃ , Al ₂ O ₃ , Na ₂ O.CO ₂ , MgO.A
L ₂ O ₃ .CO _{2 and the} like are particularly preferable because they have excellent anti-fading properties.

The metal oxide may be added to either the binder resin A or the binder resin B, but in order to impart sufficient color resistance to the visible light to near infrared ray absorbing dye, It is preferable to add it to the binder resin A in which the visible light to near infrared ray absorbing dye is added.

When a metal oxide is blended with the binder resin A, the amount of the metal oxide blended should be 1 part with respect to 100 parts of the binder resin A in order to sufficiently exhibit the anti-fading property.
It is desirable that the amount is at least 1 part, preferably at least 3 parts. In order to uniformly disperse the metal oxide in the binder resin A, the amount of the metal oxide blended is 300 parts or less, preferably 150 parts or less, relative to 100 parts of the binder resin A. Is desirable.

If the compounding amount of the metal oxide is too large, the color density of the printed matter tends to be low. It is desirable to adjust it so that it is not more than a part.

By the way, when the amount of the metal oxide compounded is 1 part or more based on 100 parts of all the binder resins,
When an image is formed on a white copying paper, which is generally used for electrophotography, by using an erasable toner, the image is erased by irradiating with visible light and / or near infrared rays, the erased image portion Has the same color on the copy paper, suppresses the gloss unique to the binder resin, and has the same gloss as the copy paper, which makes it difficult to distinguish the image-formed area from the other areas after the color is erased. is there. These advantages are remarkable when a metal oxide containing MgO or SiO ₂ is used among the above metal oxides.
For metal oxides containing iO ₂ , MgO, metal oxides containing SiO ₂ and mixtures thereof, further printing,
Since it does not impair the color developability of the decolorizable toner during image formation, it can be used particularly preferably in the present invention.

If the average particle size of the metal oxide as the anti-fading agent is too large, the image quality may be impaired. Therefore, it is preferably 5 μm or less, especially 2 μm or less. .. Also, the shape and color of the particles are not particularly limited, but in order to eliminate the gloss of the resin for binding, and to eliminate the traces when the formed print or image is erased, the shape of the particles is spherical or elliptical. The color is preferably white because the color of electrophotographic copying paper is generally white.

Specific examples of the metal soap include stearates such as lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, cadmium stearate and lead stearate. Acid salts; lauric acid salts such as cadmium laurate, zinc laurate, calcium laurate, barium laurate; chlorostearate salts such as calcium chlorostearate, barium chlorostearate, cadmium chlorostearate, barium 2-ethylhexylate, 2 2-zinc ethylhexylate, cadmium 2-ethylhexylate, 2-ethylhexylates such as lead 2-ethylhexylate; barium ricinoleate,
Ricinoleate such as zinc ricinoleate and cadmium ricinoleate; Formula: 2PbO.Pb (C ₁₇ H ₃₅ COO) ₂
Such as dibasic lead stearate; salicylates such as lead salicylate, zinc salicylate, tin salicylate, and chromium salicylate; formula: 3PbO.Pb (C ₈ H ₄ O ₄ ) H ₂ O
Such as tribasic lead maleate; Formula: 2PbO.Pb (C
₈ H ₄ O ₄ ) and other dibasic lead phthalates, and these metal soaps may be used alone or in admixture of two or more. Among these metal soaps, zinc stearate, calcium stearate, magnesium stearate, zinc laurate, lead salicylate, zinc ricinoleate, barium ricinoleate, barium 2-ethylhexylate, etc. are used for whiteness and toner. It is preferable because it has a suitable melting point.

The metal soap may be blended with either the resin A for binding or the resin B for binding, but in order to impart sufficient color resistance to the visible light to near infrared ray absorbing dye, It is preferable to add it to the binder resin A in which a visible light to near infrared absorbing dye is added.

When a metal soap is blended with the binder resin A, 0.05 part or more, preferably 0.
It is desirable that the amount is 1 or more. In order to uniformly disperse the metal soap in the binder resin A, the amount of the soap blended is preferably 200 parts or less, and more preferably 150 parts or less, relative to 100 parts of the binder resin A.

The amount of the metal soap blended does not adversely affect the triboelectric charge amount of the decolorizable toner, so that bleeding does not occur on the surface of the decolorizable toner. 1 for every 100 parts of total binding resin used
It is desirable that the content is 0 part or less, preferably 5 parts or less.
In some cases, it has been known that the addition of a dispersant improves the dispersibility of the white filler and improves the whiteness of the image after the image is erased by the decolorizable toner.

In the decolorizable toner of the present invention, a white filler may be blended as a toner property imparting agent into the toner as a decoloring auxiliary component, if necessary. Specific examples of the white filler include, for example, titanium oxide, calcium carbonate, alumina, zinc white, magnesium oxide, magnesium hydroxide, clay, and finely divided silicon. These white fillers may be used alone or in combination of two or more. Used. Among these white fillers, titanium oxide, calcium carbonate, zinc white, and the like are preferable because they have excellent coloring properties.

The amount of the white filler blended is 0.2 parts or more, and more preferably 1 part or more with respect to 100 parts of the total binder resin in order to bring out the effect of blending the white filler. Is desirable. If the blending amount of the white filler is too large, the color density peculiar to the toner tends to be low. Therefore, it is desirable that the amount be 50 parts or less, preferably 30 parts or less with respect to 100 parts of the total binder resin. .

Further, in the present invention, the decolorizable toner may optionally contain, as a toner property imparting agent, an ultraviolet absorber, a plasticizer, a lubricant, etc., alone or in admixture of two or more. Good.

Specific examples of the lubricant include silicone oil, food oil, animal oil, process oil and the like. The amount of the lubricant blended is 0.01 parts or more, and more preferably, 100 parts by weight of the total binder resin used in the decolorizable toner, in order to sufficiently bring out the effect of blending the lubricant. It is desirable that the content be 0.03 parts or more. If the compounding amount of such a lubricant is too large, the image quality of the toner tends to be adversely affected.
It is desirable that the amount is 2 parts or less, preferably 0.5 part or less with respect to the parts.

These additives may be mixed with the dye composition at the same time, but in order to sufficiently disperse and / or dissolve them, it is desirable to mix or knead with the binder resin B in advance.

As described above, the decolorizable toner of the present invention contains a visible light to near infrared ray absorbing dye, a decoloring agent and a binder resin as main components. It can be made by II.

A binder resin A containing the visible light-near infrared absorbing dye and the decoloring agent used in the above-mentioned production method I, and a binding resin A containing the visible light-near infrared absorbing dye used in the above production invention II. The wearing resin A can be prepared by a solution method.

Without using the binder resin A containing at least the visible light to near infrared absorbing dye obtained by the solution method, the binding resin containing at least the visible light to near infrared absorbing dye obtained by the heat kneading method was used. When a decolorizable toner is produced using a wearing resin, it must be heated above the softening point of the binding resin B, and the heat may cause the visible light to near infrared absorbing dye to decompose, causing discoloration or discoloration. Although unavoidable, in the production method of the present invention, the temperature rises only up to the boiling point of the organic solvent under reduced pressure, and the problem of decomposition of the dye due to heat as described above can be solved.

