JP2016090843A - Liquid developer and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid developer that gives superior image density and has excellent fixing property and cold offset resistance, and excellent storage stability for a long period of time.SOLUTION: The liquid developer comprises at least a binder resin (A), a colorant (B), a polymer dispersant (C) and a carrier liquid (D). The polymer dispersant (C) is prepared by copolymerizing at least an ethylenically unsaturated monomer having an amino group and an ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms, and has an amine value of 5 to 150 mgKOH/g. The carrier liquid (D) is an aliphatic hydrocarbon, in which a proportion of primary carbons is 55% or more and a proportion of secondary carbons is 30% or less with respect to the total number of primary to tertiary carbons in the aliphatic hydrocarbon.SELECTED DRAWING: None

Description

  The present invention relates to a liquid developer and printed matter using the same.

  In the liquid developer, since the toner particles are finely pulverized and dispersed under a wet condition, the toner particles can be made finer than a dry powder toner. Further, since the liquid developer uses an insulating liquid carrier liquid as a carrier, there is no problem due to scattering of toner particles in the image forming apparatus. Therefore, an image forming apparatus using a liquid developer has a feature that a high-definition image can be formed.

  In an electrophotographic image forming apparatus using a liquid developer, a developer in which finely divided toner particles are dispersed in a carrier liquid is used. The electrostatic latent image formed on the photoreceptor by exposure is developed using toner particles in a carrier liquid. After development, the obtained electrostatic latent image is transferred, dried and fixed on a recording medium such as paper to form an image.

  The liquid developer is obtained by dispersing toner particles in an electrically insulating carrier liquid, and the toner particles are required to have coloring property, fixing property, charging property, and dispersion stability. The toner particles are composed of additives such as a colorant, a binder resin, and a dispersant. In order to obtain an excellent image, the toner particles are stably dispersed and charged stably. (For example, refer to Patent Documents 1 and 2).

  In an electrophotographic image forming apparatus using a liquid developer, it is known to use a non-contact charging device (a scorotron charging device) as a charging device for a latent image carrier of an organic photoreceptor or an amorphous silicon photoreceptor. Yes. However, when this charging device is used, ozone is generated and members around the device including the liquid developer are easily oxidized. In particular, the electrically insulating carrier liquid contained in the liquid developer is easily oxidized, and the oxide adheres to and accumulates on the surface of the photoreceptor, so that the target electrostatic latent image is not formed, and image quality and continuous printing are achieved. There arises a problem that the stability deteriorates.

  Patent Document 3 describes that an antioxidant is added to the liquid developer, and it is considered that oxidation of the carrier liquid by ozone generated from the charging device is suppressed. However, the use of an antioxidant causes problems such as deterioration of performance, such as toner particles are not sufficiently charged and image density cannot be obtained, and fixing to a substrate and storage stability are hindered. It was.

  In order to uniformly disperse toner particles in an electrically insulating carrier liquid and maintain better storage stability, a polymer dispersant has been studied. However, if the toner particles are stably dispersed and the storage stability is improved, the amount of heat required for the toner particles to melt, contact, and coalesce in the fixing process during image output increases, and the substrate The fixability of the ink is reduced. In addition, a part of incompletely melted toner particles adheres to the surface of the thermocompression roller and causes a cold offset phenomenon in which the toner is transferred to the next paper. Therefore, it has been a difficult problem to achieve both fixing property and cold offset resistance and storage stability. Therefore, in order to achieve both the fixability and the storage stability of the liquid developer, studies have been made on a polymer dispersant that hardly inhibits the fixability (see, for example, Patent Document 4). However, there is a problem that the chargeability of the toner particles is lowered due to the influence of the polymer dispersant and a sufficient image density cannot be obtained, and the long-term stability of the image is lowered and the color development and color reproducibility are impaired. there were.

JP-A-5-333607 Special table 2007-505953 gazette JP 2008-242039 A JP 2009-145535 A

  As described above, the liquid developer has room for improvement in order to obtain a sufficient image density, to achieve both the fixing property and the cold offset resistance, and to obtain the storage stability and the continuous printing stability. There is a need for a liquid developer that solves this problem, has excellent fixability, cold offset resistance, and storage stability, and that can continuously provide a good output image.

  Therefore, the embodiment of the present invention can obtain a sufficient image density, is excellent in fixability, cold offset resistance, storage stability, and has a continuous printing stability that allows continuous good images to be obtained. An object is to provide a developer. Another object of the present invention is to provide a printed matter obtained using this liquid developer.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-described problems can be solved by the following embodiment, and have completed the present invention.

  The present invention is a liquid developer comprising at least a binder resin (A), a colorant (B), a polymer dispersant (C), and a carrier liquid (D), wherein the polymer dispersant (C) is At least an ethylenically unsaturated monomer having an amino group and an ethylenically unsaturated monomer containing an alkyl group having 9 to 24 carbon atoms, and an amine value of 5 to 150 mgKOH / g. And the carrier liquid (D) is an aliphatic hydrocarbon, and the ratio of primary carbon is 55% or more with respect to the total number of primary to tertiary carbons of the aliphatic hydrocarbon. Further, the present invention relates to a liquid developer, wherein the ratio of secondary carbon is 30% or less.

  According to the present invention, a liquid developer having a continuous printing stability capable of obtaining a sufficient image density, excellent in fixability, cold offset resistance and storage stability, and capable of continuously obtaining good images. Can be provided. Further, according to the present invention, it is possible to provide a good printed matter continuously using this liquid developer.

Hereinafter, the present invention will be described in detail.
The liquid developer according to an embodiment of the present invention is a liquid developer including at least a binder resin (A), a colorant (B), a polymer dispersant (C), and a carrier liquid (D), The polymer dispersant (C) is obtained by copolymerizing at least an ethylenically unsaturated monomer having an amino group and an ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms. The value is 5 to 150 mgKOH / g, and the carrier liquid (D) is an aliphatic hydrocarbon, and the ratio of primary carbon to the total number of primary to tertiary carbons of the aliphatic hydrocarbon Is 55% or more and the ratio of secondary carbon is 30% or less. In the liquid developer, the binder resin (A) and the colorant (B) are present as toner particles.

  The ratio of primary carbon is 55% or more and the ratio of secondary carbon is 30% or less with respect to the total number of primary to tertiary carbons in the carrier liquid (D). Oxidation due to ozone generated from the charging device (D) can be suppressed. Although there are various theories in the oxidation reaction mechanism of hydrocarbon solvents often used as a carrier liquid, it is said that oxidation starts when a hydrogen abstraction reaction occurs. In other words, the idea is that if the hydrogen abstraction reaction is difficult to occur, it is difficult to be oxidized. The ease with which a hydrogen atom bonded to a carbon atom is extracted depends on the C—H bond dissociation energy, which varies depending on the series of carbon atoms. The primary carbon is 101 Kcal / mol, the secondary carbon is 98.5 Kcal / mol, and the tertiary carbon is 96.5 Kcal / mol. This is because the hydrogen atom bonded to the primary carbon is most difficult to be extracted, that is, hardly oxidized, while the hydrogen atom bonded to the tertiary carbon is most likely to be extracted, that is, most likely to be oxidized. It is done. Therefore, by using an aliphatic hydrocarbon selected from such a concept for the carrier liquid (D), the oxidation of the carrier liquid (D) is suppressed, so that there is no adhesion and deposition of oxides. An image having a high image density, excellent color reproducibility and color developability can be obtained, and the continuous printing stability is excellent. However, this type of aliphatic hydrocarbon has a high viscosity and the solubility of the polymer dispersant is poor, or the pulverization property of the toner particles is reduced, resulting in a decrease in productivity of the liquid developer. The problem was that the reproducibility of the halftone dots was not high and the dot reproducibility and storage stability could not be obtained.

  Therefore, in order to improve the grindability of the toner particles, the polymer dispersant (C) is obtained using an ethylenically unsaturated monomer having an amino group, and preferably has a specific amine value. The adsorption rate of the polymeric dispersant (C) to the toner particles is increased, the toner particles are improved in pulverization, the toner particles have a small average particle diameter, and a low viscosity liquid developer can be efficiently obtained. An image excellent in reproducibility, color developability and color reproducibility can be obtained. Further, a liquid developer having a stable image (printed image by a copying machine, printed image by a printer, etc.) and excellent storage stability over a long period of time can be obtained. Further, the polymer dispersant (C) is obtained using an ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms, so that the solubility in the carrier liquid (D) is improved, and the toner Excellent grindability and dispersion stability of the particles can be obtained.

  Hereinafter, the binder resin (A), the colorant (B), the polymer dispersant (C), the carrier liquid (D), and the like included in the liquid developer according to the embodiment of the present invention will be described in detail.

(Toner particles)
The toner particles used in the liquid developer include at least the binder resin (A) and the colorant (B), and it is also preferable to use additives such as a pigment dispersant and a charge control agent. The polymer dispersant (C) is preferably added when the toner particles are wet-dispersed in the carrier liquid (D), but can also be added to the toner particles when the toner particles are prepared.

(Binder resin (A))
In general, the binder resin has a function of uniformly dispersing a colorant such as a pigment or a dye in the resin and a function as a binder when fixing to a substrate such as paper. 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 Styrene-vinyl naphthalene copolymer, styrene- (meth) acrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, Styrene copolymers such as styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, and crosslinked. Styrene copolymer; Polyvinyl chloride , Phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral resin Terpene resin, coumarone indene resin, petroleum resin and the like.
The binder resin (A) used for the liquid developer is particularly preferably a polyester resin (a-1) from the viewpoints of pigment dispersibility, grindability, and fixability. Furthermore, the binder resin (A) preferably exhibits a colorless, transparent, white, or light color so as not to inhibit the hue of the color material of each color.

  The polyester resin (a-1) is preferably a thermoplastic polyester, and is preferably obtained by polycondensation of a divalent or trivalent or higher alcohol component and an acid component such as a carboxylic acid.

