JP4900375B2 - Magenta toner - Google Patents

Description

  The present invention relates to a magenta toner for 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.

  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 digitalization. By this digitization, workflow of conventional printing methods (photographing, positive, scanning, data, design, EPS)・ Imposition, film, printing plate, printing) was a multi-stage process, but it has succeeded in dramatically shortening the process with digital camera shooting, DTP, CTP, and printing. 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 colorant in the binder resin as well as the hue, saturation, and color separation reflection characteristics of the colorant used. In particular, the color separation reflection characteristic is an important characteristic value for controlling the color reproducibility.

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). An object is to provide a magenta toner for setting. 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 It is an object of the present invention to provide a magenta toner for 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 good full-color image can be formed by using a magenta toner having a specific spectral reflection spectrum. It is a thing.

In general, in order to expand the color reproduction region, it is necessary to approximate the ideal spectral reflectance curve of each color. That is, the wavelength range in which a person recognizes color is 400 nm to 700 nm light (this wavelength is referred to as visible light). In yellow ink, the reflectance in the wavelength range of 500 nm to 700 nm is 100%, and the wavelength range of 400 nm to 500 nm. In the red ink, the reflectance in the wavelength region of 400 nm to 500 nm and 600 nm to 700 nm is 100%, and the reflectance in the wavelength region of 500 nm to 600 nm is 0%. Therefore, it is said that it is ideal that the reflectance in the wavelength region of 400 nm to 600 nm is 100% and the reflectance in the wavelength region of 600 nm to 700 nm is 0%. (See Table 4 for the ideal spectral reflectance spectrum)
However, the spectral reflection spectra of yellow, magenta, cyan, and black toners that are currently used in four process colors do not necessarily match the ideal spectral reflection spectrum. Since there is unnecessary absorption in a portion where the light must be completely reflected, a turbid component of the toner exists, and color reproducibility is narrowed.

That is, the present invention
Magenta toner for full color toner set,
The magenta toner includes at least a binder resin and a pigment, and
The magenta toner has a maximum reflectance of 40% to 100% in a wavelength region of 400 nm to 500 nm and a wavelength region of 500 nm to 560 nm when the maximum reflectance is 100% in a wavelength region of 400 nm to 700 nm. It has a spectral reflectance spectrum of a reflectance of 0 to 20% and a reflectance of 80% to 100% in a wavelength range of 630 nm to 700 nm, and the pigment comprises a rhodamine dye metal lake compound and the entire pigment. The present invention relates to a magenta toner comprising 0.5 to 10% by weight of a complementary color pigment.

  The present invention also relates to the magenta toner according to claim 1, wherein the metal of the metal lake compound is molybdenum and / or tungsten.

  In the present invention, the complementary color pigment is C.I. I. The magenta toner according to claim 1, which is CI Pigment Violet 1.

  The present invention also relates to the magenta toner according to any one of claims 1 to 3, wherein the full color toner includes magenta toner, cyan toner, yellow toner, and black toner.

In the present invention, the metal lake compound of the rhodamine dye is C.I. I. Pigment red 81 and / or C.I. I. The magenta toner according to claim 1, which is CI Pigment Red 169.

  By using the magenta toner for 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.), which cannot be reproduced with conventional full color toners, and the color reproducibility is remarkably improved. Thus, it is possible to produce a high-quality image stably from the beginning of development over a long period of time. In the magenta toner for 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. it can.

  Hereinafter, the present invention will be described in more detail.

  A full-color toner set in which the magenta toner of the present invention is preferably used is a full-color toner set comprising at least a binder resin, a yellow toner containing a pigment component, a magenta toner, a cyan toner, and a black toner. However, in the wavelength region of 400 nm to 700 nm, when the maximum reflectance is 100%, the wavelength region of 400 nm to 480 nm is 0 to 10%, and the reflectance in the wavelength region of 530 nm to 700 nm is 80 to 100%. The magenta toner having a reflection spectrum has a maximum reflectance of 40% to 100% and 500 nm to 560 nm in the wavelength region of 400 nm to 500 nm, assuming that the maximum reflectance is 100% in the wavelength region of 400 nm to 700 nm. Reflectivity in the wavelength region of 0 to 20%, 630 nm to 700 n When the cyan toner has a spectral reflectance spectrum of 80% to 100% and the maximum reflectance is 100% in the wavelength region of 400 nm to 700 nm, the wavelength region of 420 nm to 520 nm. It has a spectral reflectance spectrum of 50 to 100%, a peak having a maximum reflectance of 80 to 100% in this region, and a reflectance of 600 to 700 nm of 0 to 5%.

