JP2010054926A - Full-color toner set - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner set for forming a full-color image, capable of broadening a color reproduction region of RGB and reproducing colors close to the region of AdobeRGB, so as to faithfully reproduce manuscript data. <P>SOLUTION: A full-color toner set is provided, containing a polyester resin having an acid number of less than 10 KOHmg/g and a pigment component and comprising a positive charging magenta toner, a positive charging cyan toner, a positive charging yellow toner and a positive charging black toner, and characterized in that: a pigment component used in the magenta toner comprises a metal lake compound of a rhodamine dyestuff; the pigment component used in the cyan toner comprises a copper phthalocyanine compound developing indigo blue and a copper phthalocyanine compound developing green; and the pigment component used in the yellow toner comprises a monoazo yellow compound or a disazo yellow compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a full-color toner used for developing an electrostatic latent image in an electronic copying machine, a laser beam printer, or the like in which an image is formed using an electrophotographic method, an electrostatic recording method, or the like. More specifically, the present invention relates to a full-color toner for electrophotography having excellent color reproduction with high saturation, excellent copy quality, durability and stability.

  As a method for forming a full color image using an electrophotographic method, there are an analog method and a digital method. For example, in order to form a full color image by electrophotography using a digital method, the following steps are usually taken. That is, first, a color original is color-separated and read using R (red), G (green), and B (blue) color filters, and an electrostatic latent image corresponding to one color of the color-separated image is exposed. In order to form on the body, the charged photoreceptor is exposed to a laser beam corresponding to the color separation image, and the formed electrostatic latent image is represented by C (cyan), M (magenta), Y (yellow), Further, if necessary, the toner image is temporarily transferred to the intermediate transfer member after developing with one of the B (black) toners and a toner of a color corresponding to the color separation image. The photoreceptor to which the toner of one color has been transferred is cleaned, neutralized and then charged again. Further, the above steps are sequentially repeated to form a full-color toner image on the intermediate transfer member. Finally, the full-color toner image formed on the intermediate transfer member is transferred to a transfer material, and a copy is obtained by heating or heating and pressure fixing. As a transfer material for forming a color image, a synthetic resin film is also used for overhead projectors (OHP) in addition to paper. In recent years, the speed of full-color copying has progressed, and tandem developing devices (four stations) have become mainstream.

The IT revolution that began in the 1990s has led the environment surrounding the printing site to the direction of digitization remarkably, and with this digitization, the workflow of conventional printing methods (shooting and shooting)
(Position, Scan, Data, Design, EPS, Imposition, Film, Plate, Printing) was a multi-step process, but it was dramatically shortened with digital camera shooting, DTP, CTP, and printing. Succeeded in doing. As a result, “RGB” conversion of the submitted data is being standardized, and the current situation is that the data to be handled is shifting to a wider color reproduction region.

  However, the output of four process toners of yellow, magenta, cyan, and black, which are currently used in full-color printers and copiers based on electrophotography, is a hue due to subtractive color mixing. The hue becomes turbid, and the color reproduction region is inevitably narrower than that of RGB, and the difference in color reproducibility between the digital data and the output image becomes a problem. In particular, when yellow toner, which is generally developed as the final color of full-color development, is opaque, it causes yellow fogging and has a large effect on each color of underprinting toner. Therefore, yellow toner should be as transparent as possible. It is desirable to obtain secondary and tertiary colors without turbidity when overprinted with other colors.

  In image formation using such a color toner, the toner has good chargeability, fluidity, durability, transferability, etc., as in the formation of a black and white image, under any environment. In addition to the requirement that a high-quality toner image can always be formed even when a large number of sheets are continuously copied, it is also required that the color image has good color reproducibility. The color reproducibility of the toner is influenced by the dispersibility of the pigment component in the binder resin, in addition to the hue, saturation, and color separation reflection characteristics of the pigment component used.

In the output by offset printing, as a means for solving the above problems, a printing method using 5-7 color ink sets as a high-saturation printing system has been established, and as a printing method using ink sets having respective specified hues In addition, 6 colors (hexachrome printing) in which orange and green are added to four process colors and 7 colors (high fidelity printing) in which orange, green and purple are added to four process colors have been established. (See Patent Document 1)
Studies have been made to obtain a wide range of image reproduction even with full-color toners. In Patent Document 2, a favorable color developability is obtained by combining a cyan toner using phthalocyanine, a magenta toner using rhodamine 6G basic xanthene silicomolybdate, a yellow toner using diazobenzidine, and a black toner using carbon black. Although it was obtained, the balance of the combination of the three colors was poor, so the saturation of the printed matter was low, the color reproduction area was not sufficient, and the Japan color reproduction area could not be obtained. (See Patent Document 2)
Also, a combination of cyan toner using phthalocyanine, magenta toner using naphthol carmine F6B, and yellow toner using benzimidazolone has been studied, but with this combination, the blue and green color reproduction areas are at satisfactory levels. It was not possible to obtain a Japan color reproduction area. (Patent Document 3)
In addition, cyan toner containing a mixture of indigo phthalocyanine pigment and green phthalocyanine pigment has been studied. I. Yellow toner using C.I. Pigment Yellow 17 and C.I. I. Since it was a magenta toner using Pigment Red 122 quinacridone pigment, the blue reproduction region was not satisfactory, and the Japan color reproduction region could not be obtained. (Patent Document 4)
JP 2001-260516 A JP-A-9-171268 JP 2001-312102 A JP-A-5-72810

  In view of such a current situation, the present invention faithfully reproduces the input data, so that the color reproduction area of RGB is expanded, and a toner for full-color image formation that can achieve color reproduction close to the area of AdobeRGB (trademark of Adobe Systems). The purpose is to provide a set. Specifically, it has excellent color reproducibility of the image obtained including OHP color reproducibility, excellent chargeability, no toner scattering in the machine, no problems such as fluidity, offset resistance and blocking, and An object of the present invention is to provide a full-color toner set capable of stably obtaining a high-quality developed image over a long period of time.

As a result of intensive studies to solve the above problems, the present inventors have found that a positively chargeable magenta toner containing a metal lake compound of a rhodamine dye as a pigment component, and containing at least two phthalocyanine copper compounds as a pigment component Forming a good full-color image by using a full-color toner set comprising a positively-charged yellow toner and a positively-charged black toner containing a positively-charged cyan toner, a monoazo yellow compound or a disazo yellow compound as pigment components The present invention has been made by finding that it is possible.

