JP2007033702A - Electrostatic charge image developing toner and its manufacturing method, electrostatic charge image developer, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which can be used for a low-temperature fixation, has excellent electrostatic charge characteristics and also has excellent image quality characteristics; and also to provide its manufacturing method, an electrostatic charge image developer and an image forming method. <P>SOLUTION: The electrostatic charge image developing toner contains at least a colorant and a crystalline polyester resin, in which at least one of the polymerization units constituting the crystalline polyester resin has an electronic attractive group of ≥0.15 in Hammett constant derived from para position replacement of a benzoic acid and its derivative. Also, the method for manufacturing the electrostatic charge image developing toner, and the electrostatic charge image developer and image forming method are obtained. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic image developing toner used for developing an electrostatic image in an electrophotographic apparatus using an electrophotographic process such as a copying machine, a printer, a facsimile, and the like, a manufacturing method thereof, and the electrostatic image developing The present invention relates to an electrostatic charge image developer using toner and an image forming method.

  A method of visualizing image information through an electrostatic latent image, such as electrophotography, is currently widely used in various fields. In the electrophotographic method, the electrostatic latent image on the surface of the photoreceptor is developed through a charging process, an exposure process, and the like, and the electrostatic latent image is visualized through a transfer process, a fixing process, and the like.

  Many methods are known as electrophotographic methods. In general, a latent image is electrically formed by various means on the surface of a photoreceptor (latent image holding body) using a photoconductive substance, and the formed latent image is developed with toner. After forming the image, the toner image is transferred to the surface of a transfer medium such as paper, optionally via an intermediate transfer body, and is subjected to a plurality of steps of fixing by heating, pressing, and heating and pressing. An image is formed. Further, the toner remaining on the surface of the photosensitive member may be cleaned by various methods as necessary and used again for developing the toner image.

  As a fixing technique for fixing the toner image transferred to the surface of the transfer target, a hot roll fixing is performed in which the transfer target having the toner image transferred is inserted between a pair of rolls including a heating roll and a pressure roll and fixed. The law is common.

On the other hand, along with the increasing demand for energy saving in recent years for image formation,
In the electrophotographic process, so-called low-temperature fixing toner is being actively developed to save power in the fixing process, which is one of the most energy consuming processes.

  In this case, lowering the fixing temperature of the toner usually lowers the glass transition point of the toner at the same time, so that the storage stability of the toner and the storage stability (offset) of the finally obtained output image are reduced. It becomes difficult to achieve both. In order to solve this problem and achieve both low-temperature fixing and toner storage stability, the so-called sharp melt property, in which the viscosity of the toner rapidly decreases near the fixing temperature while maintaining the glass transition point of the toner at a high temperature, is known. It is necessary to have As a promising approach to the technical problem, a method using a crystalline resin having a sharp melt property as a binder resin has been proposed.

  In particular, in full-color toners for electrophotography, polyester resins have long been used as binder resins because of their color developability and excellent adhesion to paper. Crystalline polyesters as the above-mentioned crystalline resins having sharp melt properties Is being actively studied.

  In addition, due to the recent demand for higher image quality in electrophotographic technology, the study of particle reduction in so-called chemical manufacturing toner manufacturing methods such as dissolution suspension method, emulsion polymerization aggregation method, suspension polymerization method and low-temperature fixing with these crystalline resins Many studies have been reported on combining technologies. However, application of crystalline resins, particularly crystalline polyesters, to electrostatic charge developing toners has the following problems related to the electrical characteristics of the resins, which is a major obstacle to their practical use.

  When a crystalline resin is applied to a toner for electrostatic charge development intended for low-temperature fixing, the melting point of the resin is an important factor in the selection of the crystalline resin. Normally, in the case of an electrophotographic toner aiming at low-temperature fixing, it is important to select a material that melts sharply at a low temperature as much as possible, that is, has a low melting point. The compatibility with image blocking after fixing is important. Therefore, at present, studies on crystalline resins at about 80 ° C. have been widely studied (see, for example, Patent Documents 1 to 4).

  However, these low-melting crystalline resins have a resistance value of the resin that is about 1/100 to 1/1000 lower than the resin resistance that can be normally used for toner for electrostatic charge development. In the toner for electrostatic charge development that has a low charge amount as a toner and gradually leaks the charged charge with time, and the electrostatic charge developing toner has friction charging as its basic principle, the charging failure is low due to low charge and charge leakage. This is a big problem in practical use.

As described above, in the toner using the crystalline resin by the above-described method, it is extremely difficult to secure sufficient chargeability together with the low-temperature fixing property which is an advantage of the crystalline resin, and the low-temperature fixing satisfying these toner characteristics. At present, toner is not provided yet.
JP 2001-222138 A JP 2002-72557 A JP 2002-328490 A JP 2003-176339 A

  The present invention aims to solve the above-mentioned problems. That is, the present invention relates to a toner for developing an electrostatic charge image that can be fixed at a low temperature, has excellent charging characteristics, and further has excellent image quality characteristics, a method for producing the same, an electrostatic charge image developer, and an image forming method. The purpose is to provide.

In the actual situation, as a result of intensive studies, the present inventors have used the following electrostatic charge developing toner and a method for producing the same, an electrostatic charge image developer using the electrostatic charge developing toner, and an image forming method. As a result, the inventors have found that both excellent low-temperature fixing characteristics and other important charging characteristics as a toner are found, and the present invention has been completed.
That is, the present invention
<1> An electrostatic charge image developing toner containing at least a colorant and a crystalline polyester resin, wherein at least one of the polymerization units constituting the crystalline polyester resin is derived from para-position substitution of benzoic acid and its derivatives. An electrostatic charge image developing toner having an electron withdrawing group having a Hammett constant of 0.15 or more.

<2> The ratio of the polymerized units having the electron withdrawing group in the crystalline polyester resin is 0.1 mol% or more and 20 mol% or less with respect to all the polymerized units constituting the crystalline polyester resin. The toner for developing an electrostatic charge image according to <1>.
<3> The electrostatic charge developing toner according to <1> or <2>, wherein the electron withdrawing group is a group containing a fluorine atom.

<4> The polymer unit having a group containing a fluorine atom is 2,2-bis (4-hydroxyphenyl) hexafluoropropane, an alkyl ester of 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2 The toner for developing electrostatic images according to <3>, wherein the toner is at least one member selected from the group consisting of 2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane.
<5> The toner for developing an electrostatic charge image according to any one of <1> to <4>, wherein the content of the crystalline polyester resin is 1% by mass or more and 50% by mass or less. is there.

<6> A resin fine particle dispersion containing fine particles of a crystalline polyester resin and a colorant particle dispersion in which colorant particles are dispersed are mixed, and the crystalline polyester resin and the colorant particles are adjusted to a toner particle size in an aqueous medium. <1> to <5>, comprising a step of aggregating to form an aggregate, and heating and fusing the formed aggregate at a temperature equal to or higher than the melting point of the crystalline polyester resin. The method for producing a toner for developing an electrostatic image described in 1.
<7> An electrostatic image developer comprising the electrostatic image developing toner according to any one of <1> to <5> and a carrier.

<8> A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and a toner image is formed by developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. An image development process, a transfer process for transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target, and a fixing process for thermally fixing the toner image transferred to the surface of the transfer target. A forming method, wherein the toner for developing an electrostatic charge image according to any one of <1> to <5> is used as the toner.

  The present invention provides an electrostatic charge image developing toner that can be fixed at a low temperature, has excellent charging characteristics, and has excellent image quality characteristics, a method for producing the same, an electrostatic charge image developer, and an image forming method. can do.

