JP3513792B2 - Color toner for electrophotography - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in an electrophotographic color copying machine or color printer.

[0002]

2. Description of the Related Art Conventionally, in a color copying machine or a color printer using electrophotography, a toner in which a colorant is dispersed in resin particles is generally used.

Alternatively, a toner having a colorant attached to the surface of resin particles is also used. For example, JP-A-63-
23166, JP-A-63-2075, and JP-A-4-4-2.
No. 43267 proposes a method of mechanically or chemically attaching a colorant to the surface. However, with such a method, it is difficult to obtain a sufficient coloring effect because only the toner surface is colored, and further, due to separation from the surface or the like, the charging performance is changed or the above heat roller fixing is used. In some systems, there is a problem of polluting the roller surface.

A toner in which a colorant is dispersed inside resin particles is widely used. Color reproducibility and OVER HEAD P
Not only the transparency of images in ROJECTOR (hereinafter abbreviated as OHP), but also light resistance for maintaining them stably.

The transparency of the OHP image described here means O
The transparency of the HP image and the degree of hue change of the transmission color in the OHP image with respect to the reflection color on the paper. When a toner using a pigment as a colorant is used, it has excellent light resistance, but since it is insoluble, it forms dispersed particles of several tens of nm to several hundreds of nm, resulting in reduced transparency and transmission in an OHP image. Hue change of color is a problem. For example, JP-A-2-210363 and JP-A-62-15705.
No. 1 and No. 62-255956, C.I.
I. PIGMENT YELLOW 12, 13, 14,
Disazo pigments such as 16, 17 and JP-A-6-11871
No. 5, C.I. I. PIGMENT YEL
When a toner using a pigment such as LOW185 is used, the pigment is insoluble and easily aggregates to form secondary particles and tertiary particles to form dispersed particles of several tens to several hundreds nm.
There is a problem of a decrease in saturation and a decrease in transparency in an OHP image.

As a countermeasure against this, pigments have been previously used as a processed color material by a flushing method or a masterbatch method. However, this method inevitably increases the cost because the number of manufacturing steps increases. On the other hand, when a toner using a dye as a colorant is used,
Since it has solubility and is sufficiently dispersed, it has excellent transparency in an OHP image, but has a problem that the light resistance is inferior to that of a pigment. The C.I. described in JP-A-3-276161. I. SOLVENT YELLOW 162, C.I. described in JP-A-2-207274. I. Dir
CT YELLOW160, C.I. I. SOLVENTYELLOW
Although dyes such as 112 are known, although these dyes have high transparency and can obtain an OHP image without hue change, they are inferior in light resistance to pigments and cannot maintain stable performance for a long time.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color toner having high saturation and good light resistance even if a colorant is not processed in advance, a small hue change in an OHP image, and high transparency. To provide.

[0008]

[Means for Solving the Problems] In order to achieve the above object,
As a result of earnest studies by the present inventors, the above object was achieved by the color toner containing the azomethine dye according to the present invention.

(1) In a color toner comprising at least a resin and a colorant, the colorant is represented by at least the following general formula (1), and A in the general formula (1) is a general formula.
(2), (3), (5), (6) and (8) to (10)
Color toner for electrophotography which is characterized by containing a is Ru azomethine dye represented by any one of the.

General formula (1) A = NB (wherein A represents an atomic group necessary for the azomethine dye to have absorption in the visible region and / or the near infrared region, and B represents an aromatic hydrocarbon ring. Or represents a nonmetallic atomic group necessary for forming a 5- or 6-membered heteroaromatic ring.)

[0011]

[Chemical 3]

(In the formula, R ^{1 to} R ¹³ and R ^{15 to} R ²⁷ represent a hydrogen atom or a substituent, and L ^{1 to} L ³ represent a nitrogen atom or-
It represents CR ²⁸ =. However, R ²⁸ represents a hydrogen atom or a substituent. ) (2) A of the azomethine dye represented by the general formula (1)
The structure of the portion represented by the general formula (2), (3),
Be represented by any of (8), (9), and (10)
(1) The electrophotographic color toner according to (1). (3) A of the azomethine dye represented by the general formula (1)
The structure of the portion represented by the general formula ( 9) and (1
The electrophotographic color toner according to (2), which is represented by any one of 0).

[0013]

( 4 ) The structure of the portion represented by B of the azomethine dye represented by the general formula (1) is represented by the following general formula B-1.
Characterized by being represented by any one of .about.B-14
The color toner for electrophotography according to any one of (1) to (3) .