That is, the present invention relates to the following inventions (1) to (11).
(1) A positively chargeable magenta toner, a positively chargeable cyan toner, a positively chargeable yellow toner, and a positively chargeable black toner containing at least a polyester resin having an acid value of less than 10 KOHmg / g and a pigment component. In the full color toner set, the pigment component used for the magenta toner is a metal lake compound of a rhodamine dye, and the pigment component used for the cyan toner is at least a phthalocyanine copper compound exhibiting an indigo color and a phthalocyanine copper compound exhibiting a green color. And a pigment component used in the yellow toner is a monoazo yellow compound or a disazo yellow compound.
(2) In the pigment component used for the positively chargeable cyan toner, the weight ratio of the phthalocyanine copper compound exhibiting indigo color to the phthalocyanine copper compound exhibiting green color (indigo color: green) is in the range of 100: 2 to 100: 20. A (1) full color toner set.
(3) The rhodamine dye metal lake compound used for the positively chargeable magenta toner is C.I. I. Pigment red 81 or C.I. I. The full color toner set of (1) or (2), which is CI Pigment Red 169.
(4) A phthalocyanine copper compound exhibiting an indigo color is C.I. I. The full color toner set according to any one of (1) to (3), which is CI Pigment Blue 15: 3.
(5) A phthalocyanine copper compound exhibiting a green color is C.I. I. The full color toner set of any one of (1) to (4), which is CI Pigment Green 7.
(6) The full-color toner set according to any one of (1) to (5), wherein the pigment component used for the positively chargeable black toner is composed of carbon black and a pigment component exhibiting an indigo color as a complementary color.
(7) In the pigment component used for the positively chargeable black toner, the weight ratio of carbon black to the pigment component exhibiting a deep blue color (carbon black: deep blue pigment) is in the range of 100: 0.5 to 100: 20. (6) Full color toner set.
(8) The monoazo yellow compound used for the positively chargeable yellow toner is C.I. I. Pigment yellow 74 or C.I. I. The full color toner set of any one of (1) to (7), which is CI Pigment Yellow 12.
(9) The relationship among the pigment component content ratio (Y) in the positively chargeable yellow toner, the pigment component content ratio (C) in the cyan toner, and the pigment component content ratio (M) in the magenta toner is Y <C. <Full-color toner set according to any one of (1) to (8) satisfying the relationship of M.
(10) The relationship between the content ratio (Y) of the pigment component in the positively chargeable yellow toner, the content ratio (C) of the pigment component in the cyan toner, and the content ratio (M) of the pigment component in the magenta toner is as follows: ) To (c) satisfy all of the conditions (1) to (9).
(A) Y <C, and satisfies the relationship of 0.5xC ≦ Y ≦ 0.9xC.
(B) Y <M, and satisfies the relationship of 0.3xM ≦ Y ≦ 0.7xM.
(C) C <M, and satisfies the relationship of 0.6 × M ≦ C ≦ 0.9 × M.
(11) An image forming method for obtaining a full color image using the full color toner set according to any one of (1) to (10).

  By using the full color toner set provided by the present invention, it is possible to reproduce colors in an area close to Adobe RGB (trademark of Adobe Systems, Inc.) that could not be reproduced with conventional full color toners, and the color reproducibility is greatly improved. A special image can be stably formed over a long period from the beginning of development. In the full color toner set of the present invention, since a fluorescent pigment is not used as a means for improving the color reproduction region, a full color image with high saturation can be obtained without deteriorating the fading of the full color image over time.

Hereinafter, the present invention will be described in more detail.
The present invention is a full color comprising at least four colors: a polyester resin having an acid value of less than 10 KOHmg / g, a positively charged yellow toner containing a pigment component, a positively charged magenta toner, a positively charged cyan toner, and a positively charged black toner. A toner set comprising a monoazo yellow compound or disazo yellow compound as a pigment component in a yellow toner, a metal lake compound of a rhodamine dye as a pigment component in a magenta toner, and a phthalocyanine copper compound exhibiting at least an indigo color as a pigment component in a cyan toner And a phthalocyanine copper compound exhibiting a green color.

 The effect of combining three colors of yellow toner, magenta toner, and cyan toner is very large. By using these three colors in combination, the color reproduction range of a regular hue (JapanColor, etc.) is wider, and AdobeRGB. (American Systems, Inc., USA) Color reproduction over the vicinity of the reproduction area is possible. By combining these yellow, magenta and cyan color toners, the color balance is adjusted, the area of the gamut is maximized, and a full color image with a wide color reproduction region can be obtained.

  Originally, the yellow component was inferior in the reproducibility of green, orange and red, though the conventional toner had a level close to the reproduction region of AdobeRGB and RGB as a single unit. For the first time, the above-described combination of the present invention makes it possible to widen the reproduction region of green, orange, red, purple, and blue.

  By using the cyan toner in combination with the indigo color component and the green color component, it becomes possible to reach the Adobe RGB region beyond the Japan color region in reproducing the green region. Further, the use of a magenta toner containing a cyan lake and a metal lake compound of a rhodamine dye as a pigment component makes it possible to widen the violet reproduction region of the mixed color.

  The use of a single pigment component such as CI Pigment Blue 15: 3, which is a phthalocyanine copper compound exhibiting the indigo color used in conventional cyan toners, produces a regular hue in normal printing in color reproduction in the green region. (JapanColor etc.) could only reproduce colors in the range, but adding a phthalocyanine copper compound exhibiting a green color to a phthalocyanine copper compound exhibiting an indigo color, preferably using a phthalocyanine copper compound exhibiting a green color indigo. By adding 2 to 20 parts by weight with respect to 100 parts by weight of the color component, it becomes possible to reproduce the color up to the vicinity of the AdobeRGB reproduction area that could not be reproduced with a regular hue (Japan Color, etc.). However, if magenta toner and yellow toner are not used together in the combination of the present invention, the green component becomes strong, the reproduction of orange and the reproduction of purple are deteriorated, and partly inferior to the conventional color reproduction range.

  Such a wide combination of wide color reproduction regions can be achieved by using these three types of yellow toner, cyan toner, and magenta toner. If even one type is missing, color reproduction is inferior. On the contrary, the balance is lost, and the difference from the conventional regular hue is not seen.

  In the present invention, the content ratio of the pigment component is a weight ratio of the pigment component to the whole toner of each color.

  The content ratio of the pigment component contained in the full color toner of the present invention is as follows: content ratio of pigment component in yellow toner (Y) <content ratio of pigment component in cyan toner (C) <content ratio of pigment component in magenta toner The relationship (M) is preferable.

  The ratio of the magenta toner having the largest pigment component greatly contributes to the color reproduction of the purple region, and contributes to maintaining the reproduction of the red region wider than the regular hue and balancing the gamut.

By making the content ratio of the pigment component of the yellow toner relatively low, yellow transparency can be obtained, and the film thickness of the yellow toner component can be increased (the amount of adhesion is increased) when outputting a desired image density. . Increasing the film thickness of the yellow toner component greatly contributes to the combination with cyan toner and magenta toner, and has the effect of balancing and consequently expanding the gamut. More preferable blending of the pigment component is when the following conditions (a) to (c) are satisfied.
(A) Y <C, and 0.5xC ≦ Y ≦ 0.9xC
(B) Y <M, 0.3xM ≦ Y ≦ 0.7xM
(C) C <M and 0.6 × M ≦ C ≦ 0.9 × M
When the content ratio of the pigment component in the cyan toner is 1 (relative value), the content ratio of the pigment component in the yellow toner is preferably 0.5 to 0.9. If the ratio is smaller than 0.5, the transparency of the yellow toner can be obtained, but it becomes difficult to reproduce the green color. If the ratio is larger than 0.9, the transparency of the yellow toner cannot be obtained, and the purple reproduction area becomes narrow. End up. If the content ratio of the pigment component in the magenta toner is 1 (relative value), the content ratio of the pigment component in the cyan toner is preferably 0.6 to 0.9. Outside this range, the purple reproduction area becomes narrow. When the content ratio of the pigment component in the magenta toner is 1 (relative value), the content ratio of the pigment component in the yellow toner is preferably 0.3 to 0.7. Outside this range, the red reproduction area becomes narrow.