  The electrostatic image developing toner of the present invention (hereinafter sometimes simply referred to as “the toner of the present invention”) is an electrostatic image developing toner containing at least a colorant and a crystalline polyester resin, At least one of the polymerization units constituting the conductive polyester resin is an electron withdrawing group having a Hammett constant of 0.15 or more derived from para-substitution of benzoic acid and its derivatives (hereinafter simply referred to as “electron withdrawing group according to the present invention”). In some cases).

  In order to achieve the next-generation high-quality toner technology that highly balances the above-described low-temperature fixing characteristics, in particular, the low-temperature fixing characteristics of 150 ° C. or less and the charging characteristics, It has been found that a certain charge leakage is suppressed by introducing a skeleton having a strong electron-withdrawing property into the resin skeleton.

  Conventionally, various studies have been made on the chemical structure and chargeability of the triboelectric chargeability of polymer materials, and it has been found that the chargeability of polymers depends on the chemical structure. At present, what structure should be introduced regarding the control of the target charging characteristics, for example, the charging polarity such as positive charging and negative charging, has been organized systematically to some extent (charging order). However, the difference in the chargeability (charge amount) of the polymer has not yet been explained clearly by the chemical structure, that is, the chemical composition of the constituent molecules, the molecular arrangement, and the spatial arrangement. The actual situation is being examined. On the other hand, for electrostatic charge developing toners, as a charge control method, a method is used in which a charge control agent having various polar groups introduced therein is blended in the toner to control the chargeability of the toner. Even in the clear relationship between the type of group and the chargeability, the details are not clear as described above.

  However, in the application of the crystalline resin in the present invention to the toner for electrostatic charge development, charging control, that is, charging failure of the toner due to the charge amount and charge leakage is a big problem. Has not been fully explained to date. Under such circumstances, the present inventors can overcome these problems by copolymerizing acid, acid anhydride, and alcoholic monomer having a strong electron-withdrawing group in the crystalline resin skeleton. The inventors have found that this is possible and have completed the present invention.

The electron withdrawing group according to the present invention is a parameter indicating the electron donating and electron withdrawing strength of the substituent defined by the Hammett substituent constant, that is, the Hammett constant derived from para-position substitution of benzoic acid and its derivatives. Is an electron withdrawing group of 0.15 or more.
In the present invention, the Hammett constant is preferably 0.15 or more, and more preferably 0.5 or more. When the Hammett constant is less than 0.15, sufficient chargeability control cannot be achieved. The Hammett constant is preferably 1.0 or less in view of the charge amount practically used in current toners.

Specific examples of the electron withdrawing group according to the present invention include, for example, a fluorine atom (0.15), a chlorine atom (0.24), a bromine atom (0.26), an iodine atom (0.28), and —CF _3. (0.53), - CN (0.70 ), - NO 2 (0.81) , and the like (Correlation Analysis in Chemistry, Plenum, NY, 1978). The numerical value in () is the value of the Hammett constant.
The electron withdrawing group according to the present invention is preferably a group containing a fluorine atom from the viewpoint of the colorability of the resin after polymerization and the versatility as a polycondensation monomer.

  The present invention is characterized in that at least one of the polymerized units constituting the crystalline polyester resin has the electron withdrawing group according to the present invention. Examples of the polymer units constituting the crystalline polyester resin include carboxylic acids, alkyl ester derivatives of carboxylic acids, acid anhydrides, and alcohol monomers.

  In addition, the polymerized unit (monomer) having an electron withdrawing group according to the present invention may be copolymerized as a repeating component in the main skeleton of the crystalline polyester, or may be incorporated at the terminal. Specific examples thereof include, for example, 4-cyanobenzoic acid, 2-cyanobenzoic acid, 4-trifluoromethylbenzoic acid, 3-trifluoromethylbenzoic acid, 2-trifluoromethylbenzoic acid, 4-trifluoromethylphthalic acid. 4′-cyano-4-hydroxybiphenyl, 4,4′hydroxy-tetrabromobiphenyl, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3,4-anhydrodicarboxyphenyl) ) Hexafluoropropane and the like, and these alkyl esters can also be used.

  As described above, the electron withdrawing group according to the invention is preferably a fluorine atom, and as the polymer unit having a fluorine atom as the electron withdrawing group, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis ( It is preferably at least one selected from the group consisting of alkyl ester of 4-hydroxyphenyl) hexafluoropropane and 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane.

  The polymer units having an electron withdrawing group according to the present invention can be used alone or in combination of two or more. These polymerized units are incorporated into the resin skeleton or terminal of the crystalline polyester resin.

  The ratio of the polymerized units having an electron withdrawing group according to the present invention in the crystalline polyester resin is preferably 0.1 mol% or more and 20 mol% or less with respect to all polymerized units constituting the crystalline polyester resin. More preferably, it is 0.3 mol% or more and 15 mol% or less, and further preferably 1 mol% or more and 10 mol% or less. When the ratio of the polymer units having an electron withdrawing group according to the present invention is 0.1 mol% or more and 20 mol% or less, the charge control is sufficient and the crystalline structure or the melting characteristics of the crystalline polyester resin are impaired. It does not hinder the fixing characteristics.

  As another constituent component of the crystalline polyester, an aliphatic polyester obtained by reacting an aliphatic diol with an aliphatic dicarboxylic acid (including acid anhydride and acid chloride) is particularly preferable.

The crystalline polyester resin is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. Examples of the divalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid Aromatic dicarboxylic acids such as dibasic acids such as, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  In addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above, a dicarboxylic acid component having a sulfonic acid group can also be used as the acid component. Examples of the dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Furthermore, in addition to the above-mentioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond can also be contained. A dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing in that it can be radically cross-linked through the double bond. Examples of such dicarboxylic acids include, but are not limited to, maleic acid, fumaric acid, 3-hexenedioic acid, and 3-octenedioic acid. In addition, these lower esters, acid anhydrides and the like are also included. Among these, fumaric acid, maleic acid and the like are preferable from the viewpoint of cost.

  As the polyhydric alcohol component, an aliphatic diol is preferable, and a linear aliphatic diol having 2 to 20 carbon atoms in the main chain portion is more preferable. When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. Moreover, when the number of carbon atoms exceeds 20, it is difficult to obtain practical materials. The carbon number is more preferably 14 or less. Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6. -Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13- Examples include, but are not limited to, tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

  In addition, in the toner of the present invention, in order to practically use as an electrostatic charge developing toner, it is preferable to blend an amorphous resin from the viewpoint of toner particle strength, color developability, adhesion to paper, and the like. . In this case, the content of the crystalline polyester resin in the toner of the present invention is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 30% by mass or less. More preferably, it is at least 25% by mass. If the content of the crystalline polyester resin in the toner is less than 1% by mass, sufficient low-temperature fixing performance may not be obtained. If the content exceeds 50% by mass, sufficient strength as a toner, color developability, Adhesion with paper may not be obtained.

  As the non-crystalline resin, a polycondensation polymer such as the above-described crystalline polyester resin, an amorphous polymer derived from polyaddition polymerization, addition condensation polymerization, addition polymerization or the like can be used. Examples of such non-crystalline resins include conventionally known thermoplastic binder resins, and specific examples include homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene. Polymer (styrene resin); methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylic acid n- Homopolymers or copolymers of esters having vinyl groups such as propyl, lauryl methacrylate, 2-ethylhexyl methacrylate (vinyl resins); Homopolymers or copolymers of vinylnitriles such as acrylonitrile and methacrylonitrile Combined (vinyl resin); vinyl methyl ether, vinyl isobutyl ether Homopolymers or copolymers of vinyl ethers (vinyl resins); Homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone (vinyl resins); ethylene, propylene , Homopolymers or copolymers of olefins such as butadiene and isoprene (olefin resins); non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and the like And a graft polymer of a non-vinyl condensation resin and a vinyl monomer. These resins may be used alone or in combination of two or more. Among these resins, vinyl resins and polyester resins are particularly preferable.

