JP2011107301A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner with which a spectrum is sharpened and the chorma of a toner image can be heightened. <P>SOLUTION: In the toner containing at least a resin and a colorant, the colorant is a phthalocyanine derivative having central metals M1, M2 and substituents R, Z. M1 is Cu, Co, Ni, or Ti=O. M2 is Si. R is a 3-10C secondary alkyl group, a tertiary alkyl group or a cyclic alkyl group and may be substituted plurally. Z is a hydroxyl group, a halogen group, a 3-10C hydrocarbon group or an alkoxy group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a toner.

One of the colorants used in electrophotographic color toners is an organic pigment. In general, organic pigments are superior to dyes in heat resistance and light resistance, and are advantageous in storing characters and photographic images. On the other hand, the organic pigment has a problem that the spectral spectrum becomes broad and the color development is lacking.
In order to solve this problem, a technique is disclosed in which the dispersion process is strengthened to finely pulverize the copper phthalocyanine derivative, and the primary aggregates are maintained to improve the clarity and transparency (for example, see Patent Document 1). ).

JP 2008-239870 A

However, even the technique described in the above-mentioned Patent Document 1 still lacks the fineness of color development and is insufficient.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a toner capable of sharpening a spectral spectrum and increasing the saturation of a toner image.

According to the first aspect of the present invention,
In a toner containing at least a resin and a colorant,
A toner is provided in which the colorant is represented by the following general formula (I) or general formula (II).

（一般式（I）において、ＭはＣｕ、Ｃｏ、Ｎｉ、Ｔｉ＝Ｏのいずれかであり、Ｒは炭素数３〜１０の第２級アルキル基、第３級アルキル基、環状アルキル基のいずれかであり、また複数置換されていてもよい。また、一般式（II）において、ＭはＳｉであり、Ｒは炭素数３〜１０の第２級アルキル基、第３級アルキル基、環状アルキル基のいずれかであり、また、複数置換されていてもよい。Ｚはヒドロキシル基、ハロゲン基、炭素数３〜１０の炭化水素基、アルコキシ基のいずれかである。）

(In general formula (I), M is any one of Cu, Co, Ni, and Ti = O, and R is any of a secondary alkyl group, tertiary alkyl group, and cyclic alkyl group having 3 to 10 carbon atoms. In general formula (II), M is Si, and R is a secondary alkyl group having 3 to 10 carbon atoms, a tertiary alkyl group, or a cyclic alkyl. Z is any of a hydroxyl group, a halogen group, a hydrocarbon group having 3 to 10 carbon atoms, and an alkoxy group.

According to the present invention, it is possible to sharpen the spectral spectrum and increase the saturation of the toner image.
The mechanism is inferred as follows.
Many conventional colorants have a long conjugated system. Therefore, in a solid or crystalline state, due to the overlapping of molecules, in addition to the spectral characteristics inherent to the colorant molecules, the spectral characteristics acting between the molecules are mixed. For this reason, in addition to the single molecule and the spectroscopic properties of macromolecules, the width of the light absorption band is widened, and the saturation is lowered in terms of color (the purity of the color is dull). In particular, since the colorant for cyan toner has an absorption band in a long wavelength region from the viewpoint of color, many conjugated systems are longer than yellow and magenta. For this reason, it is presumed that the spectral characteristics acting between the molecules tend to be mixed, and the absorption band of the spectral absorption spectrum is broadened and the saturation is lowered.

  FIG. 1 shows a molecular structure and a simplified diagram of a conventionally used copper phthalocyanine pigment, and FIG. 2 shows a state of multi-molecularization due to overlapping of copper phthalocyanine in the z-axis direction. As shown in FIGS. 1 and 2, copper phthalocyanine has a long conjugated system, takes a planar structure (xy plane), and forms a π bond on the z-axis. For this reason, in the crystalline state, π bonds extending in the z-axis direction overlap each other vertically, so that the conjugated system is widened and electrons move easily between molecules. Therefore, unlike the color development with a single molecule, multi-molecular spectral characteristics exist. When the colorant is taken into the toner in the state shown in FIG. 2, the color developed by the toner has a broad reflection spectrum and low saturation.