  As a method for expressing the color reproduction area, an XYZ color system (CIE1931 color system), an X10Y10Z10 color system (CIE1964 color system), an L * a * b * color system (CIE1976), a Hunter Lab color system, Munsell color system, L * u * v * color system (CIE1976), and the like.

  In the L * a * b * color system, “brightness” is expressed by L * as the degree of brightness that can be compared regardless of hue, and indicates that the color becomes brighter as L * increases and becomes darker as it decreases. . In addition, “hue” that differs depending on each color is indicated by a * and b * values, a * indicates a red (+) to green (−) direction, and b * indicates a yellow (+) to blue (−) direction, In each direction, the color becomes brighter as the absolute value increases, and the color becomes dull as it approaches 0. This makes it possible to digitize one color using L *, a *, and b *. In addition to “lightness” and “hue”, there is “saturation (C)” as a method for digitizing the degree of vividness, which can be obtained by the following calculation formula (see the examples). Similarly, C shows that the color becomes brighter as the absolute value increases, and the color becomes dull as the value decreases.

  All color reproduction areas that can be represented by a single printed matter or printed matter (including color spaces other than printed matter) are called color rendering regions (gamut). The simplest way to represent gamut is a * on the horizontal axis and b *. In a two-dimensional space with a vertical axis, a solid color solid part (yellow, red, indigo) and a solid solid color overprinted part (yellow x red, red x indigo, indigo x yellow), a total of 6 colors a * vs b * Values can be expressed as plotted hexagonal areas. The larger the gamut area, the wider the color reproduction area.

The full color toner set in the present invention is a combination of toners that are not mixed together, and each toner exists as a separate composition. Each color toner, and in some cases, a developer is used in a full color copying machine, a printer, a developer for each color, and a pigment used for a yellow toner used in the full color toner set of the present invention. The component is a monoazo yellow compound or a disazo yellow compound.

 The monoazo yellow compound is specifically an acetoacetyl allylide monoazo pigment, which is represented by the chemical formula (X).

〔式中、Ｒ³はアルキル基、アルコキシ基またはニトロ基を示し、Ｒ⁴はハロゲン原子、アルキル基、アルコキシ基、カルボキシ基、ニトロ基、芳香族で置換されたスルファモイル基、またはＣａ、Ｂａ、Ｍｎ、Ｓｒ等の金属で置換されたスルホ基を示す。Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸は同一または異なって水素原子、ハロゲン原子、アルキル基またはアルコキシ基を示す。〕で表されるものである。

[Wherein R ³ represents an alkyl group, an alkoxy group, or a nitro group, and R ⁴ represents a halogen atom, an alkyl group, an alkoxy group, a carboxy group, a nitro group, an aromatic-substituted sulfamoyl group, or Ca, Ba, A sulfo group substituted with a metal such as Mn or Sr is shown. R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. ] Is represented.

 Specific examples of monoazo yellow pigments include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 130, C.I. I. Pigment yellow 133, and C.I. I. Pigment yellow 169 and the like.

  Among them, C.I. I. Pigment yellow 74, C.I. I. Pigment Yellow 73 is preferably used. As a complementary color of this monoazo yellow pigment, C.I. I. It is also possible to use Pigment Yellow 83 by adding 0.5 to 10%, preferably 2 to 5% of the above yellow pigment.

  Disazo yellow compounds include C.I. I. Pigment yellow 12 or C.I. I. Pigment Yellow 13 can be used. As a complementary color of these pigments, C.I. I. It is also possible to use Pigment Yellow 83 by adding 0.5 to 10%, preferably 2 to 5% of the above yellow pigment.

  In the positively chargeable yellow toner used in the present invention, when the image is printed on the black toner printed in the range of 1.85 to 1.90 with the density of 1.40 to 2.10, the L * If the transparency does not exceed 17, the influence on the underprinting toner when the secondary color and tertiary color are overprinted is small, and a good color reproduction region can be obtained.

 The pigment component used in the positively chargeable magenta toner used in the full color toner set of the present invention is a metal lake compound of a rhodamine dye such as rhodamine B, rhodamine 3G, or rhodamine 6G.

 The rhodamine dye is a basic system containing an amino group of a xanthene dye and has a unique bright red color. However, in spite of having its own color tone, light resistance and heat resistance are very poor like general dyes, and when used as a toner for an electrophotographic apparatus, the dye component is eluted, and the photosensitive member, fixing device, etc. There is a problem that the inside of the apparatus is contaminated or the toner aggregates in a high temperature and high humidity environment. For this reason, the dyes are raked in order to remedy the drawbacks of these dyes.

  Precipitating agents for lake-loading rhodamine dyes include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, complex acid (phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, And silicotungsto molybdic acid). Of these, lake pigments made of complex acid are preferable because of significantly improved light resistance.

 Specific examples of rhodamine dye metal lake compounds include CI Pigment Red 81, CI Pigment Red 81: 1, CI Pigment Red 81: 2, CI Pigment Red 81: 3, and C.I. CI Pigment Red 81: 4, CI Pigment Red 169, CI Pigment Violet 1, CI Pigment Violet 1: 1, CI Pigment Violet 1: 2, CI Pigment Violet 2 etc. are raised.

  Among them, C.I. I. Pigment red 81, C.I. I. It is preferable to use CI Pigment Red 169.

 And C.I. I. Pigment red 81, C.I. I. As a complementary color of the pigment of Pigment Red 169, C.I. I. It is also possible to use Pigment Violet 1 by adding 0.5 to 10%, preferably 2 to 5% of the magenta pigment.

  The pigment components used in the positively chargeable cyan toner used in the full color toner set of the present invention are at least a phthalocyanine copper compound exhibiting an indigo color and a phthalocyanine copper compound exhibiting a green color.

 Indigo-colored phthalocyanine copper compounds are substances exhibiting crystal polymorphism (homogeneous heterocrystals), and are classified into α, β, γ, ε, π, τ, ρ, χ, R types, etc., depending on the crystal structure. However, it is preferable to use a β-type having excellent crystal stability and dispersibility. Specifically, C.I. I. CI pigment blue 15: 3 and CI pigment blue 15: 4 are preferable.

The copper phthalocyanine compounds which exhibit deep blue has a specific surface area in the range of 74m ² / g~300m ² / g. If it is smaller than 74 m ² / g, it is difficult to obtain a sufficient image density, and good color reproduction cannot be achieved. On the other hand, if it exceeds 300 m ² / g, the pigment tends to aggregate and dispersion becomes difficult.

  The green phthalocyanine copper compound is a halogenated copper phthalocyanine compound in which a hydrogen atom on the benzene ring of a phthalocyanine molecule is substituted with a halogen compound. I. CI pigment green 7, CI pigment pigment green 36, CI pigment pigment green 58, and the like can be used. Among them, C.I. I. Pigment Green 7 is preferable.