[0015]

[Chemical 4]

(In the general formulas B-1 to B-14, R ⁷
Is an alkyl group or an aryl group, R ³³ is OR ³⁴ , NR ³⁵ R
Represents ³⁶ represents R ^34, R ^35, R ³⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Also R
³⁵ and R ³⁶ , R ³⁵ and B, and R ³⁶ and B may cooperate with each other to form a ring, and B may further have a condensed ring. or,
* -Represents a connector with N. ) ( 5 ) The structure of the portion represented by B of the azomethine dye represented by the general formula (1) is the same as in the general formulas B-3, B-10,
The color toner for electrophotography according to ( 4 ), which is represented by any one of B-11, B-12, B-13, and B-14.

( 6 ) The structure of the portion represented by B of the azomethine dye represented by the general formula (1) is represented by the above general formula B-1.
The electrophotographic color toner according to ( 4 ), which is represented by any one of 0, B-11, and B-14.

( 7 ) In an electrophotographic color toner comprising at least a resin and a colorant, the colorant contains at least an azomethine dye represented by the following general formula (1), and the general formula (1 ) A = N-B A is the above general formula (2) , (3), (5), (6) and
(8) to (10) represented by any one of, B is characterized by being represented by any one of formulas B-10, B-11 and B-14 (5) for electrophotography according Color toner.

( 8 ) In a color toner for electrophotography comprising at least a resin and a colorant, the colorant contains at least an azomethine dye represented by the following general formula (1), and the general formula (1 ) A = N-B A is represented by either the general formula (9) or (10), and B is the general formula B-10, B-11, or B-14 .
The electrophotographic color toner according to ( 7 ), which is represented by any of the above.

The present invention will be described more specifically.

As described above, the azomethine dye has the following structure.

General formula (1) A = NB (wherein A represents an atomic group necessary for the azomethine dye to have absorption in the visible region and / or the near infrared region, and B represents an aromatic hydrocarbon ring. Or a nonmetallic atomic group necessary for forming a 5- or 6-membered heteroaromatic ring.) General formula (1)
In, A is a general formula (2), (3), (5), (6)
And represented by any of (8) to (10), and as B , any of the following general formulas B-1 to B-14 is preferable.

[0023]

[Chemical 5]

In the general formulas B-1 to B-14, R ⁷ is an alkyl group or an aryl group, R ³³ is OR ³⁴ , NR ³⁵ R ³⁶
And R ³⁴ , R ³⁵ , and R ³⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. See also R ³⁵
And R ³⁶ , R ³⁵ and B, and R ³⁶ and B may cooperate with each other to form a ring, and B may further have a condensed ring.

R ³⁴ , R ³⁵ and R ³⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, a nitro group, a carboxyl group or a cyano group. , Halogen atom, aryl group, heterocyclic group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide Group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Sulfinyl group, phos Amino group, a phosphinyl group, phosphoryl group, phospho group, a phosphino group, an aryloxycarbonyl group or may be further substituted by a substituent which is linked with acyl groups. R ³⁵ and R ³⁶ may be the same or different.

More specifically, examples of R ³⁴ , R ³⁵ and R ³⁶ will be shown.

The alkyl group is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl and 2-hydroxy. Ethyl, 3-hydroxypropyl, benzyl, 2-methylsulfonylaminoethyl, 3-methylsulfonylaminopropyl, 2-
Methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-methoxycarbonylethyl, 2-carbamoylethyl, hexyl, 2
-Hydroxypropyl, 4-hydroxybutyl, 2-cyanoethyl, 2-acetoxyethyl.

The aryl group is an aryl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl,
Naphthyl and p-methoxyphenyl. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. May be one or more, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl,
They are imidazolyl and pyrazolyl. R ³⁵ and R ³⁶ may cooperate with each other to form a ring.

The ring to be formed is not particularly limited, but is preferably a group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, for example, a pyrrolidino, piperazino or morpholino group.

These rings may have a substituent allowed by R ³⁵ . R ³⁵ and R ³⁶ are unsubstituted alkyl groups, hydroxyl groups, alkoxycarbonyl groups,
An alkyl group substituted with a substituent linked with a cyano group, an alkoxy group, an acylamino group, an acyloxy group, or a sulfonamide group is preferable.

R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acylamino group, Amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy Represents a group, an azo group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphono group, a phosphinyl group, a phosphoryl group, a phospho group, a phosphino group, an aryloxycarbonyl group, and an acyl group.

