JP2011242720A - Electrostatic charge image development cyan toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image development cyan toner which includes cyan colorant with which high color reproduction can be achieved both in a cyan region of low lightness and in a cyan region of high lightness.SOLUTION: In an electrostatic charge image development cyan toner, a cyan colorant constituting a cyan toner particle includes a colorant compound A of hexacoordination with a porphyrin ring and a porphyrin colorant compound B of tetracoordination with a hetero ring which does not participate in the coordination in the ratio of 90:10 to 50:50.

Description

  The present invention relates to an electrostatic image developing cyan toner for use in electrophotography.

  In recent years, image quality of copying machines and printers which are color electrophotographic image forming apparatuses has been improved, and in some cases, color reproduction of “Japan Color 2003” which is a color reproduction standard of the printing industry has been achieved.

  However, in the current situation, the color reproduction area in an image formed by yellow, magenta, and cyan color toners cannot completely cover the color reproduction area on the computer display screen. The technical barrier is that the computer display screen is visually recognized by the additive color method using transmitted light, whereas the image formed by electrophotography using color toner is visually recognized by the subtractive color method using reflected light. Also due to the difference. In particular, in an electrophotographic image forming apparatus that is often used for office use, image storage stability without fading is required, and thus the selection range of cyan colorants has been particularly limited.

  In practice, a copper phthalocyanine compound has been used as a cyan colorant, and this copper phthalocyanine compound is excellent in color development in the cyan region of low brightness (dark / dark color) as a cyan color for full color image formation. However, the cyan region of high brightness (light / light color) was not sufficiently developed.

  Various technical information is disclosed in order to improve the above problems.

  For example, Patent Document 1 discloses a cyan colorant containing a phthalocyanine compound having a substituent at a central metal atom, and an electrostatic charge developing toner having high brightness and good color tone is obtained.

  Further, technical information is disclosed that it is effective to use two or more compounds in combination in order to improve the color reproducibility of the low brightness and high brightness cyan regions.

  For example, Patent Document 2 discloses a cyan pigment obtained by wet pulverizing copper phthalocyanine and nickel phthalocyanine in the presence of an inorganic salt and an organic solvent, and has a particle size that is larger than that obtained when wet pulverizing copper phthalocyanine alone. A small and highly saturated pigment is obtained.

  Patent Document 3 discloses a cyan colorant containing a specific ratio of a phthalocyanine compound having a substituent at the central metal atom and a phthalocyanine compound having no substituent at the central metal atom.

  However, as a result of detailed studies by the present inventors, a cyan toner having good color reproducibility has not been put into practical use in both low lightness and high lightness cyan regions.

JP 2009-122496 A JP 2009-151162 A JP 2009-128750 A

  The present invention has been made in consideration of the above-described circumstances, and an object of the present invention is to provide an electrostatic charge containing a cyan colorant that can provide high color reproducibility in both low-lightness and high-lightness cyan regions. The object is to provide cyan toner for image development.

  1. A cyan toner for electrostatic image development comprising cyan toner particles containing at least a resin and a cyan colorant, wherein the cyan colorant constituting the cyan toner particles is a colorant compound represented by the following general formula (1) A cyan toner for developing an electrostatic image, comprising A and a colorant compound B represented by the following general formula (2).

[Wherein M ₁ represents a central metal atom. Z ₁ represents a substituent. m1 and m2 represent 0 or 1, and m1 and m2 are not 0 at the same time. Further, when the 1 m1 and m2 are simultaneously, Z ₁ may be different, identical to one another. A _{1 to} A ₄ each independently represent an aromatic ring that may have a substituent. _However, A 1 to A ₄ is an aromatic ring comprising only carbon atoms. ]

[Wherein M ₂ represents a central metal atom. B _{1 to} B ₄ each independently represent an aromatic ring that may have a substituent. However, at least one of B _{1 to} B ₄ is a nitrogen-containing aromatic ring. ]
2. 2. The cyan toner for developing electrostatic images according to 1 above, wherein M ₁ in the general formula (1) is Si.

3. In the general formula (1), Z ₁ is an alkyl group, an aryl group, an aryloxy group, an alkoxy group, an acyloxy group, or —OSiR ₁ R ₂ R ₃ (where R ₁ , R _2, and R ₃ are each independently Or an alkyl group, an aryl group, an alkoxy group, or an aryloxy group).

  4). Any of the above 1 to 3, wherein the ratio (mA: mB) of the content mass mA of the colorant compound A and the content mass mB of the colorant compound B is 90:10 to 50:50 The cyan toner for electrostatic image development according to item 1.

  According to the cyan toner for developing an electrostatic charge image of the present invention, high color reproducibility can be obtained in both low brightness and high brightness cyan areas. The reason for this is not always clear. However, considering that the colorant compound A is excellent only in the color reproducibility of the high lightness cyan region, the colorant compound B acts complementarily, and the color reproducibility of the low lightness cyan region is also improved. This is probably because of this. In addition, it is presumed that the colorant compound A and the colorant compound B form mixed crystals and similar states at the time of toner preparation, and contribute to the formation of a pigment having a small particle size.