When a cationic dye represented by the general formula (II) is used as a visible light to near infrared ray absorbing dye, the cationic dye is a decolorizable compound represented by the general formula (III). It reacts with an agent and develops a decoloring property via a cationic dye represented by the general formula (I), and sufficient ion exchange is performed in an organic solvent.

By dissolving the visible light to near infrared ray absorbing dye and the decoloring agent in an organic solvent,
Dispersion at the molecular level is achieved, and it becomes possible to improve the reaction probability at the time of erasing.

From this point of view, therefore, the binder resin A is preferably soluble or swellable, preferably soluble in an organic solvent.

The anti-fading agent added to suppress the fading when exposed to natural light during storage is used after being dissolved or dispersed in the binder resin A dissolved in an organic solvent. It is preferable that the binder resin A does not exhibit sufficient solubility at a temperature near the softening point of the binder resin A. Such an anti-fading agent requires an extra shearing force to disperse the anti-fading agent at the time of kneading, a temperature rise occurs due to the shearing force, and promotes decomposition of the visible light to near-infrared absorbing dye. Therefore, it is desirable to dissolve or disperse in an organic solvent.

The boiling point of the organic solvent is preferably below the decomposition temperature of the visible light to near infrared absorbing dye under 1 atm. Here, if the boiling point of the organic solvent is higher than the decomposition temperature of the visible light to near infrared absorbing dye, it is difficult to distill off the solvent by reducing the pressure, and the visible light to near infrared absorbing dye is decomposed. To do.

Specific examples of the organic solvent include alcohol solvents such as methanol, ethanol, isopropanol and butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitrile solvents such as acetonitrile; ethyl acetate and acetic acid. Ester solvents such as butyl; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, anisole; amide solvents such as dimethylformamide; amine solvents such as triethylamine; aromatic solvents such as benzene, toluene, xylene and chlorobenzene Solvents: Halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, trichlene, perklene, etc. Are, acetone Among these, methyl ethyl ketone, methanol, ethanol, acetonitrile, tetrahydrofuran, benzene, toluene, xylene, dichloromethane, chloroform, dichloroethane are preferred. These organic solvents can be used not only alone but also as a mixed solvent.

The amount of the organic solvent is usually 10 parts or more, preferably 20 parts or more, relative to 100 parts of the binder resin in order to sufficiently dissolve the visible light to near infrared ray absorbing dye. Moreover, in order to avoid extra cost for removing the organic solvent, the binder resin 1 is usually used.
It is desirable that the amount is 5000 parts or less, preferably 3000 parts or less with respect to 00 parts.

In the preparation liquid of the dye composition, the anti-fading agent does not need to be dissolved in the organic solvent and may be dispersed in a pulverized state.

In the production method I, for example, the visible light to near infrared ray absorbing dye, the decoloring agent and the binder resin A are dissolved in an organic solvent and mixed or kneaded. If necessary, wax, additives and the like are added thereto. A dried product is obtained by blending and mixing or kneading, and removing the organic solvent from the obtained mixture.

Further, in the production method II, for example, the visible light to near infrared absorbing dye and the binder resin A are dissolved in an organic solvent and mixed or kneaded, and if necessary, a wax, an additive and the like are added thereto. By mixing or kneading by mixing, and removing the organic solvent from the obtained mixture, a dried product is obtained.

The dried product obtained in Process Invention I or Process Invention II can be used as it is, but after roughly crushing with, for example, a hammer mill or a cutter mill,
For example, you may pulverize with a jet mill etc.

In Process Invention I and Process Invention II,
The decolorizable toner is obtained by heating, melting and kneading the dried product, the binding resin B, and if necessary, the decoloring agent and the additive, and then cooling the resulting lump, and coarsely pulverizing the obtained lump with a hammer mill, a cutter mill or the like. Then, it is finely pulverized by a jet mill or the like to have an average particle size of about 5 to 30 μm, and if necessary, classified.

It is preferable that the binder resin B has a softening point not so low in consideration of offset resistance.

For the melt-kneading, a method of melt-kneading the dried product and the binder resin B, and if necessary, a decoloring agent, an additive, etc., using an extruder, a kneader, a roll, etc.,
Resin B for binding, and if necessary, a decoloring agent, an additive, etc. are heated and melted and kneaded in an extruder, and the dried product is supplied in the middle of the extruder by using a constant volume or constant weight feeder, and further heated and melted. Kneading method, binder resin B using a kneader, roll, etc., if necessary, after melting and kneading a decoloring agent, additives, etc., the dried product is added and further heat melting and kneading, binder resin B, if necessary, after melt-kneading a decoloring agent, an additive, etc., the obtained kneaded product and the dried product are melt-kneaded by using a kneader different from the kneader for kneading the binder resin B. There are ways to do it. In the above method, the two kneaders used may be of the same type or of different types.

The kneading of the dried product with the binder resin B and, if necessary, the decoloring agent, the additive and the like is not limited to the above-mentioned method. For example, these components are dissolved or dispersed in a solvent and mixed. It is also possible to obtain a decolorizable toner by pulverizing after distilling off the solvent.

The decolorizable toner of the present invention is irradiated with visible light to near infrared light by means of a semiconductor laser, a halogen lamp, a light emitting diode or the like after printing and fixing it on an image support made of paper or the like. By this, the printed portion can be erased. And
After the printed portion is erased, it is possible to print again by overlapping the erased portion again.

Therefore, the decolorizable toner of the present invention is used for a ticket such as an image support such as copy paper, a ticket which can be printed at the time of boarding and erased at the time of getting off, and can be used repeatedly, a ticket for boarding passengers and various admission tickets. It is also suitable for use in printing of paper pieces.

Next, the decolorizable toner of the present invention and the method for producing the same will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Example of Dye Composition for Decolorable Toner (Production Example No. MB-1 to 14) The raw materials shown in Tables 2 to 3 are shown in Table 4
Based on the blending ratio shown in, a uniform mixed solution obtained by dissolution or dispersion is vacuum heated and dried (manufactured by Okawara Seisakusho Co., Ltd.,
After heating and drying using VB-101), it was cooled, and the obtained dry mixture was pulverized using a cutter mill to obtain a dye composition.

Examples 1 to 22 The raw materials shown in Table 2 and the dye composition for decolorizable toner obtained in Production Example Nos. MB-1 to 14 were mixed at a compounding ratio shown in Table 5 using a mixer. After mixing, the mixture was heated and melted and kneaded using a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Tekko KK), and cooled to obtain a lump.

The obtained lump was crushed using a cutter mill and a jet crusher. After that, classification was performed using an air classifier to obtain a decolorizable toner having a particle size of 5 to 20 μm.

Next, 100 parts by weight of the obtained decolorizable toner was added to fine powder silica (HVK manufactured by Hoechst Japan KK).
-2150) 0.4 parts by weight was uniformly mixed using a mixer to obtain a mixture. 5 parts by weight of this mixture and a silicone resin coated ferrite carrier (Powder Tech Co., Ltd.)
Manufactured by F95-100) was uniformly mixed using a V-type blender to obtain a two-component developer.

