JP4280668B2 - Full color toner kit - Google Patents

Description

  The present invention relates to a full-color toner used for electrostatic charge development or a toner jet system. More specifically, even if the oil for preventing high temperature offset is not used or the heat and pressure fixing means using a small amount of oil is used, the saturation is high and the overhead projector (OHP) has high transparency. The present invention relates to a full-color toner kit comprising yellow toner, magenta toner, and cyan toner that can exhibit an excellent color reproduction range.

  In recent years, full-color copying machines and color printers that have been proposed use four photosensitive members and a belt-like transfer member, and electrostatic images formed on the respective photosensitive members are respectively cyan toner, magenta toner, yellow toner, and black toner. The toner is developed by superimposing the toner of each color using the subtractive color mixing action, and the toner image of each color formed by the development is transferred between the photosensitive member and the belt transfer member and transferred between the straight passes. After that, a method for forming a full color image, or a transfer material wound around the surface of the transfer body facing the photoreceptor by a mechanical action such as electrostatic force or gripper, and a development-transfer process is performed four times to obtain a full color image. The method is commonly used.

  In addition, as electrophotographic color image forming apparatuses become widespread, their applications are diversified and demands for image quality are becoming stricter. When copying images such as general photographs, catalogs, and maps, it is required to reproduce very fine and faithfully even down to the finest parts. Accordingly, the demand for color vividness is increasing. It is desired to extend the reproduction range to the same level as process ink.

  For this reason, it is necessary for the color toners to be sufficiently mixed in the heat and pressure fixing process without impairing the color reproducibility and the transparency of the overhead projector (OHP) image. When the color mixing and transparency of the toner is poor, the toner color in the lower layer does not come out when the toner is superimposed, resulting in a narrow color reproduction range, or the chromaticity of the projected image when projected with OHP. It will change and you will not be able to get the desired color.

  In addition, in the case of a full-color image, color reproduction is performed with three chromatic color toners of three primary colors, yellow toner, magenta toner, and cyan toner, or four color toners including black toner. In order to obtain an image having the color tone as described above, balance with other colors is important. Therefore, for the purpose of slightly changing the color tone of the toner, the combined use with the same color pigment / dye, the combined use with other color pigment / dye, and the like have been proposed.

For example, C.I. I. A combination of CI Pigment Blue 15: 3 and a green pigment is disclosed (for example, see Patent Documents 1 and 2).
Several pigments for magenta toner have been proposed, but quinacridone pigments have been widely used so far because they are excellent in color sharpness and transparency, and in light resistance. For example, it discloses that an attempt was made to improve the vividness of a toner by combining a quinacridone pigment and a xanthene dye or a pigment obtained by lacquering a xanthene dye (see, for example, Patent Document 3).
In addition, there are many known colorants for yellow toner, such as monoazo and disazo dyes. (For example, refer to Patent Documents 4 to 6).

However, the conventionally known colorant for yellow toner has many problems. For example, although dye-based colorants are generally excellent in transparency, they are inferior in light resistance and have problems in image storage stability. On the other hand, yellow pigments that are excellent in light resistance and heat resistance are too concealed. As a result, the transparency is extremely lowered, and it is not suitable for full color use.

  Therefore, it has been proposed to use Pigment Yellow 180, which is a disazo pigment having excellent light resistance and heat resistance, as a yellow toner (see, for example, Patent Documents 7 and 8). It was not good, and further improvements were urgently needed for full color use.

  In order to solve the above problem, an electrophotographic toner is described in which pigments are finely divided to increase the specific surface area of the pigment, and transparency and coloring power are improved (for example, see Patent Document 9). However, in general, when a pigment is made finer, its own self-aggregation is inevitably strong, so that the dispersibility in the binder resin constituting the toner is insufficient. With a bad toner, it is difficult to achieve stabilization of charging, and problems such as fogging and toner scattering have occurred.

Thus, in order to obtain an image excellent in color reproducibility in the electrophotographic system and the toner jet system, improvement of each of yellow toner, magenta toner, and cyan toner has been proposed. However, in the case of a full-color image, the color reproduction is performed with the toner of four colors including the above three colors and the black toner, and the combined use of pigments / dyes with sufficient consideration for the balance with other colors has been proposed. Although it should be, there have been few inventions of such purpose so far. In particular, among the secondary colors that are reproduced by superimposing a plurality of toners, color reproducibility is low when yellow toners such as green and red are used, and improvement thereof is required. This is because cyan toner and magenta toner, which have strong coloring power, tend to have high saturation but low brightness, whereas yellow toner generally has low coloring power and relatively high brightness. This is because the degree tends to be low. Conventional yellow toner has increased saturation by increasing the colorant to balance with other colors, but at the same time lacks transparency, resulting in poor color mixing when overlaid with other colors. This was a cause of reducing reproducibility.

JP 2001-5221 A JP-A-8-262802 Japanese Patent Laid-Open No. 64-9466 JP-A-8-36275 JP-A-2-87160 Japanese Patent Laid-Open No. 50-62442 JP-A-6-230607 JP-A-6-266163 JP-A-8-209017

  The present invention provides a full-color toner that solves the above-described problems, and more specifically, a wide color reproduction range, high transparency of an OHP sheet, excellent environmental stability, and formation of a vivid image. It is an object of the present invention to provide a full color toner kit composed of yellow toner, magenta toner, and cyan toner.

  The present inventors have found that a full color toner kit capable of solving the above-described problems can be obtained by considering the balance between the toners constituting the full color toner and defining the hue and brightness for each toner. The present invention has been completed.

That is, the present invention is as follows.
(1) In a full color toner kit comprising at least a binder resin, a colorant, and a wax-containing yellow toner, cyan toner, and magenta toner, when the powdered toner is measured under the condition of a C light source with a double field of view,
(I) a yellow toner having lightness L * and hue b * of 87 <L * and 106 <b * <120 and containing pigment yellow 74 as a colorant ;
(Ii) magenta toner in which values of lightness L * and hue a * are 35 <L * <45 and 60 <a *;
(Iii) A full-color toner kit comprising cyan toners having lightness L * and hue b * values of 35 <L * <45 and −40> b *.
(2) In a full color toner kit composed of yellow toner, cyan toner, and magenta toner containing at least a binder resin, a colorant, and a wax, when the toner in a powder state is measured under the condition of a C light source with a double field of view,
(Iv) yellow toner having a hue a * value of −15 <a * <5;
(V) a magenta toner having a hue b * value of −10 <b * <15;
(Vi) The full-color toner kit according to (1), including a cyan toner having a hue a * value of −10 <a * <0.
(3) The full-color toner kit according to (1) or (2), wherein the binder resin contains at least a polyester unit.

Further preferred configurations are as follows.
(4) The full color toner kit according to any one of (1) to (3), wherein the yellow toner contains at least a monoazo colorant and / or pigment yellow 74 as a colorant.
(5) The magenta toner is at least Pigment Red 57, a naphthol AS pigment, a quinacridone pigment, or a mixed pigment of these pigments as a colorant, according to any one of (1) to (4) Full color kit.
(6) The full-color toner kit according to any one of (1) to (5), wherein the cyan toner contains at least pigment blue 15 as a colorant.