These are alkyl groups, alkynyl groups, aryl groups, hydroxyl groups, nitro groups, cyano groups, halogen atoms, carboxylic acid groups, sulfonic acid groups or other substituents formed by oxygen, nitrogen, sulfur or carbon atoms. Further, it may be replaced.

More specifically, examples of the substituent of R ³¹ will be shown.

The halogen atom is, for example, a fluorine atom or a chlorine atom.

The alkyl group is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl and 2-hydroxycarbonyl. ethyl,
2-methoxyethyl, benzyl, 2-methylsulfonylaminoethyl, 2-methylsulfonylethyl, cyclopentyl, 2-acetamidoethyl.

The aryl group is an aryl group having a carbon number of 6 to 18, and examples thereof include phenyl, naphthyl and p-hydroxycarbonylphenyl.

As the heterocyclic group, oxygen having 1 to 5 carbon atoms,
A 5- or 6-membered heterocycle containing one or more nitrogen or sulfur atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl,
It is pyrazolyl. Alkoxy group has 1 to 1 carbon atoms
2, preferably an alkoxy group having 1 to 6 carbon atoms, for example,
Methoxy, ethoxy and 2-methoxyethoxy.

The aryloxy group has 6 to 18 carbon atoms.
Examples of the aryloxy group include phenoxy, p-methoxyphenoxy and p-tolyloxy.

The acylamino group has 1 to 12 carbon atoms,
Preferred is an acylamino group having 1 to 6 carbon atoms, such as acetamide, 2-methoxypropionamide, or benzoylamino.

The alkylamino group has 1 to 1 carbon atoms.
2, preferably an alkylamino group having 1 to 6 carbon atoms, such as dimethylamino, diethylamino, 2-hydroxyamino, 2-hydroxymethylamino, 2-hydroxyethylamino, 2-hydroxypropyl or 2-hydroxybutylamino. .

The anilino group is an anilino group having 6 to 18 carbon atoms, such as anilino, m-nitroanilino and N-.
It is methylanilino. The ureido group has 1 to 1 carbon atoms.
12, preferably 1 to 6 ureido groups, for example, methylureido and N, N-dimethylureido.

The sulfamoylamino group has 0 carbon atoms.
To 12, preferably a sulfamoylamino group having 0 to 6 carbon atoms, such as dimethylsulfamoylamino and methylsulfamoylamino.

The alkylthio group has 1 to 12 carbon atoms,
Preferred is an alkylthio group having 1 to 8 carbon atoms, for example, a methylthio, ethylthio or 2-phenoxyethylthio group.

The arylthio group is an arylthio group having 6 to 18 carbon atoms, for example, phenylthio or 4-cyanophenylthio group. The alkoxycarbonylamino group is an alkoxycarbonylamino group having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and examples thereof include methoxycarbonylamino, ethoxycarbonylamino and 3-methylsulfonylpropoxycarbonylamino.

The sulfonylamino group has 1 to 1 carbon atoms.
2, preferably a sulfonylamino group having 1 to 6 carbon atoms, such as methylsulfonylamino, p-toluenesulfonylamino or 2-methoxyethylsulfonylamino group.

The carbamoyl group has 1 to 12 carbon atoms,
Preferably, it is a carbamoyl group having 1 to 6 carbon atoms, for example,
Carbamoyl, N, N-dimethylcarbamoyl or N
An ethylcarbamoyl group.

The sulfamoyl group has 0 to 1 carbon atoms
2, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as a sulfamoyl group, a dimethylsulfamoyl group or an ethylsulfamoyl group.

The sulfonyl group is an aliphatic or aromatic sulfonyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl or 2-chloroethylsulfonyl group.

The alkoxycarbonyl group has 1 carbon atom.
To 12, preferably an alkoxycarbonyl group having 1 to 6 carbon atoms, for example, a methoxycarbonyl, ethoxycarbonyl or t-butoxycarbonyl group.

The heterocyclic oxy group is a 5- or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms. The number of heteroatoms formed and the type of element are 1
There may be one or more, for example, 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy or 2-pyridyloxy groups.

The azo group is an azo group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, for example, phenylazo, 2-
Hydroxy-4-propanoylphenylazo or 4-
It is a methanesulfonylphenylazo group.

The acyloxy group has 1 to 12 carbon atoms,
Preferred is an acyloxy group having 1 to 6 carbon atoms, for example, acetoxy, benzoyloxy, 4-hydroxybutanoyloxy group.

The carbamoyloxy group has 1 to 1 carbon atoms.
12, preferably a carbamoyloxy group having 1 to 6 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-
It is a methylcarbamoyloxy or N-phenylcarbamoyloxy group.

