JP2008216624A - Toner kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner kit having high charging stability against environmental changes, little difference in the charging property among the color toners and high charging uniformity among toner particles in each color toner. <P>SOLUTION: The toner kit has: a black toner containing a binder resin and a black colorant comprising carbon black; and at least one kind of color toner containing a binder resin and a colorant comprising a chromatic pigment. Further, the toner kit is characterized in that: the binder resin constituting the black toner has an acid value of 15 to 30 (mg KOH)/g and a hydroxyl value of less than 0.1 (mg KOH)/g; and the binder resin constituting the color toner has an acid value of 15 to 20 (mg KOH)/g and a hydroxyl value of 2 to 15 (mg KOH)/g. The binder resin constituting the black toner and the binder resin constituting the color toner are preferably made of vinyl polymers. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner kit using an electrostatic charge developing toner.

  In recent years, electrophotographic image forming apparatuses such as full-color copying machines and printers have been used effectively in confined places such as SOHO and air conditioning in factories because they are used in offices with a good environment as in the past. There is a demand for stability in various places, such as places that are not available.

However, for example, if the housing is configured to be small so that it can be used in a confined place, there is a complication such as frequent replacement of the toner kit. Further, it has not been sufficient to stably obtain a high-quality image in any place such as a place where poor environmental fluctuations occur. In addition, the following patent document 1 can be mentioned as a prior art document of this invention.
JP-A-5-341574

  The present invention has been made on the basis of the circumstances as described above. The object of the present invention is to have high charging stability against environmental fluctuations, a small difference in chargeability between the color toners, and toner particles in the color toners. It is an object of the present invention to provide a toner kit that can obtain high charge uniformity.

The toner kit of the present invention comprises a black toner containing a black colorant comprising a binder resin and carbon black, and a color toner comprising a color colorant comprising at least one binder resin and a chromatic pigment. Because
The binder resin constituting the black toner has an acid value of 15 to 30 mg · KOH / g and a hydroxyl value of less than 0.1 mg · KOH / g, and the binder resin constituting the color toner has an acid value thereof. The value is 15 to 20 mg · KOH / g, and the hydroxyl value is 2 to 15 mg · KOH / g.

  In the toner kit of the present invention, the binder resin constituting the toner of each color constituting the toner kit is preferably selected from vinyl polymers.

  Further, each color toner constituting the toner kit of the present invention is obtained by agglomerating and fusing resin fine particles containing a binder resin and coloring fine particles containing a colorant in an aqueous medium. It is preferably obtained by going through a step of forming particles.

  According to the toner kit of the present invention, basically, for each color toner, since the binder resin has a specific acid value and hydroxyl group value, the colorant is dispersed with high uniformity between the toner particles. High environmental stability against environmental fluctuations is ensured while high charging uniformity is obtained. In addition, since the acid value and the hydroxyl value relating to the binder resin of the black toner and the acid value and the hydroxyl value relating to the binder resin of the color toner are respectively designed separately, the black toner and the color are generally used. When the charge levels of the toners are compared, the charge level of the color toner having a high resistance is often higher, so that the difference in chargeability between the color toners is reduced. Therefore, the occurrence of image defects is suppressed due to high charging uniformity between toner particles, and a sufficiently high image density can be obtained even with a small amount of developer due to a small difference in charging property between toners of respective colors, thereby reducing the size of the apparatus. And can be used in any environment.

  Hereinafter, the present invention will be described in detail.

The toner kit of the present invention contains a black toner containing a black colorant comprising a binder resin and carbon black, and a color toner having a color colorant comprising at least one binder resin and a chromatic pigment. It is.
Here, the toner kit is one in which toner of at least two colors including black is filled in an appropriate toner storage container and arranged to correspond to a tandem type or a drum type, respectively.

In this toner kit, the binder resin constituting the black toner has an acid value of 15 to 30 mg · KOH / g, a hydroxyl value of less than 0.1 mg · KOH / g, and a binder constituting the color toner. The acid value of the resin is 15 to 20 mg · KOH / g, and the hydroxyl value is 2 to 15 mg · KOH / g.
Here, the acid value and hydroxyl value of the binder resin were measured in accordance with JIS K 0070, using tetrahydrofuran as the solvent instead of the diethyl ether / ethanol mixed solvent, and employing potentiometric titration as the titration method. The acid value is expressed in mg of potassium hydroxide (KOH) required to neutralize free fatty acid, resin acid, etc. contained in 1 g of sample, and the hydroxyl value is 1 g of sample. It is expressed in mg of potassium hydroxide (KOH) required to neutralize acetic acid bonded to a hydroxyl group when acetylated.

  In this toner kit, since the acid value of the binder resin constituting the black toner is 15 mg · KOH / g or more, the binder resin having a high acid value has high hydrophilicity and high affinity with carbon black. Therefore, carbon black constituting the black toner is contained in the toner particles with high dispersibility, and high charging uniformity is obtained as the black toner. Further, when the acid value of the binder resin constituting the black toner is 30 mg · KOH / g or less, charging stability against environmental fluctuations can be obtained.

  When the acid value of the binder resin constituting the black toner is less than 15 mg · KOH / g, carbon black cannot be dispersed with high dispersibility in the toner particles, and as a result, individual toner particles As a result, there is a variation in the chargeability of the image, and a sufficient image density cannot be obtained in the formed image. On the other hand, when the acid value of the binder resin constituting the black toner exceeds 30 mg · KOH / g, the resulting toner has increased hygroscopicity, resulting in decreased chargeability. For example, in a high temperature and high humidity environment. There are cases where high charging stability cannot be obtained, such as a charging failure due to moisture adsorption, and an image failure occurs in an image formed due to environmental fluctuations.

  Further, when the hydroxyl value of the binder resin constituting the black toner is 0.1 mg · KOH / g or more, for example, when the black toner is produced by a polymerization method, the dispersion stability in the aqueous medium is very high. Due to its high value, the risk of production increases, for example, the controllability of aggregation by the aggregating agent is remarkably lowered.

On the other hand, in this toner kit, since the binder resin constituting the color toner has an acid value of 15 mg · KOH / g or more, the binder resin having a high acid value has high affinity with the organic pigment. The organic pigment constituting the color coloring agent in the inside can be dispersed with high dispersibility.
Further, since the hydroxyl value of the binder resin constituting the color toner is 2 to 15 mg · KOH / g, even when a pigment species whose dispersibility is not improved only by adjusting the acid value is used, wetting with respect to the organic pigment. As a result, the dispersibility can be reliably improved, and as a result, the organic pigment constituting the color colorant in the toner particles can be reliably dispersed with a high dispersibility. And sufficient image density can be obtained in the formed image.

[Binder resin]
The binder resin for forming the black toner and the color toner constituting the toner kit of the present invention is not particularly limited, but it is preferable to use a resin made of a vinyl polymer.

  The acid value of the binder resin forming the toner can be adjusted by adjusting the amount of the acidic group-containing monomer component in the polymerizable monomer for forming the binder resin. Similarly, the hydroxyl value can be adjusted by adjusting the amount of the hydroxyl group-containing monomer component in the polymerizable monomer.