  According to the present invention, by using a toner having a specific brightness and hue, particularly a yellow toner having a high brightness and saturation, the color reproduction range in the red and green regions is wider than in the past, and developability in various environments. Thus, it is possible to provide a full color toner kit composed of yellow toner, magenta toner, and cyan toner that can eliminate the difference in color reproducibility caused by the difference in transferability and can stably form a vivid image.

Hereinafter, the present invention will be described in detail.
The full-color toner kit of the present invention is a full-color toner kit comprising at least a binder resin, a colorant, a wax-containing yellow toner, a cyan toner, and a magenta toner. If
(I) a yellow toner having lightness L * and hue b * values of 87 <L * and 106 <b * <120;
(Ii) magenta toner in which values of lightness L * and hue a * are 35 <L * <45 and 60 <a *;
(Iii) a cyan toner having lightness L * and hue b * of 35 <L * <45 and −40> b *.

  Here, a *, b *, and L * are values used as the L * a * b * color system and are useful means for expressing the color numerically. a * and b * both represent the hue. Hue is a measure of hue such as red, yellow, green, blue, and purple. L * represents lightness and indicates the degree of brightness of colors that can be compared regardless of hue. a * and b * indicate the direction of the color, respectively, a * indicates the red-green direction, and b * indicates the yellow-blue direction. C * means saturation and is obtained by the following equation (i) and indicates the degree of color vividness.

As described above, the yellow toner used in the present invention contains at least a binder resin, a colorant, and a wax, and the values of L * and b * in the powder toner are 87 <L * and 106.
The toner is in the range of <b * <120, preferably in the range of 88 <L * and 108 <b * <120.

When 87 ≧ L *, sufficient brightness cannot be obtained when other colors are superimposed, and the color reproduction range becomes narrow. Theoretically, regarding b *, the higher the numerical value, the wider the two-dimensional color reproduction plane can be secured, and the color reproduction space becomes wider, which is desirable, but it is too high as b * ≧ 120. As a result, the amount of yellow toner required to make an image is reduced, and color unevenness occurs when colors are mixed. For example, when expressing green, a uniform green is expressed by mixing yellow and cyan. At that time, if yellow exists only sparsely with respect to cyan, cyan dots are generated.
Also, the value of a * is in the range of −15 <a * <5, more preferably in the range of −10 <a * <0, from the viewpoint of color reproducibility. In the case of −15> a *, since the greenness tendency is too strong, the green reproducibility becomes good, but conversely, the red reproducibility tends to be impaired. In the case of a *> 5, since the redness tendency is too strong, the red reproducibility becomes good, but conversely, the green reproducibility tends to be impaired.

  As described above, the magenta toner used in the present invention contains at least a binder resin, a colorant, and a wax, and the values of L * and a * in the toner in a powder state are 35 <L * <45 and 60 <. The toner is in the range of a *.

In the case of 35 <L *, sufficient brightness cannot be obtained when superimposing other colors, and the three-dimensional color reproduction space is narrow in the secondary color image in the blue region by superimposing with cyan toner in particular. Become. On the other hand, when L *> 45, the total amount of toner used for producing a particularly high density image is too large, and sufficient fixing ability cannot be obtained. When a * <60, a wide two-dimensional color reproduction plane cannot be secured and the color reproduction space becomes narrow.
The value of b * is −10 <b * <15, more preferably 0 <b * <, from the viewpoint of color reproducibility.
It may be in the range of 15. In the case of −10> b *, since the tendency to bluish is too strong, blue reproducibility is improved, but on the contrary, red reproducibility is easily impaired. In the case of b *> 15, the redness tendency is too strong, and thus the red reproducibility becomes good, but conversely, the blue reproducibility tends to be impaired.

As described above, the cyan toner used in the present invention contains at least a binder resin, a colorant, and a wax, and the values of L * and b * in the toner in the powder state are 35 <L * <45 and −
The toner is in the range of 40> b *.

In the case of 35 <L *, sufficient brightness cannot be obtained when other colors are superimposed, and the three-dimensional color reproduction space is narrow especially in the secondary color image in the blue region by overlapping with magenta toner. Become. On the other hand, when L *> 45, the total amount of toner used to produce a particularly high density image increases, and sufficient fixing properties cannot be obtained. In the case of b *> − 40, a wide two-dimensional color reproduction plane cannot be secured and the color reproduction space becomes narrow.
The value of a * is preferably in the range of −10 <a * <0, more preferably −10 <a * <− 2, from the viewpoint of color reproducibility. In the case of −10> a *, since the greenness tendency is too strong, the green reproducibility becomes good, but conversely, the red reproducibility tends to be impaired. When a *> 0, the redness tendency is too strong, so the red reproducibility is good, but conversely, the green reproducibility tends to be impaired.

As described above, by using the yellow toner, magenta toner, and cyan toner that have specific values of brightness and hue in the powder state, excellent color reproducibility can be obtained and a vivid image can be formed. It becomes possible. In particular, when the brightness and hue of the yellow toner show the above values, excellent color reproducibility can be obtained regardless of the use environment. Among them, when a yellow toner having a high value as described above is used, a plurality of toners can be obtained. When the secondary color is reproduced by superimposing, the color reproducibility can be further improved particularly in the green region and the red region. The reason for this is that cyan toner and magenta toner having strong coloring power tend to have high saturation but low brightness, whereas yellow toner generally has low coloring power and relatively high brightness. Saturation tends to be low. Therefore, when reproducing green and red, the influence of cyan toner and magenta toner is large, and the low-density image does not have the coloring power of yellow toner and the saturation cannot be obtained sufficiently. This is because a large amount of toner is necessary, and the hiding power of cyan toner and magenta toner is also increased, so that not only lightness but also saturation is lowered and color reproducibility is lowered.

In the conventional yellow toner, the colorant is increased and the saturation is obtained in order to balance with other colors. However, as described above, since transparency is lacking, the color mixing property when superimposed with other colors is inferior, Color reproducibility decreases. Further, the dispersion of the colorant in the toner is deteriorated, and fogging and toner scattering occur. In general, in a color toner, the colorant affects the developability and chargeability of the toner, and particularly has a great influence due to changes in the use environment. Therefore, for example, it is possible to bring the charged physical properties of each color toner close to each other and suppress the influence by using an external additive or the like, but it is difficult to completely eliminate the influence of the colorant. In particular, due to the difference between high temperature and high humidity environment (H / H) and normal temperature and low humidity environment (N / L environment), the chargeability of toner changes and the amount of toner adhesion changes.
In particular, the color reproducibility of green and red is lowered.

On the other hand, when yellow toner, cyan toner, and magenta toner whose lightness and hue values specified in the present invention are specific values are used, the respective toners can be superposed with good balance. As a result, the color mixing becomes good regardless of the use environment, the color reproducibility of the secondary color (two-color mixing, three-color mixing) can be remarkably improved, and the above problem can be solved.

A preferred embodiment of the present invention will be described below.
The binder resin used in the toner of the present invention is (a) a polyester resin, or (b) a hybrid resin having a polyester unit and a vinyl polymer unit, or ( c) a mixture of a hybrid resin and a vinyl polymer, or (d) a mixture of a polyester resin and a vinyl copolymer, or (e) a mixture of a hybrid resin and a polyester resin, or (f) a polyester resin and a hybrid. A resin selected from either a resin or a mixture with a vinyl polymer is preferred.

