JP2000214626A - Near infrared absorber for electrophotographic toner, and electrophotographic toner containing the absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near infrared absorber for electrophotographic toner enhanced in light energy absorption factor and in the efficiency of conversion of light energy into heat energy by using a specified near infrared absorber. SOLUTION: This near infrared absorber to be used is represented by the formula in which X is an H or halogen atom or a hydroxy, alkoxy, aryloxy, alkylthio, alkylamino, arylamino, or alkylarylamino; each of R1-R8 is an H atom or an alkyl or aryl or alkoxy or aryloxy group; each of Y1-Y3 is an H atom or an aryl or alkylsulfonyl or arylsulfonyl or alkylcarbonyl or arylcarbonyl group; (n) is an integer of 0-14; L is an integer of 1-8; (m) is an integer of 0-14; n+2 L+m=16; M is 2 H atoms or a divalent metal atom or a trivalent or a tetravalent substituted metal atom or an oxy metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared absorber for electrophotographic toner used for developing an electrostatic latent image in electrophotography, and an electrophotographic toner containing the near-infrared absorber. More specifically, the present invention relates to a near-infrared absorbing agent for an electrophotographic toner and an electrophotographic toner which give a fixed image having particularly high fixing strength in a flash fixing method.

[0002]

2. Description of the Related Art Conventionally, electrophotography uses a photoconductive insulator, applies a uniform electrostatic charge to the photoconductive insulator by corona discharge or the like, and uses various means to form the photoconductive insulator. Forming an electrostatic latent image by irradiating a light image on the insulator,
Next, the latent image is developed and visualized using toner, and if necessary, a toner image is transferred onto a recording medium such as paper, and then the recording medium is pressed, heated, irradiated with solvent vapor, light, or the like. A copy is obtained by fixing the toner image thereon. The toner image transferred onto the recording medium adheres to the recording medium in a powder state to form an image. If the image is rubbed with a finger before fixing, the image is destroyed. In order to fix a toner image on a recording medium, it is necessary to melt the toner and fix it on the recording medium. As a method therefor, there are means such as the above-mentioned pressurization, heating, irradiation of solvent vapor, light and the like. Among them, flash fixing, which is a light fixing method, is performed by flashing a discharge tube such as a xenon flash lamp (800 to 1000 n).
The fixing method according to m) has the following characteristics.

[0005] Because of non-contact fixing, the resolution of an image during development is not degraded. Quick start is possible without waiting after power-on. It does not fire even if the recording medium is clogged in the fixing unit due to the system down. Glued paper, preprinted paper, paper of different thickness, etc.
Fixing is possible regardless of the material and thickness of the recording medium.

In this flash fixing method, when a flash of a discharge tube of a xenon flash lamp is irradiated, the toner absorbs the light energy of the flash and the temperature rises to soften and melt.
Adheres and penetrates the recording medium. After the flash irradiation is over,
The temperature drops and solidifies to form a fixed image, and fixing is completed.
The image is fixed on the recording medium, and the collapse of the image is eliminated.

In this flash fixing method, although the colorant contained in the conventional color toner has an absorption in the visible region, it does not absorb the flash in the near infrared region of the discharge tube used for such flash fixing. There is almost no conversion efficiency to heat energy, and sufficient fixing cannot be obtained. In addition, black coloring materials such as carbon black, which is a coloring agent contained in black toner, have an absorbing ability also in the near infrared region, but the conversion efficiency to heat energy cannot be said to be sufficient, and there are various problems. Have a point.

One of the important characteristics of the toner in the flash fixing method is that the toner needs to efficiently absorb flash light and convert light energy into heat energy. Such absorption of light energy and light energy /
In order to obtain properties relating to thermal energy conversion, toners have been proposed in which an inorganic compound such as carbon black or an organic compound near-infrared absorbing dye is added and dispersed.