 In the present invention, by using 2 to 20%, more preferably 3 to 15% of a phthalocyanine copper compound exhibiting a green color to a phthalocyanine copper compound exhibiting an indigo color, the color reproduction region of a cyan toner single color is impaired. In addition, it is possible to widen the color reproduction areas of green and purple when printed with yellow toner and magenta toner. Specifically, it is preferable to add CI Pigment Green 7 to CI Pigment Blue 15: 3 or CI Pigment Blue 15: 4 from the viewpoint of good color reproducibility. .

  As the positively chargeable black toner, a magnetic toner or a nonmagnetic toner is used depending on the process design. If the toner is a nonmagnetic toner, three kinds of pigment components of yellow, magenta, and cyan are mixed or used. If it is carbon black or magnetic toner, magnetic powder can be used.

  Black toner is used not only for black printing, but also as a complementary color of yellow, magenta, and cyan, and is used by adding an indigo component to the black pigment component in order to give the printed image a black feeling. It is preferable to do. The black colorant containing indigo color can highlight a shadow portion in a printed matter and obtain a vivid image. In the full color toner set of the present invention, it is preferable to use carbon black in the black toner for blending with the cyan component pigment preferably and uniformly.

  It is preferable to add 0.5 to 20 parts by weight of an indigo component with respect to 100 parts by weight of carbon black, and more preferably in the range of 2 to 10 parts by weight. As the indigo color component, any indigo color pigment can be used, but it is usually preferable to use CI pigment blue 15: 3 and CI pigment blue 15: 4.

  When the positively chargeable black toner is a magnetic toner, the usable magnetic material may be any alloy or compound containing a ferromagnetic element that is conventionally used in the production of magnetic toners. Examples of these magnetic materials include iron oxides such as magnetite, maghemite and ferrite, or compounds of divalent metals and iron oxides, metals such as iron, cobalt and nickel, or aluminums of these metals, cobalt, copper, lead, Examples include alloys of metals such as magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. These magnetic materials preferably have an average particle size determined by SEM of about 0.1 to 2 μm, more preferably about 0.1 to 0.5 μm. Further, the content of the magnetic substance in the toner is about 20 to 200 parts by weight, preferably 40 to 150 parts by weight, with respect to 100 parts by weight of the binder resin. Further, the saturation magnetization of the toner is preferably 15 to 35 emu / g (measuring magnetic field: 1 kilo-Oersted). Specific examples of magnetic materials in the case of magnetic toners include EPT-500 and EPT-1000 manufactured by Toda Kogyo Co., Ltd., KBC-100, KBC-100C, KBC-200 manufactured by Kanto Denka Co., Ltd., and MRD- manufactured by Titanium Kogyo Co., Ltd. Examples include MG-RF, MG-WS, MG-CZ, MG-SL, MG-1306, MG-1307, MG-1331, etc. manufactured by Mitsui Mining & Mining Co., Ltd.

  As the polyester resin used in the full-color toner of the present invention, those exhibiting colorless, white or light color are preferable so as not to disturb the hue of the pigments of the respective colors.

 In the full color toner of the present invention, the polyester resin needs to have an acid value of less than 10 mgKOH / g. More preferably, it is preferably 3 to 9.5 mgKOH / g.

 When the acid value of the polyester resin is 10 mgKOH / g or more, the negative chargeability of the polyester resin increases, and the toner cannot function sufficiently as a positively chargeable toner. Further, when it exceeds 20 mgKOH / g, there arises a problem that the storage stability and development characteristics of the obtained toner at high temperature and high humidity are deteriorated. On the other hand, if the acid value is less than 3 mgKOH / g, the compatibility with the rosin ester is lowered, and the problem that the release agent is liberated may not be sufficiently solved.

  Defining the acid value of the polyester resin within the above range is important for controlling the charge balance of the full-color toners of yellow, magenta, and cyan. Since the rhodamine dye metal lake compound used in the magenta toner has a stable positive charge, there is no problem if the acid value of the polyester resin is 20 mg KOH / g or less. Must have an acid value of less than 10 mg KOH / g.

  In the present invention, the acid value can be measured according to the method of JIS K-0070. The acid value is represented by the number of mg of potassium hydroxide required to neutralize 1 g of toner. However, when the toner contains a magnetic substance, the residue obtained by eluting the magnetic substance with an acid is 1 g of toner.

  In the full color toner of the present invention, the alcohol component constituting the polyester resin includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2, 3-butanediol, 1,4-butenediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, bisphenol A, Hydrogenated bisphenol A, 1,4-bis (hydroxymethyl) cyclohexane, diols such as bisphenol derivatives represented by the following general formula (1), glycerol, diglycerol, sorbit, sorbitan, butanetriol, trimethylolethane Trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, polyhydric alcohols and the like can be mentioned, which are used alone or in combination of two or more.

（式中Ｒはエチレンまたはプロピレン基であり、ｘ、ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）
酸成分としては、二価のカルボン酸として、フタル酸、テレフタル酸、イソフタル酸、無水フタル酸などのベンゼンジカルボン酸類またはその無水物；コハク酸、アジピン酸、セバシン酸、アゼライン酸などのアルキルジカルボン酸類またはその無水物；またさらに炭素数１６〜１８のアルキル基で置換されたコハク酸もしくはその無水物；フマル酸、マレイン酸、シトラコン酸、イタコン酸、グルタコン酸などの不飽和ジカルボン酸またはその無水物；シクロヘキサンジカルボン酸；ナフタレンジカルボン酸；ジフェノキシエタン−２，６−ジカルボン酸等が挙げられ、架橋成分としてはたらく三価以上のカルボン酸としてはトリメリット酸、ピロメリット酸、ナフタレントリカルボン酸、ブタントリカルボン酸、ヘキサントリカルボン酸、テトラ（メチレンカルボキシル）メタン、オクタンテトラカルボン酸、ベンゾフェノンテトラカルボン酸やその無水物等が挙げられ、これらは単独で或いは２種以上の組み合わせで使用される。

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)
As the acid component, divalent carboxylic acids such as benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid Or succinic acid substituted with an alkyl group having 16 to 18 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid or the anhydride thereof; Cyclohexanedicarboxylic acid; naphthalenedicarboxylic acid; diphenoxyethane-2,6-dicarboxylic acid and the like. Trivalent or higher carboxylic acids that function as crosslinking components include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, and butanetricarboxylic acid. Acid, hexanetricarboxylic acid Tetra (methylene carboxyl) methane, octane tetracarboxylic acid, and benzophenone tetracarboxylic acid anhydride and the like, which are used alone or in combination of two or more.

  A preferred alcohol component is a bisphenol derivative represented by the general formula 1, and a preferred acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenyl succinic acid or its anhydride, fumaric acid, Dicarboxylic acids such as maleic acid and maleic anhydride, and tricarboxylic acids such as trimellitic acid or its anhydride.