Furthermore, the molecular weight distribution measured by gel permeation chromatography (GPC) of the resin component has a main peak in the region of a molecular weight of 3,500 to 30,000, preferably a molecular weight of 5,000 to 20, The weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 5.0 or more. When the main peak is in a region having a molecular weight of less than 3,500, the hot offset resistance of the toner is insufficient. On the other hand, when the main peak is in the region where the molecular weight exceeds 30,000, sufficient low-temperature fixability of the toner cannot be obtained, and application to high-speed fixing becomes difficult. Mw / Mn is 5.0
If it is less, it becomes difficult to obtain good offset resistance.

  In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group.

Next, the material of the binder resin will be described.
When a polyester resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, or the like can be used as a raw material monomer.

  Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

Examples of the divalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, dodecenyl succinic acid, adipic acid, sebacic acid and azelaic acid, or anhydrides thereof. And succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;
Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid (also known as trimellitic acid), 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, Examples include 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof.

  Among the above, in particular, a bisphenol derivative represented by the following general formula (1) as a diol component, a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof (for example, , Fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.), and the polyester resin obtained by condensation polymerization of these has good charging characteristics as a color toner. preferable.

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 1,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 1.9 mol% based on the total monomer.

  Furthermore, in the present invention, when a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved wax dispersibility, low-temperature fixability, and offset resistance can be expected.

  In the binder resin, the “hybrid resin component” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.

Examples of the vinyl monomer for producing the vinyl resin include the following. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and derivatives thereof such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinyl chloride, vinyl bromide, fluoride Vinyl halides such as vinyl; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate Acrylic esters such as lorethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, unsaturated dibasic acid ester such as dimethyl fumaric acid; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof.
Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  The vinyl polymer unit of the binder resin referred to in the present invention may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case.

  Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. Examples of diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 , Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing methacrylates with acrylates; diacrylate compounds linked by a chain containing an aromatic group and an ether bond For example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the above compounds The thing which replaced the acrylate with the methacrylate is mentioned.

  As polyfunctional cross-linking agents, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and acrylates of the above compounds are replaced by methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

Examples of the polymerization initiator used for producing the vinyl polymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvalero). Nitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1, 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl- 4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone Ketone peroxides such as oxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -T-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-pro Ruperoxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxy Acetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t -Butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhexahydrotere Tallate, di -t- butyl peroxy azelate and the like.

  Next, the manufacturing method of the hybrid resin used for the binder resin of this invention is demonstrated. The hybrid resin of the present invention can be produced by the production methods shown in the following (1) to (6).

  (1) A method in which a vinyl polymer, a polyester resin, and a hybrid resin component are blended after production. The blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. The ester compound used can be used.

  (2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer unit in the presence of the vinyl polymer unit. The hybrid resin component is produced by a reaction between a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or vinyl polymer unit.

  (4) After the production of the vinyl polymer unit and the polyester unit, a hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.

  (5) After producing the hybrid resin component, vinyl polymer units and / or polyester units (alcohol, carboxylic acid) are added to carry out addition polymerization and / or polycondensation reaction to produce vinyl polymer units and polyester units. Is done. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be used as appropriate.

  (6) A vinyl polymer unit, a polyester unit, and a hybrid resin component are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. Furthermore, an organic solvent can be used as appropriate.

In the production methods of (1) to (5) above, a polymer unit having a plurality of different molecular weights and crosslinking degrees can be used as the vinyl polymer unit and / or the polyester unit.
The binder resin contained in the toner of the present invention includes a mixture of the polyester and a vinyl polymer, a mixture of the hybrid resin and a vinyl polymer, a vinyl resin in addition to the polyester resin and the hybrid resin. A mixture of polymers may be used. Preferably, it contains a hybrid resin.

The glass transition temperature of the binder resin contained in the toner of the present invention is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. The acid value of the resin is preferably 1 to 40 mgKOH / g.
Further, the Tm (° C.) of the binder resin contained in the toner of the present invention is too high, the fixability is inferior, and if it is too low, the storage stability of the toner is deteriorated. Therefore, 90 ° C. ≦ Tm ≦ 140 ° C. is good. Preferably, 95 ° C. ≦ Tm ≦ 130 ° C.

Examples of the wax used in the present invention include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; aliphatic carbonization Block copolymer of hydrogen-based wax; wax mainly composed of fatty acid ester such as carnauba wax, behenyl behenate and montanic acid ester wax; and partly or partially deoxidized fatty acid ester such as deoxidized carnauba wax Etc.
Examples thereof include a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  Particularly preferred waxes are aliphatic hydrocarbon waxes such as paraffin wax, polyethylene, and Fischer-Tropsch wax, which have a short molecular chain and little steric hindrance and excellent mobility.

In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 350-2400, more preferably in the region of 400-2000. By giving such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.
Moreover, in the endothermic curve in the differential thermal analysis (DSC) measurement of the wax, the peak temperature of the maximum endothermic peak is preferably in the range of 60 to 105 ° C, and more preferably in the range of 70 to 90 ° C. When the temperature is lower than 60 ° C., for example, the storage stability of the toner may be inferior, and when the temperature exceeds 105 ° C., it may be difficult to perform low-temperature fixing desired from the viewpoint of energy saving.

The added amount of the wax used in the present invention is 1 to 10 parts by mass, preferably 2 to 8 parts by mass with respect to 100 parts by mass of the binder resin. This is because if the amount is less than 1 part by mass, the amount of heat and pressure are required because the amount is small in order to come out on the surface of the toner at the time of melting and exhibit releasability. On the other hand, when the amount exceeds 10 parts by mass, the amount of wax in the toner is too large, which may result in poor transparency, charging characteristics, and storage stability.
The toner of the present invention has one or a plurality of endothermic peaks in the temperature range of 30 to 200 ° C. in the endothermic curve in differential thermal analysis (DSC) measurement, and the peak temperature of the maximum endothermic peak in the endothermic peak. Is preferably in the range of 60 to 105 ° C, particularly preferably in the range of 70 to 90 ° C. If the peak temperature of the maximum endothermic peak is within this range, the balance between excellent low-temperature fixability and developability will be good. When the peak temperature of the maximum endothermic peak is less than 60 ° C., the storage stability of the toner may be inferior, and when it exceeds 105 ° C., it may be difficult to perform low-temperature fixing desired from the viewpoint of energy saving. The peak temperature of the maximum endothermic peak can be set to 60 to 105 ° C. by adding the wax having the maximum endothermic peak peak temperature of 60 to 105 ° C. described above to the toner.

The following are mentioned as a coloring agent used for this invention.
Examples of the magenta colorant include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 202, 206, 207, 209, 238, 269, C.I. I. Pigment violet 19, C.I. I. Examples include magenta colored pigments such as Vat Red 1, 2, 10, 13, 15, 23, 29, and 35, preferably Pigment Red 57, naphthol AS pigment, quinacridone pigment, or a mixed pigment of these pigments. is there.
Although the above pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full color image to improve the sharpness by using a dye and a pigment together.

  Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 2, 881, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. are mentioned.

  Examples of cyan colorants include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Pigment green 7, C.I. I. The Acid Blue Party can be mentioned, but Pigment Blue 15 is preferable.