The obtained two-component type developer was set in a commercially available copying machine (FT-4525, manufactured by Ricoh Co., Ltd.), and black solid was used as an original for copying. Using a Macbeth densitometer, measure the reflection density of the obtained copy printed matter X1.
It was measured at 0 points, and the average value was taken as x1.

Then, the copy printed matter was set again in the paper tray, and copy printing was carried out again so that the images overlap, that is, the toner layers overlap. Obtained copy print X
The reflection density of 2 was measured by the above method, and the value was defined as x2.

When .vertline.x2-x1.vertline..ltoreq.0.05, the copy printed matter X2 was used as an evaluation image sample.

If | x2-x1 | ≧ 0.05, the above-mentioned re-copying operation is repeated to compare the reflection density xi of the image xi copied and printed with the previously measured reflection density xi-1. , | Xi −xi−1 | ≦ 0.05, the above-described operation was repeated to obtain a copy printed matter Xi as an evaluation image sample. Using this evaluation image sample, the image stability and color erasability as physical properties of the color erasable toner were examined according to the following methods. Further, the decomposition rate of the colored dye in the obtained decolorizable toner was also examined according to the following method.

(Image Stability) The reflection density of the obtained image sample of the decolorizable toner was measured as a density A using a Macbeth densitometer. After leaving the same sample for 24 hours under a fluorescent lamp with an irradiation surface of 1500 lux, the reflection density was taken as the density B and the measurement was carried out in the same manner as described above. The formula: (retention rate) = (density B) / (density A) × The retention rate was determined according to 100 and the image stability was evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Retention rate is 80% or more B: Retention rate is 61% or more and less than 80% C: Retention rate is 41% or more and less than 60% D: Retention rate is less than 41% (Decoloring property) The obtained image sample for evaluation of the decolorizable toner was left in a thermostatic chamber at an ambient temperature of 60 ° C. and was irradiated with light from a halogen lamp. As the halogen lamp, a double end type halogen lamp (QR 85-400 BANFI, manufactured by USHIO INC.) Was used, and the voltage was set to 85V and the color temperature was set to 3190K. The halogen lamp was placed in a thermostat from the surface of the evaluation image sample 10
It was installed at the position of cm.

After the evaluation image sample was left for 3 minutes or more, the halogen lamp was turned on for a predetermined time. The reflection density of the light-irradiated product was measured as the density C using a Macbeth densitometer, and when the condition of the density C ≦ 0.15 was satisfied, it was determined that the color was erased. The predetermined time here is 10, 20, 3
It was set to 0 or 60 seconds.

(Evaluation Criteria) A: Color disappeared after 10 hours of lamp lighting. B: The lamp disappears in 20 seconds, but does not disappear in 10 seconds. C: Color disappears after 30 seconds of lamp lighting, but does not disappear after 20 seconds. D: Color disappears in 60 seconds, but not in 30 seconds. E: Color does not disappear even when the lamp is on for 60 seconds.

(Decomposition rate of colored dye) The obtained decolorizable toner was extracted with acetonitrile, and the concentration of the colored dye in the decolorizable toner was measured by liquid chromatography (HPLC).
Was measured using. The concentration of the colored dye obtained by extraction in the decolorizable toner is defined as concentration E, and the concentration of the colored dye added to the decolorable toner is defined as concentration D, and the formula: (decomposition rate) = ((concentration D)-(concentration E)) / (concentration D)
According to × 100, the decomposition rate of the colored dye at the time of producing the decolorizable toner was determined.

(Evaluation Criteria) A: Decomposition rate is less than 5% B: Decomposition rate is 5% or more and less than 15% C: Decomposition rate is 15% or more and less than 30% D: Decomposition rate is 30% or more Comparative Examples 1-10 After uniformly mixing the raw materials shown in Tables 2 to 3 with the mixing ratio shown in Table 6 using a mixer, the mixture was heated and melted using a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Tekko KK). The mixture was kneaded and cooled to obtain a lump.

The obtained lump was crushed using a cutter mill and a jet crusher. After that, classification was performed using an air classifier to obtain a decolorizable toner having a particle size of 5 to 20 μm.

The physical properties of the obtained decolorizable toner are shown in Examples 1 to 1.
It investigated by the method similar to 22. The results are also shown in Table 6.

[0146]

[Table 22]

[0147]

[Table 23]

[0148]

[Table 24]

[0149]

[Table 25]

[0150]

[Table 26]

From the results shown in Table 5, Examples 1-22
It can be seen that the decolorizable toners obtained by the above production method are excellent in image stability and decolorization, and have a small decomposition rate of the colored dye.

From the above results, according to the method for producing a color erasable toner of the present invention, the dye in the color erasable toner obtained is less decomposed even if it is heated during kneading, and the storage is possible. It can be seen that even when natural light is radiated, there is little adverse effect such as erasing or fading, and when erasing is attempted, a erasable toner that can be easily erased can be obtained.

Examples 23 to 27 In 20 parts by weight of toluene, R shown in Table 7 as a binder resin was used.
20 parts by weight of E-7, 2.5 parts by weight of DY-1 shown in Table 3 as a dye, and 3.3 parts of SE-1 shown in Table 2 as a decolorizer.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 as a binding resin.
-11 to 80 parts by weight, WA as a wax shown in Table 7-
3 parts by weight and CC-1 shown in Table 2 as a charge control agent in the amounts shown in Table 8 were heated to 130 ° C. and melt-kneaded. Then, 26 parts by weight of the dried product was added and melted. After kneading and cooling the obtained kneaded product, it was pulverized to obtain a positively chargeable decolorizable toner having an average particle size of about 10 μm.

[0155]

[Table 27]

The decolorizable toner thus obtained has a toner density of 5
A developer was prepared by mixing with an iron powder carrier (Z-200B, manufactured by Powder Tech Co., Ltd.) for 5 minutes so as to have a weight percentage, and then the charge amount of the decolorizable toner was examined by a blow-off method. The results are shown in Table 8.

[0157]

[Table 28]

Next, based on the results shown in Table 8,
The relationship between the charge control agent amount and the charge amount was investigated. The result is shown in A of FIG.

Comparative Examples 11 to 15 20 parts by weight of RE-7 shown in Table 7 and 80 parts by weight of RE-10 as a binder resin, 3 parts by weight of WA-3 shown in Table 7 as a wax, and Table 3 as a dye. 2.5 parts by weight of DY-1 shown in Table 2 and 3. SE-1 shown in Table 2 as a decoloring agent.
5 parts by weight of CC-1 shown in Table 2 as a charge control agent are shown in Table 9.
The mixture was heated to 130 ° C., melt-kneaded, and the obtained kneaded product was cooled and pulverized to obtain a positively chargeable decolorizable toner having an average particle size of about 10 μm.

Example 23 was carried out using the obtained decolorizable toner.
After preparing a developer in the same manner as in Nos. 27 to 27, the charge amount of the decolorizable toner was examined. The results are shown in Table 9.

[0161]

[Table 29]

Next, based on the results shown in Table 9,
The relationship between the charge control agent amount and the charge amount was investigated. The result is shown in B of FIG.