  Hereinafter, the present invention will be specifically described.

  The cyan toner for developing an electrostatic image of the present invention (hereinafter also simply referred to as “cyan toner”) is composed of cyan toner particles containing the following cyan colorant.

<Cyan colorant>
The cyan colorant constituting the cyan toner of the present invention contains a phthalocyanine colorant compound A represented by the general formula (1) and an azaphthalocyanine colorant compound B represented by the general formula (2). To do.

_{M 1} in the general formula (1), _{M 2} in the general formula (2) represents a central metal atom.

Examples of the central metal atom _{M 1} in the general formula (1), for example, Si (silicon atoms), Sn (tin atom), Al (aluminum atom), can be exemplified a Ti (titanium atoms), in particular Si is preferred.

Specific examples of the central metal atom M ₂ in the general formula (2) include, for example, Mg (magnesium atom), Ca (calcium atom), Mn (manganese atom), Co (cobalt atom), Fe (iron atom), Ni ( Nickel atom), Zn (zinc atom) and the like can be exemplified, and Mg and Zn are particularly preferable.

In General Formula (1), Z ₁ represents a substituent, and examples of the substituent include an alkyl group, an aryl group, a hydroxy group, a halogen atom, an aryloxy group, an alkoxy group, an acyloxy group, or —OSiR ₁ R ₂ R _3. (However, R ₁ , R ₂ and R ₃ each independently represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group). You may have.

m1 and m2 represent 0 or 1, and m1 and m2 are not 0 at the same time. Further, when the 1 m1 and m2 are simultaneously, Z ₁ may be different, identical to one another.

Z ₁ is an alkyl group, an aryl group, an aryloxy group, an alkoxy group, an acyloxy group, or —OSiR ₁ R ₂ R ₃ (wherein R ₁ , R ₂ and R ₃ are each independently an alkyl group, an aryl group, an alkoxy group, And a group represented by an aryloxy group).

A _{1 to} A ₄ each independently represent an aromatic ring that may have a substituent. _However, A 1 to A ₄ is an aromatic ring comprising only carbon atoms.

Z ₁ is located in a direction perpendicular to the phthalocyanine ring from the central metal atom M ₁ . In addition, the perpendicular direction here means that it is not on the same plane with respect to the phthalocyanine ring, and it is not essential that the substituent is positioned at 90 ° C. accurately in the plane.

In the general formula (1), specific examples of A _{1 to} A ₄ include those represented by the following formula (A-1) to the following formula (A-7), and preferably the following formula (A -1).

The substituent that A _{1 to} A ₄ has is not particularly limited, and examples thereof include alkyl groups, alkoxy groups, aryloxy groups, alkylamino groups, arylamino groups, alkylthio groups, arylthio groups, aryl groups, heteroaryl groups, and acyl groups. Group, acyloxy group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfamoyl group, alkylcarbamoyl group, nitro group, halogen atom, -SiR ₁ R ₂ R ₃ (however, R ₁ , R ₂ and R ₃ Each independently represents a group represented by an alkyl group, an aryl group, an alkoxy group or an aryloxy group, -OSiR ₁ R ₂ R ₃ (wherein R ₁ , R ₂ and R ₃ are each independently an alkyl group) Group, aryl group, alkoxy group, aryloxy group). . In the synthesis, isomers inevitably have different substituent positions may be included, but these isomers are regarded as the same derivative without being distinguished from each other.

In general formula (2), at least one of B _{1 to} B ₄ is a nitrogen-containing aromatic ring. From the viewpoint of adjusting the color tone, it is preferable that two or more of B _{1 to} B ₄ are nitrogen-containing aromatic rings, more preferably three or all four are nitrogen-containing aromatic rings, and all four are all. Particularly preferred is a nitrogen-containing aromatic ring. Specific examples of B include, for example, those represented by the following formula (B-1) to the following formula (B-29), preferably (B-1), (B-2), (B- It is shown in 3).

  The azaphthalocyanine compound represented by the general formula (2) may include isomers inevitably having different nitrogen positions at the time of synthesis, but these isomers are regarded as the same derivative without being distinguished from each other. .

The substituent that B has is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an acyl group, and an acyloxy group. , Acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfamoyl group, alkylcarbamoyl group, nitro group, halogen atom, -SiR ₁ R ₂ R ₃ (wherein R ₁ , R ₂ and R ₃ are each independently , A group represented by an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, -OSiR ₁ R ₂ R ₃ (wherein R ₁ , R _2, and R ₃ are each independently an alkyl group, an aryl group) , An alkoxy group and an aryloxy group). In the synthesis, isomers inevitably have different substituent positions may be included, but these isomers are regarded as the same derivative without being distinguished from each other.