(Acid group-containing monomer component)
The acidic group-containing monomer is a monomer having an acidic group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and such an acidic group-containing monomer is not particularly limited. Conventionally known ones can be used. Specifically, for example, (meth) acrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrene sulfonic acid Allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, and the like.
These acidic group-containing monomers can be used alone or in combination of two or more according to the required properties.
The content of these acidic group-containing monomers varies depending on the type of the binder resin, for example, when forming a black toner having an acid value of 15 to 30 mg · KOH / g. For example, 2 to 9% by mass in the polymerizable monomer.
In addition, the content of these acidic group-containing monomers varies depending on the type of the binder resin, for example, when forming a color toner having an acid value of 15 to 20 mg · KOH / g. For example, 2 to 6% by mass in the polymerizable monomer to be formed.

(Hydroxyl-containing monomer component)
The hydroxyl group-containing monomer is not particularly limited, and conventionally known monomers can be used, and specific examples include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2- Hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid-2-hydroxybutyl, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate , Polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, monoester of polyalkylene glycol and (meth) acrylic acid, two or more block polymers of polyalkylene glycol and (meth) acrylic acid Such as monoester Rukoto can.
These hydroxyl group-containing monomers can be used alone or in combination of two or more according to the required properties.
The content of these hydroxyl group-containing monomers varies depending on the type of the binder resin, for example, when forming a black toner having a hydroxyl value of less than 0.1 mg · KOH / g. For example, the content of the polymerizable monomer is less than 0.02% by mass.
The content of these hydroxyl group-containing monomers varies depending on the type of the binder resin, for example, when forming a color toner having a hydroxyl value of 2 to 15 mg · KOH / g. The amount of the polymerizable monomer to be used is, for example, 0.5 to 5% by mass.

(Other polymerizable monomers)
In the polymerizable monomer for forming the binder resin constituting each color toner of the toner kit of the present invention, other polymerizable monomer component having neither an acidic group nor a hydroxyl group is contained. be able to.
Other polymerizable monomers are not particularly limited, and conventionally known monomers can be used. Specifically, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, pn-hexylstyrene, p- Styrene or styrene derivatives such as n-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, Isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate Methacrylic acid ester derivatives such as 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic acid n -Acrylate derivatives such as butyl, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate; ethylene, propylene, isobutylene, etc. Olefins; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride; vinyl propionate, vinyl acetate, vinyl benzoate Vinyl esters such as nyl; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, etc. N-vinyl compounds; vinyl compounds such as vinyl naphthalene and vinyl pyridine; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; aromatic single monomers such as 2-vinyl pyridine and 4-vinyl pyridine And its derivatives; monoolefin monomers such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 4-methyl-1-pentene; diolefin monomers such as butadiene, isoprene and chloroprene And vinyl monomer such body.
These other polymerizable monomers can be used singly or in combination of two or more according to the required properties.

(Crosslinkable monomer)
In the polymerizable monomer for forming the binder resin constituting each color toner of the toner kit of the present invention, a crosslinkable polymerizable monomer (hereinafter referred to as a crosslinkable polymerizable monomer) is used for the purpose of obtaining a crosslinked resin having a crosslinked structure. , "Crosslinkable monomer") component.
The crosslinkable monomer is not particularly limited and conventionally known monomers can be used. Specifically, for example, divinylbenzene, divinylnaphthalene, divinyl ether, ethylene glycol dimethacrylate, ethylene glycol diacrylate, Diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,9- Nan diacrylate, may be mentioned polyfunctional vinyl compound having two or more unsaturated bonds, such as diallyl phthalate.

[Colorant]
The black colorant forming the black toner constituting the toner kit of the present invention is made of carbon black. Specific examples of such carbon black include furnace black, channel black, acetylene black, thermal black, and lamp black.

In addition, as the colorant for forming the color toner constituting the toner kit of the present invention, a chromatic known inorganic or organic pigment can be used. Specific colorants are shown below.
Examples of the colorant for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48; 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.
Examples of the colorant for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, and the like.
Examples of the colorant for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15; 2, C.I. I. Pigment blue 15; 3, C.I. I. Pigment blue 15; 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue 66, C.I. I. And CI Pigment Green 7.

The above colorants can be used alone or in combination of two or more.
Further, the amount of the colorant added for each color is in the range of 1 to 30% by mass, preferably 2 to 20% by mass, with respect to the total amount of toner of each color.

  As the colorant, a surface-modified one can also be used. As the surface modifier, conventionally known ones can be used, and specifically, silane coupling agents, titanium coupling agents, aluminum coupling agents and the like can be preferably used.

〔Release agent〕
The toner particles constituting the black toner and the color toner of the toner kit of the present invention may contain a release agent as necessary. Various known compounds can be used as the release agent. As a method for incorporating the release agent into the toner particles, as described later, the dispersion of the release agent is agglomerated, and agglomerated together with the binder resin fine particles in the fusing step, or the polymerizability for obtaining the binder resin fine particles. Examples thereof include a method in which a release agent is dissolved in a monomer in advance, and this is emulsified and dispersed in an aqueous medium, followed by miniemulsion polymerization.
The addition amount of the release agent in the toner is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the binder resin.

[Charge control agent]
The toner particles constituting the black toner and the color toner of the toner kit of the present invention may contain a charge control agent as necessary. Various known compounds can be used as the charge control agent.

[Particle size of toner particles]
The toner particles constituting the black toner and color toner of the toner kit of the present invention preferably have a volume-based median diameter of 3 to 8 μm. When the toner particles are formed by a polymerization method, the particle size is controlled by the concentration of the aggregating agent, the amount of the organic solvent added, the fusing time, and the composition of the polymer itself in the above-described toner manufacturing method. can do.
When the volume-based median diameter is 3 to 8 μm, the reproducibility of fine lines and high image quality of photographic images can be achieved, and the amount of toner consumption can be reduced compared to the case of using a large particle size toner. be able to.

(External additive)
The black toner and color toner constituting the toner kit of the present invention can be used by adding so-called external additives for the purpose of improving fluidity, chargeability and cleaning property. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles and lubricants can be used.
As the inorganic fine particles, it is preferable to use inorganic oxide particles such as silica, titania and alumina, and these inorganic fine particles are preferably hydrophobized with a silane coupling agent or a titanium coupling agent. . As the organic fine particles, spherical particles having a number average primary particle diameter of about 10 to 2000 nm can be used. As the organic fine particles, polymers such as polystyrene, polymethyl methacrylate, and styrene-methyl methacrylate copolymer can be used.

  The addition ratio of these external additives is a ratio of 0.1 to 5.0% by mass, preferably 0.5 to 4.0% by mass in the toner. In addition, various external additives may be used in combination.

<Toner production method>
The method for producing the toner particles of each color constituting the toner kit of the present invention is not particularly limited, and kneading / pulverization method, dissolution suspension method, suspension polymerization method, emulsion polymerization method, emulsion polymerization aggregation method, miniemulsion Examples of the method for producing toner particles include obtaining toner particles having a reduced particle size in order to achieve high image quality. In view of the above, it is preferable to use an emulsion polymerization aggregation method from the viewpoint of production cost and production stability.