For example, in JP-A-58-102247, a cyanine dye is disclosed, and in JP-A-60-57858, a benzenedithiol-based metal complex dye is disclosed in JP-A-Hei.
JP-A-191492 discloses an aminium-based dye. These dyes have poor heat resistance of the dye itself, for example, are thermally decomposed when heated and melt-kneaded with a binder resin to produce a toner, and the near-infrared absorbing ability is reduced. It has various problems, such as insufficient light-to-heat conversion, and has not reached a satisfactory fixing strength. In addition, although proposals have been made with other near-infrared absorbing dyes, some dyes themselves are also colored because they also absorb in the visible region. There were problems that a clear color tone could not be recorded and that the fixing strength was poor due to insufficient light-to-heat conversion.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a near-infrared absorber for toner for electrophotography, which has improved light energy absorption, light energy / heat energy conversion efficiency, and enhanced fixing strength by flash fixing. An object of the present invention is to provide an electrophotographic toner containing the near infrared absorbing agent.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a near-infrared ray absorber represented by the following general formula (1) is used as a near-infrared ray absorber for electrophotographic toner. It has been found that the use of an absorber has excellent properties of light energy absorption and light energy / thermal energy conversion efficiency, and the present invention has been completed.

That is, the present invention relates to a near-infrared absorbing agent for an electrophotographic toner represented by the following general formula (1). Further, the present invention relates to an electrophotographic toner containing the near-infrared absorbing agent.

[0011]

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(Wherein X is each independently a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkoxy group,
An aryloxy group which may be substituted, an alkylthio group which may be substituted, an arylthio group which may be substituted, an alkylamino group which may be substituted, an arylamino group which may be substituted, Represents an optionally substituted alkylarylamino group, and adjacent Xs may form a 5- or 6-membered ring through two heteroatoms. R _{1 to} R ₈ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group. Represent. Y _{1 to} Y ₃
Are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted It is a good alkylcarbonyl group or an optionally substituted arylcarbonyl group, and Y ₂ and Y ₃ on the same nitrogen may form a cyclic imide. At least one of each of independent Y ₁ to Y _{3 is} an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted alkylcarbonyl group, and an optionally substituted aryl group or each independently of the at least one pair of Y ₂ and Y ₃ on the same nitrogen forms a cyclic imide. n represents an integer of 0 to 14, 1 represents an integer of 1 to 8, m represents an integer of 0 to 14, and n + 2l + m = 16. M represents two hydrogen atoms, a divalent metal atom or 3
Represents a substituted or tetravalent substituted metal or oxymetal. )

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The near-infrared absorbing agent for an electrophotographic toner of the present invention is a near-infrared absorbing agent represented by the general formula (1). In the general formula (1), examples of the halogen atom represented by X include fluorine, chlorine, bromine, and iodine. The alkoxy group which may be substituted is not particularly limited. For example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group,
-Butoxy group, iso-butoxy group, sec-butoxy group, n-pentoxy group, iso-pentoxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy Group, n-nonyloxy group, methoxyethoxy group, ethoxyethoxy group, ethoxyethoxyethoxy group, hydroxyethoxyethoxy group, diethylaminoethoxy group, aminoethoxy group, n-butylaminoethoxy group, benzylaminoethoxy group, methylcarbonylaminoethoxy group Phenylcarbonylaminoethoxy group, benzyloxy group and the like.

The aryloxy group which may be substituted is not particularly restricted but includes, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, naphthoxy and the like. No.

The alkylthio group which may be substituted is not particularly restricted but includes, for example, methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-dimethyl-propylthio group, n-
Hexylthio, cyclohexylthio, n-heptylthio, 2-ethylhexylthio, n-octylthio, n-nonylthio, methoxyethylthio, ethoxyethylthio, propoxyethylthio, butoxyethylthio, aminoethyl Thio group, n-butylaminoethylthio group, benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonylaminoethylthio, methylsulfonylaminoethylthio group, phenylsulfonylaminoethylthio group, dimethylaminoethylthio group, And a diethylaminoethylthio group.

The arylthio group which may be substituted is not particularly restricted but includes, for example, phenylthio, naphthylthio, 4-methylphenylthio,
4-ethylphenylthio group, 4-propylphenylthio group, 4-t-butylphenylthio group, 4-methoxyphenylthio group, 4-ethoxyphenylthio group, 4-aminophenylthio group, 4-alkylaminophenylthio Group,
4-dialkylaminophenylthio, 4-phenylaminophenylthio, 4-diphenylaminophenylthio, 4-hydroxyphenylthio, 4-chlorophenylthio, 4-bromophenylthio, 2-methylphenylthio , 2-ethylphenylthio, 2-propylphenylthio, 2-t-butylphenylthio, 2
-Methoxyphenylthio group, 2-ethoxyphenylthio group, 2-aminophenylthio group, 2-alkylaminophenylthio group, 2-dialkylaminophenylthio group,
2-phenylaminophenylthio group, 2-diphenylaminophenylthio group, 2-hydroxyphenylthio group,
4-dimethylaminophenylthio group, 4-methylaminophenylthio group, 4-methylcarbonylaminophenylthio group, 4-phenylcarbonylaminophenylthio group, 4-methylsulfonylaminophenylthio group, 4-
And a phenylsulfonylaminophenylthio group.