  Examples of the alcohol component 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, 1,4-bis (hydroxy Methyl) cyclohexane, divalent alcohols such as bisphenol derivatives represented by the following general formula (2); glycerol, diglycerol, sorbit, sorbitan, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, dipe Data erythritol, trihydric or higher alcohols such as tripentaerythritol; and the like. These are used alone or in combination of two or more.

General formula (2)

 (In the formula, R is an ethylene group or a propylene group, x and y are each an integer of 1 or more (preferably 2 or 3), 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; cyclohexane Dicarboxylic acid; naphthalenedicarboxylic acid; diphenoxyethane-2,6-dicarboxylic acid or anhydride thereof; Trivalent or higher carboxylic acids that function as crosslinking components include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, butanetricarboxylic acid, hexanetricarboxylic acid, tetra (methylenecarboxyl) methane, octanetetracarboxylic acid, benzophenonetetracarboxylic acid, Or these anhydrides etc. are mentioned. These are used alone or in combination of two or more.

  Preferred alcohol components are bisphenol derivatives represented by the general formula (2), ethylene glycol, neopentyl glycol and the like. Preferred acid components are: phthalic acid, terephthalic acid, isophthalic acid or anhydride thereof; succinic acid, n-dodecenyl succinic acid or anhydride thereof; dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride; trimellitic acid or anhydride thereof Tricarboxylic acids such as products.

  In the polycondensation of the polyester resin (a-1), the reaction may be promoted using a known and usual reaction catalyst such as at least one metal compound selected from antimony, titanium, tin, zinc and manganese. Specific examples of the reaction catalyst include di-n-butyltin oxide, stannous oxalate, antimony trioxide, titanium tetrabutoxide, manganese acetate, and zinc acetate. The addition amount of these reaction catalysts is usually preferably about 0.001 to 0.5 mol% with respect to the acid component in the obtained polyester resin (a-1).

  As the polycondensation method, a known bulk polymerization method can be used, and in order to control the molecular weight, softening temperature, etc. of the polyester resin, the kind of alcohol component and carboxylic acid to be reacted, molar ratio, reaction temperature, reaction What is necessary is just to adjust time, reaction pressure, a catalyst, etc. Furthermore, it is also possible to use a commercial item as a polyester resin. For example, there are Diacron ER-502 and Diacron ER-508 (both manufactured by Mitsubishi Rayon Co., Ltd.).

  Furthermore, in order to improve fixability and grindability, the binder resin (A) is at least selected from the group consisting of a polyester resin (a-1), a styrene resin, an acrylic resin, and a styrene-acrylic copolymer resin. It is preferable to contain 1 type of resin (a-2) (henceforth only resin (a-2)). The styrene-acrylic copolymer resin is obtained by polymerizing at least one of styrene monomers and at least one of (meth) acrylic acid and (meth) acrylic acid esters. Styrene monomers used for the resin (a-2) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p -Methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and the like.

  Examples of the (meth) acrylic acid esters used for the resin (a-2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) Isobutyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, 2-chloroethyl (meth) acrylate, Examples include phenyl (meth) acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl (meth) acrylate. A preferred styrenic monomer is styrene. Preferred (meth) acrylic acid esters are butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

  Moreover, in order to make the molecular weight of resin (a-2) larger, a polyfunctional monomer can be used as a crosslinking agent. Specifically, divinylbenzene, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri ( And (meth) acrylate.

  The resin (a-2) can be obtained by a known polymerization method such as a suspension polymerization method, a solution polymerization method, or an emulsion polymerization method. For example, in order to control the molecular weight and softening temperature of styrene-acrylic copolymer resin, the types and molar ratios of the styrene monomer, (meth) acrylic acid and (meth) acrylic acid ester, and further the reaction temperature and reaction time. The reaction pressure, polymerization initiator, crosslinking agent, etc. may be adjusted. Furthermore, it is also possible to use a commercial item as a styrene-acrylic copolymer resin. For example, there are ALMATEX CPR100, CPR200, CPR300, CPR600B (Mitsui Chemicals).

In order to obtain a binder resin (A) that is more uniformly dispersed by mixing the polyester resin (a-1) and the resin (a-2), the polyester resin (a-1) and the resin (a-2) And a method of polymerizing by adding a monomer for the other resin in the presence of one of the polymerized polyester resin (a-1) and resin (a-2). . The latter is desirable for obtaining a more uniformly dispersed binder resin. Usually, after the polyester resin (a-1) is polycondensed by bulk polymerization, the obtained polyester resin (a-1) is dissolved in a solvent. In such a system, a method of synthesizing the resin (a-2) by solution polymerization while heating as necessary and removing the solvent is preferable.
Furthermore, it is also preferable to synthesize | combine by well-known methods like the method of the patent 3531980 and Unexamined-Japanese-Patent No. 2006-178296.

  Moreover, when producing polyester resin (a-1) and resin (a-2) separately, or when using commercially available polyester resin and resin (a-2), polyester resin (a-1). And the resin (a-2) can be mixed to obtain the binder resin (A). At this time, it may be either a method in which both are dissolved in a solvent and mixing and desolvation are performed, or melt kneading is performed.

  Furthermore, the mass ratio [(a-2) / (a-1)] of the polyester resin (a-1) and the resin (a-2) contained in the binder resin (A) is preferably 1 or less. More preferably, the mass ratio is 0.5 or less. When the mass ratio exceeds 1, the pulverizability of the toner particles is lowered, and the color developability and storage stability as a liquid developer may be lowered.

(Softening temperature (T4))
The softening temperature of the binder resin (A) is preferably in the range of 80 to 140 ° C. More preferably, it is the range of 90 to 130 degreeC. The softening temperature was “Flow Tester CFT-500D” manufactured by Shimadzu Corporation, starting temperature 40 ° C., heating rate 6.0 ° C./min, test load 20 kgf, preheating time 300 seconds, die hole diameter 0.5 mm. The temperature when 4 mm of 1.0 g of the sample flows out under the condition of the die length of 1.0 mm is measured as the softening temperature (T4).

  When the softening temperature of the binder resin (A) is 80 ° C. or higher, it is not excessively softened during kneading, dispersibility of the colorant (B) is improved, and a sufficient image density as a liquid developer can be obtained. it can. Furthermore, in the fixing process during image output, the toner particles come into contact with the surface of the thermocompression roller in a molten state, so the cohesive force of the toner particles is smaller than the adhesive force between the substrate and the thermocompression roller, and part of it is completely The toner particles adhere to the surface of the thermocompression roller without being adhered to the surface, and the hot offset phenomenon that the toner particles are transferred to the next paper is less likely to occur. Further, when the softening temperature is 140 ° C. or lower, good fixability is obtained, the grindability is improved, and the color developability is enhanced.

(Average molecular weight)
The binder resin (A) has a weight average molecular weight (Mw) of 2,000 to 100 in terms of molecular weight measured by gel permeation chromatography (GPC) from the viewpoint of offset resistance, fixing property and image quality characteristics. 5,000 are preferable, and 5,000 to 50,000 are more preferable. When the weight average molecular weight (Mw) of the binder resin (A) is 2,000 or more, hot offset resistance, color reproducibility, and dispersion stability are improved. Cold offset property is improved. In addition, the binder resin (A) is a type having a molecular weight distribution curve of two peaks comprising a specific low molecular weight condensation polymer component and a specific high molecular weight condensation polymer component, or a single molecular weight distribution curve. Any of the types having

  Furthermore, in the molecular weight measured by gel permeation chromatography (GPC), the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin (A) is in the range of 2-20. It is preferable that When Mw / Mn exceeds 2, the offset resistance is increased and the non-offset region is widened to improve the low temperature fixability. When Mw / Mn is less than 20, the pulverizability of the toner particles becomes high, a sufficient image density is obtained, and the image characteristics are improved, such as high color developability.

  In addition, the molecular weight and molecular weight distribution by said GPC can be measured on the following conditions using the gel permeation chromatography (HLC-8220) by Tosoh Corporation. The column is stabilized in a 40 ° C. heat chamber, tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 0.6 mL / min, and 10 μL of a sample solution dissolved in THF is injected for measurement. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.

Ten standard polystyrene samples with a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation are used as a standard polystyrene sample for preparing a calibration curve. An RI (refractive index) detector is used as the detector. In addition, three TSKgel SuperHM-M (made by Tosoh Corporation) are used for the column.

  The measurement sample is prepared as follows. Place the sample in THF and let stand for several hours, then shake well, mix well with THF until the sample is no longer united, and let stand for more than 12 hours. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, the obtained solution is passed through a sample processing filter to obtain a sample solution for GPC measurement. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / mL.

  The content of the binder resin (A) contained in the toner particles is preferably 60 to 95 parts by mass, more preferably 70 to 90 parts by mass with respect to 100 parts by mass of the toner particles. When it is 60 parts by mass or more, the fixing property and offset resistance are improved, and when it is 95 parts by mass or less, the ratio of the binder resin (A) to the colorant (B) becomes small, and the toner particles The coloring power is improved and the image density is increased.

(Colorant (B))
As the colorant (B), yellow, magenta, cyan, and black organic pigments and organic dyes shown below, in particular, salt-forming compounds thereof; carbon black; magnetic substances are preferably used. These can be used alone or in admixture of two or more. The colorant (B) is preferably insoluble in the carrier liquid (D).

  As the yellow colorant, it is preferable to use a yellow organic pigment or a salt forming compound of a yellow dye. Examples of yellow organic pigments include benzimidazolone compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, quinophthalone compounds, azo metal complex compounds, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 138, 139, 147, 150, 168, 174, 176, 180, 181, 185, 191 etc. are preferably used. Among these, it is preferable to use a quinophthalone compound, a condensed azo compound, or a benzimidazolone compound. Further, as the salt forming compound of yellow dye, a salt forming compound of acidic dye or a salt forming compound of basic dye is used. Examples of the salt forming compound of the acid dye include C.I. I. It is preferable to use a salt-forming compound comprising acid yellow 11 or 23 (tartrazine) and a quaternary ammonium salt compound. By constituting the quaternary ammonium salt, the toner particles can maintain a stable positive charge.