  In the emulsion polymerization aggregation method, a dispersion of fine particles (hereinafter referred to as “binder resin fine particles”) made of a binder resin produced by the emulsion polymerization method is used as a dispersion of toner particle constituents such as other fine particles for coloring. And aggregating slowly while balancing the repulsive force of the fine particle surface by pH adjustment and the agglomeration force by adding an aggregating agent made of an electrolyte, and simultaneously performing association while controlling the average particle size and particle size distribution This is a method for producing toner particles by controlling the shape by fusing fine particles by heating and stirring.

As a method for producing the toner particles constituting the toner kit, the binder resin fine particles formed when the emulsion polymerization aggregation method is used may have a multilayer structure of two or more layers made of binder resins having different compositions. For example, in the case of a three-layer structure, first, a polymerizable monomer and a polymerization initiator are added to a dispersion of resin particles H prepared by an emulsion polymerization process (first stage polymerization) according to a conventional method. Then, a dispersion of composite resin particles HM in which an intermediate layer M is formed on the surface of the resin particles H (core particles) is prepared by polymerizing this system (second stage polymerization). Next, a polymerization initiator and a polymerizable monomer L for obtaining a low molecular weight resin are added to the resulting dispersion of composite resin particles HM, and the polymerizable monomer is present in the presence of the composite resin particles. By polymerizing L (third-stage polymerization), L can be obtained by forming a coating layer L made of a low molecular weight resin on the surface of the composite resin particles.
In such a binder resin fine particle having a multilayer structure, the resin constituting the outermost layer may have a specific acid value and hydroxyl value.

As a method for producing the toner particles constituting the toner kit, an example in the case of using an emulsion polymerization aggregation method is specifically shown:
(1) a coloring fine particle forming step for obtaining coloring fine particles containing a colorant;
(2) a binder resin fine particle polymerization step for obtaining binder resin fine particles containing a release agent, a charge control agent, etc., if necessary;
(3) a salting-out, agglomeration and fusing step for forming colored particles by salting out, agglomerating and fusing the binder resin fine particles and the coloring fine particles in an aqueous medium
(4) A filtration and washing step for filtering out the colored particles from the colored particle dispersion (aqueous medium) and removing the surfactant from the colored particles.
(5) A drying step of drying the washed colored particles,
(6) The process includes a step of obtaining toner particles by adding an external additive to the dried colored particles.

[Surfactant]
When the toner particles constituting the toner kit of the present invention are produced by suspension polymerization, miniemulsion polymerization aggregation or emulsion polymerization aggregation, the surfactant used for obtaining the binder resin is particularly limited. Although not intended, sulfonate (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate), sulfate ester salt (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salt (olein) Suitable examples include ionic surfactants such as sodium oxalate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, and the like. Also, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, sorbitan ester, etc. Nonionic surfactants can also be used. These surfactants are used as an emulsifier when a toner is obtained by an emulsion polymerization method, but may be used for other processes or purposes.

(Polymerization initiator)
When the toner particles constituting the toner kit of the present invention are produced by suspension polymerization, miniemulsion polymerization aggregation or emulsion polymerization aggregation, the binder resin can be polymerized using a radical polymerization initiator.
In the case of using the suspension polymerization method, an oil-soluble radical polymerization initiator can be used. As the oil-soluble polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2 ′ -Azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc. Azo or diazo polymerization initiator, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4- Dichlorobenzoyl peroxide, lauroyl peroxide, 2 Peroxide polymerization initiators such as 2-bis- (4,4-t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine, polymer initiators having a peroxide in the side chain, etc. Can be mentioned.
In the case of using the miniemulsion polymerization aggregation method or the emulsion polymerization aggregation method, a water-soluble radical polymerization initiator can be used, and the water-soluble radical polymerization initiator includes persulfates such as potassium persulfate and ammonium persulfate. Azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide, and the like.

[Chain transfer agent]
A chain generally used for the purpose of adjusting the molecular weight of the binder resin when the toner particles constituting the toner kit of the present invention are produced by suspension polymerization, miniemulsion polymerization aggregation or emulsion polymerization aggregation. A transfer agent can be used.
The chain transfer agent is not particularly limited, and examples thereof include mercaptans such as n-octyl mercaptan, n-decyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionate, terpinolene, carbon tetrabromide. And α-methylstyrene dimer and the like are used.

[Flocculant]
When the toner particles constituting the toner kit of the present invention are produced by the miniemulsion polymerization aggregation method or the emulsion polymerization aggregation method, examples of the aggregation agent used for obtaining the binder resin include alkali metal salts and alkaline earth metal salts. Can be mentioned. Examples of the alkali metal constituting the flocculant include lithium, potassium, and sodium, and examples of the alkaline earth metal constituting the flocculant include magnesium, calcium, strontium, and barium. Of these, potassium, sodium, magnesium, calcium, and barium are preferable. Examples of the counter ion (anion constituting the salt) of the alkali metal or alkaline earth metal include chloride ion, bromide ion, iodide ion, carbonate ion and sulfate ion.

<Developer>
The toner as described above can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer. When this toner is used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 μm of magnetic particles in the toner can be mentioned. Either can be used. When this toner is used as a two-component developer, the carrier is made of a conventionally known material such as a metal such as iron, ferrite, or magnetite, or an alloy of such a metal with a metal such as aluminum or lead. Magnetic particles can be used, and ferrite particles are particularly preferable. As the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a resin dispersion type carrier in which magnetic fine powder is dispersed in a binder resin, or the like may be used.
The coating resin constituting the coat carrier is not particularly limited, and examples thereof include olefin resins, styrene resins, styrene-acrylic resins, silicon resins, ester resins, and fluorine-containing polymer resins. Moreover, it does not specifically limit as resin which comprises a resin dispersion type carrier, A well-known thing can be used, For example, a styrene-acrylic-type resin, a polyester resin, a fluororesin, a phenol resin etc. can be used.
A preferable carrier is a coated carrier coated with a styrene-acrylic resin-based resin as a coating resin from the viewpoint of prevention of detachment of external additives and durability.

  The volume average particle diameter of the carrier is preferably 20 to 100 μm, more preferably 25 to 80 μm. The volume average particle diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

[Transfer material]
The transfer material on which the toner image forming the toner kit of the present invention is formed is a support for holding the toner image, and specifically, a plain paper, a high-quality paper, an art paper or a coated paper from thin paper to thick paper Examples thereof include, but are not limited to, coated printing paper such as, commercially available Japanese paper and postcard paper, plastic films for OHP, and cloth.