  Specific examples of the general formula (1) of the present invention are shown in (1-1) to (1-30) below. However, these specific examples do not limit the scope of the present invention.

  Specific examples of the general formula (2) of the present invention are shown in (2-1) to (2-21) below. However, these specific examples do not limit the scope of the present invention.

  The compound represented by the general formula (1) to the general formula (2) according to the present invention is obtained by, for example, reacting a phthalocyanine derivative represented by the following general formula (3) or the following general formula (4) with a metal derivative. Can be manufactured.

In the general formula (3), A is the same aromatic ring as A _{1 to} A ₄ in the general formula (1).

In the general formula (4), B is the same aromatic ring as B _{1 to} B ₄ in the general formula (2).

  Alternatively, the desired product can be obtained by using an isoindolediimine derivative instead of the phthalocyanine derivative.

The metal derivative is not particularly limited if the derivative containing a central metal atom M ₂ of the central metal atom M ₁ and the general formula (2) of the general formula (1). Specifically, in the case of the general formula (1), halides such as Si, Sn, Al, and Ti, carboxylic acid derivatives, alcohol derivatives, sulfates, nitrates, and the like can be given. In the case of general formula (2), halides such as Mg, Ca, Mn, Co, Fe, Ni, and Zn, carboxylic acid derivatives, alcohol derivatives, sulfates, nitrates, and the like can be given.

  The amount of the metal derivative and intermediate used in the synthesis is preferably in the range of 1: 2 to 1: 6 in terms of molar ratio.

  The synthesis reaction is preferably performed in the presence of a suitable solvent. As the solvent at this time, an organic solvent having a boiling point of 110 ° C. or higher is preferably used. For example, toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, quinoline, chloronaphthalene, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1- Examples include, but are not limited to, octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol, diethylaminoethanol, sulfolane and the like. The amount of the solvent used for the synthesis can be 1 to 100 times by mass, preferably 5 to 20 times by mass of the dicyano derivative as an intermediate.

  Further, in the synthesis reaction, 1,3-diazabicyclo [5.4.0] -7-undecene (DBU) or ammonium molybdate may be added. The addition amount can be 0.1 to 10 times mol, preferably 0.5 to 2 times mol for 1 mol of the phthalonitrile derivative which is an intermediate.

  The reaction temperature is 80 to 300 ° C, preferably 110 to 230 ° C. If it is less than 80 degreeC, reaction may become extremely slow, and when it exceeds 300 degreeC, the target object may decompose | disassemble. The reaction time can be 2 to 20 hours, preferably 5 to 15 hours. If it is less than 2 hours, there are many unreacted raw materials, and if it exceeds 20 hours, the target product may be decomposed.

  The colorant compound A represented by the general formula (1) of the present invention has strong absorption around 650 to 680 nm, while the colorant compound B represented by the general formula (2) of the present invention is: It has strong absorption around 620-650 nm.

  Although the ratio mA: mB of the content mass of the colorant compound A and the content mass of the colorant compound B is not particularly limited, it is preferably in the range of 90:10 to 50:50. This is because, in the above range, the balance of color developability in the low brightness and high brightness cyan regions is particularly excellent.

  The content of the cyan colorant is preferably 2 to 12% by mass, more preferably 4 to 8% by mass, based on the entire cyan toner particles.

<Toner production method>
Next, a toner manufacturing method according to the present invention will be described.

  The toner according to the present invention is composed of particles containing at least a resin and a colorant (hereinafter also referred to as colored particles). The colored particles constituting the toner according to the present invention are not particularly limited, and can be produced by a conventional toner production method. That is, a toner manufacturing method by a so-called pulverization method in which a toner is prepared through kneading, pulverization, and classification steps, or a so-called polymerized toner in which a polymerizable monomer is polymerized and at the same time particle formation is performed while controlling the shape and size. It can be produced by applying a production method (for example, an emulsion association method, suspension polymerization method, polyester elongation method, etc.). In the production method described above, an emulsion association method is preferred because it is easy to design a capsule structure that achieves both heat-resistant storage stability and low-temperature fixability of the toner.

  When the toner according to the present invention is produced by a pulverization method, it is preferable to produce the toner while maintaining the temperature of the kneaded material at 130 ° C. or lower. This is because when the temperature applied to the kneaded product exceeds 130 ° C., the colorant in the kneaded product may change in the agglomerated state due to the action of heat applied to the kneaded product, and the uniform aggregated state may not be maintained. Because. If variations occur in the aggregated state, the color tone of the produced toner varies, which may cause color turbidity.

  Next, the resin, wax and the like constituting the toner according to the present invention will be described with specific examples.

  First, the resin that can be used in the toner according to the present invention is not particularly limited, but a polymer formed by polymerizing a polymerizable monomer called a vinyl monomer described below is used. This is a typical example. The polymer constituting the resin that can be used in the present invention is a polymer obtained by polymerizing at least one polymerizable monomer, and these vinyl monomers are used alone. Or it is the polymer produced combining multiple types.