  As the magenta colorant, it is preferable to use a salt-forming compound of a magenta organic pigment or a magenta dye. As magenta organic pigments, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, lake compounds of basic dyes such as rhodamine lakes, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 209, 220, 221, 254, 255, 268, 269, etc., C.I. I. Pigment violet 1, 19 and the like are preferably used. Of these, quinacridone compounds, rhodamine lake pigments, naphthol pigments, and the like are preferably used. Specifically, naphthol AS (CI Pigment Red 269 etc.), rhodamine lake (CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 169 etc.), quinacridone (C.I. Pigment Red 122 etc.) Carmine 6B (C.I. Pigment Red 57: 1) is a preferred material. A combination of a quinacridone pigment and a monoazo pigment Carmine 6B (CI Pigment Red 57: 1) is preferable because it exhibits a good magenta or red color. Further, as a salt-forming compound of a magenta dye, a salt-forming compound of a rhodamine-based acidic dye or a salt-forming compound of a rhodamine-based basic dye is preferably used. Examples of the salt forming compound of the basic dye include C.I. I. It is preferable to use a salt-forming compound comprising Basic Red 1 or Basic Violet 10 and colorless (does not inhibit coloring of the pigment) organic sulfonic acid or organic carboxylic acid. Since the basic dye exhibits a good positive charge, the toner particles can maintain a stable positive charge. As the organic sulfonic acid, naphthalenesulfonic acid, naphtholsulfonic acid, naphthylaminesulfonic acid and the like are preferably used. As the organic carboxylic acid, salicylic acid derivatives, higher fatty acids and the like are preferably used.

  As the cyan colorant, it is preferable to use cyan and blue organic pigments, cyan and blue dye salt forming compounds, cyan and blue dye oil-soluble dyes, and the like. As the cyan organic pigment, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, 62, 66 and the like are preferably used. Among them, C.I. I. It is preferable to use a copper phthalocyanine compound such as CI Pigment Blue 15: 3. It is also preferable to use a compound derived from a triarylmethane dye in a form used in combination with the organic pigment. Triarylmethane dyes are effective materials in terms of both charge control and colorability because they have good positive chargeability. In particular, C.I. I. A triarylmethane oil-soluble dye such as Solvent Blue 124 or a salt-forming compound of a triarylmethane basic dye is good. C. I. As the solvent blue 124, specifically, COPY BLUE PR manufactured by Clariant is a preferable material. This is C.I. I. It was obtained by condensing Basic Red 9 (paramagenta) and aniline. Further, for the purpose of adjusting the hue, in addition to the cyan or blue organic pigment, the salt forming compound of cyan or blue dye, the oil-soluble dye of cyan or blue dye, a green pigment can be used as a complementary color. Specific examples of the green pigment include C.I. I. Halogenated phthalocyanine compounds such as CI Pigment Green 7 and 36 are preferred.

  From the viewpoint of cost and handling, it is preferable to use organic black pigments such as carbon black and perylene black, and organic black dyes such as nigrosine dyes and azo metal complex dyes as the black colorant. As carbon black, any of various types such as furnace black, channel black, acetylene black, carbon black derived from biomass can be used. Furnace black carbon and biomass carbon are preferable because they have an effect of reducing fog (background stain on the white background) in image characteristics. As the nigrosine dye, it is preferable to use a nigrosine base that is refined by wet pulverization or the like and has a volume average particle size of 0.5 to 2 μm. Since the refined nigrosine dye has a gloss, a glossy black color can be obtained. Nigrosine refinement can be obtained by the method described in JP-A-2006-171501. Further, as the black colorant, black can be obtained using the above three colorants of yellow, magenta, and cyan.

  Furthermore, in order to obtain black with good image density and contrast, it is preferable to use a colorant in which 1 to 10 parts by mass of a blue colorant is added to 100 parts by mass of the black colorant as a black colorant. . As the blue colorant, it is preferable to use a halogen-free metal phthalocyanine blue compound, a triarylmethane compound, a dioxazine violet pigment, or the like. In addition, the phthalocyanine blue compound and the triarylmethane compound have a stable positive charging property, which is effective in obtaining good black toner particles. Specifically, C.I. I. Pigment Blue 15: 3, Victoria Pure Blue Lake Pigment (CI Pigment Blue 1), C.I. I. Pigment violet 23, C.I. I. Pigment Violet 19, a salt-forming compound composed of a triarylmethane-based basic dye and a substantially colorless organic acid (a salt-forming compound of CI Basic Blue 7 and an organic acid), a triarylmethane-based oil-soluble dye Etc. are preferably used. Triarylmethane dyes are effective in controlling the chargeability of toner particles by exhibiting good positive charge, and among them, triarylmethane oil-soluble dyes having excellent dispersibility are preferred.

  The content of the colorant (B) contained in the toner particles varies depending on the type of the binder resin (A) used, but is usually 5 to 50 parts by mass, preferably 10 to 10 parts by mass with respect to 100 parts by mass of the toner particles. 30 parts by mass.

  When a full-color image using a liquid developer is obtained, a preferable image utilizing fixability and color developability can be obtained by using four basic process colors of Y, M, C, and Bk. In addition, intermediate colors such as violet and green can be used.

(Polymer dispersant (C))
Generally, the polymer dispersant (C) is added to a carrier liquid in which toner particles are present to uniformly disperse the toner particles and improve development characteristics. (C) may be added to the carrier liquid or may be added to the toner particles during kneading in the toner production. When added to the carrier liquid and the toner particles are dispersed, the polymer dispersant (C) is adsorbed on the binder resin portion on the toner particle surface, particularly on the polyester resin portion that exhibits excellent dispersion stability. It is inferred that Thus, the polymer dispersant (C) is preferably present in a state of being adsorbed on the surface of the toner particles or dispersed inside the toner particles.

  The polymer dispersant (C) is obtained from an ethylenically unsaturated monomer having at least an amino group and an ethylenically unsaturated monomer having 9 to 24 carbon atoms. A suitable polymerization method for the polymer dispersant (C) is solution polymerization of a normal acrylic resin. The ratio of the ethylenically unsaturated monomer having an amino group (molar ratio of the charged amount) is preferably 1 to 50%, more preferably 5 to 35%, and most preferably 10 to 40%. . The ratio of the ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms is preferably 50 to 99%, more preferably 65 to 95%, and most preferably 60 to 90%.

  In accordance with the molecular weight of the intended polymer dispersant (C), an ethylenically unsaturated monomer having an amino group, an ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms, and a general formula The polymer dispersant (C) can be obtained by mixing and heating the ethylenically unsaturated monomer represented by (1) and optionally a polymerization initiator, a chain transfer agent or the like. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.

(Polymerization initiator)
Although it does not specifically limit as a polymerization initiator used by superposition | polymerization of a polymer dispersing agent (C), For example, an azo type compound and an organic peroxide can be used. In the polymerization, 0.001 to 5 parts by mass of a polymerization initiator can be arbitrarily used with respect to 100 parts by mass of all monomers.

  Examples of the azo compounds include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) ), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2 ′-[2- (2-imidazolin-2-yl) Propane] and the like.

  Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

  These polymerization initiators can be used alone or in combination of two or more.

(Chain transfer agent)
As the chain transfer agent, thiol compounds such as mercaptan-based, thioglycol-based, β-mercaptopropionic acid-based, rosin-based compounds having allylic hydrogen, terpene-based compounds, and the like can be used. When using a chain transfer agent, the addition amount is 0.01 to 10.0 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of all monomers.

(Polymerization solvent)
In the synthesis of the polymer dispersant (C), a known solvent is preferably used. However, when the polymer dispersant (C) is used as a liquid developer, the polymer dispersant (C) can be taken out in a state dissolved in the solvent of the carrier liquid (D) used in the liquid developer, or It can be taken out as a solid. When the polymer dispersant (C) is added when the toner particles are wet-dispersed in the carrier liquid (D), the polymer dispersant (C) is preferably dissolved in the carrier liquid (D). In the case where the molecular dispersant (C) is used by adding it to the toner particles when preparing the toner particles, the polymer dispersant (C) is preferably a solid. There are the following three methods for obtaining the polymer dispersant (C) dissolved in the carrier liquid (D). As a first method, the carrier liquid (D) used in the liquid developing toner is polymerized using a synthetic solvent. As a second method, polymerization is performed in a solvent that can be replaced with the carrier liquid (D), and then the carrier liquid (D) is added, and only the solvent used for the polymerization is distilled off. As a third method, polymerization is performed in a mixed solution of a solvent that can be replaced with the carrier liquid (D) and the carrier liquid (D), and then only the solvent other than the carrier liquid (D) is distilled off. Therefore, as the polymerization initiator, it is preferable to use a solvent that can be replaced with the carrier liquid (D) used for the liquid developer after the synthesis to the polymer dispersant (C) or a solvent that can be distilled off.

  As a solvent that can be solvent-substituted for the carrier liquid (D), a solvent having a boiling point lower than that of the carrier liquid (D) is preferable. For example, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, ethanol, propanol, butanol and the like are used. Two or more kinds of these polymerization solvents may be mixed and used. Among these, n-propyl acetate or toluene is particularly preferable from the viewpoints of polymerization temperature, simplicity of solvent evaporation, solvent polarity, and the like. In order to take it out as a solid, the solvent is distilled off after the polymerization of the polymer dispersant (C). The solvent that can be distilled off is not particularly limited, but a solvent that can be easily distilled off as described above is preferable.

(Ethylenically unsaturated monomer having an amino group)
The ethylenically unsaturated monomer having an amino group increases the adsorption rate of the polymer dispersant (C) to the toner particles, and contributes to a stable image and excellent storage stability over a long period of time. The amino group in the ethylenically unsaturated monomer having an amino group is not particularly limited, but is preferably a secondary amino group or a tertiary amino group, and more preferably a tertiary amino group. The amino group here does not include an amino group constituting an amide bond. For example, alkyl (meth) acrylamides, which are examples of an ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms, cannot obtain the effect exhibited by an ethylenically unsaturated monomer having an amino group. Among the ethylenically unsaturated monomers having an amino group, examples of the ethylenically unsaturated monomer having a tertiary amino group include N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl. N, N-dialkylamino group-containing (meth) acrylic acid esters such as (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate; N, N-dimethyl Contains N, N-dialkylamino groups such as aminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide (Meth) acrylamides; dimethylaminostyrene, Ethylamino styrene; and the like.