  According to the above toner kit, basically, for each color toner, since the binder resin has a specific acid value and hydroxyl group value, the colorant is dispersed with high uniformity between the toner particles. While high charge uniformity is obtained, high environmental stability against environmental fluctuations is also ensured. In addition, since the acid value and the hydroxyl value related to the binder resin of the black toner and the acid value and the hydroxyl value related to the binder resin of the color toner are designed separately, respectively, the black toner and the color are generally used. When the charge levels of the toners are compared, the charge level of the color toner having a high resistance is often higher, so that the difference in chargeability between the color toners is reduced. Accordingly, the occurrence of image defects is suppressed due to high charging uniformity between toner particles, and a sufficiently high image density can be obtained even with a small amount of developer due to a small difference in charging property between toners of various colors, thereby reducing the size of the apparatus. And can be used in any environment.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Colored particles Y1 to Bk1 (for Example 1)>
[Production Example 1HL of Color Binder Resin]
(1) Production of 1 L of binder resin Monomer composition comprising 26.1 kg of styrene, 10.6 kg of n-butyl acrylate, 828 g of 2-hydroxy acrylate, 2.44 kg of maleic acid monobutyl ester in a 120 liter polymerization machine. [I] and 2.8 kg of benzoyl peroxide as a polymerization initiator were charged, mixed and dissolved, and then an aqueous solution in which 40 g of polyvinyl alcohol “GOHSENOL KH-17” (manufactured by Nippon Synthetic Chemical Co., Ltd.) was dissolved in 60 kg of ion-exchanged water With stirring, the inside of the polymerization machine was heated to 96 ° C. to conduct a polymerization reaction for 10 hours to obtain 1 L of a bead-like binder resin.
(2) Production of binder resin 1HL In a 120 liter polymerization machine, 32 kg of the above binder resin 1L, 5.22 kg of styrene, 2.13 kg of n-butyl acrylate, 165 g of 2-hydroxy acrylate, monobutyl maleate A monomer composition [II] composed of 488 g and 10 g of benzoyl peroxide as a polymerization initiator were charged, mixed and dissolved, and then 40 g of polyvinyl alcohol “GOHSENOL KH-17” (manufactured by Nippon Synthetic Chemical Co., Ltd.) was ion-exchanged. An aqueous solution dissolved in 60 kg of water was added, the inside of the polymerization apparatus was heated to 80 ° C. with stirring, and the polymerization reaction was performed for 12 hours. Thereafter, 4 kg of 10% sodium hydroxide was added, and the mixture was aged at 80 ° C. for 2 hours. The obtained polymer slurry was subjected to dehydration treatment, washing treatment and drying treatment to obtain a bead-like binder resin 1HL.
The acid value and hydroxyl value of this binder resin 1HL were measured in accordance with JIS K 0070 using tetrahydrofuran as a solvent instead of a diethyl ether / ethanol mixed solvent and employing potentiometric titration as a titration method. The results are shown in Table 1.

[Production Example 2HL for Binder for Black]
(1) Production of Binder Resin 2L A monomer composition comprising 25.1 kg of styrene, 10.4 kg of n-butyl acrylate, and 4.07 kg of maleic acid monobutyl ester was used instead of the monomer composition [I]. A bead-like binder resin 2L was obtained in the same manner as in the binder resin production example 1L except that it was used.
(2) Production of Binder Resin 2HL Binder resin 2L was used instead of binder resin 1L, and styrene 5.10 kg, n-butyl acrylate 2.08 kg, maleic acid instead of monomer composition [II] A bead-like binder resin 2HL was obtained in the same manner as in the binder resin production example 1HL except that a monomer composition consisting of 814 g of monobutyl ester was used.
The acid value and hydroxyl value of this binder resin 2HL were measured by the same method as described above. The results are shown in Table 1.

[Production Example 1 of yellow colored particles]
100 parts by weight of binder resin 1HL, 3 parts by weight of low molecular weight polypropylene as a release agent, and C.I. I. After premixing 6 parts by weight of Pigment Yellow 74, the mixture is melt-kneaded with a twin screw extruder at a kneading temperature of 140 ° C., cooled and solidified, and then pulverized and classified to give a volume-based median diameter of 7.0 μm. Some colored particles Y1 were obtained.

[Production Example 1 of Magenta Colored Particles]
C. is a magenta colorant instead of 6 parts by weight of the yellow colorant. I. Colored particles M1 were obtained in the same manner as in Production Example 1 of yellow colored particles except that 7 parts by mass of Pigment Red 122 was used.

[Production Example 1 of Cyan Colored Particles]
C. a cyan colorant instead of 6 parts by weight of the yellow colorant I. Colored particles C1 were obtained in the same manner as in Production Example 1 of yellow colored particles except that 4 parts by mass of Pigment Blue 15: 3 was used.

[Production Example 1 of black colored particles]
Similar to Production Example 1 of yellow colored particles, except that binder resin 2HL is used instead of binder resin 1HL, and that 9 parts by mass of carbon black, which is a black colorant, is used instead of 6 parts by mass of yellow colorant. Thus, colored particles Bk1 were obtained.

<Colored particles y1 to bk1 (for Comparative Example 1)>
[Production Example 1 for Comparative Yellow Colored Particles]
Comparative colored particles y1 were obtained in the same manner as in Production Example 1 of yellow colored particles except that binder resin 2HL was used instead of binder resin 1HL.

[Production Example 1 of Magenta Colored Particles for Comparison]
Colored particles m1 for comparison were obtained in the same manner as Magenta colored particle production example 1 except that binder resin 2HL was used instead of binder resin 1HL.

[Production Example 1 of cyan colored particles for comparison]
A colored particle c1 for comparison was obtained in the same manner as in Cyan Colored Particle Production Example 1 except that the binder resin 2HL was used instead of the binder resin 1HL.

[Production Example 1 for Comparatively Colored Black Colored Particles]
Comparative colored particles bk1 were obtained in the same manner as in Production Example 1 of black colored particles except that binder resin 1HL was used instead of binder resin 2HL.

<Colored particles Y2 to Bk2 (for Example 2)>
[Preparation Example 3 HML of Binder Resin Fine Particle Dispersion for Color]
(1) Preparation of core particles (first stage polymerization): Preparation of latex 3H An anionic surfactant sodium lauryl sulfate was added to a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added, the internal temperature was adjusted to 75 ° C., and then 74.5 g of styrene. A monomer composition consisting of 21.6 g of n-butyl acrylate and 1.93 g of acrylic acid was added dropwise over 1 hour, and this system was heated and stirred at 75 ° C. for 2 hours for polymerization (first stage polymerization). ) To obtain latex 3H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 3HM In a flask equipped with a stirrer, 104 g of styrene, 30.2 g of n-butyl acrylate, 2.7 g of acrylic acid, n-octyl-3- By adding 98.0 g of a crystalline compound represented by the following formula (W) as a release agent to a monomer composition composed of 5.6 g of mercaptopropionic acid ester, and humidifying and dissolving at 90 ° C. A monomer solution 3 hm was prepared.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 3H is added to this surfactant solution so as to be 28 g in terms of solid content. The monomer solution 3hm was added, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second-stage polymerization) was carried out by stirring to obtain latex 3HM composed of a dispersion of composite resin particles having a structure in which the surface of resin particles composed of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third-stage polymerization): Preparation of latex 3HML Under the temperature condition of 80 ° C., 306 g of styrene, 88.5 g of n-butyl acrylate, 7.91 g of acrylic acid, n-octyl were added to the latex 3HM. A monomer composition consisting of 10.4 g of -3-mercaptopropionic acid ester, 42 g of a 10% aqueous hydrogen peroxide solution and 42 g of a 10% aqueous ascorbic acid solution were added dropwise over 1 hour. After completion of dropping, polymerization (third-stage polymerization) is performed by heating and stirring for 2 hours, and then cooled to 28 ° C., and a dispersion of composite resin particles having a structure in which the outermost layer is a coating layer of a low molecular weight resin. Latex 3HML was obtained.
The acid value and hydroxyl value of this latex 3HML were measured by the same method as described above. The results are shown in Table 1.

