JP2011178942A - Colorant, colorant composition, electrophotographic toner, color filter, and front filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colorant having a high solidity such as preferable tone, light resistance and ozone resistance, and a colorant composition containing the same. <P>SOLUTION: The colorant composition includes as a colorant a compound represented by formula 1, wherein M is a metal atom, X and Y are each a halogen atom, a hydroxy group, an alkyl group, an alkynyl group, an alkoxy group, a siloxy group, an aryl group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a sulfamoyloxy group, an alkylsulfonyloxy group, or an alkylcarbonyloxy group, and n and m are each 0 or 1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel colorant and colorant composition, and an electrophotographic toner, a color filter and a display front filter using the same.

  In recent years, as image recording materials, materials for forming color images have been mainstream, and as application fields of colored compositions, specifically, ink-jet recording materials, electrophotographic recording materials, and sensitivity. Examples include thermal transfer recording materials, optical recording media, transfer silver halide photosensitive materials, printing inks, and recording pens. In addition, a color filter is used for recording and reproducing a color image in an imaging device such as a CCD in an imaging device and in an LCD or PDP in a display. These color image recording materials and color filters use so-called additive and subtractive primary colorants to reproduce or record full-color images, but they have absorption characteristics that can realize a preferable color gamut. Thus, there is a demand for a fast dye that can withstand various use conditions and environmental conditions.

  Furthermore, examples of the material containing a dye and required to withstand severe use conditions and environmental conditions include a photoelectric conversion material for solar cells.

  As a dye for a color filter or a front filter for a display, a squarylium dye has been studied in the past and has been put into practical use, but there are many points that cannot be satisfied with color tone and spectral absorption characteristics, Many points which were insufficient in weather resistance, especially light resistance were seen (for example, refer patent documents 1-5).

  On the other hand, with the widespread use of electrophotographic color image forming apparatuses, their applications have been diversified and demands for image quality have become stricter. When copying images such as general photographs, catalogs, and maps, it is required to reproduce very finely and faithfully, even down to the finest parts. It is desired to extend the color reproduction range. In recent years, especially in the field of printing, where high-definition is required, the electrophotographic method is required to have high definition equal to or higher than the printing quality.

  Conventionally, known organic pigments and oil-soluble 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 oil-soluble dyes, but are present in a state of being dispersed in the form of particles in the toner, resulting in increased hiding power and transparency. It will decline. In general, since the dispersibility of the pigment is poor, the transparency is impaired, the saturation is lowered, and the color reproducibility of the image is hindered. In addition, in order to make it possible to visually confirm the color of the toner in the lowermost layer, the lowermost toner in the color-superposed toner is not hidden by the upper layer, and is fixed. In addition, the transparency of the toner is required, and in order to maintain the color reproducibility of the original, the dispersibility of the colorant and the coloring power are required.

  Transparency is improved by, for example, using the flushing method as a method of dispersing the pigment to achieve the pigment dispersion diameter of the order of submicron by primary particles without aggregated secondary particles. Means for improving the charging property, fixing property, and image uniformity by coating the pigment particles with a binder resin and an outer shell resin have been proposed (see, for example, Patent Documents 6 and 7).

  However, even in the case of outputting with the toner proposed in these, it is difficult to obtain a sufficient hue and transparency in the case of a pigment toner.

  Further, in a color image forming apparatus, in principle, all color reproduction can be performed by subtractive color mixture using three primary colors of yellow, magenta, and cyan. However, in reality, when a pigment is dispersed in a thermoplastic resin. Spectral characteristics and color mixing when different color toners are overlapped reduce the color reproducible range and saturation, so there are still many issues remaining to faithfully reproduce the original color. ing.

  As described above, since a full-color image is colored by mixing two or more color toners that are superimposed, it is necessary to obtain a balanced hue. For example, color toners of yellow, magenta, and cyan are used. There has been proposed a color toner set in which the pigments and their contents are appropriately selected (see, for example, Patent Document 8). In addition, a method of forming an image using a solid color toner (dark toner) in the solid portion and a toner (light toner) having a lighter density in the highlight portion has been proposed (see, for example, Patent Document 9). . However, even if these methods are used, the color reproducibility at the time of color mixing is still insufficient.

  Further, as a unique problem that occurs when toners of different colors are mixed instead of a single color toner, for example, there is a phenomenon that the light resistance of cyan toner deteriorates when magenta toner and cyan toner are mixed. This is because the light energy absorbed by the magenta dye moves to the cyan dye. In general, when a phthalocyanine dye is used as a cyan dye, such a phenomenon hardly occurs because the light resistance is high. However, since phthalocyanine-based dyes have low ozone resistance, it is difficult to achieve both light resistance and ozone resistance when a magenta toner and a cyan toner are mixed to form a printed matter, so that these characteristics are satisfied. Development of a toner set is desired.

  Further, copper phthalocyanine colorants are widely known as phthalocyanine colorants. A toner using a copper phthalocyanine-based colorant is versatile and has excellent light resistance, but has a high baseline on the long wavelength side in the reflection spectrum of the image, and forms an image with a hue that makes it feel cloudy. There was a trend. Therefore, it is said that it is not suitable for image formation that requires high color reproducibility, which is typified by printing of company logo marks.

  Therefore, development of a toner that does not cause color turbidity by improving the copper phthalocyanine-based colorant has been studied (for example, see Patent Document 5), but has not yet been sufficiently solved.

  Further, a toner using a pigment such as a copper phthalocyanine-based colorant has versatility to obtain an image level image quality created with a printing ink, but it is difficult to exhibit color reproducibility equivalent to that of a photographic image. Therefore, a toner containing a colorant capable of expressing a hue angle optimum for color reproduction of a photographic image instead of a copper phthalocyanine colorant has been studied (for example, see Patent Documents 10 and 11). ).

  In particular, in recent years, the demand for printing an image on a display device for image processing on a CRT display or liquid crystal display, submission by electronic data, personal use, etc. is rapidly expanding. SRGB (for example, “Multimedia Systems and Equipment-Color Measurement and Management-Part2-1: Color Management-Default RGB Color Space-sRGB” can be referred to IEC-1 619). Therefore, a toner set having high color reproducibility is demanded.

  Conventionally used C.I. A method of using zinc phthalocyanine instead of I Pigment Blue 15.3 has also been proposed (see, for example, Patent Document 12). However, since the transparency of zinc phthalocyanine images is insufficient, it must be said that this is an inadequate means for color reproducibility, and further improved color reproducibility, especially in low lightness areas. It was desired to improve the saturation at the time of color mixing.

JP 2004-86133 A JP 2004-99712 A JP 2004-99713 A JP 2004-315789 A WO04 / 5981 specification JP 2003-302792 A Japanese Patent Laid-Open No. 9-26673 JP-A-11-160914 JP 2004-126248 A JP-A-5-239368 JP 2006-63171 A JP 2000-347476 A

  The present invention has been made in view of the above-mentioned problems, and its first object is to have a high color fastness and high fastness to changes in the use environment represented by light resistance and ozone resistance. It is to provide a colorant having and a colorant composition containing the same.

  As a second object, a product containing the colorant composition of the present invention, among them, a color filter having a high fastness and a good color tone represented by heat resistance and light resistance, a front filter for display, and a CRT, An object of the present invention is to provide an electrophotographic toner which has good compatibility with sRGB when printed from a screen of a display device such as a liquid crystal display and has high color reproducibility by improving saturation in a low lightness region.

As a result of diligent research, the present inventors have solved the problems and achieved the object.
That is: A colorant composition comprising a compound represented by the following general formula (1) as a colorant.

[Wherein, M represents a metal atom. X and Y are each a halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, or Represents an alkylcarbonyloxy group. n and m each represents 0 or 1; ]
2. 2. The colorant composition as described in 1 above, wherein M in the general formula (1) is at least one metal atom selected from magnesium, zinc, aluminum and silicon.

  3. As a colorant. 3. The colorant composition as described in 1 or 2 above, which comprises a compound represented by the general formula (1) and a phthalocyanine compound.

  4). 4. The colorant composition as described in 3 above, wherein the phthalocyanine compound is a compound represented by the following general formula (2).

[Wherein, A ₁ , A ₂ , A ₃ and A ₄ each represents a 5- to 6-membered aromatic ring or heterocyclic ring. R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group Carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy Group, acyloxy group, carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, carbonylamino group, sulfamoylamino group, semicarbyl group Basid group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, thio group, sulfonyl group, sulfinyl group, sulfo group or It represents a salt, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, or a group containing a phosphate amide or phosphate ester structure. o, p, q, and r each represent an integer of 1 to 4. Z ₁ and Z ₂ each represent a halogen atom, a hydroxy group, an alkyl group, an alkynyl group, an alkoxy group, a siloxy group, an aryl group, an aryloxy group, an acyloxy group, a carbamoyloxy group, or a sulfamoyloxy group. ]
5. An electrophotographic toner comprising the colorant composition according to any one of 1 to 4 above.

  6). 5. A color filter comprising the colorant composition according to any one of 1 to 4 above.

  7). 5. A display front filter comprising the colorant composition according to any one of 1 to 4 above.

  8). The coloring agent characterized by being a compound represented by following General formula (1).

[Wherein, M represents a metal atom. X and Y are each a halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, or Represents an alkylcarbonyloxy group. n and m each represents 0 or 1; ]

  According to the present invention, a robust colorant having absorption characteristics capable of realizing a preferable color gamut and capable of withstanding various use conditions typified by light resistance and heat resistance, and environmental conditions, and a colorant composition containing the colorant Things can be provided.

  Further, it is possible to provide a color filter, a display front filter, and an electrophotographic toner that contain this colorant composition and have high color reproducibility and fastness. In particular, the toner set using the electrophotographic toner of the present invention has good color tone adjustment when printing images on various displays without causing a problem with the toner production method, and particularly high color in a low lightness region. Has reproducibility.

  In addition, the hue at the time of color mixing is improved, and further, the image has excellent effects of light resistance and ozone resistance.

1 is a schematic diagram illustrating an example of a tandem full-color image forming apparatus capable of two-component development type image formation. 1 is a schematic view of a 4-cycle full-color image forming apparatus capable of image formation by a non-magnetic one-component development system. FIG. 2 is a schematic diagram illustrating an example of a developing device (toner cartridge). FIG. 3 is a schematic diagram illustrating an example of a belt fixing type fixing device using a belt and a heating roller.

  As a result of intensive studies in view of the above problems, the present inventors have found a colorant composition having high color reproducibility and fastness by using a novel compound as a colorant.

  The details of the present invention will be described below.

<< Compound Represented by Formula (1) >>
The colorant composition of the present invention is characterized by containing the compound represented by the general formula (1).

  In the general formula (1), M represents a metal atom. X and Y are each a halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, or Represents an alkylcarbonyloxy group. n and m each represents 0 or 1;

  Hereinafter, the details of the compound represented by the general formula (1) will be described.

  In the general formula (1), M represents a metal atom. As metal atoms, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu , Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi. The metal atom represented by M is preferably Mg, Ti, V, Ni, Cu, Zn, Al, Si, or Sn, and more preferably Mg, Ti, Cu, Zn, Al, or Si. Further, Mg, Zn, Al, and Si are most preferable in consideration of the recent heightened interest in environmental impacts on the environment and the influence during production or use.

  In the general formula (1), X and Y are each a halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, carbamoyloxy group, sulfamoyloxy Represents a group, an alkylsulfonyloxy group, or an alkylcarbonyloxy group.

  X and Y may be further substituted with a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), an alkyl group (aralkyl group, cycloalkyl group). , And active methine groups), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups (regardless of the position of substitution), heterocyclic groups containing quaternized nitrogen atoms (eg, pyridinio groups, imidazoliols) Group, quinolinio group or isoquinolinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group , Oxamoyl group, cyano group, thiocarbamoyl group Hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy group or propyleneoxy group units), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy Group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide Group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, merca Group, (alkyl, aryl, or heterocyclic) thio group, (alkyl, aryl, or heterocyclic) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, Sulfonylsulfamoyl group or a salt thereof, a group containing a phosphate amide or phosphate ester structure, a silyloxy group (for example, trimethylsilyloxy and t-butyldimethylsilyloxy), and a silyl group (for example, trimethylsilyl, t-butyldimethyl) Silyl or phenyldimethylsilyl) and the like.

  X and Y are preferably an alkyl group, an alkoxy group, a siloxy group, an aryloxy group, a carbamoyloxy group, a sulfamoyloxy group, and more preferably an alkoxy group, a siloxy group, a carbamoyloxy group, or a sulfamoyloxy group. It is a group.

  In the general formula (1), n and m each represents 0 or 1. n and m differ depending on the metal atom represented by M. As an example, when M is Cu, n and m are 0 at the same time, and when M is Si, n and m are 1 at the same time.

  Although the specific example of a compound represented by General formula (1) below is given, this invention is not limited only to these illustrated compounds.

  The colorant represented by the general formula (1) of the present invention is a dicyanoethylene compound or a substituted or unsubstituted 2,5-except that 3,5-diimino-1,2,4-triazole is used as a raw material. It can be synthesized by a conventionally known method for synthesizing tetraazaporphyrin from diiminopyrrole.

<< Phthalocyanine compound, compound represented by general formula (2) >>
In the colorant composition of the present invention, it is preferable to use a phthalocyanine compound as a colorant together with the compound represented by the general formula (1) according to the present invention.

  Examples of the phthalocyanine compound that can be used in the present invention include conventionally known phthalocyanine compounds without limitation, and among them, it is particularly preferable to use a compound represented by the following general formula (2).

In the general formula _{(2), A 1, A} 2, A 3 and _{A 4} represent an aromatic ring or heterocyclic ring each 5-6 membered. R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group Carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy Group, acyloxy group, carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, carbonylamino group, sulfamoylamino group, semicarbyl group Basid group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, thio group, sulfonyl group, sulfinyl group, sulfo group or It represents a salt, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, or a group containing a phosphate amide or phosphate ester structure. o, p, q, and r each represent an integer of 1 to 4. Z ₁ and Z ₂ each represent a halogen atom, a hydroxy group, an alkyl group, an alkynyl group, an alkoxy group, a siloxy group, an aryl group, an aryloxy group, an acyloxy group, a carbamoyloxy group, or a sulfamoyloxy group.

  The compound of the general formula (2) will be described in more detail.

In the general formula (2), the 5- to 6-membered aromatic ring or heterocyclic ring represented by A ₁ , A ₂ , A ₃ and A ₄ includes a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, and a pyrimidine. A ring, an imidazole ring, a pyrazole ring, etc. are mentioned. Among these, as A ₁ , A ₂ , A ₃ and A ₄ , a benzene ring and a pyridine ring are preferable, and a benzene ring is most preferable.

In the general formula (2), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an alkyl group (aralkyl group, cycloalkyl). Group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (regardless of the position of substitution), heterocyclic group containing quaternized nitrogen atom (for example, pyridinio group, Imidazolio group, quinolinio group, or isoquinolinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or its salt, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl Group, oxamoyl group, cyano group, thiocarbamoyl group, hydro Si group, alkoxy group (including a group containing ethyleneoxy group or propyleneoxy group unit repeatedly), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy, aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy Group, amino group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamido group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group Thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl , Aryl or heterocyclic) thio group, (alkyl, aryl, or heterocyclic) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or Its salts, groups containing phosphoric acid amide or phosphate ester structures, silyloxy groups (eg trimethylsilyloxy and t-butyldimethylsilyloxy), and silyl groups (eg trimethylsilyl, t-butyldimethylsilyl or phenyldimethylsilyl) ) And the like. These substituents may be further substituted with these substituents.

R _{1 to} R ₄ are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, an alkylthio group, or an arylthio group, more preferably a hydrogen atom, a chloro atom, or an alkyl group. A group, an alkoxy group, and a nitro group.

  In the general formula (2), o, p, q and r are each 0 to 4, preferably 0 to 2, more preferably 0 or 1.