  Further, as the crosslinking component of the polyester resin, in addition to using the above-described trivalent or higher carboxylic acid and trivalent or higher polyhydric alcohols, urethane cross-linking (isocyanate cross-linking) using a polyvalent isocyanate compound is also preferable. Is. The urethane-modified polyester resin can be obtained by adding a polyvalent isocyanate compound to a polyester resin and mixing and reacting them by melt kneading. The cross-linking reaction using polyvalent isocyanate is performed by addition reaction between hydroxyl group and isocyanate group in the polyester resin to obtain urethane bond, and is very reactive, especially with short reaction time in the melt-kneading process. It is a suitable compound for crosslinking to a molecular weight or increasing the molecular weight.

  The polyvalent isocyanate compound is a compound having a divalent or higher isocyanate group, and examples include diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and tetramethylene diisocyanate. .

  In the present invention, it is preferable to use a urethane-modified polyester resin because it has high mechanical strength when used as a toner and high toner durability.

  In the present invention, the acid value can be measured according to the method of JIS K-0070. The acid value is represented by the number of mg of potassium hydroxide required to neutralize 1 g of toner. However, when the toner contains a magnetic substance, the residue obtained by eluting the magnetic substance with an acid is 1 g of toner.

  In the present invention, a hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded, such as a graft copolymer using a vinyl polymer as a trunk polymer and a polyester unit as a branch polymer, is also used. be able to. As the vinyl resin, a monomer having a carboxyl group or a hydroxyl group is preferably contained as a polymerization unit. As other polymerization units, the monomers exemplified in the vinyl polymer are used as appropriate. Furthermore, as a monomer component which forms a polyester unit, the said alcohol component, acid component, etc. which are used in order to manufacture a polyester resin are used.

  The glass transition temperature (Tg) of the binder resin is preferably in the range of 50 to 70 ° C. In the present invention, the glass transition temperature (Tg) is an extension of the baseline below Tg when measured with a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) at a heating rate of 10 ° C./min. The value of the intersection with the tangent of the endothermic curve near Tg was determined and measured.

 When the binder resin of the full color toner of the present invention is a polyester resin, it may be a homopolyester or a copolyester alone or a blend of two or more of these. The polyester resin preferably has a weight average molecular weight (Mw) of 5,000 or more in terms of molecular weight measured by gel permeation chromatography (GPC) from the viewpoint of offset resistance and low-temperature fixability. More preferred is 000 to 1,000,000. When the weight average molecular weight of the polyester resin decreases, the offset resistance of the toner tends to decrease, and when the weight average molecular weight increases, the fixability tends to decrease. In addition, the polyester resin used has a type having a molecular weight distribution curve of two peaks composed of a specific low molecular weight condensation polymer component and a specific high molecular weight condensation polymer component, or has a single molecular weight distribution curve. Any type.

In the present invention, the molecular weight distribution (weight average molecular weight (Mw), number average molecular weight (Mn)) of the resin and the release agent described below is measured by GPC under the following conditions.
Equipment: GPC-150C (Waters)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow velocity: 1.0ml / min
Sample: 0.4 ml of 0.15% sample was measured under the above conditions, and the molecular weight calibration curve prepared with a monodisperse polystyrene standard sample was used for calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

  Further, an additive such as a release agent used in the production of a conventional toner can be added to the full color toner of the present invention as long as it does not have a substantial adverse effect. Examples of the release agent include aliphatic hydrocarbons, fatty acid metal salts, higher fatty acids, fatty acid esters or partially saponified products thereof, silicone oils, various oils that improve release properties (offset prevention properties) at the time of heat roll fixing. A wax is mentioned. Among these, low molecular weight polyethylene having a weight average molecular weight of about 1000 to 10000, low molecular weight polypropylene (biscol 550P, 660P, etc.), microcrystalline wax, carnauba wax, sazole wax (H1N4, H1N6), paraffin wax, etc. Waxes are preferred. These are usually added to the toner at a ratio of about 0.5 to 5% by weight with respect to 100 parts by weight of the toner.

  In the full color toner of the present invention, it is also preferable to add a rosin ester for the purpose of increasing the glossiness of the image density. By using the rosin ester, the gloss of the full color toner can be obtained. The rosin ester that can be used in the present invention is obtained by esterifying abietic acid, a disproportionated rosin, or a polymerized rosin, which are the main components of rosin, with an alcohol. The softening point of the rosin ester is preferably in the range of 70 to 140 ° C. Further, it is preferably used in the range of 0.3 to 3 parts by weight with respect to 100 parts by weight of the toner. If the amount is less than 0.3 parts by weight, the effect of increasing the glossiness is lost, and if it exceeds 3 parts by weight, the color reproduction of the toner is hindered.

  The full-color toner of the present invention may contain a charge control agent having a colorless or light color as long as it does not hinder the hue as necessary. As the charge control agent, a positive charge control agent is used according to the polarity of the electrostatic image on the electrostatic latent image carrier to be developed.

 As the positive charge control agent, quaternary ammonium salt compounds (for example, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylbenzylammonium tetrafluoroborate), quaternary ammonium salt organic tin oxide (for example, dibutyltin) Oxide, dioctyltin oxide, dicyclohexyltin oxide), diorganotin borate (dibutyltin borate, dioctyltin borate, dicyclohexyltin borate), an electron donating substance such as a polymer having an amino group, or the like is used alone or in combination of two or more. be able to.

 The charge control agent is usually used in a ratio of 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the binder resin.

 In the full color toner of the present invention, the amount of the charge control agent used in the magenta toner is preferably smaller than those of other cyan toner, yellow toner and black toner. This is because magenta toner is more positively charged than other color toners, and is effective in adjusting the balance of charge amount. For yellow toner and cyan toner, it is preferable to add at least 1.5 times the content of the charge control agent contained in the magenta toner. More preferably, when the content of the charge control agent contained in the magenta toner is 1 part, the ratio is preferably 1.5 to 2.5 parts.

  As the external additive used in the full color toner of the present invention, those such as a fluidizing agent, an abrasive, a conductivity imparting agent and a lubricant can be used. As the base material of the fluidizing agent used in the present invention, for example, fine powders such as silica, alumina, titania, magnesia, amorphous silicon-aluminum co-oxide, amorphous silicon-titanium co-oxide are used. Can do. The fluidizing agent as an external additive has not only the purpose of imparting fluidity to the toner but also the role of imparting and controlling toner chargeability. That is, the external additive adheres to the outermost part of the toner, thereby greatly affecting the chargeability of the toner.

  The particles used for the fluidizing agent can be used as they are without surface treatment, but the environmental stability is impaired by the hygroscopicity, and the fluidizing agent adheres to the surface of the photosensitive drum. There may be a problem that filming occurs and an image defect is caused. Regarding the problem that the environmental stability due to hygroscopicity is impaired, the fluidizing agent is affected by moisture in a high humidity environment, causing toner charge decay, causing fog on the image, and causing toner scattering in the machine End up. Therefore, it is preferable to carry out surface treatment of the particles used for the fluidizing agent so as to impart hydrophobicity. Further, by selecting the treatment agent used for the surface treatment, it is possible to adjust, control and stabilize the chargeability of the toner with a desired polarity level. It is necessary to select the surface treatment agent to be used.