  When a vinyl resin is used as the non-crystalline resin, it is advantageous in that a resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like. Examples of the vinyl monomer include acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethylene imine, vinyl pyridine, vinyl amine, and other vinyl polymer acids and vinyl polymer bases. Examples include monomers that are raw materials.

  In the present invention, the non-crystalline resin preferably contains the vinyl monomer as a monomer component. In the present invention, among these vinyl monomers, vinyl polymer acids are more preferable from the viewpoint of ease of formation reaction of vinyl resins, and specifically, acrylic acid, methacrylic acid, maleic acid, cinnamon. A dissociable vinyl monomer having a carboxyl group such as an acid or fumaric acid as a dissociating group is particularly preferred from the viewpoint of controlling the degree of polymerization and the glass transition point. The concentration of the dissociating group in the dissociable vinyl monomer is determined by dissolving particles such as toner particles from the surface, as described in, for example, polymer latex chemistry (Polymer Publications). Etc. can be determined. It should be noted that the molecular weight of the resin and the glass transition point from the surface of the particle to the inside can also be determined by the above method or the like.

  On the other hand, when a polyester resin is used as the non-crystalline resin in the toner of the present invention, a resin particle dispersion can be easily prepared by emulsifying and dispersing the resin by adjusting the acid value or using an ionic surfactant. This is advantageous in that it can. The amorphous polyester resin used for emulsification dispersion is synthesized by dehydration condensation of a polyvalent carboxylic acid and a polyhydric alcohol.

  Examples of polyvalent carboxylic acids in non-crystalline polyester resins include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and other aromatic carboxylic acids, maleic anhydride, fumar Examples thereof include aliphatic carboxylic acids such as acid, succinic acid, alkenyl succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polyvalent carboxylic acids can be used alone or in combination. Among these polyvalent carboxylic acids, aromatic carboxylic acids are preferably used, and trivalent or higher carboxylic acids (trimerits) together with dicarboxylic acids to form a crosslinked structure or a branched structure in order to ensure good fixability. It is preferable to use an acid or an acid anhydride thereof in combination.

  Examples of the polyhydric alcohol in the amorphous polyester resin include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin, cyclohexanediol, cyclohexanedi Examples thereof include aromatic diols such as alicyclic diols such as methanol and hydrogenated bisphenol A, ethylene oxide adducts of bisphenol A, and propylene oxide adducts of bisphenol A. One or more of these polyhydric alcohols can be used. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferable, and among these, aromatic diols are more preferable. In order to secure good fixing properties, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol in order to take a crosslinked structure or a branched structure.

  In addition, in the non-crystalline polyester resin, a monocarboxylic acid and / or monoalcohol is further added to the polyester resin obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol, and a hydroxyl group at the polymerization terminal, And / or the carboxyl group may be esterified to adjust the acid value of the polyester resin. Examples of the monocarboxylic acid include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, propionic anhydride and the like, and examples of the monoalcohol include methanol, ethanol, propanol, octanol, 2-ethylhexanol, and trifluoroethanol. , Trichloroethanol, hexafluoroisopropanol, phenol and the like.

  The method for producing the non-crystalline polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation, transesterification, etc. They are manufactured using different types of monomers. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  In the present invention, the production of these polyester resins can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction system is subjected to a reaction while reducing the pressure in the reaction system and removing water and alcohol generated during the condensation as necessary. . If the monomer is not dissolved or compatible at the reaction temperature, a high boiling point solvent is added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable to condense the monomer having poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance, and then polycondense together with the main component.

  Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium, alkaline earth metal compounds such as magnesium and calcium, metal compounds such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium, A phosphorous acid compound, a phosphoric acid compound, an amine compound, etc. are mentioned, Specifically, the following compounds are mentioned. For example, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium Tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, naphthene Zirconate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  The colorant used in the toner of the present invention is not particularly limited as long as it is a known colorant. For example, carbon black such as furnace black, channel black, acetylene black, and thermal black, inorganic such as bengara, bitumen, and titanium oxide. Pigments, Fast Yellow, Disazo Yellow, Pyrazolone Red, Chelate Red, Brilliant Carmine, Para Brown and other azo pigments, copper phthalocyanine, metal-free phthalocyanine and other phthalocyanine pigments, flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, di Examples thereof include condensed polycyclic pigments such as oxazine violet. Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrarozone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. And various pigments such as CI Pigment Blue 15: 3. These may be used alone or in combination of two or more.

  The toner of the present invention preferably contains a release agent. The release agent is not particularly limited as long as it is a known release agent. For example, carnauba wax, rice wax, can Synthetic or mineral / petroleum wax, fatty acid ester, montanic acid ester, etc. Although ester wax etc. are mentioned, it is not limited to this. Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types. The melting point of the release agent is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of storage stability. Moreover, it is preferable that it is 110 degrees C or less from a viewpoint of offset resistance, and it is more preferable that it is 100 degrees C or less.

Furthermore, the toner of the present invention may contain various other components such as an internal additive, a charge control agent, inorganic powder (inorganic fine particles), and organic fine particles, as necessary. Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, and magnetic materials such as compounds containing these metals. Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments. The inorganic powder is added mainly for the purpose of adjusting the viscoelasticity of the toner. For example, silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide, etc. Examples thereof include all inorganic fine particles used as an external additive on the toner surface.

The method for producing an electrostatic charge image developing toner of the present invention (hereinafter sometimes referred to as “the toner production method of the present invention”) includes a resin fine particle dispersion containing fine particles of a crystalline polyester resin, and colorant particles. The dispersed colorant particle dispersion is mixed, and the crystalline polyester resin and the colorant particles are aggregated to a toner particle diameter in an aqueous medium to form an aggregate, and the aggregate is formed from the crystalline polyester resin. It is characterized by having a step of heating and fusing at a temperature higher than the melting point.
In the toner production method of the present invention, it is preferable that the resin fine particle dispersion contains amorphous resin fine particles together with crystalline polyester resin fine particles.
On the other hand, the method for producing a toner of the present invention comprises attaching a non-crystalline resin to the surface of an aggregate formed by aggregating a crystalline polyester resin and colorant particles to a toner particle size in an aqueous medium. It is preferable to heat and fuse.

  The toner production method of the present invention comprises an electrophotographic toner comprising at least a colorant and a crystalline polyester resin (preferably further an amorphous resin) obtained by the present invention as a binder resin component. However, as a production method thereof, a conventional kneading pulverization method or a chemical production method such as suspension polymerization, emulsion polymerization aggregation method, dissolution suspension method or the like can be used. From the viewpoint of image quality characteristics, a chemical production method is more preferred, and an emulsion polymerization aggregation method that is most excellent in particle size distribution, which is a production method of the toner of the present invention, can be mentioned.

In the toner production in the emulsion polymerization aggregation method, the binder resin component is preferably an aqueous emulsification or dispersion of submicron particles of about 1 μm or less. However, the crystalline polyester resin and the amorphous resin in the present invention are preferably used. As a method of emulsifying fine particles and preparing a dispersion, a crystalline or non-crystalline resin that has been polymerized in advance using a commonly used surfactant such as sodium dodecylbenzenesulfonate, a polymer dispersant such as polyacrylic acid, and the like. A method of emulsifying and dispersing in water while applying a high shear force, and in this case, emulsifying and dispersing can be carried out while heating and melting above the melting point and glass transition point of the resin. Furthermore, a normal method for producing resin fine particles such as a method of phase inversion emulsification while dissolving a resin using a small amount of an organic solvent can be used.
In this case, as the shear emulsification dispersion, devices such as ultra turrax, clear mix, optimizer, gorin homogenizer, ultrasonic disperser, planetary ball mill, microdisperser, and cavitron can be used.