  Examples of the ethylenically unsaturated monomer having a secondary amino group include tert-butylaminoethyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, and the like.

  Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide and the like are preferable from the viewpoint of dispersibility. Two or more types of ethylenically unsaturated monomers having an amino group may be used in combination.

  The amine value of the polymer dispersant (C) is preferably 5 to 150 mgKOH / g. More preferably, it is 30-100 mgKOH / g. When the amine value is 5 mgKOH / g or more, the adsorption to the toner particles is sufficient, and the grindability in wet grinding is improved. Furthermore, the toner particles are prevented from agglomerating during long-term storage, the viscosity of the liquid developer and the average particle size of the toner particles are maintained, and storage stability is improved. When the amine value is 150 mgKOH / g or less, the chargeability of the toner particles becomes high, the toner particles are easily transferred to the substrate, and a good image density can be obtained. Furthermore, the solubility in the carrier liquid (D) is increased, and the grindability is improved. The amine value of the polymer dispersant (C) is the total amine value (mgKOH / g) measured according to the method of ASTM D2074.

(Ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms)
Further, in the ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms, the alkyl group having 9 to 24 carbon atoms enhances the solubility in the carrier liquid (D), and the pulverizability of the toner particles in wet pulverization. Furthermore, during storage for a long period of time, aggregation of toner particles and increase in viscosity of the liquid developer are suppressed, and an excellent storage stability effect is exhibited. When the alkyl group has 9 or more carbon atoms, the solubility in the carrier liquid (D) is high, and the dispersion stability and storage stability of the toner particles are enhanced. When the alkyl group has 24 or less carbon atoms, when the liquid developer is fixed to the substrate, the alkyl group does not hinder the contact and coalescence of the toner particles, and the fixing property does not deteriorate. Furthermore, the chargeability of the toner particles is increased, the toner particles are easily transferred to the substrate, and a sufficient image density can be obtained.

  Moreover, the alkyl group of 9-24 may have a substituent, and examples of the substituent include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, and a biphenyl group. In addition, the ethylenically unsaturated monomer represented by General formula (1) mentioned later shall not be contained in the ethylenically unsaturated monomer which has a C9-C24 alkyl group. The ethylenically unsaturated monomer represented by the general formula (1) has a hydrocarbon group having 1 to 22 carbon atoms, but the ethylenically unsaturated monomer represented by the general formula (1). Depending on the body, the effect of the ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms cannot be obtained.

  Examples of the ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms include nonyl (meth) acrylate, 8-methylnonyl (meth) acrylate, 2-methylnonyl (meth) acrylate, decyl (meth) acrylate, 2 -Methyldecyl (meth) acrylate, undecyl (meth) acrylate, 2-methylundecyl (meth) acrylate, 9-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, 11- Methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 2-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, 2-methyltetradecyl (meth) acrylate, pentadecyl (meth) acrylate, 2-methyl Ntadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 2-methylheptadecyl (meth) acrylate, octadecyl (meth) acrylate, 2-methyloctadecyl (meth) ) Acrylate, nonadecyl (meth) acrylate, 2-methylnonadecyl (meth) acrylate, icosyl (meth) acrylate, heicosyl (meth) acrylate, docosyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meta) ) Alkyl (meth) having an alkyl group having 9 to 24 carbon atoms such as acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. (Meth) acrylates such as acrylate; N-nonyl (meth) acrylamide, N- (8-methylnonyl) (meth) acrylamide, N-decyl (meth) acrylamide, N, N-didecyl (meth) acrylamide, N-undecyl (Meth) acrylamide, N- (1-methylundecyl) (meth) acrylamide, N-dodecyl (meth) acrylamide, N, N-didodecyl (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (1- Methyltridecyl) (meth) acrylamide, N-tetradecyl (meth) acrylamide, N, N-ditetradecyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N- (1-methylpentadecyl) (meth) acrylamide, N -Hexadecyl (meth) acrylic N, N-dihexadecyl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N- (1-methylheptadecyl (meth) acrylamide), N-octadecyl (meth) acrylamide, N, N-dioctadecyl (meth) ) Alkyl (meth) having an alkyl group having 9 to 24 carbon atoms such as acrylamide, N-nonadecyl (meth) acrylamide, N-icosyl (meth) acrylamide, N-henicosyl (meth) acrylamide, N-docodecyl (meth) acrylamide, etc. Acrylamides; 4-nonylphenyl (meth) acrylate, 4'-decyl-4-biphenylyl (meth) acrylate, 3-pentadecylphenyl (meth) acrylate, N- (10-phenyldecyl) (meth) acrylamide, N- (4-dodecyl fe ) (Meth) acrylamide, N- [2- (1-naphthyl) ethyl] -N-dodecyl (meth) acrylamide, N- [4- (1-pyrenyl) butyl] -N-dodecyl (meth) acrylamide, N -(Meth) acrylates and (meth) acrylamides having an aromatic ring such as octadecyl-N- [2- (1-naphthyl) ethyl] (meth) acrylamide and an alkyl group having 9 to 24 carbon atoms; 1-undecene, 1 -Dodecene, 2-dodecene, 1-tridecene, 2-tridecene, 1-tetradecene, 2-tetradecene, 4-tetradecene, 1-pentadecene, 2-pentadecene, 4-pentadecene, 1-hexadecene, 2-hexadecene, 4-hexadecene 1-heptadecene, 2-heptadecene, 4-heptadecene, 1-octadecene, 2-octadecene, 4 Octadecene, 1-docosene, 2-docosenoic, alpha-olefins having an alkyl group with a carbon number 9 to 24 and 4-docosenoic; like.

  Among these, from the viewpoint of dispersibility, (meth) acrylates such as alkyl (meth) acrylate having an alkyl group having 9 to 24 carbon atoms are preferable. Examples of the alkyl group having 9 to 24 carbon atoms include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and a linear alkyl group or a branched alkyl group is preferable. Two or more types of ethylenically unsaturated monomers having an alkyl group having 9 to 24 carbon atoms may be used in combination.

(Ethylenically unsaturated monomer represented by general formula (1))
Of the polymeric dispersant (C), the ethylenically unsaturated monomer represented by the general formula (1) is effective in improving the fixing property. By including the ethylenically unsaturated monomer represented by the general formula (1), the compatibility with the binder resin (A) is improved, and in the fixing process, the molten state of the toner particles is improved, and the substrate Improves the fixing property. Further, it is possible to suppress the cold offset phenomenon in which the toner particles that are insufficiently melted adhere to the thermocompression roller and transfer to the next paper. The ethylenically unsaturated monomer represented by the general formula (1) is, for example, ring-opening polymerization of ethylene oxide with alkyl alcohol, and then the obtained reaction product is transesterified with methyl (meth) acrylate. Alternatively, it can be obtained by reacting with (meth) acrylic acid chloride.

General formula (1)
CH ₂ = C (R ¹ ) COO (AO) _n R ²
(In the formula, R ¹ represents H or CH ₃ , R ² represents hydrogen or a hydrocarbon group having 1 to 22 carbon atoms, n represents an integer of 1 to 200, and A represents an alkylene group having 2 to 4 carbon atoms. )

  In the said General formula (1), an alkylene oxide group (AO) is a C2-C4 alkylene oxide group, for example, an ethylene oxide group, a propylene oxide group, or a butylene oxide group is mentioned. Moreover, the alkylene oxide group from which carbon number differs may exist in the same monomer.

  The number (n) of alkylene oxide groups is an integer of 1 to 200, preferably an integer of 1 to 30. When it is 200 or less, sufficient compatibility with the above-described ethylenically unsaturated monomer having an alkyl group having 9 to 24 carbon atoms in the molecule can be obtained. R2 is hydrogen or a hydrocarbon group having 1 to 22 carbon atoms. When the number of carbon atoms is 22 or less, raw materials are easily available and practical. As the hydrocarbon group having 1 to 22 carbon atoms, a substituted or unsubstituted group can be selected, an unsubstituted group is preferable, and an unsubstituted alkyl group is preferable. As the unsubstituted alkyl group, those having a branch and those having no branch can be used. Two or more types of ethylenically unsaturated monomers represented by the general formula (1) may be used in combination. R2 is more preferably hydrogen or a hydrocarbon group having 1 to 18 carbon atoms.

  Specific examples of the compound having an alkylene oxide chain include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, and poly (ethylene glycol-propylene glycol) mono (meta). ) Acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, polyethylene glycol mono (meth) acrylate monomethyl ether, polyethylene glycol mono (meth) acrylate Monobutyl ether, polyethylene glycol mono (meth) acrylate monooctyl ether, polyethylene glycol mono (me ) Acrylate monobenzyl ether, polyethylene glycol mono (meth) acrylate monophenyl ether, polyethylene glycol mono (meth) acrylate monodecyl ether, polyethylene glycol mono (meth) acrylate monododecyl ether, polyethylene glycol mono (meth) acrylate monotetradecyl ether , Polyethylene glycol mono (meth) acrylate monohexadecyl ether, polyethylene glycol mono (meth) acrylate monooctadecyl ether, poly (ethylene glycol-propylene glycol) mono (meth) acrylate octyl ether, poly (ethylene glycol-propylene glycol) mono ( (Meth) acrylate octadecyl ether, poly (ethylene glycol) B propylene glycol) mono (meth) acrylate nonylphenyl ether. Two or more of these may be used in combination.