The alkylamino group which may be substituted is not particularly restricted but includes, for example, a methylamino group, an ethylamino group, an n-propylamino group and an i-amino group.
Examples thereof include a so-propylamino group, a butylamino group, a pentylamino group, a dipentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, and a benzylamino group.

Examples of the arylamino group which may be substituted are not particularly restricted but include, for example, a phenylamino group, a 4-methylphenylamino group, a 4-methoxyphenylamino group, a hydroxyphenylamino group, And a naphthylamino group.

Examples of the alkylarylamino group which may be substituted include, but are not particularly limited to, phenylmethylamino group, phenylethylamino group, phenylpropylamino group and the like.

Examples of the substituents in which adjacent Xs may form a 5- or 6-membered ring via two heteroatoms include the following substituents.

[0021]

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In the above formula (1), examples of the optionally substituted alkyl group represented by R _{1 to} R ₈ include a methyl group,
Ethyl group, n-propyl group, iso-propyl group, n-
Butyl group, iso-butyl group, sec-butyl group, n-
Pentyl group, iso-pentyl group, 1,2-dimethyl-
Examples thereof include a propyl group, an n-hexyl group, and a benzyl group.

Examples of the aryl group which may be substituted include a phenyl group, a 2-mercaptophenyl group, a 3-mercaptophenyl group, a 4-mercaptophenyl group and a 2-mercaptophenyl group.
Examples include a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.

Examples of the alkoxy group which may be substituted include methoxy, ethoxy, n-propoxy and is
o-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, n-pentoxy group, iso-
Examples include a pentoxy group and a benzyloxy group.

Examples of the aryloxy group which may be substituted include a phenoxy group, a 2-methylphenoxy group,
-Methylphenoxy group, 4-methylphenoxy group, naphthoxy group and the like.

In the above formula (1), examples of the optionally substituted alkyl group represented by Y _{1 to} Y ₃ include a methyl group,
Ethyl group, n-propyl group, iso-propyl group, n-
Butyl group, iso-butyl group, sec-butyl group, n-
Pentyl group, iso-pentyl group, 1,2-dimethyl-
Propyl group, n-hexyl group, 1,3-dimethyl-butyl group, 1,2-dimethylbutyl group, n-heptyl group,
1,4-dimethylpentyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, n
-Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n
-Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-
Eicosyl group, benzyl group, sec-phenylethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4
-Methylbenzyl group, 2-phenylethyl group, 3-dimethylaminopropyl group, 2-dimethylaminoethyl group,
2-diisopropylaminoethyl group, 2-diethylaminoethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, 2- (1-piperidinyl) ethyl group, 3- (1-piperidinyl) propyl Group, 3-
(4-morpholinyl) propyl group, 3- (4-morpholinyl) ethyl group, 2- (1-pyrrolidinyl) ethyl group, 2-pyridylmethyl group, furfuryl group and the like.

Examples of the aryl group which may be substituted include a phenyl group, a 2-mercaptophenyl group, a 3-mercaptophenyl group, a 4-mercaptophenyl group and a 2-mercaptophenyl group.
Examples include a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.

Examples of the alkylcarbonyl group which may be substituted include an acetyl group (methylcarbonyl group),
Propionyl group, butyryl group, iso-butyryl group, valeryl group, iso-valeryl group, trimethylacetyl group, hexanoyl group, t-butylacetyl group, heptanoyl group, octanoyl group, 2-ethylhexanoyl group,
Nonanoyl, decanoyl, undecanoyl, lauroyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, oleoyl, cyclopentanecarbonyl, cyclohexanecarbonyl , 6
-Chlorohexanoyl group, 6-bromohexanoyl group,
Trifluoroacetyl group, pentafluoropropionyl group, perfluorooctanoyl group, 2,2,4,4
5,5,7,7,7-nonafluoro-3,6-dioxaheptanoyl group, methoxyacetyl group, 3,6-dioxaheptanoyl group and the like.