From the results shown in FIG. 1, Examples 23 to 2
According to the method of 7 (A in FIG. 1), it is understood that the charge amount of the obtained decolorizable toner can be easily adjusted to a predetermined value by adjusting the charge control agent amount.

On the other hand, according to the methods of Comparative Examples 11 to 15 (B in FIG. 1), the charge amount of the decolorizable toner obtained can be adjusted to a predetermined value by adjusting the charge control agent amount. It turns out to be difficult to adjust.

Examples 28 to 31 R shown in Table 7 as a binder resin was added to 20 parts by weight of toluene.
20 parts by weight of E-7, 2.5 parts by weight of DY-1 shown in Table 3 as a dye, and 3.3 parts of SE-1 shown in Table 2 as a decolorizer.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 was used as the binding resin.
-11 to 80 parts by weight, WA as a wax shown in Table 7-
3 parts by weight and CC-5 shown in Table 7 as a charge control agent in the amounts shown in Table 10 were heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added to melt the mixture. After kneading and cooling the obtained kneaded product, it was pulverized to obtain a decolorizable toner having a negatively chargeable average particle size of about 10 μm.

The color-erasable toner thus obtained has a toner density of 5
A developer was prepared by mixing with an iron powder carrier (Z-200B, manufactured by Powder Tech Co., Ltd.) for 5 minutes so as to have a weight percentage, and then the charge amount of the decolorizable toner was examined by a blow-off method. The results are shown in Table 10.

[0168]

[Table 30]

Next, based on the results shown in Table 10, the relationship between the charge control agent amount and the charge amount was examined. The result is shown in FIG.

Comparative Examples 16 to 19 20 parts by weight of RE-7 shown in Table 7 and 80 parts by weight of RE-11 as a binder resin, 3 parts by weight of WA-3 shown in Table 7 as a wax, and Table 3 as a dye. 2.5 parts by weight of DY-1 shown in Table 2 and 3. SE-1 shown in Table 2 as a decoloring agent.
5 parts by weight of CC-5 shown in Table 7 as a charge control agent are shown in Table 1.
The resulting mixture was heated to 130 ° C., melted and kneaded. The obtained kneaded product was cooled and then pulverized to obtain a visible light to near infrared erasable toner having an average particle size of about 10 μm.

Example 28 was carried out using the obtained decolorizable toner.
After the developer was prepared in the same manner as in .about.31, the charge amount of the decolorizable toner was examined. The results are shown in Table 11.

[0172]

[Table 31]

Next, based on the results shown in Table 11, the relationship between the charge control agent amount and the charge amount was examined. The result is shown in B of FIG.

From the results shown in FIG. 2, Examples 28 to 3
According to the method 1 (A in FIG. 2), it is understood that the charge amount of the obtained decolorizable toner can be easily adjusted to a predetermined value by adjusting the charge control agent amount.

On the other hand, according to the methods of Comparative Examples 16 to 19 (B in FIG. 2), the charge amount of the decolorizable toner obtained can be adjusted to a predetermined value by adjusting the charge control agent amount. It turns out to be difficult to adjust.

Example 32 To 20 parts by weight of toluene, R shown in Table 7 as a binder resin was added.
20 parts by weight of E-7, 2.5 parts by weight of DY-1 shown in Table 3 as a dye, and 3.3 parts of SE-1 shown in Table 2 as a decolorizer.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 was used as a binding resin.
-11 to 80 parts by weight, WA as a wax shown in Table 7-
3 parts by weight and 3 parts by weight of CC-1 shown in Table 2 as a charge control agent were heated to 130 ° C. and melt-kneaded.
26 parts by weight of the dried product was added thereto, melt-kneaded, and the resulting kneaded product was cooled and then pulverized to obtain a positively chargeable decolorizable toner having an average particle diameter of about 10 μm.

The decolorizable toner thus obtained has a toner density of 5
Silicone resin coated ferrite carrier (F97-253, manufactured by Powder Tech Co., Ltd.)
After mixing with 5) for 5 minutes to prepare a developer, the charge amount of the decolorizable toner was examined by the blow-off method.
The charge amount was +9.8 μC / g.

Next, the obtained developer was set in a commercially available copying machine (FT-4525, manufactured by Ricoh Co., Ltd.), and copying was performed using a black solid as an original. The reflection density of the obtained copy printed matter X1 was measured with a Macbeth densitometer.
The measurement was carried out at various points, and the average value was defined as x1.

Then, the copy printed matter was set again in the paper tray, and copy printing was performed again so that the images were overlapped, that is, the toner layers were overlapped. Obtained copy print X
The reflection density of 2 was measured by the above method, and the value was defined as x2.

When | x2-x1 | ≤0.05, the copy printed material X2 was used as an evaluation image sample.

When | x2-x1 | ≧ 0.05, the above-mentioned re-copying operation is repeated, and the reflection density xi of the image Xi printed by copying is compared with the previously measured reflection density xi-1. , | Xi−xi−1 | ≦ 0.05, the copy operation xi was used as an evaluation image sample. Using this evaluation image sample, as the physical properties of the decolorizable toner, the image stability was examined in the same manner as in Examples 1 to 22, and the decolorizing property and the background fog density were examined according to the following methods. The results are shown in Table 12.

(1) Decoloring property The obtained decoloring toner evaluation image sample was set at an ambient temperature of 6
It was left in a constant temperature bath of 0 ° C. and was irradiated with light from a halogen lamp. As the halogen lamp, a double end type halogen lamp (manufactured by USHIO INC.,
QRZ 85-400 banfi), voltage 85
V and color temperature of 3190K were set. The halogen lamp was installed at a position 10 cm from the surface of the evaluation image sample in a constant temperature bath.

After the evaluation image sample was left for 3 minutes or more, the halogen lamp was turned on for a predetermined time. The reflection density of the light-irradiated product was measured as the density C using a Macbeth densitometer, and it was determined that the density C ≦ 0.15 was erased. The predetermined time here is 10, 20, 30, and 60 seconds.

(Evaluation Criteria) A: Color disappeared after 10 hours of lamp lighting. B: The lamp disappears in 20 seconds, but does not disappear in 10 seconds. C: Color disappears after 30 seconds of lamp lighting, but does not disappear after 20 seconds. D: Color disappears in 60 seconds, but not in 30 seconds. E: Color does not disappear even when the lamp is on for 60 seconds.

(2) Background Fog Density A white toner image is used as an original to make a color-erasing toner image sample, and the image density on the surface is measured by a reflectometer (Tokyo Denshoku Co., Ltd.).
Manufactured by TC-6DS). Separately from this, the image density on the paper surface before copying was similarly measured. The value obtained by subtracting the value on the paper surface from the obtained sample value is taken as the background fog density, and the closer it is to 0, the smaller the background fog.

Further, when the obtained printed copy was irradiated with visible to near-infrared rays and the decoloring property was examined, it was confirmed that there was no residual color and the color was completely decolorized.