  In addition, when a radically polymerizable crystalline or amorphous resin is used, a polymer heterogeneous polymerization method such as an emulsion polymerization method can be applied. Further, a method of preparing resin fine particles by dissolving a prepolymerized polymer resin in a radical polymerizable vinyl monomer and then emulsifying and dispersing it to polymerize the vinyl monomer can be used as in the miniemulsion method. The method of obtaining the emulsified dispersion is not limited in any way by the present invention.

  Examples of the surfactant used herein include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

  As anionic surfactants, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, dialkylsulfosuccinate Sodium sulfate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, caproic acid Thorium, potassium stearate, and the like calcium oleate. Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.

  Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. Examples thereof include esters and sorbitan esters.

In the miniemulsion method, usually, higher alcohols typified by heptanol and octanol, and higher aliphatic hydrocarbons typified by hexadecane are often blended as a stabilizing aid in order to prevent the Ostwald Ripping phenomenon.
As the emulsion stabilizer, the above-mentioned nonionic surfactant is often used as an emulsion stabilizer.

Moreover, the pH adjustment of the emulsified dispersion is effective in order to further impart resin fine particle stability during resin emulsification, and an acid or an alkali can also be used for the pH adjustment. This pH is preferably in the range of pH 7 ± 2. If the acidity or alkalinity is too high, the resin may be hydrolyzed.
As a pH adjuster used here, a water-soluble acid or alkali is mentioned as a pH adjuster. Examples thereof include hydrochloric acid, sulfuric acid, acetic acid, perchloric acid, carbonic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide and the like.

Next, the method for producing the toner of the present invention will be described in detail.
The toner of the present invention is not particularly limited. For example, the resin emulsion of the present invention is mixed with a colorant particle dispersion and a release agent particle dispersion, and has a polarity opposite to that of the ionic surfactant. Aggregated particles having a toner diameter are formed by causing heteroaggregation with an ionic surfactant, and then heated to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and coalesce the aggregated particles, and wash and dry. Can be obtained. The toner shape is preferably from irregular to spherical. As the flocculant, an inorganic salt and a divalent or higher-valent metal complex can be suitably used in addition to the surfactant having the opposite polarity. In particular, the use of a metal complex is preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

  In the agglomeration step, in the initial stage of mixing the emulsion of the present invention, the colorant particle dispersion and the release agent particle dispersion, the balance of the amount of the ionic dispersant of each polarity is shifted in advance. Then, a polymer of an inorganic metal salt such as polyaluminum chloride is added to neutralize ionically, and then the first-stage base aggregated particles are formed at a temperature not higher than the glass transition point and stabilized, and then the second stage. Add resin fine particle dispersion treated with ionic dispersant of polarity and quantity to compensate for ionic balance deviation, and if necessary, resin contained in aggregated particles and resin contained in additional resin fine particles Slightly heated below the glass transition point of the glass, stabilized at a higher temperature, and then heated above the glass transition point to attach the particles added in the second stage of agglomeration to the surface of the base aggregated particles. Or it may be those obtained by coalescence while it is. Further, the stepwise operation of aggregation may be repeated a plurality of times. This two-stage method is effective for improving the inclusion of the release agent and the colorant.

  As the aggregating agent, a surfactant having a polarity opposite to that of the surfactant used for the dispersant, an inorganic metal salt, and a metal complex having a valence of 2 or more can be preferably used. Examples of the inorganic metal salt include metal salts such as calcium salt, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

In the step of heating and fusing, the progress of the aggregation is stopped by adjusting the pH of the suspension of the adhered aggregated particles to the range of 6.5 to 8.5 under the same stirring as in the aggregation step. The adhered aggregated particles are fused by heating at a temperature equal to or higher than the glass transition point of the binder resin.
There is no problem if the heating temperature at the time of fusion is not less than the glass transition point of the binder resin contained in the aggregated particles. The heating time may be performed to such an extent that the surface of the aggregated particles is tanned by fusion, and may be performed for about 0.5 to 1.5 hours. If it takes more time, the crystalline polyester contained in the core aggregated particles is likely to be exposed on the toner surface. This is effective for fixing property and document storage property, but adversely affects the charging property, so that it is not preferable to expose the crystalline polyester to the toner surface.

  The fused particles obtained by fusing can be made into toner particles through a solid-liquid separation process such as filtration and, if necessary, a washing process and a drying process. In this case, in order to ensure sufficient charging characteristics and reliability as a toner, it is preferable to sufficiently wash in the washing step.

  In the drying process, an arbitrary method such as a normal vibration type fluidized drying method, a spray drying method, a freeze drying method, or a flash jet method can be adopted. It is desirable that the toner particles have a moisture content after drying of 1.0% or less, preferably 0.5% or less.

  As described above, various known external additives such as inorganic fine particles and organic fine particles as described above can be added to the toner particles granulated through the drying step as described above according to the purpose.

  As inorganic fine particles as external additives, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth , Cerium chloride, bengara, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, silicon nitride and the like. Among them, silica fine particles and titanium oxide fine particles are preferable, and hydrophobized fine particles are particularly preferable. Inorganic fine particles are generally used for the purpose of improving fluidity. Organic fine particles are generally used for the purpose of improving cleaning properties and transfer properties, and specific examples include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

  When the toner used in the present invention is used as a magnetic toner, magnetic powder may be contained in the binder resin. As such magnetic powder, a substance magnetized in a magnetic field is used. Specifically, ferromagnetic powders such as iron, cobalt and nickel, or compounds such as ferrite and magnetite can be used. In particular, in the present invention, in order to obtain toner in the aqueous layer, it is necessary to pay attention to the water layer transferability of the magnetic material, and it is preferable to perform surface modification, for example, hydrophobization treatment.

<Developer for developing electrostatic image>
The electrostatic image developing toner of the present invention is used as it is as a one-component developer or as a two-component developer. When used as a two-component developer, it is used by mixing with a carrier.
There is no restriction | limiting in particular as a carrier which can be used for a two-component developer, A well-known carrier can be used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples thereof include, but are not limited to, acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins and the like.

Examples of the conductive material include metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black. It is not limited.
Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, it is a magnetic material. It is preferable. The volume average particle size of the core material of the carrier is generally 10 to 500 μm, preferably 30 to 100 μm.

In order to coat the surface of the core material of the carrier with a resin, there may be mentioned a method of coating with a coating layer forming solution in which the coating resin and, if necessary, various additives are dissolved in an appropriate solvent. The solvent is not particularly limited and may be appropriately selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. And a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater and the solvent is removed in a kneader coater. The mixing ratio (weight ratio) of the toner of the present invention and the carrier in the two-component developer is in the range of toner: carrier = 1: 100 to 30: 100, and about 3: 100 to 20: 100. A range is more preferred.

<Image forming method>
The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing for thermally fixing the toner image transferred to the surface of the transfer target. In the image forming method including the steps, the toner for developing an electrostatic charge image of the present invention is used as the toner. The developer may be either a one-component system or a two-component system. As each of the above steps, a known step in the image forming method can be used. The image forming method of the present invention may include steps other than the steps described above.

As the latent image holding member, for example, an electrophotographic photosensitive member and a dielectric recording member can be used.
In the case of an electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic latent image (latent image forming step). Next, the toner particles are attached to the electrostatic latent image by contacting or approaching a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member (developing step). The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like (transfer process). Further, the toner image transferred to the surface of the transfer target is heat-fixed by a fixing device, and a final toner image is formed.
In the heat fixing by the fixing machine, a release agent is usually supplied to a fixing member in the fixing machine in order to prevent an offset or the like.