The silyl group is a silyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyl, isopropyldiethylsilyl or t-butyldimethylsilyl group.

The silyloxy group has 3 to 12 carbon atoms,
Preferred is a silyloxy group having 3 to 6 carbon atoms, for example, a trimethylsilyloxy, triethylsilyloxy or diisopropylethylsilyloxy group.

The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonylamino, 4-cyanophenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino groups.

The imide group is an imide group having 4 to 12 carbon atoms, for example, N-succinimide or N-phthalimide group.

The heterocyclic thio group contains at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms.
To 6-membered saturated or unsaturated heterocyclic thio groups, the number of heteroatoms forming the ring and the number of kinds of elements may be one or more, for example, 2-benzothiazolylthio or 2 A pyridylthio group.

The sulfinyl group has 1 to 12 carbon atoms,
It is preferably a sulfinyl group having 1 to 6 carbon atoms, for example, a methanesulfinyl group, a benzenesulfinyl group or an ethanesulfinyl group.

The phosphono group, phosphinyl group, phosphoryl group, phospho group and phosphino group have 2 to 1 carbon atoms.
2, preferably a group having 2 to 6 carbon atoms, such as methoxyphosphonyl, ethoxyphosphonyl or phenoxyphosphonyl group. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, for example,
It is a phenoxycarbonyl, 2-methylphenoxycarbonyl or 4-sulfophenoxycarbonyl group.

The acyl group is an acyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetyl, benzoyl and 4-chlorobenzoyl groups.

When R ³¹ is a hydroxyl group, an amino group or an alkylamino group, it can be represented by the general formulas B-1 to B-1.
The compound represented by 4 may have a tautomeric structure, but it goes without saying that the general formulas B-1 to B-14 include such compounds.

Of these, R ³¹ is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acylamino group having 1 to 6 carbon atoms, or 2 to 12 carbon atoms. Dialkylamino group of 1 to 1 carbon atoms
A ureido group having 6 carbon atoms, a sulfamoylamino group having 2 to 12 carbon atoms, an alkoxycarbonylamino group having 1 to 6 carbon atoms,
A sulfonylamino group having 1 to 6 carbon atoms, a carbamoyl group having 1 to 6 carbon atoms, a sulfamoyl group having 2 to 12 carbon atoms, a sulfonyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and 1 carbon atom To an acyl group having 6 to 6 carbon atoms, a sulfonic acid group, and more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cyano group, and an alkoxy group having 1 to 6 carbon atoms. Base, carbon number 1
~ 6 acylamino group, C2-12 dialkylamino group, C1-6 ureido group, C2-12 sulfamoylamino group, C1-6 alkoxycarbonylamino group, carbon number 1 to 6 sulfonylamino group, 1 to 6 carbon carbamoyl group, 2 to 12 carbon sulfamoyl group, 1 to 6 carbon sulfonyl group, 2 to 6 carbon alkoxycarbonyl group, carboxylic acid group, sulfone It is an acid group.

R ³² is a hydrogen atom, alkyl group, aryl group, heterocyclic group, hydroxyl group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group. , An alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a sulfonyl group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an aryloxycarbonylamino group, an imide group, and a heterocyclic thio group. These are alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, nitro groups, cyano groups, halogen atoms, carboxylic acid groups, sulfonic acid groups or other substituents formed by oxygen, nitrogen, sulfur or carbon atoms. It may be further substituted, and specific examples thereof are the same as those for R ³¹ .

R ³² is preferably a hydrogen atom, having 1 to 6 carbon atoms.
Alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 acylamino group, amino group, C2-12 dialkylamino group, C1-6 ureido group, C1 To 6 sulfamoylamino groups, C1 to C6 alkoxycarbonylamino groups, and 1 carbon atoms
To a sulfonamide group having 2 to 12 carbon atoms, a sulfamoyl group having 2 to 12 carbon atoms, a sulfonyl group having 1 to 6 carbon atoms, and an imide group having 4 to 8 carbon atoms, and more preferably a hydrogen atom and 1 to 1 carbon atoms
6 is an alkyl group.

In the general formulas B-1 to B-14, * represents a site bonded to N in the general formula (1).

N ₂ represents 0 or 1, n ₃ represents 0, 1, 2
Or represents 3, and when n ₃ is 2 or more, R ³¹ may be the same or different, and when R ³¹ and R ³² are groups capable of forming a ring, they form a ring. You may.

In the general formulas B-1 to B-14, in the case of having a condensed ring structure, the number of ring members may be any number of rings, but it is preferably 5 to 7 members.

