JP2009015113A - Toner for electrophotography and polymer dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner for an electrophotography exhibiting excellent dispersibility to a thermoplastic resin, allowing good coloration, and having good transparency, light resistance, and heat resistance (sublimability). <P>SOLUTION: This toner for electrophotography contains a polymer dye having the residue of a squarylium dye as a substructure. Compounds represented by the following general formulas 1, 2, and 3 are preferable for the polymerizable squarylium dye. A general formula 1: D-(L<SB>1</SB>)<SB>n</SB>-C-(R<SB>10</SB>)= CH<SB>2</SB>. A general formula 2: X<SB>1</SB>-(L<SB>2</SB>)<SB>n</SB>-D-(L<SB>3</SB>)<SB>n</SB>-X<SB>2</SB>. A general formula 3: D-(L<SB>4</SB>)<SB>n</SB>-X<SB>3</SB>. In the formulas, D represents the squarylium dye, L represents a binding group, R<SB>10</SB>represents hydrogen, halogen, or alkyl, and X represents a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrophotographic toner and a polymer dye, and more particularly to an electrophotographic toner containing a polymer dye having a residue of a specific squarylium dye as a partial structure.

  The performance required for the color copier (registered trademark) using electrophotography and the toner for electrophotography used in a color printer includes color reproducibility, image transparency, and light resistance.

  Conventionally known organic pigments and dyes have been used as colorants used in electrophotographic toners, but each has various drawbacks. For example, organic pigments are generally superior in heat resistance and light resistance compared to dyes, but because they exist in the form of particles dispersed in the toner, the hiding power is increased and transparency is reduced. End up. In addition, since pigments are generally inferior in dispersibility, transparency and saturation are lowered, and color reproducibility of an image is hindered.

  As a method for solving such a defect of the pigment, for example, a flushing method is used as a pigment dispersion method, and a pigment dispersion diameter of submicron order by primary particles having no aggregated secondary particles is achieved to improve transparency. In addition, a means for improving the charging property, fixing property, and image uniformity by coating pigment particles with a binder resin and an outer shell resin has been proposed (see Patent Document 1).

  However, even when the toner is output using the proposed toner, it is still difficult to obtain sufficient transparency in the case of a pigment-based toner.

  On the other hand, toners using dyes (see Patent Document 2) and toners in which dyes and pigments are mixed have been disclosed. Generally, dyes are excellent in transparency and saturation, but have light resistance and heat resistance. It has the disadvantage of being greatly inferior to pigments. Regarding heat resistance, in addition to the decrease in density due to the decomposition of the dye, when the toner image is fixed by a heat roller, the dye is sublimated and easily causes contamination in the machine, and the dye dissolves in the silicone oil used at the time of fixing, Eventually, there was a problem of causing an offset phenomenon by fusing to a heating roll.

As a proposal for solving these disadvantages of dyes, for example, a means (see Patent Document 3) is disclosed that can achieve both color reproducibility and image fastness to some extent by using a specific anthraquinone dye or squarylium dye as magenta toner. However, it is still inadequate in terms of image robustness. In addition, a method for producing particles in which the colorant is a dye having a radical polymerizable double bond under certain specific conditions is also disclosed (see Patent Document 4). The colored particles are used as an electrophotographic toner. In some cases, the color reproducibility was improved to some extent, but it was still difficult to say that sufficient color reproducibility was obtained, and the light resistance was still insufficient. .
JP-A-11-160914 JP-A-5-11504 JP 2000-345059 A JP 63-304002 A

  The present invention has been made to solve the above-mentioned problems, and the object thereof is excellent dispersibility in thermoplastic resins, enables good coloring, and transparency, light resistance, heat resistance. An object of the present invention is to provide an electrophotographic toner having excellent properties (sublimation).

As a result of diligent research, the present inventors have found that the above object can be achieved by the following constitution, and have accomplished the present invention.
1.
1. An electrophotographic toner comprising a polymer dye having a residue of a squarylium dye as a partial structure.
2.
2. The toner for electrophotography according to 1 above, wherein the squarylium dye is represented by the following general formula (1) or general formula (2).

[Wherein, R ₁ and R ₄ each represent a substituent, R ₂ , R ₃ , R ₅ and R ₆ each represent a hydrogen atom or a substituent, and p and q each represents an integer of 0 to 4] To express. Q ₁ and Q ₂ each represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and may be further condensed or have a substituent. L ₅ , L ₆ , L ₇ and L ₈ each represents a methine group which may have a substituent, and R ₇ and R ₈ each represent a substituent. t and u each represents 0 or 1; ]
3.
3. The toner for electrophotography according to 1 or 2 above, which contains a homopolymer or a copolymer derived from a monomer represented by the following general formula (3).

Formula _{(3) D- (L 1)} n -C (R 10) = CH 2
[Wherein, D represents a residue of a squarylium dye, L ₁ represents a divalent linking group, R ₁₀ represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and n represents 0 or 1 Represents. ]
4).
3. The toner for electrophotography according to 1 or 2 above, which contains a homopolymer or a copolymer derived from a monomer represented by the following general formula (4).

Formula _{(4) X 1 - (L} 2) n -D- (L 3) n -X 2
[Wherein D represents a residue of a squarylium dye, L ₂ and L ₃ each represent a divalent linking group, and X ₁ and X ₂ each represent a carboxyl group, an amino group, a hydroxyl group, an isocyanato group or an epoxy group. N represents 0 or 1. ]
5).
1. A polymer compound obtained by reacting a compound represented by the following general formula (5) with a polymer having a substituent capable of reacting with the substituent X _{3 in the} compound: Or the toner for electrophotography of Claim 2.

Formula _{(5) D- (L 4)} n -X 3
[In the formula, D represents a residue of squarylium dye, L ₄ represents a divalent linking group, X ₃ represents a carboxyl group, an amino group, a hydroxyl group, an isocyanato group or an epoxy group, and n is 0 or 1 Represents. ]
6).
6. The electrophotographic toner according to any one of 1 to 5 above, which contains at least one metal-containing compound.
7).
7. The toner for electrophotography as described in 6 above, wherein the metal-containing compound is a Cu compound.
8).
8. The electrophotographic toner according to any one of 1 to 7 above, wherein the toner is a polymerized toner.
9.
A polymer dye characterized by having a residue of a squarylium dye as a partial structure.
10.
10. The polymer dye as described in 9 above, wherein the squarylium dye is represented by the following general formula (11) or (12).

[Wherein, R ₁ and R ₄ each represent a substituent, R ₂ , R ₃ , R ₅ and R ₆ each represent a hydrogen atom or a substituent, and p and q each represents an integer of 0 to 4] To express. Q ₁ and Q ₂ each represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and may be further condensed or have a substituent. L ₅ , L ₆ , L ₇ and L ₈ each represents a methine group which may have a substituent, and R ₇ and R ₈ each represent a substituent. t and u each represents 0 or 1; ]

  By using the color toner of the present invention, it is possible to provide an electrophotographic toner that is excellent in dispersibility in a thermoplastic resin, enables good coloring, and is excellent in transparency, light resistance, and heat resistance (sublimation). it can.