  Specific examples of vinyl polymerizable monomers are shown below.

Styrene or styrene derivatives Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, etc. Methacrylic acid ester derivatives Methyl methacrylate, ethyl methacrylate, n methacrylate -Butyl, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate , Dimethylaminoethyl methacrylate, etc. Acrylic acid ester derivatives Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate , Stearyl acrylate, lauryl acrylate, phenyl acrylate, etc.Olefins Ethylene, propylene, isobutylene, etc. Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. Vinyl ketones Vinyl methyl ketone , Vinyl ethyl ketone, vinyl hexyl ketone, etc. N-vinyl compounds N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, etc. Other vinyl naphtha Vinyl compounds such as vinyl and vinyl pyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc. In addition, vinyl-based polymerizable monomers constituting the resin that can be used in the toner according to the present invention Those having an ionic dissociation group shown below can also be used. Examples thereof include those having a functional group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the side chain of the monomer, and specific examples thereof include the following.

  First, those having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and the like. Examples of those having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, and 2-acrylamido-2-methylpropane sulfonic acid. Examples of those having a phosphoric acid group include acid phosphooxyethyl methacrylate. Is mentioned.

  Moreover, it is also possible to produce a resin having a crosslinked structure by using the following polyfunctional vinyls. Specific examples of polyfunctional vinyls are shown below.

Divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, etc. Next, the present invention Examples of the wax that can be used for the toner according to the present invention include the following known waxes.

Polyolefin wax Polyethylene wax, polypropylene wax, etc.Long-chain hydrocarbon wax, paraffin wax, sazol wax, etc.Dialkyl ketone wax, distearyl ketone, etc.Ester wax Carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol Tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid, distearyl maleate Amide waxes Ethylene bisstearylamide, stearic acid stearylamide, etc. The melting point of wax is usually 4 It is 0-125 degreeC, Preferably it is 50-120 degreeC, More preferably, it is 60-90 degreeC. By setting the melting point within the above range, the heat-resistant storage stability of the toner is ensured, and stable toner image formation can be performed without causing cold offset or the like even when fixing at a low temperature. Further, the wax content in the toner is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  Next, the toner according to the present invention is prepared by adding particles such as inorganic fine particles and organic fine particles having a number average primary particle size of 4 to 800 nm as external additives (= external additives) in the production process. Is possible.

<External additives and lubricants>
By adding the external additive, the fluidity and chargeability of the toner are improved, and the cleaning property is improved. The type of the external additive is not particularly limited, and examples thereof include the following inorganic fine particles, organic fine particles, and lubricants.

  As the inorganic fine particles, conventionally known fine particles can be used. For example, silica, titania, alumina, strontium titanate fine particles and the like are preferable. Moreover, what hydrophobized these inorganic fine particles as needed can also be used.

  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., HVK-2150 manufactured by Hoechst, H -200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by Cabot Corporation.

  As the titania fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercially available products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, JA- 1. Commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA, IT-OB, IT- manufactured by Idemitsu Kosan Co., Ltd. OC etc. are mentioned.

  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.

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Specifically, homopolymers such as styrene and methyl methacrylate and copolymers thereof can be used.

  Further, a lubricant can be used to further improve the cleaning property and transfer property, and examples thereof include the following higher fatty acid metal salts. That is, salts of zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, salts of manganese, iron, copper, magnesium, etc., zinc palmitate, salts of copper, magnesium, calcium, etc., linoleic acid And salts of zinc and calcium of ricinoleic acid.

  The addition amount of these external additives and lubricants is preferably 0.1 to 10.0% by mass with respect to the whole toner. Examples of methods for adding external additives and lubricants include methods using various known mixing devices such as a turbuler mixer, a Henschel mixer, a nauter mixer, and a V-type mixer.

<Developer>
The toner according to the present invention can be used as a two-component developer composed of a carrier and a toner, or as a non-magnetic one-component developer composed only of a toner.

  When the toner according to the present invention is used as a two-component developer, for example, a full-color print can be created at a high speed using a tandem image forming apparatus. In addition, by selecting a resin or a wax constituting the toner, it is possible to produce a full-color print compatible with so-called low-temperature fixing in which the paper temperature during fixing is about 100 ° C.

  In addition, carriers that are magnetic particles used when used as a two-component developer are conventionally known, for example, metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead. It is possible to use materials. Among these, ferrite particles are preferable. The carrier has a volume average particle size of preferably 15 to 100 μm, more preferably 25 to 80 μm.

