JP2007316212A - Binder resin for electrostatic charge image developing toner, method for manufacturing the same, binder resin particle dispersion liquid for electrostatic charge image developing toner, electrostatic charge image developing toner and method for manufacturing the same, electrostatic charge image developer, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder resin for an electrostatic charge image developing toner and a method for manufacturing the binder resin containing a protonic acid group with a reduced metal amount, and also to provide a dispersion liquid of binder resin particles for an electrostatic charge image developing toner using the above binder resin for an electrostatic charge image developing toner, an electrostatic charge image developing toner, a method for manufacturing the toner, an electrostatic charge image developer, and an image forming method. <P>SOLUTION: The binder resin for an electrostatic charge image developing toner comprises a noncrystalline polyester resin obtained by polycondensation of polycarboxylic acid and polyol and is characterized in that: the polyester resin contains structural units comprising substituted polycarboxylic acids having protonic acid groups except for carboxyl groups, by 0.5 to 10 mol% in the entire structural units; and tin and titanium concentrations in the polyester resin are both 100 ppm or less. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a binder resin for an electrostatic charge image developing toner used when developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer, a method for producing the same, and an electrostatic charge image developing toner. The present invention relates to a binder resin particle dispersion, an electrostatic charge image developing toner and a production method thereof, an electrostatic charge image developer, and an image forming method.

  A method for visualizing image information through an electrostatic latent image, such as electrophotography, is currently used in various fields. In electrophotography, an electrostatic latent image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process. The developer used here includes a two-component developer composed of a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone. The toner is usually produced by using a thermoplastic resin. A kneading and pulverizing method is used in which melt-kneading is performed together with a release agent such as a pigment, a charge control agent, and wax, followed by cooling, fine pulverization, and further classification. In these toners, if necessary, inorganic and organic fine particles for improving fluidity and cleaning properties may be added to the toner particle surface.

In recent years, copiers and printers based on color electrophotography, and multi-function machines such as those and facsimiles have been widely used. However, in order to achieve moderate gloss in color image reproduction and transparency to obtain an excellent OHP image, wax is used. It is generally difficult to use a release agent such as For this reason, a large amount of oil is applied to the fixing roll to assist in peeling. However, a sticky feeling of a copy image containing OHP occurs, it becomes difficult to add to the image with a pen or the like, and non-uniform gloss It often creates a feeling. In normal black and white copies, commonly used waxes such as polyethylene, polypropylene, paraffin, etc. are more difficult to use because they impair OHP transparency.
Even if the transparency is sacrificed, it is difficult to suppress the toner exposure to the surface by the conventional kneading pulverization method. Problems such as deterioration of the image quality and filming on the developing machine and the photoreceptor.

As a fundamental improvement method for these problems, an oil phase consisting of a monomer and a colorant as a resin raw material is dispersed in an aqueous phase and directly polymerized into a toner. Thus, a method for producing a toner by a polymerization method for controlling the exposure to the surface has been proposed.
In addition, as means for enabling intentional control of the toner shape and surface structure, Patent Document 1 and Patent Document 2 propose a toner manufacturing method using an emulsion polymerization aggregation method. These are generally prepared as a resin dispersion by emulsion polymerization or the like, while preparing a colorant dispersion in which a colorant is dispersed in a solvent and mixing them to form an aggregate corresponding to the toner particle size. In this method, the toner is fused and united by heating to obtain a toner.
These manufacturing methods not only realize the inclusion of the wax, but also facilitate the reduction of the toner diameter, and enable higher resolution and clearer image reproduction.

  In order to provide high-quality images in the electrophotographic process as described above and maintain stable performance of the toner under various mechanical stresses, pigment, release agent selection, amount optimization, surface application It is extremely important to improve the release property in the absence of glossiness and fixing oil and to suppress the hot offset by suppressing the exposure of the release agent and optimizing the resin characteristics.

  On the other hand, in order to reduce energy consumption, a technology capable of fixing at a lower temperature is desired. Particularly in recent years, in order to save energy, it is desirable to stop energization of the fixing machine except during use. ing. Accordingly, the temperature of the fixing device needs to be energized and instantaneously raised to the operating temperature. For this purpose, it is desirable to make the heat capacity of the fixing machine as small as possible, but in that case, the temperature fluctuation of the fixing machine tends to be larger than before. That is, the overshoot of the temperature after the start of energization increases, and on the other hand, the temperature drop due to paper passing also increases. In addition, when the paper having a width smaller than the width of the fixing device is continuously passed, the temperature difference between the paper passing portion and the non-paper passing portion becomes large. In particular, when used in high-speed copying machines and printers, the power supply capacity tends to be insufficient, and there is a strong tendency to cause the above phenomenon. Therefore, there is a strong demand for a toner for electrophotography having a wide fixing latitude, which is fixed at a low temperature and does not cause an offset to a higher temperature region.

Conventionally, vinyl polymers have been widely used as toner binder resins, and the use of high molecular weight polymers has been proposed in order to obtain non-offset properties. Since the softening point is high, in order to obtain a fixed image having excellent glossiness, it is necessary to set the temperature of the heat roller high, which is contrary to energy saving. In addition, a toner using a vinyl polymer is easily affected by a plasticized plasticizer of vinyl chloride, and the toner itself is plasticized by being in contact with the plasticizer, and becomes sticky and plasticized. There is a problem of contamination of vinyl chloride products (hereinafter referred to as vinyl chloride resistance).
In contrast, polyester resins are excellent in vinyl chloride resistance, can be manufactured relatively easily with low molecular weight, and polyester resins are more resistant than toners that contain vinyl polymers as binder resins. Polyester is energy-saving because it has excellent wettability to a support such as a transfer paper when melted, and has the advantage that it can be sufficiently fixed at a lower temperature than a vinyl polymer having an almost equal softening point. It is often used as a binder resin for toner.

  However, the polymerization of the polycondensation type resin requires a reaction for 10 hours or more under stirring at high temperature exceeding 200 ° C. under high power and under high vacuum, and causes a large amount of energy consumption. For this reason, enormous capital investment is often required to obtain durability of the reaction equipment. Further, since a tin-based catalyst such as dibutyltin oxide is used, there is a drawback that the polymer is colored. Further, when a metal catalyst such as a tin catalyst is used, a high temperature is required. Further, the residue of the metal catalyst in the resin varies depending on the lot, and when the toner is used, troubles such as toner charging failure may occur. As a method using a metal catalyst such as tin, the method disclosed in Patent Document 3 can be cited. However, these catalysts have a problem in that they remain in the particles when converted to toner after polycondensation and affect charging. Moreover, in patent document 4, limitation of the amount of sulfonic acid group containing metals and limitation of an acid value which are contained in the polyester resin are performed. Moreover, in patent document 5, the density | concentration of a sulfonic acid group is prescribed | regulated. The purpose of these is to improve the dispersibility in water. In the polycondensation, tin and titanium-based catalysts are used, and in synthesizing the resin, a high temperature of 200 ° C. or higher is used. The load on the environment is considered.

Patent Document 6 stipulates that a heavy metal having a density of 4 g / cm ³ or more is 5 ppm or less in a polyester composed of an aromatic dicarboxylic acid and an aliphatic diol. In order to polymerize such polyester, polymerization is performed using pyrimidine as a catalyst, but a high temperature of 250 ° C. or higher is required.