Formula (W): C {CH ₂ OCO (CH ₂ ) ₂₀ CH ₃ } ₄

[Preparation Example 4 HML of Binder Resin Fine Particle Dispersion for Black]
Preparation Example 3 of Colored Binder Resin Fine Particle Dispersion Initiator in which 7.4 g of polymerization initiator (KPS) was dissolved in 200 ml of ion-exchanged water in latex 3HM obtained in the same manner as in the second stage polymerization of HML. A monomer composition comprising 306 g of styrene, 88.5 g of n-butyl acrylate, 17.4 g of acrylic acid, and 10.4 g of n-octyl-3-mercaptopropionic acid ester under the temperature condition of 80 ° C. The thing was dripped over 2 hours. After completion of dropping, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization), and then cooled to 28 ° C. to obtain latex 4HML.
The acid value and hydroxyl value of this latex 4HML were measured by the same method as described above. The results are shown in Table 1.

[Production Example 2 of yellow colored particles]
(Preparation Example Y2 of Colored Fine Particle Dispersion)
While stirring a surfactant solution prepared by dissolving 90 g of anionic surfactant sodium lauryl sulfate in 1600 ml of ion-exchanged water, C.I. I. 400.0 g of Pigment Yellow 74 was gradually added, and then dispersed using a stirrer “CLEARMIX” (manufactured by M Technique Co., Ltd.) so that the dispersed particle size became 200 nm. Prepared.

(Preparation example Y2 of colored particles)
200 g of latex 3HML in terms of solid content, 3000 g of ion-exchanged water, and 45 g of the dispersion liquid Y2 for coloring fine particles, a reaction vessel (four-necked flask) equipped with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring device The mixture was stirred and the internal temperature was adjusted to 30 ° C., and a 5 mol / liter aqueous sodium hydroxide solution was added to this solution to adjust the pH to 8 to 11.0.
Next, an aqueous solution in which 20 g of magnesium chloride hexahydrate was dissolved in 20 ml of ion-exchanged water was added with stirring at 30 ° C. over 10 minutes, and after standing for 3 minutes, the temperature was raised. The temperature was raised to 75 ° C over a period of minutes. In this state, the particle size of the associated particles was measured by “Coulter Counter MS-II”. When the volume-based median diameter reached 6 to 7 μm, an aqueous solution in which 29 g of sodium citrate was dissolved in 60 ml of ion-exchanged water was used. Addition was made to stop particle growth, and further, as a ripening treatment, the fusion was continued by heating and stirring at a liquid temperature of 90 ° C. for 6 hours. Then, it cooled to 30 degreeC, hydrochloric acid was added, pH was adjusted to 2.0, and stirring was stopped. The produced salting-out, agglomeration, and fused particles were filtered, washed repeatedly with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. to obtain colored particles Y2.

[Production Example 2 of Magenta Colored Particles]
C. of magenta colorant instead of yellow colorant I. Except for using Pigment Red 122, the coloring fine particle dispersion M2 was prepared in the same manner as the coloring fine particle dispersion Y2, and instead of the coloring fine particle dispersion Y2, 45 g of the coloring fine particle dispersion Y2 was prepared. Colored particles M2 were obtained in the same manner as in the colored particle preparation example Y2 except that 51 g of the dispersion M2 was used.

[Production Example 2 of Cyan Colored Particles]
Further, instead of the yellow colorant, C.I. I. Except that Pigment Blue 15: 3 was used, the coloring fine particle dispersion C2 was prepared in the same manner as in Preparation Example Y2 of the coloring fine particle dispersion, and instead of 45 g of the coloring fine particle dispersion Y2, the coloring fine particle dispersion C2 was used. Colored particles C2 were obtained in the same manner as in the colored particle preparation example Y2 except that 33 g of the fine particle dispersion C2 was used.

[Production Example 2 of black colored particles]
Further, a dispersion of colored fine particles in the same manner as in Preparation Example Y2 of a fine particle dispersion except that carbon black “Regal 330R” (manufactured by Cabot) was used instead of the yellow colorant. Preparation of colored particles Y2 except that Bk2 was prepared, 71 g of the dispersion liquid Bk2 for coloring fine particles was used instead of 45 g of the dispersion liquid Y2 for coloring fine particles, and latex 4HML was used instead of latex 3HML In the same manner as above, colored particles Bk2 were obtained.

<Colored particles Y3 to Bk3 (for Example 3)>
[Preparation Example 5 HML of Binder Resin Fine Particle Dispersion for Color]
(1) Preparation of core particles (first stage polymerization): Preparation of latex 5H An anionic surfactant sodium lauryl sulfate was added to a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a condenser tube, and a nitrogen introducing device. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added, the internal temperature was adjusted to 75 ° C., and then 69.0 g of styrene. A monomer composition consisting of 28.2 g of n-butyl acrylate, 1.84 g of methacrylic acid and 1.04 g of 2-hydroxyethyl acrylate was added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours. Thus, polymerization (first stage polymerization) was performed to obtain latex 5H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 5HM In a flask equipped with a stirrer, 92.4 g of styrene, 37.7 g of n-butyl acrylate, 2.47 g of methacrylic acid, 2-hydroxyethyl To a monomer composition composed of 1.39 g of acrylate and 5.6 g of n-octyl-3-mercaptopropionate, 98.0 g of the crystalline compound represented by the above formula (W) was added as a release agent. A monomer solution 5hm was prepared by humidifying and dissolving at 90 ° C.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 5H is added to this surfactant solution so as to be 28 g in terms of solid content. The monomer solution was added to 5 hm, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second stage polymerization) was carried out by stirring to obtain latex 5HM composed of a dispersion of composite resin particles having a structure in which the surface of resin particles composed of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third stage polymerization): Preparation of latex 5HML To the latex 5HM was added an initiator solution in which 7.4 g of a polymerization initiator (KPS) was dissolved in 200 ml of ion-exchanged water, A monomer composition comprising 283 g of styrene, 115 g of n-butyl acrylate, 7.56 g of methacrylic acid, 4.25 g of 2-hydroxyethyl acrylate, and 10.4 g of n-octyl-3-mercaptopropionic acid ester under temperature conditions. The solution was added dropwise over 1 hour. After completion of dropping, the mixture was heated and stirred for 2 hours for polymerization (third stage polymerization), and then cooled to 28 ° C. to obtain latex 5HML.
The acid value and hydroxyl value of this latex 5HML were measured by the same method as described above. The results are shown in Table 1.