  When the toner is used as a non-magnetic one-component developer that forms an image without using a carrier, the toner is slid and pressed against the charging member and the developing roller surface during image formation. Image formation by the non-magnetic one-component development method can simplify the structure of the developing device, and thus has an advantage that the entire image forming device can be made compact. Therefore, by using the toner according to the present invention as a non-magnetic one-component developer, printing can be stably performed even when a compact color printer is provided in a severe high-temperature and high-humidity environment or a low-temperature and low-humidity environment. it can. For example, good print production can be performed in a limited space in a printing factory where the image forming environment is severe in terms of temperature and humidity.

<Cyan toner particle size>
The toner according to the present invention preferably has a volume-based median diameter (D50v) of 3 μm or more and 8 μm or less. The volume-based median diameter (D50v diameter) of the 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, Inc.). As a measurement procedure, 0.02 g of toner is blended 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). Then, 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 size of the multisizer 3 is 50 μm.

  According to the cyan toner for developing an electrostatic charge image of the present invention, high color reproducibility can be obtained in both low brightness and high brightness cyan areas. The reason for this is not always clear. However, considering that the colorant compound A is excellent only in the color reproducibility of the high lightness cyan region, the colorant compound B acts complementarily, and the color reproducibility of the low lightness cyan region is also improved. This is probably because of this. In addition, it is surmised that the colorant compound A and the colorant compound B form mixed crystals and similar states at the time of toner preparation, and contribute to the formation of a pigment having a small particle size.

In the present invention, high brightness means a range of 55 ≦ L ^* ≦ 80 in the L ^* a ^* b ^* system color system, and low brightness means a range of 30 ≦ L ^* <55. The cyan region represents a range in which the hue angle is 180 to 240 degrees.

The L ^* a ^* b ^* system color system is a means that is useful for numerically expressing colors. L ^{* in the} z-axis direction represents lightness, and a ^* and b ^{* on the} x-axis and y-axis ^. Both represent hue and saturation.

  Note that lightness refers to the relative brightness of a color. Saturation refers to the degree of vividness of the color, and is represented by the following formula (1).

Formula (1)
Saturation C ^* = (a ^* × a ^* + b ^* × b ^* ) ^1/2
Hue refers to shades of red, yellow, green, blue, purple, etc., and is represented by a hue angle.

The hue angle is, for example, an x-axis-y-axis plane representing the relationship between hue and saturation when the brightness takes a certain value, and a half line between a coordinate point (a, b) and the origin O is the x-axis An angle formed with a straight line extending in the + direction of the x axis in the counterclockwise direction from the + direction (red direction). In the x-axis-y-axis plane, the -direction of the x-axis indicated by a ^* is the green direction, the + -direction of the y-axis indicated by b ^* is the yellow direction, and the -direction of the y-axis is blue. Direction.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto. In the text, “part” means “part by mass”.

[Preparation of Cyan Toner 1 (Toner by Crushing Method)]
The following toner components were put into a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.), and the peripheral speed of the stirring blade was set to 25 m / second and mixed for 5 minutes.

100 parts by mass of polyester resin (condensation product of bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic acid, weight average molecular weight 20,000)
2 parts by weight of phthalocyanine compound (1-1) as colorant compound A 2 parts by weight of azaphthalocyanine compound (2-1) as colorant compound B 6 parts by weight of release agent (pentaerythritol tetrastearate) Charge control 1 part by weight of agent (boron dibenzylate) The mixture is kneaded with a twin-screw extrusion kneader, then coarsely pulverized with a hammer mill, then pulverized with a turbo mill pulverizer (manufactured by Turbo Kogyo Co., Ltd.), and the Coanda effect is utilized. By performing fine powder classification with the airflow classifier, colored particles having a volume-based median diameter of 5.7 μm were obtained.

  Next, the following external additives were added to the colored particles, and external addition processing was performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to produce “Cyan Toner 1”.

Silica treated with hexamethylsilazane (average primary particle size 12 nm) 0.6 parts by mass Titanium dioxide treated with n-octylsilane (average primary particle size 24 nm) 0.8 parts by mass Was performed under conditions of a peripheral speed of 35 m / sec, a processing temperature of 35 ° C., and a processing time of 15 minutes.

[Preparation of Cyan Toner 2-13, Yellow Toner 1, Magenta Toner 1 (Toner by Polymerization Method)]
[Preparation Example 1 of Cyan Colorant Fine Particle Dispersion]
While stirring and dissolving 9.2 parts by mass of sodium n-dodecyl sulfate in 160 parts by mass of ion-exchanged water and continuing stirring, 5 parts by mass of the phthalocyanine compound (1-1) as coloring agent compound A and coloring 5 parts by weight of azaphthalocyanine compound (2-1) is gradually added as the agent compound B, and then dispersed by using a mechanical disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.) A cyan colorant fine particle dispersion [1] in which fine particles are dispersed was prepared. When the particle diameter of the colorant fine particles in the cyan colorant fine particle dispersion [1] was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the volume-based median diameter was 88 nm. Met.