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 Japanese Patent Publication No.61-36529 JP-A-8-245769 JP-A-8-253570 JP 2003-292598 A

  The present invention solves the above-mentioned problems in conventional toners, and provides a binder resin for an electrostatic charge image developing toner and an electrostatic charge image developing toner having the following characteristics. That is, an object of the present invention is to provide a binder resin for an electrostatic charge image developing toner containing a protonic acid group with a reduced amount of metal and a method for producing the same. The present invention relates to a binder resin particle dispersion for an electrostatic charge image developing toner, an electrostatic charge image developing toner, a method for producing the same, an electrostatic charge image developer, and an image forming method using the binder resin for an electrostatic charge image developing toner. The purpose is to provide. Accordingly, an object is to reduce charging failure and increase in charge distribution due to residual metal.

This problem can be solved by means described in <1> to <7> below.
<1> A binder resin for an electrostatic charge image developing toner containing an amorphous polyester resin obtained by polycondensation of a polycarboxylic acid and a polyol, wherein the polyester resin has a proton acid group other than a carboxyl group An electrostatic charge characterized in that a structural unit formed from polycarboxylic acid is contained in an amount of 0.5 mol% or more and 10 mol% or less in all structural units, and tin and titanium concentrations in the polyester resin are 100 ppm or less, respectively. Binder resin for image developing toner,
<2> A method for producing an electrostatic image developing toner binder resin comprising a step of polycondensing a polycarboxylic acid and a polyol, wherein the electrostatic image developing toner binder resin is an amorphous polyester resin, The polycarboxylic acid contains a substituted polycarboxylic acid having a proton acid group other than a carboxyl group, and the substituted polycarboxylic acid is 0.5 mol% or more and 10 mol% or less with respect to the total number of moles of the polycarboxylic acid and the polyol. The method for producing a binder resin for an electrostatic charge image developing toner, wherein the tin and titanium concentrations in the polyester resin are each 100 ppm or less,
<3> A binder resin particle dispersion for an electrostatic charge image developing toner in which the binder resin for an electrostatic charge image developing toner according to <1> is dispersed;
<4> An electrostatic charge image developing toner comprising a step of aggregating the binder resin particles in a dispersion containing at least a binder resin particle dispersion to obtain aggregated particles, and a step of heating and aggregating the aggregated particles A method for producing an electrostatic charge image developing toner, wherein the binder resin particle dispersion is the binder resin particle dispersion for an electrostatic charge image developing toner according to <3>,
<5> An electrostatic charge image developing toner produced by the production method according to <4>,
<6> An electrostatic charge image developer comprising the electrostatic charge image developing toner and the carrier according to <5>,
<7> 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 toner or an electrostatic charge image developer to form a toner image. An image including a developing step for forming, a 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 step for thermally fixing the toner image transferred to the surface of the transfer target. A method for forming an image, wherein the electrostatic image developing toner according to <5> is used as the toner, or the electrostatic image developer according to <6> is used as the developer.

  According to the present invention, it is possible to provide a binder resin for an electrostatic charge image developing toner containing a protonic acid group with a reduced amount of metal and a method for producing the same. Furthermore, according to the present invention, a binder resin particle dispersion for an electrostatic charge image developing toner using the binder resin for an electrostatic charge image developing toner, an electrostatic charge image developing toner and a production method thereof, an electrostatic charge image developer, In addition, an image forming method can be provided. Thereby, it is possible to reduce charging failure and increase in charge distribution due to residual metal.

The binder resin for an electrostatic charge image developing toner of the present invention is a binder resin for an electrostatic charge image developing toner comprising an amorphous polyester resin obtained by polycondensation of a polycarboxylic acid and a polyol. , A structural unit formed from a substituted polycarboxylic acid having a protonic acid group other than a carboxyl group, 0.5 mol% or more and 10 mol% or less in all the structural units, and the tin and titanium concentrations in the polyester resin are respectively It is characterized by being 100 ppm or less.
In the present invention, the “electrostatic image developing toner” is also simply referred to as “toner”. In addition, “binder resin for electrostatic image developing toner” is also simply referred to as “binder resin”.

The present invention relates to an application of a polyester resin, particularly an amorphous polyester resin, to an electrostatic charge image developing toner.
As described above, the polyester resin is excellent in vinyl chloride resistance and is useful as a binder resin for energy-saving toners. In particular, the non-crystalline polyester resin has high fluidity at room temperature, and thus has high fluidity, and has properties that are very suitable for toners in terms of offset suppression, low-temperature fixability, image quality, and the like. Crystalline polyester resin mainly composed of linear monomers has sharp melt properties due to crystallinity and has great merit for low-temperature fixability, but has the disadvantage of poor powder flowability and image strength. The characteristics of the binder resin as the main component are considered to be more appropriate for the amorphous polyester resin.

As a result of studies on polymerization of a polyester resin at low temperature and its application to a toner resin, the present inventors have found that tin is affected by metals such as tin and titanium that are conventionally used as a polycondensation catalyst for polyester resins. In addition, toners using a polyester resin polycondensed using a metal catalyst containing titanium as a binder resin cause deterioration of charging characteristics under various environments. As a result, as a toner, I found it was not enough.
In the present invention, if any of tin and titanium atoms in the binder resin for electrostatic image developing toner exceeds 100 ppm, charging failure and increase in charge distribution are caused by residual metal.
Tin and titanium are each 100 ppm or less, preferably 30 to 90 ppm, and more preferably 40 to 80 ppm.

  In the present invention, the amorphous polyester resin preferably contains 5 ppm or more of tin and / or titanium as a catalyst, and more preferably contains 10 ppm or more of tin as a catalyst.

Further estimation is that by adding a small amount of tin and / or titanium as a catalyst, the progress of the polycondensation reaction is promoted, and the low molecular weight component is slightly reduced, and furthermore, the catalyst mainly with tin and / or titanium, It is inferred that the durability of the resin itself is improved because the polyester terminal constitutes a domain.
Further, it is considered that tin and / or titanium are contained in the polyester resin and thus effective for improving the charge rising property of the polyester toner.
On the other hand, if the amount of tin and / or titanium used is too large, a decomposition reaction or a side reaction tends to occur during resin synthesis, which is not preferable in terms of toner physical properties (charging, coloring, or resin durability).

In the present invention, the polyester resin contains a structural unit formed from a substituted polycarboxylic acid having a proton acid group other than a carboxyl group in the structure. The “substituted polycarboxylic acid” means a polycarboxylic acid having two or more carboxyl groups and a protonic acid group other than the carboxyl group. That is, in the present invention, in a non-crystalline polyester resin obtained by polycondensation of a polycarboxylic acid and a polyol, a polycarboxylic acid further containing a protonic acid group other than a carboxyl group is used as a part of the polycarboxylic acid. . The substituted polycarboxylic acid has two or more carboxyl groups, preferably 2 to 4, more preferably 2 to 3, and still more preferably a dicarboxylic acid having two.
Here, “substituted polycarboxylic acid” is also referred to as “polycarboxylic acid of the present invention”. In addition, in a non-crystalline polyester resin polycondensed using a substituted polyester as a polycondensable monomer, a structural unit formed from a substituted polycarboxylic acid is also referred to as a “structure of the present invention”.
In the substituted polycarboxylic acid, the site of a protonic acid such as sulfonic acid exhibits a catalytic effect, and a polycondensation reaction between a carboxyl group and a hydroxyl group occurs. Furthermore, since the substituted polycarboxylic acid has two or more carboxyl groups in the structure, it is incorporated into the polymer during the polycondensation during the reaction, and finally incorporated into the polyester chain. On the other hand, when a compound having no carboxyl group and having only a proton acid group other than a carboxyl group such as a sulfonic acid group is used, when the resin is used, the sulfonic acid group or the like does not exist uniformly in the resin. There is a fear that the charging characteristics may not be sufficiently obtained. By incorporating the substituted polycarboxylic acid into the polyester chain, when it is made into a resin, it can be uniformly dispersed in the resin to prevent poor charging and the like.