[Preparation Example 6HML for Dispersion of Binder Fine Particles for Black]
(1) Preparation of core particles (first stage polymerization): Preparation of latex 6H An anionic surfactant sodium lauryl sulfate was added to a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added, the internal temperature was adjusted to 75 ° C., and then 69.4 g of styrene. A monomer composition composed of 28.3 g of n-butyl acrylate and 2.30 g of methacrylic acid was added dropwise over 1 hour, and this system was heated and stirred at 75 ° C. for 2 hours to polymerize (first-stage polymerization). ) To obtain latex 6H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 6HM In a flask equipped with a stirrer, 97.1 g of styrene, 39.7 g of n-butyl acrylate, 3.22 g of methacrylic acid, n-octyl- As a mold release agent, 98.0 g of the crystalline compound represented by the above formula (W) is added to a monomer composition composed of 5.6 g of 3-mercaptopropionic acid ester, and the mixture is humidified and dissolved at 90 ° C. As a result, a monomer solution 6hm was prepared.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 6H is added to this surfactant solution so as to be 28 g in terms of solid content. The monomer solution 6hm was added, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation route to obtain emulsified particles (oil A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second stage polymerization) was performed by stirring to obtain latex 6HM composed of a dispersion of composite resin particles having a structure in which the surface of resin particles composed of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third stage polymerization): Preparation of latex 6HML To the latex 6HM was added an initiator solution prepared by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water, Under temperature conditions, a monomer composition consisting of 277 g of styrene, 113 g of n-butyl acrylate, 9.21 g of methacrylic acid, and 10.4 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of the dropping, polymerization (third stage polymerization) was performed by heating and stirring for 2 hours, and then cooled to 28 ° C. to obtain latex 6HML.
The acid value and hydroxyl value of this latex 6HML were measured by the same method as described above. The results are shown in Table 1.

[Production Example 3 of yellow colored particles]
Colored particles Y3 were obtained in the same manner as in Production Example 2 of yellow colored particles except that latex 5HML was used instead of latex 3HML.

[Production Example 3 of Magenta Colored Particles]
Colored particles M3 were obtained in the same manner as in Magenta colored particle production example 2 except that latex 5HML was used instead of latex 3HML.

[Production Example 3 of Cyan Colored Particles]
Colored particles C3 were obtained in the same manner as in Cyan Colored Particle Production Example 2 except that latex 5HML was used instead of latex 3HML.

[Production Example 3 of black colored particles]
Colored particles Bk3 were obtained in the same manner as in Production Example 2 of black colored particles except that latex 6HML was used instead of latex 4HML.

<Colored particles Y4 to Bk4 (for Example 4)>
[Preparation Example 7 HML of Colored Binder Resin Fine Particle Dispersion]
(1) Preparation of core particles (first-stage polymerization): Preparation of latex 7H An anionic surfactant sodium lauryl sulfate was added to a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added, the internal temperature was adjusted to 75 ° C., and then 67.7 g of styrene. A monomer composition consisting of 27.7 g of n-butyl acrylate, 2.76 g of methacrylic acid and 2.07 g of 2-hydroxyethyl acrylate was added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours. Thus, polymerization (first stage polymerization) was performed to obtain latex 7H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 7HM In a flask equipped with a stirrer, 94.6 g of styrene, 38.7 g of n-butyl acrylate, 3.87 g of methacrylic acid, 2-hydroxyethyl To a monomer composition composed of 2.90 g of acrylate and 5.6 g of n-octyl-3-mercaptopropionate, 98.0 g of the crystalline compound represented by the above formula (W) was added as a release agent. A monomer solution 7hm was prepared by humidifying and dissolving at 90 ° C.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 7H is added to this surfactant solution so as to be 28 g in terms of solid content. 7 hm of the monomer solution was added, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain emulsified particles (oil A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second stage polymerization) was carried out by stirring to obtain latex 7HM made of a dispersion of composite resin particles having a structure in which the surface of resin particles made of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third stage polymerization): Preparation of latex 7HML To the latex 7HM was added an initiator solution prepared by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water, A monomer composition comprising 277 g of styrene, 113 g of n-butyl acrylate, 11.3 g of methacrylic acid, 8.49 g of 2-hydroxyethyl acrylate, and 10.4 g of n-octyl-3-mercaptopropionic acid ester under temperature conditions. The solution was added dropwise over 1 hour. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 2 hours, and then cooled to 28 ° C. to obtain latex 7HML.
The acid value and hydroxyl value of this latex 7HML were measured by the same method as described above. The results are shown in Table 1.

[Preparation Example 8HML of Binder Fine Particle Dispersion for Black]
(1) Preparation of core particles (first stage polymerization): Preparation of latex 8H An anionic surfactant sodium lauryl sulfate was added to a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added to adjust the internal temperature to 75 ° C., and then 70.3 g of styrene. A monomer composition consisting of 28.7 g of n-butyl acrylate and 1.00 g of methacrylic acid was added dropwise over 1 hour, and this system was heated and stirred at 75 ° C. for 2 hours for polymerization (first stage polymerization). ) To obtain latex 8H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 8HM In a flask equipped with a stirrer, 98.3 g of styrene, 40.2 g of n-butyl acrylate, 1.51 g of methacrylic acid, n-octyl- As a mold release agent, 98.0 g of the crystalline compound represented by the above formula (W) is added to a monomer composition composed of 5.6 g of 3-mercaptopropionic acid ester, and the mixture is humidified and dissolved at 90 ° C. As a result, a monomer solution 8 hm was prepared.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 8H is added to this surfactant solution so as to be 28 g in terms of solid content. The monomer solution 8hm was added, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second stage polymerization) was carried out by stirring to obtain latex 8HM composed of a dispersion of composite resin particles having a structure in which the surface of resin particles composed of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third stage polymerization): Preparation of latex 8HML To the latex 8HM was added an initiator solution prepared by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water, and Under temperature conditions, a monomer composition consisting of 283 g of styrene, 115 g of n-butyl acrylate, 4.30 g of methacrylic acid, and 10.4 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 2 hours, and then cooled to 28 ° C. to obtain latex 8HML.
The acid value and hydroxyl value of this latex 8HML were measured by the same method as described above. The results are shown in Table 1.

[Production Example 4 of yellow colored particles]
Colored particles Y4 were obtained in the same manner as in Production Example 2 of yellow colored particles except that latex 7HML was used instead of latex 3HML.

[Production Example 4 of Magenta Colored Particles]
Colored particles M4 were obtained in the same manner as in Magenta colored particle production example 2 except that latex 7HML was used instead of latex 3HML.

[Production Example 4 of Cyan Colored Particles]
Colored particles C4 were obtained in the same manner as in Production Example 2 of cyan colored particles except that Latex 7HML was used instead of Latex 3HML.

[Production Example 4 of black colored particles]
Colored particles Bk4 were obtained in the same manner as in Production Example 2 of black colored particles except that latex 8HML was used instead of latex 4HML.

<Colored particles y2 to bk2 (for Comparative Example 2)>
[Preparation Example 9 BML of Binder Resin Fine Particle Dispersion]
(1) Preparation of core particles (first-stage polymerization): Preparation of latex 9H An anionic surfactant sodium lauryl sulfate was added to a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added, the internal temperature was adjusted to 75 ° C., and then 67.8 g of styrene. A monomer composition consisting of 27.7 g of n-butyl acrylate and 4.50 g of methacrylic acid was added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours (polymerization (first stage polymerization)). ) To obtain latex 9H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 9HM In a flask equipped with a stirrer, 94.1 g of styrene, 38.4 g of n-butyl acrylate, 7.53 g of methacrylic acid, n-octyl- As a mold release agent, 98.0 g of the crystalline compound represented by the above formula (W) is added to a monomer composition composed of 5.6 g of 3-mercaptopropionic acid ester, and the mixture is humidified and dissolved at 90 ° C. As a result, a monomer solution 9 hm was prepared.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 9H is added to this surfactant solution so as to be 28 g in terms of solid content. The monomer solution 9hm was added, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation route to obtain emulsified particles (oil A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second stage polymerization) was carried out by stirring to obtain latex 9HM composed of a dispersion of composite resin particles having a structure in which the surface of resin particles composed of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third stage polymerization): Preparation of latex 9HML To the latex 9HM was added an initiator solution prepared by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water, and Under temperature conditions, a monomer composition consisting of 269 g of styrene, 110 g of n-butyl acrylate, 21.5 g of methacrylic acid, and 10.4 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was heated and stirred for 2 hours for polymerization (third stage polymerization), and then cooled to 28 ° C. to obtain latex 9HML.
The acid value and hydroxyl value of this latex 9HML were measured by the same method as described above. The results are shown in Table 1.