  Examples of the surface treatment agent for the fluidizing agent used in the present invention include organoalkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, organochlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, octadecyltrichlorosilane, and t-butyldimethylchlorosilane. , Silazanes such as hexamethyldisilazane, organoaminosilanes such as bis (dimethylamino) dimethylsilane, and silicone oil compounds can be used.

  As the silicone oil-based compound, straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, or modified silicone oil can be used. Examples of the modifying group used in the modified silicone oil include methylstyrene group, long chain alkyl group, polyether group, carbinol group, amino group, epoxy group, carboxyl group, higher fatty acid group, mercapto group, methacryl group and the like. . Silicone oil has an effect of preventing adhesion of toner components to the surface of the photosensitive drum and filming by having excellent release properties and slipping properties.

  In the full color toner set of the present invention, it is preferable to use a larger amount of the fluidizing agent in the magenta toner than in the cyan toner, yellow toner and black toner. This is because magenta toner is more positively charged than other color toners, and is effective for adjusting the balance of the charge amount levels of the four color toners. Positive chargeability can be suppressed by adding a large amount of fluidizing agent. Here, the fluidizing agent is preferably silica.

  In addition, the amount of charge can be adjusted by using silica as a fluidizing agent in magenta toner, and using titanium oxide (titania) as a fluidizing agent in cyan toner, yellow toner, and black toner.

  As the external additive other than the fluidizing agent used in the present invention, the following known additives can be used for lubricants, abrasives, conductivity imparting agents and the like. Examples of the lubricant include polytetrafluoroethylene and zinc stearate, and examples of the abrasive include strontium titanate, calcium titanate, barium titanate, calcium carbonate, chromium oxide, silicon carbide, tungsten carbide, and silicon nitride. The body is mentioned. These abrasives have an effect of removing adhering toner components and filming substances on the surface of the photosensitive drum by polishing and scraping, and are used in combination with the above-mentioned fluidizing agent that has been surface-treated with silicone oil. A great effect can be found. As the conductivity imparting agent, a metal oxide such as tin oxide can be added. However, these examples are merely examples, and what is added to and mixed with the full color toner of the present invention is not limited to those specifically exemplified above.

  The full color toner of the present invention can also be used with a carrier as a two-component developer. As the carrier, any carrier conventionally used in a two-component dry developer can be used. Examples of such carriers include ferromagnetic powder such as iron powder or alloy powder of ferromagnetic metal, metal oxide such as iron oxide, ferrite powder composed of elements such as nickel, copper, zinc, magnesium, barium, Magnetic powder carrier made of magnetic powder such as magnetite powder, magnetic powder resin coated carrier coated with these magnetic powder with resin, binder carrier made of magnetic powder and binder resin, glass beads with or without resin coating, etc. Can be mentioned. These carriers usually have a particle size of about 15 to 100 μm, preferably about 20 to 80 μm.

  Examples of the coating resin for the magnetic powder resin-coated carrier include silicon-containing resins such as polyethylene and silicone resin, fluorine-containing resins, styrene resins, acrylic resins, styrene-acrylic resins, polyvinyl acetate, cellulose derivatives, Maleic acid resin, epoxy resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinylidene bromide, polycarbonate, polyester, polypropylene, phenol resin, polyvinyl alcohol, fumarate ester resin, polyacrylonitrile, polyvinyl ether, chloroprene rubber , Acetal resin, ketone resin, xylene resin, butadiene rubber, styrene-butadiene copolymer, polyurethane, polyamide resin, ionomer resin, polyphenylene sulfide resin, etc. That. Among these, fluorine-containing resins and silicon-containing resins are particularly preferable because the formation of spent toner is small. This magnetic powder resin coated carrier includes conductive fine particles (carbon black, conductive metal oxide, metal powder), inorganic fillers (silica, silicon nitride, boron nitride, alumina, zirconia, silicon carbide, boron carbide, oxidized (Titanium, clay, talc, glass fiber), the charge control agent exemplified above, and the like may be contained as necessary. The resin coating thickness on the carrier core material is preferably about 0.1 to 5 μm.

  In addition, electrophotographic apparatuses such as multi-function machines, printers, and copiers that use a full-color process usually use toners of four colors, yellow, magenta, cyan, and black. However, black toner is often used because of the nature of the document to be printed. Often to do. Black printing is required to have durability and printing durability higher than those of other color colors, and in the black printing process, it is preferable to use a two-component developing system comprising a toner and a carrier. On the other hand, in the case of printing in yellow, magenta, and cyan color colors, a two-component process or a one-component process may be used. In order to simplify the configuration of the electrophotographic apparatus and to obtain printing durability and printing durability, it is also preferable to use black as a two-component process and color as one component.

  It is also possible to use a trickle development method in which the carrier is filled with the toner in the toner container and a new carrier is supplied to the developing device at the same time as the toner is supplied. Thus, by collecting a part of the developer (toner and carrier) in the developing machine, the developer does not deteriorate and replacement of the developer can be made unnecessary. The trickle developer has a long history and was used around 1984.

  The full-color toner of the present invention can be manufactured using a conventionally known toner manufacturing method. The toner production methods are roughly classified into two types: a pulverization method obtained through kneading and pulverization steps, and a polymerization method obtained by chemical polymerization. In the case of the pulverization method, for example, the toner constituent materials described above may be sufficiently mixed with a mixer such as a ball mill or a Henschel mixer, and then a heat kneader such as a hot roll, kneader, uniaxial or biaxial extruder may be used. Examples thereof include a method of kneading, cooling and solidifying, mechanically pulverizing using a pulverizer such as a hammer mill, then finely pulverizing with a jet mill, mechanical pulverizer, and the like, followed by classification.

  On the other hand, in the case of a polymerization method, after dispersing other toner constituent materials in a binder resin solution, spray drying, a method for producing toner by a so-called microcapsule method, a predetermined material as a monomer for forming a binder resin And a method of obtaining a toner by emulsion or suspension polymerization. In the emulsion polymerization method, resin particles having a particle size of submicron are associated with an internal additive such as a pigment component and wax previously emulsified in water in a coagulation step to obtain a particle size of a desired toner size. In the suspension polymerization method, polymerization is performed by dispersing and heating necessary materials such as a polymerization initiator, a pigment component, a wax, and a charge control agent in a monomer.

  It is preferable that the toner base particles (toner particles before the addition of the external additive) thus obtained are sufficiently mixed with the external additive using a mixer such as a Henschel mixer.