  In addition, when tin and / or titanium is contained in the resin, if bulk polymerization is performed at a polycondensation temperature of 80 to 150 ° C., the meltability of tin and / or titanium into the polyester resin is poor and uniform during polycondensation. May not be distributed. When a toner is produced using a resin that is polycondensed in this state, a portion in which tin and / or titanium are present unevenly is formed, and a toner having uneven charge distribution can be obtained. Therefore, in order to uniformly melt tin and / or titanium into the polyester, the structure of the present invention having a structure of a proton acid other than the carboxyl group helps the melting of the polyester, thereby including tin and titanium metal. The structure can be uniformly dispersed in the polyester.

<Substituted polycarboxylic acid>
In this invention, it has a structural unit formed from the substituted polycarboxylic acid which has proton acid groups other than a carboxyl group in a structure as an acid-derived structural unit which comprises amorphous polyester. Examples of proton acid groups other than carboxyl groups include sulfonic acid groups and phosphonic acid groups.
Specific examples of the substituted polycarboxylic acid forming such a structural unit include 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and the like.

The structural unit formed from the substituted polycarboxylic acid is contained in an amount of 0.5 to 10 mol% in all structural units of the polyester resin. When it is less than 0.5 mol%, the polycondensation reaction of the polyester resin does not proceed sufficiently. Furthermore, when the toner is used, the performance as a charge control agent is not sufficiently exhibited. On the other hand, when the amount is more than 10 mol%, when the toner is used, the hygroscopicity is increased, the charging ability is locally increased, and the charging becomes nonuniform.
In the present invention, the non-crystalline polyester resin more preferably contains 1 to 9 mol% of a structural unit formed from a substituted polycarboxylic acid having a protonic acid group other than the carboxyl group in the total structural unit, It is more preferable to contain 8 mol%.
In addition, containing 0.5 to 10 mol% in all the structural units means that the substituted polycarboxylic acid is 0.5 to 10 mol% with respect to the total number of moles of polycarboxylic acid and polyol constituting the amorphous polyester. Means that. In other words, it means that the structural unit formed from the substituted polycarboxylic acid is 0.5 to 10 mol% with respect to the entire structural unit formed from the polycarboxylic acid and the polyol.
In the present invention, the non-crystalline polyester resin is preferably produced by a production method including a step of polycondensing a polycarboxylic acid and a polyol, and the substituted polycarboxylic acid having a proton acid group other than a carboxyl group as the polycarboxylic acid. It is preferable to produce the acid by using 0.5 to 10 mol% with respect to the total number of moles of polyol and polycarboxylic acid.

  In the present invention, tin and titanium contained in the electrostatic image developing toner are derived from a compound containing tin and titanium metal. For example, organic tin compounds such as dibutyltin oxide and organic compounds such as titanium tetrabutoxide are used. Examples include titanium compounds. The content of tin and titanium atoms is 100 ppm or less. In the present invention, if the content of tin or titanium exceeds 100 ppm, the resin may not be uniformly mixed when polycondensation is performed at a low temperature of 150 ° C. or lower during production.

In the present invention, the polycondensation reaction is performed by an esterification reaction (dehydration reaction) of a polycarboxylic acid and a polyol or an ester exchange reaction between a polycarboxylic acid polyalkyl ester and a polyol. Although any reaction can be used as the polycondensation reaction, a polycondensation reaction using a polycarboxylic acid and a polyol and accompanied by a dehydration reaction is preferable.
In the present invention, an amorphous polyester resin can be easily obtained by a combination of polycondensable monomers shown below.

<Polycarboxylic acid>
As the polycarboxylic acid, a dicarboxylic acid monomer is preferably used, and as the dicarboxylic acid monomer, 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,1- Cyclopentene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,2-cyclohexene dicarboxylic acid, norbornene-2,3-dicarboxylic acid, adamantane dicarboxylic acid, 1 1,4-phenylene diacetic acid, 1,4-phenylene dipropionic acid, 1,3-phenylene diacetic acid, 1,3-phenylene dipropionic acid, 1,2-phenylene diacetic acid, 1,2-phenylene dipropio Nick acid etc. can be mentioned, but it is limited to this Not shall.
Further, the polycarboxylic acid used may have various functional groups added to any of its structures. The carboxylic acid group that is a polycondensation reactive functional group may be an acid anhydride, an acid ester, or an acid chloride. However, since an intermediate between an acid ester compound and a proton is easily stabilized and tends to suppress reactivity, a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid chloride is preferably used.

<Polyol>
As the polyol, a diol monomer having two hydroxyl groups is preferably used. Examples of the diol monomer include various aromatic nucleus diols such as 1,4-dihydroxyethoxybenzene, bisphenol A ethylene oxide or propylene oxide adduct. Raised. In addition, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6-hexane glycol, 2,7-dimethyl-4,7 -Octanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, 3-methyl-1 Various aliphatic diols such as 1,5-pentanediol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol, various alicyclic diols such as 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol, etc. There is one of these It is raised to be used as a mixture of two or more.

The weight average molecular weight suitable for the non-crystalline polyester resin produced in the present invention to be suitable for toner is 5,000 to 50,000, and more preferably 7,000 to 35,000. is there. When the weight average molecular weight is 5,000 or more, the powder flowability at normal temperature is good, the toner is not blocked, and the cohesion as a toner binder resin is good. Since hot offset property is acquired, it is preferable. A weight average molecular weight of 50,000 or less is preferable because a good minimum fixing temperature can be obtained, and the time and temperature required for polycondensation are appropriate, and good production efficiency can be obtained.
In the present invention, the non-crystalline polyester resin may have a partially branched or crosslinked structure depending on the selection of the carboxylic acid valence and alcohol valence of the monomer.
A weight average molecular weight and a number average molecular weight can be measured by a well-known method, for example, can be measured by gel permeation chromatography (GPC) etc.

In this invention, it is preferable that the glass transition point Tg of an amorphous polyester resin is 50-80 degreeC, More preferably, it is the range of 50-65 degreeC. A Tg of 50 ° C. or higher is preferable because the cohesive force of the binder resin itself is good even in a high temperature range, and hot offset does not occur during fixing. Further, it is preferable that Tg is 80 ° C. or lower because sufficient solubility can be obtained and a satisfactory minimum fixing temperature can be obtained.
In the present invention, when the crystalline resin is further contained as the binder resin, the crystal melting point Tm is preferably 50 to 120 ° C, more preferably 55 to 90 ° C. A Tm of 50 ° C. or more is preferable because a good cohesive force of the binder resin itself can be obtained even in a high temperature range, and deterioration of peelability and hot offset do not occur during fixing. Further, it is preferably 120 ° C. or lower because sufficient melting can be obtained and a satisfactory minimum fixing temperature can be obtained.