In the toner of the present invention (including those contained in the two-component developer, the same applies hereinafter), when the binder resin has a cross-linked structure, it is excellent in releasability due to its effect and the amount of the release agent used. Fixing can be carried out without reducing or using a release agent.
The release agent used for image formation is preferably not used from the viewpoint of eliminating the adhesion of oil to the transfer target and image after fixing. However, when the supply amount of the release agent is 0 mg / cm ² , the fixing agent is fixed. Sometimes, when the fixing member comes into contact with a transfer medium such as paper, the amount of wear of the fixing member may increase and the durability of the fixing member may decrease. It is preferable that a small amount of the mold is supplied to the fixing member in a range of 8.0 × 10 ⁻³ mg / cm ² or less.
When the supply amount of the release agent used for image formation exceeds 8.0 × 10 ⁻³ mg / cm ² , the image quality deteriorates due to the release agent adhering to the image surface after fixing. When using transmitted light, this phenomenon may appear remarkably. Further, the adhesion of the release agent to the transfer target becomes remarkable, and stickiness may occur. Furthermore, the larger the supply amount of the release agent, the larger the capacity of the tank for storing the release agent, which causes an increase in the size of the fixing device itself.

The release agent used for image formation is not particularly limited, and examples thereof include liquid release agents such as dimethyl silicone oil, fluorine oil, fluorosilicone oil, and modified oils such as amino-modified silicone oil. Among these, modified oils such as amino-modified silicone oil are preferable because they are adsorbed on the surface of the fixing member and can form a homogeneous release agent layer, because they have excellent wettability to the fixing member. Further, from the viewpoint of forming a homogeneous release agent layer, fluorine oil and fluorosilicone oil are preferable.
The use of fluorine oil or fluorosilicone oil as a release agent for image formation does not use the electrophotographic toner of the present invention. In conventional image forming methods, the supply amount of the release agent itself is reduced. However, when the electrophotographic toner of the present invention is used, the supply amount of the release agent can be drastically reduced, so that there is no practical problem in terms of cost.

  The method for supplying the release agent to the surface of the roller or belt, which is a fixing member used for thermocompression bonding, is not particularly limited. For example, a pad method using a pad impregnated with a liquid release agent, a web method, a roller Examples thereof include a non-contact type shower method (spray method), and a web method and a roller method are particularly preferable. These methods are advantageous in that the release agent can be supplied uniformly and it is easy to control the supply amount. In order to supply the release agent uniformly to the entire fixing member by the shower method, it is necessary to use a separate blade or the like.

The supply amount of the release agent used for the image formation can be measured as follows. That is, when a normal paper (typically a copy paper manufactured by Fuji Xerox Co., Ltd., trade name J paper) used in a general copying machine is passed through a fixing member supplied with a release agent on its surface. The release agent adheres to the plain paper. The attached release agent is extracted using a Soxhlet extractor. Here, hexane is used as the solvent.
By quantifying the amount of the release agent contained in the hexane with an atomic absorption analyzer, the amount of the release agent adhering to the plain paper can be quantified. This amount is defined as the amount of release agent supplied to the fixing member.

  Examples of the transfer target (recording material) to which the toner image is transferred include plain paper, OHP sheet, and the like used in electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer object is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin or the like, art paper for printing Etc. can be used suitably.

  Since the image forming method of the present invention uses the developer of the present invention (the toner of the present invention), low-temperature fixing is possible and the toner can maintain an appropriate triboelectric charge amount. Therefore, it is excellent in energy saving at the time of image formation, and a good image can be formed while preventing the occurrence of toner scattering and the like.

  The present invention will be described below as examples. Tables 1 and 2 show a comparison of crystalline resin composition, blending amount and developer characteristics in Examples. However, the present invention is not limited to these examples. In addition, the numerical value in () in the monomer component (polymerization unit) described in the column of the crystalline polyester resin in Tables 1 and 2 represents the ratio of each monomer component in the crystalline polyester resin in mol%. Is.

<Synthesis of crystalline resin>
-Preparation of crystalline polyester resin (1) and crystalline polyester resin emulsion (1)-
In a three-necked flask, 9 mol of 1,9-nonanediol, 10 mol of 1,10-dodecanoic acid, 1 mol of 2,2-bis (4-hydroxyphenyl) hexafluoropropane (BPF) and catalyst Ti (OBu) ₄ (based on the acid component, 0.014% by mass), and the air in the container was depressurized by a depressurization operation, and was further brought into an inert atmosphere with nitrogen gas, and refluxed at 180 ° C. for 6 hours with mechanical stirring. Thereafter, the unreacted monomer was removed by distillation under reduced pressure, the temperature was gradually raised to 220 ° C., the mixture was stirred for 12 hours, and when it became viscous, the molecular weight was confirmed by GPC. A polyester (1) of 18000 (HLC-8 120GPC manufactured by Tosoh Corporation, converted in terms of styrene standard substance) was obtained. As a result of measuring the thermal characteristics of the resin with the differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation: temperature rising rate 3 ° C./min), it had a melting point of 75 ° C.

Subsequently, using the obtained crystalline polyester resin (1), a crystalline polyester resin emulsion (1) was prepared.
Crystalline polyester resin (1): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to obtain a crystalline polyester resin emulsion (1) having a center diameter of 200 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (2) and crystalline polyester resin emulsion (2)-
As in the case of the crystalline polyester resin (1), 8 mol of sebacic acid, 10 mol of hexanediol, and 1 mol of 2,2-bis (3,4-anhydrodicarboxylphenyl) hexafluoropropane (6FDA) are used as monomers. Polymerization was performed to obtain a crystalline polyester resin (2) having a weight average molecular weight of 15500 and a melting point of 76.5 ° C.

Next, a crystalline polyester resin emulsion (2) was prepared using the obtained crystalline polyester resin (2).
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to obtain a crystalline polyester resin emulsion (2) having a center diameter of 170 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (3) and crystalline polyester resin emulsion (3)-
Similarly to the crystalline polyester resin (1), the resin was polymerized using 9 mol of sebacic acid, 10 mol of nonanediol, and 1 mol of 4-trifluoromethylphthalic acid (4-TFMP) as monomers, and the weight average molecular weight 16500, A crystalline polyester resin (3) having a melting point of 74.5 ° C. was obtained.

Subsequently, using the obtained crystalline polyester resin (3), a crystalline polyester resin emulsion (3) was prepared.
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to obtain a crystalline polyester resin emulsion (3) having a center diameter of 150 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (4) and crystalline polyester resin emulsion (4)-
Similarly to the crystalline polyester resin (1), 10 mol of dodecanoic acid, 7 mol of nonanediol and 3 mol of 2,2-bis (4-hydroxyphenyl) hexafluoropropane (BPF) are used as monomers. A crystalline polyester resin (4) having a weight average molecular weight of 12,500 and a melting point of 79.5 ° C. was obtained.

Next, a crystalline polyester resin emulsion (4) was prepared using the obtained crystalline polyester resin (4).
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was carried out with a pressure discharge type gorin homogenizer for 1 hour to obtain a crystalline polyester resin emulsion (4) having a center diameter of 160 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (5) and crystalline polyester resin emulsion (5)-
Similarly to the crystalline polyester resin (1), the resin is polymerized using 10 mol of dodecanoic acid and 10 mol of nonanediol as monomers, polymerized to a weight average molecular weight of 15500, and further 0.6 mol of cyanobenzoic acid at 220 ° C. Polymerization was further performed for 5 hours, and cyanobenzoic acid was condensed to the resin terminal to obtain a crystalline polyester resin (5) having a weight average molecular weight of 16000 and a melting point of 75.5 ° C.