[Preparation Example 2 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 1 of the cyan colorant fine particle dispersion, the addition amount of the phthalocyanine compound (1-1) as the colorant compound A is set to 7 parts by mass, and the azaphthalocyanine compound (2- A cyan colorant fine particle dispersion [2] in which colorant fine particles having a particle size of 86 nm in terms of volume-based median diameter was dispersed was prepared in the same manner except that the addition amount of 1) was 3 parts by mass. .

[Preparation Example 3 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 1 of the cyan colorant fine particle dispersion, the addition amount of the phthalocyanine compound [1-1] as the colorant compound A is set to 3 parts by mass, and the azaphthalocyanine compound [2- In the same manner except that the addition amount of 1] was 7 parts by mass, a cyan colorant fine particle dispersion [3] in which colorant fine particles having a particle diameter of 93 nm in terms of volume-based median diameter was dispersed was prepared. .

[Preparation Example 4 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 2 of the cyan colorant fine particle dispersion, the particle diameter was the same except that the phthalocyanine compound (1-4) was used instead of the phthalocyanine compound (1-1) as the colorant compound A. A cyan colorant fine particle dispersion [4] in which colorant fine particles having a volume-based median diameter of 87 nm are dispersed was prepared.

[Preparation Example 5 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 2 of the cyan colorant fine particle dispersion, the particle diameter was the same except that the phthalocyanine compound (1-8) was used instead of the phthalocyanine compound (1-1) as the colorant compound A. A cyan colorant fine particle dispersion [5] in which colorant fine particles having a volume-based median diameter of 85 nm are dispersed was prepared.

[Preparation Example 6 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 2 of the cyan colorant fine particle dispersion, the particle size was the same except that the phthalocyanine compound (1-13) was used instead of the phthalocyanine compound (1-1) as the colorant compound A. A cyan colorant fine particle dispersion [6] in which colorant fine particles having a volume-based median diameter of 91 nm is dispersed was prepared.

[Preparation Example 7 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 2 of the cyan colorant fine particle dispersion, the same procedure except that the azaphthalocyanine compound (2-4) was used instead of the azaphthalocyanine compound (2-1) as the colorant compound B. A cyan colorant fine particle dispersion [7] in which colorant fine particles having a particle size of 93 nm in terms of volume-based median diameter were dispersed was prepared.

[Preparation Example 8 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 2 of the cyan colorant fine particle dispersion, the same procedure except that the azaphthalocyanine compound (2-7) was used instead of the azaphthalocyanine compound (2-1) as the colorant compound B. A cyan colorant fine particle dispersion [8] in which colorant fine particles having a particle diameter of 91 nm in terms of volume-based median diameter were dispersed was prepared.

[Preparation Example 9 of Cyan Colorant Fine Particle Dispersion]
In Preparation Example 2 of the cyan colorant fine particle dispersion, the same procedure except that the azaphthalocyanine compound (2-12) was used instead of the azaphthalocyanine compound (2-1) as the colorant compound B. A cyan colorant fine particle dispersion [9] in which colorant fine particles having a particle diameter of 93 nm in terms of volume-based median diameter were dispersed was prepared.

[Preparation Example 10 of Cyan Colorant Fine Particle Dispersion (Comparative)]
In Preparation Example 1 of the cyan colorant fine particle dispersion, instead of the colorant compound A (phthalocyanine compound [1-1]) and the colorant compound B (azaphthalocyanine compound [2-1]) in total 10 parts by mass In the same manner, except that only 10 parts by mass of the phthalocyanine compound [1-1] was used, a cyan colorant fine particle dispersion in which colorant fine particles having a particle diameter of 102 nm in terms of volume-based median diameter were dispersed [ 10] was prepared.

[Preparation Example 11 of Cyan Colorant Fine Particle Dispersion (Comparative)]
In Preparation Example 2 of the cyan colorant fine particle dispersion, nickel phthalocyanine was used instead of phthalocyanine compound [1-1] as colorant compound A, and azaphthalocyanine compound [2-1] as colorant compound B. In the same manner as above, except that copper phthalocyanine was used, a cyan colorant fine particle dispersion [11] in which colorant fine particles having a particle diameter of 105 nm in terms of volume-based median diameter was dispersed was prepared.

[Preparation Example 12 for Cyan Colorant Fine Particle Dispersion (Comparative)]
In the same manner as in Preparation Example 2 of the cyan colorant fine particle dispersion, except that copper phthalocyanine was used as the colorant compound B instead of the azaphthalocyanine compound [2-1], the volume-based median particle size was the same. A cyan colorant fine particle dispersion [12] in which colorant fine particles having a diameter of 106 nm were dispersed was prepared.

[Preparation Example 1 of Yellow Colorant Fine Particle Dispersion (for Yellow Toner)]
In Preparation Example 1 of the cyan colorant fine particle dispersion, the colorant compound A (phthalocyanine compound (1-1)) and the colorant compound B (azaphthalocyanine compound (2-1)), instead of a total of 10 parts by mass , C.I. I. Similarly, except that 10 parts by weight of Pigment Yellow 74 was used, a yellow colorant fine particle dispersion [1] in which colorant fine particles having a particle diameter of 102 nm in terms of volume-based median diameter was dispersed was prepared.