Example 33 In 20 parts by weight of toluene, R shown in Table 7 as a binder resin was used.
20 parts by weight of E-8, 2.5 parts by weight of DY-5 shown in Table 3 as a dye, and 3.2 of SE-2 shown in Table 2 as a decoloring agent.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 as a binding resin.
80 parts by weight of WA-12 and WA shown in Table 7 as wax-
3 parts by weight and 3 parts by weight of CC-3 shown in Table 7 as a charge control agent were heated to 130 ° C. and melt-kneaded.
26 parts by weight of the dried product was added thereto, melt-kneaded, and the resulting kneaded product was cooled and then pulverized to obtain a positively chargeable decolorizable toner having an average particle diameter of about 10 μm.

The color-erasable toner thus obtained has a toner density of 5
Silicone resin coated ferrite carrier (F97-253, manufactured by Powder Tech Co., Ltd.)
After mixing with 5) for 5 minutes to prepare a developer, the charge amount of the decolorizable toner was examined by the blow-off method.
The charge amount was +8.6 μC / g.

Next, using the developer thus obtained, Example 3 was used.
The image stability, decoloring property and background fog density were examined in the same manner as in 2. The results are shown in Table 12.

Further, when the obtained copy printed matter was irradiated with visible to near infrared rays and the decoloring property was examined, it was confirmed that there was no residual color and the color was completely decolorized.

Example 34 In 20 parts by weight of toluene, R shown in Table 7 as a binding resin was used.
20 parts by weight of E-7, 2.5 parts by weight of DY-1 shown in Table 3 as a dye, and 3.3 parts of SE-1 shown in Table 2 as a decolorizer.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 was used as the binding resin.
-11 to 80 parts by weight, WA as a wax shown in Table 7-
3 parts by weight and 3 parts by weight of CC-4 shown in Table 7 as a charge control agent were heated to 130 ° C. and melt-kneaded.
26 parts by weight of the dried product was added to this and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle size of about 10 μm.
m decolorizable toner was obtained.

The color-erasable toner thus obtained has a toner density of 5
After mixing with a ferrite carrier (FB-810, manufactured by Kanto Denka Kogyo Co., Ltd.) so as to have a weight% and mixing for 5 minutes so as to obtain a uniform composition, a developer was prepared. When the charge amount of the color toner was examined, the charge amount was -15.6 μC / g.

Then, the image stability, decoloring property and background fog density were examined in the same manner as in Example 32 except that the applied voltage was adjusted using the obtained developer. The results are shown in Table 12.

Further, when the obtained copy printed matter was irradiated with visible to near infrared rays and the decoloring property was examined, it was confirmed that there was no residual color and the color was completely decolorized.

Example 35 To 20 parts by weight of toluene, R shown in Table 7 as a binder resin was added.
20 parts by weight of E-7, 2.5 parts by weight of DY-5 shown in Table 3 as a dye, and SE-1 shown in Table 2 as a decolorizing agent.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 as a binder resin
-11 to 80 parts by weight, WA as a wax shown in Table 7-
3 parts by weight and 3 parts by weight of CC-5 shown in Table 7 as a charge control agent were heated to 130 ° C. and melt-kneaded.
26 parts by weight of the dried product was added to this and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle size of about 10 μm.
m decolorizable toner was obtained.

The decolorizable toner thus obtained has a toner density of 5
After mixing with a ferrite carrier (FB-810, manufactured by Kanto Denka Kogyo Co., Ltd.) so as to have a weight% and mixing for 5 minutes so as to obtain a uniform composition, a developer was prepared. When the charge amount of the color toner was examined, the charge amount was -16.3 μC / g.

Next, the image stability, the decoloring property and the background fog density were examined in the same manner as in Example 32 except that the applied voltage was adjusted using the obtained developer. The results are shown in Table 12.

When the obtained printed copy was irradiated with visible to near-infrared rays and the erasability was examined, it was found that the printed matter was completely erased without any residual color.

Example 36 In 20 parts by weight of toluene, R shown in Table 7 as a binding resin was used.
20 parts by weight of E-8, 2.0 parts by weight of DY-1 shown in Table 3 as a dye, and 3.3 parts of SE-2 shown in Table 2 as a decolorizer.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 as a binding resin was used.
80 parts by weight of -8, WA-3 shown in Table 7 as a wax
3 parts by weight of CC-1 shown in Table 2 as a charge control agent
After being heated to 130 ° C. and melt-kneaded by weight, 26 parts by weight of the dried product is added and melt-kneaded, and the obtained kneaded product is cooled and pulverized to have an average particle diameter of about 10 μm.
To obtain the decolorizable toner.

The decolorizable toner thus obtained has a toner density of 5
The silicone resin-coated ferrite carrier (P97)
5) and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +10.1 μm.
It was C / g.

Next, using the developer thus obtained, Example 3 was used.
The image stability, decoloring property and background fog density were examined in the same manner as in 2. The results are shown in Table 12.

Further, when the obtained printed copy was irradiated with visible to near-infrared rays and the decoloring property was examined, it was confirmed that there was no residual color and the color was completely decolorized.

Example 37 In 20 parts by weight of toluene, R shown in Table 7 as a binding resin was used.
20 parts by weight of E-9, 2.5 parts by weight of DY-1 shown in Table 3 as a dye, and 3.3 parts of SE-1 shown in Table 2 as a decolorizing agent.
5 parts by weight was added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, RE shown in Table 7 was used as a binding resin.
-11 to 80 parts by weight, WA as a wax shown in Table 7-
3 parts by weight and 3 parts by weight of CC-1 shown in Table 2 as a charge control agent were heated to 130 ° C. and melt-kneaded.
26 parts by weight of the dried product was added to this and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle size of about 10 μm.
m visible light to near infrared erasable toner was obtained.

The obtained decolorizable toner has a toner density of 5
Silicone resin coated ferrite carrier (F97-253, manufactured by Powder Tech Co., Ltd.)
5) and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +10.8 μm.
It was C / g.

Next, using the developer thus obtained, Example 3 was used.
The image stability, decoloring property and background fog density were examined in the same manner as in 2. The results are shown in Table 12.

Further, when the obtained printed copy was irradiated with visible to near infrared rays and the decoloring property was examined, it was confirmed that there was no residual color and the color was completely decolorized.

Example 38 In 20 parts by weight of toluene, R shown in Table 7 as a binding resin was used.
20 parts by weight of E-10, DY-1 shown in Table 3 as a dye
Was added to 3.5 parts by weight of SE-1 shown in Table 2 as a decoloring agent, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, RE shown in Table 7 was used as the binding resin.
-11 to 80 parts by weight, WA as a wax shown in Table 7-
3 parts by weight and 3 parts by weight of CC-1 shown in Table 2 as a charge control agent were heated to 130 ° C. and melt-kneaded.
26 parts by weight of the dried product was added to this and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle size of about 10 μm.
m decolorizable toner was obtained.

The obtained decolorizable toner has a toner density of 5
Silicone resin coated ferrite carrier (F97-253, manufactured by Powder Tech Co., Ltd.)
5) and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +12.4 μm.
It was C / g.

Next, using the developer thus obtained, Example 3 was used.
The image stability, decoloring property and background fog density were examined in the same manner as in 2. The results are shown in Table 12.

When the obtained printed copy was irradiated with visible to near-infrared rays and the erasability was examined, it was found that the printed matter was completely erased without any residual color.