  Hereinafter, the present invention will be described in more detail.

  The toner for electrophotography of the present invention is characterized by containing a polymer dye having a residue of a squarylium dye as a partial structure, and preferably the squarylium dye is represented by the general formula (1) or (2). The squarylium dye is a dye derived from squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione).

<Squaryllium dye represented by general formula (1)>
In the general formula (1), examples of the substituent represented by R ₁ and R ₄ include an alkyl group (methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), alkenyl groups (vinyl, allyl, etc.), alkynyl groups (ethynyl, propargyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (furyl, thienyl, etc.) , Pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, pyrazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, quinazolyl, phthalazyl, pyrrolidyl, imidazolidyl, morpholyl, oxazolidyl, etc.), alkoxy groups (methoxy, ethoxy, pro Poxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cycloalkoxy groups (cyclopentyloxy group, cyclohexyloxy, etc.), aryloxy groups (phenoxy, naphthyloxy, etc.), alkylthio groups (methylthio, ethylthio, propylthio, pentylthio) Hexylthio, octylthio, dodecylthio, etc.), cycloalkylthio groups (cyclopentylthio, cyclohexylthio, etc.), arylthio groups (phenylthio, naphthylthio, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl) Etc.), aryloxycarbonyl groups (phenyloxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl groups ( Minosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), acyl group (acetyl) , Ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy groups (acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octyl) Carbonyloxy, dodecylcarbonyloxy, phenyl Sulfonyloxy, etc.), acylamino groups (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, trifluoromethylcarbonyl Amino, phenylcarbonylamino, naphthylcarbonylamino, etc.), sulfonylamino groups (methylsulfonylamino, ethylsulfonylamino, hexylsulfonylamino, decylsulfonylamino, phenylsulfonylamino, etc.), carbamoyl groups (aminocarbonyl, methylaminocarbonyl, dimethylamino) Carbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexane Xylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc., ureido group (methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido) , Dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido, etc.), sulfinyl group (methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl group, 2-pyridyl Sulfinyl group), alkylsulfonyl group (methylsulfonyl group, Rusulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl etc.), amino group (amino, ethylamino, Dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.), cyano group, nitro group, halogen atom (fluorine, chlorine, bromine etc.), alkyl halide (fluorine) Methyl, trifluoromethyl, chloromethyl, trichloromethyl, perfluoropropyl, etc.). These substituents may further have the above substituents.

  Among the above substituents, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkoxy group, an acylamino group, a sulfonylamino group, an alkylsulfonyl group, a hydroxyl group, and the like are preferable, and a hydroxyl group, an acylamino group, and a sulfonylamino group are more preferable. It is.

p and q each represent an integer of 0 to 4, and when p or q is 2 or more, the plurality of R ₁ and R ₄ may be the same or different. p and q are each preferably 1 or 2, and p and q are preferably the same. More preferably, R ₁ and R ₄ are also the same.

The R _2, R _3, R ₅ and substituent R ₆ represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, an acyloxy group, a carbamoyl group and the like, further the above-mentioned R _1, it may have the same substituents as the substituents exemplified in R _4. R ₂ and R ₃ may be the same or different. R ₂ and R ₃ are preferably a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and more preferably an alkyl group or an aryl group.

R ₅ and R ₆ have the same meanings as R ₂ and R ₃ , respectively, preferably a hydrogen atom, an alkyl group, an aryl group, an acyl group, and a sulfonyl group, and more preferably an alkyl group and an aryl group. The combination of R ₂ and R _{3 and} the combination of R ₅ and R ₆ may be the same or different, but preferably the combination is the same.

  In the present invention, it is preferable that the general formula (1) is represented by the following general formula (6) because light resistance and heat and humidity resistance are further improved.

Wherein, R _2, R _3, R ₅ and R ₆ have the same meanings as R _2, R _3, R ₅ and R ₆ in the general formula (1).

R ₁₁ and R ₁₄ are also synonymous with R ₁ and R ₄ in the general formula (1), respectively, and may further have a substituent. R ₁₁ and R ₁₄ are preferably a halogen atom, an alkyl group, an aryl group, an acyl group, an alkoxy group, an acylamino group, a sulfonylamino group, an alkylsulfonyl group, a hydroxyl group, etc., more preferably a hydroxyl group, an acylamino group, a sulfonyl It is an amino group. R ₁₁ and R ₁₄ may be the same or different.

R ₁₂ and R ₁₃ may be the same groups as the substituents exemplified for R ₁₁ and R ₁₄ , respectively, and may further have a substituent. The substituents represented by R ₁₂ and R ₁₃ are preferably a halogen atom, an alkyl group, an aryl group, an acyl group, an alkoxy group, an acylamino group, a sulfonylamino group, an alkylsulfonyl group, a hydroxyl group and the like. R ₁₂ and R ₁₃ may be the same or different.

  r and s each represent an integer of 0 to 3, preferably 0 or 1, respectively.

<Squaryllium dye represented by formula (2)>
In the general formula (2), preferred examples of the heterocyclic ring formed by Q ₁ and Q ₂ include benzothiazole, benzoxazole, benzoselenazole, benzotelrazole, 2-quinoline, 4-quinoline, benzimidazole, and thiazoline. , Indolenine, oxadiazole, thiazole, imidazole ring, etc. In addition to the benzene ring, examples of the condensed ring include a pyridine ring, a thiophene ring, etc., but more preferred are benzothiazole, benzoxazole, benzimidazole, benzo Selenazole, 2-quinoline, 4-quinoline and indolenine ring, particularly preferably benzothiazole, benzoxazole, 2-quinoline, 4-quinoline and indolenine ring.

  As substituents on these rings, carboxyl group, phosphono group, sulfo group, halogen atom (fluorine, chlorine, bromine, iodine), cyano group, alkoxy group (methoxy, ethoxy, i-propoxy, methoxyethoxy, etc.), aryl Oxy groups (phenoxy, naphthyloxy, etc.), alkyl groups (methyl, ethyl, t-butyl, cyclopropyl, cyclohexyl, trifluoromethyl, methoxyethyl, allyl, benzyl, etc.), alkylthio groups (methylthio, ethylthio, etc.), Examples include alkenyl groups (vinyl, 1-propenyl, etc.), aryl groups (phenyl, toluyl, chlorophenyl, etc.) and the like.

L _{5 to} L ₈ each represents a methine group which may have a substituent. Examples of the substituent include substituted or unsubstituted alkyl groups (methyl, ethyl, propyl, i-propyl, cyclopropyl, butyl). , 2-carboxyethyl, benzyl, etc.), substituted or unsubstituted aryl groups (phenyl, toluyl, chlorophenyl, o-carboxyphenyl, etc.), heterocyclic groups (pyridyl, thienyl, furanyl, pyridyl, barbituric acid residues, etc.) , Halogen atoms (such as chlorine and bromine), alkoxy groups (such as methoxy and ethoxy), amino groups (such as diphenylamino, methylphenylamino, 4-acetylpiperazin-1-yl), and oxo groups.