As B of the azomethine dye represented by the general formula (1), the above general formulas B-3, B-10, B-11,
B-12, B-13 and B-14 are preferably used. More preferably, B-10, B-11, B-1
2, B-13 and B-14, particularly preferably B
-10, B-11 and B-14.

In the general formula (1), A is the general formula (1).
Of the general formulas (2), (3), (5) necessary for the azomethine dye of (1) to have absorption in the visible region and / or the near infrared region ,
A represents an atomic group represented by any of (6) and (8) to (10) , and A is the same as that derived from a compound which undergoes an oxidative coupling reaction with p-phenylenediamines to give an azomethine dye. is there. In the present invention, the visible light range represents a wavelength range of 380 to 800 nm, and the near infrared range represents a wavelength range of 800 nm to 1400 nm.

Examples of the compound that gives A include phenols, naphthols, heterocyclic compounds having active hydrogen, and open-chain active methylene compounds. Preferred A is the following general formulas (a) , (b), (e),
It is represented by any one of (r), (s), and (u) .

[0072]

[Chemical 6]

[0073]

[Chemical 7]

[0074]

[Chemical 8]

[0075] Next we describe the general formula (a) and (b). Ra ¹ , Ra ² , Ra ³ , Ra ⁴ , Rb ¹ , Rb ² , Rb
³ , Rb ⁴ , Rb ⁵ and Rb ⁶ represent a hydrogen atom or a substituent and are the same as those described for R ³¹ and R ³² of B, and the specific examples are also the same.

In the general formula (a ), Ra ¹ is preferably an acylamino group (for example, acetylamino, furoylamino, 4-hydroxycarbonylbenzoylamino or pivaloylamino group), a carboxylic acid group or a sulfonic acid group. R
a ⁴ is an acylamino group (for example, pivaloylamino group),
Alkyl groups (eg methyl, ethyl or n-decyl groups) are preferred. Ra ² is preferably a hydrogen atom, and Ra ³ is preferably a chlorine atom or a hydrogen atom.

In the general formula (b), Rb ¹ is preferably a carbamoyl group (for example, 2-hydroxycarbonylphenylcarbamoyl, methylcarbamoyl or t-butylcarbamoyl group), a carboxylic acid group or a sulfonic acid group. Rb
² , Rb ³ , Rb ⁴ and Rb ⁵ are preferably hydrogen atoms, and Rb ⁶
Is preferably a hydrogen atom, an acylamino group (eg, acetylamino group), or a urethane group (eg, methylurethane group).

[0078] Next, we describe the general formula (e). Re ¹
And Re ² represent a hydrogen atom or a substituent, and are the same as those described for R ³¹ and R ³² of B, and the specific examples are also the same. Among them, an aryl group (eg, 2-acetylaminophenyl, 4-hydroxycarbonylphenyl or phenyl group), an alkyl group (eg, methyl, ethyl, t-).
Butyl or 2-sulfophenylmethyl group) and a heterocyclic group (for example, 2-pyridyl or 2-thienyl group) are preferable.

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

Next, the general formula ( r) will be described . R r ¹
Represents a hydrogen atom or a substituent and is the same as those described for R ³¹ and R ³² of B, and the specific examples are also the same . R r ¹
Is an acylamino group (for example, acetylamino or benzoylamino group), an anilino group (for example, methylamino, anilino or o-chloroanilino group), and an alkyl group (for example, methyl, ethyl or t-butyl group), a carbamoyl group (for example, Carbamoyl or methylcarbamoyl group), cyano group and carboxylic acid group are preferred.

[0092] Next, we describe the general formula (s). R
s ¹ , Rs ² and Rs ³ represent a hydrogen atom or a substituent,
It is the same as that described for R ³¹ and R ³² of B, and the specific examples are also the same.

In the general formula (s), Rs ¹ represents a cyano group, a phenyl group, a heterocyclic group or an amino group.

One of Rs ² and Rs ³ is preferably a cyano group, and the other is preferably a cyano group or an alkoxycarbonyl group (eg, methoxycarbonyl or ethoxycarbonyl group).

Next, the general formula (u) will be described. R
u ¹ , Ru ² and Ru ³ represent a hydrogen atom or a substituent and are the same as those described for R ³¹ and R ³² of B, and the specific examples are also the same.