  More preferably, when the yellow toner has a maximum reflectance of 100% in the wavelength region of 400 nm to 700 nm, the reflectance in the wavelength region of 400 nm to 480 nm is 0 to 9% and the wavelength region of 550 nm to 700 nm. The magenta toner has a spectral reflectance spectrum of 85 to 100%, and the maximum reflectance in the wavelength region of 400 nm to 500 nm is 40% to 40% when the maximum reflectance is 100% in the wavelength region of 400 nm to 700 nm. The spectral reflectance spectrum is 60%, the reflectance in the wavelength region of 500 nm to 560 nm is 0 to 10%, the reflectance in the wavelength region of 630 nm to 700 nm is 80% to 100%, and the cyan toner is 400 nm to 700 nm. When the maximum reflectance is 100%, the wavelength range of 420 nm to 520 nm In reflectance 50-100%, and the maximum reflectivity in this region have 80 to 100% of the peak reflectivity of 600nm~700nm are preferably has a spectral reflection spectrum of 0-5%.

  In the yellow toner, when the maximum reflectance is 100% in the wavelength region of 400 nm to 700 nm, the wavelength region of 400 nm to 480 nm exceeds 10%, and the reflectance in the wavelength region of 530 nm to 700 nm is 80%. If it is smaller than%, the reproducibility of green, orange and red is inferior, which is not preferable.

  Originally yellow component is C.I. I. The conventional yellow toner using CI Pigment Yellow 180 or the like has a level close to the reproduction region of AdobeRGB and RGB as a single unit, but the reproducibility of green, orange and red is inferior. For the first time, it becomes possible to widen the reproduction region of green, orange, red, purple, and blue by using pigment components in combination so as to satisfy the spectral reflection spectrum described above.

  In the magenta toner, when the maximum reflectance is 100% in the wavelength region of 400 nm to 700 nm, the maximum reflectance in the wavelength region of 400 nm to 500 nm is smaller than 40%, and the wavelength region of 500 nm to 560 nm. If the reflectivity at 20 nm exceeds 20% and the reflectivity in the wavelength region of 630 nm to 700 nm becomes smaller than 80%, the reproducibility of purple is inferior.

  By using a pigment component in the magenta toner so as to satisfy the spectral reflection spectrum, the reproduction area of magenta, red, purple, and blue can be widened.

  In the case of cyan toner, when the maximum reflectance is 100% in the wavelength region of 400 nm to 700 nm, the reflectance in the wavelength region of 420 nm to 520 nm is smaller than 50%, and the peak of the maximum reflectance in this region is Is less than 80%, and if the reflectivity at 600 nm to 700 nm is greater than 5%, green reproducibility is inferior.

  By using a pigment component so that the cyan toner satisfies the spectral reflection spectrum, it becomes possible to reach the Adobe RGB region beyond the Japan color region in reproducing the green region. Further, by using this cyan toner in combination with the magenta toner satisfying the above spectral reflection spectrum, it becomes possible to widen the violet reproduction region of the mixed color.

  In a full color toner set in which the magenta toner of the present invention is suitably used, the effect of combining the three colors of yellow toner, magenta toner, and cyan toner satisfying the spectral reflection spectral characteristics is very large. By using it, it is possible to perform color reproduction that is wider than the region of the color reproduction range of regular hue (Japan Color, etc.) and covers the vicinity of the reproduction region of AdobeRGB (trademark of Adobe Systems). 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.

  The content of the pigment component contained in the full color toner in which the magenta toner of the present invention is preferably used is the content of the pigment component in the yellow toner (Qy) <the content of the pigment component in the cyan toner (Qc) <magenta toner. The relationship of the content (Qm) of the pigment component therein is preferable.