In the general formula (2), Z ₁ and Z ₂ are each an oxygen atom, a halogen atom, a hydroxy group, an alkyl group, an alkynyl group, an alkoxy group, a siloxy group, an aryl group, an aryloxy group, an acyloxy group, a carbamoyloxy group, or a sulfur group. Represents a famoyloxy group. These groups may be substituted with the groups represented by the aforementioned R _{1 to} R ₄ . Z ₁ and Z ₂ are preferably an alkyl group, an alkoxy group, a siloxy group, an aryloxy group, a carbamoyloxy group, and a sulfamoyloxy group, and more preferably an alkoxy group, a siloxy group, a carbamoyloxy group, a sulfayl group. Moyloxy group.

Further, when either Z ₁ or Z ₂ is an oxygen atom, a dimer may be formed by another molecule of the phthalocyanine compound represented by the general formula (2) and an ether bond.

  Hereinafter, although the specific structure of the phthalocyanine compound represented by General formula (2) is shown, this invention is not limited by this. In particular, structural isomers depending on the substitution positions of the substituents are merely examples, and are not limited thereto.

  Next, the colorant composition of the present invention and each product using the same will be described.

<< Colorant composition >>
The colorant of the present invention is preferably used as a composition with a dispersant (binder) or a composition obtained by further adding a solvent to the film formation stability.

  Examples of binders applicable to the colorant composition of the present invention include (meth) acrylate resins, polyester resins, polyamide resins, polyimide resins, polystyrene resins, polyepoxy resins, polyester resins, and amino acids. Resin, fluorine resin, phenol resin, polyurethane resin, polyethylene resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyether resin, polyether ketone resin, polyphenylene sulfide resin, polycarbonate resin, aramid Resins etc. are mentioned, preferably (meth) acrylate resins, polystyrene resins, polyethylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, etc. are preferably used, most preferably (meth) acrylate resins, Police It is a Ren-based resin. These copolymers are also preferred.

  The (meth) acrylate resin is synthesized by homopolymerizing or copolymerizing various methacrylate monomers or acrylate monomers, and by changing the monomer species and the monomer composition ratio, the desired (meth) acrylate resin A resin can be obtained. Further, in the present invention, it can be used together with a (meth) acrylate monomer and a copolymerizable monomer having an unsaturated double bond other than a (meth) acrylate monomer. Can be used by mixing a plurality of other resins together with the poly (meth) acrylate resin.

  Examples of the monomer component forming the (meth) acrylate resin used in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , Isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dimethylaminoethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, di (ethylene glycol) ethyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, isobornyl (meth) acrylate, Ethyl trimethylammonium (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, 2-acetamidomethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) ) Acrylate, 3-trimethoxysilanepropyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) ) Acrylate, glycidyl (meth) acrylate, etc., (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) are preferred. Acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  Polystyrene resins include homopolymers of styrene monomers or random copolymers, block copolymers, and graft copolymers obtained by copolymerizing monomers with other unsaturated double bonds copolymerizable with styrene monomers. Can be mentioned. Furthermore, blends and polymer alloys obtained by blending such polymers with other polymers are also included. Examples of the styrene monomer include nuclear alkyl substitution such as styrene, α-methylstyrene, α-ethylstyrene, α-methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and the like. Examples of the halogenated styrene include styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, and tribromostyrene. Among these, Styrene and α-methylstyrene are preferred.

  By homopolymerizing or copolymerizing these, the resin used in the present invention is synthesized, for example, a copolymer resin such as benzyl methacrylate / ethyl acrylate or butyl acrylate, or a copolymer such as methyl methacrylate / 2-ethylhexyl methacrylate. Polymer resin, copolymer resin of methyl methacrylate / methacrylic acid / stearyl methacrylate / acetoacetoxyethyl methacrylate, copolymer resin of styrene / acetoacetoxyethyl methacrylate / stearyl methacrylate, styrene / 2-hydroxyethyl methacrylate / Examples include stearyl methacrylate copolymers, and copolymer resins such as 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate. .

<Application field of colorant composition>
The colorant composition of the present invention has extremely high performance in fastness typified by light resistance, heat resistance, ozone resistance and the like. In addition, since it has high color reproducibility, products that require these performances at a high level, such as inkjet inks, optical recording materials, sensitizing dyes for solar cells, color filters, front filters for displays, and electrophotographic toners. Can be suitably used.

  Particularly preferred applications include color filters, display front filters, and electrophotographic toners.

  Hereinafter, a color filter, a display front filter, and an electrophotographic toner to which the colorant composition of the present invention is applied will be described in detail.

"Color filter"
When applying the colorant composition of the present invention to a color filter, when dispersing the colorant of the present invention in a resin varnish, various dispersing means such as a two-roll mill, a three-roll mill, a sand mill, and a kneader can be used. .

  In the present invention, as the resin varnish, a varnish used in a conventionally known color filter coloring composition is used. As the dispersion medium, a solvent or an aqueous medium suitable for the resin varnish is used. In addition, conventionally known additives such as a dispersion aid, a smoothing agent, and an adhesive agent are added and used as necessary.

  As the resin varnish, a photosensitive resin varnish and a non-photosensitive resin varnish are used. Examples of the photosensitive resin varnish are photosensitive resin varnishes used for ultraviolet curable inks, electron beam curable inks, etc., and non-photosensitive resin varnishes include, for example, relief printing inks, planographic inks, intaglio gravure inks, Any of varnishes used for printing inks such as stencil screen inks, varnishes used for electrodeposition coating, varnishes used for developers of electronic printing and electrostatic printing, and varnishes used for thermal transfer ribbons can be used.

  Examples of the photosensitive resin varnish include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polymethacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, and an unsaturated polyester resin. Examples of the varnish include polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, polyol acrylate resins, and varnishes to which a monomer is added as a reactive diluent.

  In the color filter of the present invention, a photopolymerization initiator such as benzoin ether or benzophenone is added to the colorant of the present invention and the above varnish, and then the mixture is ground by a conventionally known method to obtain a photosensitive colored composition. Can do. Moreover, it can replace with said photoinitiator and can be set as a thermopolymerizable coloring composition using a thermal polymerization initiator.

  When forming a color filter pattern using the photosensitive coloring composition, spin coating the photosensitive coloring composition on a transparent substrate, coating the entire surface using a low-speed rotary coater, roll coater, knife coater, or the like. A method of performing printing, or performing full printing by various printing methods or partial printing slightly larger than the pattern, adhering a photomask after preliminary drying, and exposing using a super high pressure mercury lamp to print the pattern. it can.

  Subsequently, after forming a pattern, it can develop and wash | clean, and can perform the pattern of a color filter by performing post-baking as needed.

  Examples of non-photosensitive resin varnishes include cellulose acetate resins, nitrocellulose resins, styrene (co) polymers, polyvinyl butyral resins, amino alkyd resins, polyester resins, amino resin modified polyester resins , Polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxyethyl cellulose, water-soluble styrene-maleic acid ester copolymer Examples include salts, water-soluble salts of (meth) acrylic acid ester-based (co) polymers, water-soluble aminoalkyd resins, water-soluble aminopolyester resins, water-soluble polyamide resins, and the like. .

  When forming a color filter pattern using the above-mentioned non-photosensitive coloring composition, the non-photosensitive coloring composition, for example, the above-described various printing methods using a printing ink for color filters is used on a transparent substrate. A method of printing a colored pattern directly on a substrate, a method of forming a colored pattern on a substrate by electrodeposition coating using an aqueous electrodeposition coating composition for a color filter, a method of using an electronic printing method or an electrostatic printing method, or a transfer And a method of once forming a colored pattern on the conductive substrate by the above-mentioned method and the like and transferring it to the color filter substrate. Next, baking is performed as necessary according to a conventional method, polishing for smoothing the surface, or top coating for protecting the surface is performed. Further, a black matrix is formed according to a conventional method to obtain an RGB color filter.

《Front filter for display》
The display front filter of the present invention has the colorant of the present invention in the base material or contains at least one colorant composition of the present invention, and is contained in the base material referred to in the present invention. Of course, it includes the state of being applied to the surface of the substrate, the state of being sandwiched between the substrate and the substrate, and the like.

  Further, the display front filter of the present invention is disposed in front of a self-luminous display device such as a plasma display or an organic EL display, and is used for color adjustment or blocking light emission in an unnecessary wavelength region. For this reason, the front filter for display of the present invention is characterized by having an absorption maximum in the visible region. In order to realize this, the colorant of the present invention is characterized by having an absorption maximum in the visible region in a solution state, and more preferably has an absorption maximum at 400 to 620 nm for color tone adjustment, and fluorescence. It is preferable to have an absorption maximum in the wavelength range corresponding to the valleys of the blue, green, and red spectra that are the light emission of the body. Examples of such a wavelength range include 350 to 400 nm, 480 to 520 nm, and the like. In particular, in order to cut off neon emission, it is preferable to have an absorption maximum at 560 to 620 nm, and more preferable to have an absorption maximum at 590 to 605 nm.

  Examples of the substrate applicable to the front filter for display of the present invention include a transparent resin plate, a transparent film, transparent glass, and the like, and particularly limited if the light transmittance at a wavelength of 400 to 700 nm is 40% or more. There is no. For example, polyimide, polysulfone (PSF), polyethersulfone (PES), polyethylene terephthalate (PET), polymethylene methacrylate (PMMA), polycarbonate (PC), polyetheretherketone (PEEK), polypropylene (PP), triacetyl A cellulose (TAC) etc. are mentioned. In particular, acrylic resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polymethyl methacrylate (PMMA), polycarbonate resins, and the like are preferably used.

  Although there will be no restriction | limiting in particular if the thickness of a base material has a certain amount of mechanical strength, Usually, they are 20 micrometers-10 mm, 20 micrometers-1 mm are preferable, and 20 micrometers-200 micrometers are especially preferable.

The method for producing the front filter for display of the present invention using the colorant of the present invention or the colorant composition is not particularly limited,
(1) Method of containing in transparent adhesive (2) Method of containing in polymer molded body (3) Method of coating on polymer molded body or glass surface, etc.

  Specific examples of the transparent adhesive listed in (1) include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), and ethylene-vinyl acetate adhesives (EVA). Etc., sheet-like or liquid pressure-sensitive adhesives such as polyvinyl ether, saturated amorphous polyester, melamine resin, etc., among which acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and polyvinyl butyral pressure-sensitive adhesives are preferable. The addition amount of the colorant of the present invention is usually 10 ppm to 30% by mass, preferably 10 ppm to 20% by mass, and particularly preferably 10 ppm to 10% by mass.

  (2) The polymer resin molded body mentioned in (2) includes (A) a method in which the colorant composition of the present invention is kneaded into a resin and heat-molded, and (B) an organic solvent in which a resin or resin is added. Examples thereof include a method in which a monomer and a colorant composition of the present invention are dispersed and dissolved, and a polymer molded body is produced by a casting method.

  The resin used in (A) is preferably as highly transparent as possible when produced in a plate or film form, and specifically, polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate. Phthalate, polyarylate, polyether ketone, polyamide, such as polycarbonate, polyethylene, polypropylene, nylon 6, cellulose resin such as polyimide, triacetyl cellulose, fluorine resin such as polyurethane, polytetrafluoroethylene, vinyl compound such as polyvinyl chloride , Polyacrylic acid, polyacrylic acid ester, polyacrylonitrile, vinyl polymer addition polymer, polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride and other vinylidene compounds, vinylidene fluoride / trifluoro Roechiren copolymers, copolymers of ethylene / vinyl compound-vinyl acetate copolymer, or a fluorine-based compound, polyether such as polyethylene oxide, epoxy resins, polyvinyl alcohol, and polyvinyl butyral.

  The processing conditions include adding and mixing the colorant composition of the present invention to a polymer powder or pellet as a base, mixing, heating and dissolving at 150 to 350 ° C., and molding to produce a plate, Examples thereof include a method of forming a film with an extruder, a method of producing a raw fabric with an extruder, and stretching the film biaxially to biaxially at 30 to 120 ° C. to form a film having a thickness of 10 to 200 μm. In addition, when kneading, an additive used for ordinary resin molding such as plasticity may be added.

  In the casting method (B), the colorant composition of the present invention is added and dissolved in an organic solvent solution or organic solvent of a resin or resin monomer, and if necessary, a plasticizer, a polymerization initiator, and an antioxidant are added. A plate or a film can be produced by pouring onto a mold or drum having the required surface state, solvent volatilization, drying or polymerization, solvent volatilization and drying.

  Examples of resins used include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, Examples thereof include polyvinyl-modified resins (PVA, EVA, etc.) or resin monomers of those copolymer resins. Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, or mixtures thereof.

  As a method of coating on the polymer molded body or glass surface mentioned in (3), a method of forming a colorant composition by dissolving the colorant of the present invention in a binder resin and an organic solvent and then forming a paint, uncolored And a method of dispersing a finely pulverized (50 to 500 nm) colorant of the present invention in an acrylic emulsion paint to obtain an acrylic emulsion-based aqueous paint. In the coating material, additives such as antioxidants used in ordinary coating materials may be added.

  Examples of binders include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, and polyvinyl resins. Examples thereof include a modified resin (PVB, EVA, etc.) or a copolymer resin thereof.

  Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, or mixtures thereof.

  The concentration of the colorant composition of the present invention varies depending on the Gram extinction coefficient, coating thickness, target absorption intensity, target visible light transmittance, etc., but is usually 0.1 ppm to 30 with respect to the mass of the binder resin. % By mass. Moreover, resin concentration is 1-50 mass% normally with respect to the whole coating material.

  The paint prepared by the above method is applied by forming a thin film on a base material by a known method such as a bar coder, a blade coater, a spin coater, a reverse coater, a die coater, or a coating method such as spraying. be able to.

  The front filter for display of the present invention preferably has an electromagnetic wave shielding function or a near infrared ray blocking function. As the electromagnetic wave shield, a laminate using a silver thin film or a metal mesh mainly using copper can be used. As a laminate using a silver thin film, a laminate in which a dielectric such as indium oxide, zinc oxide, titanium oxide and silver are alternately laminated is preferable. As the metal mesh, a fiber mesh obtained by vapor-depositing a metal on a fiber, an etching mesh that forms a pattern using a photolithography technique and obtains a mesh by etching, or the like can be used. In addition, a method of patterning with a metal-containing ink, a method of applying silver halide, developing and fixing, and the like are also preferably used.

  As for the near infrared ray blocking function, when an electromagnetic wave shield using a silver thin film is used, the near infrared ray can be simultaneously blocked due to scattering of silver by free electrons. In addition, when a mesh, ink patterning, or development method is used, a film that absorbs or reflects near infrared rays is used separately.

  Furthermore, a functional transparent layer such as a known antireflection layer, antiglare layer, hard coat layer, antistatic layer, or antifouling layer can be added to the display front filter of the present invention.

  In addition, for ultraviolet cut, an ultraviolet cut acrylic plate may be used for the substrate, or an ultraviolet absorbing layer may be formed on one or both sides of the substrate, but in the front filter composition for display of the present invention, You may contain a ultraviolet absorber. Examples of ultraviolet absorbers include salicylic acid derivatives (UV-1), benzophenone derivatives (UV-2), benzotriazole derivatives (UV-3), acrylonitrile derivatives (UV-4), benzoic acid derivatives (UV-5) or organic There are metal complex salts (UV-6), etc., as salicylic acid derivative (UV-1), phenyl salicylate, 4-t-tylphenyl salicylic acid, etc., as benzophenone derivative (UV-2), 2-dihydroxybenzophenone, 2-Hydroxy-4-methoxybenzophenone and the like as benzotriazole derivatives (UV-3) include 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ' -5'-di-butylphenyl) -5-chlorobenzotriazole, etc. Examples of the nitrile derivative (UV-4) include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, methyl-α-cyano-β- (p-methoxyphenyl) acrylate, and the like, benzoic acid derivatives (UV- 5), resorcinol-monobenzoate, 2 ′, 4′-di-t-butylphenyl-3,5-t-butyl-4-hydroxybenzoate, etc., and organometallic complex (UV-6), nickel Examples thereof include bis-octylphenylsulfamide, nickel salt of ethyl-3,5-di-t-butyl-4-hydroxybenzyl phosphate, and the like.