Further, Ru ¹ and Ru ² may combine with each other to form a ring structure. Among them, Ru ¹ is an alkyl group (having 1 to 12 carbon atoms, for example, methyl, ethyl, methoxyethyl, p-sulfobenzyl group), an aryl group (having 6 to 12 carbon atoms).
18 such as phenyl, o-hydroxycarbonylphenyl or 3,5-dihydroxycarbonylphenyl group), heterocyclic group (having 4 to 18 carbon atoms such as 2-furyl, 2-thienyl, 2-pyrimidinyl, imidazolyl or pyrazolyl group) Ru ² is preferably a cyano group, an acyl group (having 2 to 12 carbon atoms such as acetyl, pivaloyl or p-hydroxycarbonylbenzoyl group), an alkoxycarbonyl group (having 2 to 12 carbon atoms such as methoxycarbonyl or ethoxycarbonyl). Group), an aryloxycarbonyl group (having 7 to 18 carbon atoms, such as a phenoxycarbonyl or p-sulfophenylcarbonyl group),
Aminocarbonyl group (having 1 to 12 carbon atoms such as methylaminocarbonyl or anilinocarbonyl group), aryl group (having 6 to 18 carbon atoms such as phenyl, tolyl,
p-methoxyphenyl or o-hydroxyphenyl group), alkyl group (having 1 to 12 carbon atoms, for example, methyl,
Ethyl, allyl or prenyl groups) are preferred.

Ru ³ is an alkyl group (having 1 to 12 carbon atoms,
For example, a methyl, ethyl or hydroxycarbonylethyl group) and an aryl group (having 6 to 18 carbon atoms such as phenyl, o-chlorophenyl or 3,5-dihydroxycarbonylphenyl group) are preferable.

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] As A of the azomethine dye represented by formula (1), especially the formula (2), (3),
Those having any one of the structures (5), (6) and (8) to (10) are preferably used.

[0106]

General formulas (2) , (3), (5), (6) and
And (8) to (10), R ^{1 to} R ¹³ , R ^{15 to} R ²⁷ represent a hydrogen atom or a substituent, and L ^{1 to} L ³ represent a nitrogen atom or —CR ²⁸ ═. However, R ²⁸ represents a hydrogen atom or a substituent.

General formulas (2) , (3), (5), (6) and
And (8) to (10), R ^{1 to} R ⁴ of the general formula (2)
Is the same as Ra ¹ to Ra ⁴ of the general formula (a), respectively. The definitions of R ^{5 to} R ^{10 in} the general formula (3) are the same as Rb ¹ to Rb ^{6 in} the general formula (b), respectively . As R ^13, R ¹⁵ ~R ¹⁷ single general formula (5), Rs of the general formula (s)
^The substituents defined by ¹ , Rs ² and Rs ³ are mentioned. The definition of R ^{18 to} R ^{20 in} the general formula (6) is as follows.
Of Ru ¹ , Ru ² and Ru ³ , respectively . Definition of R ²³ single general formula (8) is the same as Rr ¹ of the general formula (r). The definitions of R ²⁴ and R ^{25 in} the general formula (9) are the same as Re ¹ and Re ^{2 in} the general formula (e), respectively.

As A, the general formulas (2), (3) , ( 8), (9) and (10) are more preferable, and the general formulas ( 9) and (10) are particularly preferable.

A of the azomethine dye represented by the general formula (1) is selected from those having the structures of the general formulas (2) to (10), and B is represented by the general formulas B-10, B-11 and B-. Those having a structure selected from 14 are preferably used. More preferably, the general formula as A is
A structure selected from ( 9) and (10),
B is an azomethine dye having a structure selected from the general formulas B-10, B-11 and B-14.

Specific examples of the dye represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0112]

[Chemical 11]

[0113]

[Chemical 12]

[0114]

[Chemical 13]

[0115]

[Chemical 14]

[0116]

[Chemical 15]

[0117]

[Chemical 16]

[0118]

[Chemical 17]

[0119]

[Chemical 18]

Examples of synthesizing dyes used in the present invention are shown below.

Synthesis Example 1 (Synthesis Route of Exemplified Dye D-29)

[0122]

[Chemical 19]

Synthesis Example 1 (Synthesis of Exemplified Dye D-29) 4.0 g of compound a and 200 ml of methanol were mixed, 3.1 g of compound b was added, and 9.1 g of sodium carbonate was dissolved in 20 ml of water while stirring. The solution was added.

Then, 4.3 g of ammonium persulfate was added to 2 parts of water.
The aqueous solution added to 0 ml was added dropwise, and the mixture was stirred for 2 hours. Thereafter, water was further added, and the precipitated crystals were separated by filtration and recrystallized from acetonitrile to obtain 3.5 g of Dye D-29.