  These substituents on the methine group may be linked to each other to form a ring such as cyclopentene, cyclohexene, squarylium ring, etc., and can also form a ring with an auxiliary color group.

The preferred substituents represented by R ₇ and R _8, an aromatic group or an aliphatic group which may have a substituent, the number of carbon atoms of the aromatic group is preferably 1 to 16, more preferably Is 5 or 6. The number of carbon atoms in the aliphatic group is preferably 1 to 18, more preferably 4 to 18, but the total number of carbon atoms of R ₇ and R ₈ is more preferably 17 or more. Examples of the unsubstituted aliphatic group and aromatic group include groups such as methyl, ethyl, propyl, butyl, octyl, decyl, i-hexadecyl, phenyl, and naphthyl.

The substituent which the heterocyclic ring formed by Q ₁ and Q ₂ may have is not particularly limited, but an alkyl group (methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, octyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, trifluoromethyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), alkenyl groups (vinyl, allyl, etc.), alkynyl groups (ethynyl, propargyl, etc.), aryl groups (phenyl, naphthyl, etc.) , Heterocyclic groups (furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, quinazolyl, phthalazinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, oxazolidinyl Etc.), alkoxy groups (methoxy, ethoxy, propyloxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy etc.), cycloalkoxy groups (cyclopentyloxy, cyclohexyloxy etc.), aryloxy groups (phenoxy, naphthyloxy etc.), Alkylthio groups (methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio, etc.), cycloalkylthio groups (cyclopentylthio, cyclohexylthio, etc.), arylthio groups (phenylthio, naphthylthio, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, Butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (phenyloxycarbonyl, Tiloxycarbonyl, etc.), sulfamoyl groups (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2- Pyridylaminosulfonyl, etc.), acyl groups (acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy groups (acetyloxy, Ethylcarbonyloxy, butylcarbonyloxy, octylcarbo Ruoxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), amide groups (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecyl Carbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), carbamoyl group (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecyl) Aminocarbonyl, phenylaminocarbonyl, naphthy Ureidocarbonyl (2-pyridylaminocarbonyl, etc.), ureido group (methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido, etc.), sulfinyl group (methylsulfinyl) , Ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, etc.), alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexyl) Sulfonyl, dodecylsulfonyl, etc.), arylsulfonyl groups (phenylsulfuryl) Nyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino group (amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.), cyano group , A nitro group, a halogen atom (fluorine, chlorine, bromine, etc.) and the like. These may be further substituted by the same substituent.

  Among these, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, sulfamoyl groups, ureido groups, amino groups, amide groups, acyl groups, alkoxycarbonyl groups, carbamoyl groups, cyano groups, halogen atoms and the like are preferable. Are more preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, a cyano group, an amide group, or a halogen atom.

  t and u represent 0 or 1, but preferably 0. Further, when a tautomer is present in the squarylium dye represented by the general formula (1) or (2) in the present invention, it is described by only one kind of description method, but is not limited to the tautomer. Also included are mixtures of multiple tautomers.

  The squarylium dyes represented by the general formula (11) and the general formula (12) are the same as the squarylium dyes represented by the general formula (1) and the general formula (2), respectively, and thus description thereof is omitted.

  When the squarylium dye residue of this invention has a site | part which can chelate with a metal ion in a molecule | numerator, it can also be used as a chelate dye residue by making it chelate with a metal containing compound as needed. In other words, the light resistance and the heat resistance can be improved by providing the dye partial structure and the dye residue with a site capable of chelating with a metal ion and coexisting with the metal-containing compound.

Examples of the metal-containing compound include inorganic or organic salts and metal complexes of metal ions, and among them, metal salts and complexes of organic acids are preferable. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the Periodic Table, preferably divalent metals, among which Al, Co, Cr, Cu, Fe, Mg, Mn , Mo, Ni, Sn, Ti and Zn are preferable, Cu, Cr, Co and Zn are more preferable, and Cu is particularly preferable. Specific examples of the metal-containing compound include salts of Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ and aliphatic carboxylic acids such as acetic acid and stearic acid, or aromatic carboxylic acids such as benzoic acid and salicylic acid. And enolate complexes of β-diketones and β-ketoesters.

  Specific examples of the metal-containing compound preferably used in the present invention are shown below, but the present invention is not limited to these.

  Subsequently, the monomer represented by the general formulas (3) and (4) and the compound represented by the general formula (5) will be described.

<Monomer represented by general formula (3)>
In the general formula (3), D represents a residue of the squarylium dye represented by the general formula (1) or (2). Here, the dye refers to a dye having spectral absorption in any region of visible light to infrared light, and examples thereof include yellow, magenta, and cyan dyes.

L ₁ represents a divalent linking group, and specifically, alkylene, arylene, —SO ₂ —, —CO—, —O—, —N (R ₁₂ ) —, each of which may have a substituent, —N (R ₁₃ ) CO—, —CON (R ₁₄ ) —, —OCO—, —COO—, —N (R ₁₅ ) SO ₂ —, —SO ₂ N (R ₁₆ ) and any two or more of these The group which consists of these combinations is mentioned.

R ₁₁ represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, t-butyl and the like. Particularly preferred are a hydrogen atom and a methyl group.

R _{12 to} R ₁₆ each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. n represents 0 or 1, but is preferably 1.

  The homopolymer derived from the monomer of the general formula (3) is specifically a radical polymer using only the monomer of the general formula (3). The copolymer derived from the monomer of the general formula (3) is specifically a radical copolymer of at least one monomer of the general formula (3) and a vinyl monomer different from the general formula (3). It is a coalescence.

  As the vinyl monomer, vinyl esters, (meth) acrylamides, and olefins are preferably used.

  Although the content unit (mass%) in the copolymer of the monomer of General formula (3) is arbitrary, Preferably it is 10-80 mass% with respect to the whole copolymer.

  The preferred number average molecular weight (Mn) of the homopolymer or copolymer derived from the monomer of the general formula (3) is 1,000 to 100,000, particularly preferably 3,000 to 20,000.

<Monomer represented by general formula (4)>
In the general formula (4), D ′ represents a residue of the squarylium dye represented by the general formula (1) or (2), and is synonymous with D in the general formula (3). It is a group.

L ₃ and L ₃ each represent a divalent linking group, but L ₃ and L ₃ may be the same or different and have the same meaning as the divalent linking group represented by L ₁ in the general formula (1). It is.

X ₁ and X ₂ each represent a carboxyl group, an amino group, a hydroxyl group, an isocyanato group or an epoxy group, but X ₁ and X ₂ are preferably the same. X ₁ and X ₂ are preferably a carboxyl group or an isocyanato group.

  n represents 0 or 1, but is preferably 1.

  The homopolymer derived from the monomer of the general formula (4) specifically means a polycondensate or a polyaddition product using only the monomer of the general formula (4). The copolymer derived from the monomer of the general formula (4) is specifically a monomer of the general formula (4) and at least one of different monomers different from the monomer of the general formula (4). It means a polycondensate or a polyadduct.