  Examples of the colorant for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 180, C.I. I. Examples thereof include yellow coloring pigments such as vat yellow 1, 3, 20 and the like, and monoazo colorants and / or pigment yellow 74 are preferable.

  Further, as the black colorant, carbon black, iron oxide, and those which are toned in black using the yellow / magenta / cyan colorant described above can be used.

  The amount of the colorant used is 1 to 10 parts by mass, preferably 3 to 8 parts by mass with respect to 100 parts by mass of the binder resin in the toner.

In the toner of the present invention, a charge control agent of an organometallic compound described below can be used.
The charge control agent for the organometallic compound is preferably an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative. Divalent or higher valent metal atoms are preferred. As divalent ^{metal, Mg 2+, Ca 2+, Sr} 2+, Pb 2+, Fe 2+, Co 2+, Ni 2+, Zn 2+, Cu 2+ , and the like, in particular Zn ²⁺ , Ca ²⁺ , Mg ²⁺ and Sr ²⁺ are preferred. Examples of the trivalent or higher metal include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ and Zr ⁴⁺ . Among these metals, Al ³⁺ and Cr ³⁺ are preferable, and Al ³⁺ and Zr ⁴⁺ are particularly preferable. Specifically, an aluminum compound of di-tert-butylsalicylic acid is particularly preferable as the charge control agent.

The charge control agent used in the present invention is used in an amount of 0.2 to 10 parts by weight, preferably 0.3 to 7 parts by weight, based on 100 parts by weight of the binder resin in the toner. 0.
This is because if the amount is less than 2 parts by mass, the effect of charging rise cannot be obtained, and if the amount is more than 10 parts by mass, the environmental fluctuation increases.

  In order to produce the color toner used in the present invention, a binder resin, a colorant, a wax, and, if necessary, a charge control agent and other additives are sufficiently mixed by a mixer such as a ball mill, and then a heating roll. Color toner by dispersing, mixing, and solidifying by cooling, solidifying and kneading using a heat kneader such as a kneader or extruder to disperse the pigments in each other, cooling and solidifying, and strict classification Particles can be obtained.

  In addition, as a method of producing the color toner used in the present invention, for example, there is a method of making a colorant master batch in an intermediate, and as a method of making the colorant master batch, a flushing treatment, that is, a colorant synthesized, and then powdered Dispersibility of the colorant by heat-mixing with the first resin in a water-containing state (paste colorant) without drying and pelletizing, or by mixing powder colorant with water and resin, and then drying and pelletizing You may use the method of improving. However, after this heating and mixing, the particle size of the colorant may grow with the amount of heat to be dried and pelletized. The method is more preferable.

  First, when making the colorant masterbatch, when the first resin and the colorant are heated and mixed, water is also present (a paste colorant or water is added), and the resin and the colorant are sufficiently dispersed uniformly. Then, the growth of the colorant is suppressed by evaporating the water to obtain a dry powder colorant masterbatch with a minimum amount of heat that does not completely evaporate the water. At this time, it is not always necessary to leave the water just to contain water, and the water content also greatly affects the toner quality. The water content of the desired colorant masterbatch in the present invention is preferably 1 to 25% by mass, more preferably 2 to 25% by mass, and further preferably 5 to 18% by mass. If it is less than 1% by mass, an excessive amount of heat is imparted to the colorant in order to reduce the water content, and as a result, it becomes easy to cause an adverse effect of growth. On the other hand, if the amount is more than 25% by mass, adhesion to the apparatus wall surface and non-uniform agglomeration will occur during mixing of raw materials, and the stability of feeding into the kneading machine will also deteriorate. This tends to cause a large difference in color uniformity and charging uniformity.

Using an appropriate water-containing colorant masterbatch in this way makes it possible to control kneading at a low temperature by adjusting the setting temperature of the kneading and screw rotation speed, as well as the heat of vaporization of water, and to easily suppress the growth of the colorant. .
The paste colorant is preferably in a state where the colorant particles are present without passing through the drying process in the colorant production process. In other words, the colorant particles are present in a state of approximately primary particles in an amount of 5 to 60% by mass with respect to the total paste colorant. The remaining 40-95% by weight of the paste colorant is water with some dispersants and auxiliaries.

Next, a procedure for manufacturing toner will be described.
For example, first, in the raw material mixing step, at least a second binder resin, a colorant master batch, and a wax are weighed and mixed in a predetermined amount as toner internal additives and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer. In the present invention, the first binder resin and the second binder resin may be the same or different.

  Further, the toner raw material mixed as described above is melt-kneaded to melt the resins and disperse the colorant and the like therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nisshin Engineering Co., Ltd. or the like. After that, if necessary, it is classified using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) or a centrifugal class turbo turbo (Hosokawa Micron Co., Ltd.), and the weight average particle diameter A 4 to 10 μm classified product is obtained.

  If necessary, it is possible to obtain a classified product by performing a surface modification = spheronization treatment in a surface modification step, for example, a hybridization system manufactured by Nara Machinery Co., Ltd. or a mechano-fusion system manufactured by Hosokawa Micron. If necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used. Furthermore, as a method of externally adding the external additive, a predetermined amount of classified toner, silica, titanium oxide, etc. are blended, and a high-speed stirrer that gives shearing force to the powder such as a Henschel mixer or a super mixer is removed. The toner can be obtained by stirring and mixing as an accessory.

In the present invention, it is preferable to externally add a fluidity improver as an external additive to the toner particles in order to improve the image quality. The fluidity improver refers to an agent that can be added to the toner particles to increase the fluidity before and after the addition.
Examples of the fluidity improver include fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder such as silica fine powder by a wet process, silica fine powder such as silica fine powder by a dry process; Treated silica fine powder whose powder is surface-treated with a treatment agent such as silane coupling agent, titanium coupling agent, silicone oil, etc .; titanium oxide fine powder; alumina fine powder, treated titanium oxide fine powder, treated alumina oxide fine powder, etc. Is mentioned.

A fluidity improver having a specific surface area of 30 m ² / g or more, more preferably 50 m ² / g or more, gives good results by nitrogen adsorption measured by the BET method. The fluidity improver is preferably added in an amount of 0.01 to 8 parts by weight, more preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner particles.
As described above, the external addition of the fluidity improver is performed by sufficiently mixing the fluidity improver and the toner particles with a mixer such as a Henschel mixer. By such a mixing operation, a toner having a fluidity improver on the toner particle surface can be obtained.

The weight average particle diameter of the toner of the present invention is preferably 4 to 10 μm, and more preferably 5 to 9 μm.
When the weight average particle size of the toner is larger than 10 μm, it means that there are few fine particles that can contribute to high image quality, and when used for image formation, a high image density is easily obtained and the toner fluidity is excellent. Although there is a merit, it is difficult to adhere faithfully on the fine electrostatic charge image on the photosensitive drum, the reproducibility of the highlight portion is lowered, and the resolution tends to be lowered. Also, the toner tends to overload the electrostatic charge image more than necessary, and the toner consumption tends to increase.
On the contrary, when the weight average particle diameter of the toner is smaller than 4 μm, the charge amount per unit mass of the toner becomes high, and when used for image formation, the image density is lowered, particularly at low temperature and low humidity. Becomes prominent. This is not suitable for applications with a high image area ratio such as graphic images. When the thickness is smaller than 4 μm, contact charging with a charging member such as a carrier is difficult to be performed smoothly, toner that cannot be sufficiently charged increases, and fogging due to scattering to a non-image portion becomes conspicuous. In order to cope with this, it is conceivable to reduce the diameter of the carrier in order to increase the specific surface area of the carrier. However, in the toner having a weight average particle diameter of less than 4 μm, toner self-aggregation easily occurs, and uniform mixing with the carrier can be performed in a short time. This is difficult to achieve, and fog tends to occur in the continuous toner replenishment durability.