Subsequently, using the obtained crystalline polyester resin (5), a polyester resin emulsion (5) was prepared.
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to obtain a polyester resin emulsion (5) having a center diameter of 150 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (6) and crystalline polyester resin emulsion (6)-
Similar to the crystalline polyester resin (1), the resin was polymerized using 10 mol of dodecanoic acid and 10 mol of nonanediol as monomers, and the Hammett constant 0.15 in the present invention having a weight average molecular weight of 19500 and a melting point of 75.5 ° C. A crystalline polyester resin (6) having no electron withdrawing group was obtained.

Next, a crystalline polyester resin emulsion (6) was prepared using the obtained crystalline polyester resin (6).
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was performed with a pressure discharge type gorin homogenizer for 1 hour to obtain a crystalline polyester resin emulsion (6) having a center diameter of 160 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (7) and crystalline polyester resin emulsion (7)-
Similar to the crystalline polyester resin (1), the resin is polymerized using 10 mol of sebacic acid and 10 mol of hexanediol as monomers, and the Hammett constant 0.15 in the present invention having a weight average molecular weight of 15500 and a melting point of 69.5 ° C. A crystalline polyester resin (7) having no electron withdrawing group was obtained.

Next, a crystalline polyester resin emulsion (7) was prepared using the obtained crystalline polyester resin (7).
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to obtain a crystalline polyester resin emulsion (7) having a center diameter of 160 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (8) and crystalline polyester resin emulsion (8)-
As with the crystalline polyester resin (1), 9.9 mol of sebacic acid, 10 mol of hexanediol, 0.02 mol of 2,2-bis (3,4-anhydrodicarboxylphenyl) hexafluoropropane (6FDA) are used as monomers. Polymerization of the resin was performed to obtain a crystalline polyester resin (8) having a weight average molecular weight of 16500 and a melting point of 76.0 ° C.

Subsequently, using the obtained crystalline polyester resin (8), a crystalline polyester resin emulsion (8) was prepared.
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was carried out with a pressure discharge type gorin homogenizer for 1 hour to obtain a crystalline polyester resin emulsion (8) having a center diameter of 173 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (9) and crystalline polyester resin emulsion (9)-
Similar to the crystalline polyester resin (1), 3 mol of sebacic acid, 11 mol of hexanediol, 4 mol of 2,2-bis (3,4-anhydrodicarboxylphenyl) hexafluoropropane (6FDA) are used as monomers. Polymerization was performed to obtain a crystalline polyester resin (9) having a weight average molecular weight of 14500 and a melting point of 79.0 ° C.

Next, a crystalline polyester resin emulsion (9) was prepared using the obtained crystalline polyester resin (9).
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to obtain a crystalline polyester resin emulsion (9) having a center diameter of 183 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (10) and crystalline polyester resin emulsion (10)-
Similar to the crystalline polyester resin (1), as monomers, 8 mol of sebacic acid, 9 mol of hexanediol, 2 mol of 2,2-bis (3,4-anhydrodicarboxylphenyl) hexafluoropropane (6FDA), 2,2- The resin was polymerized using 1 mol of bis (4-hydroxyphenyl) hexafluoropropane (BPF) to obtain a crystalline polyester resin (10) having a weight average molecular weight of 15500 and a melting point of 79.5 ° C.

Subsequently, using the obtained crystalline polyester resin (10), a crystalline polyester resin emulsion (10) was prepared.
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was carried out with a pressure discharge type gorin homogenizer for 1 hour to obtain a crystalline polyester resin emulsion (10) having a center diameter of 195 nm and a solid content of 30 parts by mass.

-Preparation of crystalline polyester resin (11) and crystalline polyester resin emulsion (11)-
Similar to the crystalline polyester resin (1), 10 mol of sebacic acid, 8 mol of hexanediol, 2,2 ′-(4,4 ′-(propane-2,2-diyl) bis (4,1-phenylene) as monomers. )) Resin polymerization using 2 mol of bis (oxy) diethanol (PPE), a crystalline polyester having a weight average molecular weight of 15500 and a melting point of 70.5 ° C. and having a group having a Hammett constant of (−0.17). Resin (11) was obtained.

Subsequently, using the obtained crystalline polyester resin (11), a crystalline polyester resin emulsion (11) was prepared.
Crystalline polyester resin (A): 90 parts by mass Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 1.8 parts by mass Ion-exchanged water: 210 parts by mass After sufficiently dispersing with Lux T50, dispersion treatment was carried out with a pressure discharge type gorin homogenizer for 1 hour to obtain a crystalline polyester resin emulsion (11) having a center diameter of 155 nm and a solid content of 30 parts by mass.

<Synthesis of non-crystalline resin>
-Preparation of non-crystalline polyester resin (1) and non-crystalline polyester resin emulsion (1)-
Terephthalic acid: 30 mol
Fumaric acid: 70 mol
Bisphenol A ethylene oxide 2-mol adduct: 20 mol
Bisphenol A propylene oxide 2 mol adduct: 80 mol
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying tower, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. After confirming the above, 1.2 parts by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. An amorphous polyester resin (1) of 9700 was obtained.

Subsequently, the obtained amorphous polyester resin (1) was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min in the molten state. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (e) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² to obtain an amorphous polyester resin emulsion (1) having an average particle size of 0.16 μm and a solid content of 30 parts by mass.

-Preparation of non-crystalline polyester resin (2) and non-crystalline polyester resin emulsion (2)-Styrene: 370 parts by mass n-butyl acrylate: 30 parts by mass Acrylic acid: 4 parts by mass Dodecanethiol: 24 parts by mass tetrabromide Carbon: 4 parts by mass Mixing and dissolving the above, 6 parts by mass of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) : Neogen SC) Dispersed in 560 parts by mass of ion exchanged water in 560 parts by mass, dispersed in a flask, emulsified, and slowly mixed for 10 minutes. After charging 50 parts by mass and carrying out nitrogen substitution, the contents inside the flask were stirred and heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued for 5 hours. did. Thus, an amorphous polyester resin emulsion (2) (resin) in which an amorphous polyester resin (2) having an average particle size of 180 nm, a glass transition point of 55 ° C., and a weight average molecular weight (Mw) of 28000 is dispersed. Particle concentration: 41.5 parts by mass) was prepared.

-Preparation of release agent dispersion-
Ester wax (Nippon Yushi Co., Ltd .: WE-2, melting point 65 ° C.): 50 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5 parts by mass 200 parts by mass or more is heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a Manton Gorin high-pressure homogenizer (Gorin), and the average particle size is 230 nm. A release agent dispersion liquid (release agent concentration: 20% by mass) obtained by dispersing the release agent was prepared.

-Preparation of colorant dispersion-
Cyan pigment (Pigment Blue 15: 3 (copper phthalocyanine), manufactured by Dainichi Seika Co., Ltd.): 1000 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R): 150 parts by mass : 9000 parts by mass The above is mixed, dissolved, and dispersed by dispersing the colorant (cyan pigment) for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine, HJP30006). An agent dispersion was prepared. The average particle diameter of the colorant (cyan pigment) in the colorant dispersion was 0.15 μm, and the colorant particle concentration was 23% by mass.