Examples of the optionally substituted arylcarbonyl group include benzoyl, o-chlorobenzoyl, m-chlorobenzoyl, p-chlorobenzoyl, o-fluorobenzoyl, m-fluorobenzoyl, p-fluorobenzoyl group, o-acetylbenzoyl group, m-acetylbenzoyl group, p-acetylbenzoyl group, o-methoxybenzoyl group, m-methoxybenzoyl group, p-methoxybenzoyl group, o-methylbenzoyl group, m- Examples include a methylbenzoyl group, a p-methylbenzoyl group, a pentafluorobenzoyl group, and a 4- (trifluoromethyl) benzoyl group.

Examples of the alkylsulfonyl group which may be substituted include a methylsulfonyl group, an ethylsulfonyl group, a trifluoromethylsulfonyl group and the like.

Examples of the arylsulfonyl group which may be substituted include a phenylsulfonyl group and a 4-methylphenylsulfonyl group.

Examples of the cyclic imide group formed by Y ₂ and Y ₃ on the same nitrogen include succinimide, maleic imide, phthalic imide and the like.

In the above formula (1), examples of the divalent metal represented by M include Cu (II), Zn (II), Fe (II),
Co (II), Ni (II), Ru (II), Rh (II), P
d (II), Pt (II), Mn (II), Mg (II), Ti
(II), Be (II), Ca (II), Ba (II), Cd
(II), Hg (II), Pb (II), Sn (II) and the like.

Examples of monosubstituted trivalent metals include Al-C
1, Al-Br, Al-F, Al-I, Ga-Cl, G
a-F, Ga-I, Ga-Br, In-Cl, In-B
r, In-I, In-F, Tl-Cl, Tl-Br, T
1-1, Tl-F, Al-C ₆H_Five, Al-C₆H_Four(CH
_Three), In-C₆H_Five, In-C₆H_Four(CH_Three), In-C
₆H_Five, Mn (OH), Mn (OC₆H_Five), Mn [OSi
(CH_Three)_Three], Fe-Cl, Ru-Cl and the like.
You.

Examples of disubstituted tetravalent metals include CrCl
_Two, SiCl_Two, SiBr_Two, SiF_Two, SiI_Two, ZrC
l_Two, GeCl_Two, GeBr_Two, GeI_Two, GeF_Two, Sn
Cl_Two, SnBr_Two, SnF_Two, TiCl_Two, TiBr_Two,
TiF_Two, Si (OH)_Two, Ge (OH)_Two, Zr (O
H)_Two, Mn (OH)_Two, Sn (OH)_Two, TiR_Two, Cr
R_Two, SiR_Two, SnR_Two, GeR_Two[R is an alkyl group;
Phenyl, naphthyl, and derivatives thereof], S
i (OR ')_Two, Sn (OR ')_Two, Ge (OR ') _Two,
Ti (OR ')_Two, Cr (OR ')_Two[R 'is alkyl
Group, phenyl group, naphthyl group, trialkylsilyl group,
Table showing dialkylalkoxysilyl groups and their derivatives
], Sn (SR ")_Two, Ge (SR ")_Two(R "is Al
Kill, phenyl, naphthyl and derivatives thereof
Represents).

Examples of oxymetals include VO, MnO,
TiO and the like.

Preferred compounds among the compounds represented by the above formula (1) are those wherein X is each independently a hydrogen atom or a halogen atom, and R _{1 to} R ₈ are each independently a hydrogen atom or a substituted one. A good alkyl group, wherein at least one of Y ₁ to Y _{3 is} an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted alkylcarbonyl group or And a compound in which 2l + m is 6 to 16. More preferred compounds are those wherein M is two hydrogen atoms, Cu, AlCl, TiO or VO.

In the compound represented by the formula (1),
By increasing the number of 1 and / or m, the absorption wavelength becomes longer, and the wavelength range of the xenon flash lamp can be widely covered.