  The toner of the present invention can be applied to a one-component developer and a two-component developer, and is not particularly limited. However, when the toner of the present invention is used for a two-component developer, the toner is Used in combination with a magnetic carrier. Examples of magnetic carriers include iron or surface-oxidized iron; metal particles such as nickel, copper, zinc, cobalt, manganese, chromium, magnesium, rare earth; alloy particles thereof; oxide particles thereof; ferrites thereof; A coated carrier in which the surface of magnetic particles is coated with a resin; a magnetic particle-dispersed resin carrier in which these magnetic particles are dispersed in resin particles can be used.

The coated carrier in which the surface of the magnetic particle is coated with a resin is particularly preferable when used in a developing method in which an AC bias is applied to the developing sleeve. As a coating method, a method of adhering a coating solution prepared by dissolving or suspending a resin as a coating material in a solvent to the surface of the magnetic particles, a method of adhering the magnetic particles and the coating material by mixing with powder, etc. Conventionally known methods can be applied.
Examples of the resin as a coating material on the surface of the magnetic particles include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These may be used alone or in combination. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the magnetic particles.

  The 50% average particle diameter of the magnetic carrier is preferably 10 to 100 μm, and more preferably 20 to 70 μm.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio of the toner concentration in the developer is usually 2 to 15% by mass, and usually good results are obtained. Above, it is more preferable that it is 4-13 mass%.

The image forming method for forming a color image using the full color kit of the present invention can be realized by a known apparatus or means in this technical field. For example, an image forming method using an image forming apparatus in which a plurality of developing devices are installed on one image carrier, or a toner image formed on an image carrier with a plurality of developing devices installed on different image carriers. Examples of the image forming method include a tandem image forming apparatus in which images are sequentially transferred onto a transfer material, but are not particularly limited.

  Further, when the toner image formed on the image carrier is transferred to a transfer material, an image forming method using an image forming apparatus that directly transfers the toner image from the image carrier to the transfer material may be used. An image forming method using an image forming apparatus that transfers a toner image on a body to an intermediate transfer member and transfers the toner image from the intermediate transfer member to a transfer material may be used.

  Hereinafter, measurement methods suitable for measuring the physical properties of the resin used in the present invention and the toner in the present invention will be described below. Examples described later are also based on these methods.

(1) Measurement of L *, a *, and b * in toner in powder state L *, a *, and b * in toner in powder state are spectral color difference meters “SE-2000” compliant with JIS Z-8722. ”(Manufactured by Nippon Denshoku Industries Co., Ltd.) and the light source is measured with a C light source with a 2-degree field of view. The measurement is performed according to the attached instruction manual. For standardization of the standard version, it is preferable to perform the measurement through a glass of 2 mm thickness and φ30 mm in an optional powder measurement cell.
More specifically, the measurement is performed in a state in which a cell filled with the sample powder is placed on the sample table (attachment) for the powder sample of the spectroscopic color difference meter. Before installing the cell on the sample table for the powder sample, fill the powder sample with 80% or more with respect to the internal volume of the cell, and apply vibration once per second on the vibration table for 30 seconds. Then, L *, a *, and b * are measured.

(2) Measurement of the molecular weight of the binder resin The column was stabilized in a heat chamber at 40 ° C., THF as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and about 100 μl of the THF sample solution was injected and measured. To do. An RI (refractive index) detector is used as the detector. As the column, it is preferable to use a combination of a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko, Examples include TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguard column manufactured by Tosoh Corporation.
The THF sample solution is prepared as follows. Place the sample in THF and let stand for several hours, then shake well, mix well with THF (until the sample is no longer integrated), and let stand for more than 12 hours. At this time, the immersion time in THF is 24 hours or longer. Thereafter, the sample is processed through a sample processing filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 manufactured by Tosoh Corporation, etc.) to obtain a THF sample solution for GPC. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko is used, and at least about 10 standard polystyrene samples are suitably used. .

(3) Measurement of softening point temperature Tm of binder resin For the measurement of the softening point temperature of the binder resin, a flow tester CFT-500 type (manufactured by Shimadzu Corporation) is used. The sample weighs about 1.0 g of a product having an opening of 250 μm. This sample is pressed with a load of 9.8 MPa for 1 minute using a molding machine.
This pressure sample was subjected to normal temperature and humidity (temperature of about 20-30 ° C., humidity of 30-70) under the following conditions.
% RH) to obtain a temperature-apparent viscosity curve. From the obtained smooth curve, the temperature (= T ^1/2 ) when the sample flows out by 50% by volume is obtained, and this is defined as the softening point temperature Tm of the resin.

RATE TEMP 6.0 (° C / min)
SET TEMP 50.0 (° C)
MAX TEMP 180.0 (° C)
INTERVAL 3.0 (° C)
PREHEAT 300.0 (seconds)
LOAD 20.0 (kg)
DIE (Diameter) 1.0 (mm)
DIE (Length) 1.0 (mm)
PLUNGER 1.0 (cm ² )

(4) Measurement temperature curve of DSC curve of toner, wax and binder resin: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C to 200 ° C, temperature increase rate 10 ° C / min)

Using a differential scanning calorimeter (DSC measuring device), DCS-7 (manufactured by PerkinElmer) or DSC2920 (manufactured by TA Instruments Japan), the measurement is performed as follows according to ASTM D3418-82.
Weigh accurately 5 mg of the measurement sample. It is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a measurement range of 30 to 200 ° C., a temperature increase rate of 10 ° C./min, and normal temperature and humidity.
The glass transition temperature (Tg) of the binder resin is the point of intersection between the base line midpoint and the differential heat curve before and after the endothermic peak of the main peak in the temperature range of 40 to 100 ° C. in the process of temperature rise II. And the glass transition temperature Tg in the present invention.
Further, the maximum endothermic peak of toner and wax is the one having the highest height from the baseline in the region above the endothermic peak of the glass transition temperature (Tg) of the resin in the process of temperature increase II, or the endothermic of the resin Tg. When it is difficult to distinguish a peak from another endothermic peak, the highest endothermic peak of the toner is defined as the highest peak from the maximum peak of the overlapping peak.

(5) Measurement of water content of water-containing colorant masterbatch and paste pigment In the present invention, "water content" means a mass-based water content based on the Karl Fischer method, that is, the total weight of water-containing colorant masterbatch or paste pigment The ratio of moisture mass, which is left for 24 hours at 23 ° C and 60% RH, and measured for gas at 125 ° C heating based on the Karl Fischer method (JIS K-0068 moisture vaporization method) using a sample prepared. It is what I asked for.