Comparative Example 20 As a binder resin, 20 parts by weight of RE-7 shown in Table 7 and 80 parts by weight of RE-10 were used, and as a wax, 3 parts by weight of WA-3 shown in Table 7 was used as a dye. 2.5 parts by weight of DY-1 shown in Table 3 and 3.5 parts by weight of SE-1 shown in Table 2 as a decolorizing agent were mixed, heated to 130 ° C., melt-kneaded, cooled, and pulverized. And the average particle size is about 10
A decolorizable toner having a particle size of μm was obtained.

The obtained decolorizable toner has a toner density of 5
Silicone resin coated ferrite carrier (F97-253, manufactured by Powder Tech Co., Ltd.)
5) and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +15.4 μm.
It was C / g.

Next, using the developer thus obtained, Example 3 was used.
The image stability, decoloring property and background fog density were examined in the same manner as in 2. The results are shown in Table 12.

Comparative Example 21 20 parts by weight of RE-8 shown in Table 7 and 80 parts by weight of RE-11 shown in Table 7 were used as a binder resin, and as a dye, a compound shown in Table 3 was used.
2.5 parts by weight of DY-5, SE-2 shown in Table 2 as a decoloring agent, 3 parts by weight of WA-3 shown in Table 7 as a wax, and CC-3 shown in Table 7 as a charge control agent. Using 3 parts by weight, heating to 130 ° C., melt-kneading, and then cooling,
By crushing, a decolorizable toner having an average particle diameter of about 10 μm was obtained. It was confirmed that the color of the obtained kneaded product was slightly lightened due to the fading of the dye.

The obtained decolorizable toner has a toner density of 5
Silicone resin coated ferrite carrier (F97-253, manufactured by Powder Tech Co., Ltd.)
5) and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +16.8 μm.
It was C / g.

Next, using the developer thus obtained, Example 3 was used.
The image stability, decoloring property and background fog density were examined in the same manner as in 2. The results are shown in Table 12.

[0224]

[Table 32]

From the results shown in Table 12, Examples 32 to
All of the decolorizable toners obtained in No. 38 are excellent in image stability because they are not discolored by kneading at the time of manufacturing the toner, and are also rapidly decolorized by irradiation with visible light to near infrared rays, and thus are excellent in decolorization. It is also understood that the background fog does not occur during printing.

From the following results, according to the method for producing a decolorizable toner of the present invention, it is easy to adjust the charge amount by the chargeable substance, and thus a decolorizable toner having a desired charge amount can be easily obtained. You can see that you can. Further, since the dye does not fade due to the kneading at the time of manufacturing the decolorizable toner, it can be seen that a decolorizable toner excellent in color developing property can be obtained.

Further, it can be seen that the decolorizable toner of the present invention is capable of rapidly decoloring upon irradiation with visible rays to near infrared rays, and does not cause fog during printing.

Examples 39 to 43 To 20 parts by weight of toluene, 20 parts by weight of RE-13 shown in Table 13 as a binder resin and DY-shown in Table 3 as a dye were used.
2.5 parts by weight of SE-5 shown in Table 13 as a decolorizing agent
Was added to 3.5 parts by weight, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product.

Next, as a binding resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, and CC-1 shown in Table 2 as a charge control agent
The amount shown in Table 14 was used, the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added and melt-kneaded. The obtained kneaded product was cooled, pulverized and positively charged. A decolorizable toner having an average particle size of about 10 μm was obtained.

[0230]

[Table 33]

An iron powder carrier (Z-200B, manufactured by Powder Tech Co., Ltd.) and the obtained decolorizable toner were mixed for 5 minutes to prepare a developer so that the toner concentration would be 5% by weight. The charge amount of the decolorizable toner was examined by the blow-off method. The results are shown in Table 14.

[0232]

[Table 34]

Next, based on the results shown in Table 14, the relationship between the charge control agent amount and the charge amount was examined. The result is shown in A of FIG.

Comparative Examples 22 to 26 20 parts by weight of RE-13 shown in Table 13 and 80 parts by weight of RE-19 as a binder resin, 3 parts by weight of WA-3 shown in Table 7 as a wax, and Table 3 as a dye. DY-
1 was used in an amount of 2.5 parts by weight, SE-1 shown in Table 2 as a decoloring agent was 3.5 parts by weight, and CC-5 shown in Table 7 was used as a charge control agent in an amount shown in Table 15 and heated to 130 ° C. After melt-kneading, the obtained kneaded product was cooled and then pulverized to obtain a positively chargeable decolorizable toner having an average particle size of about 10 μm.

Example 39 was prepared using the obtained decolorizable toner.
After preparing a developer in the same manner as in No. 43 to No. 43, the charge amount of the decolorizable toner was examined. The results are shown in Table 15.

[0236]

[Table 35]

Next, based on the results shown in Table 15, the relationship between the charge control agent amount and the charge amount was examined. The result is shown in B of FIG.

From the results shown in FIG. 3, Examples 39 to 4
According to the method of No. 3 (A in FIG. 3), it can be seen that the charge amount of the obtained decolorizable toner can be easily adjusted to a predetermined value by adjusting the charge control agent amount.

On the other hand, according to the methods of Comparative Examples 22 to 26 (B in FIG. 3), the charge amount of the decolorizable toner obtained can be adjusted to a predetermined value by adjusting the charge control agent amount. It turns out to be difficult to adjust.

Examples 44 to 47 20 parts by weight of toluene, 20 parts by weight of RE-13 shown in Table 13 as a binder resin, and DY-shown in Table 3 as a dye.
1 and 2.5 parts by weight of SE-1 shown in Table 2 as a decoloring agent were added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, as the binding resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, CC-5 shown in Table 7 as a charge control agent.
The amount shown in Table 16 was used, the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added and melt-kneaded. The obtained kneaded product was cooled, ground, and negatively charged. A decolorizable toner having an average particle size of about 10 μm was obtained.

The color-erasable toner thus obtained and an iron powder carrier (Z-200B manufactured by Powder Tech Co., Ltd.) were mixed for 5 minutes to prepare a developer so that the toner concentration would be 5% by weight. The charge amount of the decolorizable toner was examined by the blow-off method. The results are shown in Table 16.

[0243]

[Table 36]

Next, based on the results shown in Table 16, the relationship between the charge control agent amount and the charge amount was examined. The results are shown in A of FIG.

Comparative Examples 27 to 30 20 parts by weight of RE-13 shown in Table 13 and 80 parts by weight of RE-19 as a binder resin, 3 parts by weight of WA-3 shown in Table 7 as a wax, and Table 3 as a dye. DY-
1 was used in an amount of 2.5 parts by weight, SE-1 shown in Table 2 was used as a decoloring agent in an amount of 3.5 parts by weight, and CC-5 shown in Table 7 was used as a charge control agent in the amounts shown in Table 17 and heated to 130 ° C. Then, after melt-kneading, the obtained kneaded product was cooled and then pulverized to obtain a visible light to near infrared erasable toner having a positively chargeable average particle diameter of about 10 μm.

Using the obtained decolorizable toner, Example 44
After preparing a developer in the same manner as in No. 47 to No. 47, the charge amount of the decolorizable toner was examined. The results are shown in Table 17.