  Therefore, the inventors of the present invention have come to the idea of introducing a bulky substituent (sterically large substituent) into the phthalocyanine skeleton and increasing the intermolecular distance by utilizing repulsion between molecules. That is, by increasing the intermolecular distance with a pigment-based colorant that is incompatible with the binder resin and utilizing the single-molecule spectroscopic characteristics, it becomes possible to sharpen the spectroscopic spectrum as compared with the prior art. As a result, high saturation can be achieved. Since this is a control in molecular units, it is considered that a greater effect than that obtained by finely dispersing particles that are aggregates of colorant molecules by dispersion is obtained.

  FIG. 3 shows a schematic diagram of the colorant of the present invention. As shown in FIG. 3, the colorant of the present invention is a sterically large substituent to prevent overlap in the z-axis direction, and By introducing a substituent that does not cause electron transfer, it is possible to utilize the spectral characteristics of a single molecule by utilizing repulsion between molecules. Therefore, when a toner produced using the colorant of the present invention is used, the reflection spectrum is sharp and the saturation is improved.

It is the molecular structure of copper phthalocyanine which is a conventional coloring agent, and a simplified diagram. It is the figure which showed the state of polymolecularization by the overlap of the z-axis direction of the copper phthalocyanine which is a conventional coloring agent, and the arrow represents that the electron can move by the overlap of the Z-axis direction in the figure. ing. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the coloring agent of this invention, and in the figure, A shows the atomic group derived from an azaporphyrin ring, D shows the bulky substituent of this invention, and introduce | transduces the bulky substituent of D, and is between molecules. It shows that we use repulsion.

Hereinafter, the toner of the present invention will be described.
[toner]
The toner of the present invention contains at least a resin and a colorant, and the colorant is represented by the following general formula (I) or general formula (II).

（一般式（I）において、ＭはＣｕ、Ｃｏ、Ｎｉ、Ｔｉ＝Ｏのいずれかであり、Ｒは炭素数３〜１０の第２級アルキル基、第３級アルキル基、環状アルキル基のいずれかであり、また複数置換されていてもよい。また、一般式（II）において、ＭはＳｉであり、Ｒは炭素数３〜１０の第２級アルキル基、第３級アルキル基、環状アルキル基のいずれかであり、また、複数置換されていてもよい。Ｚはヒドロキシル基、ハロゲン基、炭素数３〜１０の炭化水素基、アルコキシ基のいずれかである。）

(In general formula (I), M is any one of Cu, Co, Ni, and Ti = O, and R is any of a secondary alkyl group, tertiary alkyl group, and cyclic alkyl group having 3 to 10 carbon atoms. In general formula (II), M is Si, and R is a secondary alkyl group having 3 to 10 carbon atoms, a tertiary alkyl group, or a cyclic alkyl. Z is any of a hydroxyl group, a halogen group, a hydrocarbon group having 3 to 10 carbon atoms, and an alkoxy group.

<resin>
The resin used for the toner according to the present invention is not particularly limited. A typical example is a polymer formed by polymerizing a polymerizable monomer called a vinyl monomer described below. Furthermore, a polyester resin can also be used. The polymer constituting the resin that can be used in the present invention comprises a polymer obtained by polymerizing at least one polymerizable monomer, and these polymerizable monomers are used alone. Or it is the polymer produced combining several types.

Specific examples of vinyl polymerizable monomers are shown below.
(1) Styrene or styrene derivatives For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, Examples thereof include pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, and pn-dodecyl styrene.
(2) Methacrylic acid ester derivatives For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Examples thereof include phenyl acid, diethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate.
(3) Acrylic acid ester derivatives For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, acrylic Acid phenyl is mentioned.

(4) Vinyl esters For example, vinyl propionate, vinyl acetate, vinyl benzoate and the like.
(5) Vinyl ethers For example, vinyl methyl ether and vinyl ethyl ether.
(6) Vinyl ketones Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl hexyl ketone.

(7) Others Examples include acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.
Further, as the vinyl polymerizable monomer constituting the resin that can be used in the toner according to the present invention, those having an ionic dissociation group shown below can be used. In particular, when a colorant having weak alkalinity is used, if a monomer having an ionic dissociation group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group is used in the side chain, the dispersibility in the resin can be further improved. It can be improved and is preferable.

  Specifically, examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, and fumaric acid. Examples of the monomer having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, and 2-acrylamido-2-methylpropane sulfonic acid. Examples of the monomer having a phosphoric acid group include acid phosphooxyethyl methacrylate.

  Moreover, it is also possible to produce a resin having a crosslinked structure by using the following polyfunctional vinyls. Specific examples of the polyfunctional vinyls include divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and the like.