(6) Measurement of toner particle diameter In the present invention, the average particle diameter of the toner is measured using a Coulter Counter TA-II type (manufactured by Coulter), but it is also possible to use a Coulter Multisizer (manufactured by Coulter). is there. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used.
As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles of 2.00 μm or more are measured by using the 100 μm aperture as the aperture by the measuring device. Distribution and number distribution are calculated. Then, the weight average particle diameter (D4) obtained from the volume distribution according to the present invention (the median value of each channel is used as the representative value for each channel) is obtained.
As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.

(7) Measurement of specific surface area of fluidity improver The specific surface area is determined by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method and using the BET multipoint method. To calculate the specific surface area.

Moreover, the evaluation in the Example mentioned later was performed by using the following papers and using the following evaluation methods.
Plain paper: CLC color copy paper (basis weight 80 g / cm ² : manufactured by Canon)
OHP sheet: Transparency sheet CG3700 (manufactured by 3M)

(1) Measuring method of OHP transmittance Using a color copying machine CLC-1000 (manufactured by Canon), an unfixed image of A4 half-sided solid image is created on an OHP sheet, and a fixing machine of iRC3200 (manufactured by Canon Inc.) is used. And settled. At that time, an image is created by adjusting the development contrast so that the solid portion of the OHP fixed image has an image density satisfying the following formula (ii).

（上記式中、Ｄ（ベタ紙上）：普通紙上にＯＨＰをのせベタ画像部分の反射濃度を測定したもの、Ｄ（ＲＥＦ紙上）：普通紙上にＯＨＰをのせ、ベタ白部分の反射濃度を測定したものを示す。）

(In the above formula, D (on solid paper): OHP was placed on plain paper and the reflection density of the solid image portion was measured. D (on REF paper): OHP was placed on plain paper and the reflection density of the solid white portion was measured. Show things.)

For reflection density measurement, X-rite 504 (manufactured by X-Rite) was used, and the image density was measured.
The OHP transmittance was evaluated using the above-mentioned OHP image, using the transmission light measurement mode of V-570 UV / vis / NIR Spectrophotometer manufactured by JASCO (JASCO), cyan image: 490 nm, magenta image: 722 nm, yellow Image: measured at 578 nm.
The evaluation criteria for OHP permeability are as follows.

A: Good at 80% or more B: 70% or more, good at less than 80% C: 60% or more, less than 70%, no practical problem D: 50% or more, less than 60%, practical problem E: 50% Less than bad

(2) Color reproducibility Based on the definition of the color system standardized by the International Commission on Illumination (CIE) in 1976, under normal temperature and normal humidity (N / N) environment (23 ° C / 50% RH) 0.6 mg / cm ² toner loaded per color under low humidity (N / L) environment (23 ° C / 5% RH) and high temperature high humidity (H / H) environment (30 ° C / 80% RH) Each secondary color (R, G, B) to be a quantity
The chroma C * (N / N) and the color difference ΔE (N / L to H / H) of the pattern were quantitatively evaluated and evaluated based on the following evaluation criteria. For the secondary color pattern, an unfixed image was created using a color copier CLC-1000 (manufactured by Canon) and fixed using a fixing machine of iRC3200 (manufactured by Canon Inc.). GretagMacbeth Co. Spectrolino for measurement (measurement _{condition: D 50} viewing angle 2 °) was used.

<Saturation C * of secondary color in N / N environment>

（ａ_ＮＮ ^*、ｂ_ＮＮ ^*：Ｎ／Ｎ環境での画像の色相を示す色度を表す。）

( _ANN ^* , _bNN ^* : represents chromaticity indicating the hue of an image in an N / N environment.)

The evaluation criteria are as follows.
R image A: C * ≧ 75, excellent B: 65 ≦ C * <75, good C: 55 ≦ C * <65, practical problem D: C * <55, bad G image A: C * ≧ 65 Excellent B: 55 ≦ C * <65, good C: 50 ≦ C * <55, practical problem D: C * <50 bad B image A: C * ≧ 45, excellent B: 40 ≦ C * <45 Good C: 35 ≦ C * <40, practical problem D: Bad C * <35

<Color difference ΔE between two environments (N / L to H / H)>

（Ｌ_ＮＬ ^*：Ｎ／Ｌ環境での画像の明度、
ａ_ＮＬ ^*、ｂ_ＮＬ ^*：Ｎ／Ｌ環境での画像の色相を示す色度、
Ｌ_ＨＨ ^*：Ｈ／Ｈ環境での画像の明度、
ａ_ＨＨ ^*，ｂ_ＨＨ ^*：Ｈ／Ｈ環境での色相を示す色度を表す。）

(L _NL ^* : Lightness of image in N / L environment,
a _NL ^* , b _NL ^* : chromaticity indicating the hue of the image in the N / L environment,
L _HH ^* : Brightness of the image in H / H environment,
_aHH ^* , _bHH ^* : Represents the chromaticity indicating the hue in the H / H environment. )

The evaluation criteria are as follows.
A: Excellent if ΔE ≦ 3 B: Good if 3 <ΔE ≦ 6 C: Practical problem if 6 <ΔE ≦ 9 D: Bad if 9 <ΔE

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this does not limit this invention at all. In addition, “part” representing the blending amount means “part by mass”.

<Manufacture of binder resin>

(Example of hybrid resin production)
As a monomer for a vinyl polymer unit, styrene 2.0 mol, 2-ethylhexyl acrylate 0.21 mol, fumaric acid 0.14 mol, α-methylstyrene dimer 0.03 mol, a crosslinking agent and a polymerization initiator Add 0.05 mol of dicumyl peroxide into the dropping funnel. Moreover, as a monomer of the polyester resin unit, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (3.0 mol), terephthalic acid (3.0 mol), trimellitic anhydride (1.9 mol), fumaric acid (5.0 mol) and dibutyltin oxide (0.2 g) were placed in a glass 4-liter four-necked flask. A thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater.
Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 145 ° C., the monomer for the vinyl polymer unit, the crosslinking agent and the polymerization from the previous dropping funnel The initiator was added dropwise over 4 hours. Next, the temperature was raised to 200 ° C. and reacted for 4 hours to obtain a hybrid resin. The physical property values are shown in Table 1.

(Example of polyester resin production)
3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.6 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.7 mol of terephthalic acid, 1.4 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.12 g of dibutyltin oxide are put into a 4-liter 4-neck flask made of glass, a thermometer, a stirring rod, a condenser and a nitrogen introducing tube. Was installed in a mantle heater. Under a nitrogen atmosphere, reaction was performed at 215 ° C. for 5 hours to obtain a polyester resin. The physical property values are shown in Table 1.

(Example of styrene-acrylic resin production)
・ Styrene 70 parts ・ N-butyl acrylate 24 parts ・ Monobutyl maleate 6 parts ・ Di-tert-butyl peroxide 1 part

While stirring the inside of a four-necked flask containing 200 parts of xylene, the above components were thoroughly substituted with nitrogen, and the temperature was raised to 120 ° C., followed by dropwise addition over 3.5 hours. Further, the polymerization was completed under reflux of xylene, and then the solvent was distilled off under reduced pressure to obtain a styrene-acrylic resin. The physical property values are shown in Table 1.

<Manufacture of yellow toner A>
A paste-like pigment having a solid content of 30% by mass (remaining 70% by mass) was obtained by removing water to some extent from the pigment slurry containing 70 parts by mass of the hybrid resin and P.Y74, and without passing through the drying process. A water-containing yellow masterbatch is prepared using 100 parts by weight of water.