The toner used in the present invention preferably has a volume average particle size of 3 to 15 μm, more preferably 5 to 12 μm.
[Example]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the embodiments of the present invention are not limited to these examples. In the following, all parts represent parts by weight. Detailed conditions and results of the following examples and comparative examples are shown in Tables 1 and 2 below. In addition, the binder resins, pigments and release agents used in the following examples and comparative examples are as follows.
(Binder resin)
Thermoplastic polyester resin 1
A polyester resin containing terephthalic acid, isophthalic acid, benzoic acid, stearic acid, propylene oxide-added bisphenol A and trimethylolpropane as the monomer component, and tolylene diisocyanate as the urethane crosslinking component.
Acid value: 8 mgKOH / g Tg: 55 ° C. Molecular weight Mw: 13000 Mn: 2500
Thermoplastic polyester resin 2
A polyester resin containing terephthalic acid, isophthalic acid, benzoic acid, stearic acid, propylene oxide-added bisphenol A and trimethylolpropane as the monomer component, and tolylene diisocyanate as the urethane crosslinking component.
Acid value: 4 mg KOH / g Tg: 55 ° C. Molecular weight Mw: 5500 Mn: 2200
(Pigment)
Evaluation was made using the following pigments.
Cyan pigment C.I. I. Pigment Blue 15: 3 (LIONOL BLUE GLA-SD manufactured by Toyo Ink)
C. I. Pigment Green 7 (LIONOL GREEN YS-2A manufactured by Toyo Ink)
Pigment for magenta C.I. I. Pigment Red 81 (Fuji Rose, RNN-P)
C. I. Pigment Red 169 (FANAL PINK D4810 manufactured by BASF)
Magenta pigment for comparison C.I. I. Pigment Red 57: 1 (LIONOL RED 6B 4240-P manufactured by Toyo Ink)
C. I. Pigment Red 122 (DIC Corporation KET RED309)
Yellow pigment C.I. I. Pigment Yellow 74 (FAST YELLOW 7415 manufactured by Sanyo Dye)
C. I. Pigment Yellow 12 (LIONOL Yellow 1235-P manufactured by Toyo Ink Co., Ltd.)
Comparative yellow pigment C.I. I. Pigment Yellow 180 (LTONER YELLOW HG manufactured by Clariant)
Black pigment carbon black Monarch 280 (manufactured by Cabot)
The above-mentioned C.I. I. Pigment Blue 15: 3 (LIONOL BLUE GLA-SD manufactured by Toyo Ink) was added.

  Tables 1 and 2 below show the evaluated materials and toner formulations.

  The content ratio (C) :( M) :( Y) of the pigment component in each toner is 5: 6: 4 in Examples 1 to 3, and 5: 5: in Comparative Examples 1 to 3. 5.

(Production of cyan toner)
Thermoplastic polyester resin 1 50.0 parts by weight C.I. I. Pigment Blue 15: 3 48.0 parts by weight C.I. I. Pigment Green 7 2.0 parts by weight The above materials (5 kg in total) were mixed and kneaded in a pressure kneader at a set temperature of 120 ° C. for 15 minutes and taken out. Furthermore, kneading was carried out with a three roll having a roll temperature of 95 ° C., and after cooling, the mixture was roughly crushed to 10 mm or less to obtain cyan colorant 1.
Thermoplastic polyester resin 1 86.0 parts by weight Cyan colorant 1 10.0 parts by weight Charge control agent (quaternary ammonium salt compound Bontron P-53 manufactured by Orient Chemical Industries, Ltd.) 2.0 parts by weight release agent (ethylene homopolymer) Molecular weight 850 Mw / Mn 1.08 Melting point 107 ° C.) 1.5 parts by weight Disproportionated rosin ester (Superester A-100) 0.5 part by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L ( 3000 rpm, 3 minutes), melt kneaded with a twin-screw kneading extruder (PCM30) at a supply rate of 6 kg / hr and a discharge temperature of 120 ° C., cooled and solidified, then coarsely crushed with a hammer mill, and then an I-type jet mill Finely pulverized with (IDS-2 type) and classified (DS-2 type) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm.

Subsequently, 100 parts by weight of the classified product obtained above and 0.5 parts by weight of hydrophobic silica (aminosilane treatment: RA-200HS manufactured by Nippon Aerosil Co., Ltd.) were mixed with a 10 L Henschel mixer (2000 rpm, 1 minute), and a sieving step ( After 100 mesh), cyan toner 1 was obtained.
(Production of magenta toner)
Thermoplastic polyester resin 1 50.0 parts by weight C.I. I. Pigment Red 81 50.0 parts by weight The above materials (total of 5 kg) were mixed and kneaded in a pressure kneader at a set temperature of 120 ° C. for 15 minutes and taken out. Further, kneading was carried out with three rolls at a roll temperature of 95 ° C., and after cooling, the mixture was coarsely crushed to 10 mm or less to obtain magenta colorant 1.
Thermoplastic polyester resin 1 85.0 parts by weight Magenta colorant 1 12.0 parts by weight Charge control agent (quaternary ammonium salt compound Bontron P-53 manufactured by Orient Chemical Industry Co., Ltd.) 1.0 part by weight Release agent (ethylene homopolymer) Molecular weight 850 Mw / Mn 1.08 Melting point 107 ° C.) 1.5 parts by weight Disproportionated rosin ester (Superester A-100) 0.5 part by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L ( 3000 rpm, 3 minutes), melt kneaded with a twin-screw kneading extruder (PCM30) at a supply rate of 6 kg / hr and a discharge temperature of 120 ° C., cooled and solidified, then coarsely crushed with a hammer mill, and then an I-type jet mill Finely pulverized with (IDS-2 type) and classified (DS-2 type) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm.

Next, 100 parts by weight of the classified product obtained above and 0.8 parts by weight of hydrophobic silica (R812 manufactured by Nippon Aerosil Co., Ltd.) were mixed with a 10 L Henschel mixer (2000 rpm, 3 minutes), and passed through a sieving step (100 mesh). Thereafter, magenta toner 1 was obtained.
(Production of yellow toner)
Thermoplastic polyester resin 1 50.0 parts by weight C.I. I. Pigment Yellow 74 50.0 parts by weight The above materials (5 kg in total) were mixed and kneaded in a pressure kneader at a set temperature of 110 ° C. for 15 minutes and taken out. Further, the mixture was kneaded with three rolls having a roll temperature of 90 ° C., and after cooling, coarsely crushed to 10 mm or less, whereby a yellow colorant 1 was obtained.
Thermoplastic polyester resin 1 88.0 parts by weight Yellow colorant 1 8.0 parts by weight Charge control agent (quaternary ammonium salt compound Bontron P-53 manufactured by Orient Chemical Industries, Ltd.) 2.0 parts by weight release agent (ethylene homopolymer) Molecular weight 850 Mw / Mn 1.08 Melting point 107 ° C.) 1.5 parts by weight Disproportionated rosin ester (Superester A-100) 0.5 part by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L ( 3000 rpm, 3 minutes), melt kneaded with a twin-screw kneading extruder (PCM30) at a supply rate of 6 kg / hr and a discharge temperature of 115 ° C., cooled and solidified, then coarsely pulverized with a hammer mill, and then an I-type jet mill Finely pulverized with (IDS-2 type) and classified (DS-2 type) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm.