[0247]

[Table 37]

Next, based on the results shown in Table 17, the relationship between the charge control agent amount and the charge amount was examined. The result is shown in B of FIG.

From the results shown in FIG. 4, Examples 44 to 4
According to the method of 7 (A in FIG. 4), it is understood that the charge amount of the obtained decolorizable toner can be easily adjusted to a predetermined value by adjusting the charge control agent amount.

On the other hand, according to the methods of Comparative Examples 27 to 30 (B in FIG. 4), the charge amount of the decolorizable toner obtained can be adjusted to a predetermined value by adjusting the charge control agent amount. It turns out to be difficult to adjust.

Example 48 20 parts by weight of toluene, 20 parts by weight of RE-14 shown in Table 13 as a binder resin, and DY-shown in Table 3 as a dye were used.
1 and 2.5 parts by weight of SE-1 shown in Table 2 as a decoloring agent were added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, as a binding resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, CC-5 shown in Table 7 as a charge control agent.
3 parts by weight of the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added to the mixture to melt-knead the mixture. A decolorizable toner having a particle size of about 10 μm was obtained.

A developer was prepared by mixing a silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) and the obtained decolorizable toner for 5 minutes so that the toner concentration would be 5% by weight. After that, when the charge amount of the decolorizable toner was examined by the blow-off method, the charge amount was +9.8 μC / g.

Next, the obtained developer is applied to a copying machine (Co., Ltd.).
Ricoh FT-4525), set the image stability,
The color erasability and background fog density were examined in the same manner as in Examples 1 to 22, and the color residue was examined according to the following method.
The results are shown in Table 18.

(1) Color Remaining (Yellowness Degree) The evaluation image sample of the obtained decolorizable toner was decolored under the condition that it could be completely decolored.

After erasing, 5 sheets of each, including uncopied paper, were randomly attached to the vertical wall surface after erasing, and visually distinguishing the erasing copier sample and uncopied paper from a distance of 5 m. I did. This identification is 5 males and 5 females.
A total of 10 people performed the evaluation after the color was erased and the copied sample was regarded as an uncopied paper after erasing.

(Evaluation Criteria) A: 40 to 50 points B: 30 to 39 points C: 20 to 29 points D: 0 to 19 points Example 49 20 parts by weight of toluene, RE- shown in Table 13 as a binder resin. 20 parts by weight of 14 and DY- shown in Table 3 as a dye
1 and 2.5 parts by weight of SE-1 shown in Table 2 as a decoloring agent were added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, as the binding resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, and CC-1 shown in Table 2 as a charge control agent
3 parts by weight of the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle diameter of about A 10 μm decolorizable toner was obtained.

Decolorizable toner obtained and silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) so that the toner concentration becomes 5% by weight.
Were mixed and mixed for 5 minutes to form a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +10.5 μC.
/ G.

Next, using the developer thus obtained, Example 4 was used.
In the same manner as in No. 8, the image stability, decoloring property, color residue and background fog density were examined. The results are shown in Table 18.

Example 50 20 parts by weight of toluene, 20 parts by weight of RE-15 shown in Table 13 as a binder resin, and DY-shown in Table 3 as a dye were used.
1 and 2.5 parts by weight of SE-1 shown in Table 2 as a decoloring agent were added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, as a binding resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, and CC-1 shown in Table 2 as a charge control agent
3 parts by weight of the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle diameter of about A 10 μm decolorizable toner was obtained.

[0263] The obtained decolorizable toner and silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) so that the toner concentration would be 5% by weight.
Were mixed and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +9.2 μC /
It was g.

Next, using the developer thus obtained, Example 4 was used.
In the same manner as in No. 8, the image stability, decoloring property, color residue and background fog density were examined. The results are shown in Table 18.

Example 51 20 parts by weight of toluene, 20 parts by weight of RE-16 shown in Table 13 as a binder resin, and DY-shown in Table 3 as a dye were used.
2.0 parts by weight of 1 and 3.5 parts by weight of SE-1 shown in Table 2 as a decolorizing agent were added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, as a binding resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, and CC-1 shown in Table 2 as a charge control agent
3 parts by weight of the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle diameter of about A 10 μm decolorizable toner was obtained.

The decolorizable toner obtained and a silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) so that the toner concentration becomes 5% by weight.
Were mixed and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +10.1 μC.
/ G.

Next, using the developer thus obtained, Example 4 was used.
In the same manner as in No. 8, the image stability, decoloring property, color residue and background fog density were examined. The results are shown in Table 18.

Example 52 20 parts by weight of toluene, 20 parts by weight of RE-13 shown in Table 13 as a binder resin, and DY-shown in Table 3 as a dye.
1 and 2.5 parts by weight of SE-1 shown in Table 2 as a decoloring agent were added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, as the binding resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, and CC-1 shown in Table 2 as a charge control agent
3 parts by weight of the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle diameter of about A 10 μm visible to near-infrared decolorizable toner was obtained.

The decolorizable toner obtained and a silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) so that the toner concentration becomes 5% by weight.
Were mixed and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +10.8 μC.
/ G.

Next, using the developer thus obtained, Example 4 was used.
In the same manner as in No. 8, the image stability, decoloring property, color residue and background fog density were examined. The results are shown in Table 18.

Example 53 20 parts by weight of toluene, 20 parts by weight of RE-18 shown in Table 13 as a binder resin, and DY-shown in Table 3 as a dye.
1 and 2.5 parts by weight of SE-1 shown in Table 2 as a decoloring agent were added, and the mixture was stirred and dissolved to prepare a uniform composition, which was then dried to obtain a dried product. I got it.

Next, as the binder resin, R shown in Table 13 was used.
80 parts by weight of E-19, WA shown in Table 7 as a wax
-3 is 3 parts by weight, and CC-1 shown in Table 2 as a charge control agent
3 parts by weight of the mixture was heated to 130 ° C., melt-kneaded, and then 26 parts by weight of the dried product was added and melt-kneaded. The obtained kneaded product was cooled and pulverized to have an average particle diameter of about A 10 μm decolorizable toner was obtained.

[0275] The decolorizable toner obtained and a silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) so that the toner concentration was 5% by weight.
Were mixed and mixed for 5 minutes to form a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +9.6 μC /
It was g.

Next, using the developer thus obtained, Example 4 was used.
In the same manner as in No. 8, the image stability, decoloring property, color residue and background fog density were examined. The results are shown in Table 18.

Comparative Example 31 20 parts by weight of RE-13 shown in Table 13 and 80 parts by weight of RE-15 were used as a binder resin, and 3 parts by weight of WA-3 shown in Table 7 was used as a wax. Table 3
2.5 parts by weight of DY-1 shown in Table 2 and 3.5 parts by weight of SE-1 shown in Table 2 as a decolorizing agent were mixed, heated to 130 ° C., melt-kneaded, cooled, and pulverized. A decolorizable toner having an average particle diameter of about 10 μm was obtained.

The decolorizable toner obtained and a silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) so that the toner concentration becomes 5% by weight.
Were mixed and mixed for 5 minutes to obtain a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +15.4 μC.
/ G.