(First kneading step-Creation of hydrous yellow master batch-)
First, the above raw materials are charged into a kneader-type mixer, and the temperature is raised under non-pressurization while mixing. When the maximum temperature (in this case, about 80 to 100 ° C.) is reached, the pigment in the aqueous phase is distributed or transferred to the molten resin phase, and after confirming this, the mixture is heated and melt-kneaded for 15 minutes at 90 to 100 ° C. The pigment in the paste is sufficiently transferred. Thereafter, the mixer was once stopped, the hot water was discharged, the water was distilled off by mixing for 10 minutes without heating, the mixture was cooled, and pulverized to about 1 mm by pin mill pulverization to obtain a hydrous yellow master batch A. . This water-containing yellow masterbatch A had a water content of 15% by mass, a pigment content of 30% by mass and a resin content of 55% by mass.
Next, the second kneading step was performed by the following method to produce yellow toner A.

-Hybrid resin 86.25 parts by mass-Purified normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Hydrous yellow masterbatch A (pigment content 30 parts by mass) %) 25 parts by mass

Preliminarily mixed with a Henschel mixer with the above formulation, melt-kneaded so that the temperature of the kneaded product becomes 120 ° C. with a twin-screw extruder kneader, coarsely pulverized to about 1-2 mm using a hammer mill after cooling, Subsequently, it was finely pulverized to a particle size of 20 μm or less by an air jet type fine pulverizer. Further, yellow particles (classified product) were obtained from the finely pulverized product using a classifier (elbow jet classifier).
To 100 parts by mass of the yellow particles, 1.2 parts by mass of acicular titanium oxide fine powder (MT-100T: manufactured by Teica, BET = 62, isobutyltrimethoxysilane 10 wt% treatment) was externally added by a Henschel mixer. Yellow toner A was obtained. The weight average diameter of yellow toner A is 7.0 μm, and the values of L *, a *, and b * measured in the powder state are L * = 89, a * = − 5.1, and b * = It was 112.7. Further, yellow toner A and magnetic ferrite carrier particles (average particle size 45 μm: Mn—Mg ferrite) surface-coated with a silicone resin are mixed so that the toner concentration becomes 7.0% by mass, and two-component development is performed. Agent A was designated.
With this developer A, an image was created on OHP using a modified machine from which the oil application mechanism of the fixing unit of the color copying machine CLC-1000 (manufactured by Canon) was removed, and OHP transparency was evaluated. The rate was very excellent at 91%. The evaluation results are shown in Table 2.

尚、表２中、マスターバッチをＭＢと表記する。

In Table 2, the master batch is expressed as MB.

<Manufacture of yellow toner B>
Hydrous yellow as in the hydrous yellow masterbatch A, except that 20 parts by weight of P.Y74 in powder, 10 parts by weight of S.Y162 in powder, and 20 parts by weight of distilled water were used. Yellow was obtained in the same manner as yellow toner A except that master batch B (water content: 15% by mass, pigment content: 30% by mass, resin content: 55% by mass) was obtained, and then hydrous yellow master batch B was used. Toner B was prepared. As a result of various evaluations, as shown in Table 2, the OHP permeability was also good.

<Manufacture of yellow toner C>
70 parts by mass of polyester resin, PY Water was removed to some extent from the pigment slurry containing 180, and 100 parts by mass of a paste-like pigment having a solid content of 30% by mass (with the remaining 70% by mass being water) obtained without passing through the drying process once. In the same manner as in the water-containing yellow master batch A, a water-containing yellow master batch C (water content: 15% by mass, pigment content: 30% by mass, resin content: 55% by mass) was obtained. Next, yellow toner C was prepared in the same manner as yellow toner A, except that hydrous yellow masterbatch C was used.
Next, a yellow toner C was produced in the same manner as the yellow toner A except that the following materials were used in the second kneading step.

-Polyester resin 83.5 parts by mass-Purified normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Hydrous yellow masterbatch C (pigment content 30 parts by mass) %) 30 parts by mass

  As a result of various evaluations of the obtained yellow toner C, as shown in Table 2, the OHP permeability was slightly deteriorated, but it was a level with no problem.

<Manufacture of yellow toner D>
Using 70 parts by mass of styrene acrylic resin and 30 parts by mass of P.Y. 17 powder, charged into a kneader-type mixer, the temperature was raised under pressure without mixing, and the mixture was melted and kneaded at 90 to 110 ° C. for 30 minutes. To fully transfer the pigment. Then, it was cooled and pulverized to about 1 mm by pin mill pulverization to obtain a dry yellow masterbatch D (water content: 0.4% by mass).
Next, yellow toner D was produced in the same manner as yellow toner A, except that the following materials were used in the second kneading step.

Styrene acrylic resin 79 parts by mass Refined normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass 1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass Dry yellow masterbatch D (pigment content 30% by mass) ) 30 parts by mass

  As a result of various evaluations on the obtained yellow toner D, the dispersion state of the pigment in the toner was poor, the L * value in the powder state was low as shown in Table 2, and the OHP permeability was considerably poor. It was.

<Manufacture of magenta toner E>
PR Water was removed to some extent from the pigment slurry containing 122, 67 parts by weight of a paste-like pigment having a solid content of 30% by weight (the remaining 70% by weight of water) obtained without passing through the drying process, R. Water was removed to some extent from the pigment slurry containing 150, and 33 parts by mass of a paste-like pigment having a solid content of 30% by mass (with the remaining 70% by mass being water) obtained without passing through the drying process once. In the same manner as in the water-containing yellow masterbatch A, a water-containing magenta masterbatch E (water content: 2% by mass, pigment content: 30% by mass, resin content: 68% by mass) was obtained.
Next, magenta toner E was produced in the same manner as yellow toner A except that the following materials were used in the second kneading step.

-Hybrid resin 83 parts by mass-Purified normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Hydrous magenta masterbatch E (pigment content 30% by mass) 25 parts by mass

  The obtained magenta toner E was evaluated in various ways. As shown in Table 2, the OHP permeability was also good.

<Manufacture of magenta toner F>
70 parts by mass of hybrid resin, 30 parts by mass of powder P.R57: 1, and distilled water 2
Using 0 parts by mass, the mixture is charged into a kneader-type mixer, heated under non-pressurization while mixing, and melted and kneaded at 90 to 110 ° C. for 30 minutes to sufficiently transfer the pigment. Then, it was cooled and pulverized to about 1 mm by pin mill pulverization to obtain a dry magenta master batch F (water content: 0.2% by mass).
Next, magenta toner F was produced in the same manner as yellow toner A, except that the following materials were used in the second kneading step.

-Hybrid resin 88.1 parts by mass-Purified normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Dried magenta masterbatch F (pigment content 30 parts by mass) %) 17 parts by mass

  As a result of various evaluations of the obtained magenta toner F, as shown in Table 2, the OHP permeability was also good.