<Example 1>
"Manufacture of toner particles (1)"
-Crystalline polyester resin emulsion (1): 150.2 parts by mass (solid content 45 parts by mass)
-Amorphous polyester resin emulsion (1): 800 parts by mass (solid content 240 parts by mass)
Colorant dispersion: 22.87 parts by mass (solid content 5.3 parts by mass)
-Release agent dispersion: 50 parts by mass (solid content 10 parts by mass)
Nonionic surfactant (IGEPAL CA897): 0.5 parts by mass Ion exchange water: 1010 parts by mass

  Among the above raw materials, 240 parts by mass (72 parts by mass of solid content) of the non-crystalline polyester resin emulsion (1) is left in a 5 L cylindrical stainless steel container, and dispersed and mixed for 30 minutes while applying shear force at 8000 rpm with Ultraturrax. To do. Next, 0.14 parts by mass of a 10% nitric acid aqueous solution of polyaluminum chloride was added dropwise as a flocculant. At this time, the pH of the raw material dispersion was controlled in the range of 4.2 to 4.5. The pH was adjusted with 0.3N nitric acid or 1N aqueous sodium hydroxide as required. Thereafter, the raw material dispersion is transferred to a polymerization kettle equipped with a stirrer and a thermometer and heated to promote the growth of the aggregated particles at 40 ° C. When the volume average particle diameter reaches 5.0 μm, it is first arranged. Further, 240 parts by mass of the non-crystalline polyester resin emulsion (1) was gradually added, the temperature was raised to 50 ° C., and the particle size was adjusted to 6.0 μm. Further, after raising the pH to 9.0, the temperature was raised to 90 ° C. and maintained at 90 ° C. for 2 hours, and then the pH was gradually lowered to 6.5, then the heating was stopped and the mixture was allowed to cool. Thereafter, the mixture was sieved with a 45 μm mesh, washed repeatedly with water and then dried with a freeze dryer to obtain toner particles (1). As a result of measuring the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the result was 6.0 μm and the volume average particle size distribution was 1.22. .

“Production and Evaluation of Developer 1”
To 100 parts by mass of the obtained toner particles (1), 1 part by mass of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., R972) is externally added and mixed using a Henschel mixer to obtain an electrostatic image developing toner. Obtained. 100 parts by mass of ferrite particles (manufactured by Powdertech, average particle size 50 μm) and 1 part by mass of a methacrylate resin (manufactured by Ryo Rayon Co., Ltd., molecular weight 95000) are placed in a pressure kneader together with 500 parts by mass of toluene and mixed at room temperature for 15 minutes. Then, the temperature was raised to 70 ° C. while mixing under reduced pressure, and toluene was distilled off, followed by cooling and sizing using a 105 μm sieve to produce a ferrite carrier (resin-coated carrier). The ferrite carrier and the electrostatic image developing toner were mixed to prepare a two-component electrostatic image developer (1) having a toner concentration of 7% by mass.

  The obtained electrostatic charge image developer (1) was used to measure and evaluate the absolute value of the charge amount (μC / g) in an environment of 80% RH and 28 ° C. with a bromometer. The amount showed a good initial chargeability of -45 μC / g. Further, as a result of measuring the charge amount after holding the developer for one week under the same environmental conditions, the charge amount of 95% with respect to the initial charge amount was maintained, and good charge maintaining characteristics were exhibited.

Further, for the evaluation of fixing and image quality, image formation (image formation including a latent image forming process, a developing process, a transfer process, and a fixing process) is performed using a Docu Center Color 500CP remodeling machine manufactured by Fuji Xerox Co., Ltd. Initial image quality and image quality after 10,000 sheets were evaluated. The results are shown in Tables 1 and 2. In this case, the particle size distribution of the toner as the image quality characteristics, and the scattering of the toner, the image density, and the image density unevenness as the image quality defects derived from the charging characteristics (initial charging and charge deterioration) were visually evaluated. As a result, the fixing temperature is 110 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained. It was.
The image quality evaluation is evaluated according to the following criteria.
○: There is no scattering of toner, and the image density and image uniformity are good.
(Triangle | delta): Although scattering of a toner and the nonuniformity of image quality are some, it is in a tolerance level practically.
X: Toner scattering, image quality, image unevenness, and practical problems.

<Example 2>
“Preparation of toner particles (2)”
In Example 1, toner particles (2) were obtained in the same manner as in Example 1, except that the crystalline polyester resin emulsion (2) was used instead of the crystalline polyester resin emulsion (1). As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.), it was 5.9 μm and the volume average particle diameter distribution was 1.23. .

"Production of developer (2) and image quality evaluation"
In Example 1, a developer (2) was prepared in the same manner as in Example 1 except that the toner particles (2) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was -40 μC / g, and the charge retention rate for one week was 94%, indicating good charging characteristics. Furthermore, the fixing temperature is 105 ° C., which is possible at an unprecedented low temperature. As image quality characteristics, there is no toner scattering, sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 3>
“Preparation of toner particles (3)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) Crystalline polyester resin emulsion (3) 100.3 parts by mass (solid content 30.1 parts by mass) Amorphous resin polyester resin emulsion (1) 849 parts by mass (solid content 254.7 parts by mass) Toner particles (3) were obtained in the same manner as in Example 1 except that they were used. As a result of measuring the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the result was 6.0 μm and the volume average particle size distribution was 1.23. .

"Production of developer (3) and image quality evaluation"
In Example 1, a developer (3) was prepared in the same manner as in Example 1 except that the toner particles (3) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was −48 μC / g, and the charge retention rate for one week was a good charge characteristic of 95%. Further, the fixing temperature is 115 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, and a sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 4>
“Preparation of toner particles (4)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) 50.1 parts by mass (15.0 parts by mass of solid content) of the emulsion of crystalline polyester resin emulsion (4), 900 parts by mass (270 parts by mass of solid content) of the non-crystalline polyester resin emulsion (1) Toner particles (4) were obtained in the same manner as in Example 1 except that they were used. As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.), the result was 6.1 μm and the volume average particle diameter distribution was 1.23. .

“Production of developer (4) and evaluation of image quality”
In Example 1, a developer (4) was prepared in the same manner as in Example 1 except that the toner particles (4) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was -45 μC / g, and the charge retention rate for one week was 95%. Further, the fixing temperature is 115 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, and a sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 5>
"Preparation of toner particles (5)"
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) Crystalline polyester resin emulsion (5) 200.5 parts by mass (solid content 60.1 parts by mass) Non-crystalline polyester resin emulsion (1) 749.7 parts by mass (solid content 224.9 parts by mass) Toner particles (5) were obtained in the same manner as in Example 1 except that they were used. As a result of measuring the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the result was 6.2 μm and the volume average particle size distribution was 1.22. .

“Production of developer (5) and image quality evaluation”
In Example 1, a developer (5) was prepared in the same manner as in Example 1 except that the toner particles (5) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was -40 μC / g, and the charge retention rate for one week was 94%, indicating good charging characteristics. Furthermore, the fixing temperature is 105 ° C., which is possible at an unprecedented low temperature. As image quality characteristics, there is no toner scattering, sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 6>
“Preparation of Toner Particles (6)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) Crystalline polyester resin emulsion (2) 200.5 parts by mass (solid content 60.1 parts by mass) Noncrystalline polyester resin emulsion (2) Emulsion 541.9 parts by mass (solid content 224.9 parts by mass) In addition, toner particles (6) were obtained in the same manner as in Example 1 except that the ion exchange water in Example 1 was changed to 1217 parts by mass. As a result of measuring the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the result was 6.2 μm and the volume average particle size distribution was 1.22. .

"Production of developer (6) and evaluation of image quality"
In Example 1, a developer (6) was prepared in the same manner as in Example 1 except that the toner particles (6) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was -40 μC / g, and the charge retention rate for one week was 94%, indicating good charging characteristics. Furthermore, the fixing temperature is 110 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 7>
“Production of toner particles (7)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) , Crystalline polyester resin emulsion (8) 200.5 parts by mass (solid content 60.1 parts by mass) Non-crystalline polyester resin emulsion (2) Emulsion liquid 749.7 parts by mass (solid content 224.9 parts by mass) ) Was used in the same manner as in Example 1 except that the toner particles (7) were obtained. As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.), the result was 6.1 μm and the volume average particle diameter distribution was 1.23. .