Furthermore, the amorphous polyester resin shown below can also be used.
A known polyester resin can be used as the non-crystalline polyester resin used in the present invention. The amorphous polyester resin is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In addition, as said amorphous polyester resin, a commercial item may be used and what was synthesize | combined may be used. The non-crystalline polyester resin may be one type of non-crystalline polyester resin, or may be a mixture of two or more types of non-crystalline polyester resin.

  Examples of the polyhydric alcohol component in the non-crystalline polyester resin include divalent alcohol components such as ethylene glycol, propylene glycol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5- Pentanediol, 1,6-hexanediol, neopentylene glycol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, bisphenol A, hydrogenated bisphenol A, and the like can be used. As the trivalent or higher alcohol component, glycerin, sorbitol, 1,4-sorbitan, trimethylolpropane, or the like can be used.

  Examples of the divalent carboxylic acid component condensed with the polyhydric alcohol component include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, and naphthalenedicarboxylic acid; Maleic acid, fumaric acid, succinic acid, alkenyl succinic acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1 , 14-tetradecanedicarboxylic acid, aliphatic carboxylic acids such as 1,18-octadecanedicarboxylic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid; and lower alkyl esters and acid anhydrides of these acids. These can be used alone or in combination of two or more.

  Among these polyvalent carboxylic acids, especially when alkenyl succinic acid or its anhydride is used, it is more easily compatible with crystalline polyester resin due to the presence of alkenyl groups having higher hydrophobicity than other functional groups. Can do. Examples of the alkenyl succinic acid component include n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid or acid anhydrides thereof, acid Mention may be made of chlorides and lower alkyl esters having 1 to 3 carbon atoms.

Further, by containing a trivalent or higher carboxylic acid, the polymer chain can take a crosslinked structure, and by taking the crosslinked structure, it is possible to suppress a decrease in elastic modulus in a high temperature range, The offset property can be improved.
Examples of the trivalent or higher carboxylic acid include trimellitic acid such as 1,2,4-benzenetricarboxylic acid and 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, hemimellitic acid, Trimesic acid, melophanoic acid, planitic acid, pyromellitic acid, meritic acid, 1,2,3,4-butanetetracarboxylic acid or their acid anhydrides, acid chlorides, lower alkyl esters having 1 to 3 carbon atoms, etc. Of these, trimellitic acid is particularly preferred. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, as an acid component, it is preferable that the dicarboxylic acid component which has a sulfonic acid group other than the above-mentioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid is contained. The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, when the resin is dispersed or emulsified in water to prepare a dispersion of resin particles, if the dicarboxylic acid component has a sulfonic acid group, it is emulsified or suspended without using a surfactant. It is also possible.

  For the above reasons, the amorphous polyester resin has a component reacted with at least one of alkenyl succinic acid and its anhydride and at least one of trimellitic acid and its anhydride. Although it is desirable to contain it, it is desirable that the component is contained in the high molecular weight component of the amorphous polyester resin, which plays a major role in compatibilization with the crystalline polyester resin and fixation of the crystalline polyester resin.

<Colorant>
The colorant used in the toner according to the present invention is represented by the general formula (I) or the general formula (II).
In the general formula (I) or the general formula (II), M is particularly preferably Cu or Si, and the substituent R to be introduced is as large as possible, and preferably does not significantly affect the color. For example, it is a tertiary alkyl group such as a t-butyl group, or an alicyclic group such as a cyclohexyl group or an adamantyl group.
The colorant used in the present invention can be produced by introducing a substituent R or a substituent Z after synthesizing phthalocyanine.
Specifically, the substituent R generally needs to be introduced at the raw material stage from the viewpoint of solubility of phthalocyanine. For example, when R is i-propyl group, 4-i-propylphthalic anhydride is used as a raw material, and when R is t-butyl group, 4-t-butylphthalic anhydride is used as a raw material, It can be synthesized by heating in urea in the presence of a catalyst such as ammonium molybdate.
Substituent Z is synthesized by reacting silyl chloride having the desired substituent in the presence of a base using dihydroxysilicon phthalocyanine obtained by heating dichlorosilicon phthalocyanine in the presence of sodium hydroxide and pyridine. can do.