  Specifically, the content (Qy) of the pigment component in the yellow toner is 2 to 11% by weight based on the total weight of the yellow toner, and the content (Qc) of the pigment component in the cyan toner is based on the total weight of the cyan toner. The content (Qm) of the pigment component in the magenta toner is preferably 4 to 15% by weight based on the total weight of the magenta toner.

  The most pigment component of magenta toner 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 of the pigment component of the yellow toner relatively low, yellow transparency can be obtained, and when the desired image density is output, the film thickness of the yellow toner component can be increased (the amount of adhesion is increased). . 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.

  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. 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.

  A full color toner set in which the magenta toner of the present invention is preferably used is a combination of toners that are not mixed together, and each toner exists as a separate composition. The toner of each color, and in some cases, the developer, is stored and used in a developer and a development housing for each color in a full-color copying machine and printer.

  The pigment component used in the yellow toner used in the full color toner set in which the magenta toner of the present invention is preferably used is preferably a disazo yellow compound. Specific pigments include C.I. I. Pigment yellow 12 and / or C.I. I. Pigment Yellow 13. As a complementary color of these pigments, C.I. I. It is also possible to use CI Pigment Yellow 83 by adding 0.5 to 10% by weight, preferably 2 to 5% by weight of the above yellow pigment.

  Transparency in which the L * value does not exceed 17 when the yellow toner is overprinted in the density range of 1.40 to 2.10 on the black toner printed in the range of the image density of 1.85 to 1.90. In this case, there is little influence on the underprinting toner when the secondary color and tertiary color are overprinted, and a good color reproduction region can be obtained.

  The pigment component used in the magenta toner of the present invention is preferably rhodamine dye molybdenum such as rhodamine B, rhodamine 3G, rhodamine 6G, or tungsten metal lake compound. Specific pigments include C.I. I. Pigment red 81 and / or C.I. I. Pigment Red 169. As a complementary color of these pigments, C.I. I. It is also preferable to use Pigment Violet 1 by adding 0.5 to 10% by weight, preferably 2 to 5% by weight, of the magenta pigment.

The pigment component used in the cyan toner used in the full color toner set in which the magenta toner of the present invention is preferably used is preferably a copper phthalocyanine compound. Copper phthalocyanine-based compounds are substances that exhibit crystal polymorphism (homogeneous heterocrystals), and are classified into α, β, γ, ε, π, τ, ρ, χ, R, and the like depending on the crystal structure. , crystalline stability, it is preferred to use the β-type dispersion is excellent, it is preferred even at fine β type copper phthalocyanine ranges specific surface area of 74m ² / g~100m 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 100 m ² / g, the pigment tends to cause soft aggregation and dispersibility becomes difficult.

  In the present invention, a copper halide phthalocyanine compound obtained by substituting a hydrogen atom on the benzene ring of a phthalocyanine molecule with a halogen compound is added to the copper phthalocyanine compound in an amount of 2 to 20% by weight, more preferably 3 to 15% by weight. This makes it possible to widen the color reproduction areas of green and purple when overprinting with yellow toner and magenta toner without impairing the color reproduction area of the cyan toner single color. Specifically, it is preferable to add CI Pigment Green 7 to CI Pigment Blue 15: 3 or CI Pigment Blue 15: 4.

  Depending on the process design, magnetic toner and non-magnetic toner will be used as black toner. If non-magnetic toner is used, a mixture of three pigment components of yellow, magenta and cyan, or carbon black, If it is a magnetic toner, magnetic powder can be used.

  The black toner is used not only for black printing but also as a complementary color of three colors, yellow, magenta, and cyan. In order to give a black feel to the printed matter, an indigo component is added to the black colorant component. It is preferable to use it. 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 black toner is a magnetic toner, the usable magnetic material may be any alloy or compound containing a ferromagnetic element conventionally used in the production of a magnetic toner. 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. 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 and KBC-200 manufactured by Kanto Denka Co., Ltd., MRD-BL manufactured by Titanium Kogyo Co., Ltd., and the like. Examples include MG-RF and MG-WS manufactured by Metal Mining.