  The ultraviolet absorber described above preferably used in the present invention has high transparency and is excellent in the effect of preventing deterioration of an optical device such as a polarizing plate, a liquid crystal element, or a plasma display, and a benzotriazole ultraviolet absorber or a benzophenone ultraviolet absorber. A benzotriazole-based ultraviolet absorber with less unnecessary coloration is more preferable.

  In order to obtain an electronic display or a plasma display panel display device using the display front filter of the present invention, any known display device or commercially available display device can be used without particular limitation.

  A plasma display panel display device is a device that displays a color image according to the following principle. A cell corresponding to each pixel (R (red), G (green), B (blue)) provided between two glass plates is provided between the front glass plate and the rear glass plate, and the cell Xenon gas or neon gas is sealed in the inside, and a phosphor corresponding to each pixel is applied to the back glass plate side in the cell. By discharge between the display electrodes, the xenon gas and neon gas in the cell are excited to emit light, and ultraviolet rays are generated. By irradiating the phosphor with this ultraviolet ray, visible light corresponding to each pixel is generated. Then, an address electrode is provided on the rear glass plate, and by applying a signal to the address electrode, which discharge cell is displayed is controlled, and a color image is displayed.

  The front filter for display of the present invention can be suitably used as a neon cut filter that selectively blocks light emission of neon gas in the cell. As described above, the plasma display performs color display by phosphor emission, but when neon atoms are excited and return to the ground state, it is known to emit so-called neon orange light centered around 600 nm. (Journal of the Institute of Image Information Media, Vol. 51, No. 4, P. 459-463 (1997)). For this reason, the plasma display has a drawback that a bright red color cannot be obtained because orange is mixed with red. In order to eliminate this drawback, it is desired to cut off neon light emission. Therefore, when the compound of the present invention is used as a composition for a neon emission absorption filter, the compound of the present invention preferably has an absorption maximum at 560 to 620 nm in a solution state and absorbs at 580 to 605 nm. More preferably, it has a maximum. At this time, the transmittance of the filter at the absorption maximum in the wavelength region of 560 to 620 nm is preferably in the range of 0.01 to 80%, and more preferably in the range of 1 to 70%. In order to improve the color reproducibility of the display, the absorption waveform in the wavelength region of 560 to 620 nm is preferably sharp. Specifically, in the absorption waveform at 560 to 620 nm, the half width value (the width of the wavelength region showing the absorbance at half of the absorbance at the absorption maximum) is preferably 15 to 100 nm, and more preferably 20 to 70 nm. More preferably, it is 25-50 nm.

<Electrophotographic toner>
The electrophotographic toner of the present invention (hereinafter also simply referred to as toner) is a toner using a colorant composition containing a compound represented by the general formula (1) of the present invention, and is light and ozone resistant. And has a wider color gamut than images formed using conventional toners and printing inks, and can exhibit stable color reproducibility. In particular, in recent years, there are many cases where an image displayed on a computer screen is printed out, but since the color gamut of conventional color printing is much narrower than the color gamut of a computer display, the image on the display is printed out. There was a big difference in color tone. However, by using the toner of the present invention, a print image closer to the color gamut of the computer display than before can be obtained. Thus, it can be said that the toner of the present invention greatly contributes to the expansion of the color gamut in the printed image.

  In the present invention, in addition to the colorant represented by the general formula (1) of the present invention, another phthalocyanine colorant, preferably a silicon phthalocyanine colorant represented by the general formula (2) is used in combination. As a result, an electrophotographic toner having even better performance can be obtained.

  There are no particular restrictions on the type of colorant and the number of colorants when two colorants are used in combination as described above, but one type of colorant represented by the general formula (1) and other phthalocyanines It is preferable to use one or more colorants in combination, and it is more preferable to use one other phthalocyanine colorant in combination.

  Further, the amount of the colorant represented by the general formula (1) of the present invention is not particularly limited at the time of toner production, but it is represented by the general formula (1) with respect to the total amount of the colorant used. The colorant is preferably used in an amount of 10 to 80% by mass, more preferably 15 to 60% by mass, and most preferably 20 to 50% by mass.

[Combination colorant]
The toner of the present invention is obtained by salting out / fusion-bonding composite resin particles described later and colorant particles.

  The colorant constituting the toner of the present invention (colorant particles used for salting out / fusion with composite resin particles) can be used in combination with the colorant represented by the general formula (1) of the present invention. In addition to the colorant represented by the general formula (2) according to the present invention, various inorganic pigments, organic pigments, and dyes can be used.

<Inorganic pigment>
A conventionally well-known thing can be used as an inorganic pigment. Specific inorganic pigments are exemplified below.

  Examples of the black inorganic pigment include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite.

  These inorganic pigments can be used alone or in combination as required. Moreover, the addition amount of a pigment is 2-20 mass% with respect to a polymer, Preferably 3-15 mass% is selected.

  When used as a magnetic toner, the above magnetite can be added. In this case, it is preferable to add 20 to 60% by mass in the toner from the viewpoint of imparting predetermined magnetic properties.

<Organic pigments and dyes>
Conventionally known organic pigments and dyes can also be used. Specific organic pigments and dyes are exemplified below.

  Examples of the magenta or red pigment include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the pigment for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, and the like.

  Examples of the pigment for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

  Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc. can be used, and mixtures thereof can also be used.

<Surface modifier>
The colorant (colorant particles) constituting the toner of the present invention may be surface-modified. A conventionally well-known thing can be used as a surface modifier, Specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent etc. can be used preferably. Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, vinyltrimethyl. Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureido Examples thereof include propyltriethoxysilane. Examples of titanium coupling agents include TTS, 9S, 38S, 41B, 46B, 55, 138S, and 238S, which are commercially available under the trade name “Plenact” manufactured by Ajinomoto Co., Inc., and commercial products A manufactured by Nippon Soda Co., Ltd. -1, B-1, TOT, TST, TAA, TAT, TLA, TOG, TBSTA, A-10, TBT, B-2, B-4, B-7, B-10, TBSTA-400, TTS, TOA -30, TSDMA, TTAB, TTOP and the like. Examples of the aluminum coupling agent include “Plenact AL-M” manufactured by Ajinomoto Co., Inc.

  The addition amount of these surface modifiers is preferably 0.01 to 20% by mass, and more preferably 0.1 to 5% by mass with respect to the colorant.

  Examples of the method for modifying the surface of the colorant particles include a method in which a surface modifier is added to the dispersion of the colorant particles and this system is heated to react.

  The surface-modified colorant particles are collected by filtration, washed with the same solvent and filtered, and then dried.

<Oil-soluble dye>
One preferred form of the toner according to the present invention is that the colorant is an oil-soluble dye. Oil-soluble dyes are usually dyes that are soluble in organic solvents that do not have water-soluble groups such as carboxylic acids and sulfonic acids and are insoluble in water. However, oil-soluble dyes are oil-soluble by salting water-soluble dyes with long-chain bases. The dye which shows is also included. For example, acid dyes, direct dyes, and salt-forming dyes of reactive dyes and long chain amines are known.

  Although not limited to the following, for example, Variast Yellow 4120, Varifast Yellow 3150, Varifast Yellow 3108, Varifast Yellow 2310N, Varifast R1 304, Valifast R3, 304 , BaliFast Blue 2610, Valifast Blue 2606, VariFast Blue 1603, Oil Yellow GG-S, Oil Yellow 3G, Oil Yellow 129, Oil Yellow 107, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105 Il Red RR, Oil Red OG, Oil Red 5B, Oil Pink 312, Oil Blue BOS, Oil Blue 613, Oil Blue 2N, Oil Black BY, Oil Black BS, Oil Black 860, Oil Black 5970Oil Black 5960 5905, Kayset Yellow SF-G, Kayase Yellow K-CL, Kayase Yellow GN, Kayase Yellow A-G, Kayset Yellow 2G, Kayset Red SF-4G, Kayase Red Kad SetK-4 -BR, Kayset Magenta 312, Kay set Blue K-FL, FS Yellow 1015, FS Magenta 1404, FS Cyan 1522, FS Blue 1504, C.I. I. Solvent Yellow 88, 83, 82, 79, 56, 29, 19, 16, 14, 04, 03, 02, 01, C.I. I. Solvent Red 84: 1, C.I. I. Solvent Red 84, 218, 132, 73, 72, 51, 43, 27, 24, 18, 01, C.I. I. Solvent Blue 70, 67, 44, 40, 35, 11, 02, 01, C.I. I. Solvent Black 43, 70, 34, 29, 27, 22, 7, 3, C.I. I. Solvent Violet 3, C.I. I. SolventGreen 3 and 7, Plast Yellow DY352, Plast Red 8375, Mitsui Chemicals MS Yellow HD-180, MS Red G, MS Msgenta HM-1450H, MS Blue HM-1384, Sumitomo Chemical ES Red 3001, ES Red 3002 , ES Red 3003, TS Red 305, ES Yellow 1001, ES Yellow 1002, TS Yellow 118, ES Orange 2001, ES Blue 6001, TS Turq Blue 618, Bayer's MACROL Yellow Yellow 6G, CeresB , MACROLEX Red Vio let R and the like.

  Disperse dyes can be used as the oil-soluble dye, and are not limited to the following, but examples thereof include C.I. I. Disperse Yellow 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 119, 122, 124, 126, 160, 184: 1, 186, 198, 199, 204, 224 and 237; C . I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; C.I. I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1, 177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 257, 266, 267, 287, 354, 358, 365 and 368 and C.I. I. Disperse Green 6: 1 and 9 etc. are mentioned.

  In addition, azomethine dyes derived from couplers such as cyclic methylene compounds such as phenol, naphthols, pyrazolones and pyrazolotriazoles, and open-chain methylene compounds, and indoaniline dyes are also preferably used as oil-soluble dyes.

[Colorant content]
In the toner of the present invention, the content of the colorant represented by the general formula (1) is preferably in the range of 2 to 20% by mass with respect to the resin, and further contains 3 to 15% by mass of the colorant. It is preferable from the viewpoint that a sufficient concentration can be obtained and the protective ability of the colorant by the resin can be expressed.

(Image stabilizer)
In the toner of the present invention, an image stabilizer, for example, a compound described and cited on pages 10 to 13 of JP-A-8-29934 may be added to improve the storage stability of the colorant. And commercially available phenolic, amine, sulfur and phosphorus compounds. For the same purpose, for example, an organic ultraviolet absorbent or an inorganic ultraviolet absorbent may be added as an ultraviolet absorbent.

  Examples of organic ultraviolet absorbers include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole. Benzotriazole compounds such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, etc., phenyl salsylate, 4-t-butylphenyl salsylate, 2, Hydroxybenzoate systems such as 5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate Compounds and the like.

  Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, iron oxide, and barium sulfate. Organic ultraviolet absorbers are preferred, and ultraviolet absorbers include 50% transmittance. The wavelength at is preferably 350 to 420 nm, more preferably 360 nm to 400 nm. When the wavelength is lower than 350 nm, the ultraviolet blocking ability is weak, and when the wavelength is higher than 420 nm, the coloring becomes strong. Although there is no restriction | limiting in particular about addition amount, The range of 10-200 mass% is preferable with respect to a coloring agent, and 50-150 mass% is more preferable. It is also preferable to use these in combination.

[Silanol compound]
The toner of the present invention preferably contains a silanol compound represented by the following general formula (S).

General formula (S)
(R) _m Si (OH) _n
In general formula (S), R represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or a siloxy group, m and n each represents an integer of 1 to 3, and m + n = 4. When m is 2 or 3, Rs may be the same or different.

In the general formula (S), examples of the alkyl group represented by R include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, and an n-octyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. Examples of the heterocyclic group include a pyridyl group, a pyrimidyl group, a quinolyl group, a pyrazolyl group, and an imidazolyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and an n-octoxy group. These may be further substituted by the substituents mentioned for R _{1 to} R ₄ in the general formula (2). R is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, or a siloxy group. In the case of a siloxy group, it is an oligomer, and more preferably a hydrogen atom or carbon number. An alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms.

  As the silanol compound according to the present invention, those having knowledge in the field can be easily synthesized according to a known method, or can be obtained as a commercial product. For example, JP-A-63-22759, JP-A-63-316789, JP-A-63-5093, JP-A-3-157388, JP-A-6-256355, JP-A-8-143581, JP-A-2002-20390, etc. Cited as a reference.

  Hereinafter, the specific structure of the silanol compound represented by the general formula (S) according to the present invention is shown, but the structural isomers depending on the substitution positions of the substituents are only shown as examples and are not limited thereto. .

  The content of the silanol compound represented by the general formula (S) is not particularly limited, but is preferably 100 to 500 ppm, and more preferably 100 to 350 ppm with respect to the electrostatic image developing toner. By setting the content of the silanol compound according to the present invention to 100 ppm or more, the objective effect of the present invention can be exhibited, and by setting the content to 500 ppm or less, the toner for developing an electrostatic charge image does not become too soft, and the toner This is preferable because deterioration of storage stability, fixing rate, or odor does not cause a problem.

  The addition amount in the production process of the silanol compound represented by the general formula (S) is preferably 100 to 350 ppm with respect to the toner for developing an electrostatic charge image. The present invention is effective in improving the dispersibility of the release agent (wax), and the residual amount of the organic silanol compound in the toner after drying under reduced pressure can be set within the range specified in the present invention. However, the present invention is not limited to this.

  As a method for adding the silanol compound represented by the general formula (S) to the toner for developing an electrostatic image, for example, a polymerization process including a step of polymerizing the following polymerizable monomer in an aqueous medium to produce a resin. In the case of a legal toner, a method of adding a silanol compound at the time of preparing a colorant dispersion is preferable, but a method of adding it to a polymerizable monomer at the time of preparing resin particles is also included. When the production method of the polymerization method toner is the following multistage polymerization method, a method of adding at the same time as the addition of the release agent is also mentioned.

  In the present invention, the silanol compound is quantified by a head space type gas chromatograph using a detection method used in a normal gas chromatograph such as an internal standard method. In this method, toner is sealed in an open / close container, heated at the time of thermal fixing of a copying machine, etc., and the container is filled with volatile components, and the gas in the container is quickly injected into the gas chromatograph for volatilization. In addition to measuring the amount of components, MS (mass spectrometry) is also performed.

  Below, the measuring method by a head space gas chromatograph is demonstrated in detail.

<Headspace gas chromatograph measurement method>
1. Sample collection: 0.8 g sample is taken in a 20 ml headspace vial. The sample amount is weighed to 0.01 g (necessary for calculating the area per unit mass). Seal the vial with a septum using a dedicated crimper.

  2. Heating the sample: Place the sample in a constant temperature bath at 170 ° C. and heat for 30 minutes.

  3. Setting of gas chromatographic separation conditions: A carrier coated with silicon oil SE-30 so as to have a mass ratio of 15% packed in a column having an inner diameter of 3 mm and a length of 3 m is used as a separation column. The separation column is attached to a gas chromatograph, and He is used as a carrier to flow at 50 ml / min. The temperature of the separation column is set to 40 ° C., and measurement is performed while the temperature is increased to 260 ° C. at 15 ° C./min. Hold for 5 minutes after reaching 260 ° C.

  4). Introduction of sample: The vial bottle is taken out from the thermostat, and 1 ml of gas generated from the sample is immediately collected with a gas tight syringe and injected into the separation column.

  5. Calculation: A calibration curve is prepared in advance using the organic silanol compound used as the internal reference substance, and the concentration of each component is determined.