The near-infrared absorber for electrophotography of the present invention is produced by a method described in JP-A-8-225752. For example, after reacting a phthalocyanine compound represented by the following general formula (2) with at least one of a 2-aminothiophenol derivative represented by the following general formula (3) or an analog thereof, sulfoamidation and / or amide And / or an imidization reaction.

[0040]

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(Wherein Z is independently a halogen atom, a nitro group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, Represents an arylthio group, an alkylamino group which may be substituted, or an arylamino group which may be substituted, p represents an integer of 4 to 16, and at least 4 of Zs are a halogen atom. M represents two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent substituted metal or oxymetal)

[0042]

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(In the formula, Y ₄ represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and R _{9 to} R ₁₂ represent a hydrogen atom, an optionally substituted alkyl group. Group, an optionally substituted aryl group,
Represents an optionally substituted alkoxy group or an optionally substituted aryloxy group. )

In the general formula (2), a halogen atom represented by Z, an alkoxy group which may be substituted, an aryloxy group which may be substituted, an alkylthio group which may be substituted, Examples of the arylthio group which may be substituted, the alkylamino group which may be substituted, and the arylamino group which may be substituted include those described above.

In the general formula (3), an optionally substituted alkyl group or an optionally substituted aryl group represented by Y ₄ , or a substituted or unsubstituted aryl group represented by R _{9 to} R _12. Examples of the alkyl group which may be substituted, the aryl group which may be substituted, the alkoxy group which may be substituted, and the aryloxy group which may be substituted include those described above.

The reaction between the phthalocyanine compound represented by the general formula (2) and the 2-aminothiophenol derivative represented by the general formula (3) or an analog thereof is carried out under the usual nucleophilic substitution reaction conditions, , Sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium t-butoxide and the like. Alternatively, when the compound of formula (3) isolated as a sodium salt, a potassium salt or a zinc salt is used, the amount of the base used can be reduced or the reaction can be carried out without using the base at all.

This reaction may be carried out in the presence of a solvent. In this case, dimethylformamide (D
MF), dimethyl sulfoxide (DMSO), N, N '
Polar solvents such as dimethylimidazolidinone (DMI) and sulfolane; ketone solvents such as acetone and methyl ethyl ketone; and aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene and dichlorobenzene.

The reaction conditions are usually such that a phthalocyanine compound represented by the general formula (2) and a base (4 to 100 equivalents based on the phthalocyanine compound) are mixed with a solvent (1 to 1000 times by weight based on the phthalocyanine compound). Or a 2-aminothiophenol derivative represented by the general formula (3) or an analog thereof (4 to 30 times equivalent to the phthalocyanine compound (2)) while stirring or dissolving. And react at 50-220 ° C. Equation (3)
The addition of the 2-aminothiophenol derivative represented by the formula (1) or an analog thereof may be performed before, during, or after the temperature is raised. Further, they may be added at once, or may be added in portions. Further, the phthalocyanine compound may be added after the base is added using the 2-aminothiophenol derivative itself as a solvent. The 2-aminothiophenol derivative or analog used may be one kind or a mixture of several kinds. Further, a nucleophilic reagent other than the 2-aminothiophenol derivative represented by the formula (3) or an analog thereof, such as thiols and alcohols, can also be added at the same time.

The reaction may be carried out under normal pressure or under pressure, and a quaternary ammonium salt, crown ether or the like may be added as a reaction accelerator.

After completion of the reaction, the next sulfoamidation, amidation or imidation reaction is produced by a conventional method. For example, a sulfoamidating reagent and / or an amidating reagent and / or an imidizing reagent (1 to 100 equivalents based on the phthalocyanine compound (2)) are added to the reaction mixture, and the reaction is continued, or the reaction mixture is once an intermediate. After isolating the phthalocyanine compound reacted with the 2-aminothiophenol derivative, a sulfoamidation, amidation or imidation reaction is performed to obtain a target near-infrared absorbing agent. After completion of the reaction, the target compound is precipitated, usually by discharging into water or an alcohol solution such as methanol, ethanol, propanol, butanol, and pentanol, separated by filtration, and dried to obtain a near-infrared absorbing agent. .

Further, the obtained near-infrared absorbing agent can be purified by column chromatography, if necessary.

Next, the electrophotographic toner of the present invention will be described.

The toner for electrophotography of the present invention comprises at least a binder resin, the above-mentioned near-infrared absorbing agent, and a coloring agent.