<Release agent>
Examples of the release agent include polyolefin waxes such as polyethylene wax and polypropylene wax, branched chain hydrocarbon waxes such as microcrystalline wax, long chain hydrocarbon waxes such as paraffin wax and sazol wax, and distearyl ketone. Dialkyl ketone wax, carnauba wax, montan wax, behenate behenate, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-octadecane Ester wax such as diol distearate, tristearyl trimellitic acid, distearyl maleate, ethylenediamine behenylamide, tristearyl trimellitic acid Such as amide-based waxes such as de the like.
The addition amount of the release agent to the toner is preferably 1 to 30% by mass.

  As an external additive, in addition to known hydrophobic silica and hydrophobic metal oxide, cerium oxide particles, titanate particles, fatty acids having 20 to 50 carbon atoms, or higher alcohol particles may be used in combination. It is preferable from the viewpoint of filming resistance. When adding cerium oxide particles or titanate particles, it is preferable to use particles having a number average particle size of 150 to 800 nm from the viewpoint of enhancing filming resistance.

[Toner production method]
Hereinafter, a specific example is given about the manufacturing method for manufacturing the toner of this invention.
The toner according to the present invention can be produced by a known production method such as a pulverization method, a suspension polymerization method, or an emulsion association method.

Hereinafter, as an example of a method for producing a toner according to the present invention, a method for producing a toner having a core-shell structure by an emulsion association method will be described.
(1) Core resin particle emulsification step In this step, particles that form the core of the toner are produced. First, resin particles to be a binder resin for the core are emulsified. The emulsified resin particles are preferably 30 to 300 nm. For example, a dispersion of core resin particles is prepared by emulsifying and dispersing a polymerizable monomer and adding a polymerization initiator to advance the polymerization reaction. Without using the polymerization reaction, the resin particles can be prepared by dissolving or dispersing the resin and, if necessary, the release agent or colorant in the solvent and then dispersing and removing the solvent in the aqueous medium. At this time, if the release agent is dissolved in the polymerizable monomer or resin solution to prepare an emulsified (dispersed) liquid, the release agent particles are detached after the toner particles are completed, thereby contaminating the members of the image forming apparatus. It is preferable because it can be suppressed.

(2) Aggregation / fusion process The dispersion of the colorant particles represented by the general formula (I) or (II) is added to the dispersion of the resin particles for the core, and the release agent particles are added as necessary. Add the dispersion. Next, a flocculant is added, and when the resin particles for core, the colorant particles, and the release agent are added in the aqueous medium, the added release agent particles are further aggregated and fused to form the core particles. Form. A series of processes of aggregation and fusion may be referred to as an association process.
As the aggregation / fusion method, a salting-out fusion method is preferable. The salting-out fusion method is a method in which aggregation and fusion are advanced in parallel, and when the core particles have grown to a desired particle diameter, an aggregation stop agent is added to stop the particle growth. In this method, heating for controlling the particle shape is continued as necessary.

The size of the core particle is preferably 3 to 10 μm in volume-based median diameter, and particularly preferably 3 to 7 nm. The volume-based median diameter of the core particles is the data processing software “Software V3.51” for Coulter Multisizer 3 (Beckman Coulter).
Is measured and calculated using a device connected to a computer system (manufactured by Beckman Coulter, Inc.).
As a measurement procedure, 0.02 g of a sample is conditioned with 20 ml of a surfactant solution (for example, a surfactant solution in which a neutral detergent containing a surfactant component is diluted 10-fold with pure water for the purpose of dispersing the sample). Then, ultrasonic dispersion is performed for 1 minute to prepare a sample dispersion. The prepared dispersion is pipetted into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand until the display concentration of the measuring instrument becomes 5 to 10%. By setting this concentration range, a reproducible measurement value can be obtained. In the measuring device, the measurement particle count number is 25000, the aperture diameter is 50 μm, and the frequency value is calculated by dividing the measurement range of 1 to 30 μm into 256 parts. The particle diameter of 50% from the larger volume integrated fraction is defined as the volume-based median diameter.

  An aqueous medium means that the main component (50% by mass or more) is made of water. Examples of components other than water include organic solvents that dissolve in water. For example, methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like can be mentioned.

In addition, it is good also as passing through a maturing process after an aggregation / fusion process.
Specifically, the heating temperature is lowered in the agglomeration / fusion process to suppress the progress of fusion between the particles, and the core particles are made uniform. Thereafter, in the aging step, the surface of the core particles is controlled to have a uniform shape by lowering the heating temperature and increasing the time.