"Production of developer (7) and image quality evaluation"
In Example 1, a developer (7) was prepared in the same manner as in Example 1 except that the toner particles (7) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was -30 μC / g, and the charge retention rate for one week was 80%. Furthermore, the fixing temperature is 110 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 8>
"Preparation of toner particles (8)"
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) , Crystalline polyester resin emulsion (9) 200.5 parts by mass (solid content 60.1 parts by mass) Non-crystalline polyester resin emulsion (2) Emulsion liquid 749.7 parts by mass (solid content 224.9 parts by mass) ) Was used in the same manner as in Example 1 to obtain toner particles (8). As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the result was 6.0 μm and the volume average particle diameter distribution was 1.24. .

“Production of developer (8) and evaluation of image quality”
In Example 1, a developer (8) was prepared in the same manner as in Example 1 except that the toner particles (8) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was -50 μC / g, and the charge retention rate for one week was 92%, indicating good charging characteristics. Furthermore, the fixing temperature is 120 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 9>
"Preparation of toner particles (9)"
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) Crystalline polyester resin emulsion (10) 200.5 parts by mass (solid content 60.1 parts by mass) Non-crystalline polyester resin emulsion (2) Emulsion liquid 749.7 parts by mass (solid content 224.9 parts by mass) ) Was used in the same manner as in Example 1 to obtain toner particles (9). As a result of measuring the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.), the volume average particle size distribution was 5.7 μm. .

"Production of developer (9) and image quality evaluation"
In Example 1, a developer (9) was produced in the same manner as in Example 1 except that the toner particles (9) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was -44 μC / g, and the charge retention rate for one week was 95%. Furthermore, the fixing temperature is 110 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Example 10>
“Preparation of Toner Particles (10)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) Except for using 10 parts by mass of crystalline polyester resin emulsion (2) (solid content: 3.0 parts by mass), non-crystalline polyester resin emulsion (1) emulsion of 940 parts by mass (solid content: 282 parts by mass), In the same manner as in Example 1, toner particles (10) were obtained. As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the volume average particle diameter distribution was 5.5 μm. .

“Production of developer (10) and evaluation of image quality”
In Example 1, a developer (10) was prepared in the same manner as in Example 1 except that the toner particles (10) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was −49 μC / g, and the charge retention rate for one week was a good charge characteristic of 95%. Further, the fixing temperature can be as low as 130 ° C., and no toner scattering is obtained as image quality characteristics, and sufficient image density and uniform image quality are obtained, and good image quality characteristics that are practically satisfactory are obtained.

<Example 11>
“Preparation of Toner Particles (11)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) Except for using 516 parts by mass of crystalline polyester resin emulsion (2) (solid content of 155 parts by mass) and non-crystalline polyester resin emulsion (1) emulsion of 433 parts by mass (solid content of 130 parts by mass) In the same manner as in Example 1, toner particles (11) were obtained. As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the volume average particle diameter distribution was 5.8 μm. .

"Production of developer (11) and image quality evaluation"
In Example 1, a developer (11) was prepared in the same manner as in Example 1 except that the toner particles (11) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount was −39 μC / g, and the charge retention rate for one week was 84%. Furthermore, the fixing temperature can be as low as 100 ° C., and the toner has no image scattering as the image quality characteristics. Sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

<Comparative Example 1>
“Preparation of Toner Particles (12)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) The crystalline polyester resin emulsion (6) 150.2 parts by mass (solid content 45.0 parts by mass), the non-crystalline polyester resin emulsion (1) 800 parts by mass (solid content 240 parts by mass), In the same manner as in Example 1, toner particles (12) were obtained. As a result of measuring the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter Inc.), the volume average particle size distribution was 6.5 μm. .

"Production of developer (12) and evaluation of image quality"
In Example 1, a developer (12) was produced in the same manner as in Example 1 except that the toner particles (12) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount showed a low charge property of −15 μC / g, and the charge retention rate after one week was 45%. Furthermore, the fixing temperature was 110 ° C., and fixing at a lower temperature was possible compared to the conventional case, but as the image quality characteristics, toner scattering was noticeably observed, and the initial image density and uniformity thereof were insufficient. It was a problem in practical use.

<Comparative example 2>
“Preparation of Toner Particles (13)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) , Crystalline polyester resin emulsion (7) 749.7 parts by mass (solid content 224.9 parts by mass), non-crystalline polyester resin emulsion (2) 578 parts by mass (solid content 240 parts by mass), and Example 1 Toner particles (13) were obtained in the same manner as in Example 1 except that the ion exchange water was changed to 1217 parts by mass. As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.), the volume average particle diameter distribution was 6.4 μm. .

"Production of developer (13) and image quality evaluation"
In Example 1, a developer (13) was prepared in the same manner as in Example 1 except that the toner particles (13) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount showed a low charge property of −18 μC / g, and the charge retention rate after one week was 46%. Furthermore, the fixing temperature was 110 ° C., and fixing at a lower temperature was possible compared to the conventional case, but as the image quality characteristics, toner scattering was noticeably observed, and the initial image density and uniformity thereof were insufficient. It was a problem in practical use.

<Comparative Example 3>
“Preparation of Toner Particles (14)”
In Example 1, instead of the crystalline polyester resin emulsion (1) 150.2 parts by mass (solid content 45 parts by mass) and the non-crystalline polyester resin emulsion (1) 800 parts by mass (solids content 240 parts by mass) The crystalline polyester resin emulsion (11) 150.2 parts by mass (solid content 45.0 parts by mass), the non-crystalline polyester resin emulsion (1) 800 parts by mass (solid content 240 parts by mass), In the same manner as in Example 1, toner particles (10) were obtained. As a result of measuring the volume average particle diameter of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the volume average particle diameter distribution was 6.3 μm. .

"Production of developer (14) and evaluation of image quality"
In Example 1, a developer (14) was prepared in the same manner as in Example 1 except that the toner particles (14) were used instead of the toner particles (1), and image quality evaluation similar to that in Example 1 was performed. went. As a result, the toner charge amount showed a low charge of -12 μC / g, and the charge retention rate after one week was 35%. Furthermore, the fixing temperature was 115 ° C., and fixing was possible at a lower temperature than in the past. However, as the image quality characteristics, toner scattering was noticeably observed, and the initial image density and uniformity thereof were insufficient. It was a problem in practical use.

  From Tables 1 and 2, Examples 1 to 11 satisfy all characteristics in toner fixing characteristics, charging characteristics, and image quality characteristics as compared with Comparative Examples 1 to 3, and low temperature fixing characteristics that have been considered difficult so far. In addition, it can be seen that the toner has both excellent charging properties important as a toner and has excellent image quality characteristics.

Claims (4)

An electrostatic charge image developing toner containing at least a colorant and a crystalline polyester resin,
At least one of the polymerized units constituting the crystalline polyester resin has an electron withdrawing group having a Hammett constant of 0.15 or more derived from para-substitution of benzoic acid and its derivatives. Toner.   A resin fine particle dispersion containing fine particles of a crystalline polyester resin is mixed with a colorant particle dispersion in which colorant particles are dispersed, and the crystalline polyester resin and the colorant particles are aggregated to a toner particle size in an aqueous medium. 2. The method for producing a toner for developing an electrostatic charge image according to claim 1, further comprising a step of forming an aggregate, and heating and fusing the formed aggregate at a temperature equal to or higher than the melting point of the crystalline polyester resin. .   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier. A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and a developing step for developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner to form a toner image. And a transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step of thermally fixing the toner image transferred to the surface of the transfer target. There,
An image forming method using the toner for developing an electrostatic charge image according to claim 1 as the toner.