6). Equipment (1) Headspace conditions Headspace device: HP7694 “Head Space Sampler” manufactured by Hewlett-Packard Company
Temperature conditions:
Transfer line: 200 ° C
Loop temperature: 200 ° C
Sample amount: 0.8 g / 20 ml vial (2) GC / MS conditions GC: HP5890 manufactured by Hewlett-Packard Company
MS: HP5971 manufactured by Hewlett-Packard Company
Column: HP-624 30m x 0.25mm
Oven temperature: 40 ° C (3min) -15 ° C / min-260 ° C
Measurement mode: SIM
The toner of the present invention preferably has a production method (polymerization method) in which a polymerizable monomer is polymerized in an aqueous medium. This production method comprises polymerizing the polymerizable monomer by suspension polymerization to produce resin particles. Prepare resin particles by emulsion polymerization or miniemulsion polymerization in a liquid (in an aqueous medium) to which an emulsion of required additives is added, and if necessary, prepare fine resin particles. After adding the charge controllable resin particles, an organic solvent, an aggregating agent such as a salt, and the like are added, and the resin particles are produced by a method of agglomerating and fusing.

[Toner production method]
(Suspension polymerization method)
As an example of a method for producing the toner of the present invention, a charge control resin is dissolved in a polymerizable monomer, and various constituent materials such as a colorant, a mold release agent, and a polymerization initiator are added. Then, various constituent materials are dissolved or dispersed in the polymerizable monomer using a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser or the like. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in oil droplets of a desired size as a toner in an aqueous medium containing a dispersion stabilizer using a homomixer or a homogenizer. Thereafter, the stirring mechanism is transferred to a reaction device (stirring device) which is a stirring blade described later, and the polymerization reaction is advanced by heating. After completion of the reaction, the dispersion stabilizer is removed, filtered, washed, and dried to prepare the toner of the present invention. In the present invention, the “aqueous medium” refers to a medium containing at least 50% by mass of water.

(Emulsion polymerization method)
As another method for producing the toner of the present invention, a method in which resin particles are prepared by salting out / fusion in an aqueous medium is preferable. The method is not particularly limited, and examples thereof include methods described in JP-A Nos. 5-265252, 6-329947, and 9-15904. That is, a method of salting out, agglomerating, and fusing a plurality of fine particles composed of resin particles and colorants, etc., or particles composed of resin and colorant, in particular, dispersing these in water using an emulsifier After that, a coagulant with a critical coagulation concentration or higher is added for salting out, and at the same time, the particle size is gradually increased while forming a fused particle by heating and fusing above the glass transition temperature of the polymer itself. When the desired particle size is reached, stop the growth of the particle size by adding a large amount of water, further smooth the particle surface while heating and stirring to control the shape, and keep the particles in a fluid state while containing water The toner of the present invention can be formed by drying with heating. Here, a solvent that is infinitely soluble in water, such as alcohol, may be added simultaneously with the flocculant.

  In the toner manufacturing method of the present invention, the composite resin fine particles and the colorant particles formed through the process of polymerizing the polymerizable monomer after dissolving the crystalline substance in the polymerizable monomer are salted out / fused. A method of wearing is preferably used. When the crystalline substance is dissolved in the polymerizable monomer, the crystalline substance may be dissolved and dissolved, or may be melted and dissolved.

  In addition, as a method for producing the toner of the present invention, a step of salting out / fusing composite resin fine particles and colorant particles obtained by a multistage polymerization method is preferably used. Here, the multistage polymerization method will be described below.

(Method for producing composite resin particles obtained by multistage polymerization method)
When the multistage polymerization method is used, the toner production method of the present invention is preferably composed of the following steps.

1: Multi-stage polymerization step 2: Salting out / fusion step of salting out / fusing composite resin particles and colorant particles to obtain toner particles 3: Filtering off the toner particles from a dispersion system of toner particles, Filtration / washing process for removing surfactants from toner particles 4: Drying process for drying washed toner particles 5: A process for adding external additives to dried toner particles.

  Hereinafter, each step will be described in detail.

<Multistage polymerization process>
The multi-stage polymerization step is a polymerization method performed for expanding the molecular weight distribution of the resin particles so as to obtain a toner in which offset generation is prevented. That is, in order to form phases having different molecular weight distribution in one resin particle, the polymerization reaction is performed in multiple stages, and the obtained resin particle has a molecular weight gradient from the center of the particle toward the surface layer. It is intended to be formed. For example, a method of forming a low molecular weight surface layer by first obtaining a high molecular weight resin particle dispersion and then newly adding a polymerizable monomer and a chain transfer agent is employed.

  In the present invention, it is preferable to employ a multi-stage polymerization method of three-stage polymerization or more from the viewpoint of production stability and crushing strength of the resulting toner. Hereinafter, a two-stage polymerization method and a three-stage polymerization method, which are representative examples of the multistage polymerization method, will be described. The toner obtained by such a multistage polymerization reaction preferably has a lower molecular weight as the surface layer from the viewpoint of crushing strength.

<Two-stage polymerization method>
The two-stage polymerization method is a method for producing composite resin particles composed of a central portion (core) formed from a high molecular weight resin containing a crystalline substance and an outer layer (shell) formed from a low molecular weight resin. is there.

  This method will be described in detail. First, a crystalline substance is dissolved in a monomer to prepare a monomer solution, and the monomer solution is added to oil droplets in an aqueous medium (for example, a surfactant aqueous solution). After the dispersion, this system is polymerized (first stage polymerization) to prepare a dispersion of high molecular weight resin particles containing a crystalline substance.

  Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the dispersion of the resin particles, and the monomer is polymerized in the presence of the resin particles (second-stage polymerization). Thus, a coating layer made of a low molecular weight resin (monomer polymer) is formed on the surface of the resin particles.

<Three-stage polymerization method>
The three-stage polymerization method is a method for producing composite resin particles composed of a central part (core) formed from a high molecular weight resin, an intermediate layer containing a crystalline substance, and an outer layer (shell) formed from a low molecular weight resin. It is. The toner of the present invention exists as the composite resin particles as described above.

  This method will be specifically described. First, a dispersion of resin particles obtained by a polymerization process (first-stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant). In the aqueous medium, a monomer solution obtained by dissolving a crystalline substance in a monomer is dispersed in oil droplets, and then this system is polymerized (second-stage polymerization) to obtain resin particles (cores). A coating layer (intermediate layer) made of a resin (monomer polymer) containing a crystalline substance is formed on the surface of the particles, and a dispersion of composite resin particles (high molecular weight resin-intermediate molecular weight resin) is prepared. Prepare.

  Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the obtained dispersion of composite resin particles, and the monomer is polymerized in the presence of the composite resin particles (third-stage polymerization). ), A coating layer made of a low molecular weight resin (monomer polymer) is formed on the surface of the composite resin particles. In the above method, the incorporation of the intermediate layer is preferable because the crystalline substance can be finely and uniformly dispersed.

  One aspect of the toner production method of the present invention is that the polymerizable monomer is polymerized in an aqueous medium. That is, when forming resin particles (core particles) or a coating layer (intermediate layer) containing a crystalline substance, the crystalline substance is dissolved in the monomer, and the resulting monomer solution is oiled in an aqueous medium. It is a method of obtaining latex particles by dispersing in drops and adding a polymerization initiator to this system for polymerization treatment.

  The aqueous medium used in the present invention refers to a medium comprising 50% by mass to 100% by mass of water and 0-50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, and the like, and an alcohol-based organic solvent that does not dissolve the obtained resin is preferable.

  As a suitable polymerization method for forming resin particles or a coating layer containing a crystalline substance, the crystalline substance is a monomer in an aqueous medium in which a surfactant having a concentration equal to or lower than the critical micelle concentration is dissolved. The monomer solution dissolved in is dispersed in oil droplets using mechanical energy to prepare a dispersion, and a water-soluble polymerization initiator is added to the resulting dispersion to cause radical polymerization in the oil droplets. A method (hereinafter referred to as “mini-emulsion method” in the present invention), and the effects of the present invention can be exhibited more preferably. In the above method, an oil-soluble polymerization initiator may be used instead of or together with the water-soluble polymerization initiator.

  According to the mini-emulsion method that mechanically forms oil droplets, unlike the usual emulsion polymerization method, there is little detachment of the crystalline substance dissolved in the oil phase, and it is sufficient in the resin particles or coating layer to be formed. Any amount of crystalline material can be introduced.

  Here, the disperser for dispersing oil droplets by mechanical energy is not particularly limited. For example, a stirring device “CLEARMIX” (M Technique (Equation Technique) equipped with a rotor that rotates at high speed is used. Co., Ltd.), ultrasonic disperser, mechanical homogenizer, manton gorin, pressure homogenizer, and the like. Further, the dispersed particle diameter is preferably 10 nm to 1000 nm, more preferably 50 nm to 1000 nm, and particularly preferably 30 nm to 300 nm.

  By giving a distribution to the dispersed particle diameter, the phase separation structure of the crystalline substance in the toner particles, that is, the ferret horizontal diameter, the shape factor, and the coefficient of variation thereof may be controlled.

  In addition, as other polymerization methods for forming resin particles or a coating layer containing a crystalline substance, known methods such as an emulsion polymerization method, a suspension polymerization method, and a seed polymerization method can be employed. These polymerization methods can also be employed to obtain resin particles (core particles) or coating layers constituting the composite resin particles that do not contain a crystalline substance.

  The particle diameter of the composite resin particles obtained in this polymerization step is in the range of 10 to 1000 nm in terms of mass average particle diameter measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.). Is preferred.

  Moreover, it is preferable that the glass transition temperature (Tg) of a composite resin particle exists in the range of 48 to 74 degreeC, More preferably, it is 52 to 64 degreeC.

  The softening point of the composite resin particles is preferably in the range of 95 ° C to 140 ° C.

  The toner of the present invention is obtained by fusing resin particles on the surface of the resin and colored particles by a salting-out / fusing method to form a resin layer. This will be described below.

<Salting out / fusion process>
This salting-out / fusion step is carried out by salting out / bonding the composite resin particles and the colorant particles obtained in the multi-stage polymerization step (to cause salting-out and fusion at the same time) to form an irregular shape ( This is a step of obtaining non-spherical toner particles.

  In the present invention, salting out / fusion means that salting out (aggregation of particles) and fusion (disappearance of the interface between particles) occur simultaneously or salting out and fusion occur simultaneously. . In order to perform salting-out and fusion at the same time, it is preferable to agglomerate particles (composite resin particles, colorant particles) under a temperature condition higher than the glass transition temperature (Tg) of the resin constituting the composite resin particles. .

  In this salting-out / fusion process, internal additive particles such as charge control agents (fine particles having a number average primary particle size of about 10 nm to 1000 nm) may be salted out / fused together with the composite resin particles and the colorant particles. Good. The colorant particles may be surface-modified, and conventionally known ones can be used as the surface modifier.

<Aging process>
The aging step is a step subsequent to the salting-out / fusion step, and after the resin particles are fused, the temperature is kept near the melting point of the crystalline substance, preferably the melting point ± 20 ° C., and stirring is continued at a constant strength. This is a step of phase-separating the crystalline substance. In this step, it is possible to control the ferret horizontal diameter, shape factor, and variation coefficient of the crystalline material.

  Moreover, in this invention, it is preferable that the total value of the bivalent (trivalent) metal element used for a coagulant | flocculant and the monovalent | monohydric metal element added as an aggregation terminator mentioned later is 350-35000 ppm. The residual amount of metal ions in the toner can be measured by using a fluorescent X-ray analyzer “System 3270” (manufactured by Rigaku Denki Kogyo Co., Ltd.) and using a metal species of a metal salt used as a flocculant (for example, calcium chloride). It can be determined by measuring the intensity of the fluorescent X-ray emitted from the derived calcium or the like. As a specific measurement method, a plurality of toners having a known content ratio of the flocculant metal salt are prepared, each toner 5g is pelletized, the content ratio (mass ppm) of the flocculant metal salt, and the metal species of the metal salt The relationship (calibration curve) with the fluorescent X-ray intensity (peak intensity) is measured. Next, the toner (sample) whose content of the flocculant metal salt is to be measured is similarly pelletized, and the fluorescent X-ray intensity from the metal species of the flocculant metal salt is measured. Amount "can be determined.

<Filtration and washing process>
In this filtration / washing step, a filtration treatment for filtering the toner particles from the toner particle dispersion obtained in the above step, and a surfactant or salt from the filtered toner particles (cake-like aggregate). A cleaning process for removing deposits such as a depositing agent is performed. Here, the filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a filtration method using a filter press or the like.

<Drying process>
This step is a step of drying the washed toner particles, but in the present invention, a step of drying under reduced pressure is preferred.

  Examples of the vacuum dryer used in this step include, but are not limited to, a vacuum spray dryer, a vacuum freeze dryer, and a vacuum dryer. Specifically, it is preferable to use a stationary shelf dryer, a movable shelf dryer, a fluidized bed dryer, a rotary dryer, a stirring dryer, or the like that can be decompressed.

  The conditions for drying under reduced pressure may be any temperature as long as the drying temperature is equal to or lower than the Tg of the resin used in the toner, and the degree of reduced pressure, the drying time, and the like are not particularly limited and can be set as appropriate.

  In addition, when the toner particles subjected to the drying under reduced pressure are aggregated by weak interparticle attractive force, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

  The toner of the present invention forms composite resin particles in the absence of a colorant, adds a dispersion of the colorant particles to the dispersion of the composite resin particles, and saltes out the composite resin particles and the colorant particles. It is preferably prepared by fusing.

  Thus, the polymerization reaction for obtaining the composite resin particles is not inhibited by preparing the composite resin particles in a system in which no colorant is present. Therefore, according to the toner of the present invention, the excellent offset resistance is not impaired, and the fixing device is not contaminated or the image is not stained due to the accumulation of toner.

  In addition, as a result of the polymerization reaction for obtaining the composite resin particles being reliably performed, no monomer or oligomer remains in the obtained toner particles, and the heat fixing step of the image forming method using the toner In this case, no odor is generated.

  Furthermore, since the surface characteristics of the obtained toner particles are uniform and the charge amount distribution is sharp, an image with excellent sharpness can be formed over a long period of time. According to such a toner having a uniform composition, molecular weight, and surface characteristics between toner particles, an image forming method including a fixing process using a contact heating method maintains good adhesion (high fixing strength) to an image support. However, it is possible to improve the offset resistance and the anti-winding property, and an image having an appropriate gloss can be obtained.

  Next, each component used in the toner manufacturing process will be described in detail.

(Polymerizable monomer)
As a polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is an essential constituent, and a crosslinkable monomer is used as necessary. Moreover, it is desirable to contain at least one monomer having an acidic polar group or a monomer having a basic polar group as described below.

(1) Hydrophobic monomer As a hydrophobic monomer which comprises a monomer component, it does not specifically limit and a conventionally well-known monomer can be used. Moreover, it can be used combining 1 type (s) or 2 or more types so that the required characteristic may be satisfy | filled.

  Specifically, monovinyl aromatic monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers , Halogenated olefin monomers and the like can be used.

  Examples of vinyl aromatic monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2, Examples thereof include styrene monomers such as 4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof.

  Examples of acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, methyl methacrylate, methacrylic acid. Examples include butyl acid, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate.

  Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

  Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

  Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like.

(2) Crosslinkable monomer A crosslinkable monomer may be added to improve the properties of the resin particles. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

(3) Monomer having an acidic polar group Monomers having an acidic polar group include (a) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH) and (b) a sulfone group (— Mention may be made of α, β-ethylenically unsaturated compounds having SO ₃ H).

  Examples of the α, β-ethylenically unsaturated compound (a) having a —COO group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, maleic acid. Examples thereof include acid monooctyl esters and metal salts thereof such as Na and Zn.

Examples of the α, β-ethylenically unsaturated compound having a —SO ₃ H group in (b) include sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and its Na salt. .

(4) Monomer having a basic polar group As the monomer having a basic polar group, (i) 1-12 carbon atoms having an amine group or a quaternary ammonium group, preferably 2-8, particularly preferably 2. (Meth) acrylic acid esters of aliphatic alcohols, (ii) (meth) acrylic acid amides or (meth) acrylic acid amides optionally monosubstituted or disubstituted with alkyl groups of 1 to 18 carbon atoms on N, (iii) Examples thereof include a vinyl compound substituted with a heterocyclic group having N as a ring member and (iv) N, N-diallyl-alkylamine or a quaternary ammonium salt thereof. Among them, (i) aliphatic alcohol (meth) acrylic acid ester having an amine group or quaternary ammonium group is preferable as a monomer having a basic polar group.