Synthesis Example 2 (Synthesis Route of Exemplified Dye D-26)

[0126]

[Chemical 20]

Synthesis Example 2 (Synthesis of Exemplified Dye D-26) 2.0 g of compound c and 2.0 g of compound d were added to methanol 2
Dissolve in 00 ml, 25% 20% potassium carbonate aqueous solution
Add. Next, 5.0% 30% ammonium persulfate aqueous solution
ml was added dropwise, and the mixture was further stirred for 2 hours.

Thereafter, water was further added to separate the precipitated green solid by filtration, and the crystal was recrystallized from acetonitrile to give a dye D-26.
1.2 g was obtained.

The addition amount of the azomethine dye of the present invention to the toner is 0.0 with respect to the binder resin (also referred to as a binder resin).
1 to 15 parts by weight, preferably 1.0 to 10 parts by weight are used. As the binder resin for toner, all commonly used binders can be used. For example, styrene resin, acrylic resin, styrene / acrylic resin, polyester resin, etc. may be mentioned.

In the present invention, inorganic fine powder or organic fine particles may be externally added to the toner for the purpose of improving fluidity, controlling charge, and the like. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. It is preferable that these have a number average primary particle diameter of 10 to 500 nm, and further, 0.1 to 20% by weight is added to the toner.

As the release agent, all the release agents which have been conventionally used can be used. Specific examples thereof include olefins such as low molecular weight polypropylene / low molecular weight polyethylene / ethylene-propylene copolymer, and microcrystalline wax / carnauba wax / sazol wax / paraffin wax. The addition amount of these is preferably 1 to 5% by weight in the toner.

The charge control agent may be added if necessary, but is preferably colorless in view of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure. As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin coated carrier in which the surface of the magnetic material particles is coated with a resin may be used. The average particle size of this carrier is 15 to 150 μ in volume average particle size.
m is preferred.

The image forming method to which the toner of the present invention is applied is not particularly limited. For example, a method of repeatedly forming a color image on a photoconductor and then transferring the color image to form an image, or a photoconductor Examples of the method include sequentially transferring the images formed on the intermediate transfer member or the like, forming a color image on the intermediate transfer member or the like, and then transferring the image to an image forming member such as paper to form a color image.

[0134]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. In the text, "part" means "part by weight".

<< Preparation of Working Samples >><Colorant> <Production of Color Toner> 100 parts of polyester resin, the number of parts of the colorant to be added shown below, 3 parts of polypropylene, mixing, kneading meat, crushing, classifying,
A powder having a volume average particle size of 8.5 μm was obtained.

Further, 100 parts of this powder and 1.0 part of silica fine particles (particle diameter 12 nm, hydrophobicity 60) were mixed with a Henschel mixer to obtain a color toner.

[0137] <Production of Carrier> Styrene / methyl methacrylate = 6/4 copolymer fine particles 40 g, specific gravity 5.0, weight average particle diameter 45 μm, 10
Cu-Zn ferrite particles 1960 having a saturation magnetization of 25 emu / g when an external magnetic field of 00 oersted is applied.
g was put into a high-speed stirring type mixer and mixed at a product temperature of 30 ° C. for 15 minutes, then the product temperature was set to 105 ° C., a mechanical impact force was repeatedly applied for 30 minutes, and the carrier was cooled.

<Preparation of Developer> Carrier 418.5
20 g of each toner and 31.5 g of each toner using a V-type mixer.
After mixing for a minute, a developer for a live-copy test was prepared.

<< Evaluation Device, Conditions >> In the examples, the actual image evaluation was carried out using a Konica 9028 (manufactured by Konica Corporation) as an image forming device.

<< Evaluation Items, Method >> The test was conducted with the developer using the color toner of the present invention on the paper and the OHP by the above-mentioned image forming method, respectively on the reflection image (the image on the plain paper) and the transmission image (the OHP image). Was prepared and evaluated by the method described below. Note that the toner adhesion amount is 0.7 ±
The evaluation was made in the range of 0.05 (mg / cm ² ).

Saturation: Macbeth Color-Ey
At 7000, the saturation of an image on plain paper prepared by using ASTM D65 as a light source with a 2 degree visual field was measured and compared.

Light resistance: "Xenon Long Life Weather Meter" (Xenon Arc Lamp, 7
After performing an exposure test for 7 days at 0000 lux at 44.0 ° C., the same Macbeth Color-E was used.
The chromaticity before and after the exposure test was measured with ye 7000, and C
The color differences calculated by the MC (2: 1) color difference formula were compared.