(Other copolymerizable polymerizable monomers)
Other unsaturated compounds that may be included as polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) (Meth) acrylates such as alkyl (meth) acrylates having 1 to 8 carbon atoms such as acrylate; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acryl Amide, N-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-isopentyl (meth) acrylamide, N-neopentyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-isohexyl (meth) (Meth) such as acrylamide, Nn-heptyl (meth) acrylamide, N- (6-methylheptyl) (meth) acrylamide, N-octyl (meth) acrylamide, N- (7-methyloctyl) (meth) acrylamide Acrylamides: 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 4-ethyl-2-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene , 1-nonene, 2-nonene, 1-decene, 2-decene, etc. α- olefins having 8 alkyl group; and the like.

  Furthermore, cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate; aromatic rings such as benzyl (meth) acrylate (meth) Acrylates: Vinyl such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate can be exemplified. Unsaturated compounds other than those described above can also be used as long as they do not affect the physical properties.

  Further, the weight average molecular weight (Mw) of the polymer dispersant (C) is not limited to a specific range, but in consideration of dispersibility and pulverization properties when the toner particles are wet-dispersed, gel permeation chromatography ( The molecular weight measured by GPC) is preferably 500 to 40,000, and more preferably 2,000 to 30,000. The weight average molecular weight (Mw) can be measured by the method described above.

  The ratio of the ethylenically unsaturated monomer represented by the general formula (1) to the polymer dispersant (C) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, Preferably it is 10-30 mass%.

The polymer dispersant (C) is preferably added in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the liquid developer. More preferably, it is the range of 0.5-5 mass parts. When the amount is 0.1 part by mass or more, the dispersibility and pulverization properties of the toner particles are improved, and the storage stability is improved. When the addition amount is 10 parts by mass or less, the chargeability of the toner particles is increased, so that a sufficient image density can be obtained and the fixability is also improved. When the toner particles contain the polymer dispersant (C), the above range is a range including the amount of the polymer dispersant (C) contained in the toner particles.

(Other dispersants)
As the dispersant, in addition to the polymer dispersant (C) used in the present invention, a dispersant conventionally used in a liquid developer may be used. Specifically, fatty acid metal salts such as cobalt naphthenate, zinc naphthenate, copper naphthenate, manganese naphthenate, cobalt octylate and zirconium octylate, titanate coupling agents of organic titanates such as lecithin and titanium chelate, alkoxy Examples include titanium polymers, polyhydroxy titanium carboxylate compounds, titanium alkoxides, succinimide compounds, polyimine compounds, fluorine-containing silane compounds, and pyrrolidone compounds. In particular, titanium alkoxide, a succinimide compound, a fluorine-containing silane compound, a pyrrolidone-based compound, and the like may be mixed and used in an appropriate amount within a range of 5 parts by mass or less with respect to 100 parts by mass of the liquid developer. In this case, the dispersant is used in such a manner that the dispersant having the same polarity as the toner particles is adsorbed on the toner particles, and the dispersant having the opposite polarity to the toner particles is not adsorbed on the toner particles and dispersed in the carrier liquid. It becomes a form to make it. At this time, the standard for discussing the polarity is the polarity with respect to the carrier liquid. In addition, this behavior is determined after an actual image test and is obtained empirically.

(Carrier liquid (D))
The carrier liquid (D) used for the liquid developer is an aliphatic hydrocarbon, and the proportion of primary carbon is 55% with respect to the total number of primary to tertiary carbons of the aliphatic hydrocarbon. The secondary carbon ratio is 30% or less. In this range, that is, when the proportion of primary carbon is 55% or more and the secondary carbon is 30% or less, the oxidation resistance to ozone generated by the charging device is sufficient, and image quality and continuous printing are achieved. There is no loss of stability. Examples of the aliphatic hydrocarbon include linear paraffinic hydrocarbons, isoparaffinic hydrocarbons, naphthenic hydrocarbons, and the like. Among these, paraffinic hydrocarbons with very little residual aromatic hydrocarbon are preferable, and isoparaffinic hydrocarbons with a large amount of primary carbon are more preferable. Further, those having lipophilic properties, chemically stable and insulating properties are preferred. Further, the carrier liquid is preferably chemically inert with respect to a substance or apparatus used in the image forming apparatus, in particular, a member for a development process such as a photosensitive member and its peripheral part.

  The dry point in the distillation range of the carrier liquid (D) is preferably in the range of 200 to 360 ° C. Especially preferably, it is the range of 240-320 degreeC. When the temperature is 200 ° C. or higher, the liquid developer does not dry at room temperature and solid matter does not precipitate, so that the regulation blade around the development does not stick and image contamination does not occur. Moreover, since it is easy to remove carrier liquid (D) as it is 360 degrees C or less, sufficient fixability is acquired. Here, the dry point in the distillation range is determined by the method defined by ASTM D86, ASTM D1078, and JIS K2254.

  Moreover, as a carrier liquid (D), it is preferable to use a Kauri butanol numerical value (KB value: ASTM D1133) of 40 or less. More preferably, it is the range of 20-30. The aniline point (JIS K2256) is preferably in the range of 60 to 105 ° C., more preferably 70 to 95 ° C., in order to obtain a stable carrier liquid. When the Kauributanol value is 40 or less, or the aniline point is 60 ° C. or more, the solubility as a solvent is low, and the carrier liquid does not dissolve the toner particles, so that the storage stability and color reproducibility of the toner particles are improved. It is possible to prevent the occurrence of problems such as an increase in color and contamination of a substrate such as paper by coloring the carrier liquid. When the aniline point is 105 ° C. or lower, the compatibility with the dispersant and additives added when dispersing the toner particles in the carrier liquid is high, the dispersibility is improved, and a sufficient image density can be obtained. .

Specifically describing the insulating property of the carrier liquid (D), the dielectric constant is 10 or less, preferably 1 to 5, and more preferably 2 to 3. At the same time, the electric resistivity of the carrier liquid (D) is preferably 10 ⁹ Ω · cm or more, more preferably 10 ¹⁰ Ω · cm or more, and particularly preferably 10 ¹¹ to 10 ¹⁶ Ω · cm. Here, the electrical resistivity can be determined by combining a universal electrometer MMA-II-17D manufactured by Kawaguchi Electric Manufacturing Co., Ltd. and a liquid electrode LP-05. When the electrical resistivity is 10 ⁹ Ω · cm or more, the chargeability of the toner particles becomes high, and a sufficient image density can be obtained, and color reproducibility and color developability are improved.

Further, the density (JIS K2249) at 15 ° C. of the carrier liquid (D) is preferably in the range of 0.67 to 0.9 g / cm ³ . More preferably, it is in the range of 0.70 to 0.85 g / cm ³² . This range is preferable because toner particles and a dispersant can exist stably, and thus excellent fixing properties and image density can be obtained. The carrier liquid (D) preferably has a kinematic viscosity (ASTM D445) in the range of 1 to 25 mm ² / s. Especially preferably, it is the range of 3-15 mm < ² > / s. This range is preferable in that the charged particles can be moved at the time of the phenomenon, and have sufficient volatility, and the carrier liquid can be easily removed from the medium on which the final image is formed in the fixing step. When the kinematic viscosity is 1 mm ² / s or more, the viscosity of the liquid developer increases, so that the transfer property to the developing roller is high, and a sufficient image density can be obtained. Further, the toner particles after development are prevented from moving, and the fineness of the image is improved. Further, when the kinematic viscosity is 25 mm ² / s or less, the fluidity of the toner particles is improved and electrophoresis tends to occur, so that a sufficient image density can be obtained. Furthermore, the permeability to a substrate such as paper is high, and the carrier liquid can be easily removed when the toner particles are fixed, so that sufficient fixability can be obtained. In particular, the fixability in the superimposed image is greatly improved.

  Specifically preferred carrier liquids (D) are branched paraffin solvent mixtures, especially isoparaffinic, such as “Shellsol ™” (manufactured by Shell Chemicals), “IP Solvent 2028” (manufactured by Idemitsu Kosan). A hydrocarbon is preferred.

(Other additives)
(Pigment dispersant)
Examples of pigment dispersants that are internally added to the toner particles include polyamine-based resin-type dispersant Solsperse 24000SC, Solsperse 32000 (manufactured by Lubrizol Corporation), Azisper PB821 (manufactured by Ajinomoto Fine-Techno Corporation); resin-type dispersant of acrylic copolymer BYK-116 (manufactured by Big Chemie) or the like can be used. In particular, when producing via a colored master batch having a high pigment concentration, it is preferable to add at the time of producing the master batch. The addition amount of the pigment dispersant is preferably 3 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the colorant (B) from the viewpoint of improving the dispersibility of the toner particles. Further, from the viewpoint of improving the pulverization property and productivity of the toner particles, the amount is preferably 40 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass of the colorant (B).

(Dye derivative)
In the toner particles, it is also possible to use a dye derivative as long as the color developability of the colorant (B) is not impaired. Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic dye (organic pigment, organic dye), anthraquinone, acridone, or triazine. Can be mentioned. Of these, pigment derivatives are preferred, and the structure is a compound represented by the following general formula (3).
P-Ln Formula (3)
(Wherein P is an organic pigment residue, anthraquinone residue, acridone residue or triazine residue, L is a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group, n Is an integer from 1 to 4)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments;
Slen pigments; metal complex pigments and the like.

  Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types. The addition amount of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 4 parts by mass or less, more preferably 1.5 parts by mass or less, with respect to 100 parts by mass of the colorant.

  In the liquid developer, the appropriate addition amount of the dye derivative varies depending on the type of the colorant (B) to be used, but generally it is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the colorant (B). It is preferable to use in. Thereby, the dispersion stability of the toner particles is maintained, and the stability of the charging polarity of the toner particles can be maintained. In the liquid developer, it is preferable to use a basic dye derivative since the toner particles have positive chargeability.

(Charge control agent)
The toner particles in the liquid developer may contain a colorless or light-color charge control agent as long as the hue does not hinder the hue. 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. In the liquid developer, the toner particles are preferably positively charged, and a positive charge control agent is usually used.

  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 (eg, dibutyltin borate, dioctyltin borate, dicyclohexyltin borate), an electron donating substance such as a polymer having an amino group, or a combination of two or more thereof Can be used. The triarylmethane dye described above can also be used as a positive charge control agent.