  As the specific monomer of the compound that forms a polycondensation or polyadduct with the monomer of the general formula (4), those having two substituents that react with the monomer of the general formula (4) are preferable. Compound and its acid chloride, diol compound, diisocyanate compound, diamine compound (all are described later), diepoxy compound (1,3-butadiene diepoxide, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol diester Glycidyl ether, etc.).

  Although the content unit (mass%) in the copolymer of the monomer of General formula (4) is arbitrary, Preferably it is the range of 50-90 mass% with respect to the whole copolymer.

  The preferable Mn of the homopolymer or copolymer derived from the monomer of the general formula (4) is 1,000 to 100,000, particularly preferably 3,000 to 20,000.

<Compound represented by formula (5)>
In the general formula (5), D represents the residue of the squarylium dye represented by the general formula (1) or (2), which has the same meaning as D in the general formula (2).

L ₄ represents a divalent linking group and has the same meaning as the divalent linking group represented by L ₁ in the general formula (1).

X ₃ represents a carboxyl group, an amino group, a hydroxyl group, an isocyanato group or an epoxy group, preferably a carboxyl group or an isocyanato group. n represents 0 or 1, but is preferably 1.

The substituent capable of reacting with the substituent X ₃ represents a hydroxyl group, an amino group or a carboxyl group, preferably a hydroxyl group or an amino group. Specifically, the polymer having a substituent capable of reacting with X ₃ is a polymer in which a hydroxyl group is partially substituted, such as a homopolymer or copolymer of 2-hydroxyethyl (meth) acrylate, ( Polymers partially substituted with carboxyl groups such as homo- or copolymers of (meth) acrylic acid, polymers partially substituted with hydroxyl groups such as partially saponified polyvinyl acetate, ethylene -The polymer etc. which have a hydroxyl group in one component of a copolymer like the hydrolyzate of a vinyl acetate copolymer are mentioned. More preferably, a polyvinyl butyral resin and a polyvinyl alcohol resin are mentioned.

  Specific examples of the polyvinyl butyral resin include # 2000-L, # 3000-1, # 3000-2, # 3000-4, # 3000-K, # 4000-1, and # 4000-2 manufactured by Denki Kagaku Kogyo Co., Ltd. , # 5000-A, # 6000-C, # 6000-EP; BL-1, BL-1H, BL-2, BL-2H, BL-5, BL-10, BL-S, manufactured by Sekisui Chemical Co., Ltd. BL-SH, BX-10, BX-L, BM-1, BM-2, BM-5, BM-S, BM-SH, BH-3, BH-6, BH-S, BX-1, BX- 3, BX-5, KS-10, KS-1, KS-3, KS-5, and the like. Polyvinyl alcohol resins include PVA PVA-102, PVA-117, PVA-CSA, PVA-617, PVA-505 manufactured by Kuraray Co., Ltd., special brand sizing agent PVA, hot melt molding PVA, etc. There is.

  Specific examples of the monomer represented by the general formulas (3) and (4) and the compound represented by the general formula (5) are shown below, but the present invention is not limited thereto.

  Although the synthesis example of these compounds is given to the following, the aspect of this invention is not limited to these.

  <Synthesis Example 1 (Synthesis of Monomer 3-1)>

  To 50 ml of toluene, 5.37 g of Intermediate 1, 0.5 g of p-toluenesulfonic acid monohydrate and 1.72 g of methacrylic acid were added and heated and refluxed for 2 hours. 200 ml of ethyl acetate was added to the reaction solution, and the mixture was washed 3 times with 200 ml of saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 5.58 g of monomer (3-1). The structure was identified by MASS and H-NMR.

  Other monomers represented by the general formula (3) can also be synthesized according to the above.

  The polymer derived from this monomer may be a homopolymer of the monomer of the general formula (3) or a copolymer of an ethylene-like monomer and a monomer of the general formula (3). In any case, two or more monomers represented by the general formula (3) may be used.

  Among these, a copolymer of the monomer of the general formula (3) and the following ethylene-like monomer is preferable.

  Acrylic acid, α-alkyl (meth) acrylic acid, α-chloroacrylic acid, amides or esters derived from these acids (acrylamide, methacrylamide, butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl (meth ) Acrylate, ethyl (meth) acrylate, propyl acrylate, butyl (meth) acrylate, t-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, β-hydroxy methacrylate), vinyl esters (eg , Vinyl acetate, vinyl propionate, vinyl laurate, etc.), (meth) acrylonitrile, aromatic vinyl compounds (styrene and vinyl toluene, divinylbenzene, vinyl Derivatives such as cetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinyl alkyl ethers (such as vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- (or 4) -) Vinylpyridine and the like. Of these, (meth) acrylic acid esters and maleic acid esters are particularly preferred.

  Two or more ethylene-like monomers can be used at the same time. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diseton acrylamide, and the like can be used.

  The ethylene-like monomer for copolymerization with the monomer of the general formula (3) includes the physical properties and / or chemical properties (for example, solubility) of the formed copolymer, additives (high-boiling solvent, polymer). And the like, the flexibility of the copolymer, and the thermal stability can be selected to be positively affected.

  Although the synthesis example of the polymer using the monomer represented with General formula (3) below is shown, this invention is not limited to these.

<Synthesis Example 2 (Synthesis of Polymer P-1)>
After degassing a mixture of 5.0 g of the monomer (3-1) and 100 ml of tetrahydrofuran (THF), 1 ml of a dioxane solution (concentration 0.04 g / ml) of azobisisobutyronitrile was added with stirring in a nitrogen stream. The mixture was heated to 80 ° C. to initiate polymerization. After 2 hours, another 1 ml was added and reacted for 3 hours. Thereafter, the reaction solution was cooled, 100 ml of ethyl acetate was added, and the mixture was washed several times with 100 ml of saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the organic layer was concentrated under reduced pressure, the residue was dissolved in THF, and purified by reprecipitation using methanol to obtain 3.63 g of polymer (P-1). The number average molecular weight determined by gel permeation chromatography (GPC method) was 6,800.

<Synthesis Example 3 (Synthesis of Polymer P-2)>
A mixture of 3.00 g of monomer (3-1), 6.00 g of styrene and 80 ml of dioxane was heated to 80 ° C. with stirring in a nitrogen stream, and then 2 ml of a dioxane solution of dimethyl azobisisobutyrate (concentration 0.04 g / ml). In addition, polymerization was started. After 2 hours, an additional 2 ml was added and reacted for 3 hours. Thereafter, the reaction solution was cooled, 200 ml of ethyl acetate was added, and the mixture was washed several times with 200 ml of saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the organic layer was concentrated under reduced pressure, the residue was dissolved in THF, and purified by reprecipitation using methanol to obtain 7.26 g of copolymer (P-2). According to the quantitative analysis of nitrogen, the synthesized polymer dye contains 33% by mass of (3-1). Moreover, the number average molecular weight by GPC method was 7,900.

  Next, although the synthesis example of the polymer using the monomer represented by General formula (4) of this invention is shown, this invention is not limited to these.

  <Synthesis Example 4 (Synthesis of Monomer 4-12)>

  6.24 g of Intermediate 2 and 1.14 g of squaric acid were dissolved in a mixed solution of 25 ml of butanol and 25 ml of toluene and heated at 100 ° C. for 2 hours. Ethyl acetate was added and the precipitated crystals were recrystallized from ethanol to obtain 4.89 g of monomer (4-12). The structure was identified by MASS and H-NMR.