The binder resin used is not particularly limited, but generally used polymer resins can be used, for example, polystyrene, copolymers of styrene and acrylate or methacrylate, polyesters Resins, epoxy resins, polyamide resins, phenolic resins, hydrocarbon resins, petroleum resins and the like,
These may be used alone or as a mixture.

The near-infrared absorbing agent is as described above, and the amount of addition depends on the flash fixing strength of the toner and the like, but is preferably 0.01 to 50% by weight based on the binder resin. Furthermore, in order to control the fixing strength, other near-infrared absorbing dyes, for example, anthraquinone dyes, cyanine dyes, squarylium dyes, aminium dyes, immonium dyes, nickel dithiol dyes, phthalocyanine dyes, naphthalocyanine A system dye or the like may be added.

The colorant is not particularly limited, but includes pigments and dyes which are generally used. For example, in the case of a black toner, carbon black and a nigrosine dye are used. Is a quinophthalone dye, azo dye, azomethine dye, anthraquinone dye, benzidine dye, quinacridone dye, rhodamine dye, quinoimine dye, xanthene dye, phthalocyanine dye, triphenylmethane dye, etc. Which can produce a color tone of The amount of these used is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the binder resin.

The electrophotographic toner may further include, if necessary, various plasticizers, release agents, ultraviolet absorbers, etc. for the purpose of adjusting charge control agents, fluidity modifiers, thermal characteristics, physical characteristics, and the like. Can also be added.

Examples of the charge control agent include a quaternary ammonium salt, a guanamine derivative, an amine-modified styrene-acryl resin, and a benzothiazole derivative as the positive charge control agent, and a metal complex of alkyl salicylic acid as the negative charge control agent. And polycyclic salicylic acid metal salts, metal complexes of dicarboxylic acids, and the like, whereby the charge can be adjusted. The amount to be added is determined in consideration of conditions such as the chargeability of the resin, the content of the colorant, and the chargeability of other additives, etc., and is composed of a binder resin, a near-infrared absorber and a colorant. 0.01 to 5 parts by weight of the colored toner resin
Parts by weight are preferred.

Further, as the fluidity modifier, for example, colloidal silica may be mentioned, and its addition amount is preferably 0.01 to 5 parts by weight based on 1 part by weight of the colored toner resin. Further, a polyolefin-based wax and a natural wax can be used in combination.

The toner can be manufactured by a known method. For example, a binder resin, a near-infrared absorbing agent, and a coloring agent, and various additives to be added as necessary, are melt-kneaded and uniformly dispersed by a kneader for pressure, a roll mill, an extruder, and the like, and then a pulverizer, a jet mill. And the like, and classified by a classifier to obtain a desired toner.

The toner thus produced can be used by any of the known fixing methods such as hot roll, pressure fixing, solvent fixing, and light fixing. Great effect. The electrophotographic toner of the present invention can be mixed with a carrier and used as a two-component toner. Examples of the carrier include a ferrite powder, a fine powder magnetic substance dispersed in a resin, and a resin-coated carrier in which the carrier surface is coated with a resin.

[0062]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, "parts" indicates parts by weight.

Example 1 Synthesis Example of Near-Infrared Absorber (a) I. Pigment Green 7 10.0
Part, 2- (n-octylamino) thiophenol
7 parts and 39.2 parts of potassium carbonate were added to 200 parts of dimethylformamide and reacted at 120 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then discharged into 500 parts of methanol. The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to isolate 26.5 parts of a phthalocyanine compound. Further, the phthalocyanine compound is converted to pyridine 3
To 70 parts, 7.0 parts of acetyl chloride was added (at room temperature,
(1 hour), and then reacted at 50 ° C. for 2 hours.

The reaction mixture was discharged into 1000 parts of ice water.
The precipitate was collected by suction filtration, washed with water and methanol, and then dried to obtain 29.4 parts of a near-infrared absorbent of the following formula (a).

[0065]

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Preparation Method of Toner Binder resin (styrene-acrylic acid copolymer; “Hymer TB-1000F” (trade name) manufactured by Sanyo Chemical Industries) 95
Part, the above-mentioned near-infrared absorbing agent (a) 2 parts, and the colorant (C.I.
Pigment Blue 15: 1) 5 parts were coarsely pulverized with a ball mill and then finely pulverized with a jet mill pulverizer. Further classification was performed to select and prepare 1 to 20 μm, and 10 parts of the carrier iron (manufactured by Nippon Tekko Co., Ltd., “EFV25
(0/400) (trade name)) was uniformly mixed to obtain a blue toner.