  Examples of (meth) acrylic acid esters of aliphatic alcohols having an amine group or quaternary ammonium group (i) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the above four compounds. A quaternary ammonium salt, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, etc. can be mentioned.

  (Ii) (Meth) acrylic acid amide or optionally mono- or dialkyl-substituted (meth) acrylic acid amide on N includes acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N, N-dimethylacrylamide, N-octadecylacrylamide and the like can be mentioned.

  Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member in (iii) include vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, vinyl-N-ethylpyridinium chloride and the like.

  Examples of (iv) N, N-diallyl-alkylamine include N, N-diallylmethylammonium chloride and N, N-diallylethylammonium chloride.

(Polymerization initiator)
The radical polymerization initiator used in the present invention can be appropriately used as long as it is water-soluble. For example, persulfates (for example, potassium persulfate, ammonium persulfate, etc.), azo compounds (for example, 4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) Salt), peroxide compounds and the like. Furthermore, the radical polymerization initiator can be combined with a reducing agent as necessary to form a redox initiator. Use of a redox initiator is preferred because the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be shortened.

  The polymerization temperature may be any temperature as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator, but for example, a range of 50 ° C. to 90 ° C. is used. However, it is possible to perform polymerization at room temperature or higher by using a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (ascorbic acid or the like).

(Surfactant)
In particular, in order to perform miniemulsion polymerization using the above-described polymerizable monomer, it is preferable to disperse oil droplets in an aqueous medium using a surfactant. The surfactant that can be used in this case is not particularly limited, and the following ionic surfactants can be given as examples of suitable compounds.

  Examples of the ionic surfactant include sulfonate (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol- 6-sulfonate sodium, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate sodium, etc.) , Sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearyl Potassium, calcium oleate and the like).

  Nonionic surfactants can also be used. Specifically, for example, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, And sorbitan esters.

  In the present invention, these surfactants are mainly used as an emulsifier during emulsion polymerization, but may be used for other steps or for other purposes.

(Molecular weight distribution of resin particles and toner)
The toner of the present invention preferably has a peak or shoulder at 100,000 to 1,000,000 and 1,000 to 50,000, and further has a peak or shoulder of 100,000 to 1,000,000, More preferably, it is present at 25,000 to 150,000 and 1,000 to 50,000.

  The molecular weight of the resin particles is both a high molecular weight component having a peak or shoulder in the region of 100,000 to 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 50,000. A resin containing at least is preferable. More preferably, an intermediate molecular weight resin having a peak or shoulder at a peak molecular weight of 15,000 to 100,000 is preferably used.

  The molecular weight measurement method of the toner or resin is preferably measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent. That is, 1.0 ml of THF is added to 0.5 to 5 mg of a measurement sample, more specifically 1 mg, and the mixture is sufficiently dissolved by stirring at room temperature using a magnetic stirrer or the like. Subsequently, after processing with a membrane filter having a pore size of 0.45 to 0.50 μm, the solution is injected into GPC. The measurement conditions of GPC are measured by stabilizing the column at 40 ° C., flowing THF at a flow rate of 1.0 ml / min, and injecting about 100 μl of a sample having a concentration of 1 mg / ml. The column is preferably used in combination with a commercially available polystyrene gel column. For example, combinations of Shodex GPC KF-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko KK and TSKgel G1000H, G2000H, G3000H, G4000H, G5000H, G6000H, G7000H, and TSKguard column manufactured by Tosoh Corporation And so on. As a detector, a refractive index detector (IR detector) or a UV detector may be used. In the measurement of the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodisperse polystyrene standard particles. About 10 points may be used as polystyrene for preparing a calibration curve.

(Flocculant)
The flocculant used in the present invention is preferably selected from metal salts.

  Examples of the metal salt include monovalent metals such as alkali metal salts such as sodium, potassium and lithium, divalent metals such as alkaline earth metal salts such as calcium and magnesium, and divalent metals such as manganese and copper. Examples thereof include trivalent metal salts such as salts, iron and aluminum.

  Specific examples of these metal salts are shown below. Specific examples of the monovalent metal salt include sodium chloride, potassium chloride, lithium chloride, and divalent metal salts such as calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Examples of the trivalent metal salt include aluminum chloride and iron chloride. These are appropriately selected according to the purpose. In general, a divalent metal salt has a smaller critical aggregation concentration (coagulation value or coagulation point) than a monovalent metal salt, and a trivalent metal salt has a smaller critical aggregation concentration.

  The critical flocculation concentration referred to in the present invention is an index related to the stability of the dispersion in the aqueous dispersion, and indicates the concentration at which flocculation occurs when a flocculant is added. This critical coagulation concentration varies greatly depending on the latex itself and the dispersant. For example, it is described in Seizo Okamura et al., Polymer Chemistry 17,601 (1960), etc., and according to these descriptions, the value can be known. As another method, a desired salt is added to the target particle dispersion at different concentrations, the ζ potential of the dispersion is measured, and the salt concentration at the point where the ζ potential changes is determined as the critical aggregation concentration. It is also possible.

  In the present invention, the polymer fine particle dispersion is treated with a metal salt so as to have a concentration equal to or higher than the critical aggregation concentration. At this time, as a matter of course, whether the metal salt is added directly or as an aqueous solution is arbitrarily selected according to the purpose. When added as an aqueous solution, the added metal salt must be equal to or higher than the critical aggregation concentration of the polymer particles with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.

  The concentration of the metal salt which is a flocculant in the present invention may be not less than the critical aggregation concentration, but is preferably 1.2 times or more, more preferably 1.5 times or more the critical aggregation concentration.

(Release agent)
The toner of the present invention is preferably a toner obtained by fusing resin particles encapsulating a release agent in an aqueous medium. In this way, the resin particles in which the release agent is encapsulated in the resin particles are salted out / fused in the aqueous medium with the colorant particles, whereby a toner in which the release agent is finely dispersed can be obtained.

  In the toner of the present invention, low molecular weight polypropylene (number average molecular weight = 1500 to 9000), low molecular weight polyethylene, and the like are preferable as the release agent, and ester compounds represented by the following formula are particularly preferable.

R ^1- (OCO-R ² ) _n
In the formula, n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, particularly preferably 4. R ¹ and R ² each represents a hydrocarbon group that may have a substituent. R ¹ has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 5 carbon atoms. R ² has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.

  Next, the example of a typical compound is shown below.

  The amount of the compound added is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 15% by mass with respect to the total toner.

  The toner of the present invention is preferably prepared by encapsulating the release agent in resin particles by the miniemulsion polymerization method, and salting out and fusing together with the toner particles.

(Charge control agent)
In the toner of the present invention, materials capable of imparting various functions as toner materials can be added in addition to the colorant and the release agent. Specific examples include charge control agents. These components can be added simultaneously with the resin particles and the colorant particles in the salting out / fusion step described above, and can be added by various methods such as a method included in the toner and a method of adding to the resin particles themselves.

  As the charge control agent, various known ones that can be dispersed in water can be used. Specific examples include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof.

(External additive)
To the toner of the present invention, so-called external additives can be added and used for the purpose of improving fluidity and improving cleaning properties. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles and lubricants can be used.

  Examples of inorganic fine particles that can be used as an external additive include conventionally known fine particles. Specifically, silica fine particles, titanium fine particles, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic.

  Specific examples of the silica fine particles include commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., and HVK-2150 manufactured by Hoechst Co., Ltd. , H-200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5 manufactured by Cabot Corporation.

  Specific examples of the titanium fine particles include, for example, commercial products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products MT-100S, MT-100B, MT-500BS, and MT-600 manufactured by Teika Co., Ltd. , MT-600SS, JA-1, commercial products manufactured by Fuji Titanium Co., Ltd. TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T, commercial products IT-S manufactured by Idemitsu Kosan Co., Ltd. IT-OA, IT-OB, IT-OC and the like.

  Specific examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  Examples of the organic fine particles that can be used as the external additive include spherical fine particles having a number average primary particle diameter of about 10 to 2000 nm. Examples of the constituent material of the organic fine particles include polystyrene, polymethyl methacrylate, styrene-methyl methacrylate copolymer, and the like.

  Examples of the lubricant that can be used as an external additive include metal salts of higher fatty acids. Specific examples of such higher fatty acid metal salts include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, and other stearic acid metal salts; zinc oleate, manganese oleate, iron oleate, olein Oleic acid metal salts such as acid copper and magnesium oleate; palmitate metal salts such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate; linoleic acid metal salts such as zinc linoleate and calcium linoleate; ricinol Examples include ricinoleic acid metal salts such as zinc acid and calcium ricinoleate.

  The addition amount of the external additive is preferably about 0.1 to 5% by mass with respect to the toner.

<External additive addition process>
This step is a step of adding an external additive to the dried toner particles.

  Examples of the apparatus used for adding the external additive include various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer.

(Toner particles)
The particle size of the toner of the present invention is preferably 3 to 10 μm, more preferably 3 to 8 μm in terms of number average particle size. This particle size can be controlled by the concentration of the flocculant (salting-out agent), the amount of organic solvent added, the fusing time, and the polymer composition in the toner production method.

  When the number average particle diameter is 3 to 10 μm, toner particles having high adhesion force that fly and adhere to the heating member and generate offset in the fixing process are reduced, and transfer efficiency is increased and halftone The image quality is improved, and the image quality of fine lines and dots is improved.

  The number average particle size of the toner can be measured using a Coulter Counter TA-II, Coulter Multisizer, SLAD 1100 (Laser Diffraction Particle Size Measuring Device manufactured by Shimadzu Corporation) or the like.

  In the present invention, a Coulter Multisizer is used, and an interface (manufactured by Nikka Machine Co., Ltd.) for outputting the particle size distribution and a personal computer are connected. The aperture in the Coulter Multisizer was 100 μm, and the volume distribution of toner of 2 μm or more (for example, 2 to 40 μm) was measured to calculate the particle size distribution and average particle size.

<Preferable shape factor range of toner particles>
As for the shape factor of the toner of the present invention, 1.0 to 1.6 is 65 number% or more, preferably 1.2 to 1.6 is 65 number% or more, particularly preferably 1.2 to 1. 6 is 70% by number or more.

  The shape factor of the toner of the present invention is represented by the following formula and indicates the degree of roundness of the toner particles.

Shape factor = ((maximum diameter / 2) ² × π) / projection area Here, the maximum diameter is the distance between the parallel lines when the projected image of toner particles on a plane is sandwiched between two parallel lines. The maximum particle width. The projected area refers to the area of the projected image of the toner particles on the plane. In the present invention, this shape factor is obtained by taking a photograph in which the toner particles are magnified 2000 times with a scanning electron microscope, and then using “SCANNING IMAGE ANALYZER” (manufactured by JEOL Ltd.) based on this photograph. It was measured by performing analysis. At this time, the shape factor of the present invention was measured by the above formula using 100 toner particles.

  As the toner of the present invention, when the particle size of the toner particle is D (μm), the natural logarithm lnD is taken on the horizontal axis, and the number-based particle size distribution is divided into a plurality of classes at intervals of 0.23. In the histogram shown, the sum (M) of the relative frequency (m1) of the toner particles included in the most frequent class and the relative frequency (m2) of the toner particles included in the next most frequent class after the most frequent class is 70. % Of the toner is preferable.

  When the sum (M) of the relative frequency (m1) and the relative frequency (m2) is 70% or more, the dispersion of the particle size distribution of the toner particles becomes narrow. Therefore, selective development can be performed by using the toner in the image forming process. Can be reliably suppressed.

  In the present invention, the histogram showing the particle size distribution based on the number is a natural logarithm lnD (D: particle size of individual toner particles) having a plurality of classes (0 to 0.23: 0.23) at intervals of 0.23. 0.46: 0.46-0.69: 0.69-0.92: 0.92-1.15: 1.15-1.38: 1.38-1.61: 1.61-1. 84: 1.84 to 2.07: 2.07 to 2.30: 2.30 to 2.53: 2.53 to 2.76, and so on). This histogram was created by transferring the particle size data of the sample measured by the Coulter Multisizer to the computer via the I / O unit according to the following conditions and using the particle size distribution analysis program in the computer. is there.

<Measurement condition>
1: Aperture: 100 μm
2: Sample preparation method: electrolytic solution [ISOTON R-11 (manufactured by Coulter Scientific Japan)] 50-100 ml, an appropriate amount of a surfactant (neutral detergent) was added and stirred, and 10-20 mg of a measurement sample was added thereto. Add. This system is prepared by dispersing for 1 minute with an ultrasonic disperser.

  In the toner of the present invention, the median diameter (D50v) on a volume basis is preferably 3 μm or more and 8 μm or less. By setting the volume-based median diameter in the above range, for example, it is possible to faithfully reproduce a very minute dot image at a level of 1200 dpi (dpi; number of dots per inch (2.54 cm)).

  The toner of the present invention is one of the problems to be able to faithfully reproduce the color of a photographic image, but a photographic image is formed by setting the volume-based median diameter to a small diameter level in the above range. The dot image is miniaturized and a high-definition photographic image equivalent to or higher than the printed image is obtained. In particular, in a printing field called “on-demand printing” where a print order is received at a level of several hundred to several thousand copies, high-quality prints containing high-definition photographic images can be quickly delivered to the user.

  The volume-based median diameter (D50v diameter) of toner can be measured and calculated using a device in which a computer system for data processing is connected to Multisizer 3 (manufactured by Beckman Coulter).

  As a measurement procedure, 0.02 g of toner was mixed with 20 ml of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing the toner). After that, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is injected into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand with a pipette until a measurement concentration of 5 to 10% is reached, and the measuring machine count is set to 2500. To do. The aperture diameter of the multisizer 3 is 50 μm.

  The toner of the present invention preferably has a coefficient of variation (CV value) in the volume-based particle size distribution of 2% to 21%, more preferably 5% to 15%.

  The coefficient of variation (CV value) in the volume-based particle size distribution represents the degree of dispersion in the particle size distribution of the toner particles on the volume basis, and is defined by the following equation.

CV value (%) = (standard deviation in number particle size distribution) / (median diameter (D50v) in number particle size distribution) × 100
The smaller the CV value, the sharper the particle size distribution, and the larger the toner particle size. In other words, since toners with uniform sizes can be obtained, it is possible to reproduce a fine dot image and fine lines required for digital image formation with higher accuracy. Further, when printing a photographic image, it is possible to create a high-quality photographic image of an image level made with printing ink or higher by using small-diameter toner having a uniform size.

  The toner of the present invention preferably has a softening point temperature (Tsp) of 70 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower. The colorant used in the toner of the present invention has a stable property that the spectrum does not change even under the influence of heat, but is added to the toner during fixing by setting the softening point in the above range. The influence of heat can be further reduced. Therefore, since image formation can be performed without imposing a burden on the colorant, it is expected that a wider and more stable color reproducibility is expressed.

  In addition, by setting the softening point of the toner within the above range, the toner image can be fixed at a temperature lower than that of the prior art, and environmentally friendly image formation with reduced power consumption can be realized.

The softening point of the toner can be controlled by, for example, the following methods alone or in combination. That is,
(1) Adjusting the type and composition ratio of monomers used for resin formation (2) Adjusting the molecular weight of the resin according to the type and addition amount of the chain transfer agent (3) Adjusting the type and addition amount of wax and the like.

Further, the method for measuring the softening point temperature of the toner is specifically “Flow Tester CFT-500 (manufactured by Shimadzu Corporation)”, molded into a columnar shape with a height of 10 mm, and at a heating rate of 6 ° C./min. While being heated, a pressure of 1.96 × 10 ⁶ Pa is applied from the plunger, and the pressure is pushed out from a nozzle having a diameter of 1 mm and a length of 1 mm. Thereby, a curve between the plunger drop amount and temperature of the flow tester (softening flow curve) ), And the temperature at the first outflow is the melting start temperature, and the temperature for the drop of 5 mm is the softening point temperature.