In the present invention, a catalyst may be used in the polycondensation of the amorphous polyester. However, in the present invention, the substituted polycarboxylic acid having a protonic acid group other than a carboxyl group has catalytic activity, so that a polycondensation reaction can be carried out without using a catalyst.
In the polycondensation of the amorphous polyester, an acid having a surface active effect may be used as a catalyst.
Examples of acids having surface-active effects include alkyl benzene sulfonic acids such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, keryl benzene sulfonic acid, camphor sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl Naphthalene sulfonic acid, alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutyl phenyl phenol sulfuric acid, dibutyl phenyl phenol sulfuric acid, dodecyl sulfuric acid, etc. Higher fatty acid sulfate, higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, high Fatty acid amide alkylated sulfates, naphthenyl alcohol sulfates, sulfated fats, sulfosuccinates, various fatty acids, sulfonated higher fatty acids, higher alkyl phosphates, alcohol sulfates, naphthenic acids, and all these salt compounds are used Yes, and a plurality may be combined as necessary.

Furthermore, examples of the acid having surface activity include scandium dodecylbenzenesulfonate having a dodecylbenzenesulfonate group attached to a rare earth metal.
The acid having the surface active effect may be used alone, or may be used in combination with sodium dodecylbenzenesulfonate or sodium dodecylsulfate which are neutralizing surfactants.

Further, a rare earth catalyst may be used in combination with the catalyst. Specific examples of the rare earth-containing catalyst include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), and europium (Eu). , Gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc. are particularly effective. An alkylbenzene sulfonate, an alkyl sulfate ester salt, or a compound having a triflate structure is effective. The metal triflate has a structural formula of X (OSO ₂ CF ₃ ) ₃ , where X is a rare earth element. Among these, the metal triflate has X as scandium (Sc), yttrium (Y). , Ytterbium (Yb) and samarium (Sm) are more preferable.
Also preferred are lanthanoid triflates. The lanthanoid triflate is described in detail in Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54.

The hydrolase is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase in the present invention include EC (enzyme number) 3.1 group such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase, lipoprotein lipase and the like. (See Maruo and Tamiya's “Enzyme Handbook” Asakura Shoten (1982) etc.) Hydrolase and epoxide classified as EC 3.2 that act on glycosyl compounds such as esterase, glucosidase, galactosidase, glucuronidase, and xylosidase EC3. Acting on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin, etc. classified into EC3.3 group such as hydrase. Can be mentioned hydrolases such classified hydrolases classified into groups, the EC3.7 group such as furo retinoic hydrolase.
Among the above esterases, enzymes that hydrolyze glycerol esters to liberate fatty acids are called lipases, but lipases are highly stable in organic solvents, catalyze ester synthesis reactions in high yields, and are available at a lower price. There are advantages such as what you can do. Therefore, also in the manufacturing method of polyester of this invention, it is preferable to use a lipase from the surface of a yield or cost.
Lipases of various origins can be used, but preferred are Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, Rhizopus Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, and steapsin. Among these, it is preferable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.
These compounds having a catalytic action may be used alone or in combination.

In the present invention, the method for producing the amorphous polyester resin is not particularly limited, and is a general polymerization method such as polycondensation in water performed by emulsifying a monomer or initiator in water, or bulk polymerization, solution polymerization, interfacial polymerization, etc. Among these, the bulk polymerization method is preferable among them. Bulk polymerization can be carried out under atmospheric pressure, but general conditions such as reduced pressure and nitrogen flow can be used for the purpose of increasing the molecular weight of the resulting polyester molecule.
Moreover, when performing bulk polymerization, it is preferable that polycondensation temperature is 80 to 150 degreeC, More preferably, it is 90 to 130 degreeC, More preferably, it is 100 to 120 degreeC.
A polycondensation temperature of 80 ° C. or higher is preferable because the solubility of the monomer is good, sufficient reactivity is obtained, and a good molecular weight is obtained. A polycondensation temperature of 150 ° C. or lower is preferable because an amorphous polyester resin can be produced with low energy. Moreover, since coloring of the resin resulting from high temperature, decomposition | disassembly of produced | generated polyester, etc. do not occur, it is preferable.

  The binder resin produced as described above is a so-called chemical method in which a mechanical particle production method such as a pulverization method or a resin particle dispersion is produced using the binder resin, and a toner is produced from the resin particle dispersion. A toner can be manufactured by a manufacturing method. In the present invention, the toner is preferably produced by a chemical production method.

(Binding resin particle dispersion for electrostatic image developing toner)
In the present invention, the binder resin particle dispersion for electrostatic charge image developing toner (hereinafter also simply referred to as “resin particle dispersion”) is a resin particle in which resin particles containing at least a binder resin are dispersed in a dispersion medium. In the dispersion, the binder resin includes the binder resin for electrostatic image developing toner of the present invention.

<Aqueous medium>
In the present invention, the dispersion medium of the resin particle dispersion is preferably an aqueous medium.
Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used alone or in combination of two or more.
The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.

The median diameter (center diameter) of the resin particle dispersion of the present invention is preferably from 0.05 μm to 2.0 μm, more preferably from 0.1 μm to 1.5 μm, still more preferably from 0.1 μm to 1. 0 μm or less. This median diameter within the above range is preferable because the dispersion state of the resin particles in the aqueous medium is stabilized as described above. Further, when used for toner preparation, it is preferable because the particle diameter can be easily controlled and the releasability and offset property during fixing are excellent.
In addition to the median diameter of the particles in the resin particle dispersion, it is also important that there is no generation of ultrafine powder or ultracoarse powder, and the ratio of particles of 0.01 μm or less or 5.0 μm or more is 10% or less. It is preferable that there is, more preferably 5% or less.
The median diameter of the resin particles can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

The resin particle dispersion of the present invention can be produced by a known method using the binder resin for electrostatic image developing toner of the present invention.
Examples of the method for producing the resin particle dispersion of the present invention include a method including a dispersion step in which the binder resin-containing material is dispersed in an aqueous medium to obtain a resin particle dispersion.
In the dispersion step, it is preferable to carry out dispersion by adding a surfactant or the like in order to increase the dispersion efficiency or improve the stability of the resin particle dispersion.
Examples of the method for dispersing and granulating the binder resin of the present invention in an aqueous medium include, for example, a suspension polymerization method, a dissolution suspension method, a miniemulsion method in an aqueous medium when the binder resin is produced. Examples include a microemulsion method, a multistage swelling method, and an emulsion polymerization method including seed polymerization.
In the present invention, when emulsification polycondensation of the binder resin in an aqueous medium, the preferable emulsification temperature is preferably lower in consideration of energy saving, polymer production rate and thermal decomposition rate of the produced polymer. , Preferably it is 40-150 degreeC, More preferably, it is 60-130 degreeC. It is preferable that the emulsification temperature is 150 ° C. or lower because the required energy does not become excessive and the molecular weight is not lowered due to decomposition of the resin due to high heat. Moreover, it is preferable for the temperature to be 40 ° C. or higher because the resin viscosity is moderate and the formation of fine particles is easy.

The method for dispersing and particleizing the binder resin in an aqueous medium can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. Of these, the self-emulsification method and the phase inversion emulsification method are preferably applied in consideration of the energy required for emulsification, the particle size controllability of the obtained emulsion, stability, and the like.
The self-emulsification method and the phase inversion emulsification method are described in “Application Technology of Ultrafine Particle Polymer (CMC Publishing)”. As the polar group used for self-emulsification, a carboxyl group, a sulfone group, and the like can be used. When applied to the non-crystalline polyester binder resin for toner of the present invention, a carboxyl group is preferably used.