  As the binder resin used in the full color toner in which the magenta toner of the present invention is suitably used, a resin exhibiting colorless, white, or light color is preferable so as not to disturb the hue of the pigment of each color.

  Examples of binder resins that can be used include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Styrenes such as methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymer or cross-linked Tylene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy Examples thereof include resins, xylene resins, polyvinyl butyral, terpene resins, coumarone indene resins, and petroleum resins. Of these, polyester resins and styrene copolymers are preferably used.

  In the full color toner in which the magenta toner of the present invention is suitably used, a polyester resin is the most preferable binder resin. Examples of the alcohol component constituting the polyester resin include 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, Diols such as 4-bis (hydroxymethyl) cyclohexane, bisphenol derivatives represented by the following general formula (1), glycerol, diglycerol, sorbit, sorbitan, butanetriol, trimethylolethane, trimethylolpropane, pentae Suritoru, 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.

  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.

  Further, in the styrene copolymer included in the styrene polymer, examples of the comonomer for the styrene monomer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, and acrylic acid. Monocarboxylic acid having a double bond such as -2-ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, or a substituted product thereof; For example, dicarboxylic acids having a double bond such as maleic acid, methyl maleate, butyl maleate, and dimethyl maleate, and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate, and vinyl benzoate For example, ethylene monomers such as ethylene, propylene and butylene; vinyl monomers such as vinyl methyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; can give. These may be used alone or in combination of two or more.

  As a crosslinking agent used when producing a crosslinked styrene-based copolymer, a compound having two or more polymerizable double bonds is mainly used. For example, aromatic divinyl such as divinylbenzene and divinylnaphthalene. Compound; carboxylic acid ester having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; And compounds having three or more vinyl groups are used alone or as a mixture. The styrenic polymer is a styrenic polymer having at least one peak in the region of 3 × 10 3 to 5 × 10 4 in the molecular weight distribution measured by GPC, and at least one other peak or shoulder in the region of 10 5 or more. A copolymer is preferred from the standpoint of fixability.

  In producing the vinyl polymer, a polymerization initiator is used. Any conventionally known polymerization initiator can be used. Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroperoxide, tertiary butyl peroxybenzoate, ditertiary butyl peroxide, cumene hydroperoxide, dicumyl peroxide, azo Isobutyronitrile, azobisvaleronitrile, and the like are preferably used conventionally. The use ratio of the polymerization initiator to the vinyl monomer is generally 0.2 to 5% by mass. The polymerization temperature is appropriately selected according to the type of monomer and initiator used.

  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.

In a full color toner in which the magenta toner of the present invention is suitably used, the binder resin preferably has an acid value in the range of 5 to 20 mgKOH / g. When the acid value of the binder resin is smaller than 5 mgKOH / g, the compatibility with the disproportionated rosin ester is lowered, and the problem that the release agent is liberated is not sufficiently solved. When the acid value of the binder resin 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.
When the binder resin of the full color toner for which the magenta toner of the present invention is suitably used 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. The thing of 000-1,000,000 is more preferable. 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.

  Further, an additive such as a release agent that has been used in the production of conventional toners can be added to the full-color toner in which the magenta toner of the present invention is suitably used 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, waxes such as low molecular weight polyethylene having a weight average molecular weight of about 1000 to 10,000, low molecular weight polypropylene, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax are preferable. These are usually added to the toner in an amount of about 0.5 to 5% by weight.

  In a full color toner in which the magenta toner of the present invention is suitably used, 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 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 in which the magenta toner of the present invention is preferably used may contain a colorless or light-color charge control agent as long as it does not hinder the hue as necessary. As the charge control agent, a positive charge control agent or a negative 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), electron donating substances such as polymers having amino groups, etc. are used alone or in combination of two or more. be able to.

  On the other hand, as negative charge control agents, aromatic hydroxycarboxylic acid zinc salt, calcium salt, chromium salt, aryloxycarboxylic acid divalent or trivalent metal salt or metal chelate (complex) such as salicylic acid or salicylic acid derivative, etc. , Fatty acid soaps, naphthenic acid metal salts and the like. These charge control agents are usually used at 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.