[Production Example 2 for Comparative Yellow Colored Particles]
Colored particles y2 for comparison were obtained in the same manner as in Production Example 2 of yellow colored particles except that latex 4HML was used instead of latex 3HML.

[Production Example 2 of Magenta Colored Particles for Comparison]
Colored particles m2 for comparison were obtained in the same manner as in Magenta colored particle production example 2 except that latex 4HML was used instead of latex 3HML.

[Production example 2 of cyan colored particles for comparison]
A colored particle c2 for comparison was obtained in the same manner as in Cyan Colored Particle Production Example 2 except that latex 4HML was used instead of latex 3HML.

[Production Example 2 for Comparative Colored Black Colored Particles]
Colored particles bk2 for comparison were obtained in the same manner as in Production Example 2 of black colored particles, except that 9HML was used instead of latex 4HML.

<Colored particles y3 to bk3 (for Comparative Example 3)>
[Preparation Example 10 HML of Binder Resin Fine Particle Dispersion]
(1) Preparation of core particles (first stage polymerization): Preparation of latex 10H An anionic surfactant sodium lauryl sulfate in a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added, the internal temperature was adjusted to 75 ° C., and then 65.2 g of styrene. , 26.6 g of n-butyl acrylate, 1.93 g of acrylic acid and 6.21 g of 2-hydroxyethyl acrylate were added dropwise over 1 hour, and this system was heated and stirred at 75 ° C. for 2 hours. Thus, polymerization (first-stage polymerization) was performed to obtain latex 10H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 10HM In a flask equipped with a stirrer, 91.3 g of styrene, 37.3 g of n-butyl acrylate, 2.70 g of acrylic acid, 2-hydroxyacrylate To a monomer composition composed of 8.70 g and n-octyl-3-mercaptopropionic acid ester 5.6 g, 98.0 g of the crystalline compound represented by the above formula (W) is added as a release agent, A monomer solution 10 hm was prepared by humidifying at 90 ° C. and dissolving.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 10H is added to this surfactant solution so as to be 28 g in terms of solid content. The monomer solution was added to 10 hm, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second-stage polymerization) was performed by stirring to obtain latex 10HM composed of a dispersion of composite resin particles having a structure in which the surface of resin particles composed of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third stage polymerization): Preparation of latex 10HML To the latex 10HM was added an initiator solution in which 7.4 g of a polymerization initiator (KPS) was dissolved in 200 ml of ion-exchanged water, A monomer composition comprising 261 g of styrene, 106 g of n-butyl acrylate, 7.71 g of acrylic acid, 24.9 g of 2-hydroxyacrylate, and 10.4 g of n-octyl-3-mercaptopropionic acid ester under temperature conditions is 1 It was added dropwise over time. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 2 hours, and then cooled to 28 ° C. to obtain latex 10HML.
The acid value and hydroxyl value of this latex 10HML were measured by the same method as described above. The results are shown in Table 1.

[Production Example 3 for Comparative Yellow Colored Particles]
Colored particles y3 for comparison were obtained in the same manner as in Production Example 2 of yellow colored particles, except that latex 10HML was used instead of latex 3HML.

[Production Example 3 of Magenta Colored Particles for Comparison]
Colored particles m3 for comparison were obtained in the same manner as in Magenta colored particle production example 2 except that latex 10HML was used instead of latex 3HML.

[Production Example 3 for Comparative Cyan Colored Particles]
Colored particles c3 for comparison were obtained in the same manner as in Cyan Colored Particle Production Example 2 except that latex 10HML was used instead of latex 3HML.

[Production Example 3 for Comparative Black Colored Particles]
Colored particles bk3 for comparison were obtained in the same manner as in Production Example 2 of black colored particles except that 3HML was used instead of latex 4HML.

<Colored particles y4 to bk4 (for Comparative Example 4)>
[Preparation Example 11 HML of Binder Resin Fine Particle Dispersion]
(1) Preparation of core particles (first stage polymerization): Preparation of latex 11H An anionic surfactant sodium lauryl sulfate was added to a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. A surfactant solution (aqueous medium) in which 7.08 g was dissolved in 3010 ml 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 prepared by dissolving 9.2 g of potassium persulfate (KPS) as a polymerization initiator in 200 ml of ion-exchanged water was added, the internal temperature was adjusted to 75 ° C., and then 70.7 g of styrene. A monomer composition consisting of 28.9 g of n-butyl acrylate and 0.386 g of acrylic acid was added dropwise over 1 hour, and this system was heated and stirred at 75 ° C. for 2 hours for polymerization (first stage polymerization). ) To obtain latex 11H made of a dispersion of resin particles made of high molecular weight resin.
(2) Formation of intermediate layer (second stage polymerization): Preparation of latex 11HM In a flask equipped with a stirrer, 99.0 g of styrene, 40.4 g of n-butyl acrylate, 0.54 g of acrylic acid, n-octyl- As a mold release agent, 98.0 g of the crystalline compound represented by the above formula (W) is added to a monomer composition composed of 5.6 g of 3-mercaptopropionic acid ester, and the mixture is humidified and dissolved at 90 ° C. Thus, a monomer solution 11hm was prepared.
On the other hand, a surfactant solution in which 1.6 g of sodium lauryl sulfate is dissolved in 2700 ml of ion-exchanged water is heated to 98 ° C., and the latex 11H is added to this surfactant solution so as to be 28 g in terms of solid content. The monomer solution 11hm was added, and the monomer solution was mixed and dispersed for 8 hours by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain emulsified particles (oil A dispersion containing a droplet) was prepared.
Next, an initiator solution prepared by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion exchange water and 750 ml of ion exchange water are added to this dispersion, and the system is heated at 98 ° C. for 12 hours. Then, polymerization (second stage polymerization) was carried out by stirring to obtain latex 11HM made of a dispersion of composite resin particles having a structure in which the surface of resin particles made of high molecular weight resin was coated with intermediate molecular weight resin.
(3) Formation of outer layer (third stage polymerization): Preparation of latex 11HML An initiator solution prepared by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water was added to the latex 11HM, Under temperature conditions, a monomer composition consisting of 281 g of styrene, 114.8 g of n-butyl acrylate, 1.54 g of acrylic acid, and 10.4 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of dropping, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization), and then cooled to 28 ° C. to obtain latex 11HML.
The acid value and hydroxyl value of this latex 11HML were measured by the same method as described above. The results are shown in Table 1.