(Developer)
The toner of the present invention may be used as a one-component developer or a two-component developer.

  When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 μm of magnetic particles in the toner can be used. be able to.

  Further, it can be mixed with a carrier and used as a two-component developer. In this case, conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used as the magnetic particles of the carrier. Ferrite particles are particularly preferable. The magnetic particles preferably have a volume average particle size of 15 to 100 μm, more preferably 25 to 80 μm.

  The volume average particle diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  The carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicone resin, ester resin, or fluorine-containing polymer resin is used. In addition, the resin for constituting the resin-dispersed carrier is not particularly limited, and a known resin can be used. For example, a styrene-acrylic resin, a polyester resin, a fluorine resin, a phenol resin, or the like is used. be able to.

(Image forming method)
Next, an image forming method using the toner of the present invention will be described. First, an image forming method when the toner according to the present invention is used as a two-component developer will be described.

  FIG. 1 is a schematic view showing an example of an image forming apparatus that can be used when a toner according to the present invention is used as a two-component developer.

  In FIG. 1, 1Y, 1M, 1C and 1K are photoreceptors, 4Y, 4M, 4C and 4K are developing devices, 5Y, 5M, 5C and 5K are primary transfer rolls as primary transfer means, and 5A is a secondary transfer. Secondary transfer rolls as means, 6Y, 6M, 6C and 6K are cleaning devices, 7 is an intermediate transfer member unit, 24 is a heat roll type fixing device, and 70 is an intermediate transfer member.

  This image forming apparatus is called a tandem color image forming apparatus, and includes a plurality of sets of image forming units 10Y, 10M, 10C, and 10K, an endless belt-shaped intermediate transfer body unit 7 as a transfer unit, and a recording member P. An endless belt-shaped sheet feeding / conveying means 21 and a heat roll type fixing device 24 as a fixing means. A document image reading device SC is disposed on the upper part of the main body A of the image forming apparatus.

  As one of the different color toner images formed on each photoconductor, an image forming unit 10Y that forms a yellow image includes a drum-shaped photoconductor 1Y as a first photoconductor, and a periphery of the photoconductor 1Y. A charging unit 2Y, an exposure unit 3Y, a developing unit 4Y, a primary transfer roll 5Y as a primary transfer unit, and a cleaning unit 6Y. An image forming unit 10M that forms a magenta image as another different color toner image is disposed around a drum-shaped photoconductor 1M as a first photoconductor, and the photoconductor 1M. A charging unit 2M, an exposure unit 3M, a developing unit 4M, a primary transfer roll 5M as a primary transfer unit, and a cleaning unit 6M. In addition, an image forming unit 10C that forms a cyan image as one of other different color toner images is disposed around the photoconductor 1C as a drum-type photoconductor 1C as a first photoconductor. The charging unit 2C, the exposure unit 3C, the developing unit 4C, the primary transfer roll 5C as the primary transfer unit, and the cleaning unit 6C are provided. Further, an image forming unit 10K that forms a black image as one of other different color toner images is disposed around a drum-shaped photosensitive member 1K as a first photosensitive member, and the photosensitive member 1K. It has a charging means 2K, an exposure means 3K, a developing means 4K, a primary transfer roll 5K as a primary transfer means, and a cleaning means 6K.

  The endless belt-like intermediate transfer body unit 7 has an endless belt-like intermediate transfer body 70 as an intermediate transfer endless belt-like second image carrier that is wound around a plurality of rolls and is rotatably supported.

  Each color image formed by the image forming units 10Y, 10M, 10C, and 10K is sequentially transferred onto the rotating endless belt-shaped intermediate transfer body 70 by the primary transfer rolls 5Y, 5M, 5C, and 5K, and is combined. A colored image is formed. A recording member P such as a sheet as a transfer material accommodated in the sheet feeding cassette 20 is fed by the sheet feeding / conveying means 21, passes through a plurality of intermediate rolls 22 A, 22 B, 22 C, 22 D, and a registration roll 23, and is secondary. A color image is transferred onto the recording member P at a time by being conveyed to a secondary transfer roll 5A as a transfer means. The recording member P to which the color image has been transferred is fixed by the heat roll type fixing device 24, is sandwiched by the paper discharge roll 25, and is placed on the paper discharge tray 26 outside the apparatus.

  On the other hand, after the color image is transferred to the recording member P by the secondary transfer roll 5A, the residual toner is removed from the endless belt-shaped intermediate transfer body 70 from which the recording member P is separated by the curvature by the cleaning means 6A.

  During the image forming process, the primary transfer roll 5K is always in pressure contact with the photoreceptor 1K. The other primary transfer rolls 5Y, 5M, and 5C are in pressure contact with the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.

  The secondary transfer roll 5A comes into pressure contact with the endless belt-shaped intermediate transfer body 70 only when the recording member P passes through the secondary transfer roll 5A and secondary transfer is performed.

  Further, the housing 8 can be pulled out from the apparatus main body A through the support rails 82L and 82R.

  The housing 8 includes image forming units 10Y, 10M, 10C, and 10K, and an endless belt-shaped intermediate transfer body unit 7.

  The image forming units 10Y, 10M, 10C, and 10K are arranged in tandem in the vertical direction. An endless belt-shaped intermediate transfer body unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1K in the figure. The endless belt-shaped intermediate transfer body unit 7 includes an endless belt-shaped intermediate transfer body 70 that can be rotated by winding rolls 71, 72, 73, 74, and 76, primary transfer rolls 5Y, 5M, 5C, and 5K, and a cleaning unit. 6A.

  The image forming units 10Y, 10M, 10C, and 10K and the endless belt-shaped intermediate transfer body unit 7 are integrally pulled out from the main body A by the drawer operation of the housing 8.

  In this way, toner images are formed on the photoreceptors 1Y, 1M, 1C, and 1K by charging, exposure, and development, and the toner images of the respective colors are superimposed on the endless belt-shaped intermediate transfer body 70, and are collectively applied to the recording member P. The image is transferred and fixed by the fixing device 24 by pressing and heating. The photoreceptors 1Y, 1M, 1C, and 1K after transferring the toner image to the recording member P are cleaned with the cleaning device 6A to remove the toner remaining on the photoreceptor, and then the above-described charging, exposure, and development cycle. The next image formation is performed.

  Next, an image forming method when the toner according to the present invention is used as a non-magnetic one-component developer will be described.

  FIG. 2 is an example of a full-color image forming apparatus that uses a non-magnetic one-component developer. An image forming apparatus 100 shown in FIG. 2 is a typical image forming apparatus in which the above-described developing device 20 can be mounted. 2 includes a charging brush 2 for uniformly charging the surface of a photosensitive drum 1 to a predetermined potential around a rotating electrostatic latent image carrier (hereinafter also referred to as a photosensitive drum) 1, and a photosensitive member. A cleaner 6 for removing residual toner on the drum 1 is provided.

  The laser scanning optical system 3 scans and exposes the photosensitive drum 1 uniformly charged by the charging brush 2 to form an electrostatic latent image on the photosensitive drum 1. The laser scanning optical system 3 includes a laser diode, a polygon mirror, and an fθ optical element, and print data for each of yellow, magenta, cyan, and black is transferred from the host computer to the control unit. Then, based on the print data for each color, a laser beam is sequentially output, and the photosensitive drum 1 is scanned and exposed to form an electrostatic latent image for each color.

  The developing device unit 40 that accommodates the developing device 4 supplies toner of each color to the photosensitive drum 1 on which the electrostatic latent image is formed to perform development. The developing device unit 40 is provided with four developing devices 4Y, 4M, 4C, and 4Bk each containing non-magnetic one-component toners of yellow, magenta, cyan, and black around the support shaft 33. Rotating to the center, each developing device 4 is guided to a position facing the photosensitive drum 1.

  The developing device unit 40 rotates around the support shaft 33 each time an electrostatic latent image of each color is formed on the photosensitive drum 1 by the laser scanning optical system 3, and stores the corresponding color toner. 4 is guided to a position facing the photosensitive drum 1. Then, each of the developing devices 4Y, 4M, 4C, and 4Bk sequentially supplies each charged color toner to the photosensitive drum 1 for development.

  In the image forming apparatus of FIG. 2, an endless intermediate transfer belt 7 is provided downstream of the developing device unit 40 in the rotation direction of the photosensitive drum 1, and is driven to rotate in synchronization with the photosensitive drum 1. The intermediate transfer belt 7 comes into contact with the photosensitive drum 1 at a portion pressed by the primary transfer roller 5 and transfers a toner image formed on the photosensitive drum 1. Further, a secondary transfer roller 73 is rotatably provided so as to face the support roller 72 that supports the intermediate transfer belt 7, and on the intermediate transfer belt 7 at a portion where the support roller 72 and the secondary transfer roller 73 face each other. The toner image is pressed and transferred onto a recording material P such as recording paper.

  A cleaner 8 for removing residual toner on the intermediate transfer belt 7 is provided between the full-color developing device unit 40 and the intermediate transfer belt 7 so as to be able to contact with and separate from the intermediate transfer belt 7.

  The paper feeding means 60 that guides the recording material P to the intermediate transfer belt 7 includes a paper feeding tray 61 that houses the recording material P, and a paper feeding roller 62 that feeds the recording material P stored in the paper feeding tray 61 one by one. It is composed of a timing roller 63 for feeding the fed recording material P to the secondary transfer site.

  The recording material P to which the toner image has been pressed and transferred is conveyed to the fixing device 24 by a conveying means 66 constituted by an air suction belt or the like, and the toner image transferred by the fixing device 24 is fixed on the recording material P. After fixing, the recording material P is transported through the vertical transport path 80 and discharged onto the upper surface of the apparatus main body 100.

  The image forming apparatus shown in FIG. 2 is one in which a replaceable developing device 4 is loaded to form an image.

  The developing device 4 shown in FIG. 3A is usually called a toner cartridge, and stores a predetermined amount of toner inside a part where components such as a developing roller are arranged. The developing device supplied in the form of a toner cartridge is loaded at a predetermined position in the image forming apparatus, and then the developer stored therein is supplied to the photosensitive drum for development, and a predetermined number of images are formed and developed. When the agent runs out, it is removed from the apparatus and a new toner cartridge is loaded.

  FIG. 3B is a schematic diagram illustrating an example of a cross-sectional configuration of the developing device 4. Hereinafter, the developing device 4 is also referred to as a toner cartridge 4. The toner cartridge 4 has a buffer chamber 42 adjacent to the developing roller 41 and a hopper 43 adjacent to the buffer chamber 42.

  The developing roller 41 has a conductive cylindrical base and an elastic layer formed on the outer periphery of the base using a material having high hardness such as silicone rubber.

  In the buffer chamber 42, a blade 44, which is a toner regulating member, is disposed in pressure contact with the developing roller 41. The blade 44 regulates the charge amount and adhesion amount of toner on the developing roller 41. It is also possible to further provide an auxiliary blade 45 for assisting regulation of the toner charge amount and adhesion amount on the developing roller 41 on the downstream side of the blade 41 with respect to the rotation direction of the developing roller 41.

  A supply roller 46 is pressed against the developing roller 41. The supply roller 46 is driven to rotate in the same direction as the developing roller 41 (counterclockwise direction in the drawing) by a motor (not shown). The supply roller 46 has a conductive cylindrical substrate and a foam layer formed of urethane foam or the like on the outer periphery of the substrate.

  The hopper 43 contains toner T as a one-component developer. The hopper 43 is provided with a rotating body 47 for stirring the toner. A film-like conveying blade is attached to the rotating body 47, and the toner is conveyed by the rotation of the rotating body 47 in the arrow direction. The toner conveyed by the conveying blades is supplied to the buffer chamber 42 through a passage 44 provided in a partition wall that separates the hopper 43 and the buffer chamber 42. The shape of the conveying blade is bent while conveying the toner in front of the rotation direction of the blade as the rotating body 47 rotates, and returns to a straight state when the left end of the passage 48 is reached. In this way, the blades supply the toner to the passage 48 by returning the shape of the blades straightly through the curved state.

  The passage 48 is provided with a valve 321 for closing the passage 48. This valve is a film-like member, one end of which is fixed to the upper right side surface of the passageway 48 of the partition wall. When toner is supplied from the hopper 43 to the passageway 48, the passageway 48 is opened by being pushed rightward by the pressing force from the toner. It is like that. As a result, toner is supplied into the buffer chamber 42.

  Further, a regulating member 322 is attached to the other end of the valve 321. The regulating member 322 and the supply roller 46 are arranged so as to form a slight gap even when the valve 321 closes the passage 48. The regulating member 322 adjusts so that the amount of toner accumulated at the bottom of the buffer chamber 42 does not become excessive, so that a large amount of toner collected from the developing roller 41 to the supply roller 46 does not fall to the bottom of the buffer chamber 42. Adjusted.

  In the toner cartridge 4, the developing roller 41 is rotated in the direction of the arrow during image formation, and the toner in the buffer chamber 42 is supplied onto the developing roller 41 by the rotation of the supply roller 46. The toner supplied onto the developing roller 41 is charged and thinned by a blade 44 and an auxiliary blade 45 and then transported to a region facing the image carrier to develop an electrostatic latent image on the image carrier. Provided. The toner that has not been used for development returns to the buffer chamber 42 as the developing roller 41 rotates, and is scraped and collected from the developing roller 41 by the supply roller 46.

  The toner of the present invention does not change the crystal structure of the colorant in the toner at the heating temperature at the time of fixing in the prior art, and a toner image having stable color reproducibility can be obtained with a known fixing device. It is done. By the way, in recent years, there is a movement to reduce the energy consumption of the image forming apparatus from the viewpoint of consideration for the global environment. Of these, the reduction of energy consumption in the fixing process has attracted attention, and so-called low-temperature fixing technology for fixing a toner image at a temperature lower than the current fixing temperature has been adopted.

  That is, when the toner of the present invention is a toner compatible with low-temperature fixing, the surface temperature of the heating member in the fixing device is preferably set to less than 140 ° C., and the surface temperature of the heating member is set to less than 130 ° C. Is more preferable.

  Under the set temperature, it is required to efficiently supply heat supplied from the heating member to the transfer sheet, and so-called belt fixing using a heat-resistant belt as either the heating member or the pressure member. The method is preferred.

  FIG. 4 shows an example of a belt fixing type fixing device (a type using a belt and a heating roller) capable of fixing the toner according to the present invention.

  The fixing device 24 shown in FIG. 4 is a type that uses a belt and a heating roller to secure a nip width, and is pressed against the fixing roller 240 via the fixing roller 240, the seamless belt 241, and the seamless belt 241. The pressure pad (pressure member) 242a, the pressure pad (pressure member) 242b, and the lubricant supply member 243 constitute main parts.

  The fixing roller 240 is formed of a heat-resistant elastic layer 240b and a release layer (heat-resistant resin layer) 240c around a metal core (cylindrical metal core) 240a, and a heat source is provided inside the core 240a. A halogen lamp 244 is arranged. The surface temperature of the fixing roller 240 is measured by the temperature sensor 245, and the halogen lamp 244 is feedback-controlled by a temperature controller (not shown) based on the measurement signal so that the surface of the fixing roller 240 is adjusted to a constant temperature. The seamless belt 241 contacts the fixing roller 240 so as to be wound at a predetermined angle, thereby forming a nip portion.

  Inside the seamless belt 241, a pressure pad 242 having a low friction layer on its surface is disposed in a state of being pressed against the fixing roller 240 via the seamless belt 241. The pressure pad 242 is provided with a pressure pad 242a to which a strong nip pressure is applied and a pressure pad 242b to which a weak nip pressure is applied, and is held by a holder 242c made of metal or the like.

  A belt traveling guide is attached to the holder 242c so that the seamless belt 241 slides and rotates smoothly. The belt running guide is preferably a member having a low coefficient of friction because it rubs against the inner surface of the seamless belt 241, and a member having low thermal conductivity is preferred so that heat cannot be taken away from the seamless belt 241. In addition, as a specific example of the material of the seamless belt 241, a polyimide is mentioned, for example.