[Preparation Example 1 of Magenta Colorant Fine Particle Dispersion (for Magenta Toner)]
In Preparation Example 1 of magenta colorant fine particle dispersion, colorant compound A (phthalocyanine compound (1-1)) and colorant compound B (azaphthalocyanine compound (2-1)), instead of a total of 10 parts by mass , C.I. I. Similarly, except that 10 parts by mass of Pigment Red 122 was used, a magenta colorant fine particle dispersion [1] in which colorant fine particles having a particle diameter of 106 nm in terms of volume-based median diameter were dispersed was prepared.

[Production Example 1 of resin fine particle dispersion]
An interface in which 7.08 g of an anionic surfactant (sodium dodecylbenzenesulfonate: SDS) was previously dissolved in 2760 g of ion-exchanged water in a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen introducing device. The activator solution (aqueous medium) was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. On the other hand, a monomer mixed solution composed of 72.0 g of a compound represented by the following formula (W), 115.1 g of styrene, 42.0 g of n-butyl acrylate, and 10.9 g of methacrylic acid was added to 80 ° C. as a release agent. A first monomer solution was prepared by warming and dissolving. The first monomer solution (80 ° C.) is mixed and dispersed in the surfactant solution (80 ° C.) by a mechanical disperser having a circulation path, and emulsified particles (oil Drop) dispersion was prepared. Next, an initiator solution prepared by dissolving 0.84 g of a polymerization initiator (potassium persulfate: KPS) in 200 g of ion-exchanged water is added to the dispersion, and the system is heated and stirred at 80 ° C. for 3 hours. Polymerization (first stage polymerization) was performed to prepare a latex.

  Next, a solution prepared by dissolving 8.00 g of a polymerization initiator (KPS) and 10.0 g of 2-chloroethanol as a water-soluble chain transfer agent in 240 g of ion-exchanged water was added to this latex. Then, a second monomer solution consisting of 383.6 g of styrene, 140.0 g of n-butyl acrylate, and 36.4 g of methacrylic acid was added dropwise over 126 minutes. After completion of the dropwise addition, polymerization (second stage polymerization) was carried out by heating and stirring for 60 minutes, followed by cooling to 40 ° C. to prepare a resin fine particle dispersion [LX-1] containing resin fine particles [1].

Formula (W): C {CH ₂ OCO (CH ₂ ) ₂₀ CH ₃ } ₄
[Production of cyan toner base particles 1]
1250 g of resin fine particle dispersion [LX-1], 2000 g of ion-exchanged water, and 165 g of cyan colorant fine particle dispersion [1] were added to 5 liters of four liters equipped with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring device. The solution for association was prepared by stirring in a necked flask. After adjusting the internal temperature of this associating solution to 30 ° C., a 5 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 10.0. Next, an aqueous solution in which 52.6 g of magnesium chloride hexahydrate was dissolved in 72 g of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, temperature increase was started, and the system was heated to 90 ° C. over 6 minutes (temperature increase rate = 10 ° C./min). In this state, the average particle diameter of the associated particles was measured with “Coulter Multisizer TA-III” (manufactured by Beckman Coulter). When the volume-based median diameter reached 6.5 μm, 115 g of sodium chloride was added. An aqueous solution dissolved in 700 g of ion-exchanged water was added to stop particle growth, and further, fusion was continued by heating and stirring at a liquid temperature of 90 ° C. ± 2 ° C. for 6 hours. Then, it cooled to 30 degreeC on the conditions of 6 degreeC / min, hydrochloric acid was added, pH was adjusted to 2.0, and stirring was stopped. The produced association particles were separated into solid and liquid, and washing with 15 liters of ion-exchanged water was repeated 4 times, followed by drying with hot air at 40 ° C. to obtain cyan toner base particles [1].

[Production of Cyan Toner 2]
To the cyan toner base particles [1], 1% by mass of hydrophobic silica (number average primary particle size = 12 nm, hydrophobicity = 68) and hydrophobic titanium oxide (number average primary particle size = 20 nm, hydrophobicity = 63) was added and mixed with a “Henschel mixer” (manufactured by Mitsui Miike Chemical Co., Ltd.). Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to produce cyan toner [2] composed of cyan toner base particles [1].

  Note that the particle size of cyan toner base particles does not change depending on the addition of hydrophobic silica.

[Production of cyan toners 3 to 13]
In the production of the cyan toner base particles 1, the cyan toner base particles are similarly used except that the cyan colorant fine particle dispersions [2] to [12] are used instead of the cyan colorant fine particle dispersion [1]. Cyan toners [3] to [13] composed of cyan toner base particles [2] to [12] are obtained by obtaining external additives [2] to [12] and carrying out external additive treatment in the same manner as in the production of cyan toner 2. Manufactured. Cyan toners [11] to [13] are for comparison.