(3) Shelling step In the shelling step, a dispersion of resin particles for shell is added to the dispersion of core particles. The dispersion may be a dispersion of resin particles having the same composition as the known binder resin particles for toner, or may be a dispersion of the same resin particles as the core resin particles. However, in order to achieve both heat-resistant storage stability and low-temperature fixability, it is preferable to set the copolymerization ratio so that the glass transition point is higher by 5 to 25 ° C. than the core resin particles.
In the shelling process, the shell resin particles are fused on the surface of the core particles, and it is possible to form a thin shell layer covering the entire surface of the core particles.

(4) Cooling / Washing Step In the cooling / washing step, the dispersion of toner particles obtained by shelling is cooled at a cooling rate of 1 to 20 ° C./min, for example. When cooled to a predetermined temperature, the toner particles are solid-liquid separated from the cooled dispersion of toner particles. Solid-liquid separation may be any method other than centrifugation, such as vacuum filtration using a Nutsche or the like, filtration using a filter press or the like. Next, the toner cake obtained by solid-liquid separation (wet toner particles prepared in a cylindrical shape such as a cake) is washed to remove deposits such as surfactants and salting-out agents.

(5) Drying step In the drying step, the washed toner cake is dried. For the drying treatment, a spray dryer, a vacuum freeze dryer, a vacuum dryer or the like can be used. The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

(6) External Addition Processing Step In the external addition processing step, an external additive is mixed with toner particles obtained by drying to obtain an electrostatic charge developing toner.

[Production of developer]
The toner of the present invention may be used, for example, as a one-component magnetic toner containing a magnetic material, used as a two-component developer mixed with a so-called carrier, or a non-magnetic toner alone. Any of these can be suitably used.
In the toner of the present invention, when used as a two-component developer mixed with a carrier, it is possible to suppress the occurrence of toner filming (carrier contamination) on the carrier, and when used as a one-component developer, The occurrence of toner filming on the frictional charging member of the apparatus can be suppressed.

As the carrier constituting the two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, ferrite and magnetite, alloys of those metals with metals such as aluminum and lead can be used, It is particularly preferable to use ferrite particles.
The carrier preferably has a volume average particle diameter of 15 to 100 μm, more preferably 25 to 60 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.

  As the carrier, it is preferable to use a carrier 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 known resins can be used. For example, styrene-acrylic resin, polyester resin, fluorine resin, phenol resin, etc. are used. can do.

[Image forming method]
The above toner can be suitably used in an image forming method including a fixing step by a contact heating method. Specifically, as an image forming method, an electrostatic latent image formed electrostatically on, for example, an image carrier using the toner as described above, and a developer in a developing device by a friction charging member. The toner image is obtained by making it manifest by charging. Then, this toner image is transferred onto a sheet, and then the toner image transferred onto the sheet is fixed on the sheet by a contact heating type fixing process, thereby obtaining a visible image.

[Fixing method]
As a suitable fixing method using the toner of the present invention, a so-called contact heating method can be mentioned. Examples of the contact heating method include a heat pressure fixing method, a heat roll fixing method, and a pressure contact heat fixing method in which fixing is performed by a rotating pressure member including a fixedly arranged heating body.
In the fixing method of the hot roll fixing method, usually, an upper roller provided with a heat source inside a metal cylinder made of iron or aluminum whose surface is coated with a fluororesin, etc., and a lower roller formed of silicone rubber or the like Is used.

  As the heat source, a linear heater is used, and the surface temperature of the upper roller is heated to about 120 to 200 ° C. by the heater. A pressure is applied between the upper roller and the lower roller, and the lower roller is deformed by this pressure, so that a so-called nip is formed in the deformed portion. The width of the nip is 1 to 10 mm, preferably 1.5 to 7 mm. The fixing linear velocity is preferably 40 mm / sec to 600 mm / sec. If the width of the nip is too small, heat cannot be uniformly applied to the toner, and fixing unevenness may occur. On the other hand, when the nip width is excessive, melting of the polyester resin contained in the toner particles is promoted, and fixing offset may occur.

Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.
1. Synthesis of Colorant (1) Synthesis of Colorants I-1 to I-12 As raw materials for phthalocyanine (tetraazaporphine ring), 4-i-propylphthalic anhydride (15.0 g, 0.1 mol), urea ( 30 g), ammonium nitrate (16 g, 0.2 mol), and ammonium molybdate (0.1 g) were added, and the mixture was stirred at 165 ° C. for 6 hours.
After cooling, 2-ethylhexanol (70 ml), DBU (30.4 g, 0.2 mol) cuprous chloride (2.5 g, 0.025 mol) was added as a raw material for M of the general formula (I), Stir at 180 ° C. for 5 hours.
After cooling, the precipitate was filtered, and washed with 30 ml each of 5% aqueous sodium hydroxide solution, 5% aqueous hydrochloric acid solution and water three times in order to obtain 9.8 g of blue powder (I-1).
Hereinafter, as shown in Table 1, coloring agents I-2 to I-12 were synthesized by selecting phthalocyanine (tetraazaporphine ring) raw materials and M raw materials, respectively.

(2) Synthesis of Colorant Compound II-1 As raw materials for phthalocyanine (tetraazaporphine ring), 4-t-butylphthalic anhydride (15.1 g, 0.1 mol), urea (30 g), ammonium nitrate (16 g, 0 0.2 mol) and ammonium molybdate (0.1 g) were added, and the mixture was stirred at 165 ° C. for 6 hours. After cooling, 2-ethylhexanol (70 ml), DBU (30.4 g, 0.2 mol), silicon tetrachloride (3.5 g, 0.025 mol) was added as a raw material for M of the general formula (II), Stir at 180 ° C. for 5 hours. After cooling, the precipitate was filtered and washed three times with 30 ml each of 5% aqueous sodium hydroxide solution, 5% aqueous hydrochloric acid solution and water to obtain 9.4 g of dichlorosilicon phthalocyanine.
Dichlorosilicon phthalocyanine (9.4 g), NaOH (2.5 g), water (200 ml) was added to a mixed solution of pyridine (60 ml), and the mixture was reacted for 1 hour under reflux heating. The product was filtered hot and washed with pyridine, acetone and water in this order. Subsequently, after stirring at room temperature several times in water (100 ml), neutrality was confirmed, and the crystals were filtered and dried to obtain 5.8 g of dihydroxysilicon phthalocyanine.
Dihydroxysilicon phthalocyanine (5.8 g), tri-n-butylamine (10 ml), and quinoline (180 ml) were added in nitrogen atmosphere, and trimethylsilyl chloride (5.2 g) was added as a raw material for substituent Z at 140 to 150 ° C. The reaction was performed for 6 hours. The product was cooled to room temperature and then added to a mixture of methanol and water. The precipitated crystals were separated by filtration, the crystals were heated and suspended in toluene, cooled, filtered and dried to obtain a colorant compound (II-1).

(3) Synthesis of Colorant II-2 to II-4 In the synthesis of Colorant Compound II-1, the same procedure was applied except that trimethylsilyl chloride was added as a raw material for substituent Z to the raw material shown in Table 1. Thus, colorant compounds II-2 to II-4 were obtained.

2. Preparation of Colorant Fine Particle Dispersion (1) Preparation of Colorant Fine Particle Dispersion 1 A solution prepared by stirring and dissolving 11.5 parts by mass of sodium n-dodecyl sulfate in 160 parts by mass of ion-exchanged water was stirred, and the solution Colorant I-1: 24.5 parts by mass was gradually added.
Next, by performing a dispersion treatment using a stirring device “Clearmix W Motion CLM-0.8” (M Technique Co., Ltd.), a “colorant fine particle dispersion 1” having a volume-based median diameter of 126 nm is obtained. Prepared.

(2) Preparation of Colorant Fine Particle Dispersions 2 to 16 In the preparation of “Colorant Fine Particle Dispersion 1”, Colorant I-1 was changed to Colorant I-2 to I-12 and Colorant Compound II-1 to II, respectively. Colorant fine particle dispersions 2 to 16 were prepared in the same procedure except for changing to -4.

3. Preparation of toner (1) Preparation of toner 1 (1-1) Preparation of resin particles for core formation (i) First stage polymerization In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, a structural formula A surfactant solution prepared by dissolving 4 parts by mass of the anionic surfactant shown in 3040 parts by mass of ion-exchanged water was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. .
To this surfactant solution, an initiator solution in which 10 parts by mass of a polymerization initiator (potassium persulfate: KPS) is dissolved in 400 parts by mass of ion-exchanged water is added to a temperature of 75 ° C. The monomer mixture was added dropwise over 1 hour.
Styrene: 532 parts by mass n-butyl acrylate: 200 parts by mass Methacrylic acid: 68 parts by mass n-octyl mercaptan: 16.4 parts by mass After dropwise addition of the monomer mixture, the system is heated at 75 ° C. for 2 hours. Then, polymerization was carried out with stirring (this is referred to as first-stage polymerization) to prepare “resin particles j1”.