  Other monomers represented by the general formula (4) can also be synthesized according to the above. Next, typical monomers to be subjected to polycondensation or polyaddition reaction with the monomer represented by the general formula (4) are shown below.

  Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α-dimethylsuccinic acid, acetone dicarboxylic acid, sebacic acid, 1,9-nonanedicarboxylic acid, fumaric acid , Maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-butyl terephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate) dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ω-poly (ethyleneoxy) dicarboxylic acid, p-xylylene dicarboxylic acid and the like.

  As tetracarboxylic acid, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenone Tetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylmethanetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid and the like.

  In place of these di- and tetracarboxylic acids, their acid chlorides, esters, and acid anhydrides can be more preferably used.

  Examples of the diamine include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o- (m-, p-) phenylenediamine, piperazine, 2,5-dimethylpiperazine, 4 4,4'-diaminophenyl ether, 3,3'-diaminodiphenyl sulfone, xylylenediamine, benzidine and the like, and tetraamines include biphenyl-3,4,3 ', 4'-tetraamine and the like.

  Examples of the diol include ethylene glycol, 1,2 (or 1,3) -propanediol, 1,3 (or 2,3) -butanediol, 2,2, -dimethyl-1,3-propanediol, 1,4 -Pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,6-hexanediol, 2,5- Hexanediol, 2-methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2-methyl-2-propyl1,3 -Propanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 2,2,4-trimethyl- , 3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol (average molecular weight = 200, 300, 400, 600, 1000, 1500, 4000), polypropylene Examples include glycol (average molecular weight = 200, 400, 1000), polyester polyol, 4,4′-dihydroxydiphenyl-2,2-propane, 4,4-dihydroxyphenylsulfone, and the like.

  Examples of the polyhydric alcohol include diglycerol, pentaerythritol, sorbitol, and 3-methylpentane-1,3,5-triol.

  Diisocyanate compounds include ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 1,3-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p- Examples include phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexylisocyanate).

  Although the synthesis example of the polymer using the monomer of General formula (4) is shown below, this invention is not limited to these.

<Synthesis Example 5 (Synthesis of Polymer P-3)>
In a vessel equipped with a stirrer and a nitrogen introduction tube, 2.71 g of the dye monomer (4-12) and 35 g of N-methyl-2-pyrrolidone were added and dissolved in a nitrogen atmosphere, and then 0.5 g of triethylamine was added and −15 Cooled to ° C. Then, stirring was strengthened, 1.02 g of terephthalic acid dichloride was added, and the mixture was stirred at 0 ° C. for 2 hours and further at room temperature for 1 hour. The resulting viscous polymer solution was filtered and re-precipitated dropwise into vigorously stirred methanol. This was separated by filtration, washed with methanol, and dried under reduced pressure at 50 ° C. for 12 hours to obtain 3.11 g of a polymer (P-3).

  Next, although the synthesis example of the compound represented by General formula (5) is shown, this invention is not limited to these.

  <Synthesis Example 6 (Synthesis of Compound 5-6 and Synthesis of Intermediate 5)>

  2.06 g of Intermediate 3 and 1.14 g of squaric acid were dissolved in a mixed solution of 25 ml of butanol and 25 ml of toluene and heated at 100 ° C. for 2 hours. An additional 2.64 g of intermediate 4 was added to the reaction solution, and the mixture was further heated at 100 ° C. for 2 hours. Ethyl acetate was added and the precipitated crystals were recrystallized from ethanol to obtain 3.89 g of Compound (5-6). The structure was identified by MASS and H-NMR.

  To 50 ml of toluene, 3.89 g of the above compound (5-6) and 0.1 ml of DMF (dimethylformamide) were added, and 1.46 g of thionyl chloride was added dropwise, followed by heating and refluxing for 4 hours. After completion of the reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure to obtain 4.00 g of Intermediate 5.

  Other compounds represented by the general formula (5) can also be synthesized according to the above.

  Hereinafter, although the synthesis example of the polymer obtained by reaction with the polymer which has General formula (5) and a hydroxyl group is shown, this invention is not limited to these.

<Synthesis Example 7 (Synthesis of Polymer P-4)>
Polyvinyl butyral (3.00 g) having a PVA polymerization degree of 450 and a hydroxyl group of 36 mol% was dissolved in 50 ml of THF, and 2.26 ml of pyridine was added. The mixture was cooled with ice water, and 4.00 g of Intermediate 5 dissolved in 20 ml of THF was added dropwise over 30 minutes while maintaining the internal temperature at 0 to 5 ° C. After returning to room temperature, the mixture was stirred for 5 hours, and ethyl acetate and water were added to the reaction solution, followed by washing with 1 mol / L hydrochloric acid until pH = 2. Further, after washing with a 10% by mass aqueous sodium hydrogen carbonate solution until pH = 9-10, the solution was neutralized, washed with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The obtained polymer was dissolved in THF and re-precipitated by dropping dropwise into vigorously stirred n-hexane. After completion of dropping, the mixture was stirred for 1 hour and then filtered. The filtrated product was dried under reduced pressure at 40 ° C. and 665 Pa or less to obtain 5.37 g of a polymer (P-4).

<Synthesis Example 8 (Synthesis of Polymer P-5)>
A mixture of 3.00 g of monomer (3-12), 6.00 g of styrene, and 80 ml of dioxane was heated to 80 ° C. with stirring in a nitrogen stream, and then 2 ml of a dioxane solution of dimethyl azobisisobutyrate (concentration 0.04 g / ml) was added. Polymerization was started. After 2 hours, an additional 2 ml was added and reacted for 3 hours. Thereafter, the reaction solution was cooled, 200 ml of ethyl acetate was added, and the mixture was washed several times with 200 ml of saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the organic layer was concentrated under reduced pressure, the residue was dissolved in THF, and reprecipitation purification was performed using methanol to obtain 6.59 g of a copolymer (P-2). . The polymer dye synthesized by quantitative analysis of nitrogen was found to contain 31% by mass of (3-12). The number average molecular weight determined by gel permeation chromatography (GPC method) was 6,200.

<Synthesis Example 9 (Synthesis of Polymer P-6)>
A mixture of 3.00 g of monomer (3-10), 6.00 g of styrene and 80 ml of dioxane was heated to 80 ° C. with stirring in a nitrogen stream, and then 2 ml of a dioxane solution of dimethyl azobisisobutyrate (concentration 0.04 g / ml) was added. Polymerization was started. After 2 hours, an additional 2 ml was added and reacted for 3 hours. Thereafter, the reaction solution was cooled, 200 ml of ethyl acetate was added, and the mixture was washed several times with 200 ml of saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the organic layer was concentrated under reduced pressure, the residue was dissolved in tetrahydrofuran, and reprecipitation purification was performed using methanol to obtain 6.59 g of a copolymer (P-2). . The polymer dye synthesized by quantitative analysis of nitrogen was found to contain 32% by weight of (3-10). Moreover, the number average molecular weight by GPC method was 6,500.