<Manufacture of magenta toner G>
70 parts by mass of polyester resin, 30 parts by mass of powdered P.R122, and 20 distilled water
Using a part by mass, the mixture is charged into a kneader-type mixer, heated with no pressure while mixing, and melted and kneaded at 90 to 110 ° C. for 30 minutes to sufficiently transfer the pigment. Then, it was cooled and pulverized to about 1 mm by pin mill pulverization to obtain a dry magenta master batch G (water content: 0.2% by mass).
Next, a magenta toner G was produced in the same manner as the yellow toner A except that the following materials were used in the second kneading step.

Polyester resin 79 parts by mass Refined normal paraffin (maximum endothermic peak temperature 78 ° C.) 4 parts by mass 1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass Dry magenta master batch G (pigment content 30% by mass) 30 parts by mass

  As a result of various evaluations of the obtained magenta toner G, as shown in Table 2, it was a slightly bluish magenta color, and the OHP permeability was slightly deteriorated, but it was at a level causing no problem.

<Manufacture of magenta toner H>
Using 70 parts by mass of hybrid resin and 30 parts by mass of powdered P.R53: 1, charging into a kneader-type mixer, heating the mixture under pressure without mixing, and heating and kneading at 90 to 110 ° C. for 30 minutes To fully transfer the pigment. Then, it was cooled and pulverized to about 1 mm by pin mill pulverization to obtain a dry magenta master batch H (water content: 0.15% by mass).
Next, magenta toner H was produced in the same manner as yellow toner A, except that the following materials were used in the second kneading step.

-Hybrid resin 79 parts by mass-Purified normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Dried magenta masterbatch H (pigment content 30% by mass) 30 parts by mass

  As a result of various evaluations of the obtained magenta toner H, the dispersion state of the pigment in the toner was poor, the L * value in the powder state was low as shown in Table 2, and the OHP permeability was considerably poor. It was.

<Manufacture of Cyan Toner I>
P.B. Water was removed to some extent from the pigment slurry containing 15: 3, and 100 parts by mass of a paste-like pigment having a solid content of 30% by mass (the remaining 70% by mass of water) obtained without going through a drying process was used. Except for the above, a water-containing cyan master batch I (water content: 2.2% by mass, pigment content: 30% by mass, resin content: 67.8% by mass) was obtained in the same manner as the water-containing yellow master batch A. .
Next, cyan toner I was produced in the same manner as yellow toner A, except that the following materials were used in the second kneading step.

-Hybrid resin 91 parts by mass-Refined normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Hydrous cyan master batch I (pigment content 30% by mass) 13.3 parts by mass

  As a result of various evaluations of the obtained cyan toner I, as shown in Table 2, the OHP permeability was also good.

<Manufacture of cyan toner J>
70 parts by mass of polyester resin, 30 parts by mass of powdered P.B15: 3, and distilled water 2
Using 0 parts by mass, the mixture is charged into a kneader-type mixer, heated under non-pressurization while mixing, and melted and kneaded at 90 to 110 ° C. for 30 minutes to sufficiently transfer the pigment. Then, it was cooled and pulverized to about 1 mm by pin mill pulverization to obtain a dry cyan master batch J (water content: 0.3% by mass).
Next, cyan toner J was produced in the same manner as yellow toner A, except that the following materials were used in the second kneading step.

Polyester resin 90.9 parts by mass Refined normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass 1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass Dry cyan master batch J (pigment content 30 parts by mass) %) 13 parts by mass

  As a result of various evaluations of the obtained cyan toner J, as shown in Table 2, the OHP permeability was slightly deteriorated, but it was a level with no problem.

<Manufacture of cyan toner K>
Using 70 parts by weight of styrene acrylic resin, 15 parts by weight of powdered P.R53: 1 and 15 parts by weight of powdered P.G7, charged into a kneader-type mixer and heated up under pressure without mixing. Then, the mixture is heated, melted and kneaded at 90 to 110 ° C. for 30 minutes to sufficiently transfer the pigment. Then, it was cooled and pulverized to about 1 mm by pin mill pulverization to obtain a dry cyan master batch K (water content: 0.2% by mass).
Next, cyan toner K was produced in the same manner as yellow toner A, except that the following materials were used in the second kneading step.

-Styrene acrylic resin 86 parts by mass-Purified normal paraffin (maximum endothermic peak temperature 78 ° C) 4 parts by mass-1,4-di-t-butylsalicylic acid aluminum compound 1 part by mass-Dried cyan masterbatch K (pigment content 30% by mass) 20 parts by mass

  As a result of various evaluations of the obtained cyan toner K, the dispersion state of the pigment in the toner is poor, and as shown in Table 2, the L * value in the powder state is low, and the toner is a very green toner. The permeability was also very bad.

< Examples 1-3 and 5 and Reference Example 4 >
The color toner combinations shown in Table 3 were evaluated for the saturation of the secondary color in the N / N environment and the color difference between the N / L and H / H environments. As a result, as shown in Tables 3 and 4, the saturation of each secondary color was close to that of the process ink and was a vivid image. Also, the color difference between environments was very good.

尚、表３及び表４中、イエローをＹ、マゼンタをＭ、シアンをＣと表記する。

In Tables 3 and 4, yellow is represented as Y, magenta as M, and cyan as C.

< Examples 6 to 7 and Reference Example 8 >
The same evaluation as in Example 1 was performed with the combination of color toners shown in Table 3, and the results are shown in Tables 3 and 4. As a result, although the saturation in Example 6 and the color difference between environments in Examples 7 and 8 were slightly worse, they were at a level causing no practical problems.

<Comparative Examples 1-3>
The same evaluation as in Example 1 was performed with the combination of color toners shown in Table 3, and the results are shown in Tables 3 and 4. As a result, the saturation of the secondary color was not sufficient, and in addition, the color difference between environments was large.

<Comparative example 4>
The same evaluation as in Example 1 was performed with the combination of color toners shown in Table 3, and the results are shown in Tables 3 and 4. As a result, the saturation of the secondary color and the level of color difference between environments were also very bad.

Claims (4)

In a full color toner kit composed of at least a binder resin, a colorant, and a wax-containing yellow toner, cyan toner, and magenta toner, when the toner in a powder state is measured under the condition of a C light source with a double field of view,
(I) a yellow toner having lightness L * and hue b * of 87 <L * and 106 <b * <120 and containing pigment yellow 74 as a colorant ;
(Ii) magenta toner in which values of lightness L * and hue a * are 35 <L * <45 and 60 <a *;
(Iii) A full-color toner kit comprising cyan toners having lightness L * and hue b * values of 35 <L * <45 and −40> b *. In a full color toner kit composed of at least a binder resin, a colorant, and a wax-containing yellow toner, cyan toner, and magenta toner, when the toner in a powder state is measured under the condition of a C light source with a double field of view,
(Iv) yellow toner having a hue a * value of −15 <a * <5;
(V) a magenta toner having a hue b * value of −10 <b * <15;
The full-color toner kit according to claim 1, further comprising (vi) a cyan toner having a hue a * value of −10 <a * <0.   The full-color toner kit according to claim 1, wherein the binder resin contains at least a polyester unit. The yellow toner comprises a colorant masterbatch having a water content of 1 to 25% by mass obtained by heating and mixing a first binder resin, a colorant, and water, a second binder resin, and a wax. The full-color toner kit according to any one of claims 1 to 3, wherein the toner is a toner produced by at least melting and kneading to obtain a kneaded product and pulverizing the obtained kneaded product .