(Ii) Second stage polymerization (formation of intermediate layer)
The following compound was added to a flask equipped with a stirrer to prepare a monomer mixture.
Styrene: 101.1 parts by mass n-butyl acrylate: 62.2 parts by mass Methacrylic acid: 12.3 parts by mass n-octyl mercaptan: 1.75 parts by mass The following release agent was added to the monomer mixture. Then, it heated and melt | dissolved at 80 degreeC and the monomer solution was adjusted.
Paraffin wax “HNP-57” (manufactured by Nippon Wax Co., Ltd.): 93.8 parts by mass On the other hand, surfactant obtained by dissolving 3 parts by mass of the anionic surfactant used in the first stage polymerization in 1560 parts by mass of ion-exchanged water. The agent solution was heated to 80 ° C., and 32.8 parts by mass of the resin particle j1 dispersion was added to the surfactant solution in terms of solid content. After the addition, the monomer solution in which the release agent is dissolved is mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path, and emulsified having a dispersed particle size of 340 nm. A dispersion containing the particles was prepared.
Next, an initiator solution in which 6 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to this dispersion, and this system was heated and stirred at 80 ° C. for 3 hours for polymerization (second stage). Polymerization) was performed to obtain a dispersion of “resin particles j2.”

(Iii) Third stage polymerization (formation of outer layer)
An 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 dispersion of resin particles j2 obtained as described above, and the temperature is 80 ° C. A monomer mixture composed of the following compounds 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 of the monomer mixture, polymerization was carried out by heating and stirring for 2 hours. After step polymerization, the mixture was cooled to 28 ° C. to prepare “core-forming resin particles j3”. The glass transition temperature Tg of the core-forming resin particles j3 prepared by the third stage polymerization was 28.1 ° C.
The glass transition temperature was measured as follows.

<Measurement of glass transition temperature>
This can be performed using a DSC-7 differential scanning calorimeter (manufactured by PerkinElmer) and a TAC7 / DX thermal analyzer controller (manufactured by PerkinElmer). As a measurement procedure, a sample of 4.5 to 5.0 mg is precisely weighed to 2 digits after the decimal point, sealed in an aluminum pan (KITNO.0219-0041), and set in a DSC-7 sample holder. The reference used an empty aluminum pan. The measurement was performed at a temperature of 0 to 200 ° C., a temperature increase rate of 10 ° C./min, and a temperature decrease rate of 10 ° C./min, with heat-cool-heat control, and analysis was performed based on the data at 2nd.Heat. The glass transition temperature is obtained by drawing an extension line of the baseline before the rise of the first endothermic peak and a tangent line indicating the maximum slope between the rise portion of the first peak and the peak vertex, and using the intersection as the glass transition temperature. Ask.

(1-2) Formation of core particles The following materials were charged and stirred in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device.
Dispersion of core-forming resin particles j3 (solid equivalent): 420.7 parts by mass Ion exchange water: 900 parts by weight Colorant fine particle dispersion 1: 200 parts by weight After adjusting the temperature in the container to 30 ° C., this The pH was adjusted to 10 by adding a 5 mol / liter aqueous sodium hydroxide solution to the solution.
Subsequently, stirring the said preparation liquid, the aqueous solution which melt | dissolved 2 mass parts of magnesium chloride hexahydrate in 1000 mass parts of ion-exchange water was added over 10 minutes at 30 degreeC. After standing for 3 minutes, the temperature was raised and the system was heated to 65 ° C. over 60 minutes. In this state, the particle size of the associated particles was measured with “Cole Counter TA-II” (manufactured by Beckman Coulter), and when the volume-based median diameter (D ₅₀ ) reached 5.5 μm, sodium chloride 40 An aqueous solution prepared by dissolving 2 parts by mass in 1000 parts by mass of ion-exchanged water was added to stop the particle size growth. Further, as a ripening treatment, the fusion was continued by heating and stirring at a liquid temperature of 70 ° C. for 1 hour to form core particles. When the circularity of the obtained core particles was measured by “FPIA2100” (manufactured by Sysmex Corporation), the average circularity was 0.912.