  As the external additive used in the full color toner in which the magenta toner of the present invention is preferably used, a fluidizing agent, an abrasive, a conductivity-imparting agent, a lubricant and the like 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 by imparting desired positive and negative polarities. 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.

  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 obtained. 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 in which the magenta toner of the present invention is preferably used can be used as a two-component developer together with a carrier. 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.

  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 toner according to 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 as described above are sufficiently mixed by a mixer such as a ball mill or a Henschel mixer, and then kneaded well using a thermal kneader such as a hot roll kneader, a uniaxial or biaxial extruder. Then, after cooling and solidification, a method of manufacturing by a method of coarsely pulverizing mechanically using a pulverizer such as a hammer mill, then finely pulverizing with a jet mill, a mechanical pulverizer, etc., and then classifying.

  On the other hand, in the case of the polymerization method, a method for producing toner by the so-called microcapsule method in which other toner constituent materials are dispersed in a binder resin solution and then spray-dried, and a predetermined material as a monomer for forming the 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 colorant or wax that has been pre-emulsified in water in the aggregation 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 colorant, a wax, and a charge control agent in a monomer.

  It is preferable to use the toner base particles thus obtained by sufficiently mixing the external additive with 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.

  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. The binder resins and pigments used in the following examples and comparative examples are as follows.

(Binder resin)
Thermoplastic polyester resin 1
Polyester resin composed of terephthalic acid, isophthalic acid, trimellitic acid, propylene oxide-added bisphenol A, and ethylene glycol.
Acid value: 10 mg KOH / g OH value: 43 mg KOH / g Tg 58 ° C
Molecular weight Mw: 28200 Mn: 2500
Thermoplastic polyester resin 2
Polyester resin composed of terephthalic acid, isophthalic acid, trimellitic acid, propylene oxide-added bisphenol A, and ethylene glycol.
Acid value: 18 mg KOH / g OH value: 36 mg KOH / g Tg 59 ° C
Molecular weight Mw: 32000 Mn: 2600

(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)
C. I. Pigment Violet 1 (FANAL VIOLET D5480 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 (KET RED309 manufactured by Dainippon Ink & Chemicals, Inc.)
Yellow pigment C.I. I. Pigment Yellow 12 (LIONOL YELLOW 1235-P manufactured by Toyo Ink Co., Ltd.)
C. I. Pigment Yellow 13 (LIONOL YELLOW FG-1310 manufactured by Toyo Ink)
C. I. Pigment Yellow 83 (LIONOL YELLOW FG-1842 manufactured by Toyo Ink)
(Comparative yellow pigment)
C. I. Pigment Yellow 180 (LTONER YELLOW HG manufactured by Clariant)
Black Black Carbon Black Monarch 880
The above-mentioned C.I. I. Pigment Blue 15: 3 (LIONOL BLUE GLA-SD manufactured by Toyo Ink) was added.
Table 1, Table 2, Table 3, and Table 4 show the colorant, toner formulation, and spectral reflectance spectrum of the toner evaluated.

(Production of cyan toner)
Thermoplastic polyester resin 1 50.0 parts by weight C.I. I. Pigment Blue 15: 3 47.0 parts by weight C.I. I. Pigment Green 7 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 30 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 85.0 parts by weight Cyan colorant 1 12.0 parts by weight Charge control agent (calcium salt compound of 3,5-di-tert-butylsalicylic acid) 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 Polymerized rosin ester (Pencel D-125) 0.5 parts by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L (3000 rpm, 3 The mixture was 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, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS- 2 type) and finely pulverized 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 0.5 parts by weight of hydrophobic titanium oxide (STT-30A manufactured by Titanium Industry Co., Ltd.) were mixed with a 10 L Henschel mixer (2000 rpm, 1 minute), and a sieving step (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 48.5 parts by weight C.I. I. Pigment Violet 1 1.5 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 30 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 84.0 parts by weight Magenta colorant 1 13.0 parts by weight Charge control agent (calcium salt compound of 3,5-di-tert-butylsalicylic acid) 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 Polymerized rosin ester (Pencel D-125) 0.5 parts by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L (3000 rpm, 3 The mixture was 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, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS- 2 type) and finely pulverized 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 0.5 parts by weight of hydrophobic titanium oxide (STT-30A manufactured by Titanium Industry Co., Ltd.) were mixed with a 10 L Henschel mixer (2000 rpm, 1 minute), and a sieving step (100 mesh) ) To obtain magenta toner 1.