  A homopolymer or copolymer derived from a monomer of general formula (3), a homopolymer or copolymer derived from a monomer of general formula (4), and a compound of formula (5) and a hydroxyl group The polymer obtained by the reaction with the polymer to be contained (hereinafter collectively referred to as the polymer dye of the present invention) is preferably substantially water-insoluble and soluble in an organic solvent.

  In the present invention, “substantially insoluble in water” means that the solubility in water is 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass. “Substantially soluble in an organic solvent” means that the solubility in an organic solvent is 1.0 to 100% by mass, preferably 5.0 to 100% by mass.

  Specific examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, acetone, dichloromethane, dichloroethane, tetrahydrofuran, etc. Among them, ethyl acetate is preferable.

  Hereinafter, a method for producing an electrophotographic color toner of the present invention (hereinafter also abbreviated as color toner or simply toner) will be described.

<Dye dispersion method>
In the color toner of the present invention, the polymer dye is directly dispersed in a thermoplastic latex resin, or a fine particle dispersion of the polymer dye is mixed, and further using a desired additive described later, a kneading / pulverizing method, suspension weight It can be produced by other known methods such as a combination method, an emulsion polymerization method, an emulsion dispersion granulation method, and an encapsulation method. Among these production methods, the emulsion polymerization method is preferred from the viewpoints of production cost and production stability in consideration of the reduction in the toner particle size accompanying the increase in image quality.

  In the emulsion polymerization method, a thermoplastic resin emulsion produced by emulsion polymerization is mixed with a dispersion of other toner particle components such as a dye solid dispersion, and the repulsive force of the particle surface generated by pH adjustment and aggregation by addition of an electrolyte. Toner particles are produced by slowly agglomerating while maintaining a balance of force, and performing association while controlling the particle size and particle size distribution, and at the same time, fusing and shape control between the fine particles by heating and stirring.

<Liquid drying method>
The toner of the present invention may use the above polymer dye instead of the latex resin. The latex resin may contain a polymer dye as a solid dispersion.

  In order to contain the polymer dye as a solid dispersion in the latex resin, for example, the polymer dye alone or the polymer dye and the resin are dissolved or dispersed in a water-immiscible organic solvent such as ethyl acetate or toluene, and emulsified in water. After dispersion, the polymer dye fine particle dispersion obtained by the in-liquid drying method for removing the organic solvent can be aggregated with the (thermoplastic) latex resin.

  The emulsifying / dispersing device is not limited. For example, an ultrasonic dispersing device, a high-speed stirring type dispersing device, or the like is used. On the other hand, it is also possible to agglomerate a colored fine particle dispersion obtained by mixing a solid of a polymer dye with a surfactant and atomizing with a medium type stirrer with a (thermoplastic) latex resin.

  The solid dispersion of the polymer dye is preferably a small particle having a particle size of 10 to 100 nm, more preferably a small particle having a particle size of 10 to 80 nm. Since the solid dispersion has a small particle size and monodispersity, light scattering can be suppressed, and concealing particles that block light can be eliminated. By these effects, the transparency of the single color of the toner is improved, and it is possible to greatly improve the saturation with respect to the amount of attached dye.

<Emulsifier = Surfactant>
When emulsifying and dispersing the polymer dye, a normal anionic emulsifier (surfactant) and / or a nonionic emulsifier (surfactant) can be used as necessary.

  Examples of ordinary nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether, sorbitan monolaurate and sorbitan Sorbitan higher fatty acid esters such as monostearate and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxy such as polyoxyethylene monolaurate and polyoxyethylene monostearate Higher fatty acid esters of ethylene, higher glycerin fatty acid esters such as oleic acid monoglyceride, stearic acid monoglyceride, polyoxye Len - polyoxypropylene - may be mentioned block copolymers or the like.

  Examples of the anionic emulsifier include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfates such as sodium lauryl sulfate, and polyoxyethylene such as sodium polyethoxyethylene lauryl ether sulfate. Such as ethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate, etc. Examples thereof include alkyl sulfosuccinic acid ester salts and derivatives thereof.

  In the present invention, since the dye is in a polymer state, there is no fear of dye sublimation or oil contamination during heat fixing, which is generally regarded as a problem in toner using the dye.

<Thermoplastic latex resin>
The thermoplastic latex resin is preferably a thermoplastic resin with high adhesion to the polymer dye, and particularly preferably a solvent-soluble one. Furthermore, if the latex precursor is solvent-soluble, a curable resin that forms a three-dimensional structure can also be used. As the thermoplastic resin, those generally used as a binder resin for toner are used without particular limitation. For example, acrylic resins such as styrene resins and (meth) alkyl acrylates, styrene-acrylic copolymer resins, polyester resins, silicon resins, olefin resins, amide resins, and epoxy resins are preferably used.

  In order to improve transparency and color reproducibility of the superimposed image, a resin having high transparency, low melting property and high sharp melt property is required. As the thermoplastic resin having such characteristics, styrene resin, acrylic resin, and polyester resin are suitable.

  The number average molecular weight (Mn) is 3,000 to 6,000, preferably 3,500 to 5,500, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 6, Preferably it is 2.5-5.5. Further, it is desirable to use a resin having a glass transition point (Tg) of 50 to 70 ° C, preferably 55 to 70 ° C, and a softening temperature of 90 to 110 ° C, preferably 90 to 105 ° C.

  When Mn of the thermoplastic resin is in the above range, it is possible to prevent the image portion from peeling off when the full-color solid image is folded and to prevent image defects (decrease in bending fixability). It also suppresses a decrease in fixing strength due to a decrease in heat melting property. In addition, when Mw / Mn is within the above range, occurrence of high temperature offset, toner translucency, and deterioration of color mixing during full color image formation are reduced. In addition, when Tg is in the above range, toner aggregation during storage is suppressed, and deterioration in fixing property and color mixing during full color image formation are prevented. Further, when the softening temperature is in the above range, high temperature offset hardly occurs, and fixing strength, translucency, and gloss of a full color image are improved.

  The toner particles of the present invention preferably have a volume average particle diameter of 4 to 10 μm, preferably 6 to 9 μm, from the viewpoint of high-definition image reproducibility.

<Other additives>
In the toner of the present invention, in addition to the above-described thermoplastic latex resin, the polymer dye of the present invention, or polymer dye fine particles containing the polymer dye, known charge control agents, offset preventive agents, and the like can be used. .

  The charge control agent is not particularly limited. As the negative charge control agent used for the color toner, a colorless, white, or light color charge control agent that does not adversely affect the color tone and translucency of the color toner can be used. For example, metal complexes of zinc or chromium of salicylic acid derivatives, calixarene compounds, organoboron compounds, fluorine-containing quaternary ammonium salt compounds and the like are suitable. Examples of the salicylic acid metal complex include those described in JP-A Nos. 53-127726 and 62-145255, and examples of calixarene compounds include those described in JP-A No. 2-201378. As the boron compound, for example, those described in JP-A-2-221967 and JP-A-3-1162 can be used. When using such a charge control agent, it is desirable to use 0.1 to 10 parts by mass, preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the thermoplastic latex resin (binder resin). .