This blue toner is set in a commercial copying machine,
After recording the unfixed image, flash fixing was performed using a xenon flash lamp. Using a cellophane tape (manufactured by Sumitomo 3M, "Scotch Mending Tape" (trade name)), the recorded image obtained from this was used to calculate the residual ratio of the recorded image after the tape was peeled off according to the following formula, and evaluated as the fixing strength. . As a result, the residual ratio was 90% and the fixing strength was good.

Residual rate (%) = (image density after tape peeling) / (image density before tape peeling) × 100 (image density is measured by Macbeth densitometer “TR-924”)

Example 2 Synthesis Example of Near-Infrared Absorber (b) I. Pigment Green 7 10.0
Part, 2- (n-octylamino) thiophenol19.
0 parts, 5.55 parts of 2-aminothiophenol and 39.2 parts of potassium carbonate were added to 200 parts of dimethylformamide and reacted at 120 ° C. for 10 hours. After the reaction mixture was cooled to room temperature, it was discharged into 500 parts of methanol. The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to isolate 25.6 parts of a phthalocyanine compound. Further, the phthalocyanine compound and 1.0 part of 4-dimethylaminopyridine were added to 300 parts of pyridine, and 13.0 parts of benzoyl chloride was added (at room temperature for 1 hour), followed by reaction at 50 ° C. for 2 hours.

The reaction mixture was discharged into 1000 parts of ice water.
The precipitate was collected by suction filtration, washed with water and methanol, and then dried to obtain 30.4 parts of a near-infrared absorbent of the following formula (b).

[0071]

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Preparation Method of Toner A blue toner was prepared in the same manner as in the preparation method of the toner of Example 1, except that the near-infrared absorbing agent (a) was changed to the near-infrared absorbing agent (b). A peeling test was performed on the thus-prepared blue toner in the same manner as in Example 1. As a result, the residual ratio was 91%, and the fixing strength was good.

Example 3 Synthesis Example of Near-Infrared Ray Absorber (c) In Example 2, p-butane was replaced with benzoyl chloride.
A compound was synthesized in the same manner except that trifluoromethylbenzoyl chloride was used, and the following near-infrared absorbing agent (c)
I got

[0074]

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Preparation Method of Toner A blue toner was prepared in the same manner as in the preparation method of the toner of Example 1, except that the near-infrared absorbing agent (a) was changed to the near-infrared absorbing agent (c). A peeling test was performed on the thus-prepared blue toner in the same manner as in Example 1. As a result, the residual ratio was 92%, and the fixing strength was good.

Example 4 Synthesis Example of Near-Infrared Absorber (d) I. Pigment Green 7 10.0
Parts, 16.7 parts of 2-aminothiophenol and 39.2 parts of potassium carbonate were added to 200 parts of dimethylformamide and reacted at 120 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, it was discharged into 500 parts of methanol. The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to isolate 19.5 parts of a phthalocyanine compound. Further, the phthalocyanine compound and 1.0 part of 4-dimethylaminopyridine were added to 300 parts of pyridine, and 25.0 parts of 2-ethylhexanoyl chloride was added (at room temperature for 1 hour).
The reaction was performed at 50 ° C. for 2 hours. The reaction mixture was ice water 1000
Was discharged to the department. After collecting the precipitate by suction filtration, washing with water,
After washing with methanol, drying was performed to obtain 23.4 parts of a near-infrared absorbing agent represented by the following formula (d). I got

[0077]

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Method for Preparing Toner Binder resin (polyester resin; NE-21, manufactured by Kao Corporation)
50 "(trade name) ART-2009), 1320 parts, 10 parts of the above-mentioned near-infrared absorbent (d), and a coloring agent (CI Pi)
gment Yellow 81) 80 parts, a charge control agent (“Kayacharge N-4” (trade name), manufactured by Nippon Kayaku) 2
0 parts, wax (manufactured by Sanyo Chemical, "Viscole 550P")
(Trade name)) After melt-kneading 50 parts, the mixture was roughly pulverized by a ball mill and then finely pulverized by a jet mill pulverizer. Further classification was performed to select and prepare 1 to 20 μm.