Further, instead of using the charge control agent, a resin charge control agent can be used. Of a positively charged, the general formula _{- {CH 2 -CH (C 6} H 5)} a- {CH 2 -CH (COOC 4 H 9)} b- {CH 2 -C (CH 3) COOC 2 H 4 N ⁺ CH ₃ (C ₂ H ₅ ) ₂ CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ } c
A quaternary ammonium salt represented by (the quaternary ammonium salt part is 3-35 parts by mass, the styrene and the acrylic part are 97-65 parts by mass, thereby determining the values of a, b and c) Examples of the functional group include a styrene-acrylic polymer copolymerized with a styrene-acrylic resin. Specifically, 2-ethylhexyl acrylate / acryloylamino-2-methyl-1-propanesulfonic acid / styrene copolymer, butyl acrylate / N, N-diethyl-N-methyl-2- (methacryloyloxy) ethyl Ammonium = p-toluenesulfonate / styrene copolymer and the like. Since these are colorless and transparent, they are suitable for use in color toners. Further, the resin charge control agent is preferably added in an amount of preferably 1.0 to 20 parts by mass, more preferably 2.0 to 8 parts by mass with respect to 100 parts by mass of the binder resin (A).

(Production method)
A method for producing the liquid developer will be described. The liquid developer is preferably obtained, for example, through the following five processes.

(1) Preparation of Colored Master Batch for Toner Particles The binder resin (A) and the colorant (B) are heated in such a ratio that the concentration of the colorant (B) in the master batch is 10 to 60 parts by mass. Kneading is performed using a roll or the like, and after cooling, coarse crushing is performed to obtain a colored master batch. In addition to the binder resin (A) and the colorant (B), a pigment dispersant, a dye derivative, and the like can also be added.

(2) Preparation of toner particle chips (dilution of colored master batch)
The colored masterbatch obtained in (1) and the binder resin (A) are mixed with a mixer such as a super mixer, preliminarily dispersed, and then melt-kneaded, whereby the colored masterbatch is bound to the binder resin (A). Diluted in and developed to obtain a chip for toner particles. At the time of performing preliminary dispersion and melt-kneading here, a pigment dispersant, a polymer dispersant (C), a charge control agent, and the like may be added. Further, it is preferable that the toner particle chip has a particle size of 10 mm or less by rough crushing with a hammer mill, a sample mill or the like. In addition, the steps (1) and (2) can be integrated. In that case, all steps during the preliminary dispersion in the step (2) without passing through the coloring masterbatch step (1). The material may be charged to produce a toner particle chip. As the melt-kneading, a known kneader such as a pressure kneader, a Banbury mixer, a uniaxial or biaxial extruder can be used.

(3) Dry pulverization of toner particles The toner particle chip obtained in (2) is finely pulverized to an average particle size of 7 μm or less. For fine pulverization, it is usually preferable to use a jet airflow pulverizer such as a jet mill or a mechanical pulverizer such as a turbo mill or a kryptron.

(4) Wet pulverization of toner particles The dry pulverized toner particles obtained in (3) are developed in a solvent having the same composition as that of the carrier liquid (D), and the average particle size is measured using a wet pulverizer (disperser). Is pulverized to a range of 0.5 to 4 μm, preferably 1 to 3 μm. At this time, it is also effective to add a polymer dispersant (C) having a function of adsorbing the toner particles. Through the wet pulverization and dispersion steps, the dispersant is adsorbed in the toner particles and stabilized in terms of charging. When performing wet pulverization (dispersion), it is desirable to cool so that the temperature during pulverization does not exceed 50 ° C. When the temperature is 50 ° C. or lower, the particle size distribution can be controlled without causing fusion of the toner particles.

  As a wet pulverizer that can be used for wet pulverization of toner particles, a pulverization medium is used, and examples thereof include a container drive medium mill and a medium stirring mill. Examples of the container drive medium mill include a rolling ball mill, a vibrating ball mill, a planetary ball mill, a centrifugal fluidizing mill, and the like, and examples of the medium agitating mill include a tower type pulverizer, a stirring tank type mill, a distribution tank type mill (horizontal type, Vertical type), annular mill and the like. In any of the above apparatuses, miniaturization by wet pulverization is possible, but among them, the use of a medium stirring mill is preferable from the viewpoint of productivity, pulverization ability, control of particle size distribution, and the like. Furthermore, among them, the use of a wet pulverizer classified as a horizontal distribution tank type mill, which is sealed and horizontal, is filled with microbeads and used as a medium (medium), enables precise wet pulverization and dispersion. It is preferable in carrying out. Specific examples include a dyno mill (DYNO-MILL) manufactured by WAB (Shinmaru Enterprises), a sand mill, and the like. In the horizontal type wet pulverizer, since the dispersion medium is hardly affected by gravity, a uniform distribution close to ideal can be obtained in the pulverizer. Further, since it has a completely sealed structure, there is no loss of balance due to foaming or evaporation of the solvent, and stable pulverization is possible.

  In the wet pulverizer, the major factors that determine the pulverization properties are the type of pulverization media, the particle size of the pulverization media, the filling rate of the dispersion media in the pulverizer, the type of agitator disk, the concentration of the sample to be pulverized, the solvent Types are listed. Among these, the type of pulverized media and the particle size of the media greatly contribute to pulverization.

The types of grinding media include glass beads (SiO ₂ 70-80%, NaO 12-16%, etc.), zircon beads (ZrO ₂ 69%), depending on the viscosity, specific gravity, required particle size of grinding and dispersion, and the like. SiO ₂ 31%), zirconia beads (ZrO ₂ 95% or more), alumina (Al ₂ O ₃ 90% or more), titania (TiO ₂ 77.7%, Al ₂ O ₃ 17.4%), steel balls, etc. However, it is preferable to use zirconia beads or zircon beads in order to obtain good grindability. The particle diameter (diameter) of the pulverization media can be used in the range of 0.1 mm to 3.0 mm, and in particular, the range of 0.3 to 1.4 mm is preferable. When it is 0.1 mm or more, the load in the pulverizer can be reduced, and it is possible to prevent the toner particles from melting due to heat generation and difficult to pulverize. When the thickness is 3.0 mm or less, sufficient pulverization can be performed. The filling rate of the dispersion medium is preferably 40 to 85% by mass. When it is 85% by mass or less, the load in the pulverizer can be reduced, and it is possible to prevent the toner particles from melting due to heat generation and difficult to pulverize. Further, if it is 40% by mass or more, the pulverization efficiency is improved, so that miniaturization is easy. When the concentration of toner particles in the slurry is high (concentration of 40 to 50% by mass), the filling rate is preferably 40 to 70% by mass.

  The agitator disk inside the wet grinder also affects the grindability control. The peripheral speed of the disk is preferably 4 to 16 m / s. If it is 4 m / s or more, the grinding time can be shortened. In addition, when it is 16 m / s or less, heat generation due to contact with the pulverizing medium (medium) is reduced, and fusion of toner particles can be prevented. Examples of the material of the agitator disk include hardened steel, stainless steel, alumina, zirconia, polyurethane, polyethylene, and engineering plastic. Among them, zirconia is preferably used.

  Examples of the material of the grinding cylinder on the inner wall of the wet pulverizer include special hardened steel, stainless steel, alumina, zirconia, ZTA, glass, and polyethylene. Among them, it is preferable to use zirconia reinforced alumina ceramics called ZTA.

(5) Purification of liquid developer Toner particles (at least containing binder resin (A) and colorant (B)) obtained in (4), carrier liquid (D), and polymer dispersion To the material containing the agent (C), a carrier liquid (D) and, if necessary, a dispersant are further added and mixed, and the liquid developer is purified while controlling the concentration of toner particles. The polymer dispersant (C) may be added in any of the steps (1) to (5), but should be added to the material obtained in the step (4) together with the carrier liquid (D) for preparation. Thus, a liquid developer in which toner particles are stably dispersed can be obtained.

(Liquid developer properties)
The toner particles preferably have an average particle diameter (D50) of 0.5 to 4 μm, more preferably 1 to 3 μm. In the present invention, the particle size is measured using a laser diffraction scattering particle size analyzer Microtrac HRA manufactured by Nikkiso Co., Ltd., and the average particle size (D50) is a cumulative 50 percent diameter value.

  Further, the toner particles having a particle diameter of 2 μm or less with respect to all the toner particles are contained in an amount of 50% by volume or less, the toner particles having a particle diameter of 1 to 3 μm are contained in an amount of 5 to 60% by volume, and the particle diameter is 5 μm or more. The toner particles are more preferably 35% by volume or less from the viewpoint of development characteristics for obtaining color developability. When the toner particles having a particle size of 2 μm or less are 50% by volume or less, the polymer dispersant (C) is highly adsorbed to the toner particles, and excellent storage stability is obtained. Furthermore, the pulverization property becomes high in wet pulverization of toner particles, and the viscosity control of the liquid developer becomes easy. When the toner particles having a particle diameter of 5 μm or more are 35% by volume or less, there are effects that a sufficient image density can be obtained and color development and color reproducibility are improved. The toner particles having a particle diameter of 1 to 3 μm are preferably contained in an amount of 5 to 60% by volume in order to obtain dispersion stability of the toner particles and excellent storage stability over a long period of time.

  The concentration of the toner particles in the liquid developer is preferably 10 to 30% by mass with respect to 100% by mass of the liquid developer. More preferably, it is 12-25 mass%. When the content is 10% by mass or more, the carrier liquid (D) can be easily removed, and the fixability of the toner particles is improved. When the content is 30% by mass or less, the viscosity of the liquid developer is lowered, the mobility of the toner particles is improved, and a sufficient image density is obtained. Furthermore, toner particle aggregation is weakened and storage stability is increased.