Transparency: The transparency of the OHP image was evaluated by the following method.
The OHP sheet on which the toner is not carried by Hitachi "330 type autographic spectrophotometer" measures the visible spectral transmittance of the image as a reference, Magenta 650n
The spectral transmittance at m and cyan of 500 nm was obtained and used as a measure of the transparency of the OHP image.

Hue Change: Macbeth Color-
Eye 7000 with ASTM D65 2 as a light source
The hues of the image on the plain paper and the image on the OHP prepared by using the visual field were measured, and the hue differences of both images were compared.

<< Evaluation Results >> The above results are shown in Table 1.

[0146]

[Table 1]

As is clear from Table 1, since the color toner of the present invention exhibits faithful color reproduction and high OHP quality without processing the colorant in advance, the color toner of the present invention is a full-color toner. Suitable to use. Further, since it has good light resistance, it is possible to provide an image that can be stored for a long period of time.

[0148]

EFFECTS OF THE INVENTION According to the present invention, by using a colorant which is sufficiently dispersed in a binder resin and exhibits excellent light resistance, the chroma is high and the light resistance is good without processing the colorant in advance. Therefore, it is possible to provide a color toner having a small change in hue in an OHP image and high transparency.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03G 9/09

Claims (8)

(57) [Claims] 1. In a color toner comprising at least a resin and a colorant, the colorant is represented by at least the following general formula (1), and A in the general formula (1) is represented by the general formula (2):
Any of (3), (5), (6) and (8) to (10)
Color toner for electrophotography which is characterized by containing a represented Ru azomethine dye or. General formula (1) A = NB (In the formula, A represents an atomic group necessary for the azomethine dye to have absorption in the visible region and / or the near infrared region, and B represents an aromatic hydrocarbon ring or a 5-membered group. Alternatively, it represents a nonmetallic atomic group necessary for forming a 6-membered heteroaromatic ring.) (In the formula, R ^{1 to} R ¹³ , R ^{15 to} R ²⁷ are hydrogen atoms or substituted
Represents a group, L ^{1 to} L ³ represent a nitrogen atom or -CR ²⁸ =
You However, R ²⁸ represents a hydrogen atom or a substituent. ) 2. The structure of the portion represented by A of the azomethine dye represented by the general formula (1) is represented by the general formula (2),
The color toner for electrophotography according to claim 1, which is represented by any one of (3), (8), (9), and (10) . 3. The structure of the portion represented by A of the azomethine dye represented by the general formula (1) is represented by the general formula (9) and
The color toner for electrophotography according to claim 2, which is represented by any one of (10) . 4. An azomethine dye represented by the general formula (1)
The structure of the portion represented by B of the following general formulas B-1 to B-
It is represented by any one of claims 14 to 15.
4. The color toner for electrophotography according to any one of 3 above. [Chemical B] (In the general formulas B-1 to B-14, R ⁷ is an alkyl group.
Or an aryl group, R ³³ represents OR ³⁴ , NR ³⁵ R ³⁶ , and R
³⁴ , R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group or an alkyl group.
It represents a reel group or a heterocyclic group. Also R ³⁵ and R ³⁶ , R
³⁵ and B and R ³⁶ and B may cooperate with each other to form a ring.
In addition, B may further have a condensed ring. Also, * -is N
Represents a connector. ) 5. An azomethine dye represented by the general formula (1)
The structure of the portion represented by B in the formula B-3, B-
10, B-11, B-12, B-13 and B-14
The electron according to claim 4, wherein the electron is represented by a shift.
Color toner for photographs. 6. An azomethine dye represented by the general formula (1)
The structure of the portion represented by B in the formula B-10, B
-11 or B-14.
The color toner for electrophotography according to claim 4. 7. An electron comprising at least a resin and a colorant.
In photographic color toners, the colorant is at least
Not containing the azomethine dye represented by the general formula (1)
In the general formula (1) A = N-B A, the general formulas (2), (3), (5), (6) and
Represented by any one of (8) to (10), B is the general formula
It is represented by any one of B-10, B-11, and B-14.
6. A color toner for electrophotography according to claim 5, wherein
-. 8. An electron comprising at least a resin and a colorant.
In photographic color toners, the colorant is at least
Not containing the azomethine dye represented by the general formula (1)
Ri, general formula (1) A = N-B A is represented by any one of formulas (9) or (10)
And B is represented by the general formula B-10, B-11 and B-14.
The electric power according to claim 7, which is represented by one of the following:
Color toner for child photographs.