Subsequently, 100 parts by weight of the classified product obtained above and 0.5 parts by weight of hydrophobic silica (aminosilane treatment: RA-200HS manufactured by Nippon Aerosil Co., Ltd.) were mixed with a 10 L Henschel mixer (2000 rpm, 1 minute), and a sieving step ( 100 mesh), yellow toner 1 was obtained.
(Production of black toner)
Thermoplastic polyester resin 1 50.0 parts by weight Carbon black (Monarch 280) 47.0 parts by weight C.I. I. Pigment Blue 15: 3 3.0 parts by weight The above materials (total 5 kg) were mixed and kneaded in a pressure kneader at a set temperature of 120 ° C. for 15 minutes and taken out. Further, the mixture was kneaded with three rolls having a roll temperature of 95 ° C., and after cooling, coarsely crushed to 10 mm or less to obtain black colorant 1.
Thermoplastic polyester resin 1 86.0 parts by weight Black colorant 1 10.0 parts by weight Charge control agent (quaternary ammonium salt compound Bontron P-53 manufactured by Orient Chemical Industry Co., Ltd.) 2.0 parts by weight Release agent (ethylene homopolymer) Molecular weight 850 Mw / Mn 1.08 Melting point 107 ° C.) 1.5 parts by weight Disproportionated rosin ester (Superester A-100) 0.5 part by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L ( 3000 rpm, 3 minutes), melt kneaded with a twin-screw kneading extruder (PCM30) at a supply rate of 6 kg / hr and a discharge temperature of 120 ° C., cooled and solidified, then coarsely crushed with a hammer mill, and then an I-type jet mill Finely pulverized with (IDS-2 type) and classified (DS-2 type) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm.

Subsequently, 100 parts by weight of the classified product obtained above and 0.5 parts by weight of hydrophobic silica (aminosilane treatment: RA-200HS manufactured by Nippon Aerosil Co., Ltd.) were mixed with a 10 L Henschel mixer (2000 rpm, 1 minute), and a sieving step ( After 100 mesh), black toner 1 was obtained.
(Image test)
Using the obtained cyan toner 1, magenta toner 1, yellow toner 1 and black toner 1, a full color developer was obtained. For black toner 1, a ferrite carrier coated with a silicone resin having an average particle diameter of 60 μm (DFC-350C, manufactured by Dowa Iron Powder Co., Ltd.) is used to set the toner concentration to 6%, and as a black developer, and cyan toner. 1, magenta toner 1 and yellow toner 1 were put into a developing device as they were to obtain a non-magnetic one-component developer.
The image test conditions were as follows.
Full color copier: FP-C1 made by Matsushita Electric Industrial Co., Ltd.
(Black is a two-component developer, yellow, magenta, and cyan are non-magnetic one-component developers)
Copy paper: Color application paper manufactured by Fuji Xerox Co., Ltd. Ncolor127 (127.9 g / m2) A4 size image creation conditions: Four types of monochrome images of yellow, cyan, magenta, and black, and a two-color solid print overlapping portion (yellow x magenta red , Magenta x cyan, purple, cyan x yellow, green) and yellow, magenta, and cyan three-color solid color overprint portions.

Moreover, evaluation of each obtained image printed matter was performed.
Printed matter measurement condition Image density: The density value of a solid portion (yellow, magenta, cyan, black) solid portion of the printed matter was measured by Gretag Macbeth D196.
Colorimetry: L *, a *, b of single-color solid portion (yellow, magenta, cyan) and single-color solid printed portion (yellow × magenta, magenta × cyan, cyan × yellow) of the printed matter with X-Rite 938 * Measured value. The C value was determined from a * and b * by the following formula.
Gloss: 60 ° -60 ° reflective gloss was measured with a digital gloss meter manufactured by Murakami Color Research Laboratory. The results are shown in Table 0. Compared to the comparative example, the C value of the example is large, and the chroma of the printed matter is high. As a result of plotting each a * and b * value in a two-dimensional space with a * as the horizontal axis and b * vertical axis and comparing them with a two-dimensional gamut, it can be seen that the color reproduction region of the example is wide. Tables 3 and 4 show the results.

［実施例２〜３，比較例１〜３］
表１、２に記載の条件にすること以外は実施例１と同様にして、フルカラートナーを得た。これらフルカラートナーの組み合わせについて実施例１と同様にして、現像性の評価を行った。結果を表１、表２、表３、表４に示す。

[Examples 2-3, Comparative Examples 1-3]
A full color toner was obtained in the same manner as in Example 1 except that the conditions described in Tables 1 and 2 were used. The combination of these full-color toners was evaluated for developability in the same manner as in Example 1. The results are shown in Table 1, Table 2, Table 3, and Table 4.

  The full-color toner set of the present invention has a wide color reproduction area and develops an electrostatic latent image in an electrophotographic copying machine, a laser beam printer, or the like in which an image is formed using electrophotography, electrostatic recording, or the like. It can be preferably used as a full-color toner used in the above.

Claims (11)

  A full color toner set comprising a positively chargeable magenta toner, a positively chargeable cyan toner, a positively chargeable yellow toner, and a positively chargeable black toner, containing at least a polyester resin having an acid value of less than 10 KOHmg / g and a pigment component The pigment component used for the magenta toner is a metal lake compound of a rhodamine dye, the pigment component used for the cyan toner is at least a phthalocyanine copper compound exhibiting an indigo color and a phthalocyanine copper compound exhibiting a green color, and A full-color toner set, wherein the pigment component used in the yellow toner is a monoazo yellow compound or a disazo yellow compound.   In the pigment component used for the positively chargeable cyan toner, the weight ratio of the phthalocyanine copper compound exhibiting indigo color to the phthalocyanine copper compound exhibiting green color (indigo color: green) is in the range of 100: 2 to 100: 20. The full-color toner set according to claim 1, wherein:   Rhodamine dye metal lake compounds used for positively chargeable magenta toners are C.I. I. Pigment red 81 or C.I. I. The full-color toner set according to claim 1, wherein the toner is Pigment Red 169.   A phthalocyanine copper compound exhibiting an indigo color is C.I. I. The full-color toner set according to claim 1, which is CI Pigment Blue 15: 3.   A green phthalocyanine copper compound is C.I. I. The full color toner set according to claim 1, which is CI Pigment Green 7.   6. The full-color toner set according to claim 1, wherein the pigment component used for the positively chargeable black toner comprises carbon black and a pigment component exhibiting an indigo color as a complementary color.   In the pigment component used for the positively chargeable black toner, the weight ratio of carbon black to the pigment component exhibiting a deep blue color (carbon black: deep blue pigment) is in the range of 100: 0.5 to 100: 20. The full-color toner set according to claim 6.   A monoazo yellow compound used for positively chargeable yellow toner is C.I. I. Pigment yellow 74 or C.I. I. The full color toner set according to claim 1, which is CI Pigment Yellow 12.   The relationship among the content ratio (Y) of the pigment component in the positively chargeable yellow toner, the content ratio (C) of the pigment component in the cyan toner, and the content ratio (M) of the pigment component in the magenta toner is Y <C <M. The full-color toner set according to claim 1, wherein the relationship is satisfied. The relationships among the content ratio (Y) of the pigment component in the positively chargeable yellow toner, the content ratio (C) of the pigment component in the cyan toner, and the content ratio (M) of the pigment component in the magenta toner are as follows. The full-color toner set according to claim 1, wherein all of the conditions (c) are satisfied.
(A) Y <C, and satisfies the relationship of 0.5xC ≦ Y ≦ 0.9xC.
(B) Y <M, and satisfies the relationship of 0.3xM ≦ Y ≦ 0.7xM.
(C) C <M, and satisfies the relationship of 0.6 × M ≦ C ≦ 0.9 × M.   A full-color image is obtained using the full-color toner set according to claim 1.