When an organic solvent is used in the dispersion step, the method for producing a resin particle dispersion of the present invention may include a step of removing at least a part of the organic solvent and a step of forming resin particles.
For example, after emulsifying the binder resin-containing material, it is preferable to solidify as particles by removing a part of the organic solvent. As a specific method of solidification, after the polycondensation resin-containing material is emulsified and dispersed in an aqueous medium, while stirring the solution, an inert gas such as air or nitrogen is fed into the organic solvent at the gas-liquid interface. A method of drying (waste wind drying method), a method of drying while holding under reduced pressure and bubbling an inert gas as necessary (pressure reduction topping method), and further, a polycondensation resin-containing material is an aqueous medium There is a method in which an emulsified dispersion liquid emulsified and dispersed or an emulsion liquid containing a polycondensation resin is discharged from the pores in a shower-like manner and dropped into a dish-shaped receiver and dried while repeating this (shower-type solvent removal method). . It is preferable to remove the solvent by selecting or combining these methods as appropriate based on the evaporation rate of the organic solvent to be used, solubility in water, and the like.

As a chemical production method of the toner using the binder resin for electrostatic image developing toner of the present invention, a general production method can be used, but an aggregation and coalescence method is preferable. The aggregation coalescence method is a known aggregation method in which a latex in which a binder resin is dispersed in water is produced and aggregated (aggregated) with other toner raw materials.
The method for producing an electrostatic charge image developing toner (also simply referred to as “toner”) of the present invention comprises a step of aggregating the binder resin particles in a dispersion containing at least a binder resin particle dispersion to obtain aggregated particles ( Hereinafter, it is also referred to as “aggregation step”) and a process for heating and coalescing the aggregated particles (hereinafter also referred to as “fusion step”). The adhesion resin particle dispersion is the binder resin particle dispersion for electrostatic image developing toner of the present invention.

  Using the resin particle dispersion prepared as described above, so-called latex, it is possible to produce a toner whose toner particle diameter and distribution are controlled using an aggregation (association) method. More specifically, the latex (resin particle dispersion) prepared as described above is mixed with a colorant particle dispersion and a release agent particle dispersion, and a flocculant is added to cause heteroaggregation, thereby producing a toner diameter. The agglomerated particles are formed, and then heated to a temperature not lower than the glass transition point or the melting point of the resin particles to fuse and coalesce the agglomerated particles, and are washed and dried. In this manufacturing method, the toner shape can be controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

In the agglomeration step of the present invention, the resin particle dispersion other than the resin particle dispersion of the present invention and the resin particle dispersion of the present invention can be mixed to carry out the steps after the aggregation. At that time, after the resin particle dispersion of the present invention is aggregated in advance and the first aggregated particles are formed, the resin particle dispersion of the present invention or another resin particle dispersion is further added to form a second shell on the surface of the first particles. It is also possible to make the particles multi-layered, such as forming a layer. Of course, it is also possible to produce multilayer particles in the reverse order of the above example.
Further, for example, in the aggregation step, the resin particle dispersion containing the binder resin of the present invention and the colorant particle dispersion are aggregated in advance, and after forming the first aggregated particles, the resin particles further containing the binder resin of the present invention It is also possible to form a second shell layer on the surface of the first particles by adding a dispersion or another resin particle dispersion. In this illustration, the colorant dispersion is separately prepared, but naturally the colorant may be blended in advance with the resin particles.

  After completing the coalescence and coalescence process of the aggregated particles, the desired toner particles are obtained through an optional washing process, solid-liquid separation process, and drying process. It is preferable to perform replacement washing. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  As a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as cohesion control and toner chargeability. The metal salt compound used for aggregation is obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin particle dispersion, but the metal elements constituting the inorganic metal salt are a periodic table (long period table). 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, and 3B, and those having a valence of 2 or more and soluble in the form of ions in the resin particle aggregation system. Good. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium sulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is more than 1, more than 2, more than 3, and the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

In the present invention, for example, the following colorants can be used.
Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.
Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, permanent yellow NCG, and the like. be able to.
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.
Red pigments include Bengala, Cadmium Red, Red Plum, Mercury Sulfide, Watch Young Red, Permanent Red 4R, Risor Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C , Rose Bengal, Eoxin Red, Alizarin Lake and the like.

Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate.
Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.
Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

These colorants are used alone or in combination. For these colorants, for example, a dispersion of colorant particles is prepared by using a media-type disperser such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, or a high-pressure counter-collision disperser. be able to. Further, these colorants can be dispersed in an aqueous system by a homogenizer using a polar surfactant.
The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner.
The colorant is preferably added in the range of 4 to 15% by weight with respect to the total weight of the toner constituting solids.
When using a magnetic material as the black colorant, 12 to 240% by weight can be added unlike other colorants.

The blending amount of the colorant can be appropriately selected from the necessary amount for securing the color developability at the time of fixing. The median diameter (center diameter) of the colorant particles in the toner is preferably 100 to 330 nm, which is preferable because OHP transparency and color developability can be secured.
The median diameter (center diameter) of the colorant particles can be measured, for example, with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.).

Further, when used as a magnetic toner, magnetic powder may be included. Specifically, a material that is magnetized in a magnetic field is used, but a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used.
When the toner is obtained in the aqueous phase in the present invention, it is necessary to pay attention to the aqueous phase transfer property of the magnetic material. Preferably, the surface of the magnetic material is preferably modified in advance and subjected to, for example, a hydrophobic treatment. preferable.

When producing a toner using the polycondensation resin dispersion of the present invention, an addition polymerization resin particle dispersion prepared by using a conventionally known emulsion polymerization or the like can be used together.
Examples of addition polymerization monomers for preparing these resin particle dispersions include styrenes such as styrene and parachlorostyrene, vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, propion. Vinyl esters such as vinyl acid, vinyl benzoate, vinyl butyrate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, Methylene aliphatic carboxylic esters such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide such as vinyl methyl ether, vinyl ethyl ether, vinyl Monomers having N-containing polar groups such as N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, methacrylic acid, acrylic Homopolymers and copolymers of vinyl monomers such as vinyl carboxylic acids such as acid, cinnamic acid and carboxyethyl acrylate, and various waxes can also be used.

  In the case of addition polymerization monomers, emulsion polymerization can be carried out using an ionic surfactant or the like to produce a resin particle dispersion, and in the case of other resins, it is oily and the solubility in water is compared. If it is soluble in a low solvent, dissolve the resin in those solvents, disperse it in water with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heat or reduce the pressure. A resin particle dispersion can be obtained by evaporating the solvent.

  Also, magnetic materials such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese and other metals, alloys, and compounds containing these metals are used as internal additives, and quaternary ammonium salt compounds, nigrosine-based as charge control agents. Various commonly used charge control agents such as compounds, dyes consisting of complexes of aluminum, iron, chromium, etc. and triphenylmethane pigments can be used, but the ionic strength that affects aggregation and temporary stability Materials that are difficult to dissolve in water are preferred in terms of control and reduction of wastewater contamination.

  Examples of internal additives include various commonly used charge control agents such as quaternary ammonium salt compounds and nigrosine compounds as charge control agents. However, stability during production and reduction of wastewater contamination can be used. Therefore, materials that are difficult to dissolve in water are suitable.