(Production of yellow toner)
Thermoplastic polyester resin 1 50.0 parts by weight C.I. I. Pigment Yellow 12 49.0 parts by weight C.I. I. Pigment Yellow 83 1.0 part by weight The above materials (5 kg in total) were taken out by mixing and kneading in a pressure kneader at a set temperature of 110 ° C. for 20 minutes. 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 87.5 parts by weight Yellow colorant 1 9.5 parts by weight Charge control agent (calcium salt compound of 3,5-di-tert-butylsalicylic acid) 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 Polymerized rosin ester (Pencel D-125) 0.5 parts by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L (3000 rpm, 3 The mixture was 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, coarsely crushed with a hammer mill, and then an I-type jet mill (IDS- 2 type) and finely pulverized 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 0.5 parts by weight of hydrophobic titanium oxide (STT-30A manufactured by Titanium Industry 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 40.0 parts by weight Carbon black (Monarch 880) 57.0 parts by weight C.I. I. Pigment Blue 15: 3 3.0 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. 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 89.0 parts by weight Black colorant 1 8.0 parts by weight Charge control agent (calcium salt compound of 3,5-di-tert-butylsalicylic acid) 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 Polymerized rosin ester (Pencel D-125) 0.5 parts by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L (3000 rpm, 3 The mixture was 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, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS- 2 type) and finely pulverized 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 0.5 parts by weight of hydrophobic titanium oxide (STT-30A manufactured by Titanium Industry Co., Ltd.) were mixed with a 10 L Henschel mixer (2000 rpm, 1 minute), and a sieving step (100 mesh) ) To obtain black toner 1.

(Image test)
Ferrite carrier coated with silicone resin having an average particle diameter of 60 μm using the cyan toner 1, magenta toner 1, yellow toner 1 and black toner 1 obtained above (DFC-350C manufactured by Dowa Iron Powder Co., Ltd.) Was used to prepare a color developer at a toner concentration of 6% for each color. The image test conditions were as follows.
Full color copier: Canon CLC-730
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 overprinting portions were output.

Moreover, evaluation of each obtained image printed matter was performed.
(Printed matter measurement conditions)
Image density: The density value of a solid portion (yellow, magenta, cyan, black) of the printed matter was measured with 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 5 and 6 show the results.

Reflectance: Spectral reflectance was measured under the following conditions using SpectroEye manufactured by Gretag Macbeth. Light source D50 2 degree field of view Measurement optics 45 ° / 0 ° Without polarizing filter Absolute white paper standard White backing and reflectivity are in the range of 1.40 to 1.50 for yellow toner and image for cyan toner The measurement was performed under conditions where the density value was in the range of 1.60 to 1.75, and in the case of magenta toner, the image density value was in the range of 1.50 to 1.65.

[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, Table 4, Table 5, and Table 6.

  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 (5)

Magenta toner for full color toner set,
The magenta toner includes at least a binder resin and a pigment, and
The magenta toner has a maximum reflectance of 40% to 100% in a wavelength region of 400 nm to 500 nm and a wavelength region of 500 nm to 560 nm when the maximum reflectance is 100% in a wavelength region of 400 nm to 700 nm. It has a spectral reflectance spectrum of a reflectance of 0 to 20% and a reflectance of 80% to 100% in a wavelength range of 630 nm to 700 nm, and the pigment comprises a rhodamine dye metal lake compound and the entire pigment. A magenta toner comprising 0.5 to 10% by weight of a complementary color pigment.   2. The magenta toner according to claim 1, wherein the metal of the metal lake compound is molybdenum and / or tungsten. The complementary color pigment is C.I. I. The magenta toner according to claim 1, which is CI Pigment Violet 1. The magenta toner according to claim 1, wherein the full-color toner includes magenta toner, cyan toner, yellow toner, and black toner. A metal lake compound of a rhodamine dye is C.I. I. Pigment red 81 and / or C.I. I. The magenta toner according to claim 1, which is CI Pigment Red 169.