[Preparation Example 12 HML of Binder Resin Fine Particle Dispersion]
Binder resin fine particle dispersion example 11 To latex 11HM obtained in the same manner as in HML, an initiator solution prepared by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water was added. Under temperature conditions, a monomer composition composed of 281 g of styrene, 114.8 g of n-butyl acrylate, 1.54 g of acrylic acid, and 10.4 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 2 hours. . After completion of dropping, the mixture was heated and stirred for 2 hours for polymerization (third stage polymerization), and then cooled to 28 ° C. to obtain latex 12HML.
The acid value and hydroxyl value of this latex 12HML were measured by the same method as described above. The results are shown in Table 1.

[Production Example 4 for Comparative Yellow Colored Particles]
Colored particles y4 for comparison were obtained in the same manner as in Production Example 2 of yellow colored particles except that latex 11HML was used instead of latex 3HML.

[Production Example 4 of Magenta Colored Particles for Comparison]
Colored particles m4 for comparison were obtained in the same manner as in Magenta colored particle production example 2 except that latex 11HML was used instead of latex 3HML.

[Production Example 4 for Comparative Cyan Colored Particles]
Colored particles c4 for comparison were obtained in the same manner as in Cyan Colored Particle Production Example 2 except that latex 11HML was used instead of latex 3HML.

[Production Example 4 for Comparatively Colored Black Colored Particles]
Colored particles for comparison bk4 were obtained in the same manner as in Production Example 2 of black colored particles except that 12HML was used instead of latex 4HML.

[External additive treatment of colored particles]
In each of the colored particles Y1 to Y4, M1 to M4, C1 to C4, Bk1 to Bk4, and the colored particles for comparison y1 to y4, m1 to m4, c1 to c4, bk1 to bk4, hydrophobic silica “TG-811F” (Made by Cabozil) at a rate of 1% by mass and strontium titanate particles at a rate of 1.5% by mass. Further, “NX90” (made by Nippon Aerosil Co., Ltd.) is added at 1.0%. Toners Y1 to Y4 and M1 to M4 are added at a ratio of mass%, mixed by “Henschel mixer” (manufactured by Mitsui Mining Co., Ltd.), and then coarse particles are removed using a sieve having an opening of 45 μm. , C1 to C4, Bk1 to Bk4, and comparative toners y1 to y4, m1 to m4, c1 to c4, and bk1 to bk4 were obtained.
In addition, the shape and particle size of these colored particles do not change depending on the addition of the external additive particles.

<Examples 1-4 and Comparative Examples 1-4>
Using the above toner,
Full color toner kit [1] comprising toners Y1, M1, C1, and Bk1
Full color toner kit [2] consisting of toners Y2, M2, C2, and Bk2
Full color toner kit consisting of toners Y3, M3, C3 and Bk3 [3]
Full color toner kit comprising toners Y4, M4, C4 and Bk4 [4]
Full color toner kit [X1] for comparison comprising toners y1, m1, c1 and bk1
Full color toner kit [X2] for comparison comprising toners y2, m2, c2 and bk2
Full color toner kit for comparison [X3] comprising toners y3, m3, c3 and bk3
A full color toner kit for comparison [X4] comprising toners y4, m4, c4 and bk4
The following evaluation was performed using a full-color printer “Magicor 2300DL” (manufactured by Konica Minolta) equipped with a full-color toner kit using a non-magnetic one-component developer. The results are shown in Table 2.

-Measuring method of toner charge amount;
After printing 10 print patterns with a B / W ratio of 6%, a blank paper pattern is printed, the toner on the developing roller at that time is sucked, the charge amount of the toner is measured with an electrometer, and the mass is measured. The toner charge amount was determined by measurement.

[Evaluation of charging stability against environmental fluctuations]
Full color toner kit with toner left in a low temperature and low humidity environment (temperature 10 ° C, relative humidity 15%) for 24 hours, and full color toner kit with toner left in a high temperature and high humidity environment (temperature 30 ° C, relative humidity 85%) for 24 hours The toner charge amount is measured by using the toner, and the toner charge amount difference ΔQ between the toner related to the low temperature and low humidity environment and the toner related to the high temperature and high humidity environment is less than 20 μC / g, “◯”, and larger than 20 μC / g Was evaluated as charging stability against environmental fluctuation.

[Evaluation of difference in chargeability between color toners]
Under the same environment, yellow toner, magenta toner, cyan toner, and black toner are respectively used to measure the charge amount of the toner, and the toner charge amount differences ΔQ for each color are all 10 μC / g or less. Charging uniformity (charge amount difference between toners of each color) was evaluated by assigning “◯” and “X” for other cases.

(Evaluation of image density)
A single color image is formed by using yellow toner, magenta toner, cyan toner, and black toner independently so that the toner adhesion amount on the recording material is 49 / m ^2, and the image transmission density ( TD) is measured by “TD904” (manufactured by Macbeth Co., Ltd.), and a monochrome color image with yellow toner, a monochrome color image with magenta toner, and a monochrome color image with cyan toner have an image transmission density of 0.9 or more. “Good”, “less than 0.9” means “X”, and for a monochrome color image with black toner and a monochrome color image with cyan toner, “◯”, 1.2 when the image transmission density is 1.2 or more What was less than was evaluated as "x".

[Evaluation of image fog]
In a room temperature environment, 4500 full-color images were printed so that the toner adhesion amount on the recording material was 4 g / m ^2, and the 4500th full-color image was visually observed. “○”, “O” when fogging occurred slightly but no problem in practical use, “△” when fogging occurred, “X” when fogging was a lot and there were problems in use .

[Evaluation of Nakanosuke]
4500 full-color images were printed so that the toner adhesion amount on the recording material was 1.0 (± 0.1) mg / cm ² under normal temperature and normal temperature environment, and the 4500th full-color image was visually observed. “No” indicates no leakage, “△” indicates that there is no problem in practical use, but “△” indicates that there is no problem in practical use, and “×” indicates that there is a large number of intermediate leakage that is problematic in practice. evaluated.

  As described above, in Examples 1 to 4 according to the toner kit of the present invention, high charging stability with respect to environmental fluctuations, charging uniformity between toners of each color can be obtained, and sufficient image density can be obtained and image fogging can be achieved. In addition, it was confirmed that the charging uniformity between the toner particles can be obtained without causing the occurrence of neutral leakage.

Claims (3)

A toner kit having a black toner containing a black colorant comprising a binder resin and carbon black, and a color toner comprising a color colorant comprising at least one binder resin and a chromatic pigment,
The binder resin constituting the black toner has an acid value of 15 to 30 mg · KOH / g and a hydroxyl value of less than 0.1 mg · KOH / g, and the binder resin constituting the color toner has an acid value thereof. A toner kit having a value of 15 to 20 mg · KOH / g and a hydroxyl value of 2 to 15 mg · KOH / g.   The toner kit according to claim 1, wherein the binder resin constituting the toner of each color constituting the toner kit is selected from vinyl polymers.   The toner of each color constituting the toner kit is a step of forming toner particles by aggregating and fusing resin fine particles containing a binder resin and coloring fine particles containing a colorant in an aqueous medium. The toner kit according to claim 1, wherein the toner kit is obtained by passing through the toner kit.