Specific examples of the release agent used in the present invention include, for example, various ester waxes, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that show a softening point by heating, oleic acid amide, erucic acid amide, and ricinol. Fatty acid amides such as acid amide, stearic acid amide, etc., plant wax such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal wax such as beeswax, montan wax, Examples thereof include mineral and petroleum waxes such as ozokerite, ceresin, paraffin wax, microcrystalline wax, microcrystalline wax, and Fischer-Tropsch wax, and modified products thereof.
These waxes are hardly dissolved in a solvent such as toluene at room temperature or very little even if dissolved.
These waxes are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, heated above the melting point, and have a strong shearing ability and pressure discharge type dispersers. A dispersion liquid of particles having a median diameter (center diameter) of 1 μm or less can be prepared by dispersing the particles in a fine particle form using a gorin homogenizer (manufactured by Gorin).

These release agents are preferably added in the range of 5 to 25% by weight with respect to the total weight of the toner constituent solids, in order to ensure the releasability of the fixed image in the oilless fixing system.
The median diameter of the obtained release agent particle dispersion was measured, for example, with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). In addition, when using a release agent, after the resin particles, colorant particles, and release agent particles are aggregated, it is possible to add resin particle dispersion to adhere the resin particles to the surface of the aggregated particles. From the viewpoint of securing the property.

In addition, the toner of the present invention is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic fine particles such as silica, alumina, titania and calcium carbonate, vinyl resin, polyester, silicone and the like. The resin fine particles can be used by being added to the toner particle surfaces while being sheared in a dry state.
When adhering to the toner surface in water, examples of inorganic fine particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate. It can be used by dispersing with a surfactant, polymer acid or polymer base.

  In the present invention, a surfactant can be used for emulsion polymerization of a resin, dispersion of a colorant, dispersion of resin particles, dispersion of a release agent, aggregation, stabilization of aggregated particles, and the like. Specifically, sulfate surfactants, sulfonates, phosphates, soaps and other anionic surfactants, amine salts, quaternary ammonium salts and other cationic surfactants, polyethylene glycols, It is also effective to use a nonionic surfactant such as an alkylphenol ethylene oxide adduct system or a polyhydric alcohol system, and as a dispersing means, a general method such as a ball mill, sand mill, or dyno mill having a rotary shearing homogenizer or media Can be used

  After completing the coalescence and coalescence process of the aggregated particles, the desired toner particles are obtained through an optional washing process, solid-liquid separation process, and drying process. It is preferable to perform replacement washing. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

The cumulative volume average particle diameter D ₅₀ of the toner of the present invention is preferably in the range of 3.0 to 9.0 μm, more preferably in the range of 3.0 to 8.0 μm. It is preferable that the cumulative volume average particle diameter of the toner is 3.0 μm or more because adhesion is appropriate and good developability is obtained. Further, it is preferable that the cumulative volume average particle diameter is 9.0 μm or less because good image resolution can be obtained.
The volume average particle size distribution index GSDv of the toner of the present invention is preferably 1.30 or less. It is preferable that GSDv is 1.30 or less because the resolution is good and image defects such as toner scattering and fogging do not occur.

The cumulative volume average particle diameter D ₅₀ and the volume average particle size distribution index of the present invention are measured by a measuring instrument such as Coulter Counter TAII (manufactured by Beckman-Coulter) or Multisizer II (manufactured by Beckman-Coulter).
The volume average particle size distribution index is obtained as follows. Specifically, the cumulative distribution is drawn from the smaller diameter side to the particle size range (channel) divided based on the measured particle size distribution, and the particle diameter that becomes 16% cumulative is represented by volume D _16v. , D _16P , the particle size that is 50% cumulative is _defined as volume D _50v , D _50P , and the particle size that is 84% cumulative is defined as volume D _84v and number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

  The influence of the coarse powder ratio on the image quality increases as the toner diameter is smaller or the toner shape is closer to a sphere, and particularly when the toner diameter is 7 microns or less and the toner shape factor SF1 is in the range of 100 to 130. In some cases, the reduction of the coarse powder ratio is particularly important.

In the present invention, the shape factor of the toner is preferably from 100 to 145, more preferably from 110 to 145 from the viewpoint of image formability.
SF1 is defined as follows.
SF1 = (ML ² / A) × (π / 4) × 100
Here, ML: Absolute maximum length of toner particles A: Projection area of toner particles The shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer. It is requested in this way. In measuring the shape factor SF1, first, an optical microscope image of the toner dispersed on the slide glass is taken into a Luzex image analyzer through a video camera, and SF1 of the above formula is calculated for 50 or more toners to obtain an average value. Can be obtained.

(Electrostatic image developer)
The electrostatic image developing toner of the present invention can be used as an electrostatic image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development according to an electrostatic latent image can be applied.
The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.
The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is usually 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method)
Further, the electrostatic image developing toner and the electrostatic image developer of the present invention can be used in an ordinary electrostatic image developing system (electrophotographic system) 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 step for thermally fixing the toner image transferred to the surface of the transfer target. The electrostatic image developing toner of the present invention is used as the toner, or the electrostatic image developer of the present invention is used as the developer.
For each of the above steps, a known step can be used in the image forming method, and are described in, for example, JP-A-56-40868 and JP-A-49-91231.
Further, the image forming method of the present invention may include steps other than the above-described steps. For example, a cleaning step for removing the electrostatic charge image developer remaining on the electrostatic latent image carrier is preferable. Can be mentioned. In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

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 onto the surface of the transfer medium is thermally fixed by a fixing device (fixing step), and a final toner image is formed.
In the heat fixing by the fixing device, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all.
For the toner, prepare the following binder resin particle dispersion, colorant particle dispersion, and release agent particle dispersion, respectively, mix them at a predetermined ratio, and add the metal salt polymer while stirring. , Ionized neutralization to form aggregated particles. Next, inorganic hydroxide was added to adjust the pH in the system from weakly acidic to neutral, and then the mixture was heated to a temperature equal to or higher than the glass transition point of the resin particles to be fused and united. After completion of the reaction, a desired toner was obtained through sufficient washing, solid-liquid separation, and drying processes.
Hereinafter, each preparation method is demonstrated.

The cumulative volume average particle diameter (D ₅₀ ) of the toner particles was measured using a Coulter counter (TAII type, manufactured by Coulter Inc.).
On the other hand, the median diameter (center diameter) of the resin particles, the colorant, and the release agent was measured using a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Seisakusho).

The structural unit of the resin was measured by NMR (nuclear magnetic resonance method). Specifically, the sample sample was dissolved in tetrahydrofuran and reprecipitated in hexane. The precipitated product was filtered and then vacuum-dried at 50 ° C. for 16 hours. This was repeated twice.
Further, the dried sample sample was dissolved in tetrahydrofuran and reprecipitated in water. After filtering this, it vacuum-dried again at 50 degreeC for 24 hours. A prescribed amount (0.01 g) of this sample was taken and S-NMR was measured.
An example is 5-sulfoisophthalic acid. Using a resin in which 5-sulfoisophthalic acid has been removed and an arbitrary amount of 5-sulfoisophthalic acid mixed, create a number check quantitative curve and compare it with the strength determined by measurement. The amount of each constituent unit was determined. Other substituted carboxylic acids can be obtained by the same method.