Next, a ferrite carrier (manufactured by Hitachi Metals, Ltd.)
"KBN-100") was uniformly mixed to obtain a yellow toner. The yellow toner thus produced was subjected to a peel test in the same manner as in Example 1. As a result, the residual rate was 87%, and the fixing strength was good.

Example 4 A toner was prepared as follows using the above-mentioned near-infrared absorbing agent (c).

95 parts of a binder resin (epoxy resin; "Epiclon 1191" (trade name), manufactured by Dainippon Ink and Chemicals, Inc.)
5 parts of the above-mentioned near-infrared absorbing agent (c) and a coloring agent (CI Pi)
gment Red 207) and 1 part of a charge control agent ("Bontron P-51" (trade name), manufactured by Orient Chemical Co., Ltd.) are melt-kneaded, coarsely ground by a ball mill, and then finely ground by a jet mill. did. Classify 1
〜20 μm was selected and prepared. Next, a ferrite carrier ("KBN-100" (trade name), manufactured by Hitachi Metals, Ltd.) was uniformly mixed to obtain a red toner. A peeling test was performed on the thus-prepared red toner in the same manner as in Example 1. As a result, the residual ratio was 90%, and the fixing strength was good.

Examples 5 to 15 Toners were prepared in the same manner as in Example 1, except that the near-infrared absorbing agent shown in Table 1 was used instead of the near-infrared absorbing agent (a). A peel test was performed. As a result, in the peeling test using all the toners containing the near infrared absorbing agent, the residual ratio was as high as 80% or more, and the fixing strength in flash fixing was excellent.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

Comparative Example A toner was prepared in the same manner as in Example 1 except that the following compound (e) was used, and the fixing property was evaluated. As a result, the residual ratio of the recorded image in the tape peeling test was 30% or less, and the fixing strength was poor and the fixing was insufficient as compared with the toner using the near-infrared absorbing agent of the present invention.

[0088]

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[0089]

The near-infrared absorber for electrophotographic toner according to the present invention has excellent properties of light energy absorption and light energy / heat energy conversion efficiency. It can be suitably used for the toner used in the system.

Continued on the front page (72) Inventor Kazuhiro Seino 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Ryu 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Mitsui Chemicals Inc. ) 2H005 AA06 CA22 FB03

Claims (5)

[Claims] 1. A near-infrared absorbent for toner for electrophotography represented by the following general formula (1). Embedded image (In the formula, X is each independently a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted A good arylthio group, an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted alkylarylamino group, wherein adjacent X is a 5-membered ring through two heteroatoms or A six-membered ring may be formed.
R _{1 to} R ₈ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group. Represent. Y _{1 to} Y ₃ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, An alkylcarbonyl group which may be substituted,
It is an arylcarbonyl group which may be substituted, and Y ₂ and Y ₃ on the same nitrogen may form a cyclic imide.
However, at least one of each of independent Y ₁ to Y _{3 is} an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted alkylcarbonyl group, and an optionally substituted alkylsulfonyl group. An arylcarbonyl group or Y ₂ on the same nitrogen independently of each other
And at least one pair of Y ₃ forms a cyclic imide. n
Represents an integer of 0 to 14; l represents an integer of 1 to 8;
Represents an integer of 0 to 14, and n + 2l + m = 16.
M represents two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent substituted metal or oxymetal. ) 2. In the general formula (1), X is each independently a hydrogen atom or a halogen atom; R _{1 to} R ₈ are each independently a hydrogen atom or an optionally substituted alkyl group; Wherein at least three of Y ₁ to Y ₃ are an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted alkylcarbonyl group, or an optionally substituted arylcarbonyl group The near-infrared absorber for an electrophotographic toner according to claim 1, wherein 2l + m is 6 to 16. 3. M is two hydrogen atoms, Cu, AlC
3. The method according to claim 1, wherein the metal is one of l, TiO, and VO.
The near-infrared absorber for electrophotographic toner according to the above. 4. An electrophotographic toner comprising the near-infrared absorbing agent for an electrophotographic toner according to claim 1. 5. The electrophotographic toner according to claim 4, wherein the toner is for flash fixing electrophotography.