  The toner image formed with the toner of the present invention is finally transferred onto the transfer material P, and fixed on the transfer material by a fixing process to form an image. The transfer material P used for the image formation is a support for holding a toner image, and is usually called an image support, a recording material, or transfer paper. Specifically, various transfer materials such as plain paper and fine paper from thin paper to thick paper, coated printing paper such as art paper and coated paper, commercially available Japanese paper and postcard paper, plastic film for OHP, cloth, etc. However, it is not limited to these.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<Production of color filter>
[Production of color filter CF-1]
In order to obtain an RGB color filter, a red (R) mosaic pattern, a green (G) mosaic pattern, and a blue (B) mosaic pattern were formed on a glass plate by the following method. Using the components shown below, photosensitive coating agents for red (R), green (G) and blue (B) color filters were prepared. The used photosensitive polyimide resin varnish is a photosensitive polyimide resin varnish containing a photosensitizer.

(Preparation of photosensitive coating agent for color filters)
<Photosensitive coating agent for red (R) color filter>
Colorant represented by general formula (1): Exemplified compound (1-1) 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts <Photosensitive coating agent for green (G) color filter>
Coloring material G-1 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts <Photosensitive coating agent for blue (B) color filter>
The following colorant B-1 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts

(Production of color filter)
The glass plate treated with the silane coupling agent was set on a spin coater, and the above-described photosensitive coating agent for red (R) color filter was spin-coated at 300 rpm for 5 seconds and then at 2000 rpm for 5 seconds. Next, after prebaking at 80 ° C. for 15 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed with an ultrahigh pressure mercury lamp at a light amount of 900 mJ / cm ² .

  Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass plate.

  Next, the green mosaic pattern and the blue mosaic pattern are formed using the green (G) color filter photosensitive coating agent and the blue (B) color filter photosensitive coating agent, respectively. Coating and baking were performed in the same manner as the pattern formation.

  Next, a black matrix was formed according to a conventional method, and a color filter CF-1 was produced.

[Production of color filters CF-2 to 8]
Except having changed the example compound (1-1) which is a coloring agent used with the photosensitive coating agent for red (R) color filters in preparation of the said color filter CF-1 to each coloring agent of Table 1, it changed. Similarly, color filters CF-2 to 6 of the present invention and comparative color filters CF-7 and 8 were produced.

<Evaluation of color filter>
About each obtained color filter, according to the following method, evaluation of color tone, heat resistance, and light resistance was performed.

[Evaluation of color tone]
About each produced said color filter, the color tone was visually observed with 10 monitors and the color tone was evaluated according to the following reference | standard. As an evaluation rank, it is desirable that it is more than (circle).

◎: Vivid and clear color tone ○: Vivid color tone △: Dull color tone [Evaluation of heat resistance]
The prepared color filter was heated at 150 ° C. for 3 hours with a hot plate arranged so as to be in contact with the crow substrate surface of the color filter, and then the chromaticity difference of the red color filter before and after heating, that is, ΔEab1 was measured. This was taken as a measure of heat resistance. For the measurement of chromaticity, a color difference meter CR-400 (manufactured by Konica Minolta Sensing) was used. It shows that the smaller the value of ΔEab1, the smaller the change in chromaticity after high-temperature storage and the better the heat resistance.

[Evaluation of light resistance]
The color filter produced above was irradiated with a xenon lamp at 70000 lux for 7 days, and then the chromaticity difference of the red color filter before and after the xenon lamp irradiation, that is, ΔEab2, was measured, and this was used as a measure of light resistance. A color difference meter CR-400 (manufactured by Konica Minolta Sensing) was used for the measurement of chromaticity. It shows that the smaller the value of ΔEab2, the smaller the change in chromaticity after the xenon lamp irradiation, and the better the light resistance.

  The results obtained as described above are shown in Table 1.

  As is clear from the results shown in Table 1, the color filters CF-1 to CF-6 of the present invention have fastness such as heat resistance and light resistance compared to the comparative color filters CF-7 and CF-8. It was remarkably improved and the color tone was found to have excellent characteristics, and it was confirmed that it had excellent properties as a color filter applicable to liquid crystal color displays and the like.

Example 2
<< Preparation of front filter for display >>
[Preparation of front filter 1 for display: the present invention]
On a polyethylene terephthalate (PET) film (thickness: 100 μm), a 0.4% methyl ethyl ketone / toluene mixed solution of the exemplified compound (1-17), which is a colorant represented by the general formula (1) of the present invention (methyl ethyl ketone / 0.5 g of toluene = 1: 1) and 6.5 g of 20% methyl ethyl ketone / toluene mixed solution of polyester resin were mixed, and then coated and dried with a bar coater to form a coating film having a dry film thickness of 5 μm. Thus, a front filter 1 for display was obtained. The front filter 1 for display has a minimum value in the range of 585 to 600 nm as a transmittance curve, and there is no clear minimum value other than this, and the wavelength of the minimum value of visible light transmittance is the wavelength of neon light emission. The region is 580 to 600 nm. Therefore, the front filter for display 1 has a high transmittance and can effectively absorb neon light emission. Therefore, a neon light emission cut filter and a front filter for display can be provided.

[Preparation of front filter 2 for display: the present invention]
A 0.5% methyl ethyl ketone / toluene mixed solution of the exemplified compound (1-40), which is a colorant represented by the general formula (1) of the present invention, on a PET film (thickness: 100 μm) (methyl ethyl ketone / toluene = 1: 1). ) And 4.0 g of 35% methyl ethyl ketone / toluene mixed solution of acrylic resin, and then coated with a bar coater and dried to form a coating film having a dry film thickness of 5 μm. A front filter 2 was obtained. This display front filter 2 has a minimum value in the range of 580 to 595 nm as a transmittance curve, and there is no clear minimum value other than this, and the wavelength of the minimum value of visible light transmittance is in the wavelength range of neon light emission. There is some 580-600 nm. Therefore, this display front filter 2 has a high transmittance and can provide a neon light emission cut filter and a display front filter capable of effectively absorbing neon light emission.

[Preparation of Front Filter 3 for Display: Present Invention]
An ultraviolet absorbing coating solution containing an isocyanate resin as a binder and zinc oxide as an ultraviolet absorber on the PET resin on the side opposite to the colorant-containing layer surface of the produced front filter 1 for display (Sumitomo Osaka Cement Co., Ltd.) ) Was coated with a bar coater and dried to form an ultraviolet absorbing layer having a dry film thickness of 3 μm, and a front filter 3 for display was obtained. This display front filter 3 did not cause a change in the minimum wavelength of the visible light transmittance with respect to the display front filter 1.

  Using a xenon fade meter (FAL-25X-HC.B.EC) manufactured by Suga Test Instruments Co., Ltd., the xenon light was bombarded for 48 hours on the ultraviolet absorption layer forming surface of the display front filter 3 and then used for display. The dye residual ratio% at the visible region maximum absorption wavelength from the unexploded sample of the front filter 3 was calculated to be 87.3%. Further, after storage for 240 hours in an environment of 60 ° C. and 90% RH, the dye residual ratio% at the visible region maximum absorption wavelength of the display front filter 3 was calculated to be 95.7%, which was light resistance and heat and humidity resistance. And a neon light emission cut filter having a UV absorbing layer and a front filter for display.

[Preparation of Front Filter 4 for Display: Present Invention]
Near-infrared absorbing dyes (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p- are respectively formed on the PET resin surface opposite to the colorant-containing layer surface of the produced front filter 1 for display. 0.3 g of 0.5% cyclohexanone solution of phenylenediimmonium hexafluoride antimonate) and 3.0 g of 20% cyclohexanone solution of polyester resin are mixed, dried by a bar coater, and dried. A front filter 4 for display was obtained by forming a coating film having a thickness of 6 μm. As a result of measuring the spectral absorption characteristics of the front filter 4 for display with a Hitachi spectrophotometer (U-3500), the wavelengths at the minimum value of the transmittance were 592 nm and 1100 nm.

  Next, the display front filter 4 was subjected to a xenon fade meter manufactured by Suga Test Instruments Co., Ltd. for 48 hours, and the unexposed sample of the display front filter 4 was exposed to the near-infrared absorbing layer surface for 48 hours. The dye residual degree% at the maximum absorption wavelength in the visible region was calculated to be 92.6%. Moreover, when the dye residual rate% in the visible region maximum absorption wavelength of the front filter for display 4 after storage for 240 hours in an environment of 60 ° C. and 90% RH was calculated, it was 95.9%, and the near-infrared absorbing layer was It was possible to provide a neon emission cut filter having a front filter for display.

[Preparation of Front Filter 5 for Display: Present Invention]
0.5 g of a 0.5% cyclohexanone solution of N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimmonium hexafluoride antimonate as a near infrared absorbing dye, 0.5 g of a 0.4% cyclohexanone solution of Example Compound (1-17), which is a colorant represented by the general formula (1) of the present invention, and 6.5 g of a 20% cyclohexane solution of a polyester resin are mixed. A coating film having a dry film thickness of 6 μm was formed on a PET film (thickness: 100 μm) by coating and drying using a bar coater. Next, 2- (2'-hydroxy-5'-methylphenyl)-is formed on the PET resin surface on the side opposite to the surface containing the near-infrared absorbing dye and the colorant of the present invention of the front filter for display. An ultraviolet absorbing coating solution containing benzotriazole as an ultraviolet absorber was coated with a bar coater and dried to form an ultraviolet absorbing layer having a dry film thickness of 3 μm. Thus, a display front filter 5 was obtained.

  Using a xenon fade meter manufactured by Suga Test Instruments Co., Ltd., after xenon light was bombarded for 48 hours against the UV absorbing layer surface of the display front filter 5, it was visible based on the unexploded sample of the display front filter 5 It was 88.5% as a result of calculating the pigment residual degree% in the area | region maximum absorption wavelength. Further, the dye residual ratio% at the maximum absorption wavelength in the visible region of the display front filter 5 after storage for 480 hours in an environment of 60 ° C. and 90% RH was 93.4%.

[Preparation of Front Filter 6 for Display: Present Invention]
(Formation of electromagnetic wave cut layer and non-glare layer)
An ITO (Sn (tin) -containing indium oxide) thin film was formed on a PET film (thickness: 100 μm) using an indium oxide-tin oxide complex and using argon gas and oxygen gas. Next, on the surface opposite to the surface on which the ITO film was formed, a near-infrared absorption layer and a neon emission absorption layer were laminated with a thickness of 6 μm using the coating liquid used in the production of the display front filter 4. . Next, on the ITO surface opposite to the surface on which the near infrared absorption and neon light emission absorption layer is formed, the surface of the PMMA plate having an antiglare layer with a thickness of 3 mm, which is AR-coated, and the PET film is not formed When the front surface filter 6 for display was produced by pasting together with the ITO surface, a good filter with high smoothness could be produced.

[Preparation of display front filter 7: comparative example]
In the production of the front filter 2 for display, the same procedure except that the following comparative compound 3 was used as the colorant instead of the exemplified compound (1-17) which is the colorant represented by the general formula (1) of the present invention. Thus, a display front filter 7 having an ultraviolet absorbing layer was produced.

  The display front filter 7 produced above was exposed to xenon light from the UV absorbing layer surface for 48 hours using a xenon feather meter and subjected to a light resistance test. It was 68.2% when dye residual degree% (measurement of light resistance) in maximum absorption wavelength was computed. In addition, after the display front filter 7 was stored in an environment of 60 ° C. and 90% RH for 480 hours and subjected to a moist heat resistance test, the dye residual ratio at the maximum absorption wavelength in the visible region with respect to the untreated sample of the display front filter 7 % (Scale of wet heat resistance) was calculated to be 80.8%, which was found to be inferior in light resistance and wet heat resistance as compared with the case where the colorant represented by the general formula (1) of the present invention was used. .

[Preparation of front filter 8 for display: comparative example]
In the production of the front filter 3 for display, the same procedure except that the comparative compound 3 was used as a colorant instead of the exemplified compound (1-17) which is the colorant represented by the general formula (1) of the present invention. Thus, a display front filter 8 having a near-infrared absorbing layer was produced.

  Subsequently, the light resistance test was performed in the same manner as in the evaluation of the front filter 7 for display, and the residual ratio (%) of the dye was measured. As a result of the heat and humidity resistance test conducted in the same manner, the dye residual ratio was 70.3%.

  From the above, the display front filter using the colorant of the present invention is excellent in light resistance and wet heat resistance. As a result, it was possible to provide a neon emission absorption filter having a high transmittance and capable of effectively absorbing neon emission, and a display front filter having an ultraviolet absorption layer, an infrared absorption layer, and the like.

Example 3
<Preparation of toner for electrophotography>
[Preparation of cyan toner]
Cyan toners 1 to 22 were prepared according to the following method.

[Preparation of Cyan Toner 1: Preparation of toner by pulverization method]
The following toner components were put into a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.), the peripheral speed of the stirring blade was set to 25 m / sec, and a mixing process was performed for 5 minutes to prepare a mixture.

Polyester resin (Bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic acid condensate, weight average molecular weight 20,000)
100 parts by mass Colorant represented by general formula (1): exemplary compound (1-17) 1.8 parts by mass Colorant represented by general formula (2): exemplary compound (2-1) 4.2 mass Parts (Exemplary Compound (1-17): Exemplified Compound (2-1) = 30: 70 (mass%))
Silanol compound: Exemplified compound (S-1) 0.05 parts by weight Release agent: 6 parts by weight of pentaerythritol tetrastearate Charge control agent: 1 part by weight of boron dibenzylate Next, the above mixture was kneaded with a twin screw extruder kneader. Then, after roughly pulverizing with a hammer mill, pulverizing with a turbo mill pulverizer (manufactured by Turbo Kogyo Co., Ltd.), and further finely pulverizing with an air classifier utilizing the Coanda effect, the volume-based median diameter is 5 .5 μm colored particles 1 were obtained.

  Next, the following external additives were added to the colored particles 1, and external addition processing was performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to prepare cyan toner 1.

Silica treated with hexamethylsilazane (average primary particle size 12 nm)
0.6 part by mass n-octylsilane-treated titanium dioxide (average primary particle size 24 nm)
0.8 parts by mass The external addition treatment using a Henschel mixer was performed under the conditions of a peripheral speed of a stirring blade of 35 m / second, a treatment temperature of 35 ° C., and a treatment time of 15 minutes.

[Preparation of Cyan Toner 2: Preparation of Toner by Emulsion Polymerization (Invention)]
(Preparation of colorant fine particle dispersion 1)
11.5 parts by mass of sodium n-dodecyl sulfate was added to 160 parts by mass of ion-exchanged water, and dissolved and stirred to prepare a surfactant aqueous solution. In this surfactant aqueous solution, 1.8 parts by mass of the exemplified compound (1-1) as the colorant represented by the general formula (1) and the exemplified compound (1) as the colorant represented by the general formula (2) 2-4) was added in an amount of 4.2 parts by mass, and 0.05 parts by mass of the exemplified compound (S-1) was gradually added as a silanol compound, and Clearmix W Motion CLM-0.8 (M Technique Co., Ltd.) was added. ) Was used for dispersion treatment to prepare a colorant fine particle dispersion 1.

  The colorant fine particles 1 in the colorant fine particle dispersion 1 had a volume-based median diameter of 98 nm. The volume-based median diameter was measured using MICROTRAC UPA-150 (manufactured by HONEYWELL) under the following measurement conditions.

Sample refractive index: 1.59
Sample specific gravity: 1.05 (in terms of spherical particles)
Solvent refractive index: 1.33
Solvent viscosity: 0.797 (30 ° C), 1.002 (20 ° C)
0 point adjustment: Prepared by introducing ion-exchanged water into the measurement cell.

(Preparation of resin particle 1 for core part)
The core part resin particles 1 having a multilayer structure were produced through the first stage polymerization, the second stage polymerization, and the third stage polymerization shown below.

<First stage polymerization>
4 parts by mass of the following anionic surfactant SA1 along with 3040 parts by mass of ion-exchanged water was added to a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device to prepare an aqueous surfactant solution.