As a measuring method of the glass transition point, a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC50) was used. The sample was weighed into a 10 mg aluminum pan container and set in a device. This was scanned with the following program.
(1) The temperature was raised from room temperature to 150 ° C. at a rate of temperature rise of 10 ° C./min and held at 150 ° C. for 10 minutes.
(2) The temperature was lowered to −10 ° C. at −10 ° C./min and held at −10 ° C. for 10 minutes.
(3) The temperature was increased from −10 ° C. to 150 ° C. at a temperature increase rate of 10 ° C./min.
The glass transition point was the temperature at the intersection of the extension line of the base line and the rising line in the endothermic part of (3).

Example 1
<Preparation of resin particle dispersion (1)>
1,4-cyclohexanedicarboxylic acid 18.0 parts by weight Bisphenol A 1-EO 30.7 parts by weight (ethylene oxide 2-mole adduct in terms of both ends)
4-Sulfonaphthalene-2,7-dicarboxylic acid 3.7 parts by weight Tin compound: Dibutyltin oxide (manufactured by Wako Pure Chemical Industries) 0.004 part by weight Titanium compound: Titanium tetrabutoxide (manufactured by Wako Pure Chemical Industries) 0.005 parts by weight The above Was placed in a flask equipped with a stirrer, and polycondensation was performed at 120 ° C. for 24 hours in a nitrogen atmosphere to obtain an amorphous polyester resin. When this resin was taken out and measured with a fluorescent X-ray apparatus, the content of tin atoms was 10 ppm, and the content of titanium atoms was 10 ppm.

  The structural unit (mol%) formed from the substituted polycarboxylic acid having a protonic acid group other than a carboxyl group in the obtained resin was subjected to NMR analysis of the obtained resin as described above, and the structure was identified. It was determined by measuring the acid content.

50 parts by weight of the resin was put into a three-necked flask connected with a stirrer and a cooling tube, and the temperature was raised to 95 ° C., and then stirring was continued while gradually adding 1N NaOH. When 100 parts by weight of NaOH aqueous solution was added in total, the resin was in a slurry state.
50 parts by weight of this aqueous resin solution was put into a flask containing 100 parts by weight of ion-exchanged water adjusted to 85 ° C., emulsified with a homogenizer (manufactured by IKA, Ultra Turrax) for 10 minutes, and further in an ultrasonic bath. And then emulsified for 10 minutes, and then the flask was cooled with room temperature water.
The resin particle dispersion (1) thus obtained had a resin particle median diameter of 148 nm, a polymerization average molecular weight of 8,500, and a solid content concentration of 30 wt%. The glass transition point was 65 ° C.

<Preparation of anionic resin particle dispersion>
Styrene 460 parts by weight n-butyl acrylate 140 parts by weight Acrylic acid 12 parts by weight Dodecanethiol 9 parts by weight The above components were mixed and dissolved to prepare a solution. On the other hand, 12 parts by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 250 parts by weight of ion-exchanged water, and the above solution was added and dispersed and emulsified in a flask (monomer emulsion A). .
Furthermore, 1 part by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 555 parts by weight of ion-exchanged water and charged into a polymerization flask.
The polymerization flask was sealed, a reflux tube was installed, and the polymerization flask was heated to 75 ° C. with a water bath while being slowly stirred while injecting nitrogen, and held. 9 parts by weight of ammonium persulfate was dissolved in 43 parts by weight of ion-exchanged water and dropped into the polymerization flask via a metering pump over 20 minutes, and then the monomer emulsion A was added for 200 minutes through the metering pump. It was dripped over. Thereafter, the polymerization flask was kept at 75 ° C. for 3 hours while continuing the stirring slowly to complete the polymerization. As a result, an anionic resin particle dispersion having a median diameter of 210 nm, a glass transition point of 53.5 ° C., a weight average molecular weight of 31,000, and a solid content of 42% was obtained.

<Preparation of Colorant Particle Dispersion (1)>
Blue (cyan) pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., PB15: 3) 20 parts by weight Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight The above components are mixed and dissolved, and a homogenizer ( Dispersion was carried out for 5 minutes by an ultrasonic bath (Ultra Tarax, manufactured by IKA) to obtain a cyan pigment dispersion.
The median diameter of the pigment in the dispersion was 121 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15% by weight to obtain a colorant particle dispersion (1).

<Preparation of release agent particle dispersion>
30 parts by weight of polyethylene wax (Toyo Petrolite, Polywax 725, melting point 103 ° C.)
Cationic surfactant (manufactured by Kao Corporation, Sanizol B50) 3 parts by weight Ion-exchanged water 67 parts by weight After the components were heated to 95 ° C. and sufficiently dispersed with a homogenizer (IKA, Ultra Turrax T50), When a dispersion treatment was performed using a pressure discharge type homogenizer (Gorin homogenizer, manufactured by Gorin Co., Ltd.), the median diameter of the dispersed release agent particles was 460 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 30% by weight to obtain a release agent particle dispersion.

<Preparation of toner particles>
Resin particle dispersion (1) 120 parts by weight Anionic resin particle dispersion 40 parts by weight Colorant particle dispersion (1) 60 parts by weight Release agent particle dispersion 40 parts by weight (release agent 10.9 parts by weight)
Polyaluminum chloride (10% by weight aqueous solution, manufactured by Asada Chemical Co., Ltd.) 15 parts by weight The above components are dispersed in a round stainless steel flask at 5,000 rpm for 3 minutes using a homogenizer (manufactured by IKA, Ultra Turrax T50). Then, after the flask is covered with a stirrer having a magnetic seal, a thermometer and a pH meter, a heating mantle heater is set, and the minimum number of revolutions at which the entire dispersion in the flask is stirred The mixture was heated to 62 ° C. with stirring at 1 ° C./1 min while being stirred, and maintained at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was confirmed with a Coulter counter (TAII, manufactured by Nikka Kisha Co., Ltd.). Immediately after the temperature rise was stopped, 50 parts by weight of the resin particle dispersion (1) was added and held for 30 minutes, and then an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water, washed with water, dispersed in ion-exchanged water so that the solid content is 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Then, the slurry obtained by sufficiently filtering and washing with water through ion exchange water again was freeze-dried to obtain a cyan toner (toner C1).

<Preparation and evaluation of developer>
The obtained final toner had a cumulative volume average particle size of 6.9 μm. The shape factor SF1 was 140, and the volume average particle size distribution index GSDv was 1.15.
To 100 parts by weight of the obtained toner particles, 1 part by weight of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., R972) was externally added and mixed using a Henschel mixer to obtain an electrostatic charge image developing toner.

<Evaluation of charge amount>
100 parts by weight of ferrite particles (manufactured by Powdertech, average particle size 50 μm) and 1 part by weight of a methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 95,000) are placed in a pressure kneader together with 500 parts by weight of toluene. After mixing for a minute, 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 prepare a ferrite carrier (resin-coated carrier).
This ferrite carrier and the electrostatic image developing toner were mixed to prepare a two-component electrostatic image developer having a toner concentration of 7% by weight.
Put the prepared developer in a V blender, stir for 20 minutes, put it in the developer of A color full-color copier (Fuji Xerox Co., Ltd.), and measure the charge amount with a blow-off charge meter (Toshiba) after setup. (The mesh uses a 20 μm opening). If the charge amount was 10 to 40 μC / g, the determination was ○, and the other range was ×.