  There are no particular restrictions on the anti-offset agent, for example, polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax, carnauba wax, sazol wax, rice wax, candelilla wax, jojoba oil wax, beeswax wax. Etc. can be used. The added amount of such wax is 0.5 to 5 parts by mass, preferably 1 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin (binder resin). This is because by making the addition amount within this range, the effect of the addition is sufficiently exhibited, and the decrease in translucency and color reproducibility can be prevented.

  The toner of the present invention can be used by adding and mixing a post-treatment agent from the viewpoint of imparting toner fluidity and improving cleaning properties, and is not particularly limited. Examples of such post-treatment agents include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titania fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, and strontium titanate and titanium. Inorganic titanate compound fine particles such as zinc oxide can be used, and it is possible to use single or different additives in combination.

  These fine particles are desirably used after being surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil, etc. from the viewpoints of environmental stability and heat-resistant storage stability. On the other hand, it is desirable to use 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass.

  The toner of the present invention can be used as a two-component developing toner used by mixing with a carrier, or as a one-component developing toner not using a carrier.

  Examples of the carrier used in combination with the toner of the present invention include those conventionally known as carriers for two-component development. For example, a carrier composed of magnetic particles such as iron or ferrite, a resin-coated carrier obtained by coating such magnetic particles with a resin, or a binder-type carrier obtained by dispersing magnetic fine powder in a binder resin. is there.

  Among these carriers, the use of a resin-coated carrier using a silicone resin, a copolymer resin (graft resin) of an organopolysiloxane and a vinyl monomer or a polyester resin as a coating resin is used from the viewpoint of toner spent etc. preferable. In particular, a carrier coated with a resin obtained by reacting an isocyanate with a copolymer resin of an organopolysiloxane and a vinyl monomer is preferable from the viewpoint of durability, environmental stability, and spent resistance.

  As the vinyl monomer, it is necessary to use a monomer having a substituent such as a hydroxyl group reactive with isocyanate. In addition, it is preferable to use a carrier having a volume average particle diameter of 20 to 100 μm, preferably 20 to 60 μm from the viewpoint of ensuring high image quality and preventing carrier fog.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these embodiments. In the examples, “part” or “%” is based on mass unless otherwise specified.

Example 1
The following pulverized toner and polymerized toner were prepared.

<Crushing toner>
100 parts of a polyester resin, 2 parts of a colorant shown in Table 1, and 3 parts of a polypropylene resin (Biscol 550P: manufactured by Sanyo Chemical Co., Ltd.) were mixed, kneaded, pulverized and classified to obtain a powder having an average particle size of 8.5 μm . Further, 100 parts of this powder and 1.0 part of silica fine particles (R805: manufactured by Nippon Aerosil Co., Ltd., particle diameter 12 nm, hydrophobicity 60) were mixed with a Henschel mixer to obtain a pulverized color toner (1).

<Polymerized toner 1>
“Preparation of Colorant Dispersion 1”
An aqueous dispersion of the colorant was prepared by adding 6 g of the colorant shown in Table 1 to a solution obtained by dissolving 1.5 g of sodium dodecyl sulfate in 200 ml of pure water, and applying stirring and ultrasonic waves. Separately, an emulsified dispersion was prepared by emulsifying low molecular weight polypropylene (number average molecular weight = 3,200) in water so as to have a solid concentration of 30% with a surfactant while applying heat.

"Production of color toner"
60 g of low molecular weight polypropylene emulsified dispersion is mixed with the above colorant dispersion 1, and further 220 g of styrene, 40 g of butyl acrylate, 12 g of methacrylic acid, 5.4 g of t-dodecyl mercaptan as a chain transfer agent, and 2,000 ml of degassed pure water. Then, the emulsion polymerization was carried out by maintaining at 70 ° C. for 3 hours while stirring under a nitrogen stream.

  Sodium hydroxide was added to 1,000 ml of the resulting dispersion of the colorant-containing resin fine particles to adjust the pH to 7.0, 270 ml of a 2.7 mol% aqueous potassium chloride solution was added, and 160 ml of i-propyl alcohol and ethylene oxide were added. 9.0 g of polyoxyethylene octyl phenyl ether having an average polymerization degree of 10 was dissolved in 67 ml of pure water and added, and the reaction was carried out by stirring for 6 hours while maintaining at 75 ° C. The obtained reaction liquid was filtered and washed with water, and further dried and crushed to obtain colored particles.

  100 parts of these colored particles and 1.0 part of silica fine particles R805 (supra, particle diameter 12 nm, hydrophobization degree 60) are mixed with a Henschel mixer, and polymerization method 1 color toner (2, 5, 7, 12, 13) was obtained.

<Polymerized toner 2>
“Preparation of Colorant Dispersion 2”
The coloring agent 3.0g shown in Table 1 and ethyl acetate 50.0g were put into the separable flask, and it stirred and dissolved completely. Next, 80.0 g of an aqueous solution containing 1.0 g of a 27% solution of surfactant EC-27C (manufactured by Kao Corporation) was added dropwise and stirred, and then an ultrasonic disperser UH-600 (manufactured by SMT) Was emulsified for 5 minutes. Thereafter, ethyl acetate was removed under reduced pressure to obtain a colorant dispersion 2.

"Production of color toner"
"Preparation of thermoplastic resin (latex)"
Surfactant in which 7.08 g of sodium dodecylbenzenesulfonate (SDS) was previously dissolved in 2,760 g of ion-exchanged water in a 5,000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen introducing device The solution (aqueous medium) was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.

  On the other hand, 72.0 g of a compound having the following structure as a release agent is added to a monomer mixture composed of 115.1 g of styrene, 42.0 g of butyl acrylate and 10.9 g of methacrylic acid, and heated to 80 ° C. to dissolve. A monomer solution was prepared.

  The monomer solution (80 ° C.) is mixed and dispersed in the surfactant solution (80 ° C.) by a mechanical disperser having a circulation path, and emulsified particles (oil droplets) having a uniform dispersed particle size. A dispersion was prepared. Next, an initiator solution in which 0.84 g of a polymerization initiator (potassium persulfate: KPS) is dissolved in 200 g of ion-exchanged water is added to this dispersion, and this system is heated and stirred at 80 ° C. for 3 hours. Polymerization (first stage polymerization) was performed to prepare a latex. Next, an initiator solution prepared by dissolving 7.73 g of a polymerization initiator (KPS) in 240 ml of ion-exchanged water was added to the latex, and after 15 minutes, at 80 ° C., 383.6 g of styrene and 140.0 g of butyl acrylate. A monomer mixture composed of 36.4 g of methacrylic acid and 13.7 g of t-dodecyl mercaptan was added dropwise over 126 minutes. After completion of the dropwise addition, polymerization (second stage polymerization) was performed by heating and stirring for 60 minutes, followed by cooling to 40 ° C. to obtain a latex.