Anionic surfactant SA1
_{C 10 H 21 (OCH 2 CH} 2) 2 SO 3 Na
A polymerization initiator solution prepared by dissolving 10 parts by mass of potassium persulfate (KPS) as a polymerization initiator in 400 parts by mass of ion-exchanged water is added to the prepared surfactant aqueous solution, and the temperature is adjusted to 75 ° C. After raising the temperature, the monomer mixture 1 composed of the following compounds was dropped into the reaction vessel over 1 hour.

Styrene 532 parts by weight n-butyl acrylate 200 parts by weight Methacrylic acid 68 parts by weight n-octyl mercaptan 16.4 parts by weight The monomer mixture 1 was added dropwise, and the liquid was heated and stirred at 75 ° C. for 2 hours. Thus, polymerization (first stage polymerization) was performed to prepare resin particles. Let this resin particle be resin particle A1. The weight average molecular weight of the resin particles A1 prepared by the first stage polymerization was 16,500.

<Second stage polymerization>
Into a flask equipped with a stirrer, the monomer mixture 2 composed of the following compounds was added, and subsequently 93.8 parts by mass of paraffin wax HNP-57 (manufactured by Nippon Wax Co., Ltd.) was added as a release agent. And dissolved by heating to 90 ° C. In this way, a monomer solution 3 was prepared.

Styrene 101.1 parts by weight n-butyl acrylate 62.2 parts by weight Methacrylic acid 12.3 parts by weight n-octyl mercaptan 1.75 parts by weight On the other hand, 3 parts by weight of the anionic surfactant SA1 was added to ion-exchanged water 1560. A surfactant aqueous solution was prepared by dissolving in parts by mass and heated to 98 ° C. In this surfactant aqueous solution, 32.8 parts by mass (in terms of solid content) of the prepared resin particles A1 are added, and further, the monomer solution 3 containing the paraffin wax is added, and then the circulation path is changed. It was mixed and dispersed for 8 hours with Clairemix (manufactured by MTechnic Co., Ltd.). By this mixing and dispersion, an emulsified particle dispersion containing emulsified particles having an average dispersed particle size of 340 nm was prepared.

  Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion-exchanged water is added to this emulsified particle dispersion, and this system is heated and stirred at 98 ° C. for 12 hours. Polymerization (second stage polymerization) was performed to prepare resin particles. Let this resin particle be resin particle A2. The weight average molecular weight of the resin particles A2 prepared by the second stage polymerization was 23,000.

<Third stage polymerization>
A polymerization initiator solution prepared by dissolving 5.45 parts by mass of potassium persulfate in 220 parts by mass of ion-exchanged water is added to the resin particle A2 prepared by the second stage polymerization, and the following compound is obtained under a temperature condition of 80 ° C. The monomer mixture 4 consisting of was added dropwise over 1 hour.

Styrene 293.8 parts by mass n-butyl acrylate 154.1 parts by mass n-octyl mercaptan 7.08 parts by mass After completion of the dropwise addition, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization). The core part resin particle 1 was prepared by cooling to 28 ° C. The weight average molecular weight of the core portion resin particles 1 produced by the third stage polymerization was 26,800.

(Preparation of resin particle 1 for shell)
In the preparation of the resin particles 1 for the core part, the polymerization reaction and the treatment after the reaction were performed in the same manner except that the monomer mixture 1 used in the first stage polymerization was changed to the monomer mixture 5 below. As a result, resin particles 1 for shells were prepared.

Styrene 624 parts by weight 2-ethylhexyl acrylate 120 parts by weight Methacrylic acid 56 parts by weight n-octyl mercaptan 16.4 parts by weight (Preparation of toner)
Toner 2 was prepared according to the following procedure.

<Formation of core part>
In a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, nitrogen introduction device,
420.7 parts by mass of resin particles 1 for core part (solid content conversion)
900 parts by mass of ion-exchanged water 200 parts by mass of the colorant particle dispersion 1 were added and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / L sodium hydroxide aqueous solution was added to adjust the pH to a range of 8 to 11.

  Next, an aqueous solution in which 2 parts by mass of magnesium chloride hexahydrate was dissolved in 1000 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, the heating was started, and the system was heated to 65 ° C. over 60 minutes to associate the particles. In this state, the particle size of the associated particles was measured using Multisizer 3 (manufactured by Coulter). When the volume-based median diameter of the associated particles reached 5.5 μm, 40.2 parts by mass of sodium chloride was added to ion-exchanged water. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass.

  After the association was stopped, the core part 1 was prepared by continuing the fusion by heating and stirring for 1 hour at a liquid temperature of 70 ° C. as an aging treatment.

  It was 0.912 as a result of measuring the average circularity of the core part 1 by FPIA2000 (made by Systex).

<Formation of shell>
Next, after heating the liquid containing the core part 1 prepared above to 65 ° C., 96 parts by mass of the resin particles 1 for the shell are added, and 2 parts by mass of magnesium chloride hexahydrate is added to the ion-exchanged water 1000 An aqueous solution dissolved in parts by mass was added over 10 minutes, and then the temperature was raised to 70 ° C. and stirring was performed for 1 hour. In this way, after the shell resin particles 1 were fused to the surface of the core portion 1, an aging treatment was performed at 75 ° C. for 20 minutes to form a shell.

  Thereafter, an aqueous solution in which 40.2 parts by mass of sodium chloride was dissolved in 1000 parts by mass of ion-exchanged water was added to stop shell formation. Further, the colored particles produced by cooling to 30 ° C. at a rate of 8 ° C./min are filtered, washed repeatedly with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. Colored particles 2 having a shell were produced.

<External treatment>
The following external additives were added to the colored particles 2 prepared above, and external addition processing was performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to prepare cyan toner 2.

Silica treated with hexamethylsilazane (average primary particle size 12 nm)
0.6 part by mass n-octylsilane-treated titanium dioxide (average primary particle size 24 nm)
0.8 parts by mass The external addition treatment using a Henschel mixer was performed under the conditions of a peripheral speed of a stirring blade of 35 m / second, a treatment temperature of 35 ° C., and a treatment time of 15 minutes.

[Preparation of Cyan Toners 3 to 18: Preparation of Toner by Emulsion Polymerization (Invention)]
In the preparation of the cyan toner 2, as the colorant to be used, the type and addition amount of the colorant represented by the general formula (1) and the type and addition amount of the colorant represented by the general formula (2) are shown in Table 2. Cyan toners 3 to 18 were prepared in the same manner except that the conditions were changed.

  In preparing the cyan toners 3 to 18, the total amount of the colorant is 6 parts by mass, and the colorant represented by the general formula (1) and the colorant represented by the general formula (2) shown in Table 2 are used. It was made to become mass% ratio of.

[Preparation of cyan toners 19 to 22: Preparation of toner by emulsion polymerization method (comparative example)]
In the preparation of the cyan toner 2, as the colorant to be used, the type and amount of the following comparative compound and the type and amount of the colorant represented by the general formula (2) were changed to the conditions described in Table 2. In the same manner, cyan toners 19 to 22 were prepared.

  In preparing the cyan toners 19 to 22, the total amount of the colorant was 6 parts by mass, and the mass% ratio of the comparative compound described in Table 2 to the colorant represented by the general formula (2) was set. .

[Preparation of yellow, magenta and black toner]
(Preparation of yellow toner)
In the preparation of the cyan toner 2, the colorant is C.I. I. A yellow toner was prepared in the same manner except that the pigment yellow 74 was used.

(Preparation of magenta toner)
In the preparation of the cyan toner 2, the colorant is C.I. I. A magenta toner was prepared in the same manner except that the pigment red 122 was used.

(Preparation of black toner)
A black toner was prepared in the same manner as in the preparation of the cyan toner 2 except that the colorant was changed to carbon black “MOGAL L” (manufactured by Cabot Corporation).

[Developer preparation]
Cyan developer 1 having a toner concentration of 6% by mass is prepared by mixing the above-prepared cyan toners 1 to 22, a yellow toner, a magenta toner, and a black toner with a ferrite carrier coated with a silicone resin and having a volume average particle diameter of 60 μm. To 22 and a yellow developer, a magenta developer, and a black developer were prepared.

<Evaluation of toner for electrophotography>
[Evaluation equipment]
As an evaluation apparatus, a commercially available composite printer bizhub Pro C500 (manufactured by Konica Minolta Business Technologies Co., Ltd.), which is an image forming apparatus of the two-component development system shown in FIG. 1, is used. It was loaded.

  Further, the belt fixing type fixing device shown in FIG. 4 was mounted on the printer for evaluation. Various conditions such as the surface material and surface temperature of the heating roller in this belt fixing type fixing device were as follows.

Fixing speed: 230mm / sec
Heat roller surface material: Polytetrafluoroethylene (PTFE)
Heating roller surface temperature: 125 ° C
In the evaluation, the respective toners prepared in the evaluation apparatus were loaded in order, and the following items were evaluated in an environment of normal temperature and normal humidity (25 ° C., 55% RH).

[Image formation]
In the image formation, a halftone image having an image density of 0.4, a solid white image, a solid black image having an image density of 0.8, and a fine line image are respectively obtained in an environment of normal temperature and humidity (25 ° C., 55% RH). An image that was divided into quarters was printed on A4 size paper.

[Image evaluation]
Using a toner set composed of each toner, a reflection image (image on paper) was created on each sheet using the above-described image forming apparatus, and evaluated by the following method. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

(Evaluation of saturation of cyan image)
Using the cyan toner of the present invention prepared above and the comparative cyan toner, a cyan solid image having a hue angle of 240 degrees and a maximum saturation of lightness of 40 and 70 was output in the CIELAB color space. The saturation of each cyan toner image in the lightness 40 and lightness 70 images was measured using a spectrophotometer Gretag Macbeth Spectrolino (manufactured by Gretag Macbeth), and the saturation of each cyan image formed using the comparative cyan toner 19 As a standard, the saturation improvement rate was measured, and the saturation was evaluated according to the following criteria.

A: The saturation improvement rate is 20% or more with respect to the reference toner (cyan toner 19). B: The saturation improvement rate is 15% or more and less than 20% with respect to the reference toner (cyan toner 19). C: Saturation improvement rate is 10% or more and less than 15% with respect to the reference toner (cyan toner 19) D: Saturation improvement rate is less than 10% with respect to the reference toner (cyan toner 19) (Evaluation of color reproducibility)
Using the toner set prepared above, solid images of cyan / yellow / magenta and R / G / B were formed, and the color reproduction area was measured to measure the area expansion ratio of the color reproduction area. . In the evaluation, the color gamut of the Japan color for printing is set to 100, centering on a single color of cyan formed by cyan toner to be evaluated and a solid image of G and B mainly formed by cyan toner. The color gamut areas were compared, and color reproducibility was evaluated according to the following criteria.

A: The color reproduction gamut expansion width is 10% or more with respect to the printing Japan color gamut. B: The color reproduction gamut expansion width is 5% or more and less than 10% with respect to the printing Japan color gamut. C: The expansion range of the color reproduction gamut is 1% or more and less than 5% of the color gamut of the printing Japan color. D: The expansion width of the color reproduction gamut is less than 1% of the color gamut of the printing Japan color. Evaluation of)
<Evaluation of light resistance>
Using the toner set prepared above, solid color images of R, G, and B were formed, and these images were exposed to xenon light for 7 days using a xenon fade meter. Each mixed color image before and after the exposure is visually observed by 10 subjects, and when the hue change is not observed at all, a maximum of 10 points, the hue variation is extremely large, and the residual ratio of the cyan image is 10% or less The case was evaluated as one point, the average value of 10 evaluation points was obtained, and the light resistance was evaluated according to the following criteria. In the evaluation rank, if it was A or B, it was determined that the light resistance was within an allowable range.

A: Average score of 10 people is 9.0 or more B: Average score of 10 people is 8.0 or more and less than 9.0 C: Average score of 10 people is 7.0 or more and less than 8.0 D: Average score of 10 people is less than 7.0 <Evaluation of ozone resistance>
Using the toner set prepared above, solid color images of R, G, and B were formed, and these images were formed under the condition that the ozone gas concentration was set to 5 ppm (25 ° C .; 60% RH). I was exposed to ozone gas for a day. Each mixed color image before and after the exposure is visually observed by 10 subjects, and when the hue change is not observed at all, a maximum of 10 points, the hue variation is extremely large, and the residual ratio of the cyan image is 10% or less The case was evaluated as 1 point, the average value of 10 evaluation points was obtained, and ozone resistance was evaluated according to the following criteria. In addition, if it was A or B in an evaluation rank, it was judged that it was in the tolerance | permissible_range as ozone resistance.

A: Average score of 10 people is 9.0 or more B: Average score of 10 people is 8.0 or more and less than 9.0 C: Average score of 10 people is 7.0 or more and less than 8.0 D: Average score of 10 people is less than 7.0 <Transparency evaluation>
A cyan solid image was formed using a cyan toner on a commercially available OHP sheet (made of a polyester film having a thickness of 75 μm), and a visible spectral transmittance was measured using a 330-type self-recording spectrophotometer (manufactured by Hitachi, Ltd.). Evaluation by measurement was performed. That is, using a non-toner-loaded OHP sheet as a reference, the visible spectral transmittance of the fixed image was measured, the difference in spectral transmittance at 590 nm was determined, and the transparency of the OHP image was evaluated. The evaluation was performed by setting the toner adhesion amount on the OHP sheet to be 0.7 ± 0.05 mg / cm ² .

A: Transmittance is 85% or more B: Transmittance is 80% or more and less than 85% C: Transmittance is less than 80% Evaluation rank A or B where transmittance is 80% or more If so, it was judged that the transparency was high.

  Table 3 shows the evaluation results obtained as described above.

  As is clear from the results shown in Table 3, the image formed using the electrophotographic toner (cyan toner) of the present invention has good color reproducibility, light resistance and ozone resistance when each color toner is mixed. Thus, it can be seen that the color reproduction range is further expanded and the transparency is improved.

1 Photoconductor (Photoconductor drum)
4 Development device (toner cartridge)
6 Cleaning Device 7 Intermediate Transfer Belt 10 Image Forming Unit 24 Fixing Device 240 Heating Roller 241 Pressure Belt (Seamless Belt)
P Transfer material (recording material)

Claims (8)

A colorant composition comprising a compound represented by the following general formula (1) as a colorant.

[Wherein, M represents a metal atom. X and Y are each a halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, or Represents an alkylcarbonyloxy group. n and m each represents 0 or 1; ]   The colorant composition according to claim 1, wherein M in the general formula (1) is at least one metal atom selected from magnesium, zinc, aluminum, and silicon.   As a colorant. The colorant composition according to claim 1, comprising a compound represented by the general formula (1) and a phthalocyanine compound. The colorant composition according to claim 3, wherein the phthalocyanine compound is a compound represented by the following general formula (2).

[Wherein, A ₁ , A ₂ , A ₃ and A ₄ each represents a 5- to 6-membered aromatic ring or heterocyclic ring. R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group Carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy Group, acyloxy group, carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, carbonylamino group, sulfamoylamino group, semicarbyl group Basid group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, thio group, sulfonyl group, sulfinyl group, sulfo group or It represents a salt, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, or a group containing a phosphate amide or phosphate ester structure. o, p, q, and r each represent an integer of 1 to 4. Z ₁ and Z ₂ each represent a halogen atom, a hydroxy group, an alkyl group, an alkynyl group, an alkoxy group, a siloxy group, an aryl group, an aryloxy group, an acyloxy group, a carbamoyloxy group, or a sulfamoyloxy group. ]   An electrophotographic toner comprising the colorant composition according to any one of claims 1 to 4.   A color filter comprising the colorant composition according to any one of claims 1 to 4.   A front filter for a display, comprising the colorant composition according to claim 1. The coloring agent characterized by being a compound represented by following General formula (1).

[Wherein, M represents a metal atom. X and Y are each a halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, or Represents an alkylcarbonyloxy group. n and m each represents 0 or 1; ]

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