(1-3) Preparation of Shell Resin Particles In preparing the core-forming resin particles j3, a monomer mixed solution in which the monomer mixed solution used in the first stage polymerization was changed to the following compound and addition amount was used. A shell resin particle was prepared by performing a polymerization reaction and a post-reaction treatment in the same procedure except for the above.
Styrene: 624 parts by mass 2-ethylhexyl acrylate: 120 parts by mass Methacrylic acid: 56 parts by mass n-octyl mercaptan: 16.4 parts by mass The glass transition temperature (Tg) of the obtained shell resin particles was 62.6 ° C. .

(1-4) Formation of Shell Layer Next, 96 parts by mass (in terms of solid content) of the dispersion of the shell resin particles prepared above was added at 65 ° C., and 2 parts by mass of magnesium chloride hexahydrate was added to ion-exchanged water. An aqueous solution dissolved in 1000 parts by mass was added over 10 minutes. After the addition, the temperature is raised to 70 ° C. (shelling temperature), and stirring is continued for 1 hour to fuse the shell resin particles to the surface of the core particles. Thereafter, an aging treatment was performed at 75 ° C. for 20 minutes to form a shell layer on the core particles.
Here, 40.2 parts by mass of sodium chloride was added, cooled to 30 ° C. at 6 ° C./min, filtered, washed repeatedly with ion-exchanged water at 45 ° C., and then warmed with 40 ° C. hot air. Toner 1 having a shell layer on the core surface was dried.

(2) Production of Toners 2 to 16 Toners 2 to 16 were produced in the same manner as in the production of the toner 1 except that the colorant fine particle dispersion 1 was changed to the colorant fine particle dispersions 2 to 16, respectively.

4). Evaluation (1) Maximum saturation << Definition of maximum saturation >>
The maximum saturation of a toner single color image is defined as follows.
(I) When the content of the toner colorant is set to be large, the saturation increases almost proportionally with the increase in the toner adhesion amount. However, if the content exceeds a certain level, the saturation increases even if the adhesion amount increases. It stops and it starts to decline. The saturation at which the saturation changes from rising to falling even though the toner adhesion amount is rising is defined as the maximum saturation in this case.
(Ii) When the toner adhesion amount is proportional to the saturation, the saturation of the toner image when the toner adhesion amount on the transfer paper that can be set by the image forming apparatus is maximized is defined as the maximum saturation in this case. .
The maximum saturation of the toner is a value measured at a hue angle at which C ^* calculated from the following formula takes a maximum value.
Formula: Saturation C ^* = [(a ^* ) ² + (b ^* ) ² ] ^1/2
At this time, a transfer paper having a basis weight of 128 g / m ² and a lightness of about 93 is used. Specific examples of such transfer paper include “POD gloss coated paper” manufactured by Oji Paper Co., Ltd. It is done.
《Maximum saturation measurement method》
Using a commercially available full-color MFP “bizhub PRO C6500 (manufactured by Konica Minolta Business Technologies Co., Ltd.)”, each developer was introduced, and images with different adhesion amounts on paper at room temperature and normal humidity (20 ° C., 50%) Collect.
Next, the L ^*, a ^*, b ^* of the toner image was measured using a spectrophotometer “Gretag Macbeth Spectrolino” (manufactured by Gretag Macbeth). Measurement conditions were as follows: a D65 light source as a light source, a φ4 mm reflection measurement aperture, a measurement wavelength range of 380 to 730 nm with an interval of 10 nm, a viewing angle (observer) of 2 °, and a dedicated white tile for reference alignment. is there. The maximum saturation C ^* is calculated from the following formula from a and b.
Formula: Saturation C ^* = [(a ^* ) ² + (b ^* ) ² ] ^1/2
The calculated saturation is shown in Table 2 below.

  As is apparent from the results in Table 2, it can be seen that the toners 1 to 11 of the present invention have higher maximum saturation than the toners 12 to 16 of the comparative examples.

Claims (1)

In a toner containing at least a resin and a colorant,
A toner wherein the colorant is represented by the following general formula (I) or general formula (II).

(In general formula (I), M is any one of Cu, Co, Ni, and Ti = O, and R is any of a secondary alkyl group, tertiary alkyl group, and cyclic alkyl group having 3 to 10 carbon atoms. In general formula (II), M is Si, and R is a secondary alkyl group having 3 to 10 carbon atoms, a tertiary alkyl group, or a cyclic alkyl. Z is any of a hydroxyl group, a halogen group, a hydrocarbon group having 3 to 10 carbon atoms, and an alkoxy group.

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