  In the liquid developer, the polymer dispersion adsorption rate of the polymer dispersant (C) to the toner particles is: adsorption rate = (amount of dispersant adsorbed on the toner particles) / (dispersant content in the liquid toner). Defined and can be measured as follows. 10 g of liquid developer is weighed and centrifuged at 19,000 rpm for 20 minutes using a centrifuge CR22H manufactured by Hitachi Koki Co., Ltd. 1 g of the separated supernatant solution is weighed, and the carrier liquid (D) is volatilized in an oven at 160 ° C. for 1 hour. The residual polymer dispersant (C) is weighed, and the adsorption rate to the toner particles is calculated from the obtained value. The adsorption rate is preferably 50% or more. More preferably, it is 70% or more. If it exceeds 50%, the dispersion stability of the toner particles becomes high, and the average particle diameter and viscosity of the liquid developer do not increase even during long-term storage, and stable color development and color reproducibility can be obtained. . In order for the adsorption rate of the polymer dispersant (C) to the toner particles to be 50% or more, the amine value of the polymer dispersant (C), the carbon number of the alkyl group of the ethylenically unsaturated monomer, the general formula The number of carbon atoms of the alkylene oxide group (AO) represented by (1), the number of alkylene oxide groups, and the number of carbon atoms of R2 may be controlled, and further the respective mass ratios may be controlled.

The viscosity (η) of the liquid developer of the embodiment is preferably 5 to 180 mPa · s, and the electrical resistivity of the liquid developer is preferably 10 ¹⁰ to 10 ¹⁵ Ω · cm. The viscosity (η) of the liquid developer can be measured using, for example, an E-type viscometer TV-22 manufactured by Toki Sangyo Co., Ltd. Adjust the solid content in the liquid developer to 25% and adjust it to 25 ° C. Then set the 1 ° 34 'cone on the TV-22 viscometer and measure the viscosity after 1 minute at 20 rpm. Can be obtained. When the viscosity (η) is 5 mPa · s or more, the fineness of the image after development is improved, and when it is 180 mPa · s or less, the mobility of toner particles during development is increased and high-speed development is possible. There is an effect that the image density can be obtained. The electrical resistivity can be measured in the same manner as in the carrier liquid measurement method described above. When it is 10 ¹⁰ Ω · cm or more, the electrostatic latent image on the photosensitive member can be easily held.

  The development process that can be preferably used in the use of the liquid developer is to supply the liquid developer to a developing roller made of conductive rubber, remove the charge before transfer using an amorphous silicon photoconductor exposed to LED, and remove the intermediate transfer member. It is preferable to perform development via the substrate. The photoreceptor preferably has a surface potential of +450 to 550 V, a residual potential of +50 V or less, and the bias applied to the developing roller is preferably in the range of +250 to 450 V.

  The printing substrate to be printed with the liquid developer is not particularly limited, and examples include generally used fine paper, coated paper, PET sheet, and PP sheet. As coated paper, all widely used coated papers that have been used for various purposes in the past are all targeted. Specifically, for example, fine coated paper, lightweight coated paper, coated paper, art paper, mat coated paper And cast coated paper, and the thickness and shape thereof are not limited at all. Particularly in coated paper, by using the liquid developer of this embodiment, good image quality can be obtained, and sharp characters and barcodes can be printed. These may have a smooth surface of the printing substrate, may have irregularities, or may be transparent, translucent, or opaque. Further, two or more of these printing substrates may be bonded to each other. Furthermore, a peeling adhesive layer or the like may be provided on the opposite side of the printing surface, and an adhesive layer or the like may be provided on the printing surface after printing.

  Although the printed matter printed with the liquid developer is not particularly limited, it is used for general commercial use, paper package, packaging film, seal, label use and the like. For example, in general commercial use, catalogs using high-quality paper, coated paper, etc., books or forms such as magazines, in paper container packages, packaging containers or outer boxes using coated paper, cardboard, etc., in packaging films , Flexible packaging containers using PET sheets, PP sheets and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the embodiment of the present invention is not limited to these examples. In the following, “part” means “part by mass” unless otherwise specified.

Moreover, in the Example, it carried out using the material described below.
(Binder Resin Synthesis Example 1)
Into a flask equipped with a reflux condenser, distillation, etc., a nitrogen gas inlet tube, a thermometer, and a stirrer, polyhydric alcohol shown in Table 1, a polybasic acid, and 2 parts of dibutyltin oxide were added as a catalyst. Nitrogen gas was introduced with stirring, and the mixture was heated to 200 ° C. and reacted for 4 hours while maintaining the temperature of the reaction system. Furthermore, it was made to react under reduced pressure for 1 hour. The pressure was returned to normal pressure, the temperature of the reaction system was lowered to 100 ° C. or lower, and polycondensation was stopped to obtain a binder resin 1 which was a polyester resin.

Bisphenol A propylene oxide adduct: In general formula (2), R = propylene group and x = y = 2.
Bisphenol A ethylene oxide adduct: In the general formula (2), R = ethylene group and x = y = 2.

(Binder Resin Synthesis Example 2)
The obtained binder resin 1 was put in an equal amount of toluene and heated to be dissolved. Nitrogen gas was introduced with stirring, and the mixture was further heated to the boiling point of toluene, and 2 mixed solutions containing styrene-based monomers, acrylic esters, and di-t-butyl peroxide as a polymerization initiator shown in Table 3 were added. Solution polymerization was carried out while dropping over time. After completion of the dropwise addition, the reaction was further continued at the boiling point of toluene for 2 hours, and 1 part of di-t-butyl peroxide was added to terminate the polymerization. Next, it heated up to 180 degreeC and toluene was removed, and the binder resin 2 containing a polyester resin and a styrene-acryl copolymer resin was obtained.

(Binder Resin Synthesis Example 3)
Synthesis was performed in the same manner as in Synthesis Example 2 except that the raw materials and preparation amounts shown in Table 2 were used, and a binder resin 3 was obtained.

(Binder Resin Synthesis Examples 4 and 5)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the raw materials and preparation amounts described in Table 3 were used, and binder resins 4 and 5 were obtained.

Table 4 shows the physical property values of the obtained binder resins 1 to 5.

(Synthesis example 1 of polymer dispersant)
In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, a condenser, and a stirrer, 90.1 parts of Shellsol TM (manufactured by Shell Chemicals) was charged and replaced with nitrogen gas. The reaction vessel was heated to 110 ° C., 20.0 parts of N, N-dimethylaminoethyl methacrylate, 80.0 parts of stearyl methacrylate, and 2,2′-azobis (2-methylpropionic acid) as a polymerization initiator. A mixture containing 9.0 parts of dimethyl (V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)) was dropped over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 110 ° C. for 3 hours, 0.9 part of V-601 (manufactured by Wako Pure Chemical Industries) was added, and the reaction was further continued at 110 ° C. for 1 hour to obtain a polymer dispersant 1 solution. Got. The weight average molecular weight (Mw) of the polymer dispersant 1 was 7,000. 1 g of this was sampled and heat-dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Shellzol TM was added to the polymer dispersant 1 solution so that the nonvolatile content of the polymer dispersant solution was 50% by mass. As a result, a 50% by mass solution of the polymer dispersant 1 with a nonvolatile content was obtained.

(Synthesis Examples 2 to 4 of polymer dispersant)
Synthesis was performed in the same manner as in Polymer Dispersant Synthesis Example 1 except that the raw materials and preparation amounts shown in Table 5 were used, and solutions of polymer dispersants 2 to 4 were obtained. The amine value and weight average molecular weight of each polymer dispersant were as shown in Table 7.

(Comparative Polymer Dispersant Synthesis Examples 1 and 2)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the raw materials and preparation amounts shown in Table 6 were used, and solutions of comparative polymer dispersants 1 and 2 were obtained. The amine value and weight average molecular weight of each polymer dispersant were as shown in Table 7.

In the table: DM: N, N-dimethylaminoethyl methacrylate AAm: Acrylamide STMA: Stearyl methacrylate C-1: R1 = CH3, R2 = CH3, n = 9 in formula (1), A = ethylene group BA: butyl acrylate

Table 6 shows the physical property values of the obtained polymer dispersant.

(Coloring agent)
Cyan colorant C.I. I. Pigment Blue 15: 3 (copper phthalocyanine blue)
Lionol Blue FG7919 (Toyo Color)
Magenta colorant C.I. I. Pigment Red 122 (Quinacridone Magenta)
Hosterperm Pink E (manufactured by Clariant)
C. I. Pigment Red 57: 1 (Kermin 6B)
Permanent Rubin L6B (manufactured by Clariant)
Yellow colorant C.I. I. Pigment Yellow 180 (Benz Imidazolone Yellow)
Novoperm Yellow P-HG (manufactured by Clariant)
Black colorant carbon black NIPEX150 (manufactured by Orion Engineered Carbons Degussa)
As the blue component, C.I. I. Pigment Blue 15: 3 added

(Pigment dispersant)
Solsperse 24000SC Acid value: 25 mgKOH / g
Basic resin type dispersant (polyamine resin)

(Carbon series of carrier liquid)
The carrier liquid can derive a ratio in the total number of carbons of the aliphatic hydrocarbons from primary to tertiary by 1H-NMR measurement. All 1H-NMR measurements were performed using JNM-ECX400P manufactured by JEOL (400 MHz, solvent: chloroform-d, standard substance: tetramethylsilane). Specifically, the integrated values are obtained in the range of 1H-NMR chemical shifts of 0.6 to 1.0 ppm, 1.0 to 1.45 ppm, and 1.45 to 1.8 ppm, respectively. , And the number of hydrogen bonded to the secondary and tertiary carbons, and the ratio of the number of hydrogens of each carbon series in the sum is calculated. Calculate the ratio of the hydrogen number to the number of hydrogens bonded to each series of carbons (for example, the number of hydrogens is 3 for the first class, 2 for the second class, and 1 for the third class). And calculate the carbon number ratio of each carbon series in the sum.
Table 7 shows the ratio and dry point in the total number of primary to tertiary carbons of the aliphatic hydrocarbons calculated by 1H-NMR measurement for the carrier liquid (D).