Next, using the developer thus obtained, Example 4 was used.
In the same manner as in No. 8, the image stability, decoloring property, color residue and background fog density were examined. The results are shown in Table 18.

Comparative Example 32 20 parts by weight of RE-13 shown in Table 13 and 80 parts by weight of RE-19 were used as a binder resin, and 2.5 parts by weight of DY-13 shown in Table 13 was used as a dye. As a colorant, 3.5 parts by weight of SE-1 shown in Table 2, 3 parts by weight of WA-3 shown in Table 7 as a wax, and 3 parts by weight of CC-1 shown in Table 2 as a charge control agent were used. After heating, melt-kneading, then cooling and crushing, the average particle size is about 10 μm.
To obtain the decolorizable toner.

Decolorizable toner obtained and silicone resin-coated ferrite carrier (F97-2535, manufactured by Powder Tech Co., Ltd.) so that the toner concentration becomes 5% by weight.
Were mixed and mixed for 5 minutes to form a uniform composition to prepare a developer, and the charge amount of the decolorizable toner was examined by the blow-off method. The charge amount was +16.8 μC.
/ G.

Next, using the developer thus obtained, Example 4 was used.
In the same manner as in No. 8, the image stability, decoloring property, color residue and background fog density were examined. The results are shown in Table 18.

[0283]

[Table 38]

From the results shown in Table 18, Examples 48-
The decolorizable toner obtained in No. 53 is excellent in image stability because it does not fade due to kneading at the time of manufacturing the toner, and also has excellent decoloring property because it is rapidly erased by irradiation with visible light to near infrared rays. It can be seen that there is no residual color and no background fog occurs during printing.

From the above results, according to the method for producing a visible light ray-near-infrared color erasable toner of the present invention, it is easy to adjust the charge amount by the charging substance, so that the visible light ray having a desired charge amount can be used. It is understood that the near-infrared color erasable toner can be easily obtained. Further, since the dye does not fade due to the kneading during the production of the visible light to near infrared decolorizable toner, a visible light to near infrared decolorable toner excellent in color developability can be obtained.

Further, it can be seen that the visible light to near infrared ray erasable toner of the present invention has the effect of rapidly erasing the color by irradiation with visible light to near infrared ray and not causing fog during printing.

[0287]

EFFECTS OF THE INVENTION The decolorizable toner of the present invention has the effect that it can be decolored quickly at the time of erasing and the quality of the formed image is excellent.

Further, according to the method for producing a decolorizable toner of the present invention, it is easy to adjust the charge amount of the decolorizable toner obtained, and it is difficult for the dye to fade due to the kneading during the production of the toner. Is played.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the charge control agent amount and the charge amount of the decolorizable toners obtained in Examples 23 to 27 and Comparative Examples 11 to 15.

FIG. 2 is a graph showing the relationship between the charge control agent amount and the charge amount of the decolorizable toners obtained in Examples 28 to 31 and Comparative Examples 16 to 19.

FIG. 3 is a graph showing the relationship between the charge control agent amount and the charge amount of the decolorizable toners obtained in Examples 39 to 43 and Comparative Examples 22 to 26.

FIG. 4 is a graph showing the relationship between the charge control agent amount and the charge amount of the decolorizable toners obtained in Examples 44 to 47 and Comparative Examples 27 to 30.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03G 9/08 361 381 (72) Inventor Akira Yamauchi 5-1 Ogimachi, Kawasaki-ku, Kawasaki-shi, Kanagawa Showa Denko Chemicals Research Laboratory (72) Inventor Yuki Abe 3-2-15 Meiwadori, Hyogo-ku, Kobe City, Hyogo Prefecture Bando Chemical Co., Ltd. (72) Inventor Harumi Nagami Meiwatsuzo, Hyogo-ku, Kobe City, Hyogo Prefecture 2-15, Bando Kagaku Co., Ltd. (72) Inventor Kiyotaka Yamaguchi 3-2-15 Meiwatsu, Hyogo-ku, Kobe-shi, Hyogo Bando Kagaku Co., Ltd. (72) Takayuki Yoshida Meiwa, Hyogo-ku, Kobe-shi, Hyogo 3-2-15 Tsudori, Bando Kagaku Co., Ltd. (72) Inventor Mitsuhiro Uchino 3-21-15 Meiwadori, Hyogo-ku, Kobe, Hyogo Bando Kagaku Within the corporation

Claims (15)

[Claims] 1. A decolorizable toner containing a visible light to near infrared ray absorbing dye, a decoloring agent and a binding resin as main components, wherein the binding resin A contains a visible light to near infrared ray absorbing dye. Is dispersed in the binding resin B, and the decolorizing agent is blended in at least one of the binding resin A and the binding resin B. 2. The decolorizable toner according to claim 1, wherein the binder resin A and the binder resin B are incompatible with each other. 3. The decolorizable toner according to claim 1, wherein a decoloring agent is mixed with the binder resin B. 4. The decolorizable toner according to claim 1, wherein a decoloring agent is mixed with the binder resin A. 5. The binding resin A is 8 to 30 mg KOH / g
The decolorizable toner according to claim 1, which has an acid value of. 6. The binder resin A has a b * value of 20 in L * a * b color coordinates measured by a color difference meter in a 30% ethyl acetate solution.
The decolorizable toner according to claim 1, which is as follows. 7. The decolorizable toner according to claim 1, wherein the binding resin B contains a chargeable substance. 8. A method for producing a decolorizable toner containing a visible light to near infrared absorbing dye, a decoloring agent and a binder resin as main components, the method comprising: A method for producing a color-erasable toner, which comprises melting and kneading a binder resin A and a binder resin B contained therein, heating, melting and kneading the mixture, followed by pulverization. 9. A visible light to near infrared absorbing dye, a decolorizing agent and a binder resin are dissolved in an organic solvent and mixed or kneaded, and then the organic solvent is removed to remove the visible light to near infrared absorbing dye and the decolorizing agent. The method for producing a decolorizable toner according to claim 8, wherein a binder resin A containing a colorant is prepared. 10. A method for producing a decolorizable toner containing a visible light to near infrared ray absorbing dye, a decoloring agent and a binder resin as main components, the method comprising a visible ray to near infrared ray absorbing dye. A method for producing an erasable toner, which comprises melting and kneading a resin A, a binder resin B and an erasing agent with heating, cooling and pulverizing. 11. A binding resin containing a visible light-near infrared absorbing dye after dissolving the visible light-near infrared absorbing dye and the binding resin in an organic solvent, mixing or kneading, and then removing the organic solvent. The method for producing a decolorizable toner according to claim 10, wherein A is prepared. 12. The method for producing a decolorizable toner according to claim 8, wherein the binder resin A is incompatible with the binder resin B. 13. The binding resin A is 8 to 30 mgKOH /
The method for producing a decolorizable toner according to claim 8 or 10, which has an acid value of g. 14. The binding resin A has a b * value of 2 at L * a * b color coordinates measured by a color difference meter in a 30% ethyl acetate solution.
The method for producing a decolorizable toner according to claim 8 or 10, which is 0 or less. 15. The method for producing a decolorizable toner according to claim 8, wherein the binder resin B contains a chargeable substance.