[Production Example 1 of Yellow Toner]
In the production of cyan toner 2, yellow toner base particles [1] were obtained in the same manner except that yellow colorant fine particle dispersion [1] was used instead of cyan colorant fine particle dispersion [1]. A yellow toner [1] composed of yellow toner particles [1] was produced by performing an external additive treatment in the same manner as in the production of toner 1.

[Magenta Toner Production Example 1]
Magenta toner base particles [1] were obtained in the same manner as in the production of cyan toner 2, except that magenta colorant fine particle dispersion [1] was used instead of cyan colorant fine particle dispersion [1]. A magenta toner [1] composed of magenta toner base particles [1] was produced by performing an external additive treatment in the same manner as in the production of toner 2.

(Preparation of developer)
Each of the cyan toners [1] to [13], the yellow toner [1], and the magenta toner [1] is coated with a silicone resin-coated volume-based median diameter 60 μm ferrite carrier, and the cyan toner has a density of 6 Cyan developers [1] to [13], a yellow developer [1], and a magenta developer [1], which are two-component developers, were prepared by mixing so as to be in mass%. The cyan developers [1] to [10] are according to the present invention, and the cyan developers [11] to [13] are for comparison.

<Examples 1-10, Comparative Examples 1-3>
Particle size of the dispersion The particle size of the colorant fine particles in the cyan colorant fine particle dispersions [1] to [12] was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.) Evaluation was made according to the following criteria. The results are shown in Table 1.

A: Less than 100 nm B: 100 nm or more Colorability in low lightness cyan region Using a cyan developer [1] to [13], a yellow developer [1], and a magenta developer [1], a full-color high-speed multifunction device “bizhub C 6500 "(manufactured by Konica Minolta Business Technologies Co., Ltd.), a print image forming operation is performed under the condition that the fixing linear velocity is set to 310 mm / min (about 65 sheets / min), and a patch image (L ^* = 40, hue angle h = 210 °) was printed on “POD gloss-coated paper 128 g / m ² ” (manufactured by Oji Paper Co., Ltd.), and color development was evaluated according to the following criteria. The results are shown in Table 1.

Color developability A: Saturation C ^* is 28 or more B: Saturation C ^* is 26 or more and less than 28 C: Saturation C ^* is less than 26 If the above criteria are A or B, it indicates a practically satisfactory color development .

Color development of high brightness cyan area A patch image (L ^* = 70, hue angle = 210 °) corresponding to the high brightness cyan area is printed on “POD gloss coated paper 128 g / m ² ” (manufactured by Oji Paper Co., Ltd.), and color development Was evaluated according to the following criteria.

Color developability A: Saturation C ^* is 45 or more B: Saturation C ^* is 40 or more and less than 45 C: Saturation C ^* is less than 40 If the above criterion is A or B, the color development is practically acceptable. .

  As described above, according to the cyan developer [1] to [10] containing the colorant compound A and the colorant compound B of the present invention, good color development can be obtained in both the low lightness and high lightness cyan regions. Was confirmed.

Claims (4)

A cyan toner for electrostatic image development comprising cyan toner particles containing at least a resin and a cyan colorant, wherein the cyan colorant constituting the cyan toner particles is a colorant compound represented by the following general formula (1) A cyan toner for developing an electrostatic image, comprising A and a colorant compound B represented by the following general formula (2).

[Wherein M ₁ represents a central metal atom. Z ₁ represents a substituent. m1 and m2 represent 0 or 1, and m1 and m2 are not 0 at the same time. Further, when the 1 m1 and m2 are simultaneously, Z ₁ may be different, identical to one another. A _{1 to} A ₄ each independently represent an aromatic ring that may have a substituent. _However, A 1 to A ₄ is an aromatic ring comprising only carbon atoms. ]

[Wherein M ₂ represents a central metal atom. B _{1 to} B ₄ each independently represent an aromatic ring that may have a substituent. However, at least one of B _{1 to} B ₄ is a nitrogen-containing aromatic ring. ] The cyan toner for developing electrostatic images according to claim ₁ , wherein M ₁ in the general formula (1) is Si. In the general formula (1), Z ₁ is an alkyl group, an aryl group, an aryloxy group, an alkoxy group, an acyloxy group, or —OSiR ₁ R ₂ R ₃ (where R ₁ , R _2, and R ₃ are each independently The cyan toner for developing electrostatic images according to claim 1, wherein the cyan toner is an alkyl group, an aryl group, an alkoxy group, or an aryloxy group.   The ratio (mA: mB) of the content mass mA of the colorant compound A and the content mass mB of the colorant compound B is a ratio of 90:10 to 50:50. The cyan toner for developing electrostatic images according to any one of the above.