<Image quality evaluation>
Further, the image quality was evaluated by performing image formation using a Docu Center Color 500CP remodeling machine manufactured by Fuji Xerox Co., Ltd., and evaluating the initial image quality.
The image quality was evaluated according to the following evaluation criteria.
-Evaluation criteria-
○: No problem in the image △: Some dirt was observed but there was no practical problem ×: Large dirt was observed and it was practically unusable

(Example 2)
In Example 1, 3.7 parts by weight of substituted polycarboxylic acid (4-sulfonaphthalene-2,7-dicarboxylic acid) was changed to 3.2 parts by weight of 5-sulfoisophthalic acid, and titanium tetrabutoxide was added to 0.0025 parts by weight. The procedure was the same as in Example 1 except for the change.
As a result, the concentration (mol%) of the structural unit formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 5.3 mol% in all structural units as measured by NMR.

(Example 3)
In Example 1, 3.7 parts by weight of substituted polycarboxylic acid (4-sulfonaphthalene-2,7-dicarboxylic acid) was changed to 0.47 parts by weight of 5-sulfoisophthalic acid, and dibutyltin oxide was changed to 0.008 parts by weight. The procedure was the same as in Example 1 except that.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 0.8 mol% in all structural units as measured by NMR.

Example 4
The same procedure as in Example 1 was conducted except that 3.7 parts by weight of 4-sulfonaphthalene-2,7-dicarboxylic acid was changed to 5.3 parts by weight of 5-sulfoisophthalic acid.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 9.6 mol% in all structural units as measured by NMR.

(Example 5)
The same procedure as in Example 1 was performed except that dibutyltin oxide was changed to 0.04 parts by weight in Example 2 and titanium tetrabutoxide was not used.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 5.1 mol% in all structural units as measured by NMR.

Example 6
In Example 1, 3.7 parts by weight of 4-sulfonaphthalene-2,7-dicarboxylic acid, which is a substituted polycarboxylic acid, was changed to 3.2 parts by weight of 5-sulfoisophthalic acid, and 0.005% by weight of titanium tetrabutoxide. The same procedure as in Example 1 was conducted except that the part was changed to 0.05 part by weight of titanium oxide.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was measured by NMR and found to be 5.2 mol% in all structural units.

(Example 7)
3.7 parts by weight of the substituted polycarboxylic acid (4-sulfonaphthalene-2,7-dicarboxylic acid) described in Example 1 was changed to 5.6 parts by weight of 5-sulfoisophthalic acid, and the polymerization temperature was 70 ° C. The procedure was the same as in Example 1 except that the change was made.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 9.3 mol% in all structural units as measured by NMR.

(Example 8)
In Example 1, 3.7 parts by weight of the substituted polycarboxylic acid (4-sulfonaphthalene-2,7-dicarboxylic acid) was changed to 5.4 parts by weight of 5-sulfoisophthalic acid, and the polymerization temperature was changed to 160 ° C. The procedure was the same as in Example 1 except for the change.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 9.2 mol% in all structural units as measured by NMR.

Example 9
The same procedure as in Example 1 was conducted except that 3.7 parts by weight of the substituted polycarboxylic acid (4-sulfonaphthalene-2,7-dicarboxylic acid) was changed to 0.49 parts by weight of 5-sulfoisophthalic acid in Example 1. .
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 0.7 mol% in all structural units as measured by NMR.

(Example 10)
In Example 1, 3.7 parts by weight of the substituted polycarboxylic acid (4-sulfonaphthalene-2,7-dicarboxylic acid) was changed to 6.0 parts by weight of 5-sulfoisophthalic acid, and 0.04 by weight of dibutyltin oxide. The same procedure as in Example 1 was conducted except that the polymerization temperature was changed to 160 ° C.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 9.9 mol% in all structural units as measured by NMR.

(Comparative Example 1)
The same procedure as in Example 2 was performed except that 5-sulfoisophthalic acid was changed to 14.5 parts by weight in Example 2 and dibutyltin oxide and titanium tetrabutoxide were not added.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 20.1 mol% in all structural units as measured by NMR.

(Comparative Example 2)
The same procedure as in Example 2 was performed except that 5-sulfoisophthalic acid was changed to 0.006 parts by weight in Example 2 and dibutyltin oxide and titanium tetrabutoxide were not added.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 0.01 mol% in all structural units as measured by NMR.

(Comparative Example 3)
The same procedure as in Example 1 was carried out except that 4-sulfonaphthalene-2,7-dicarboxylic acid was changed to 0.007 parts by weight in Example 1 and dibutyltin oxide and titanium tetrabutoxide were not added.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 0.01 mol% in all structural units as measured by NMR.

(Comparative Example 4)
The same procedure as in Example 1 was carried out except that 5-sulfoisophthalic acid was not used in Example 2 and polycondensation was performed using 0.09 parts by weight of dibutyltin oxide.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 0 mol% in all structural units as measured by NMR.

(Comparative Example 5)
In Example 2, the procedure was the same except that 5-sulfoisophthalic acid was changed to 3.0 parts by weight, 0.09 part by weight of dibutyltin oxide was used, and titanium tetrabutoxide was not added.
As a result, the structural unit (mol%) formed from 5-sulfoisophthalic acid, which is a substituted polycarboxylic acid, was 5.5 mol% in all structural units as measured by NMR.
The results are shown in Table 1 below.

Claims (7)

A binder resin for an electrostatic charge image developing toner comprising an amorphous polyester resin obtained by polycondensation of a polycarboxylic acid and a polyol,
The polyester resin contains a structural unit formed from a substituted polycarboxylic acid having a protonic acid group other than a carboxyl group, in a total structural unit of 0.5 mol% to 10 mol%,
The binder resin for an electrostatic charge image developing toner, wherein tin and titanium concentrations in the polyester resin are each 100 ppm or less. A method for producing a binder resin for an electrostatic charge image developing toner comprising a step of polycondensing a polycarboxylic acid and a polyol,
The binder resin for electrostatic charge image developing toner is an amorphous polyester resin,
The polycarboxylic acid contains a substituted polycarboxylic acid having a proton acid group other than a carboxyl group,
The substituted polycarboxylic acid is 0.5 mol% or more and 10 mol% or less with respect to the total number of moles of the polycarboxylic acid and the polyol,
The method for producing a binder resin for an electrostatic charge image developing toner, wherein tin and titanium concentrations in the polyester resin are each 100 ppm or less.   A binder resin particle dispersion for an electrostatic charge image developing toner, wherein the binder resin for an electrostatic charge image developing toner according to claim 1 is dispersed. A step of aggregating the binder resin particles in a dispersion containing at least a binder resin particle dispersion to obtain aggregated particles; and
A method for producing an electrostatic charge image developing toner comprising a step of heating and aggregating the aggregated particles,
The method for producing an electrostatic image developing toner, wherein the binder resin particle dispersion is the binder resin particle dispersion for an electrostatic image developing toner according to claim 3.   An electrostatic charge image developing toner produced by the production method according to claim 4.   An electrostatic image developer comprising the electrostatic image developing toner according to claim 5 and a carrier. A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing the electrostatic latent image formed on the surface of the latent image holding body with toner or an electrostatic charge image developer to form a toner image;
Transferring the toner image formed on the surface of the latent image holding body to the surface of the transfer target; and
An image forming method comprising a fixing step of thermally fixing the toner image transferred to the surface of the transfer material,
An image forming method using the electrostatic image developing toner according to claim 5 as the toner, or the electrostatic image developer according to claim 6 as the developer.