Mold release agent: C (CH ₂ OCOC ₂₁ H ₄₃ ) ₄
"Production of color toner"
250 g of the latex 1, 2,000 ml of ion-exchanged water, and 13.5 g of the colorant dispersion 2 were placed in a 5-liter four-necked flask equipped with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring device and stirred. . After adjusting the internal temperature to 30 ° C., a 5 mol / L aqueous sodium hydroxide solution was added to this solution to adjust the pH to 10.0. Next, an aqueous solution in which 52.6 g of magnesium chloride hexahydrate was dissolved in 72 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, temperature increase was started, and the system was heated to 90 ° C. over 6 minutes (temperature increase rate = 10 ° C./min). In this state, the particle size of the associated particles was measured with “Coulter Counter TA-II”, and when the volume average particle size reached 6.5 μm, an aqueous solution in which 115 g of sodium chloride was dissolved in 700 ml of ion-exchanged water was added. Then, the particle growth was stopped, and the fusion was continued by heating and stirring at a liquid temperature of 90 ° C. ± 2 ° C. for 6 hours.

  Then, it cooled to 30 degreeC on the conditions of 6 degreeC / min. Then, the associated particles are filtered out from the dispersion of the associated particles, and re-dispersed in 10 times the amount of ion-exchanged water (PH = 3) by mass ratio with respect to the entire associated particles. After the process of separating the associated particles from water was repeated twice, the particles were washed with only ion-exchanged water and dried with hot air at 40 ° C. to obtain colored particles.

  100 parts of these colored particles and 1.0 part of silica fine particles R805 (supra, particle diameter 12 nm, hydrophobization degree 60) are mixed with a Henschel mixer, and polymerization method 2 color toner (3,4,6,8-10) Got.

<Production of developer for live-action test>
Each toner obtained as described above and a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin are mixed for 20 minutes using a V-type mixer, and a developer (No. 1-13) were obtained. Table 1 shows the contents of the developer.

  * Developer No. in which a metal-containing compound is added in addition to a polymer dye as a colorant. In No. 4, a polymer dye was used in parts by mass described in the above toner production method, and a metal-containing compound was additionally added so that the squarylium partial structure: metal atom = 1: 1.

<Performance evaluation>
A color copying machine (bizhub C250: manufactured by Konica Minolta Business Technologies, Inc.) is used as an image forming apparatus, and a reflection image (image on paper) and a transmission image (image on paper) are respectively formed on paper and OHP by each developer using the color toner of the present invention. OHP image) was prepared, and performance evaluation was performed by the following method. The toner adhesion amount was in the range of 0.7 ± 0.05 (mg / cm ² ).

"transparency"
The transparency of the image is determined by measuring the visible spectral transmittance of the transmitted image with a “330 type self-recording spectrophotometer” manufactured by Hitachi, Ltd. with reference to an OHP sheet on which toner is not supported, and measuring the spectrum at λmax and λmax-100 nm. The difference in transmittance was determined and evaluated in 4 ranks as follows. When this value is 70% or more, it can be determined that the film has good permeability.

A: 90% or more B: 80% to less than 90% B: 70% to less than 80% X: less than 70%

《Light resistance》
The light fastness was measured by performing a 7-day exposure test on the reflected image using a “Xenon Long Life Weather Meter” (Xenon Arc Lamp, 70,000 lux, 44.0 ° C.) manufactured by Suga Test Instruments Co., Ltd. .

A: Particularly excellent with no decrease in image density. B: Excellent with almost no decrease in image density. Δ: Although there is a slight decrease in image density, it is a level that does not cause any practical problems. There is a problem in image quality.

《Heat resistance (sublimation)》
The fixing roller after producing 10,000 reflection images and the collected silicon oil were observed, and the coloring was visually evaluated according to the following evaluation criteria.

○: The fixing roller and silicone oil are not colored. ×: The fixing roller and silicone oil are colored. The results are shown in Table 2.

  As is apparent from Table 2, the toner for electrophotography (developer No. 1 to 10) of the present invention compared to the pigment system (developer No. 11) and the comparative dye system (developer No. 12 and 13). Is excellent in overall performance of transparency, light resistance and heat resistance.

  As described above, by using the color toner of the present invention, it is possible to provide an image showing excellent storage stability over a long period of time because an image quality with high transparency and light resistance can be obtained. The heat resistance (sublimation), which was regarded as a problem with the used toner, could also be improved.

Claims (10)

1. An electrophotographic toner comprising a polymer dye having a residue of a squarylium dye as a partial structure. The electrophotographic toner according to claim 1, wherein the squarylium dye is represented by the following general formula (1) or general formula (2).

[Wherein, R ₁ and R ₄ each represent a substituent, R ₂ , R ₃ , R ₅ and R ₆ each represent a hydrogen atom or a substituent, and p and q each represents an integer of 0 to 4] To express. Q ₁ and Q ₂ each represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and may be further condensed or have a substituent. L _5, L _6, L ₇ and L ₈ each represents a methine group which may have a substituent, R ₇ and R ₈ each represent a substituent. t and u each represents 0 or 1; ] The toner for electrophotography according to claim 1, comprising a homopolymer or a copolymer derived from a monomer represented by the following general formula (3).
Formula _{(3) D- (L 1)} n -C (R 10) = CH 2
[Wherein, D represents a residue of a squarylium dye, L ₁ represents a divalent linking group, R ₁₀ represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and n represents 0 or 1 Represents. ] The electrophotographic toner according to claim 1, comprising a homopolymer or a copolymer derived from a monomer represented by the following general formula (4).
Formula _{(4) X 1 - (L} 2) n -D- (L 3) n -X 2
[Wherein D represents a residue of a squarylium dye, L ₂ and L ₃ each represent a divalent linking group, and X ₁ and X ₂ each represent a carboxyl group, an amino group, a hydroxyl group, an isocyanato group or an epoxy group. N represents 0 or 1. ] A polymer compound obtained by reacting a compound represented by the following general formula (5) with a polymer having a substituent capable of reacting with the substituent X _{3 in the} compound: The toner for electrophotography according to 1 or 2.
Formula _{(5) D- (L 4)} n -X 3
[In the formula, D represents a residue of squarylium dye, L ₄ represents a divalent linking group, X ₃ represents a carboxyl group, an amino group, a hydroxyl group, an isocyanato group or an epoxy group, and n is 0 or 1 Represents. ] The electrophotographic toner according to claim 1, comprising at least one metal-containing compound. The electrophotographic toner according to claim 6, wherein the metal-containing compound is a Cu compound. The toner for electrophotography according to claim 1, wherein the toner is a polymerized toner. A polymer dye characterized by having a residue of a squarylium dye as a partial structure. The polymer dye according to claim 9, wherein the squarylium dye is represented by the following general formula (11) or (12).

Wherein each R ₁ and R ₄ represents a substituent, each R _2, R _3, R ₅ and R ₆ represents a hydrogen atom or a substituent, the each integer p and q are 0-4 To express. Q ₁ and Q ₂ each represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and may be further condensed or have a substituent. L ₅ , L ₆ , L ₇ and L ₈ each represents a methine group which may have a substituent, and R ₇ and R ₈ each represent a substituent. t and u each represents 0 or 1; ]