C. I. Pigment Blue 15: 3
(Lionol Blue FG7919) 18 parts by weight binder resin 1 80 parts by weight Solsperse 24000SC 2 parts by weight The above materials (total 5 kg) were mixed in a Henschel mixer having a volume of 20 L (3,000 rpm, 3 minutes) and then biaxially kneaded. Melting and kneading were performed with an extruder (PCM30) at a supply rate of 6 kg / hr and a discharge temperature of 145 ° C., and further, kneading was performed with three rolls having a roll temperature of 140 ° C. After cooling and solidifying, coarsely pulverized with a hammer mill and then finely pulverized with an I-type jet mill (IDS-2 type) to obtain a pulverized cyan product 1 having an average particle size of 5.0 μm.

Furthermore, cyan pulverized product 1-25 parts by mass Shellsol TM ---- 72 parts by mass polymer dispersant 1 ------ 3 parts by mass was weighed, sufficiently stirred and mixed, and Shellsol TM Cyan pulverized product 1 was dispersed in the solution (slurry concentration was 25% by mass). The slurry in which the cyan pulverized product 1 is dispersed is subjected to a circulation operation for 60 minutes using a wet pulverizer which is a medium stirring mill, Dino Mill Multilab (Shinmaru Enterprises Co., Ltd., capacity 1.4 L), Wet grinding was performed.
The wet pulverization conditions at this time were as follows. Agitator disk (material: zirconia) peripheral speed 10 m / s, cylinder ZTA, media (material: zirconia) diameter 1.25 mm, filling rate 70%, solution flow rate 45 kg / h, cooling water 5 L / min, pressure 0.1 kg / cm ^{2 After} 60 minutes of wet pulverization, the slurry was taken out and passed through a mesh having a mesh size of 33 μm (manufactured by SUS304) to obtain a liquid developer 1C (including cyan toner particles 1). When the particle size distribution of the cyan toner particles 1 was confirmed, the average particle size (D50) was 2.6 μm. The viscosity (η) of the liquid developer 1C was 50 mPa · s.

Using the raw materials shown in Table 4, Table 6, and Table 7 in the same manner as in Example 1, pulverized toner products and liquid developers were produced, respectively. The particle size was measured using a Nikkiso Co., Ltd. laser diffraction / scattering particle size analyzer Microtrac HRA, the solvent using Exol D80 (Exxsol ™) (ExxonMobil Corporation), and under an environmental condition of 23 ° C. and 50% RH. The average particle size (D50) is a value of a cumulative 50 percent diameter. The viscosity (η) of the liquid developer was measured using an E-type viscometer TV-22 manufactured by Toki Sangyo Co., Ltd. Adjust the solid content in the liquid developer to 25% and adjust it to 25 ° C. Then set the 1 ° 34 'cone on the TV-22 viscometer and measure the viscosity after 1 minute at 20 rpm. Asked.

  In the live-action test, a commercially available liquid developing copier (Savin 870: manufactured by Sabin) was used, an amorphous silicon photoconductor was used under an environmental condition of 23 ° C./50% RH, and the surface potential of the photoconductor was +450. An image test of 3000 sheets was performed from the initial stage with ˜500 V, residual potential +50 V or less, and developing roller bias set to +250 to 450 V. The 500th image was used for the evaluation of the image density and the fixing rate, and the second and subsequent images were used for the evaluation of the cold offset resistance. Further, regarding the continuous printing stability, the image quality of the 500th sheet and the 3000th sheet was confirmed. At this time, the image was produced in a single color for each color, the paper was OK topcoat made by Oji Paper, and the thermocompression bonding was performed at a speed of 30 m / min and 160 ° C.

(Image density)
First, the image density was measured with a Gretag Macbeth densitometer (D-196). Here, it is practically preferable that the density value of each color is 1.2 or more for yellow, 1.4 or more for magenta and cyan, and 1.6 or more for black. More preferably, yellow is 1.3 or more, magenta and cyan are 1.5 or more, and black is 1.7 or more.

(Image quality)
Regarding the image quality, the occurrence of image streaks due to the adhesion of oxide to the photoconductor and the like due to the ozone generation of the charging device was visually evaluated for a 100% solid image portion of 10 cm × 10 cm.
◯: No image streak Δ: Image streak occurs ×: Many image streaks occur

(Fixing rate)
For the fixing rate, an image density ID (ID1) at the time of output was measured using a printed image in which a solid portion of 1 cm × 1 cm was output. Thereafter, a mending tape (Scotch 810 manufactured by 3M) was attached to the printed matter, and a 1 kg cylindrical brass weight was rolled and reciprocated once. Thereafter, the mending tape was removed, the image density ID (ID2) was measured again, and a value obtained by calculating (ID2) / (ID1) × 100 was obtained as a fixing rate (%). Here, if the fixing rate is 80% or more, it is practically preferable, and if it is 90% or more, it is more preferable.

(Cold offset resistance)
With respect to cold offset resistance, after being output by the above liquid developing copier, ten output images are sequentially thermocompression bonded by an external fixing device at a speed of 30 m / min and a nip thickness of 6 mm. When the output image was thermocompression bonded, it was confirmed whether or not there was a re-transferred toner image on the tenth output image (paper). The temperature at which the re-transferred toner image does not exist was evaluated in four ranks. Here, if the thermocompression-bonding roll temperature is less than 140 ° C, it is practically preferable, and if it is less than 120 ° C, it is more preferable.
A: Thermocompression roll temperature is less than 120 ° C B: Thermocompression roll temperature is 120 ° C or more and less than 140 ° C C: Thermocompression roll temperature is 140 ° C or more and less than 160 ° C D: Thermocompression roll temperature is 160 ° C or more

(Storage stability)
The storage stability of the liquid developer was evaluated as follows. The obtained liquid developer was allowed to stand in a constant temperature and humidity atmosphere at 25 ° C. and 50% for 3 months. The average particle diameter (D50) and viscosity (η) of the liquid developer after 3 months of standing were measured and evaluated at a rate increased from the value before the start of the test.

Average particle size (D50)
A: Average particle diameter after test (D50) / average particle diameter before test (D50) is less than 1.1 B: average particle diameter after test (D50) / average particle diameter before test (D50) is 1. 1 or more and less than 1.2 C: average particle diameter after test (D50) / average particle diameter before test (D50) is 1.2 or more Here, average particle diameter after test (D50) / average particle diameter before test If (D50) is less than 1.2, it is practically preferable, and if it is less than 1.1, it is more preferable.

Viscosity (η)
A: Viscosity after testing (η) / viscosity before testing (η) is less than 1.1 B: viscosity after testing (η) / viscosity before testing (η) is 1.1 or more and less than 1.4 C: Viscosity after test (η) / viscosity before test (η) is 1.4 or more Here, viscosity after test (η) / viscosity before test (η) is less than 1.4, which is practically preferable. If it is less than 1.1, it is more preferable.

Detailed physical property values and test results of the liquid developer are shown in Table 10.

  In Comparative Example 1, since the polymer dispersant (C) does not contain a monomer containing an alkyl group having 9 to 24 carbon atoms, the solubility in a carrier and the steric repulsion force are reduced, and the pulverization property and the storage property are reduced. Stability decreased. In Comparative Example 2, since the polymer dispersant (C) did not contain an ethylenically unsaturated monomer having an amino group, the adsorptive power to the toner particles was decreased, and the pulverization property and the storage stability were decreased. In Comparative Examples 3 to 10, since the ratio of primary carbon in the carrier liquid (D) is not 55% or more, or the ratio of secondary carbon is not 30% or less, the carrier liquid (D) is oxidized by ozone, Image streaks will occur. On the other hand, the liquid developers of Examples 1 to 13 have good image density, fixing rate, cold offset resistance, and storage stability, no image streaking, and excellent continuous printing stability. Further, Example 5 is particularly excellent in image density and fixing rate, Example 7 is excellent in pulverizing property and storage stability, and Example 8 is particularly excellent in pulverizing property, image density, fixing rate, and storage stability. In addition, since the image density, the fixing property, the cold offset property, and the continuous printing stability are excellent, a printed matter having excellent image quality over a long period of time was obtained.

  The liquid developer according to the embodiment of the present invention is excellent in image quality such as color reproducibility and color developability, continuous printing stability and storage stability, and forms an image using electrophotography, electrostatic recording method, etc. Can be preferably used as a liquid developer used for developing an electrostatic latent image in an electronic copying machine, a printer, an on-demand printing machine, and the like.

Claims (7)

A liquid developer comprising at least a binder resin (A), a colorant (B), a polymer dispersant (C), and a carrier liquid (D), wherein the polymer dispersant (C) is at least amino An ethylenically unsaturated monomer having a group and an ethylenically unsaturated monomer containing an alkyl group having 9 to 24 carbon atoms, having an amine value of 5 to 150 mgKOH / g, and The carrier liquid (D) is an aliphatic hydrocarbon, and the ratio of primary carbon is 55% or more with respect to the total number of primary to tertiary carbons of the aliphatic hydrocarbon; A liquid developer, wherein the proportion of grade carbon is 30% or less.
The liquid developer according to claim 1, wherein the dry point of the carrier liquid (D) is 200 ° C. or higher.
The polymer dispersant (C) has a weight average molecular weight Mw of 500 ≦ Mw ≦ 40000, and is obtained by copolymerizing a monomer containing an ethylenically unsaturated monomer represented by the following general formula (1). The liquid developer according to claim 1 or 2.
General formula (1)
CH ₂ = C (R ¹ ) COO (AO) _n R ²
(In the formula, R ¹ represents H or CH ₃ , R ² represents hydrogen or a hydrocarbon group having 1 to 22 carbon atoms, n represents an integer of 1 to 200, and A represents an alkylene group having 2 to 4 carbon atoms. )
The liquid developer according to claim 1, wherein the binder resin (A) has a weight average molecular weight Mw of 2000 ≦ Mw ≦ 100,000.
The binder resin (A) includes a polyester resin and a styrene resin, an acrylic resin, or a resin selected from the group consisting of styrene-acrylic copolymer resins. The liquid developer described in 1.
Mass ratio [(a-2) / (a) of polyester resin (a-1) and resin (a-2) selected from the group consisting of styrene resin, acrylic resin, or styrene-acrylic copolymer resin -1)] is 1 or less, The liquid developer according to claim 5.
A printed matter obtained using the liquid developer according to claim 1.